Compound, polymer, composition, composition for forming film, pattern forming method, method for forming insulating film, and method for producing compound

Abstract

A compound having an unsaturated double bond and one or more halogens. A method for producing an iodine-containing vinyl monomer, which comprises: a) a step for preparing an iodine-containing alcoholic matrix having a valeryl group having a general structure represented by formula (1-1) (wherein the definition of a variable moiety in formula (1-1) is as defined in the description); and b) a step for dehydrating the iodine-containing alcoholic matrix to obtain an iodine-containing vinyl monomer having a general structure represented by formula (1) (wherein the definitions of variable moieties in formula (1) are as defined in the description). # imgabs0 #

Description

[0001] This application is a divisional application of a Chinese patent application with an application date of August 7, 2020, an application number of 202080056621.5, and an invention title of "Compound, Polymer, Composition, Composition for Film Formation, Pattern Formation Method, Method for Forming Insulating Film, Method for Manufacturing Compound, and Method for Manufacturing Iodine-Containing Vinyl Polymer and Its Acetylated Derivative". Technical Field

[0002] The present invention relates to a compound, a polymer, a composition, a composition for film formation, a pattern formation method, a method for forming an insulating film, and a method for manufacturing a compound. In addition, the present invention relates to a method for manufacturing an iodine-containing vinyl polymer and its acetylated derivative. Background Art

[0003] In recent years, in the manufacture of semiconductor elements and liquid crystal display elements, due to the progress of lithography technology, the miniaturization of semiconductors (patterns) and pixels has been progressing rapidly. For the miniaturization of pixels, generally, the wavelength of the exposure light source is shortened. Specifically, ultraviolet rays typified by g-rays and i-rays were used in the past, but now, a method of performing exposure using far ultraviolet rays such as KrF excimer laser (248 nm) and ArF excimer laser (193 nm) has become the center of mass production, and furthermore, the introduction of extreme ultraviolet (EUV: Extreme Ultraviolet) lithography (13.5 nm) is carried out. In addition, an electron beam (EB: Electron Beam) is also used to form a fine pattern.

[0004] Conventional resist materials used so far are polymer-based resist materials that can form an amorphous film. For example, polymer-based resist compositions such as polymethyl methacrylate, polyhydroxystyrene having an acid dissociable group, or polyalkyl methacrylate can be mentioned (for example, refer to Non-Patent Document 1). In the past, an ultraviolet ray, far ultraviolet ray, electron beam, extreme ultraviolet ray, etc. were irradiated onto a resist film produced by coating a solution of these resist compositions on a substrate to form a line pattern of about 10 to 100 nm.

[0005] In addition, the reaction mechanism of lithography based on an electron beam or extreme ultraviolet is different from that of ordinary photolithography (Non-Patent Documents 2 and 3). Furthermore, in lithography based on an electron beam or extreme ultraviolet, a fine pattern of several nm to more than ten nm is targeted. If the size of the resist pattern becomes smaller like this, a resist composition with higher sensitivity to the exposure light source is required. In particular, lithography based on extreme ultraviolet requires further high sensitivity in terms of productivity.

[0006] As a resist material for improving the problems described above, a resist composition containing a metal complex containing titanium, tin, hafnium, zirconium, etc. has been proposed (for example, refer to Patent Document 1).

[0007] In addition, if the size of the resist pattern becomes small like this, a resist composition with higher sensitivity to the exposure light source is required. As a raw material monomer thereof, 4-hydroxystyrene containing iodine has been proposed (for example, refer to Patent Documents 2 to 3), but a synthesis method of iodine-containing hydroxystyrene and its acetylated derivative has not been disclosed.

[0008] On the other hand, many methods for synthesizing hydroxystyrene and its acetylated derivative that do not contain iodine are known (for example, Patent Documents 4 to 6). However, these methods generally require expensive reagents, harsh conditions, and have low yields. In addition, if these synthesis methods are applied to iodine-containing hydroxystyrene and its acetylated derivative, the yield generally becomes even lower.

[0009] Prior Art Documents

[0010] Patent Documents

[0011] Patent Document 1: Japanese Patent Application Laid-Open No. 2015-108781

[0012] Patent Document 2: US2019 / 0187342 Gazette

[0013] Patent Document 3: WO2019 / 187881 Gazette

[0014] Patent Document 4: US4,316,995 Gazette

[0015] Patent Document 5: US5,274,060 Gazette

[0016] Patent Document 6: WO2005 / 097719 Gazette

[0017] Non-Patent Documents

[0018] Non-Patent Document 1: Shinji Okazaki, et al., "40 Years of Lithography Technology", S&T Publishing, December 9, 2016

[0019] Non-Patent Document 2: H. Yamamoto, et al., Jpn. J. Appl. Phys. 46, L142 (2007)

[0020] Non-Patent Document 3: H. Yamamoto, et al., J. Vac. Sci. Technol. B23, 2728 (2005) Summary of the Invention

[0021] Problems to be Solved by the Invention

[0022] However, the film-forming compositions developed in the past have a problem that the sensitivity to an exposure light source is not high enough in the formation of finer patterns.

[0023] In order to solve these problems, an object of the present invention is to provide a compound, a polymer, a composition, a resist composition, a pattern forming method, a method for forming an insulating film, and a method for producing a compound that can obtain a resist having excellent exposure sensitivity.

[0024] In addition, as described above, the method for producing an iodine-containing hydroxystyrene and its acetylated derivative is unknown, and usually requires expensive reagents and severe conditions, and there is a problem of low yield.

[0025] In order to solve these problems, an object of the present invention is to provide a method for producing an iodine-containing vinyl polymer (iodine-containing hydroxystyrene) and its acetylated derivative with high yield without expensive reagents and severe conditions.

[0026] Means for Solving the Problems

[0027] The present inventors conducted intensive studies to solve the above problems, and as a result, found that a compound having a specific structure or a polymer containing the compound as a structural unit can improve the exposure sensitivity of a resist composition, thereby completing the present invention.

[0028] That is, the present invention is as follows. [1]

[0030] A compound having an unsaturated double bond and one or more halogens. [2]

[0032] The compound according to the above [1], having one or more hydrophilic groups or one dissociable group. [3]

[0034] The compound according to the above [1] or [2], which is represented by the following formula (1).

[0035]

[0036] (In formula (1),

[0037] Each X is independently I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms having one or more and five or less substituents selected from the group consisting of I, F, Cl, and Br,

[0038] L 1Each independently is a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphonic acid group, a urethane group, a urea group, an amide group, an imide group, or a phosphoric acid group, and the aforementioned L 1 The ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphine group, phosphonic acid group, urethane group, urea group, amide group, imide group, or phosphoric acid group of

[0039] Y each independently is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate group, a nitro group, an amino group, a carboxyl group, a mercapto group, an ether group, a thioether group, a phosphine group, a phosphonic acid group, a urethane group, a urea group, an amide group, an imide group, or a phosphoric acid group, and the alkoxy group, ester group, carbonate group, amino group, ether group, thioether group, phosphine group, phosphonic acid group, urethane group, urea group, amide group, imide group, and phosphoric acid group of the aforementioned Y optionally have substituents,

[0040] R a 、R b 、and R c each independently is H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms optionally having substituents,

[0041] A is an organic group having 1 to 30 carbon atoms,

[0042] Z each independently is an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, or a carbonate group, and the alkoxy group, ester group, acetal group, carboxyalkoxy group, or carbonate group of the aforementioned Z optionally has a substituent,

[0043] p is an integer of 1 or more, m is an integer of 1 or more, n is an integer of 0 or more, and r is an integer of 0 or more.) [4]

[0045] The compound according to the aforementioned [3] is represented by the following formula (1a).

[0046]

[0047] (In formula (1a),

[0048] X, L 1 、Y, A, Z, p, m, n, and r are the same as the definitions in formula (1).) [5]

[0050] The compound according to the aforementioned [3] is represented by the following formula (1b).

[0051]

[0052] (In formula (1b),

[0053] X, L1 、 Y, A, Z, p, m, n, and r are the same as defined in formula (1),

[0054] R a1 、R b1 、 and R c1 are each independently H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms optionally with substituents,

[0055] R a1 、R b1 、 and R c1 at least any one of them is I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms optionally with substituents.) [6]

[0057] The compound according to any one of the foregoing [3] to [5], wherein n + r is an integer of 1 or more. [7]

[0059] The compound according to any one of the foregoing [3] to [6], wherein Y is each independently a group represented by the following formula (Y-1).

[0060] -L 2 -R 2 (Y-1)

[0061] (In formula (Y-1),

[0062] L 2 is a group that is cleaved by the action of an acid or a base,

[0063] R 2 is a linear, branched or cyclic aliphatic group having 1 to 30 carbon atoms; an aromatic group having 1 to 30 carbon atoms; a linear, branched or cyclic aliphatic group containing a heteroatom having 1 to 30 carbon atoms; an aromatic group containing a heteroatom having 1 to 30 carbon atoms, and the foregoing R 2 's aliphatic group, aromatic group, aliphatic group containing a heteroatom, aromatic group containing a heteroatom optionally further has substituents.) [8]

[0065] The compound according to any one of the foregoing [3] to [7], wherein A is an aromatic ring. [9]

[0067] The compound according to any one of the foregoing [3] to [7], wherein A is an alicyclic structure.

[10]

[0069] The compound according to any one of the foregoing [3] to [9], wherein A is a heterocyclic structure.

[11]

[0071] The compound according to any one of the foregoing [3] to

[10] , wherein n is 2 or more.

[12]

[0073] The compound according to any one of the foregoing [1] to

[11] , which contains a functional group capable of increasing its solubility in an alkaline developer by the action of an acid or a base.

[13]

[0075] The compound according to any one of the foregoing [3] to

[12] , wherein X is I, and L 1 is a single bond.

[14]

[0077] The compound according to any one of the foregoing [3] to

[12] , wherein X is an aromatic group and is a group formed by introducing one or more F, Cl, Br, or I into the aromatic group.

[15]

[0079] The compound according to any one of the foregoing [3] to

[12] , wherein X is an alicyclic group and is a group formed by introducing one or more F, Cl, Br, or I into the alicyclic group.

[16]

[0081] A composition containing 1 mass ppm or more and 10 mass% or less of the compound represented by formula (1C) with respect to the total amount of the compound according to any one of the foregoing [1] to

[15] .

[0082]

[0083] (In formula (1C), formula (1C1), and formula (1C2),

[0084] X, L 1 , Y, A, Z, p, m, n, and r are the same as defined in formula (1),

[0085] R sub represents formula (1C1) or formula (1C2),

[0086] R a1 、R b1 、and R c1 are each independently H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms optionally having a substituent,

[0087] R a1 、R b1 、and R c1At least one of the above is I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent,

[0088] p-1 is an integer greater than 0,

[0089] * is the bonding site with the adjacent structural unit. )

[17]

[0091] A composition comprising the compound according to any one of [1] to

[15] above and a compound represented by formula (1D) in an amount of 1 ppm by mass or more and 10% by mass or less relative to the compound.

[0092]

[0093] (In formula (1D), formula (1D1), or formula (1D2),

[0094] X, L 1 , Y, A, Z, p, m, n, and r are the same as those in formula (1),

[0095] R sub2 Representing formula (1D1) or formula (1D2),

[0096] R a1 , R b1 , and R c1 are each independently H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent,

[0097] R a1 , R b1 , and R c1 At least one of the above is I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent,

[0098] n2 represents an integer greater than or equal to 0 and less than or equal to 4,

[0099] p-1 is an integer greater than 0,

[0100] * is the bonding site with the adjacent structural unit. )

[18]

[0102] A composition comprising 1 mass ppm or more and 10 mass % or less of a compound represented by formula (1E) based on the compound described in any one of [3] to

[15] above.

[0103]

[0104] (In formula (1E),

[0105] X is independently F, Cl, Br, or an organic group having 1 or more and 5 or less substituents selected from the group consisting of F, Cl, and Br and having 1 to 30 carbon atoms,

[0106] L 1 is independently a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphate group, and the ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphine group, phosphonic acid group, carbamate group, urea group, amide group, imide group, or phosphate group of the aforementioned L 1 optionally has a substituent,

[0107] Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate group, a nitro group, an amino group, a carboxyl group, a mercapto group, an ether group, a thioether group, a phosphine group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate group, amino group, ether group, thioether group, phosphine group, phosphonic acid group, carbamate group, urea group, amide group, imide group, and phosphate group of the aforementioned Y optionally have a substituent,

[0108] R a 、R b 、and R c are independently H, F, Cl, Br, or an organic group having 1 to 60 carbon atoms optionally having a substituent,

[0109] A is an organic group having 1 to 30 carbon atoms,

[0110] Z is independently an alkoxy group, an ester group, an acetal group, or a carbonate group,

[0111] wherein X, L 1 、Y, R a 、R b 、R c 、A, and Z do not contain I,

[0112] p is an integer of 1 or more, m' is an integer of 0 or more, n is an integer of 0 or more, and r is an integer of 0 or more.)

[19]

[0114] A composition comprising the compound according to any one of the aforementioned [1] to

[15] ,

[0115] The impurity containing K is 1 mass ppm or less relative to the aforementioned compound in terms of elemental conversion.

[20]

[0117] The composition according to the aforementioned

[19] , wherein the peroxide is 10 mass ppm or less relative to the aforementioned compound.

[21]

[0119] The composition according to the foregoing

[19] or

[20] , wherein impurities containing one or more elements selected from the group consisting of Mn, Al, Si, and Li are 1 mass ppm or less in terms of elements relative to the foregoing compound.

[22]

[0121] The composition according to any one of the foregoing

[19] to

[21] , wherein the phosphorus-containing compound is 10 mass ppm or less relative to the foregoing compound.

[23]

[0123] The composition according to any one of the foregoing

[19] to

[22] , wherein maleic acid is 10 mass ppm or less relative to the foregoing compound.

[24]

[0125] A polymer comprising a structural unit derived from the compound according to any one of the foregoing [1] to

[15] .

[25]

[0127] The polymer according to the foregoing

[24] further comprises a structural unit represented by the following formula (C6).

[0128]

[0129] (In formula (C6),

[0130] X C61 is a hydroxyl group or a halogen group,

[0131] R C61 are each independently an alkyl group having 1 to 20 carbon atoms,

[0132] * is a bonding site with an adjacent structural unit.)

[26]

[0134] A film-forming composition containing the compound according to any one of the foregoing [1] to

[15] or the polymer according to the foregoing

[24] or

[25] .

[27]

[0136] The film-forming composition according to the foregoing

[26] further comprises an acid generator, a base generator, or a base compound.

[28]

[0138] A method for forming a resist pattern, comprising:

[0139] A step of forming a resist film on a substrate using the film-forming composition, the film-forming composition containing the compound according to any one of the foregoing [1] to

[15] or the polymer according to the foregoing

[24] or

[25] ;

[0140] A step of pattern-exposing the aforementioned resist film; and

[0141] A step of developing the resist film after the aforementioned exposure.

[29]

[0143] A method for forming an insulating film, which includes the method described in the aforementioned

[28] .

[30]

[0145] A method for producing a compound represented by the following formula (0), which includes a double bond introduction step of introducing an unsaturated double bond into a substituent Q of a compound represented by the following formula (S1).

[0146]

[0147] (In formula (S1),

[0148] X 0 is an organic group having 1 to 30 carbon atoms,

[0149] L 1 each independently represents a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphonic acid group, a urethane group, a urea group, an amide group, an imide group, or a phosphoric acid group,

[0150] Y each independently represents a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate group, a nitro group, an amino group, a carboxyl group, a mercapto group, an ether group, a thioether group, a phosphine group, a phosphonic acid group, a urethane group, a urea group, an amide group, an imide group, or a phosphoric acid group, and the alkoxy group, ester group, carbonate group, amino group, ether group, thioether group, phosphine group, phosphonic acid group, urethane group, urea group, amide group, imide group, and phosphoric acid group of the aforementioned Y may optionally have a substituent,

[0151] A is an organic group having 1 to 30 carbon atoms,

[0152] Z each independently represents an alkoxy group, an ester group, an acetal group, or a carbonate group,

[0153] Q is an organic group having 1 to 30 carbon atoms having a hydroxyl group, an aldehyde group, a carboxyl group, or a ketone group,

[0154] p is an integer of 1 or more, m' is an integer of 0 or more, n is an integer of 0 or more, and r is an integer of 0 or more.)

[0155]

[0156] (In formula (0),

[0157] X is independently I, F, Cl, Br, or an organic group having 1 or more and 5 or less substituents selected from the group consisting of I, F, Cl, and Br and having 1 to 30 carbon atoms,

[0158] L 1 are independently a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphino group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphoric acid group,

[0159] Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate group, a nitro group, an amino group, a carboxyl group, a mercapto group, an ether group, a thioether group, a phosphino group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphoric acid group, and the alkoxy group, ester group, carbonate group, amino group, ether group, thioether group, phosphino group, phosphonic acid group, carbamate group, urea group, amide group, imide group, and phosphoric acid group of the aforementioned Y may optionally have a substituent,

[0160] R a 、R b 、and R c are independently H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may optionally have a substituent,

[0161] A is an organic group having 1 to 30 carbon atoms,

[0162] Z is independently an alkoxy group, an ester group, an acetal group, or a carbonate group,

[0163] p is an integer of 1 or more, m' is an integer of 0 or more, n is an integer of 0 or more, and r is an integer of 0 or more.)

[31]

[0165] A process for producing the compound according to the aforementioned

[30] , wherein the compound represented by the aforementioned formula (S1) is a compound represented by the following formula (SA1),

[0166] The production method includes the step shown in the following A1 and the step shown in the following A2.

[0167] A1) A step of obtaining a compound represented by the following formula (SA2) using the compound represented by the aforementioned formula (SA1) and using a compound represented by the following formula (RM1) or malononitrile

[0168] A2) A step of producing formula (1) using formula (SA2) and a fluorine source

[0169]

[0170] (In formula (SA1), (RM1), and (SA2),

[0171] X0 、L 1 、Y, A, Z, p, m', n, r are the same as defined in formula (S1), (0).

[0172] Q 1 is an aldehyde or a ketone.

[0173] LG is a group selected from a hydroxyl group, an alkoxy group, a carbonate group, an acetal group, and a carboxyl group. The alkoxy group, carbonate group, acetal group, and carboxyl group contain an optionally substituted aliphatic group or aromatic group having 1 to 60 carbon atoms.

[0174] R 3 is a hydrogen group, or an optionally substituted carboxyl group or ester group having 1 to 60 carbon atoms.

[0175] R 4 is a hydrogen group.

[0176] R 5 、R 6 are each independently H, F, Cl, Br, or an optionally substituted organic group having 1 to 60 carbon atoms.

[0177] XA is a group selected from a hydrogen group and a halogen group.)

[32]

[0179] The method for producing the compound according to the foregoing

[31] , wherein in the step shown by A2, the decarbonation reaction of the compound shown by formula (SA2) is carried out at 100 °C or lower using the foregoing fluorine source.

[33]

[0181] The method for producing the compound according to the foregoing

[31] or

[32] , wherein in the step shown by A1, a reducing agent is also used to obtain the compound shown by the foregoing formula (SA2).

[34]

[0183] The method for producing the compound according to any one of the foregoing

[30] to

[33] , wherein in the foregoing formula (S1), A is benzene, toluene, or a heteroaromatic ring.

[35]

[0185] The method for producing the compound shown by the following formula (1), which includes: the step shown by the following B1A; the step of forming the compound shown by the following formula (SB1) using at least one of the compounds shown by the following formula (SB2A) and the following formula (SB3A) obtained through at least one of the steps shown by the following B2A and B3A; and the double bond introduction step of introducing an unsaturated double bond into the substituent Qb of the compound shown by formula (SB1).

[0186] Step of preparing the following matrix SB1A, the matrix SB1A containing one or more amino groups and containing a parent nucleus B having an aldehyde group or a ketone group

[0187] B2A) Step of introducing iodine into the aforementioned parent nucleus B to obtain a compound represented by the following formula (SB2A)

[0188] B3A) Step of replacing an amino group with a halogen group by Sandmeyer reaction to obtain a compound represented by formula (SB3A)

[0189]

[0190] (In formula (1),

[0191] Each X is independently I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms having one or more substituents selected from the group consisting of I, F, Cl, and Br,

[0192] L 1 Each is independently a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphate group, and the ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphine group, phosphonic acid group, carbamate group, urea group, amide group, imide group, or phosphate group of the aforementioned L 1 optionally has a substituent,

[0193] Each Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate group, a nitro group, an amino group, a carboxyl group, a mercapto group, an ether group, a thioether group, a phosphine group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate group, amino group, ether group, thioether group, phosphine group, phosphonic acid group, carbamate group, urea group, amide group, imide group, and phosphate group of the aforementioned Y optionally have a substituent,

[0194] R a 、R b 、and R c Each is independently H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms optionally having a substituent,

[0195] A is an organic group having 1 to 30 carbon atoms,

[0196] Each Z is independently an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, or a carbonate group, and the alkoxy group, ester group, acetal group, carboxyalkoxy group, or carbonate group of the aforementioned Z optionally has a substituent,

[0197] p is an integer of 1 or more, m is an integer of 1 or more, n is an integer of 0 or more, and r is an integer of 0 or more.

[0198] In formulas (SB1A), (SB2A), (SB3A), and (SB1),

[0199] Zb represents a hydrogen group or an amino group optionally having a substituent, the substituent including an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, rb represents an integer of 1 or more, and L 1b , X b1 , B, pb, and mb’ have the same meanings as L, X, A, p, and m in formula (1), respectively. X b2 represents I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 or more and 5 or less substituents selected from the group consisting of I, F, Cl, and Br, and Qb is an organic group having 1 to 30 carbon atoms and having a hydroxyl group, an aldehyde group, a carboxyl group, or a ketone group.)

[36]

[0201] The production method according to the foregoing

[35] , characterized in that an organophosphorus compound and a base are used in the step of introducing a double bond.

[37]

[0203] The production method of the compound according to the foregoing

[30] , which includes a halogen introduction step of reacting a halogenating agent with the compound represented by the above formula (S1) to introduce a halogen atom.

[38]

[0205] The production method of the compound according to any one of the foregoing

[30] to

[34] , wherein the compound represented by the above formula (SA1) is at least one of the compounds represented by the following formula (SB2A) and the following formula (SB3A) obtained through the step represented by B1A below and at least one of the steps represented by B2A and B3A below.

[0206] B1A) A step of preparing the following substrate SB1A, the substrate SB1A including one or more amino groups and including a parent nucleus B having an aldehyde group or a ketone group

[0207] B2A) A step of introducing iodine into the foregoing parent nucleus B to obtain the compound represented by the following formula (SB2A)

[0208] B3A) A step of replacing an amino group with a halogen group through a Sandmeyer reaction to obtain the compound represented by formula (SB3A)

[0209]

[0210] (In formulas (SB1A), (SB2A), (SB3A), and (SA1A),

[0211] Zb represents a hydrogen group or an amino group optionally having a substituent, the substituent including an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, rb represents an integer of 1 or more, L 1b , X b1 , B, pb, mb’ have the same meanings as L, X, A, p, m in formula (1), respectively. X b2 represents I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 or more and 5 or less substituents selected from the group consisting of I, F, Cl, and Br, and Qb has the same meaning as Q in formula (S1).)

[39]

[0213] The method for producing the compound according to the foregoing

[36] , wherein in the step represented by B2A, at least an iodine source and an oxidizing agent are used to introduce iodine into the foregoing mother nucleus B

[40]

[0215] The method for producing the compound according to the foregoing

[30] , wherein the compound represented by the foregoing formula (SA1) is a compound produced by the step represented by B1B below and at least one of the steps represented by B2B and B3B below

[0216] B1B) A step of preparing the following substrate SB1B, the substrate SB1B including one or more amino groups and including a mother nucleus B having an aldehyde group or a ketone group

[0217] B2B) A step of introducing iodine into the mother nucleus B to obtain a compound represented by formula (SB2B)

[0218] B3B) A step of substituting an amino group with a halogen group to obtain a compound represented by formula (SB3B)

[0219]

[0220] (In formula (SB1B), (SB2B), (SB3B), and (SA1B),

[0221] Zb represents a hydrogen group or an amino group optionally having a substituent, the substituent including an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, rb represents an integer of 1 or more, L 1b , X b1 , B, pb, mb’ have the same meanings as L, X, A, p, m in formula (1), respectively.

[0222] X b2 represents I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 or more and 5 or less substituents selected from the group consisting of I, F, Cl, and Br, and Qb has the same meaning as Q in formula (S1).)

[41]

[0224] The method for producing a compound according to the foregoing

[40] , further comprising the step shown in B4a below.

[0225] B4a) Wittig step

[42]

[0227] The method for producing a compound according to the foregoing

[38] or the foregoing

[41] , wherein in the step shown in B2B above, at least an iodine source and an oxidizing agent are used to introduce iodine into the foregoing parent nucleus B.

[43]

[0229] The method for producing a compound according to any one of the foregoing

[40] to the foregoing

[42] , wherein the foregoing parent nucleus B contains an aromatic ring structure optionally having a heteroatom.

[44]

[0231] The method for producing a compound represented by the following formula (1), characterized by comprising: a halogen-introducing step of reacting a halogenating agent with a compound represented by the following formula (S1) to introduce a halogen atom; and

[0232] a double-bond introducing step of introducing an unsaturated double bond into the substituent Q,

[0233] wherein the step of introducing a double bond uses an organophosphorus compound and a base.

[0234]

[0235] (In formula (S1),

[0236] X 0 is an organic group having 1 to 30 carbon atoms,

[0237] L 1 each independently is a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphino group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphoric acid group,

[0238] Y each independently is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate group, a nitro group, an amino group, a carboxyl group, a mercapto group, an ether group, a thioether group, a phosphino group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphoric acid group, and the alkoxy group, ester group, carbonate group, amino group, ether group, thioether group, phosphino group, phosphonic acid group, carbamate group, urea group, amide group, imide group, and phosphoric acid group of the foregoing Y optionally have substituents,

[0239] A is an organic group having 1 to 30 carbon atoms,

[0240] Z each independently is an alkoxy group, an ester group, an acetal group, or a carbonate group,

[0241] Q is an organic group having 1 to 30 carbon atoms with a hydroxyl group, an aldehyde group, a carboxyl group, or a ketone group,

[0242] p is an integer of 1 or more, m' is an integer of 0 or more, n is an integer of 0 or more, and r is an integer of 0 or more.)

[0243]

[0244] (In formula (1),

[0245] Each X is independently I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms with 1 or more and 5 or less substituents selected from the group consisting of I, F, Cl, and Br,

[0246] L 1 Each is independently a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphate group,

[0247] Each Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate group, a nitro group, an amino group, a carboxyl group, a mercapto group, an ether group, a thioether group, a phosphine group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate group, amino group, ether group, thioether group, phosphine group, phosphonic acid group, carbamate group, urea group, amide group, imide group, and phosphate group of the aforementioned Y may optionally have substituents,

[0248] R a 、R b 、and R c Each is independently H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms that may optionally have substituents,

[0249] A is an organic group having 1 to 30 carbon atoms,

[0250] Each Z is independently an alkoxy group, an ester group, an acetal group, or a carbonate group,

[0251] p is an integer of 1 or more, m is an integer of 1 or more, n is an integer of 0 or more, and r is an integer of 0 or more.)

[0252] Furthermore, the present inventors conducted in-depth research to solve the above problems, and as a result, found that by going through specific processes, a method for producing an iodine-containing vinyl polymer and its acetylated derivative with high yield without the need for expensive reagents and harsh conditions was provided, thus completing the present invention.

[0253] That is, the present invention is as follows.

[45]

[0255] A method for manufacturing an iodine-containing vinyl monomer, comprising:

[0256] a) a step of preparing an iodine-containing alcoholic substrate having a general structure represented by formula (1-1); and

[0257] b) a step of dehydrating the aforementioned iodine-containing alcoholic substrate to obtain an iodine-containing vinyl monomer having a general structure represented by formula (1),

[0258]

[0259] (In formula (1-1),

[0260] R 1 ~R 5 are each independently H, OH, OCH 3 , halogen, or a linear or branched alkyl group, and R 6 ~R 10 are each independently H, OH, OCH 3 , halogen, or cyano,

[0261] wherein at least one of R 1 ~R 5 is OH, at least one of R 1 ~R 5 is iodine, and one of R 6 ~R 10 is OH or OCH 3 )

[0262]

[0263] (In formula (1),

[0264] R 1 ~R 5 are each independently H, OH, OCH 3 , halogen, or a linear or branched alkyl group, and R 6 ~R 8 are each independently H, OH, OCH 3 , halogen, or cyano,

[0265] wherein at least one of R 1 ~R 5 is OH, and at least one of R 1 ~R 5 is iodine.

[46]

[0267] The method for manufacturing an iodine-containing vinyl monomer according to the aforementioned

[45] , wherein the step of preparing an iodine-containing alcoholic substrate having a general structure represented by the aforementioned formula (1-1) includes:

[0268] c) A step of preparing an iodo-ketone matrix having the general structure shown in formula (1-2); and

[0269] d) A step of reducing the aforementioned iodo-ketone matrix to obtain an iodo-alcohol matrix having the general structure shown in the aforementioned formula (1-1),

[0270]

[0271] (In formula (1-2),

[0272] R 1 ~R 5 are each independently H, OH, OCH 3 , halogen, or a linear or branched alkyl group, and R 7 , R 8 and R 10 are each independently H, OH, OCH 3 , halogen, or cyano,

[0273] wherein at least one of R 1 ~R 5 is OH, and at least one of R 1 ~R 5 is iodine.

[47]

[0275] According to the method for producing an iodo-vinyl monomer described in the aforementioned

[45] , wherein the step of preparing an iodo-alcohol matrix having the general structure shown in the aforementioned formula (1-1) includes:

[0276] e) A step of preparing an alcohol matrix having the general structure shown in formula (1-3); and

[0277] f) A step of introducing iodine into the aforementioned alcohol matrix to obtain an iodo-alcohol matrix having the general structure shown in the aforementioned formula (1-1),

[0278]

[0279] (In formula (1-3),

[0280] R 11 ~R 15 are each independently H, OH, OCH 3 or a linear or branched alkyl group,

[0281] R 6 ~R 10 are each independently H, OH, OCH 3 , halogen, or cyano,

[0282] wherein R 11 ~R15 At least one of them is OH, R 6 ~R 10 One of them is OH or OCH 3 ).

[48]

[0284] According to the method for producing an iodine-containing vinyl monomer described in the foregoing

[46] , wherein the step of preparing an iodine-containing ketone substrate having the general structure represented by the formula (1-2) includes:

[0285] g) A step of preparing a ketone substrate having the general structure represented by the formula (1-4); and

[0286] h) A step of introducing iodine into the foregoing ketone substrate to obtain an iodine-containing ketone substrate having the general structure represented by the formula (1-2),

[0287]

[0288] (In the formula (1-4),

[0289] R 11 ~R 15 Each independently is H, OH, OCH 3 or a linear or branched alkyl group,

[0290] R 7 、R 8 and R 10 Each independently is H, OH, OCH 3 、a halogen or a cyano group,

[0291] wherein at least one of R 11 ~R 15 is OH).

[49]

[0293] According to the method for producing an iodine-containing vinyl monomer described in the foregoing

[47] , wherein the step of preparing an alcohol substrate having the general structure represented by the formula (1-3) includes:

[0294] i) A step of preparing a ketone substrate having the general structure represented by the formula (1-4); and

[0295] j) A step of reducing the foregoing ketone substrate to obtain an alcohol substrate having the general structure represented by the formula (1-3),

[0296]

[0297] (In the formula (1-4),

[0298] R 11 ~R 15Each independently is H, OH, OCH 3 or a linear or branched alkyl group,

[0299] R 7 、R 8 and R 10 Each independently is H, OH, OCH 3 、halogen or cyano group,

[0300] wherein at least one of R 11 to R 15 is OH).

[50]

[0302] A method for producing an iodoacetylated vinyl monomer, comprising:

[0303] k) a step of preparing an iodo vinyl monomer having a general structure represented by formula (1); and

[0304] l) a step of acetylating the aforementioned iodo vinyl monomer to obtain an iodoacetylated vinyl monomer having a general structure represented by formula (2),

[0305]

[0306] (In formula (1),

[0307] R 1 to R 5 Each independently is H, OH, OCH 3 、halogen or a linear or branched alkyl group, R 6 to R 8 Each independently is H, OH, OCH 3 、halogen or cyano group,

[0308] wherein at least one of R 1 to R 5 is OH, and at least one of R 1 to R 5 is iodine)

[0309]

[0310] (In formula (2),

[0311] R 16 to R 20 Each independently is H, OH, OCH 3 、OAc、halogen or a linear or branched alkyl group,

[0312] R 6 to R 8 Each independently is H, OH, OCH 3, a halogen or a cyano group,

[0313] wherein at least one of R 16 ~R 20 is Oac, and at least one of R 16 ~R 20 is iodine).

[51]

[0315] A method for manufacturing an iodine-containing alcoholic matrix, comprising:

[0316] c) a step of preparing an iodine-containing ketonic matrix having a general structure represented by formula (1-2); and

[0317] d) a step of reducing the aforementioned iodine-containing ketonic matrix to obtain an iodine-containing alcoholic matrix having a general structure represented by formula (1-1),

[0318]

[0319] (In formula (1-2),

[0320] R 1 ~R 5 are each independently H, OH, OCH 3 , a halogen, or a linear or branched alkyl group, and R 7 , R 8 and R 10 are each independently H, OH, OCH 3 , a halogen, or a cyano group,

[0321] wherein at least one of R 1 ~R 5 is OH, and at least one of R 1 ~R 5 is iodine)

[0322]

[0323] (In formula (1-1),

[0324] R 1 ~R 5 are each independently H, OH, OCH 3 , a halogen, or a linear or branched alkyl group, and R 6 ~R 10 are each independently H, OH, OCH 3 , a halogen, or a cyano group,

[0325] wherein at least one of R 1 ~R 5 is OH, and at least one of R 1 ~R 5 is iodine, and R6 ~R 10 One of them is OH or OCH 3 )

[52]

[0327] A method for manufacturing an iodine-containing alcoholic matrix, comprising:

[0328] e) A step of preparing an alcoholic matrix having a general structure represented by formula (1-3); and

[0329] f) A step of introducing iodine into the aforementioned alcoholic matrix to obtain an iodine-containing alcoholic matrix having a general structure represented by formula (1-1),

[0330]

[0331] (In formula (1-3),

[0332] R 11 ~R 15 Each independently is H, OH, OCH 3 or a linear or branched alkyl group,

[0333] R 6 ~R 10 Each independently is H, OH, OCH 3 , a halogen or a cyano group,

[0334] wherein at least one of R 11 ~R 15 is OH, and one of R 6 ~R 10 is OH or OCH 3 )

[0335]

[0336] (In formula (1-1),

[0337] R 1 ~R 5 Each independently is H, OH, OCH 3 , a halogen or a linear or branched alkyl group, R 6 ~R 10 Each independently is H, OH, OCH 3 , a halogen or a cyano group,

[0338] wherein at least one of R 1 ~R 5 is OH, at least one of R 1 ~R 5 is iodine, and one of R 6 ~R 10 is OH or OCH3 )。

[53]

[0340] A method for manufacturing an iodo-ketone matrix, comprising:

[0341] g) a step of preparing a ketone matrix having a general structure represented by formula (1-4); and

[0342] h) a step of introducing iodine into the aforementioned ketone matrix to obtain a ketone matrix having a general structure represented by formula (1-2),

[0343]

[0344] (In formula (1-4),

[0345] R 11 ~R 15 are each independently H, OH, OCH 3 or a linear or branched alkyl group,

[0346] R 7 、R 8 and R 10 are each independently H, OH, OCH 3 、halogen or cyano group,

[0347] wherein at least one of R 11 ~R 15 is OH)

[0348]

[0349] (In formula (1-2),

[0350] R 1 ~R 5 are each independently H, OH, OCH 3 、halogen or a linear or branched alkyl group, R 7 、R 8 and R 10 are each independently H, OH, OCH 3 、halogen or cyano group,

[0351] wherein at least one of R 1 ~R 5 is OH, and at least one of R 1 ~R 5 is iodine).

[54]

[0353] A method for manufacturing an alcoholic matrix, comprising:

[0354] i) Step of preparing a ketonic substrate having the general structure represented by formula (1-4); and

[0355] j) Step of reducing the aforementioned ketonic substrate to obtain an alcoholic substrate having the general structure represented by formula (1-3),

[0356]

[0357] (In formula (1-4),

[0358] R 11 ~R 15 are each independently H, OH, OCH 3 or a linear or branched alkyl group,

[0359] R 7 、R 8 and R 10 are each independently H, OH, OCH 3 、halogen or cyano group,

[0360] wherein at least one of R 11 ~R 15 is OH)

[0361]

[0362] (In formula (1-3),

[0363] R 11 ~R 15 are each independently H, OH, OCH 3 or a linear or branched alkyl group,

[0364] R 6 ~R 10 are each independently H, OH, OCH 3 、halogen or cyano group,

[0365] wherein at least one of R 11 ~R 15 is OH, and one of R 6 ~R 10 is OH or OCH 3 ).

[0366] Advantages of the Invention

[0367] According to the present invention, it is possible to provide a compound, a polymer, a composition, a resist composition, a pattern forming method, a method for forming an insulating film, and a method for manufacturing a compound, from which a resist having excellent exposure sensitivity can be obtained.

[0368] Further, according to the present invention, a method for producing an iodine-containing vinyl polymer and its acetylated derivative with high yield without the need for expensive reagents and harsh conditions can be provided. Detailed Embodiments

[0369] <<First Embodiment>>

[0370] Hereinafter, the first embodiment of the present invention will be described (hereinafter sometimes referred to as "this embodiment"). It should be noted that this embodiment is an example for explaining the present invention, and the present invention is not limited to this embodiment.

[0371] In this specification, the meanings of the respective terms are as follows.

[0372] "(Meth)acrylate" means at least one selected from acrylate, haloacrylate, and methacrylate. Haloacrylate means an acrylate in which a halogen has been substituted at the position of the methyl group of methacrylate. Other terms having the expression "(meth)" are also interpreted in the same manner as (meth)acrylate.

[0373] "(Co)polymer" means at least one selected from homopolymer and copolymer.

[0374] [Compound (A)]

[0375] The compound of this embodiment (hereinafter also referred to as "compound (A)") has an unsaturated double bond and one or more halogens. In addition, compound (A) may also have one or more hydrophilic groups or one decomposable group. From the viewpoint of the roughness of the pattern, it is preferably to have one or more hydrophilic groups or one decomposable group. That is, the compound of this embodiment has: one or more halogens, one or more hydrophilic groups or one decomposable group, and an unsaturated double bond. In addition, compound (A) may also have one or more hydrophilic groups or one decomposable group.

[0376] Examples of the halogen include I, F, Cl, and Br. Among these, from the viewpoints of the sensitization effect based on EUV and the reduction of the roughness of the pattern, I, F, or Br is preferred, I or F is more preferred, and I is further preferred. The number of halogens is preferably an integer of 1 or more and 5 or less, more preferably an integer of 2 or more and 4 or less, and further preferably 2 or 3.

[0377] "Hydrophilic group" refers to a group that improves the affinity of an organic compound with water by bonding with the organic compound. As hydrophilic groups, hydroxyl group, nitro group, amino group, carboxyl group, mercapto group, phosphino group, phosphonic acid group, phosphoric acid group, ether group, thioether group, carbamate group, urea group, amide group, and imide group can be mentioned. Among these, from the viewpoints of the sensitization effect based on EUV and the reduction of the roughness of the pattern, hydroxyl group and carboxyl group are preferred, and hydroxyl group is more preferred. The number of hydrophilic groups is preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 or more and 3 or less, still more preferably 1 or 2, and particularly preferably 2.

[0378] "Decomposable group" refers to a group that decomposes in the presence of an acid or a base, or by the action of radiation, electron beam, extreme ultraviolet light (EUV), or irradiation from a light source such as ArF or KrF. The decomposable group is not particularly limited. For example, the acid dissociable functional group described in International Publication WO2013 / 024778 can be used. Among the decomposable groups, a hydrolyzable group is preferred. "Hydrolyzable group" refers to a group that undergoes hydrolysis in the presence of an acid or a base. As hydrolyzable groups, for example, alkoxy group, ester group, acetal group, and carbonate group can be mentioned. The number of decomposable groups is preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 or more and 3 or less, still more preferably 1 or 2, and particularly preferably 2.

[0379] The unsaturated double bond is preferably a polymerizable unsaturated double bond. The group having an unsaturated double bond is not particularly limited. For example, vinyl group, isopropenyl group, (meth)acryloyl group, haloacryloyl group, etc. can be mentioned. As haloacryloyl group, for example, α-fluoropropenyl group, α-chloropropenyl group, α-bromopropenyl group, α-iodopropenyl group, α,β-dichloropropenyl group, and α,β-diiodopropenyl group can be mentioned. Among these unsaturated double bonds, isopropenyl group and vinyl group are preferred. The number of unsaturated double bonds is preferably an integer of 1 or more and 3 or less, more preferably an integer of 1 or more and 2 or less, and still more preferably 1.

[0380] The compound (A) of the present embodiment is preferably represented by the following formula (1). The compound (A) preferably contains a functional group that can improve its solubility in an alkaline developer by the action of an acid or a base. It is preferred that any one of the following Z, Y, and X contains a functional group that can improve its solubility in an alkaline developer by the action of an acid or a base.

[0381]

[0382] In formula (1),

[0383] X is each independently I, F, Cl, Br, or an organic group having 1 to 5 substituents selected from the group consisting of I, F, Cl, and Br and having 1 to 30 carbon atoms. Among these, X is preferably each independently I, F, Cl, or Br, more preferably each independently I, F, or Br, still more preferably each independently I or F, and further preferably each independently I.

[0384] In the present embodiment, "substituted" means that one or more hydrogen atoms in a functional group are substituted with a substituent, provided that there is no special definition. The "substituent" is not particularly limited. For example, a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a mercapto group, a heterocyclic group, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, and an amino group having 0 to 30 carbon atoms can be mentioned.

[0385] The alkyl group can be in any form of a straight-chain aliphatic hydrocarbon group, a branched-chain aliphatic hydrocarbon group, or a cyclic aliphatic hydrocarbon group.

[0386] Examples of the alkyl group having 1 to 30 carbon atoms are not limited to the following. For example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, a n-hexyl group, a n-dodecyl group, a valeryl group, etc. can be mentioned.

[0387] Examples of the aryl group having 6 to 30 carbon atoms are not limited to the following. For example, a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a pyrenyl group, a perylenyl group, etc. can be mentioned.

[0388] Examples of the alkenyl group having 2 to 30 carbon atoms are not limited to the following. For example, an ethynyl group, a propenyl group, a butynyl group, a pentynyl group, etc. can be mentioned.

[0389] Examples of the alkynyl group having 2 to 30 carbon atoms are not limited to the following. For example, an acetylene group, an ethynyl group, etc. can be mentioned.

[0390] Examples of the alkoxy group having 1 to 30 carbon atoms are not limited to the following. For example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, etc. can be mentioned.

[0391] As the "organic group having 1 or more and 5 or less substituents selected from the group consisting of I, F, Cl, and Br and having 1 to 30 carbon atoms", there is no particular limitation, and examples thereof include monoiodophenyl, diiodophenyl, triiodophenyl, tetraiodophenyl, pentaiodophenyl, monoiodohydroxyphenyl, diiodohydroxyphenyl, triiodohydroxyphenyl, monoiodoacetoxyphenyl, diiodoacetoxyphenyl, triiodoacetoxyphenyl, monoiodo - tert - butoxycarbonylphenyl, diiodo - tert - butoxycarbonylphenyl, triiodo - tert - butoxycarbonylphenyl, monoiododihydroxyphenyl, diiododihydroxyphenyl, triiododihydroxyphenyl, monoiododiacetoxyphenyl, diiododiacetoxyphenyl, triiododiacetoxyphenyl, monoiodo - di - tert - butoxycarbonylphenyl, diiodo - di - tert - butoxycarbonylphenyl, triiodo - di - tert - butoxycarbonylphenyl, monoiodotrihydroxyphenyl, diiodotrihydroxyphenyl, monoiodotriacetoxyphenyl, diiodotriacetoxyphenyl, monoiodo - tri - tert - butoxycarbonylphenyl, diiodo - tri - tert - butoxycarbonylphenyl, monoiodonaphthyl, diiodonaphthyl, triiodonaphthyl, tetraiodonaphthyl, pentaiodonaphthyl, monoiodohydroxynaphthyl, diiodohydroxynaphthyl, triiodohydroxynaphthyl, monoiodoacetoxynaphthyl, diiodoacetoxynaphthyl, triiodoacetoxynaphthyl, monoiodo - tert - butoxycarbonylnaphthyl, diiodo - tert - butoxycarbonylnaphthyl, triiodo - tert - butoxycarbonylnaphthyl, monoiododihydroxynaphthyl, diiododihydroxynaphthyl, triiododihydroxynaphthyl, monoiododiacetoxynaphthyl, diiododiacetoxynaphthyl, triiododiacetoxynaphthyl, monoiodo - di - tert - butoxycarbonylnaphthyl, diiodo - di - tert - butoxycarbonylnaphthyl, triiodo - di - tert - butoxycarbonylnaphthyl,

[0392] monoiodotrihydroxynaphthyl, diiodotrihydroxynaphthyl, monoiodotriacetoxynaphthyl, diiodotriacetoxynaphthyl, monoiodo - tri - tert - butoxycarbonylnaphthyl, diiodo - tri - tert - butoxycarbonylnaphthyl, monoiodoadamantyl, diiodoadamantyl, triiodoadamantyl, monoiodohydroxyadamantyl, diiodohydroxynaphthyl, monoiodoacetoxynaphthyl, diiodoacetoxyadamantyl, monoiodo - tert - butoxycarbonyladamantyl, diiodo - tert - butoxycarbonyladamantyl, triiodo - tert - butoxycarbonyladamantyl, monoiododihydroxyadamantyl, monoiododiacetoxyadamantyl, monoiodo - di - tert - butoxycarbonyladamantyl, monoiodocyclohexyl, diiodocyclohexyl, triiodocyclohexyl, monoiodohydroxycyclohexyl, diiodohydroxynaphthyl, monoiodoacetoxynaphthyl, diiodoacetoxycyclohexyl, monoiodo - tert - butoxycarbonylcyclohexyl, diiodo - tert - butoxycarbonylcyclohexyl, triiodo - tert - butoxycarbonylcyclohexyl, monoiododihydroxycyclohexyl, monoiododiacetoxycyclohexyl, monoiodo - di - tert - butoxycarbonylcyclohexyl,

[0393] monobromophenyl, dibromophenyl, tribromophenyl, tetrabromophenyl, pentabromophenyl, monobromohydroxyphenyl, dibromohydroxyphenyl, tribromohydroxyphenyl, monobromoacetoxyphenyl, dibromoacetoxyphenyl, tribromoacetoxyphenyl, monobromotert - butoxycarbonylphenyl, dibromotert - butoxycarbonylphenyl, tribromotert - butoxycarbonylphenyl, monobromodihydroxyphenyl, dibromodihydroxyphenyl, tribromodihydroxyphenyl, monobromodiacetoxyphenyl, dibromodiacetoxyphenyl, tribromodiacetoxyphenyl, monobromodi - tert - butoxycarbonylphenyl, dibromodi - tert - butoxycarbonylphenyl, tribromodi - tert - butoxycarbonylphenyl,

[0394] monobromotrihydroxyphenyl, dibromotrihydroxyphenyl, monobromotriacetoxyphenyl, dibromotriacetoxyphenyl, monobromotri - tert - butoxycarbonylphenyl, dibromotri - tert - butoxycarbonylphenyl, monobromoadamantyl, dibromoadamantyl, tribromoadamantyl, monobromo - hydroxyadamantyl, dibromo - hydroxynaphthyl, monobromoacetoxynaphthyl, dibromoacetoxyadamantyl, monobromotert - butoxycarbonyladamantyl, dibromotert - butoxycarbonyladamantyl, tribromotert - butoxycarbonyladamantyl, monobromodihydroxyadamantyl, monobromodiacetoxyadamantyl, monobromo - di - tert - butoxycarbonyladamantyl,

[0395] monofluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, monofluorohydroxyphenyl, difluorohydroxyphenyl, trifluorohydroxyphenyl, monofluoroacetoxyphenyl, difluoroacetoxyphenyl, trifluoroacetoxyphenyl, monofluorotert - butoxycarbonylphenyl, difluorotert - butoxycarbonylphenyl, trifluorotert - butoxycarbonylphenyl, monofluorodihydroxyphenyl, difluorodihydroxyphenyl, trifluorodihydroxyphenyl, monofluorodiacetoxyphenyl, difluorodiacetoxyphenyl, trifluorodiacetoxyphenyl, monofluorodi - tert - butoxycarbonylphenyl, difluorodi - tert - butoxycarbonylphenyl, trifluorodi - tert - butoxycarbonylphenyl, monofluorotrihydroxyphenyl, difluorotrihydroxyphenyl, monofluorotriacetoxyphenyl, difluorotriacetoxyphenyl, monofluorotri - tert - butoxycarbonylphenyl, difluorotri - tert - butoxycarbonylphenyl, monofluoroadamantyl, difluoroadamantyl, trifluoroadamantyl, monofluoro - hydroxyadamantyl, difluoro - hydroxynaphthyl, monofluoroacetoxynaphthyl, difluoroacetoxyadamantyl, monofluorotert - butoxycarbonyladamantyl, difluorotert - butoxycarbonyladamantyl, trifluorotert - butoxycarbonyladamantyl, monofluorodihydroxyadamantyl, monofluorodiacetoxyadamantyl, monofluoro - di - tert - butoxycarbonyladamantyl,

[0396] monochlorophenyl, dichlorophenyl, trichlorophenyl, tetrachlorophenyl, pentachlorophenyl, monochlorohydroxyphenyl, dichlorohydroxyphenyl, trichlorohydroxyphenyl, monochloroacetoxyphenyl, dichloroacetoxyphenyl, trichloroacetoxyphenyl, monochlorotert-butoxycarbonylphenyl, dichlorotert-butoxycarbonylphenyl, trichlorotert-butoxycarbonylphenyl, monochlorodihydroxyphenyl, dichlorodihydroxyphenyl, trichlorodihydroxyphenyl, monochlorodiacetoxyphenyl, dichlorodiacetoxyphenyl, trichlorodiacetoxyphenyl, monochlorodi-tert-butoxycarbonylphenyl, dichlorodi-tert-butoxycarbonylphenyl, trichlorodi-tert-butoxycarbonylphenyl,

[0397] monochlorotrihydroxyphenyl, dichlorotrihydroxyphenyl, monochlorotriacetoxyphenyl, dichlorotriacetoxyphenyl, monochlorotri-tert-butoxycarbonylphenyl, dichlorotri-tert-butoxycarbonylphenyl, monochloroadamantyl, dichloroadamantyl, trichloroadamantyl, monochlorohydroxyadamantyl, dichlorohydroxynaphthyl, monochloroacetoxynaphthyl, dichloroacetoxyadamantyl, monochlorotert-butoxycarbonyladamantyl, dichlorotert-butoxycarbonyladamantyl, trichlorotert-butoxycarbonyladamantyl, monochlorodihydroxyadamantyl, monochlorodiacetoxyadamantyl, monochlorodi-tert-butoxycarbonyladamantyl, etc.

[0398] For example, X can be an aromatic group, and is a group formed by introducing one or more F, Cl, Br or I into the aromatic group. As such an aromatic group, for example, groups having a benzene ring such as a phenyl group having 1 to 5 halogens, groups having a heteroaromatic ring such as furan, thiophene, pyridine having 1 to 5 halogens, for example, a phenyl group having 1 to 5 I, a phenyl group having 1 to 5 F, a phenyl group having 1 to 5 Cl, a phenyl group having 1 to 5 Br, a naphthyl group having 1 to 5 F, a naphthyl group having 1 to 5 Cl, a naphthyl group having 1 to 5 Br, a naphthyl group having 1 to 5 I, a phenol group having 1 to 4 F, a phenol group having 1 to 4 Cl, a phenol group having 1 to 4 Br, a phenol group having 1 to 4 I, a furyl group having 1 to 3 F, a furyl group having 1 to 3 Cl, a furyl group having 1 to 3 Br, a furyl group having 1 to 3 I, a thiophenyl group having 1 to 3 F, a thiophenyl group having 1 to 3 Cl, a thiophenyl group having 1 to 3 Br, a thiophenyl group having 1 to 3 I, a pyridyl group having 1 to 4 F, a pyridyl group having 1 to 4 Cl, a pyridyl group having 1 to 4 Br, a pyridyl group having 1 to 4 I, a benzodiazole group having 1 to 5 F, a benzodiazole group having 1 to 5 Cl, a benzodiazole group having 1 to 5 Br, a benzodiazole group having 1 to 5 I, a benzimidazole group having 1 to 4 F, a benzimidazole group having 1 to 4 Cl, a benzimidazole group having 1 to 4 Br, a benzimidazole group having 1 to 4 I, a benzoxazole group having 1 to 4 F, a benzoxazole group having 1 to 4 Cl, a benzoxazole group having 1 to 4 Br, a benzoxazole group having 1 to 4 I, a benzothiophene group having 1 to 4 F, a benzothiophene group having 1 to 4 Cl, a benzothiophene group having 1 to 4 Br, a benzothiophene group having 1 to 4 I. In addition, X can be an alicyclic group, and is a group formed by introducing one or more F, Cl, Br or I into the alicyclic group. As such an alicyclic group, for example, an adamantyl group having 1 to 3 halogens can be cited, and an adamantyl group having 1 to 3 F, an adamantyl group having 1 to 3 Cl, an adamantyl group having 1 to 3 Br, an adamantyl group having 1 to 3 I, a cyclopentyl group having 1 to 3 F, a cyclopentyl group having 1 to 3 Cl, a cyclopentyl group having 1 to 3 Br, a cyclopentyl group having 1 to 3 I, a bicycloundecyl group having 1 to 3 F, a bicycloundecyl group having 1 to 3 Cl, a bicycloundecyl group having 1 to 3 Br, a bicycloundecyl group having 1 to 3 I, a norbornyl group having 1 to 3 F, a norbornyl group having 1 to 3 Cl, a norbornyl group having 1 to 3 Br, a norbornyl group having 1 to 3 I, etc. can be cited.

[0399] L 1is a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphonic acid group, a urethane group, a urea group, an amide group, an imide group, or a phosphoric acid group. Among these, L 1 is preferably a single bond. L 1 The ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphine group, phosphonic acid group, urethane group, urea group, amide group, imide group, or phosphoric acid group of may have substituents. As such substituents, for example, as described above.

[0400] m is an integer of 1 or more, preferably an integer of 1 or more and 5 or less, more preferably an integer of 2 or more and 4 or less, and still more preferably 2 or 3.

[0401] Y are each independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate group, a nitro group, an amino group, a carboxyl group, a mercapto group, an ether group, a thioether group, a phosphine group, a phosphonic acid group, a urethane group, a urea group, an amide group, an imide group, or a phosphoric acid group, and the alkoxy group, ester group, carbonate group, amino group, ether group, thioether group, phosphine group, phosphonic acid group, urethane group, urea group, amide group, imide group, and phosphoric acid group of the aforementioned Y may have substituents.

[0402] Y may be exemplified by those selected from the group consisting of an alkoxy group [* 3 -O-R 2 , an ester group [* 3 -O-(C═O)-R 2 or * 3 -(C═O)-O-R 2 , an acetal group [* 3 -O-(C(R 21 )) 2 )-O-R 2 (R 21 are each independently H, or a hydrocarbon group having 1 to 10 carbon atoms.)], a carboxyalkoxy group [* 3 -O-R 22 -(C═O)-O-R 2 (R 22 is a divalent hydrocarbon group having 1 to 10 carbon atoms.)], and a carbonate group [* 3 -O-(C═O)-O-R 2 . From the viewpoint of high sensitivity, the ester group is preferably a tertiary ester group. It should be noted that in the formula, * 3 is the bonding site to A.

[0403] Among these, from the viewpoint of high sensitivity, Y is preferably a tertiary ester group, an acetal group, a carbonate group or a carboxyalkoxy group, more preferably an acetal group, a carbonate group or a carboxyalkoxy group, and still more preferably an acetal group or a carboxyalkoxy group. Further, from the viewpoint of manufacturing a polymer with stable quality based on radical polymerization, an ester group, a carboxyalkoxy group and a carbonate group are preferred.

[0404] Y is preferably each independently a group represented by the following formula (Y-1).

[0405] -L 2 -R 2 (Y-1)

[0406] In the formula (Y-1),

[0407] L 2 is a group that is cleaved by the action of an acid or a base. Examples of the group that is cleaved by the action of an acid or a base include, for example, a group selected from an ester group [* 1 -O-(C=O)-* 2 or * 1 -(C=O)-O-* 2 , an acetal group [* 1 -O-(C(R 21 ) 2 )-O-* 2 (R 21 are each independently H or a hydrocarbon group having 1 to 10 carbon atoms.)], a carboxyalkoxy group [* 1 -O-R 22 -(C=O)-O-* 2 (R 22 is a divalent hydrocarbon group having 1 to 10 carbon atoms.)], and a carbonate group [* 1 -O-(C=O)-O-* 2 and at least one divalent linking group selected from the group consisting of. From the viewpoint of high sensitivity, the ester group is preferably a tertiary ester group. It should be noted that in the formula, * 1 is the bonding site to A, and * 2 is the bonding site to R 2 . Among these, from the viewpoint of high sensitivity, L 2 is preferably a tertiary ester group, an acetal group, a carbonate group or a carboxyalkoxy group, more preferably an acetal group, a carbonate group or a carboxyalkoxy group, and still more preferably an acetal group or a carboxyalkoxy group. Further, from the viewpoint of manufacturing a polymer with stable quality based on radical polymerization, an ester group, a carboxyalkoxy group and a carbonate group are preferred.

[0408] In addition, as other effects, when the compound (A) of the present embodiment is used as a polymerization unit of a copolymer, for the purpose of controlling the polymerizability of the resin and making the degree of polymerization within a desired range, Y is preferably a group represented by the formula (Y-1). Since the compound A has an X group, it has a great influence on the active species during the polymer formation reaction, and it is difficult to achieve the desired control. Therefore, by making the hydrophilic group in the compound A have a group represented by the formula (Y-1) as a protecting group, fluctuations in copolymer formation and polymerization inhibition caused by the hydrophilic group can be suppressed.

[0409] R 2 is a linear, branched or cyclic aliphatic group having 1 to 30 carbon atoms; an aromatic group having 6 to 30 carbon atoms; a linear, branched or cyclic aliphatic group containing a heteroatom having 1 to 30 carbon atoms; a linear, linear or cyclic aromatic group containing a heteroatom having 1 to 30 carbon atoms. The aliphatic group, aromatic group, aliphatic group containing a heteroatom, and aromatic group containing a heteroatom of the aforementioned R 2 may optionally further have a substituent. It should be noted that the aforementioned groups are used as the substituents here, and preferably a linear, branched or cyclic aliphatic group having 1 to 20 carbon atoms; an aromatic group having 6 to 20 carbon atoms. Among these, R 2 is preferably an aliphatic group. The aliphatic group in R 2 is preferably a branched or cyclic aliphatic group. The number of carbon atoms of the aliphatic group is preferably 1 or more and 20 or less, more preferably 3 or more and 10 or less, and further preferably 4 or more and 8 or less. The aliphatic group is not particularly limited, and examples thereof include methyl, isopropyl, sec-butyl, tert-butyl, isobutyl, cyclohexyl, methylcyclohexyl, and adamantyl. Among these, tert-butyl, cyclohexyl, or adamantyl is preferred.

[0410] L 2 is * 1 -(C=O)-O-* 2 or a carboxyalkoxy group, when it is cleaved by the action of an acid or a base, a carboxyl group is formed, and the solubility difference and dissolution rate difference between the cleaved part and the non-cleaved part in the development treatment are enlarged, so the resolution is improved. In particular, the residue at the bottom of the pattern of the fine line pattern is suppressed, so it is preferred.

[0411] As Y, the following specific examples can be cited. Each is independently a group represented by any one of the following formulas (Y-1-1) to (Y-1-7).

[0412]

[0413] As the alkoxy group that can be used as Y, alkoxy groups having 1 or more carbon atoms can be mentioned. From the viewpoint of the solubility of the resin after being combined with other monomers and resinized, alkoxy groups having 2 or more carbon atoms are preferred, and alkoxy groups having 3 or more carbon atoms or having a cyclic structure are more preferred.

[0414] Specific examples of the alkoxy group that can be used as Y are as follows, but are not limited thereto.

[0415]

[0416] As the amino group and amide group that can be used as Y, primary amino groups, secondary amino groups, tertiary amino groups, groups having a quaternary ammonium salt structure, amides having substituents, etc. can be suitably used. Specific examples of the amino group or amide group that can be used are as follows, but are not limited thereto.

[0417]

[0418] n is an integer of 0 or more, preferably an integer of 1 or more, more preferably an integer of 1 or more and 5 or less, still more preferably an integer of 1 or more and 3 or less, even more preferably 1 or 2, and particularly preferably 2.

[0419] R a 、R b 、and R c are each independently H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms optionally having a substituent. As the substituent of the organic group having 1 to 60 carbon atoms, there is no particular limitation, and for example, I, F, Cl, Br, or other substituents can be mentioned. As other substituents, there is no particular limitation, and for example, hydroxyl group, alkoxy group, ester group, acetal group, carbonate group, nitro group, amino group, carboxyl group, mercapto group, ether group, thioether group, phosphino group, phosphonic acid group, carbamate group, urea group, amide group, imide group, phosphoric acid group can be mentioned. Among them, the alkoxy group, ester group, carbonate group, amino group, ether group, thioether group, phosphino group, phosphonic acid group, carbamate group, urea group, amide group, imide group, and phosphoric acid group may further have a substituent. It should be noted that as the substituent here, a linear, branched or cyclic aliphatic group having 1 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms can be mentioned.

[0420] R a 、R b 、and R c The carbon number of the organic group optionally having a substituent in is preferably 1 to 30.

[0421] As the organic group having 1 to 60 carbon atoms optionally having a substituent, there is no particular limitation, and examples thereof include a linear or branched aliphatic hydrocarbon group having 1 to 60 carbon atoms, an alicyclic hydrocarbon group having 4 to 60 carbon atoms, and an aromatic group having 6 to 60 carbon atoms optionally containing a heteroatom.

[0422] The linear or branched aliphatic hydrocarbon group having 1 to 60 carbon atoms is not particularly limited. For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-dodecyl, pentanoyl, 2-ethylhexyl can be mentioned.

[0423] The alicyclic hydrocarbon group is not particularly limited. For example, cyclohexyl, cyclododecyl, dicyclopentyl, tricyclodecyl, adamantyl, etc. can be mentioned. Further, an aromatic group optionally containing a heteroatom such as benzodiazolyl, benzotriazolyl, benzothiazolyl can also be appropriately selected. In addition, a combination of these organic groups can be selected.

[0424] The aromatic group having 6 to 60 carbon atoms and optionally containing a heteroatom is not particularly limited. For example, phenyl, naphthyl, biphenyl, anthryl, pyrenyl, benzodiazolyl, benzotriazolyl, benzothiadiazolyl can be mentioned.

[0425] Among these organic groups having 1 to 60 carbon atoms and optionally having a substituent, methyl is preferred from the viewpoint of producing a polymer with stable quality.

[0426] R a When R is an organic group having 1 or more and 8 or less carbon atoms, or a group selected from F, Cl, and I, n and r are preferably 0 or more.

[0427] A is an organic group having 1 to 30 carbon atoms. A can be a monocyclic organic group, can be a polycyclic organic group, and can also have a substituent. A is preferably an aromatic ring optionally having a substituent. The carbon number of A is preferably 6 to 14, more preferably 6 to 10.

[0428] A is preferably a group represented by any one of the following formulas (A-1) to (A-4), more preferably a group represented by the following formulas (A-1) to (A-2), and further preferably a group represented by the following formula (A-1).

[0429]

[0430] A can be an alicyclic structure optionally having a substituent. Here, the "alicyclic structure" is a saturated or unsaturated carbocyclic ring having no aromaticity. As the aforementioned alicyclic structure, for example, a saturated or unsaturated carbocyclic ring having 3 to 30 carbon atoms can be mentioned, and a saturated or unsaturated carbocyclic ring having 3 to 20 carbon atoms is preferred. As the aforementioned alicyclic structure, for example, a group having cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloeicosyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclopentadienyl, cyclooctadienyl, adamantyl, bicycloundecenyl, decahydronaphthyl, norbornyl, norbornadienyl, cubane, basketane, housane, etc. can be mentioned.

[0431] In addition, A can be an optionally substituted heterocyclic structure. There is no particular limitation on the heterocyclic structure. For example, cyclic nitrogen-containing structures such as pyridine, piperidine, piperidone, benzodiazole, benzotriazole, etc., triazine, cyclic carbamate structure, cyclic urea, cyclic amide, cyclic imide, furan, pyran, cyclic ethers such as dioxolane, alicyclic groups having a lactone structure such as caprolactone, butyrolactone, nonalactone, decalactone, undecalactone, bicycloundecalactone, phthalide, etc. can be mentioned.

[0432] p is an integer of 1 or more, preferably an integer of 1 or more and 3 or less, more preferably an integer of 1 or more and 2 or less, and further preferably 1.

[0433] Each Z is independently an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, or a carbonate group. These groups may have substituents, and examples of the substituents include hydrocarbon groups having 1 to 60 carbon atoms which may also be optionally substituted. r is an integer of 0 or more, preferably an integer of 0 or more and 2 or less, more preferably an integer of 0 or more and 1 or less, and further preferably 0.

[0434] Z may be, for example, selected from the group consisting of alkoxy groups [* 3 -O-R 2 , ester groups [* 3 -O-(C=O)-R 2 or * 3 -(C=O)-O-R 2 , acetal groups [* 3 -O-(C(R 21 ))-O-R 2 (wherein R 2 are each independently H or a hydrocarbon group having 1 to 10 carbon atoms.)], carboxyalkoxy groups [* 21 -O-R 3 -(C=O)-O-R 22 (wherein R 2 is a divalent hydrocarbon group having 1 to 10 carbon atoms.)], and carbonate groups [* 22 -O-(C=O)-O-R 3 and at least one group selected from the group consisting of. From the viewpoint of high sensitivity, the ester group is preferably a tertiary ester group. It should be noted that in the formula, * 2 is the bonding site to A. 3 is the bonding site to A.

[0435] Among these, from the viewpoint of high sensitivity, Z is preferably a tertiary ester group, an acetal group, a carbonate group or a carboxyalkoxy group, more preferably an acetal group, a carbonate group or a carboxyalkoxy group, and further preferably an acetal group or a carboxyalkoxy group. In addition, from the viewpoint of manufacturing a polymer with stable quality based on radical polymerization, an ester group, a carboxyalkoxy group and a carbonate group are preferred.

[0436] As described above, n is an integer of 0 or more, r is an integer of 0 or more, and at least one of n or r can be an integer of 1 or more. That is, n + r can be an integer of 1 or more.

[0437] Among the above compounds (A), the compound represented by the following formula (1a) is preferred.

[0438]

[0439] (In formula (1a),

[0440] X, L 1 , Y, A, Z, p, m, n, and r have the same definitions as in formula (1).)

[0441] As the compound (A) of the present embodiment (especially the compound represented by formula (1a)), for example, compounds having the following structures can be mentioned.

[0442]

[0443]

[0444]

[0445] Among the above compounds (A), from the viewpoint of further improving sensitivity, the compound represented by the following formula (1b) is preferred.

[0446]

[0447] (In formula (1b),

[0448] X, L 1 , Y, A, Z, p, m, n, and r have the same definitions as in formula (1),

[0449] R a1 , R b1 , and R c1 are each independently H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms optionally having substituents,

[0450] R a1 , R b1 , and R c1 at least one of them is I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms optionally having substituents.)

[0451] R a1 , R b1 , and R c1 The organic group having 1 to 60 carbon atoms optionally having substituents among them and the aforementioned Ra , R b , and R c in the optional organic group having 1 to 60 carbon atoms with substituents have the same meaning. R a1 is preferably an optional organic group having 1 to 60 carbon atoms with substituents, more preferably a methyl group. R b1 , and R c1 is preferably H.

[0452] As the compound (A) of the present embodiment (especially the compound represented by the formula (1b)), for example, compounds having the following structures can be cited.

[0453]

[0454]

[0455]

[0456]

[0457] The above compound (A) can be, for example, a compound represented by the following formula (1C). In addition, there is no particular limitation. As described later, the compound represented by the following formula (1C) is preferably used in combination with a compound (A) other than this compound.

[0458]

[0459] (In the formula (1C), formula (1C1), and formula (1C2),

[0460] X, L 1 , Y, A, Z, p, m, n, and r have the same definitions as in the formula (1),

[0461] Rsub represents the formula (1C1) or formula (1C2),

[0462] R a1 , R b1 , and R c1 are each independently H, I, F, Cl, Br, or an optional organic group having 1 to 60 carbon atoms with substituents,

[0463] R a1 , R b1 , and R c1 at least any one of them is I, F, Cl, Br, or an optional organic group having 1 to 60 carbon atoms with substituents,

[0464] p - 1 is an integer of 0 or more,

[0465] * is the bonding site of each formula.)

[0466] When a compound represented by the formula (1C) is used in a composition containing the compound (A) of the present embodiment, the composition may use the compound represented by the following formula (1C) in combination with a compound (A) other than the compound. In this case, the composition is preferably prepared such that the compound represented by the formula (1C) is in the range of 1 mass ppm or more and 10 mass% or less, more preferably 1 mass ppm or more and 5 mass% or less, still more preferably 1 mass ppm or more and 3 mass% or less, and particularly preferably 1 mass ppm or more and 1 mass% or less with respect to the total amount of the compound (A). For the resin form after forming a resin from the starting materials including the composition prepared in this way, by having sites containing X and sites containing Y or Z present at a high density in the adjacent region, it becomes a starting point for improved sensitivity. Furthermore, the solubility in the resin locally increases, thereby reducing the residue defects after development in the lithography process.

[0467] As the compound (A) of the present embodiment (particularly the compound represented by the formula (1C)), for example, compounds having the structures shown below can be mentioned.

[0468]

[0469] In addition, the compound (A) of the present embodiment can be used in combination with, for example, a compound represented by the following formula (1D).

[0470]

[0471] (In the formula (1D), formula (1D1), or formula (1D2),

[0472] X, L 1 , Y, A, Z, p, m, n, and r are the same as defined in the formula (1),

[0473] Rsub2 represents the formula (1D1) or formula (1D2),

[0474] R a1 、R b1 、and R c1 are each independently H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms optionally having substituents,

[0475] R a1 、R b1 、and R c1 at least any one of which is I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms optionally having substituents,

[0476] n2 represents an integer of 0 or more and 4 or less,

[0477] p - 1 is an integer of 0 or more,

[0478] * is a bonding site with an adjacent constituent unit.)

[0479] When a compound represented by the formula (1D) is used in a composition containing the compound (A) of the present embodiment, the composition can use the compound represented by the following formula (1D) in combination with a compound (A) other than the compound. In this case, the composition is preferably prepared such that the compound represented by the formula (1D) is in the range of 1 mass ppm or more and 10 mass% or less, more preferably 1 mass ppm or more and 5 mass% or less, further preferably 1 mass ppm or more and 3 mass% or less, and particularly preferably 1 mass ppm or more and 1 mass% or less with respect to the total amount of the compound (A). For the resin form in the case of forming a resin from the starting materials of the composition thus prepared, by making the site containing X and the site containing Y or Z coexist at a high density in the adjacent region, it becomes the starting point for improving the sensitivity. Furthermore, the solubility in the resin locally increases, thereby enabling the reduction of residue defects after development in the lithography process.

[0480] As the compound (A) of the present embodiment (particularly the compound represented by the formula (1D)), for example, compounds having the following structures can be cited.

[0481]

[0482] A composition containing the compound (A) of the present embodiment may contain a compound represented by the following formula (1E). When using this compound, the composition containing the compound (A) of the present embodiment preferably contains the compound represented by the formula (1E) in the range of 1 mass ppm or more and 10 mass% or less with respect to the total amount of the compound (A), more preferably 1 mass ppm or more and 5 mass% or less, further preferably 1 mass ppm or more and 3 mass% or less, and particularly preferably 1 mass ppm or more and 1 mass% or less.

[0483] The composition thus prepared tends to have improved stability. The reason is not yet certain, but it is presumed that it is stabilized by the equilibrium reaction of iodine atoms between the iodine-containing compound (A) and the iodine-free compound (1E).

[0484] In this case, the aforementioned composition preferably uses, as the compound (1E), a compound having a structure in which iodine atoms are detached from the compounds exemplified as the compound (A) above in combination.

[0485] In addition, the stability of the composition thus produced is increased, so that not only the storage stability is improved, but also a resin having a stable property, an etching resistance property imparting stable performance, and further a reduction in residue defects after development in a lithography process are caused.

[0486] As a method of using the compound represented by the formula (1E) in the composition containing the compound (A) in a range of 1 mass ppm or more and 10 mass% or less with respect to the compound (A), there is no particular limitation, and examples thereof include a method of adding the compound (1E) to the compound (A), a method of by-producing the compound (1E) in the production of the compound (A), and the like.

[0487]

[0488] (In the formula (1E),

[0489] X is each independently F, Cl, Br, or an organic group having 1 or more and 5 or less substituents selected from the group consisting of F, Cl, and Br and having 1 to 30 carbon atoms,

[0490] L 1 is each independently a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphonic acid group, a urethane group, a urea group, an amide group, an imide group, or a phosphoric acid group, and the ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphine group, phosphonic acid group, urethane group, urea group, amide group, imide group, or phosphoric acid group of the foregoing L 1 optionally has a substituent,

[0491] Y is each independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate group, a nitro group, an amino group, a carboxyl group, a mercapto group, an ether group, a thioether group, a phosphine group, a phosphonic acid group, a urethane group, a urea group, an amide group, an imide group, or a phosphoric acid group, and the alkoxy group, ester group, carbonate group, amino group, ether group, thioether group, phosphine group, phosphonic acid group, urethane group, urea group, amide group, imide group, and phosphoric acid group of the foregoing Y optionally have a substituent,

[0492] R a 、R b 、and R c are each independently H, F, Cl, Br, or an organic group having 1 to 60 carbon atoms optionally having a substituent,

[0493] A is an organic group having 1 to 30 carbon atoms,

[0494] Z is each independently an alkoxy group, an ester group, an acetal group, or a carbonate group,

[0495] wherein, X, L 1 、Y, R a 、R b, R c , A and Z do not contain I,

[0496] p is an integer of 1 or more, m' is an integer of 0 or more, n is an integer of 0 or more, and r is an integer of 0 or more.

[0497] When the compound represented by the formula (1E) is contained in an amount greater than 10% by mass relative to the compound (A), the effect of improving the sensitivity when forming a polymer containing the compound (A) and using it for lithography purposes may be reduced. On the other hand, when the amount is less than 1 ppm, the effect of improving the stability over time may not be fully exhibited.

[0498] For the purpose of further improving the effect of stability over time, m' of the compound represented by the formula (1E) is preferably 0.

[0499] As the compound (1E) of the present embodiment, for example, compounds having the structures shown below can be cited.

[0500]

[0501]

[0502]

[0503]

[0504] [Method for producing compound (A)]

[0505] The compound represented by the formula (1) can be produced by various known synthesis methods.

[0506] As an example of the synthesis method, there is no particular limitation, and it can be synthesized by introducing a halogen group of I, F, Cl, or Br into a hydroxy-containing aromatic aldehyde derivative and then converting the aldehyde group into a vinyl group. As an example of other synthesis methods, the following methods can be appropriately selected: a method in which iodine monochloride reacts in an organic solvent by subjecting a hydroxybenzaldehyde derivative to an iodination reaction (for example, Japanese Patent Laid-Open No. 2012-180326); a method in which iodine is added dropwise to an aqueous alkaline solution of phenol in the presence of β-cyclodextrin under alkaline conditions (Japanese Patent Laid-Open Nos. 63-101342 and 2003-64012), etc.

[0507] In the present embodiment, particularly in the case of introducing multiple iodine atoms, an iodination reaction using iodine monochloride in an organic solvent is preferably used. By introducing the synthesized iodine into the aldehyde moiety of the hydroxybenzaldehyde derivative to convert it into a vinyl group, the compound (A) of the present embodiment can be synthesized. As a method for converting the aldehyde moiety into a vinyl group, the Wittig reaction (for example, the methods described in Synthetic Communications; Vol. 22; nb4; 1992 p513, Synthesis; Vol. 49; nb. 23; 2017; p5217), a method of reacting malonic acid under a base (for example, the methods described in Tetrahedron; Vol. 46; nb. 40; 2005; p6893, Tetrahedron; Vol. 63; nb. 4; 2007; p900, US2004 / 118673), etc. can be suitably used. As a method for synthesizing the compound (A) of the present embodiment, for example, the methods described in the above references can be suitably used, but it is not limited thereto.

[0508] The manufacturing method of the compound represented by the formula (0) is shown below. The compound represented by the formula (0) includes both a halogen-free compound and a halogen-containing compound. For example, a halogen can be introduced into the compound represented by the formula (0) having an amino group or the like instead of a halogen, etc. without a halogen by the Sandmeyer reaction or the like to produce the compound represented by the formula (1).

[0509] Regarding the manufacturing method of the compound represented by the formula (0) of the present embodiment,

[0510] It preferably includes a step of introducing an unsaturated double bond into the substituent Q of the compound represented by the following formula (S1) (hereinafter, sometimes referred to as "double bond introduction step"). In addition, this manufacturing method may include a step of reacting a halogenating agent with the compound represented by the following formula (S1) to introduce a halogen atom (hereinafter, sometimes referred to as "halogen introduction step").

[0511] It should be noted that in this manufacturing method, the order of the halogen introduction step and the double bond introduction step is not particularly limited, and either step can be carried out first.

[0512] By manufacturing the compound represented by the formula (0) by this method, it is possible to stably, with good yield, and effectively manufacture an unsaturated double bond moiety (and a halogen group when having a halogen) that is low in manufacturing stability and requires attention during processing. In addition, in the case of having a halogen introduction step, even if the halogen group is an atom with a large atomic radius such as iodine, the compound to be manufactured can be stably, with good yield, and effectively manufactured.

[0513]

[0514] (In the formula (0),

[0515] X is each independently I, F, Cl, Br, or an organic group having 1 or more and 5 or less substituents selected from the group consisting of I, F, Cl, and Br and having 1 to 30 carbon atoms,

[0516] L 1 is each independently a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphino group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphoric acid group,

[0517] Y is each independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate group, a nitro group, an amino group, a carboxyl group, a mercapto group, an ether group, a thioether group, a phosphino group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphoric acid group, and the alkoxy group, ester group, carbonate group, amino group, ether group, thioether group, phosphino group, phosphonic acid group, carbamate group, urea group, amide group, imide group, and phosphoric acid group of the aforementioned Y may optionally have substituents,

[0518] R a 、R b 、and R c are each independently H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may optionally have substituents,

[0519] A is an organic group having 1 to 30 carbon atoms,

[0520] Z is each independently an alkoxy group, an ester group, an acetal group, or a carbonate group,

[0521] p is an integer of 1 or more, m' is an integer of 0 or more, n is an integer of 0 or more, and r is an integer of 0 or more.)

[0522]

[0523] (In formula (S1),

[0524] X 0 is an organic group having 1 to 30 carbon atoms,

[0525] L 1 is each independently a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphino group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphoric acid group,

[0526] Y is each independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate group, a nitro group, an amino group, a carboxyl group, a mercapto group, an ether group, a thioether group, a phosphino group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphoric acid group, and the alkoxy group, ester group, carbonate group, amino group, ether group, thioether group, phosphino group, phosphonic acid group, carbamate group, urea group, amide group, imide group, and phosphoric acid group of the aforementioned Y may optionally have substituents.

[0527] A is an organic group having 1 to 30 carbon atoms.

[0528] Z is each independently an alkoxy group, an ester group, an acetal group, or a carbonate group.

[0529] Q is an organic group having 1 to 30 carbon atoms and having a hydroxyl group, an aldehyde group, a carboxyl group, or a ketone group.

[0530] p is an integer of 1 or more, m' is an integer of 0 or more, n is an integer of 0 or more, and r is an integer of 0 or more.)

[0531] It should be noted that Q is an organic group having 1 to 30 carbon atoms and having a hydroxyl group, an aldehyde group, a carboxyl group, or a ketone group, and the number of carbon atoms in this case refers to the total number of carbon atoms including these functional groups when having an aldehyde group or a carboxyl group. From the viewpoint of preventing side reactions, Q is preferably an organic group having 1 to 30 carbon atoms and having a hydroxyl group, and more preferably hydroxymethyl.

[0532] As the step of introducing a halogen atom (halogen introduction step), the aforementioned method of introducing a halogen group can be cited. It should be noted that there is no particular limitation on the halogenating agent. For example, iodinating agents such as iodine monochloride, iodine, and N-iodosuccinimide, fluorinating agents such as potassium fluoride and tetramethylammonium fluoride, chlorinating agents such as thionyl chloride and dichloromethyl methyl ether, brominating agents such as bromine molecule, carbon tetrabromide, and N-bromosuccinimide can be cited. Among these, iodinating agents are preferred, and iodine monochloride is more preferred.

[0533] The ratio of the halogenating agent in the step of introducing a halogen atom to the compound represented by the formula (S1) is preferably 1.2 molar times or more, more preferably 1.5 molar times or more, and further preferably 2.0 molar times or more.

[0534] The reaction temperature in the step of introducing a halogen atom is not particularly limited, and is preferably 40 to 80 °C. The reaction time is not particularly limited, and is preferably 1 to 3 hours.

[0535] When Q is an organic group having 1 to 30 carbon atoms with a hydroxyl group, the production method of the present embodiment may include a step of oxidizing an alcohol and introducing an aldehyde group after the step of introducing a halogen atom. The oxidizing agent used in the oxidation is not particularly limited as long as it can introduce an aldehyde. For example, manganese dioxide and chromium trioxide can be cited. The reaction temperature in the step of introducing an aldehyde group is not particularly limited, and is preferably 10 to 40 °C. The reaction time is not particularly limited, and is preferably 1 to 6 hours.

[0536] As described above, for the step of introducing an unsaturated double bond into the substituent Q (double bond introduction step), an unsaturated double bond can be introduced by a Wittig reaction, a method of reacting malonic acid under a base, or the like.

[0537] As the solvent used in the reaction, a commonly available solvent can be used. For example, an alcohol, an ether, a hydrocarbon, a halogen-based solvent, etc. can be appropriately used within the range that does not impair the above reaction. Multiple solvents can also be mixed and used within the range that does not impair the above reaction. Since water hinders the reaction, a dehydrated solvent is preferably used.

[0538] The reaction temperature and reaction time depend on the substrate concentration and the catalyst used, but usually, the reaction can be carried out at a reaction temperature of -20 °C to 100 °C, a reaction time of 1 hour to 10 hours, and a pressure of normal pressure, reduced pressure, or increased pressure. In addition, the reaction can be appropriately carried out by a known method such as a batch method, a semi-batch method, or a continuous method.

[0539] In addition, a polymerization inhibitor can be added in a series of reactions, and a commercially available product that can usually be obtained can be used. For example, 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl radical, N-nitrosophenylhydroxylamine ammonium salt, N-nitrosophenylhydroxylamine aluminum salt, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, N-nitrosodiphenylamine, N-nitroso-N-methylaniline, nitrosonaphthol, p-nitrosophenol, nitrosocompounds such as N,N'-dimethyl-p-nitrosoaniline, phenothiazine, methylene blue, sulfur-containing compounds such as 2-mercaptobenzimidazole, amines such as N,N'-diphenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, 4-hydroxydiphenylamine, aminophenol, quinones such as hydroxyquinoline, hydroquinone, methylhydroquinone, p-benzoquinone, methyl ether of hydroquinone, phenols such as p-methoxyphenol, 2,4-dimethyl-6-tert-butylphenol, catechol, 3-tert-butylcatechol, 2,2-methylenebis-(6-tert-butyl-4-methylphenol), imides such as N-hydroxyphthalimide, oximes such as cyclohexanone oxime, p-quinonedioxime, and dialkyl thiodipropionate. As the addition amount, it is, for example, 0.001 to 10 parts by mass, preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the (meth)acrylic acid compound represented by the general formula (b).

[0540] The compound represented by formula (0) obtained by the reaction can be separated and purified into a desired highly pure monomer by filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, separation and purification methods using activated carbon, etc., methods based on combinations thereof, as well-known purification methods.

[0541] [Production method of compound of formula (0)]

[0542] As a preferred production method of the compound of formula (0), when the compound represented by the above formula (S1) is the compound represented by the following formula (SA1) and includes the step shown by the following A1, a production method including the step shown by the following A2 can be selected.

[0543] A1) A step of obtaining the compound represented by the following formula (SA2) using the compound represented by the above formula (SA1) and using the compound represented by the following formula (RM1) or malononitrile

[0544] A2) A step of producing formula (0) using formula (SA2) and a fluorine source

[0545]

[0546] (In formulae (SA1), (RM1) and (SA2),

[0547] X 0 、L 1 、Y, A, Z, p, m', n, r are the same as defined in formulae (S1) and (0),

[0548] Q 1 is an aldehyde or a ketone,

[0549] LG is a group selected from a hydroxyl group, an alkoxy group, a carbonate group, an acetal group, a carboxyl group, and the alkoxy group, carbonate group, acetal group, carboxyl group include an aliphatic group or an aromatic group optionally having a substituent having 1 to 60 carbon atoms,

[0550] R 3 is a hydrogen group, or a carboxyl group or an ester group having 1 to 60 carbon atoms optionally having a substituent,

[0551] R 4 is a hydrogen group,

[0552] R 5 、R 6 are each independently H, F, Cl, Br, or an organic group having 1 to 60 carbon atoms optionally having a substituent,

[0553] XA is a group selected from a hydrogen group and a halogen group. R 3 can bond with LG to form a cyclic structure.)

[0554] As described above, step A1 is a step of obtaining the compound represented by formula (SA2) by using the compound represented by formula (SA1) and using the compound represented by formula (RM1) or malononitrile.

[0555] Specific examples of the compound represented by formula (RM1) include maleic acid, dimethyl maleate, diethyl maleate, dipropyl maleate, diisopropyl maleate, maleic anhydride and other maleate derivatives, ethyl acetate, propyl acetate, butyl acetate, ethyl α-chloroacetate, propyl α-chloroacetate, butyl α-chloroacetate and other acetate derivatives. RM1 is preferably a derivative selected from malonic acid, malonate derivatives, acetic acid derivatives, and acetate derivatives.

[0556] As step A1, as the Knoevenagel reaction or the Doebner reaction, a general method can be used. For example, the conditions described in Journal of Molecular Catalysis B: Enzymatic, 82, 92-95; 2012, Tetrahedron Letters, 46(40), 6893-6896; 2005, etc. can be used. Specifically, the compound described in formula (SA2) can be obtained by reacting the compound represented by formula (RM1) or malononitrile with a base in a solvent. In addition, an acid can also be used in combination with the base.

[0557] As the base, various known compounds can be used. For example, nitrogen-containing cyclic compounds containing structures such as pyridine, piperidine, pyrrolidine, oxazole, dioxazole, triazole, morpholine, etc., and nitrogen-containing compounds such as tertiary amines such as tributylamine, trimethylamine, and trihydroxyethylamine can be suitably used.

[0558] The acid that can be used in combination with the base is not particularly limited, and weak acids such as acetic acid and propionic acid can be preferably used in combination.

[0559] The balance between the acidity and basicity of the reaction system is not particularly limited. When the compound of this embodiment in which m is an integer of 1 or more is used as the target compound, the reaction is preferably carried out under acidic conditions.

[0560] In Step A1, when LG is an alkoxy group, a carbonate group, an acetal group, or a carboxyl group, it is preferable to further add a reaction for converting LG into a hydroxyl group by treatment such as hydrolysis to obtain the compound represented by formula (SA3). The treatment such as hydrolysis is not particularly limited as long as it can convert the LG group into a hydroxyl group. As an example of the reaction conditions, for instance, an acid such as hydrochloric acid, sulfuric acid, or p-toluenesulfonic acid can be used in combination as a catalyst, and the deprotection reaction can be carried out under temperature conditions such as reflux. Additionally, as other examples of the reaction conditions, an inorganic base such as sodium hydroxide or potassium hydroxide, or an organic base such as a tertiary amine can be used as the base, and the reaction can be refluxed under solvent conditions such as toluene or xylene to carry out the deprotection reaction.

[0561]

[0562] (In formula (SA3),

[0563] X 0 、L 1 、Y, A, Z, p, m', n, and r are the same as defined in formulas (S1) and (0),

[0564] R 5 、R 6 each independently represents H, F, Cl, Br, or an organic group having 1 to 60 carbon atoms optionally having substituents.)

[0565] In Step A1, a reducing agent can be further used to obtain the compound represented by formula (SA2). When using a reducing agent to obtain the compound represented by formula (SA2), RM1 with higher stability can be used, which is advantageous in terms of conversion rate and purity. As the reducing agent, various reducing agents can be used.

[0566] As the reducing agent, a variety of reducing agents that function under the reaction conditions of this embodiment are used. There is no limitation on the appropriate reducing agent, and examples include metal hydrides and metal hydride complexes. Specifically, for example, borane·dimethyl sulfide, diisobutylaluminum hydride, sodium borohydride, lithium borohydride, potassium borohydride, zinc borohydride, lithium tri-tert-butylborohydride, potassium tri-tert-butylborohydride, lithium triethylborohydride, lithium aluminum hydride, lithium tri-tert-butoxyaluminum hydride, sodium bis(2-methoxyethoxy)aluminum hydride, etc. can be cited.

[0567] The amount of the reducing agent can be appropriately set according to the substrate, reducing agent, and reaction conditions used, and there is no particular limitation. Generally, 1 to 500 parts by mass is appropriate relative to 100 parts by mass of the reaction raw material. From the perspective of yield, 10 to 200 parts by mass is preferred.

[0568] Among the compounds represented by the above formula (S1), for A, from the aspects of the stability of the X group in the resin, the effect of improving lithography performance such as the sensitivity improvement per unit mass brought to the X group, and the solubility of the resin in the developer when incorporated as a constituent unit of the copolymer in the lithography resin, and the effect of suppressing partial crystallinity in the resin matrix, benzene, toluene, or a heteroaromatic ring is preferred.

[0569] As the reaction solvent for the deprotection reaction, various solvents can be used. As long as it is a solvent that dissolves the compound of the above formula (SA2), there is no particular limitation, and methanol, ethanol, propanol, butanol, alcohol solvents, cyclohexanone, cyclopentanone, MEK, MIBK and other ketone solvents, ethyl acetate, butyl acetate, ethyl propionate, isobutyl propionate, ethyl lactate, γ-butyrolactone and other linear or cyclic ester solvents, ether solvents such as diethyl ether, diethylene glycol, PGMEA, PGME and other glycol solvents, aromatic solvents such as toluene and benzene, amide solvents such as DMF, water, etc. can be suitably used.

[0570] As described above, step A2 is a step of de-carbonating the carboxyl group of the compound represented by (SA2) or the carboxyl group or ester group introduced into R 5 by using a fluorine source.

[0571] As the fluorine source, various compounds that generate fluorides can be used, and quaternary amine salts of fluorides such as tetrabutylammonium fluoride, tetramethylammonium fluoride, and tetra(hydroxyethyl)ammonium fluoride, metal cation species salts of fluorides such as tetramethylaluminum, phosphonium salts of fluorides such as tetra(octadecyl)phosphonium, fluoride salts of alkali metals such as KF and NaF can be suitably used.

[0572] For step A2, by performing a de-carbonation reaction on the compound described in formula (SA2) or formula (SA3) using a fluorine source at a low temperature of 100 °C or lower, the compound described in formula (1) can be obtained. Through the selection of the parent nucleus A, and the functional groups Z, Y, L 1 group, and X group, for formula (SA2) having a structure that is concerned about modification and decomposition at high temperatures, as the reaction temperature, at a lower temperature of 80 °C or lower, or 60 °C or lower, more preferably 50 °C or lower, the compound represented by formula (1) can be obtained.

[0573] In the reaction of a series of processes A2, a polymerization inhibitor can be added, and commercially available products that can usually be obtained can be used. For example, 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl radical, ammonium N-nitrosophenylhydroxylamine, aluminum N-nitrosophenylhydroxylamine, ammonium N-nitroso-N-(1-naphthyl)hydroxylamine, N-nitrosodiphenylamine, N-nitroso-N-methylaniline, nitrosonaphthol, p-nitrosophenol, nitroso compounds such as N,N'-dimethyl-p-nitrosoaniline, phenothiazine, methylene blue, sulfur-containing compounds such as 2-mercaptobenzimidazole, amines such as N,N'-diphenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, 4-hydroxydiphenylamine, aminophenol, quinones such as hydroxyquinoline, hydroquinone, methylhydroquinone, p-benzoquinone, methyl ether of hydroquinone, phenols such as p-methoxyphenol, 2,4-dimethyl-6-tert-butylphenol, catechol, 3-tert-butylcatechol, 2,2-methylenebis-(6-tert-butyl-4-methylphenol), imides such as N-hydroxyphthalimide, oximes such as cyclohexanone oxime, p-quinonedioxime, and dialkyl thiodipropionate, etc. As the addition amount, it is, for example, 0.001 to 10 parts by mass, preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the (meth)acrylic acid compound represented by the general formula (b).

[0574] The manufacturing method of the compound represented by the following formula (1) includes: the process shown by B1A below; the process of forming the compound represented by the following formula (SB1) by using at least one of the compounds represented by the following formula (SB2A) and the following formula (SB3A) obtained through at least one of the processes shown by B2A and B3A below; and a double bond introduction process of introducing an unsaturated double bond into the substituent Qb of the compound represented by the formula (SB1).

[0575] B1A) A process of preparing the following substrate SB1A, the substrate SB1A containing one or more amino groups and containing a parent nucleus B having an aldehyde group or a ketone group

[0576] B2A) A process of introducing iodine into the aforementioned parent nucleus B to obtain the compound represented by the following formula (SB2A)

[0577] B3A) A process of replacing the amino group with a halogen group through the Sandmeyer reaction to obtain the compound represented by the formula (SB3A)

[0578]

[0579] (In the formula (1),

[0580] Each X is independently I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having one or more and five or less substituents selected from the group consisting of I, F, Cl, and Br.

[0581] L 1 Each independently represents a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphoric acid group. The ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphine group, phosphonic acid group, carbamate group, urea group, amide group, imide group, or phosphoric acid group of the aforementioned L 1 may optionally have a substituent on its ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphine group, phosphonic acid group, carbamate group, urea group, amide group, imide group, or phosphoric acid group.

[0582] Y each independently represents a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate group, a nitro group, an amino group, a carboxyl group, a mercapto group, an ether group, a thioether group, a phosphine group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphoric acid group. The alkoxy group, ester group, carbonate group, amino group, ether group, thioether group, phosphine group, phosphonic acid group, carbamate group, urea group, amide group, imide group, and phosphoric acid group of the aforementioned Y may optionally have a substituent.

[0583] R a R b and R c each independently represents H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms that may optionally have a substituent.

[0584] A is an organic group having 1 to 30 carbon atoms.

[0585] Z each independently represents an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, or a carbonate group. The alkoxy group, ester group, acetal group, carboxyalkoxy group, or carbonate group of the aforementioned Z may optionally have a substituent.

[0586] p is an integer of 1 or more, m is an integer of 1 or more, n is an integer of 0 or more, and r is an integer of 0 or more.

[0587] In formulas (SB1A), (SB2A), (SB3A), and (SB1),

[0588] Zb represents a hydrogen group or an amino group that may optionally have a substituent, and the substituent includes an optionally substituted hydrocarbon group having 1 to 30 carbon atoms. rb represents an integer of 1 or more. Qb, L 1b , X b1 , B, pb, and mb' have the same meanings as Q, L, X, A, p, and m in formula (1), respectively. X B2 represents I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms that has 1 or more and 5 or fewer substituents selected from the group consisting of I, F, Cl, and Br.)

[0589] The process of introducing a double bond can use an organophosphorus compound and a base. As the organophosphorus compound, for example, an oxyacid of phosphorus, an alkylated oxyacid of phosphorus, a phosphate, etc. can be used. As the oxyacid of phosphorus, for example, phosphoric acid, pyrophosphoric acid, etc. can be cited. As the alkylated oxyacid of phosphorus, dimethylphosphonic acid, triethyl phosphate, etc. can be cited. And as the phosphate, for example, diammonium hydrogen phosphate, etc. can be cited, but it is not limited to these. In addition, the organophosphorus compound can be only one kind or a combination of two or more kinds. As the base, for example, alkali metal hydrides such as potassium hydride and sodium hydride, alkali metal carbonates such as potassium carbonate and cesium carbonate, quaternary ammonium salts (tetramethylammonium hydroxide), alcoholates (sodium ethoxide, potassium tert-butoxide (t-BuOK)), metal amides (lithium diisopropylamide (LDA), potassium hexamethyldisilazide (KHMDS), lithium 2,2,6,6-tetramethylpiperidine (LiTMP)), alkyl metals (alkyl lithium, alkyl aluminum), pyridine-based (pyridine, DMAP), non-pyridine-based heterocyclic amines (DBU, DBN, imidazole), etc. can be cited.

[0590] As another preferred method for obtaining the compound represented by the above formula (SA1), a method including the following step (B1A) and including at least any one of the following steps (B2A) or (B3A) can be selected: step (B1A) of preparing a starting compound (SB1A), the starting compound (SB1A) having an aromatic parent nucleus B as A, having at least one amino group on the parent nucleus B, and having an alcohol group and a group selected from at least one of an aldehyde group, a ketone group, and a carboxyl group as a carbonyl group; step (B2A) of introducing iodine into the parent nucleus B to obtain the formula (SB2A); and further step (B3A) of replacing the amino group with a halogen group by the Sandmeyer reaction to obtain the formula (SB3A).

[0591]

[0592] (In the formulas (SB1A), (SB2A), (SB3A), and (SA1A),

[0593] Zb represents a hydrogen group or an optionally substituted amino group, the substituent including an optionally substituted hydrocarbon group having 1 to 30 carbon atoms,

[0594] rb represents an integer of 1 or more,

[0595] Qb, L 1b 、X b1 、B、pb、mb’ have the same meanings as Q, L, X, A, p, m in the formula (1). X B2 represents I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms having one or more and five or less substituents selected from the group consisting of I, F, Cl, and Br.)

[0596] That is, in the method for producing the compound represented by the above formula (SA1), it is preferable that the compound represented by the above formula (SA1) is obtained through the step represented by B1A and at least one of the steps represented by B2A and B3A, and is at least one of the compounds represented by the formula (SB2A) and the formula (SB3A).

[0597] B1A) A step of preparing a substrate SB1A, the substrate SB1A containing one or more amino groups and a parent nucleus B having an alcohol group, an aldehyde group or a ketone group

[0598] B2A) A step of introducing iodine into the above parent nucleus B to obtain a compound represented by the formula (SB2A); B3A) A step of substituting an amino group with a halogen group by a Sandmeyer reaction to obtain a compound represented by the formula (SB3A)

[0599] In this production method, a double bond introduction step (step B1A) and a halogen introduction step (step B2A or B3A) are sequentially carried out.

[0600] In the method described in step (B2A), the iodination introduction reaction of the compound represented by the formula (SB1A) (substance SB1A) can be carried out by reacting at least an iodinating agent with the compound represented by the formula (SB1A). For example, it can be carried out under the known iodine introduction reaction conditions described in non-patent documents such as Adv. Synth. Catal. 2007, 349, 1159 - 1172, Organic Letters; Vol. 6; (2004); p. 2785 - 2788, and patent documents such as US5300506, US5434154, US2009 / 281114, EP1439164, WO2006 / 101318 to obtain the target compound. Examples of iodinating agents that can be used include iodine compounds, iodine monochloride, N-iodosuccinimide, benzyltrimethyliodosonium chloride, tetraethylammonium iodide, tetra-n-butylammonium iodide, lithium iodide, sodium iodide, potassium iodide, 1-chloro-2-iodoethane, silver iodofluoride, tert-butyl hypoiodite, 1,3-diiodo-5,5-dimethylhydantoin, iodine-morpholine complex, trifluoroacetyl hypoiodite, iodine-iodic acid, iodine-periodic acid, iodine-hydrogen peroxide, 1-iodoheptafluoropropane, triphenyl phosphate-methyl iodide, iodine-thallium(I) acetate, 1-chloro-2-iodoethane, iodine-copper(II) acetate, etc., but are not limited thereto.

[0601] In the iodination reaction, one or more additives may be added for the purpose of promoting the reaction and suppressing by-products. Examples of the additives include acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, p-toluenesulfonic acid, iron(III) chloride, aluminum chloride, copper(II) chloride, antimony pentachloride, silver sulfate, silver nitrate, silver trifluoroacetate, etc., bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate, potassium bicarbonate, etc., oxidizing agents such as ammonium cerium(IV) nitrate, sodium persulfate, etc., inorganic compounds such as sodium chloride, potassium chloride, mercury(II) oxide, cerium oxide, etc., organic compounds such as acetic anhydride, etc., and porous substances such as zeolite, etc.

[0602] In step (B2A), it is preferable to use at least an iodine source and an oxidizing agent to introduce iodine into the mother nucleus B. Using an iodine source and an oxidizing agent is preferable from the viewpoints of improving reaction efficiency and purity. Examples of the iodination source include the above-mentioned iodinating agents. Examples of the oxidizing agent include periodic acid, hydrogen peroxide, and specified additives (hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, etc.).

[0603] From the viewpoint of solubility in the developer, the mother nucleus B in the matrix SB1A preferably has an aromatic ring structure optionally having a heteroatom. In addition, as the aromatic ring structure possessed by the mother nucleus B, from the viewpoint of the balance between solubility in the developer and the effect of improving sensitivity, at least any one of furan, thiophene, pyrrole, and indole is preferable.

[0604] The reaction of step (B2A) can also be carried out without a solvent. Examples of the reaction solvents that can be used include halogen-based solvents such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, etc., alkyl-based solvents such as hexane, cyclohexane, heptane, pentane, octane, etc., aromatic hydrocarbon-based solvents such as benzene, toluene, etc., alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, etc., ether-based solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran, etc., acetic acid, dimethylformamide, dimethyl sulfoxide, water, etc.

[0605] The reaction temperature of step (B2A) is not particularly limited, and any temperature from the freezing point to the boiling point of the solvent used in the reaction can be used, and 0°C - 150°C is particularly preferable.

[0606] The iodine substitution reaction of the compound represented by formula (SB1A) in step (B2A) can be carried out by reacting at least an iodinating agent with the compound represented by formula (SB1A). For example, it can be carried out by the Sandmeyer reaction using the methods described in Chemistry-A European Journal, 24(55), 14622 - 14626; 2018, Synthesis (2007)(1), 81 - 84, etc., and the target compound can be obtained under known iodine substitution reaction conditions.

[0607] (Method for producing the compound represented by formula (1C))

[0608] As an example of the method for producing the compound represented by formula (1C), in the case of the method for producing the compound represented by formula (1) described above and Ra being a hydrogen group, the compound represented by formula (1C) can be obtained by dimerizing the compound represented by formula (1) obtained in this production method. As the easiest method for dimerizing the compound represented by formula (1), by setting the obtained compound (1) under high-temperature conditions or basic conditions, the active methylene site formed by the elimination of the aforementioned Ra group can be used as a starting point to carry out dimerization.

[0609] The compound represented by the above formula (SA1) can be produced by a production method including the step shown in B1B below and including at least one of the steps shown in B2B and B3B below.

[0610] B1B) Step of preparing the following substrate SB1B, the substrate SB1B containing one or more amino groups and a parent nucleus B having an aldehyde group or a ketone group

[0611] B2B) Step of introducing iodine into the parent nucleus B to obtain the compound represented by formula (SB2B)

[0612] B3B) Step of replacing the amino group with a halogen group to obtain the compound represented by formula (SB3B)

[0613]

[0614] (In formulae (SB1B), (SB2B), (SB3B), and (SA1B),

[0615] Zb represents a hydrogen group or an optionally substituted amino group, the substituent including an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, rb represents an integer of 1 or more, Qb, L 1b 、X b1 、B、pb、mb’ have the same meanings as Q, L, X, A, p, m in formula (1). X B2 represents I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms having one or more and five or fewer substituents selected from the group consisting of I, F, Cl, and Br.)

[0616] The production method of the compound represented by the above formula (SA1) may further include the step shown in B4a below. Including the step shown in B4a is preferable from the aspect of the reaction purity of the formed compound.

[0617] B4a) Wittig reaction

[0618] The Wittig process is a process for forming an alkene by the Wittig reaction, and there is no limitation. It is a process for forming an alkene from the carbonyl site of an aldehyde or a ketone using phosphorus ylides. As the phosphorus ylide, triphenylalkylphosphonium bromides such as triphenylmethylphosphonium bromide that can form a stable phosphorus ylide can be used. In addition, a phosphonium salt as the phosphorus ylide can be reacted with a base to form a phosphorus ylide in the reaction system and used for the above reaction. As the base, conventionally known bases can be used, and for example, an alkali metal salt of an alcoholate can be suitably used.

[0619] In the process shown in the above B2B, at least an iodine source and an oxidizing agent can be used to introduce iodine into the above-mentioned parent nucleus B. It is preferable to use an iodine source and an oxidizing agent from the viewpoints of reaction efficiency and purity.

[0620] It is preferable that the above-mentioned parent nucleus B contains an aromatic ring structure optionally having a heteroatom from the viewpoint of the balance between solubility in a developer and the effect of improving sensitivity.

[0621] The method for producing a compound represented by the following formula (1) is a method for producing a compound represented by the following formula (1) including the following steps: a halogen-introducing step of reacting a halogenating agent with a compound represented by the following formula (S1) to introduce a halogen atom, and a double-bond introducing step of introducing an unsaturated double bond into the substituent Q. An organic phosphorus compound and a base can be used in the step of introducing a double bond.

[0622]

[0623] (In the formula (S1),

[0624] X 0 is an organic group having 1 to 30 carbon atoms,

[0625] L 1 each independently represents a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphino group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphoric acid group,

[0626] Y each independently represents a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate group, a nitro group, an amino group, a carboxyl group, a mercapto group, an ether group, a thioether group, a phosphino group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphoric acid group, and the alkoxy group, ester group, carbonate group, amino group, ether group, thioether group, phosphino group, phosphonic acid group, carbamate group, urea group, amide group, imide group, and phosphoric acid group of the foregoing Y optionally have substituents,

[0627] A is an organic group having 1 to 30 carbon atoms,

[0628] Z each independently represents an alkoxy group, an ester group, an acetal group, or a carbonate group,

[0629] Q is an organic group having 1 to 30 carbon atoms with a hydroxyl group, aldehyde group, carboxyl group or ketone group,

[0630] p is an integer of 1 or more, m' is an integer of 0 or more, n is an integer of 0 or more, and r is an integer of 0 or more.)

[0631]

[0632] (In formula (1),

[0633] X is each independently I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms having 1 or more and 5 or less substituents selected from the group consisting of I, F, Cl, and Br,

[0634] L 1 is each independently a single bond, ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphino group, phosphonic acid group, carbamate group, urea group, amide group, imide group, or phosphoric acid group,

[0635] Y is each independently a hydroxyl group, alkoxy group, ester group, acetal group, carbonate group, nitro group, amino group, carboxyl group, mercapto group, ether group, thioether group, phosphino group, phosphonic acid group, carbamate group, urea group, amide group, imide group, or phosphoric acid group, and the alkoxy group, ester group, carbonate group, amino group, ether group, thioether group, phosphino group, phosphonic acid group, carbamate group, urea group, amide group, imide group, and phosphoric acid group of Y may optionally have substituents,

[0636] R a 、R b 、and R c are each independently H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms that may optionally have substituents,

[0637] A is an organic group having 1 to 30 carbon atoms,

[0638] Z is each independently an alkoxy group, ester group, acetal group, or carbonate group,

[0639] p is an integer of 1 or more, m is an integer of 1 or more, n is an integer of 0 or more, and r is an integer of 0 or more.)

[0640] The compound in this embodiment is preferably obtained in bold form by the above reaction and then further purified to remove residual metal impurities. That is, from the viewpoints of preventing the deterioration of the resin over time and storage stability, and further from the viewpoints of process adaptability and defect-induced manufacturing product yield when resinized and applied to semiconductor manufacturing processes, it is preferable to avoid the residual metal impurities caused by the mixing of metal components used as reaction aids in the manufacturing process of the compound or those mixed from the reaction kettle for manufacturing and other manufacturing equipment.

[0641] As the residual amount of the aforementioned metal impurities, it is preferably less than 1 ppm, more preferably less than 100 ppb, further preferably less than 50 ppb, further more preferably less than 10 ppb, and most preferably less than 1 ppb with respect to the resin, respectively. In particular, regarding metal species such as Fe, Ni, Sb, W, and Al classified as transition metals, if the metal residual amount is 1 ppm or more, there is a concern that it may become a factor in the modification and deterioration of the material over time due to the interaction with the compound in the present embodiment. In addition, when it is further 1 ppm or more, when using the produced compound to produce a resin for semiconductor processes, the metal residue amount cannot be sufficiently reduced, and there is a concern that it may become a factor in the reduction of the product yield due to defects caused by residual metals and performance deterioration in the semiconductor manufacturing process.

[0642] The purification method is not particularly limited and includes: a step of dissolving the compound in the present embodiment in a solvent to obtain a solution (S), and a step of bringing the obtained solution (S) into contact with an acidic aqueous solution to extract impurities in the compound in the present embodiment (first extraction step). The solvent used in the step of obtaining the solution (S) contains an organic solvent that is not arbitrarily miscible with water.

[0643] According to the aforementioned purification method, the content of various metals that can be contained in the resin in the form of impurities can be reduced.

[0644] More specifically, the compound in the present embodiment can be dissolved in an organic solvent that is not arbitrarily miscible with water to obtain a solution (S), and then the solution (S) is brought into contact with an acidic aqueous solution for extraction treatment. Thereby, after the metal components contained in the solution (S) are transferred to the aqueous phase, the organic phase and the aqueous phase are separated to obtain a resin with a reduced metal content.

[0645] The organic solvent that is not arbitrarily miscible with water used in the above purification method is not particularly limited, and an organic solvent that can be safely applied to semiconductor manufacturing processes is preferred. Specifically, it is an organic solvent with a solubility in water at room temperature of less than 30%, more preferably less than 20%, and particularly preferably less than 10%. The amount of the organic solvent used is preferably 1 to 100 mass times the total amount of the resin used.

[0646] Specific examples of the solvent that is not miscible with water are not limited to the following. For example, ethers such as diethyl ether and diisopropyl ether, esters such as ethyl acetate, n-butyl acetate, and isoamyl acetate, ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 2-pentanone; glycol ether acetates such as ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol monoethyl ether acetate; aliphatic hydrocarbons such as n-hexane and n-heptane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane and chloroform. Among these, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethyl acetate, etc. are preferred, methyl isobutyl ketone, ethyl acetate, cyclohexanone, and propylene glycol monomethyl ether acetate are more preferred, and methyl isobutyl ketone and ethyl acetate are even more preferred. For methyl isobutyl ketone, ethyl acetate, etc., since the saturated solubility of the compounds in this embodiment is relatively high and the boiling point is relatively low, the load in the processes of distilling off the solvent industrially and drying to remove it can be reduced. These solvents can be used alone respectively, and in addition, two or more of them can be used in combination.

[0647] As the acidic aqueous solution used in the above purification method, it is appropriately selected from the aqueous solutions obtained by dissolving generally known organic compounds or inorganic compounds in water. It is not limited to the following. For example, inorganic acid aqueous solutions obtained by dissolving inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid in water, or organic acid aqueous solutions obtained by dissolving organic acids such as acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid in water can be cited. These acidic aqueous solutions can be used alone respectively, and in addition, two or more of them can be used in combination. Among these acidic aqueous solutions, an inorganic acid aqueous solution of one or more selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, or an organic acid aqueous solution of one or more selected from the group consisting of acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid is preferred, an aqueous solution of sulfuric acid, nitric acid, and carboxylic acids such as acetic acid, oxalic acid, tartaric acid, and citric acid is more preferred, an aqueous solution of sulfuric acid, oxalic acid, tartaric acid, and citric acid is further preferred, and an aqueous solution of oxalic acid is even more preferred. It is considered that polycarboxylic acids such as oxalic acid, tartaric acid, and citric acid coordinate with metal ions to produce a chelating effect, so there is a tendency to be able to remove metals more effectively. In addition, according to the purpose of the purification method in this embodiment, the water used here is preferably water with a low metal content, such as ion-exchanged water, etc.

[0648] The pH of the acidic aqueous solution used in the above purification method is not particularly limited, but considering the influence on the above resin, it is preferable to adjust the acidity of the aqueous solution. Generally, the pH range is about 0 to 5, and preferably the pH is about 0 to 3.

[0649] The amount of the acidic aqueous solution used in the above purification method is not particularly limited. From the viewpoints of reducing the number of extraction times for removing metals and the overall liquid volume to ensure operability, it is preferable to adjust this amount. From the above viewpoints, relative to 100% by mass of the above solution (S), the amount of the acidic aqueous solution is preferably 10 to 200% by mass, more preferably 20 to 100% by mass.

[0650] In the above purification method, by bringing the above acidic aqueous solution into contact with the above solution (S), the metal component can be extracted from the above resin in the solution (S).

[0651] In the above purification method, the above solution (S) may further contain an organic solvent that is miscible with water arbitrarily. In the case of containing an organic solvent that is miscible with water arbitrarily, the amount of the above resin that can be added can be increased. In addition, the liquid separation property is improved, and there is a tendency to perform purification with high kettle efficiency. The method of adding an organic solvent that is miscible with water arbitrarily is not particularly limited. For example, a method of adding it in advance to a solution containing an organic solvent, a method of adding it in advance to water or an acidic aqueous solution, and a method of adding it after bringing a solution containing an organic solvent into contact with water or an acidic aqueous solution are all applicable. Among these, the method of adding it in advance to a solution containing an organic solvent is preferable in terms of the operability of the operation and the ease of managing the input amount.

[0652] As the organic solvent that is miscible with water arbitrarily used in the above purification method, there is no particular limitation, and an organic solvent that can be safely applied to a semiconductor manufacturing process is preferable. The amount of the organic solvent that is miscible with water arbitrarily is not particularly limited as long as it is within the range where the solution phase and the water phase are separated. Relative to the total amount of the resin used, it is preferably 0.1 to 100 times by mass, more preferably 0.1 to 50 times by mass, and further preferably 0.1 to 20 times by mass.

[0653] Specific examples of the organic solvent that is miscible with water arbitrarily used in the above purification method are not limited to the following. Examples include ethers such as tetrahydrofuran and 1,3-dioxolane; alcohols such as methanol, ethanol, and isopropyl alcohol; ketones such as acetone and N-methylpyrrolidone; and glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), and propylene glycol monoethyl ether, and aliphatic hydrocarbons. Among these, N-methylpyrrolidone, propylene glycol monomethyl ether, etc. are preferable, and N-methylpyrrolidone and propylene glycol monomethyl ether are more preferable. These solvents can be used alone respectively, and in addition, two or more of them can be used in combination.

[0654] The temperature during the extraction treatment is usually 20 to 90 °C, preferably in the range of 30 to 80 °C. The extraction operation is carried out, for example, by sufficiently mixing using stirring or the like and then allowing to stand. Thereby, the metal components contained in the solution (S) are transferred to the aqueous phase. In addition, by this operation, the acidity of the solution is reduced, and the deterioration of the above-mentioned resin can be suppressed.

[0655] The above mixed solution is separated into a solution phase containing the resin and the solvent and an aqueous phase by standing, and thus, the solution phase is recovered by decantation or the like. The standing time is not particularly limited, and from the viewpoint of better separating the solution phase containing the solvent from the aqueous phase, it is preferable to adjust the standing time. Usually, the standing time is 1 minute or more, preferably 10 minutes or more, more preferably 30 minutes or more. In addition, the extraction treatment may be carried out only once, but it is also effective to repeat the operations of mixing, standing, and separating multiple times.

[0656] In the above purification method, after the first extraction step, it preferably includes the following step (second extraction step): further bringing the solution phase containing the resin into contact with water to extract impurities in the resin. Specifically, for example, it is preferable that after carrying out the above extraction treatment using an acidic aqueous solution, the solution phase containing the resin and the solvent extracted and recovered from the aqueous solution is further subjected to an extraction treatment using water. The above extraction treatment using water is not particularly limited. For example, it can be carried out by sufficiently mixing the solution phase and water using stirring or the like and then allowing the resulting mixed solution to stand. The mixed solution after standing is separated into the solution phase containing the resin and the solvent and the aqueous phase, and thus the solution can be recovered by decantation or the like.

[0657] In addition, the water used here is preferably water with a low metal content, such as ion-exchanged water, etc., according to the purpose of the present embodiment. The extraction treatment may be carried out only once, but it is also effective to repeat the operations of mixing, standing, and separating multiple times. In addition, the usage ratio, temperature, time, and other conditions of the two in the extraction treatment are not particularly limited, and can be the same as in the case of the previous contact treatment with the acidic aqueous solution.

[0658] For the moisture that may be mixed into the solution containing the resin and the solvent thus obtained, it can be easily removed by carrying out operations such as reduced-pressure distillation. In addition, if necessary, a solvent can be added to the above solution to adjust the concentration of the resin to any concentration.

[0659] The purification method of the compound of the present embodiment can also be carried out by passing a solution obtained by dissolving the aforementioned resin in a solvent through a filter for purification.

[0660] According to the purification method of the substance of the present embodiment, the content of various metal components in the above-mentioned resin can be effectively and significantly reduced. The amounts of these metal components can be measured by the method described in the examples below.

[0661] It should be noted that "liquid passing" in this embodiment means that the above-mentioned solution passes from the outside of the filter through the inside of the filter and then moves to the outside of the filter again. For example, it excludes the way of simply contacting the above-mentioned solution on the surface of the filter and the way of moving the above-mentioned solution to the outside of the ion exchange resin while contacting on the surface (that is, the way of simple contact).

[0662] [Filter purification process (liquid passing process)]

[0663] In the filter liquid passing process of this embodiment, the filter used for removing the metal components in the above-mentioned solution containing resin and solvent can generally be a commercially available product for liquid filtration. The filtration accuracy of the filter is not particularly limited. The nominal pore diameter of the filter is preferably 0.2 μm or less, more preferably less than 0.2 μm, further preferably 0.1 μm or less, still further preferably less than 0.1 μm, and further preferably 0.05 μm or less. In addition, the lower limit value of the nominal pore diameter of the filter is not particularly limited and is generally 0.005 μm. The nominal pore diameter mentioned here refers to the nominal pore diameter indicating the separation performance of the filter. For example, it is the pore diameter determined by test methods determined by the filter manufacturer through methods such as the bubble point test, mercury intrusion method test, and standard particle capture test. When using a commercially available product, it is the value recorded in the manufacturer's catalog data. By making the nominal pore diameter 0.2 μm or less, the content of metal components after passing the solution through the filter once can be effectively reduced. In this embodiment, in order to further reduce the content of each metal component in the solution, the filter liquid passing process can be carried out more than twice.

[0664] As the form of the filter, a hollow fiber membrane filter, a membrane filter, a pleated membrane filter, and a filter filled with filter materials such as non-woven fabric, cellulose, and diatomaceous earth can be used, etc. Among the above, the filter is preferably one or more selected from the group consisting of a hollow fiber membrane filter, a membrane filter, and a pleated membrane filter. In addition, especially from the perspective of high-precision filtration accuracy and the size of the filtration area compared with other forms, it is particularly preferred to use a hollow fiber membrane filter.

[0665] Examples of the material of the aforementioned filter include polyolefins such as polyethylene and polypropylene, polyethylene-based resins imparted with functional groups having ion exchange ability based on graft polymerization, polar group-containing resins such as polyamide, polyester, and polyacrylonitrile, and fluorine-containing resins such as polytetrafluoroethylene (PTFE). Among the above, the filter material of the filter is preferably one or more selected from the group consisting of polyamide, polyolefin resin, and fluororesin. In addition, from the perspective of the reduction effect of heavy metals such as chromium, polyamide is particularly preferred. It should be noted that from the perspective of avoiding the dissolution of metals from the filter material, it is preferred to use a filter other than a sintered metal material.

[0666] As polyamide-based filters (hereinafter referred to as trademarks), not limited to the following, for example, Ployfix Nylon series manufactured by KITZMICROFILTER CORPORATION, Ultipleat P-Nylon 66, Ultipoa N66 manufactured by Nihon Pall Ltd., LifeASSURE PSN series, LifeASSURE EF series manufactured by 3M Corporation, etc.

[0667] As polyolefin-based filters, not limited to the following, for example, Ultipleat PE Kleen, IonKleen manufactured by Nihon Pall Ltd., Protego series, MicrogardPlus HC10, Optimizer D manufactured by Entegris Japan Co., Ltd.

[0668] As polyester-based filters, not limited to the following, for example, JURAFLOW DFE manufactured by Central filter mfg. Co., Ltd., Pleats Type PMC manufactured by Nihon Filter Co., Ltd.

[0669] As polyacrylonitrile-based filters, not limited to the following, for example, Ultra filter AIP-0013D, ACP-0013D, ACP-0053D manufactured by ADVANTEC TOYO KAISHA, LTD.

[0670] As fluororesin-based filters, not limited to the following, for example, EnflonHTPFR manufactured by Nihon Pall Ltd., LifeASSURE FA series manufactured by 3M Corporation, etc.

[0671] These filters can be used separately or in combination of two or more.

[0672] In addition, the above filters may contain: ion exchangers such as cation exchange resins, cation charge regulators that generate Zeta potential in the filtered organic solvent solution, etc.

[0673] As filters containing ion exchangers, not limited to the following, for example, Protego series manufactured by Entegris Japan Co., Ltd., KURANGRAFT manufactured by KURASHIKI TEXTILE MANUFACTURING CO., LTD.

[0674] In addition, as a filter (hereinafter, a trademark) containing a substance having a positive Zeta potential such as polyamide polyamine epichlorohydrin cationic resin, it is not limited to the following. For example, Zeta plus 40QSH, Zetaplus 020GN, or LifeASSURE EF series manufactured by 3M Corporation, etc. can be cited.

[0675] [Use of Compound (A)]

[0676] The compound (A) of the present embodiment can be added directly or in the form of a polymer described later to the film-forming composition, thereby improving the sensitivity to the exposure light source. The compound (A) or its polymer is preferably used in a photoresist.

[0677] [Composition]

[0678] The composition of the present embodiment contains the compound (A). The content of the compound (A) in the present embodiment is preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably 99% by mass or more.

[0679] As another preferred form of the composition of the present embodiment, it is preferably at least a compound represented by the formula (1) other than the formula (1C) and a compound represented by the formula (1C) as the compound (A). As the ratio of the monomer represented by the formula (1C) contained, it is preferably a small amount of 1 mass ppm or more and 10 mass% or less relative to the monomer represented by the formula (1), more preferably 20 mass ppm or more to 2 mass% or less, and preferably contained at 50 mass ppm or more and 1 mass% or less.

[0680] By setting the content rate of the compound represented by the formula (1C) within the described range, the interaction between resins during resinification can be reduced. By suppressing the crystallinity caused by the interaction between resins after film formation using this resin, the locality of solubility in the developer at the molecular level from several nanometers to several tens of nanometers can be reduced, and the reduction of pattern quality such as line edge roughness and residue defects of the pattern formed in a series of lithography processes including exposure, post-exposure baking, and development can be suppressed, and the resolution can be further improved.

[0681] Regarding these effects related to lithography performance, the compounds represented by the formula (1) and the compounds represented by the formula (1C) having a mother nucleus A into which a halogen element, particularly iodine or fluorine, is introduced have a change (shift) in hydrophilicity and hydrophobicity and an increase in polarization in the polar part compared to the compounds having a hydroxy styrene skeleton into which iodine or the like is not introduced. Therefore, the influence is greater in the compounds represented by the formula (1C).

[0682] In the composition of the present embodiment, the impurity containing K (potassium) is preferably 1 mass ppm or less, more preferably 0.5 mass ppm or less, still more preferably 0.1 mass ppm or less, and even more preferably 0.005 mass ppm or less in terms of elemental conversion relative to the compound (A).

[0683] In the composition of the present embodiment, one or more elemental impurities selected from the group consisting of Mn (manganese), Al (aluminum), Si (silicon), and Li (lithium) (preferably one or more elemental impurities selected from the group consisting of Mn and Al) are preferably 1 ppm or less, more preferably 0.5 ppm or less, and still more preferably 0.1 ppm or less in terms of elemental conversion relative to the compound (A).

[0684] The amounts of K, Mn, Al, etc. are measured by inorganic elemental analysis (IPC - AES / IPC - MS). As an inorganic elemental analysis device, for example, "AG8900" manufactured by Agilent Technologies Japan, Ltd. can be cited.

[0685] In the composition of the present embodiment, the phosphorus - containing compound is preferably 10 ppm or less, more preferably 8 ppm or less, and still more preferably 5 ppm or less relative to the compound (A).

[0686] In the composition of the present embodiment, maleic acid is preferably 10 ppm or less, more preferably 8 ppm or less, and still more preferably 5 ppm or less relative to the compound (A).

[0687] The amounts of the phosphorus - containing compound and maleic acid are calculated by gas chromatography - mass spectrometry (GC - MS), based on the area fraction of the GC chart and the peak intensity ratio of the target peak to the reference peak.

[0688] In the composition of the present embodiment, the peroxide is preferably 10 mass ppm or less, more preferably 1 ppm or less, and still more preferably 0.1 ppm or less relative to the compound (A).

[0689] Regarding the amount of peroxide, by the ammonium ferric thiocyanate method (hereinafter referred to as the AFTA method), after adding trichloroacetic acid to the sample, ammonium ferrous sulfate and potassium thiocyanate are added, the standard curve of a known peroxide as a standard substance is obtained, and the absorbance at a measurement wavelength of 480 μm is measured for quantification.

[0690] In the composition of the present embodiment, the water content is preferably 100,000 ppm or less, more preferably 20,000 ppm or less, still more preferably 1,000 ppm or less, still further preferably 500 ppm or less, and still further preferably 100 ppm or less, relative to the compound (A). The water content is measured by the Karl Fischer method (Karl Fischer moisture determination apparatus).

[0691] [Polymer (A)]

[0692] The polymer (A) of the present embodiment contains a structural unit derived from the above-mentioned compound (A). By including a structural unit derived from the compound (A) in the polymer (A), the sensitivity to the exposure light source can be improved when compounded into the resist composition. In particular, even when extreme ultraviolet light is used as the exposure light source, sufficient sensitivity is exhibited and a fine line pattern with a narrow line width is formed well.

[0693] In addition, the sensitivity of conventional resist compositions to the exposure light source sometimes decreases over time during storage or the like, and there are difficulties in actual implementation for semiconductor manufacturing. However, according to the polymer (A) of the present embodiment, the stability of the resist composition is improved, and a decrease in the sensitivity to the exposure light source can be suppressed even during long-term storage.

[0694] The polymer (A) of the present embodiment contains a structural unit derived from the compound (A).

[0695] As the structural unit derived from the compound (A), it is a structural unit represented by the following formula (4).

[0696]

[0697] In formula (4), X, L 1 , Y, R a , R b , R c , A, Z, p, m, n and r are the same as defined in formula (1).

[0698] The polymer (A) is obtained by polymerizing the compound (A) of the present embodiment or copolymerizing the compound (A) with other monomers. The polymer (A) can be used, for example, as a material for forming a film for lithography.

[0699] As the structural unit derived from the compound (A), it is preferably a structural unit represented by the following formula (5).

[0700]

[0701] In formula (5), X, L 1 , Y, A, p, m and n are the same as defined in formula (1).

[0702] As a structural unit derived from compound (A), it is more preferably a structural unit represented by the following formula (6).

[0703]

[0704] In formula (6), X, L 1 , Y, R a1 , R b1 , R c1 , A, Z, p, m, n and r are the same as defined in formula (1b).

[0705] The amount of the structural unit derived from compound (A) is preferably 5 mol% or more, more preferably 8 mol% or more, and still more preferably 10 mol% or more, based on the total amount of the monomer components of polymer (A). In addition, the amount of the structural unit derived from compound (A) is 100 mol% or less, preferably 80 mol% or less, more preferably 50 mol% or less, and still more preferably 30 mol% or less, based on the total amount of the monomer components of polymer (A).

[0706] As one of the preferred embodiments of the polymer of the present embodiment, preferably, as the structural unit of polymer (A), the monomer represented by compound (A) contains at least the compound represented by formula (1) other than that represented by formula (1C) and the compound represented by formula (1C). As the proportion of the monomer represented by formula (1C), it preferably contains a small amount of 10 ppm or more and 10% by mass or less, more preferably 20 ppm or more to 2% by mass or less, and preferably 50 ppm or more and 1% by mass or less, relative to the monomer represented by formula (1).

[0707] By setting the content rate of the compound represented by formula (1C) within the described range, the interaction between resins during resinification can be reduced. By suppressing the crystallinity caused by the interaction between resins after film formation using this resin, the locality of solubility in the developer at the molecular level from several nanometers to several tens of nanometers can be reduced, and the reduction of pattern quality such as line edge roughness and residue defects of the pattern formed in the pattern formation process in a series of lithography processes including exposure, post-exposure baking, and development can be suppressed, and the resolution can be further improved.

[0708] Regarding these effects related to lithography performance, for the compounds represented by formula (1) and the compounds represented by formula (1C) having a mother nucleus A into which a halogen element, particularly iodine or fluorine, is introduced, the hydrophilic-hydrophobic property changes (shifts), and the polarization in the polar part increases, so the influence is greater in the monomer represented by formula (1C).

[0709] As other monomers copolymerized with the compound (A), it is preferable to include an aromatic compound having an unsaturated double bond as a substituent as a polymerization unit and a polymerization unit having a functional group capable of enhancing its solubility in an alkali developing solution by the action of an acid or a base.

[0710] There is no particular limitation on the other monomers. For example, compounds described in International Publication WO2016 / 125782, International Publication WO2015 / 115613, Japanese Patent Application Laid-Open No. 2015 / 117305, International Publication WO2014 / 175275, Japanese Patent Application Laid-Open No. 2012 / 162498, or compounds represented by the following formula (C1) or formula (C2) can be cited. Among these, compounds represented by the following formula (C1) or formula (C2) are preferred.

[0711] From the viewpoints of the quality of the pattern shape after exposure and development in the lithography process, particularly roughness and pattern collapse suppression, it is preferable that the dissolution rate R of the resin in which the unexposed portion during exposure becomes a pattern convex portion in the alkali developing solution min is more than three orders of magnitude different from the dissolution rate R of the resin in which the exposed portion during exposure becomes a pattern concave portion in the alkali developing solution max and it is preferable that the difference in dissolution rate due to the presence or absence of the protecting group is large. In addition, the detachment rate of the protecting group during post-exposure baking (PEB) and development is large. From these viewpoints, it is preferable that the other monomers copolymerized with the compound (A) in the polymer (A) have a structural unit represented by the following formula (C1).

[0712]

[0713] In formula (C1),

[0714] R C11 is H or methyl,

[0715] R C12 is H or an alkyl group having 1 to 4 carbon atoms,

[0716] R C13 together with the carbon atom to which R C13 is bonded, forms a cycloalkyl group or a heterocycloalkyl group having 4 to 20 carbon atoms,

[0717] * is the bonding site with the adjacent structural unit.

[0718] R C12 is preferably H or an alkyl group having 1 to 3 carbon atoms, and R C13 is preferably, together with the carbon atom to which R C13 is bonded, a cycloalkyl group or a heterocycloalkyl group having 4 to 10 carbon atoms. The cycloalkyl group or heterocycloalkyl group of R C13 may have a substituent (for example, an oxo group).

[0719] The amount of the structural unit represented by the formula (C1) is preferably 5 mol% or more, more preferably 10 mol% or more, and still more preferably 20 mol% or more, based on the total amount of the monomer components of the polymer (A). Further, the amount of the structural unit represented by the formula (C1) is preferably 90 mol% or less, more preferably 80 mol% or less, and still more preferably 70 mol% or less, based on the total amount of the monomer components of the polymer (A).

[0720] Regarding other monomers copolymerized with the compound (A) in the polymer (A), from the viewpoints of the quality of the pattern shape after exposure and development in the lithography process, particularly the roughness and the suppression of pattern collapse, the structural unit represented by the following formula (C2) is preferred.

[0721]

[0722] In the formula (C2),

[0723] R C21 is H or methyl,

[0724] R C22 and R C23 are each independently an alkyl group having 1 to 4 carbon atoms,

[0725] R C24 is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms,

[0726] R C22 R C23 and R C24 Two or three of them, together with the carbon atom to which they are bonded, may form an alicyclic structure having 3 to 20 carbon atoms,

[0727] * is a bonding site to an adjacent structural unit.

[0728] R C22 is preferably an alkyl group having 1 to 3 carbon atoms, and R C24 is a cycloalkyl group having 5 to 10 carbon atoms. Further, the above-mentioned alicyclic structure formed by R C22 R C23 and R C24 may contain a plurality of rings such as adamantyl group. Further, the above-mentioned alicyclic structure may have substituents (for example, hydroxyl group, alkyl group).

[0729] The amount of the structural unit represented by the formula (C2) is preferably 5 mol% or more, more preferably 10 mol% or more, and still more preferably 20 mol% or more, relative to the total amount of the monomer components of the polymer (A). Further, the amount of the structural unit represented by the formula (C2) is preferably 80 mol% or less, more preferably 60 mol% or less, and still more preferably 40 mol% or less, relative to the total amount of the monomer components of the polymer (A).

[0730] There is no limitation on the monomer raw material of the structural unit represented by the formula (C2), and examples thereof include 2-methyl-2-(meth)acryloyloxyadamantane, 2-ethyl-2-(meth)acryloyloxyadamantane, 2-isopropyl-2-(meth)acryloyloxyadamantane, 2-n-propyl-2-(meth)acryloyloxyadamantane, 2-n-butyl-2-(meth)acryloyloxyadamantane, 1-methyl-1-(meth)acryloyloxycyclopentane, 1-ethyl-1-(meth)acryloyloxycyclopentane, 1-methyl-1-(meth)acryloyloxycyclohexane, 1-ethyl-1-(meth)acryloyloxycyclohexane, 1-methyl-1-(meth)acryloyloxycycloheptane, 1-ethyl-1-(meth)acryloyloxycycloheptane, 1-methyl-1-(meth)acryloyloxycyclooctane, 1-ethyl-1-(meth)acryloyloxycyclooctane, 2-ethyl-2-(meth)acryloyloxidecahydro-1,4:5,8-dimethanonaphthalene, and 2-ethyl-2-(meth)acryloyloxynorbornane. Commercially available products can be used as these monomers.

[0731] Other monomers copolymerized with the compound (A) in the polymer (A) preferably have a structural unit represented by the following formula (C3).

[0732]

[0733] In the formula (C3), R C31 is H or methyl, and m, A, and * are as defined in the above formula (4).

[0734] Other monomers copolymerized with the compound (A) in the polymer (A) preferably have a structural unit represented by the following formula (C4).

[0735]

[0736] In the formula (C4), B represents an organic group having 5 to 30 carbon atoms containing an aromatic ring, and R C31 , m, and * are as defined in the above formula (C3).

[0737] Other monomers copolymerized with the compound (A) in the polymer (A) preferably have a structural unit represented by the following formula (C5).

[0738]

[0739] In formula (C5), B’ represents an organic group having 5 to 30 carbon atoms containing an aromatic ring, and R C31 , m, and * are as defined in the above formula (C3).

[0740] Regarding other monomers copolymerized with compound (A) in polymer (A), from the viewpoints of exposure sensitivity, pattern shape quality, especially roughness, and pattern collapse suppression in the lithography process during pattern formation after exposure and development, the structural unit represented by the following formula (C6) is preferred.

[0741]

[0742] In formula (C6),

[0743] X C61 is a hydroxyl group or a halogen group,

[0744] R C61 each independently represents an alkyl group having 1 to 20 carbon atoms,

[0745] * is the bonding site with the adjacent structural unit.

[0746] X C61 is preferably F, Cl, Br, or I, more preferably Cl or I, and even more preferably I. R C61 is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

[0747] The amount of the structural unit represented by formula (C6) is preferably 20 mol% or more, more preferably 30 mol% or more, and even more preferably 40 mol% or more, based on the total amount of the monomer components of polymer (A). In addition, the amount of the structural unit represented by formula (C6) is preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less, based on the total amount of the monomer components of polymer (A).

[0748] The monomer raw material for the structural unit represented by formula (C6) is not limited. For example, methyl 2-chloroacrylate, ethyl 2-chloroacrylate, butyl 2-chloroacrylate, methyl 2-bromoacrylate, ethyl 2-bromoacrylate, butyl 2-bromoacrylate, methyl 2-iodoacrylate, ethyl 2-iodoacrylate, and butyl 2-iodoacrylate can be mentioned. As these monomers, commercially available products can be used.

[0749] Next, a method for manufacturing the polymer (A) will be described. For the polymerization reaction, the monomers as constituent units are dissolved in a solvent, a polymerization initiator is added, and the reaction is carried out while heating or cooling. The reaction conditions can be arbitrarily set by the type of polymerization initiator, the initiation method such as heat and light, temperature, pressure, concentration, solvent, additives, etc. Examples of the polymerization initiator include radical polymerization initiators such as azobisisobutyronitrile and peroxides, and anionic polymerization initiators such as alkyllithium and Grignard reagents.

[0750] As the solvent used in the polymerization reaction, commercially available products that can usually be obtained can be used. For example, various solvents such as alcohols, ethers, hydrocarbons, and halogen-based solvents can be appropriately used within the range that does not hinder the reaction. Multiple solvents can also be mixed and used within the range that does not hinder the above reaction.

[0751] The polymer (A) obtained in the polymerization reaction can be purified by a known method. Specifically, it can be carried out by combining ultrafiltration, crystallization, microfiltration, acid cleaning, cleaning with water having a conductivity of 10 mS / m or less, and extraction.

[0752] [Composition for film formation]

[0753] The composition for film formation of the present embodiment contains the compound (A) or the polymer (A), and is a composition particularly suitable for lithography technology. Without particular limitation, the aforementioned composition can be used for film formation applications for lithography, such as resist film formation applications (i.e., "resist composition"). Furthermore, the aforementioned composition can be used for upper layer film formation applications (i.e., "upper layer film formation composition"), intermediate layer formation applications (i.e., "intermediate layer formation composition"), lower layer film formation applications (i.e., "lower layer film formation composition"), etc. According to the composition of the present embodiment, a film with high sensitivity can be formed, and a good resist pattern shape can also be imparted.

[0754] The film-forming composition of the present embodiment can also be used as an optical component forming composition for applying lithography technology. In addition to being used in the form of a thin film or sheet, the optical component is also used as a plastic lens (prismatic lens, cylindrical lens, microlens, Fresnel lens, viewing angle control lens, contrast improvement lens, etc.), a retardation film, an electromagnetic wave shielding film, a prism, an optical fiber, a solder resist for flexible printed wiring, an anti-plating agent, an interlayer insulating film for a multilayer printed circuit board, a photosensitive optical waveguide, a liquid crystal display, an organic electroluminescence (EL) display, an optical semiconductor (LED) element, a solid-state imaging element, an organic thin film solar cell, a dye-sensitized solar cell, and an organic thin film diode (TFT). The aforementioned composition can be suitably used, in particular, as an embedding film and a planarizing film on a photodiode, a planarizing film before and after a color filter, a microlens, a planarizing film on a microlens, and a conformal film, which are components of a solid-state imaging element requiring a high refractive index.

[0755] The film-forming composition of the present embodiment contains a compound (A) or a polymer (A), and may contain other components such as a substrate (B), a solvent (S), an acid generator (C), an acid diffusion control agent (E), etc. as needed. Hereinafter, each component will be described.

[0756] 〔Substrate (B)〕

[0757] In the present embodiment, the "substrate (B)" refers to a compound (including a resin) other than the compound (A) or the polymer (A), and is suitable as a substrate for a g-ray, i-ray, KrF excimer laser (248 nm), ArF excimer laser (193 nm), extreme ultraviolet (EUV) lithography (13.5 nm), or electron beam (EB) resist (for example, a substrate for lithography, a substrate for resist). As long as it is such a substrate, there is no particular limitation, and it can be used as the substrate (B) in the present embodiment. Examples of the substrate (B) include novolak resin, cresol novolak resin, hydroxystyrene resin, (meth)acrylic resin, hydroxystyrene-(meth)acrylic copolymer, cycloolefin-maleic anhydride copolymer, cycloolefin, vinyl ether-maleic anhydride copolymer, and inorganic resist materials having metal elements such as titanium, tin, hafnium, and zirconium, and derivatives thereof. Among them, from the viewpoint of the shape of the obtained resist pattern, novolak resin, cresol novolak resin, hydroxystyrene resin, (meth)acrylic resin, hydroxystyrene-(meth)acrylic copolymer, and inorganic resist materials having metal elements such as titanium, tin, hafnium, and zirconium, and derivatives thereof are preferred.

[0758] As the aforementioned derivatives, there is no particular limitation. For example, compounds into which dissociative groups are introduced, compounds into which crosslinking groups are introduced, etc. can be cited. The aforementioned derivatives into which dissociative groups and crosslinking groups are introduced can exhibit dissociation reactions and crosslinking reactions by the action of light, acids, etc.

[0759] The "dissociative group" refers to a characteristic group that undergoes cleavage to generate functional groups such as base-soluble groups that cause changes in solubility. As the base-soluble group, there is no particular limitation, and examples thereof include a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, a hexafluoroisopropanol group, etc. A phenolic hydroxyl group and a carboxyl group are preferred, and a phenolic hydroxyl group is particularly preferred.

[0760] The "crosslinking group" refers to a group that undergoes crosslinking in the presence or absence of a catalyst. As the crosslinking group, there is no particular limitation. For example, an alkoxy group having 1 to 20 carbon atoms, a group having an allyl group, a group having a (meth)acryloyl group, a group having an epoxy(meth)acryloyl group, a group having a hydroxyl group, a group having a urethane(meth)acryloyl group, a group having a glycidyl group, and a group having a vinylphenylmethyl group can be cited.

[0761] 〔Solvent (S)〕

[0762] For the solvent in this embodiment, as long as the above-mentioned compound (A) or polymer (A) is at least soluble, a publicly known solvent can be suitably used. The solvent is not particularly limited. For example, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monon-propyl ether acetate, and ethylene glycol monon-butyl ether acetate can be mentioned; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monon-propyl ether acetate, and propylene glycol monon-butyl ether acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether; lactate esters such as methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, and n-pentyl lactate; aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-pentyl acetate, n-hexyl acetate, methyl propionate, and ethyl propionate; other esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl 3-methoxy-3-methylpropionate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate, and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; ketones such as acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone (CPN), and cyclohexanone (CHN); amides such as N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpyrrolidone; lactones such as γ-lactone. The solvent used in this embodiment is preferably a safe solvent, more preferably at least one selected from PGMEA, PGME, CHN, CPN, 2-heptanone, anisole, butyl acetate, and ethyl lactate, and still more preferably at least one selected from PGMEA, PGME, CHN, CPN, and ethyl lactate.

[0763] In the film-forming composition of this embodiment, the solid content concentration is not particularly limited, and is preferably 1 to 80% by mass, more preferably 1 to 50% by mass, still more preferably 2 to 40% by mass, and even more preferably 2 to 10% by mass relative to the total mass of the film-forming composition.

[0764] [Acid generator (C)]

[0765] In the film-forming composition of the present embodiment, it preferably contains at least one acid generator (C) that directly or indirectly generates an acid upon irradiation with radiation. The radiation is at least one selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), X-ray, and ion beam. The acid generator (C) is not particularly limited. For example, the substances described in International Publication WO2013 / 024778 can be used. The acid generator (C) can be used alone or in combination of two or more.

[0766] The compounding amount of the acid generator (C) is preferably 0.001 to 49% by mass, more preferably 1 to 40% by mass, still more preferably 3 to 30% by mass, and even more preferably 10 to 25% by mass with respect to the total mass of the solid components. By using the acid generator (C) within the above range, there is a tendency to obtain a pattern profile with high sensitivity and low edge roughness. In the present embodiment, as long as an acid is generated in the system, the method for generating the acid is not particularly limited. If an excimer laser is used instead of ultraviolet rays such as g-rays and i-rays, finer processing may be achieved. In addition, if an electron beam, extreme ultraviolet, X-ray, or ion beam is used as the high-energy ray, further finer processing can be achieved.

[0767] 〔Acid diffusion control agent (E)〕

[0768] The film-forming composition of the present embodiment may contain an acid diffusion control agent (E). The acid diffusion control agent (E) controls the diffusion of the acid generated by the acid generator upon irradiation with radiation in the resist film, thereby preventing an undesirable chemical reaction in the unexposed area. By using the acid diffusion control agent (E), there is a tendency to improve the storage stability of the composition of the present embodiment. In addition, by using the acid diffusion control agent (E), the resolution of the film formed using the composition of the present embodiment can be improved, and the change in the line width of the resist pattern caused by the variation in the post-exposure delay development time before irradiation with radiation and the post-exposure delay development time after irradiation with radiation can be suppressed, and there is a tendency for the process stability to become excellent. As the acid diffusion control agent (E), there is no particular limitation, and radiation-decomposable basic compounds such as nitrogen atom-containing basic compounds, basic sulfonium compounds, and basic iodonium compounds can be mentioned.

[0769] As the acid diffusion control agent (E), there is no particular limitation. For example, the substances described in International Publication WO2013 / 024778 can be used. The acid diffusion control agent (E) can be used alone or in combination of two or more.

[0770] The compounding amount of the acid diffusion controller (E) is preferably 0.001 to 49% by mass, more preferably 0.01 to 10% by mass, still more preferably 0.01 to 5% by mass, and still more preferably 0.01 to 3% by mass, relative to the total mass of the solid components. When the compounding amount of the acid diffusion controller (E) is within the foregoing range, there is a tendency to prevent deterioration of resolution, pattern shape, dimensional fidelity, etc. Further, even when the post-exposure delay development time from electron beam irradiation to heating after radiation exposure becomes long, deterioration of the shape of the upper portion of the pattern can be suppressed. In addition, when the compounding amount of the acid diffusion controller (E) is 10% by mass or less, there is a tendency to prevent a decrease in sensitivity, developability of the unexposed portion, etc. In addition, by using such an acid diffusion controller, the storage stability of the resist composition is improved, the resolution is increased, and the line width change of the resist pattern caused by fluctuations in the post-exposure delay development time before radiation exposure and the post-exposure delay development time after radiation exposure can be suppressed, and there is a tendency for the process stability to become excellent.

[0771] 〔Other component (F)〕

[0772] The film-forming composition of the present embodiment may contain, as other component (F), one or two or more kinds of various additives such as a crosslinking agent, a dissolution accelerator, a dissolution controller, a sensitizer, a surfactant, and an organic carboxylic acid or an oxyacid of phosphorus or a derivative thereof, as needed.

[0773] (Crosslinking agent)

[0774] The film-forming composition of the present embodiment may contain a crosslinking agent. The crosslinking agent can crosslink at least any one of the compound (A), the polymer (A), and the substrate (B). As the crosslinking agent, an acid crosslinking agent that can crosslink the substrate (B) intramolecularly or intermolecularly in the presence of the acid generated from the acid generator (C) is preferable. As such an acid crosslinking agent, for example, a compound having one or more groups capable of crosslinking the substrate (B) (hereinafter referred to as "crosslinkable group") can be cited.

[0775] As crosslinkable groups, for example, (i) hydroxyl groups, hydroxyalkyl groups (alkyl groups having 1 to 6 carbon atoms), alkoxy groups having 1 to 6 carbon atoms (alkyl groups having 1 to 6 carbon atoms), acetoxy groups (alkyl groups having 1 to 6 carbon atoms), etc., hydroxyalkyl groups or groups derived therefrom; (ii) carbonyl groups such as formyl groups and carboxyl groups (alkyl groups having 1 to 6 carbon atoms) or groups derived therefrom; (iii) groups containing nitrogen-containing groups such as dimethylaminomethyl, diethylaminomethyl, dihydroxymethylaminomethyl, dihydroxyethylaminomethyl, morpholinomethyl; (iv) glycidyl ether groups, glycidyl ester groups, glycidylamino groups, etc., glycidyl group-containing groups; (v) allyloxy groups having 1 to 6 carbon atoms (alkyl groups having 1 to 6 carbon atoms), aralkyloxy groups having 1 to 6 carbon atoms (alkyl groups having 1 to 6 carbon atoms), etc., such as benzyloxymethyl, benzoyloxymethyl, groups derived from aromatic groups; (vi) polymerizable multiple bond-containing groups such as vinyl groups and isopropenyl groups. As the crosslinkable groups of the crosslinking agent in the present embodiment, hydroxyalkyl groups and alkoxyalkyl groups are preferred, and alkoxymethyl groups are particularly preferred.

[0776] The crosslinking agent having a crosslinkable group is not particularly limited. For example, an acid crosslinking agent described in International Publication WO2013 / 024778 can be used. The crosslinking agent can be used alone or in combination of two or more.

[0777] In the present embodiment, the compounding amount of the crosslinking agent relative to the total mass of the solid components is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and still more preferably 20% by mass or less.

[0778] (Dissolution promoter)

[0779] The dissolution promoter is a component having the function of increasing the solubility of the solid components in the developer when the solubility is too low, thereby moderately increasing the dissolution rate of the aforementioned compound during development. As the dissolution promoter, a low molecular weight dissolution promoter is preferred. For example, low molecular weight phenolic compounds can be cited. As the low molecular weight phenolic compounds, for example, bisphenols, tris(hydroxyphenyl)methane, etc. can be cited. These dissolution promoters can be used alone or in combination of two or more.

[0780] The compounding amount of the dissolution promoter is appropriately adjusted according to the type of the aforementioned solid components used, and is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, still more preferably 0 to 1% by mass, and particularly preferably 0% by mass of the total mass of the solid components.

[0781] (Dissolution controller)

[0782] A dissolution controller is a component that has the function of controlling the solubility of solid components when their solubility in the developer is too high, thereby moderately reducing the dissolution rate during development. As such a dissolution controller, a substance that does not undergo chemical changes during processes such as baking of the resist film, radiation irradiation, and development is preferred.

[0783] There is no particular limitation on the dissolution controller. For example, aromatic hydrocarbons such as phenanthrene, anthracene, and acenaphthene can be cited; ketones such as acetophenone, benzophenone, and phenylnaphthyl ketone; sulfones such as methylphenyl sulfone, diphenyl sulfone, and dinaphthyl sulfone, etc. These dissolution controllers can be used alone or in combination of two or more.

[0784] The blending amount of the dissolution controller is appropriately adjusted according to the type of the aforementioned compound used, and is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, further preferably 0 to 1% by mass, and particularly preferably 0% by mass of the total mass of the solid components.

[0785] (Sensitizer)

[0786] A sensitizer is a component that has the function of absorbing the energy of the irradiated radiation and transferring the energy to the acid generator (C), thereby increasing the amount of acid generated, and improving the apparent sensitivity of the resist. As such a sensitizer, for example, benzophenone derivatives, diacetyl derivatives, pyrene derivatives, phenothiazine derivatives, fluorene derivatives, etc. can be cited, and there is no particular limitation. These sensitizers can be used alone or in combination of two or more.

[0787] The blending amount of the sensitizer is appropriately adjusted according to the type of the aforementioned compound used, and is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, further preferably 0 to 1% by mass, and particularly preferably 0% by mass of the total mass of the solid components.

[0788] (Surfactant)

[0789] The surfactant is a component that functions to improve the coatability, striation, developability of the resist, etc. of the composition of the present embodiment. The surfactant can be any of an anionic surfactant, a cationic surfactant, a non-ionic surfactant, or an amphoteric surfactant. As a preferred surfactant, a non-ionic surfactant can be mentioned. The non-ionic surfactant has good affinity with the solvent used in the production of the composition of the present embodiment, and can further enhance the effect of the composition of the present embodiment. Examples of the non-ionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyethylene glycol, etc., and there is no particular limitation. As commercially available products of these surfactants, there are those with the following trade names, EFTOP (manufactured by jemco), MEGAFACE (manufactured by Dainippon Ink and Chemicals, Inc.), FLUORAD (manufactured by Sumitomo 3M Limited), AsahiGuard, Surflon (the above are manufactured by Asahi Glass Co., Ltd.), Pepol (manufactured by Toho Chemical Industry Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), etc.

[0790] The blending amount of the surfactant is appropriately adjusted according to the type of the aforementioned solid component used, and is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, still more preferably 0 to 1% by mass, and particularly preferably 0% by mass of the total mass of the solid components.

[0791] (organic carboxylic acid or oxygen-containing acid of phosphorus or its derivative)

[0792] For the purpose of preventing sensitivity deterioration or improving the shape of the resist pattern, the stability of post-exposure delay development, etc., an organic carboxylic acid or an oxygen-containing acid of phosphorus or its derivative can also be contained as an optional component. It should be noted that the organic carboxylic acid or the oxygen-containing acid of phosphorus or its derivative can be used in combination with an acid diffusion control agent, or can be used alone. As the organic carboxylic acid, for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, etc. are suitable. As the oxygen-containing acid of phosphorus or its derivative, derivatives such as phosphoric acid, dibutyl phosphate, diphenyl phosphate and other phosphates or their esters, sulfonic acids, dimethyl sulfonate, dibutyl sulfonate, phenyl sulfonic acid, diphenyl sulfonate, dibenzyl sulfonate and other sulfonic acids or their esters, phosphonic acids, phenylphosphonic acid and other phosphonic acids and their esters can be mentioned. Among these, sulfonic acid is particularly preferred.

[0793] The organic carboxylic acid, the oxyacid of phosphorus, or their derivatives can be used alone or in combination of two or more. The blending amount of the organic carboxylic acid, the oxyacid of phosphorus, or their derivatives is appropriately adjusted according to the type of the aforementioned compounds used, preferably 0 to 49% by mass, more preferably 0 to 5% by mass, still more preferably 0 to 1% by mass, and particularly preferably 0% by mass, based on the total mass of the solid components.

[0794] [Other additives]

[0795] Furthermore, one or two or more additives other than the above components can be blended as needed in the composition of the present embodiment. Examples of such additives include dyes, pigments, and adhesion aids. For example, if a dye or a pigment is blended, the latent image in the exposed area can be visualized, thereby mitigating the influence of halation during exposure, and thus it is preferred. In addition, if an adhesion aid is blended, the adhesion to the substrate can be improved, and thus it is preferred. Furthermore, as other additives, antihalation agents, storage stabilizers, defoamers, shape modifiers, etc., specifically 4-hydroxy-4'-methylchalcone, etc. can be cited.

[0796] In the composition of the present embodiment, the total amount of any component (F) can be set to 0 to 99% by mass, preferably 0 to 49% by mass, more preferably 0 to 10% by mass, still more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass, based on the total mass of the solid components.

[0797] [Method for forming a resist pattern]

[0798] The method for forming a resist pattern of the present embodiment includes:

[0799] a step of forming a resist film on a substrate using a film-forming composition containing compound (A) or polymer (A);

[0800] a step of pattern-exposing the aforementioned resist film; and

[0801] a step of developing the resist film after the aforementioned exposure.

[0802] As the coating method in the step of forming a resist film, there is no particular limitation, and examples thereof include a spin coater, a dip coater, and a roll coater. As the substrate, there is no particular limitation, and examples thereof include a silicon wafer, metal, plastic, glass, and ceramic. After forming the resist film, heat treatment can be performed at a temperature of about 50°C to 200°C. The film thickness of the resist film is not particularly limited, and is, for example, 50 nm to 1 μm.

[0803] In the exposure process, exposure can be carried out through a specified mask pattern, or shot exposure without a mask can be performed. The thickness of the coating film is, for example, 0.1 to 20 μm, preferably about 0.3 to 2 μm. During exposure, light of various wavelengths can be used, such as ultraviolet rays, X-rays, etc. For example, as the light source, it is suitable to select far ultraviolet rays such as F2 excimer laser (wavelength 157 nm), ArF excimer laser (wavelength 193 nm), KrF excimer laser (wavelength 248 nm), extreme ultraviolet rays (wavelength 13 nm), X-rays, electron beams, etc. Among these, extreme ultraviolet rays are preferred. In addition, exposure conditions such as the exposure dose are appropriately selected according to the above-mentioned resin and / or compound blending composition, the types of various additives, etc.

[0804] In the present embodiment, in order to stably form a high-precision fine pattern, it is preferable to perform a heat treatment at a temperature of 50 to 200 °C for 30 seconds or more after exposure. In this case, when the temperature is lower than 50 °C, there is a concern that the sensitivity fluctuation caused by the type of substrate is large. Thereafter, using an alkali developer, development is usually carried out under the conditions of 10 to 50 °C and 10 to 200 seconds, preferably 20 to 25 °C and 15 to 90 seconds, thereby forming a specified resist pattern.

[0805] As the above-mentioned alkali developer, for example, an alkaline aqueous solution in which an alkaline compound such as alkali metal hydroxide, ammonia water, alkylamines, alkanolamines, heterocyclic amines, tetraalkylammonium hydroxides, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1,5-diazabicyclo-[4.3.0]-5-nonene, etc. is dissolved at a concentration usually of 1 to 10% by mass, preferably 1 to 3% by mass, is used. In addition, a water-soluble organic solvent and a surfactant can be appropriately added to the developer formed from the above-mentioned alkaline aqueous solution.

[0806] The composition of the present embodiment can also be used as a composition for forming an optical component applying lithography technology. In addition to being used in the form of a thin film or a sheet, the optical component is also useful as a plastic lens (prismatic lens, cylindrical lens, microlens, Fresnel lens, viewing angle control lens, contrast improvement lens, etc.), a retardation film, an electromagnetic wave shielding film, a prism, an optical fiber, a solder resist for flexible printed wiring, an anti-plating agent, an interlayer insulating film for a multilayer printed circuit board, a photosensitive optical waveguide, a liquid crystal display, an organic electroluminescence (EL) display, an optical semiconductor (LED) element, a solid-state imaging element, an organic thin film solar cell, a dye-sensitized solar cell, and an organic thin film diode (TFT). In particular, the aforementioned composition can be suitably used as an embedding film and a planarizing film on a photodiode, a planarizing film before and after a color filter, a microlens, a planarizing film and a conformal film on a microlens, which are components of a solid-state imaging element requiring a high refractive index.

[0807] In addition, the composition of the present embodiment can be used as a patterning material for lithography applications. As an application of the lithography process, it can be used in various applications such as semiconductors, liquid crystal display panels, display panels using OLEDs, power devices, CCDs, and other sensors. Especially when used in the integrated circuits of semiconductors and devices, for the following purposes, the composition of the present embodiment can be appropriately utilized. The purpose is as follows: Through the process of forming device elements on a silicon wafer, based on the pattern formed by using the composition of the present embodiment on the upper surface side of an insulating layer such as a silicon oxide film or other oxide films, a pattern is formed on the insulating film on the substrate side by etching, and then a metal film and a semiconductor material are laminated based on the formed insulating film pattern to form a circuit pattern, thereby constructing a semiconductor element or other devices.

[0808] <<Second Embodiment>>

[0809] Hereinafter, a second embodiment of the present invention will be described. The second embodiment relates to a method for manufacturing an iodine-containing vinyl monomer, preferably iodine-containing hydroxystyrene, having the following formula (1). The manufacturing method of the second embodiment can be used as a method for manufacturing the compound of the first embodiment.

[0810] [Method for Manufacturing Iodine-Containing Vinyl Monomer Shown by Formula (1)]

[0811] The second embodiment is a method for manufacturing an iodine-containing vinyl monomer, preferably iodine-containing hydroxystyrene, having the following formula (1).

[0812]

[0813] (In formula (1), R 1 ~R 5 are each independently H, OH, OCH 3 , halogen, or a linear or branched alkyl group, and R 6 ~R 8 are each independently H, OH, OCH 3 , halogen, or cyano, where at least one of R 1 ~R 5 is OH, and in addition, at least one is iodine)

[0814] Examples of the hydroxystyrene produced by the method of the present embodiment include, but are not limited to, 2-hydroxystyrene containing iodine, 3-hydroxystyrene containing iodine, 4-hydroxystyrene containing iodine, 3-methoxy-4-hydroxystyrene containing iodine, 3,5-dimethoxy-4-hydroxystyrene containing iodine, 2,3-dihydroxystyrene containing iodine, 2,4-dihydroxystyrene containing iodine, 2,5-dihydroxystyrene containing iodine, 2,6-dihydroxystyrene containing iodine, 3,4-dihydroxystyrene containing iodine, 3,5-dihydroxystyrene containing iodine, 2,3,4-trihydroxystyrene containing iodine, 2,4,6-trihydroxystyrene containing iodine, 3,4,5-trihydroxystyrene containing iodine, and α-cyano-4-hydroxystyrene containing iodine. At least one iodine is introduced, preferably two or more iodine atoms are introduced. At least one OH is introduced, preferably two or more OH groups are introduced.

[0815] Specific examples of the hydroxystyrene produced by the method of the present embodiment include, but are not limited to, the following.

[0816]

[0817] (iodine-containing alcoholic matrix)

[0818] The iodine-containing alcoholic matrix used in the present invention is an iodine-containing alcoholic matrix having the formula (1-1).

[0819]

[0820] (In formula (1-1), R 1 ~R 5 are each independently H, OH, OCH 3 , halogen, or a linear or branched alkyl group, and R 6 ~R 10 are each independently H, OH, OCH 3 , halogen, or cyano, provided that at least one of R 1 ~R 5 is OH, and at least one is iodine, and one of R 6 ~R 10 is OH or OCH 3 ).

[0821] Examples of suitable iodo-alcoholic matrices include, without limitation, iodo-containing 2-(1-hydroxyethyl)phenol, iodo-containing 3-(1-hydroxyethyl)phenol, iodo-containing 4-(1-hydroxyethyl)phenol, iodo-containing 4-(1-hydroxyethyl)-1-methoxyphenol, iodo-containing 4-(1-hydroxyethyl)-2,6-dimethoxyphenol, iodo-containing 3-(1-hydroxyethyl)benzene-1,2-diol, iodo-containing 4-(1-hydroxyethyl)benzene-1,3-diol, iodo-containing 2-(1-hydroxyethyl)benzene-1,4-diol, iodo-containing 6-(1-hydroxyethyl)benzene-1,5-diol, iodo-containing 4-(1-hydroxyethyl)benzene-1,2-diol, iodo-containing 5-(1-hydroxyethyl)benzene-1,3-diol, iodo-containing 4-(1-hydroxyethyl)benzene-1,2,3-triol, iodo-containing 2-(1-hydroxyethyl)benzene-1,3,5-triol, iodo-containing 5-(1-hydroxyethyl)benzene-1,2,3-triol, iodo-containing 2-(1-cyano-1-hydroxyethyl)phenol, iodo-containing 2-(2-hydroxyphenyl)ethanol, iodo-containing 2-(3-hydroxyphenyl)ethanol, iodo-containing 2-(4-hydroxyphenyl)ethanol, iodo-containing 2-(3-methoxy-4-hydroxyphenyl)ethanol, iodo-containing 2-(3,5-dimethoxy-4-hydroxyphenyl)ethanol, iodo-containing 2-(2,3-dihydroxyphenyl)ethanol, iodo-containing 2-(2,4-dihydroxyphenyl)ethanol, iodo-containing 2-(2,5-dihydroxyphenyl)ethanol, iodo-containing 2-(2,6-dihydroxyphenyl)ethanol, iodo-containing 2-(3,4-dihydroxyphenyl)ethanol, iodo-containing 2-(3,5-dihydroxyphenyl)ethanol, iodo-containing 2-(2,3,4-trihydroxyphenyl)ethanol, iodo-containing 2-(2,4,6-trihydroxyphenyl)ethanol, iodo-containing 2-(3,4,5-trihydroxyphenyl)ethanol, and iodo-containing 1-cyano-2-(4-hydroxyphenyl)ethanol. Iodine is introduced at least 1, preferably 2 or more. OH is introduced at least 1, preferably 2 or more. OH may be substituted with OMe.

[0822] Specific examples of the iodo-alcoholic matrix used in the present invention include, without limitation, the following.

[0823]

[0824]

[0825] These iodo-alcoholic matrices can be obtained by many methods. From the viewpoints of availability of raw materials and yield, it is desirable to obtain them by the method described below.

[0826] The method for producing the iodo-vinyl monomer represented by formula (1) includes:

[0827] a) A process for preparing an iodine-containing alcoholic matrix of formula (1-1); and

[0828] b) A process for dehydrating the aforementioned iodine-containing alcoholic matrix.

[0829] As the solvent that can be used in the dehydration process, a variety of solvents including polar aprotic solvents and protic polar solvents are used. A single protic polar solvent or a single polar aprotic solvent can be used. Furthermore, a mixture of polar aprotic solvents, a mixture of protic polar solvents, a mixture of polar aprotic solvents and protic polar solvents, and a mixture of aprotic or protic solvents and non-polar solvents can be used, preferably a polar aprotic solvent or a mixture thereof. The solvent is effective but not an essential component. There is no limitation on suitable polar aprotic solvents, and examples include ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, ester solvents such as ethyl acetate, γ-butyrolactone, nitrile solvents such as acetonitrile, hydrocarbon solvents such as toluene, hexane, amide solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidone, N,N-dimethylacetamide, hexamethylphosphoramide, hexamethylphosphorous triamide, and dimethyl sulfoxide. Dimethyl sulfoxide is preferred. There is no limitation on suitable protic polar solvents, and examples include alcohol solvents such as water, methanol, ethanol, propanol, butanol, di(propylene glycol) methyl ether, di(ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol, and n-butanol.

[0830] The amount of the solvent used can be appropriately set according to the matrix, catalyst, and reaction conditions used, and there is no particular limitation. Generally, 0 to 10,000 parts by mass is appropriate relative to 100 parts by mass of the reaction raw materials, and from the viewpoint of yield, 100 to 2,000 parts by mass is preferred.

[0831] As the catalyst that can be used in the dehydration process, a variety of catalysts that function under the reaction conditions of the present embodiment are used. An acid catalyst is preferred. There is no limitation on examples of suitable acid catalysts. For example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid, organic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid, Lewis acids such as zinc chloride, aluminum chloride, iron chloride, boron trifluoride, and solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid, or phosphomolybdic acid can be cited. These acid catalysts can be used alone or in combination of two or more. Among these, from the viewpoint of manufacturing, organic acids and solid acids are preferred, and from the viewpoints of availability and ease of handling in manufacturing, hydrochloric acid or sulfuric acid is preferably used.

[0832] The amount of the catalyst can be appropriately set according to the matrix, catalyst, reaction conditions, etc. used, and there is no particular limitation. Generally, 0.0001 to 100 parts by mass is appropriate relative to 100 parts by mass of the reaction raw materials, and from the viewpoint of yield, 0.001 to 10 parts by mass is preferred.

[0833] As the polymerization inhibitor that can be used in the dehydration step, various polymerization inhibitors that function under the reaction conditions of the present embodiment are used. The polymerization inhibitor is effective but not an essential component. Examples of suitable polymerization inhibitors are not limited, and hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, phenothiazine, N-oxyl (nitroxide) inhibitors, such as Prostab (registered trademark) 5415 (bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, CAS#2516-92-9, sold by (Ciba Specialty Chemicals, Tarrytown, NY)), 4-hydroxy-TEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl, CAS#2226-96-2, sold by TCI), and Uvinul (registered trademark) 4040P (1,6-hexamethylene-bis(N-formyl-N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)amine, sold by BASF Corporation (BASF Corp., Worcester, MA)).

[0834] The amount of the polymerization inhibitor can be appropriately set according to the matrix, catalyst, reaction conditions, etc. used, and there is no particular limitation. Generally, 0.0001 to 100 parts by mass is appropriate relative to 100 parts by mass of the reaction raw materials, and from the viewpoint of yield, 0.001 to 10 parts by mass is preferred.

[0835] As the polymerization inhibitor that can be used in the dehydration process, various polymerization inhibitors that function under the reaction conditions of the present embodiment are used. The polymerization inhibitor is effective but not an essential component. It is also effective to use a polymerization retarder in combination with an inhibitor. Polymerization retarders are widely known in the art and are compounds used to delay the polymerization reaction but cannot completely prevent polymerization. Common retarders are aromatic nitro compounds such as dinitro-o-cresol (DNOC) and dinitrobutylphenol (DNBP). The manufacturing method of the polymerization retarder is common and widely known in the art (for example, refer to U.S. Patent No. 6,339,177; Park et al., Polymer (Korea) (1988), 12(8), 710-19), and its use in the control of styrene polymerization is well documented (for example, refer to Bushby et al., Polymer (1998), 39(22), 5567-5571).

[0836] The amount of the polymerization inhibitor can be appropriately set according to the matrix, catalyst, reaction conditions, etc. used, and there is no particular limitation. Generally, 0.0001 to 100 parts by mass is appropriate relative to 100 parts by mass of the reaction raw material, and from the viewpoint of yield, 0.001 to 10 parts by mass is preferred.

[0837] (Reaction conditions)

[0838] An iodine-containing alcoholic matrix having the formula (1-1), a catalyst, and a solvent are added to a reactor to form a reaction mixture. Any suitable reactor can be used.

[0839] In addition, known methods such as batch, semi-batch, and continuous methods can be appropriately selected for carrying out.

[0840] The reaction temperature is not particularly limited. The preferred range varies depending on the concentration of the matrix, the stability of the formed product, the choice of catalyst, and the desired yield. Generally, a temperature of 0°C to 200°C is appropriate, and from the viewpoint of yield, a temperature of 10°C to 190°C is preferred, more preferably a temperature of 25°C to 150°C, and further preferably a temperature of 50°C to 100°C.

[0841] In the reaction using 1-(4-hydroxy-3,5-diiodophenyl)ethanol as the matrix, the preferred temperature range is 0°C to 100°C.

[0842] The reaction pressure is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. An inert gas such as nitrogen can be used, and an aspirator pump can be additionally used to adjust the pressure. The reaction under high pressure is not limited, and conventional pressure reactors including an oscillating vessel, a rocker vessel, and a stirred autoclave can be used. In the reaction using 1-(4-hydroxy-3,5-diiodophenyl)ethanol as the substrate, the preferred reaction pressure is reduced pressure to normal pressure, and reduced pressure is preferred.

[0843] From the viewpoint of reaction rate, it is preferred to carry out the reaction while removing low-boiling products such as water and methanol generated from the reaction system. As a method for removing the low-boiling products, a conventionally known appropriate method can be used. For example, removal can be carried out by evaporation, and evaporation under reduced pressure is preferably used for removal.

[0844] The reaction time is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. However, most reactions are carried out in less than 6 hours, and usually the reaction time is 15 minutes to 600 minutes.

[0845] In the reaction using 1-(4-hydroxy-3,5-diiodophenyl)ethanol as the substrate, the preferred reaction time range is 15 minutes to 600 minutes.

[0846] For separation and purification, it can be carried out using a conventionally known appropriate method after the reaction. For example, the reaction mixture is poured onto ice water and extracted in a solvent such as ethyl acetate or diethyl ether. Then, the solvent is removed by evaporation under reduced pressure to recover the product. Separation and purification into a desired high-purity monomer can be carried out by filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, separation and purification methods based on activated carbon, etc., and methods based on combinations thereof, which are widely known in the technical field.

[0847] [Method (I) for producing an iodoalcoholic substrate represented by formula (1-1)]

[0848] The iodo-ketonic substrate used in the production of formula (1-1) is an iodo-ketonic substrate having formula (1-2).

[0849]

[0850] (In formula (1-2), R 1 ~R 5 are each independently H, OH, OCH 3 , halogen, or a linear or branched alkyl group, and R 7 , R 8 and R 10Each independently is H, OH, OCH 3 , a halogen or a cyano group, wherein, R 1 ~R 5 At least one of them is OH, and further, at least one of them is iodine).

[0851] Examples of suitable iodo-ketonic substrates are not limited, and include 2-hydroxybenzyl methyl ketone containing iodine, 3-hydroxybenzyl methyl ketone containing iodine, 4-hydroxybenzyl methyl ketone containing iodine, 3-methoxy-4-hydroxybenzyl methyl ketone containing iodine, 3,5-dimethoxy-4-hydroxybenzyl methyl ketone containing iodine, 2,3-dihydroxybenzyl methyl ketone containing iodine, 2,4-dihydroxybenzyl methyl ketone containing iodine, 2,5-dihydroxybenzyl methyl ketone containing iodine, 2,6-dihydroxybenzyl methyl ketone containing iodine, 3,4-dihydroxybenzyl methyl ketone containing iodine, 3,5-dihydroxybenzyl methyl ketone containing iodine, 2,3,4-trihydroxybenzyl methyl ketone containing iodine, 2,4,6-trihydroxybenzyl methyl ketone containing iodine, 3,4,5-trihydroxybenzyl methyl ketone containing iodine, 4-hydroxybenzyl α-cyano methyl ketone. Iodine is introduced at least one, preferably two or more. OH is introduced at least one, preferably two or more.

[0852] Specific examples of the iodo-ketonic substrate used in the present invention are not limited, and the following can be shown.

[0853]

[0854] These iodo-ketonic substrates can be obtained by many methods, and from the viewpoints of availability of raw materials and yield, it is desirable to obtain them by the method described below.

[0855] The method for producing the iodo-alcoholic substrate represented by the formula (1-1) includes:

[0856] c) a step of preparing an iodo-ketonic substrate having the formula (1-2); and

[0857] d) a step of reducing the aforementioned iodo-ketonic substrate.

[0858] As the solvent that can be used in the reduction step, various solvents including polar aprotic solvents and protic polar solvents are used. A single protic polar solvent or a single polar aprotic solvent can be used. Further, a mixture of polar aprotic solvents, a mixture of protic polar solvents, a mixture of polar aprotic solvents and protic polar solvents, and a mixture of aprotic or protic solvents and nonpolar solvents can be used. A polar aprotic solvent or a mixture thereof is preferred. From the viewpoint of suppressing side reactions, a mixture of a polar aprotic solvent and a protic polar solvent is preferred. As the protic polar solvent, alcohol solvents such as water, methanol, ethanol, propanol, and butanol are further preferred. The solvent is effective but not an essential component. There is no limitation on the appropriate polar aprotic solvent, and examples thereof include ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether; ester solvents such as ethyl acetate and γ-butyrolactone; nitrile solvents such as acetonitrile; hydrocarbon solvents such as toluene and hexane; amide solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidone, N,N-dimethylacetamide, hexamethylphosphoramide, and hexamethylphosphorous triamide; and dimethyl sulfoxide. Dimethyl sulfoxide is preferred. There is no limitation on the appropriate protic polar solvent, and examples thereof include alcohol solvents such as water, methanol, ethanol, propanol, and butanol; di(propylene glycol) methyl ether, di(ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol, and n-butanol.

[0859] The amount of the solvent can be appropriately set according to the substrate, catalyst, reaction conditions, etc. used, and there is no particular limitation. Generally, 0 to 10,000 parts by mass is appropriate relative to 100 parts by mass of the reaction raw material. From the viewpoint of yield, 100 to 2,000 parts by mass is preferred.

[0860] As the reducing agent that can be used in the reduction step, various reducing agents that function under the reaction conditions of the present embodiment are used. There is no limitation on the appropriate reducing agent, and examples thereof include metal hydrides and metal hydride complexes. Examples include borane·dimethyl sulfide, diisobutylaluminum hydride, sodium borohydride, lithium borohydride, potassium borohydride, zinc borohydride, lithium tri-tert-butylborohydride, potassium tri-tert-butylborohydride, lithium triethylborohydride, lithium aluminum hydride, lithium tri-tert-butoxyaluminum hydride, and sodium bis(methoxyethoxy)aluminum hydride.

[0861] The amount of the reducing agent can be appropriately set according to the substrate, reducing agent, reaction conditions, etc. used, and there is no particular limitation. Generally, 1 to 500 parts by mass is appropriate relative to 100 parts by mass of the reaction raw material. From the viewpoint of yield, 10 to 200 parts by mass is preferred.

[0862] As a quenching agent, various quenching agents that function under the reaction conditions of the present embodiment are used. The quenching agent has the function of inactivating the reducing agent. The quenching agent is effective but not an essential component. There is no limitation on suitable quenching agents, and examples include ethanol, aqueous ammonium chloride, water, hydrochloric acid, sulfuric acid, and the like.

[0863] The amount of the quenching agent can be appropriately set according to the amount of the reducing agent used, and there is no particular limitation. Generally, 1 to 500 parts by mass is appropriate relative to 100 parts by mass of the reducing agent, and from the viewpoint of yield, 50 to 200 parts by mass is preferred.

[0864] (Reaction conditions)

[0865] An iodo-ketone substrate having the formula (1-2), a reducing agent, and a solvent are added to a reactor to form a reaction mixture. Any suitable reactor can be used.

[0866] In addition, known methods such as batch, semi-batch, and continuous methods can be appropriately selected to carry out the reaction.

[0867] The reaction temperature is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of the reducing agent, and the desired yield. Generally, a temperature of 0°C to 200°C is appropriate, and from the viewpoint of yield, a temperature of 0°C to 100°C is preferred, more preferably a temperature of 0°C to 70°C, and further preferably a temperature of 0°C to 50°C.

[0868] In the reaction using 4'-hydroxy-3',5'-diiodoacetophenone as the substrate, the preferred temperature range is 0°C to 100°C.

[0869] The reaction pressure is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of the reducing agent, and the desired yield. An inert gas such as nitrogen can be used, and in addition, a suction pump or the like can be used to adjust the pressure. The reaction under high pressure is not limited, and conventional pressure reactors including an oscillating vessel, a rocker vessel, and a stirred autoclave can be used.

[0870] In the reaction using 4'-hydroxy-3',5'-diiodoacetophenone as the substrate, the preferred reaction pressure is reduced pressure to atmospheric pressure, and reduced pressure is preferred.

[0871] The reaction time is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of the reducing agent, and the desired yield. However, most reactions are carried out in less than 6 hours, and generally the reaction time is 15 minutes to 600 minutes.

[0872] In the reaction using 4'-hydroxy-3',5'-diiodoacetophenone as a substrate, the preferred reaction time range is from 15 minutes to 600 minutes.

[0873] Separation and purification can be carried out using appropriate methods known in the art after the reaction. For example, the reaction mixture is poured onto ice water and extracted in a solvent such as ethyl acetate or diethyl ether. Then, the solvent is removed by evaporation under reduced pressure to recover the product. The product can be separated and purified into a desired high-purity compound by filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, separation and purification methods based on activated carbon, etc., and methods based on combinations thereof.

[0874] [Method for producing an iodine-containing alcoholic substrate represented by formula (1-1) (II)]

[0875] The alcoholic substrate used in the production of formula (1-1) is an alcoholic substrate having formula (1-3).

[0876]

[0877] (In formula (1-3), R 11 ~R 15 are each independently H, OH, OCH 3 or a linear or branched alkyl group, and R 6 ~R 10 are each independently H, OH, OCH 3 , a halogen or a cyano group, where at least one of R 11 ~R 15 is OH, and one of R 6 ~R 10 is OH or OCH 3 ).

[0878] Examples of suitable alcoholic matrices include, without limitation, 2-(1-hydroxyethyl)phenol, 3-(1-hydroxyethyl)phenol, 4-(1-hydroxyethyl)phenol, 4-(1-hydroxyethyl)-1-methoxyphenol, 4-(1-hydroxyethyl)-2,6-dimethoxyphenol, 3-(1-hydroxyethyl)benzene-1,2-diol, 4-(1-hydroxyethyl)benzene-1,3-diol, 2-(1-hydroxyethyl)benzene-1,4-diol, 6-(1-hydroxyethyl)benzene-1,5-diol, 4-(1-hydroxyethyl)benzene-1,2-diol, 5-(1-hydroxyethyl)benzene-1,3-diol, 4-(1-hydroxyethyl)benzene-1,2,3-triol, 2-(1-hydroxyethyl)benzene-1,3,5-triol, 5-(1-hydroxyethyl)benzene-1,2,3-triol, 2-(1-cyano-1-hydroxyethyl)phenol, 2-(2-hydroxyphenyl)ethanol, 2-(3-hydroxyphenyl)ethanol, 2-(4-hydroxyphenyl)ethanol, 2-(3-methoxy-4-hydroxyphenyl)ethanol, 2-(3,5-dimethoxy-4-hydroxyphenyl)ethanol, 2-(2,3-dihydroxyphenyl)ethanol, 2-(2,4-dihydroxyphenyl)ethanol, 2-(2,5-dihydroxyphenyl)ethanol, 2-(2,6-dihydroxyphenyl)ethanol, 2-(3,4-dihydroxyphenyl)ethanol, 2-(3,5-dihydroxyphenyl)ethanol, 2-(2,3,4-trihydroxyphenyl)ethanol, 2-(2,4,6-trihydroxyphenyl)ethanol, 2-(3,4,5-trihydroxyphenyl)ethanol, 1-cyano-2-(4-hydroxyphenyl)ethanol. At least one OH is introduced, preferably two or more OHs are introduced. OH may be substituted with OMe.

[0879] Specific examples of the alcoholic matrix used in the present embodiment include, without limitation, the following.

[0880]

[0881]

[0882] These alcoholic matrices can be obtained by many methods. From the viewpoints of availability of raw materials and yield, it is desirable to obtain them by the method described later.

[0883] The method for producing the iodine-containing alcoholic matrix represented by the formula (1-1) includes:

[0884] e) a step of preparing an alcoholic matrix having the formula (1-3);

[0885] f) a step of introducing iodine into the above-mentioned alcoholic matrix.

[0886] As the solvent that can be used in the iodine introduction step, various solvents including polar aprotic solvents and protic polar solvents are used. A single protic polar solvent or a single polar aprotic solvent can be used. Further, a mixture of polar aprotic solvents, a mixture of protic polar solvents, a mixture of polar aprotic solvents and protic polar solvents, and a mixture of aprotic or protic solvents and nonpolar solvents can be used. A protic polar solvent or a mixture thereof is preferred, and from the viewpoint of suppressing side reactions, a mixture of a protic polar solvent and water is preferred. The solvent is effective but not an essential component. There is no limitation on suitable polar aprotic solvents, and examples include ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether, ester solvents such as ethyl acetate and γ-butyrolactone, nitrile solvents such as acetonitrile, hydrocarbon solvents such as toluene and hexane, amide solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidone, N,N-dimethylacetamide, hexamethylphosphoramide, and hexamethylphosphorous triamide, and dimethyl sulfoxide. Dimethyl sulfoxide is preferred. There is no limitation on suitable protic polar solvents, and examples include alcohol solvents such as water, methanol, ethanol, propanol, and butanol, di(propylene glycol) methyl ether, di(ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol, and n-butanol.

[0887] The amount of the solvent used can be appropriately set according to the substrate, catalyst, reaction conditions, etc. used, and there is no particular limitation. Usually, 0 to 10,000 parts by mass is appropriate relative to 100 parts by mass of the reaction raw material, and from the viewpoint of yield, 100 to 2,000 parts by mass is preferred.

[0888] (Reaction conditions)

[0889] An alcoholic substrate having the formula (1-3), a catalyst, and a solvent are added to a reactor to form a reaction mixture. Any suitable reactor can be used.

[0890] In addition, a known method such as a batch method, a semi-batch method, or a continuous method can be appropriately selected to carry out the reaction.

[0891] The reaction temperature is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of the catalyst, and the desired yield. Usually, a temperature of 0°C to 200°C is appropriate, and from the viewpoint of yield, a temperature of 0°C to 100°C is preferred, more preferably a temperature of 0°C to 70°C, and further preferably a temperature of 0°C to 50°C.

[0892] In the reaction using 1-(4-hydroxyphenyl)ethanol as the substrate, the preferred temperature range is 0°C to 100°C.

[0893] The reaction pressure is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the product formed, the choice of catalyst, and the desired yield. Inert gases such as nitrogen can be used, and additionally, an aspirator pump or the like can be used to adjust the pressure. The reaction under high pressure is not limited, and conventional pressure reactors including an oscillating vessel, a rocker vessel, and a stirred autoclave can be used.

[0894] In the reaction using 1-(4-hydroxyphenyl)ethanol as the substrate, the preferred reaction pressure is reduced pressure to atmospheric pressure, preferably reduced pressure.

[0895] The reaction time is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the product formed, the choice of catalyst, and the desired yield. However, most reactions are carried out in less than 6 hours, and usually the reaction time is 15 minutes to 600 minutes.

[0896] In the reaction using 1-(4-hydroxyphenyl)ethanol as the substrate, the preferred reaction time range is 15 minutes to 600 minutes.

[0897] Separation and purification can be carried out using appropriate methods known in the art after the reaction is completed. For example, the reaction mixture is poured onto ice water and extracted in a solvent such as ethyl acetate or diethyl ether. Then, the solvent is removed by evaporation under reduced pressure to recover the product. The product can be separated and purified into a desired high-purity compound by filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, separation and purification methods based on activated carbon, etc., and methods based on combinations thereof that are widely known in the art.

[0898] [Method for producing an iodo-ketonic substrate represented by formula (1-2)]

[0899] The ketonic substrate used in the production of formula (1-2) is a ketonic substrate having formula (1-4).

[0900]

[0901] (In formula (1-4), R 11 ~R 15 are each independently H, OH, OCH 3 or a linear or branched alkyl group, and R 7 ~R 8 and R 10 are each independently H, OH, OCH 3 , a halogen, or a cyano group, provided that at least one of R 11 ~R 15 is OH).

[0902] Examples of suitable ketonic substrates include, without limitation, 2-hydroxyphenyl methyl ketone, 3-hydroxyphenyl methyl ketone, 4-hydroxyphenyl methyl ketone, 3-methoxy-4-hydroxyphenyl methyl ketone, 3,5-dimethoxy-4-hydroxyphenyl methyl ketone, 2,3-dihydroxyphenyl methyl ketone, 2,4-dihydroxyphenyl methyl ketone, 2,5-dihydroxyphenyl methyl ketone, 2,6-dihydroxyphenyl methyl ketone, 3,4-dihydroxyphenyl methyl ketone, 3,5-dihydroxyphenyl methyl ketone, 2,3,4-trihydroxyphenyl methyl ketone, 2,4,6-trihydroxyphenyl methyl ketone, 3,4,5-trihydroxyphenyl methyl ketone, 4-hydroxyphenyl α-cyano methyl ketone.

[0903] Specific examples of the ketonic substrate used in the present embodiment include, without limitation, the following.

[0904]

[0905] These ketonic substrates can be obtained by many methods.

[0906] The method for producing the iodine-containing ketonic substrate represented by formula (1-2) includes:

[0907] g) a step of preparing a ketonic substrate having the formula (1-4); and

[0908] h) a step of introducing iodine into the aforementioned ketonic substrate.

[0909] As the solvent that can be used in the iodine introduction step, various solvents including polar aprotic solvents and protic polar solvents are used. A single protic polar solvent or a single polar aprotic solvent can be used. Further, a mixture of polar aprotic solvents, a mixture of protic polar solvents, a mixture of polar aprotic solvents and protic polar solvents, and a mixture of aprotic or protic solvents and nonpolar solvents can be used. A protic polar solvent or a mixture thereof is preferred, and a mixture of a protic polar solvent and water is preferred from the viewpoint of suppressing side reactions. The solvent is effective but not an essential component. Examples of suitable polar aprotic solvents include, without limitation, ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether, ester solvents such as ethyl acetate and γ-butyrolactone, nitrile solvents such as acetonitrile, hydrocarbon solvents such as toluene and hexane, amide solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidone, N,N-dimethylacetamide, hexamethylphosphoramide, and hexamethylphosphorous triamide, and dimethyl sulfoxide. Dimethyl sulfoxide is preferred. Examples of suitable protic polar solvents include, without limitation, water, alcohol solvents such as methanol, ethanol, propanol, and butanol, di(propylene glycol) methyl ether, di(ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol, and n-butanol.

[0910] The amount of the solvent can be appropriately set according to the matrix, catalyst, reaction conditions, etc. used, and there is no particular limitation. Generally, 0 to 10,000 parts by mass is appropriate relative to 100 parts by mass of the reaction raw material. From the viewpoint of yield, 100 to 2,000 parts by mass is preferred.

[0911] (Reaction conditions)

[0912] The ketone matrix having the formula (1-4), the catalyst and the solvent are added to a reactor to form a reaction mixture. Any suitable reactor can be used.

[0913] In addition, known methods such as batch, semi-batch, continuous, etc. can be appropriately selected to carry out the reaction.

[0914] The reaction temperature is not particularly limited. The preferred range varies depending on the concentration of the matrix, the stability of the formed product, the choice of catalyst, and the desired yield. Generally, a temperature of 0°C to 200°C is appropriate. From the viewpoint of yield, a temperature of 0°C to 100°C is preferred, more preferably a temperature of 0°C to 70°C, and further preferably a temperature of 0°C to 50°C.

[0915] In the reaction using 4'-hydroxyacetophenone as the matrix, the preferred temperature range is 0°C to 100°C.

[0916] The reaction pressure is not particularly limited. The preferred range varies depending on the concentration of the matrix, the stability of the formed product, the choice of catalyst, and the desired yield. An inert gas such as nitrogen can be used, and in addition, a suction pump, etc. can be used to adjust the pressure. The reaction under high pressure is not limited, and conventional pressure reactors including an oscillating vessel, a rocker vessel, and a stirred autoclave can be used.

[0917] In the reaction using 4'-hydroxyacetophenone as the matrix, the preferred reaction pressure is reduced pressure to normal pressure, and reduced pressure is preferred.

[0918] The reaction time is not particularly limited. The preferred range varies depending on the concentration of the matrix, the stability of the formed product, the choice of catalyst, and the desired yield. However, most reactions are carried out in less than 6 hours, and generally the reaction time is 15 minutes to 600 minutes.

[0919] In the reaction using 4'-hydroxyacetophenone as the matrix, the preferred reaction time range is 15 minutes to 600 minutes.

[0920] Separation and purification can be carried out using appropriate methods known in the art after the reaction. For example, the reaction mixture is poured onto ice water and extracted in a solvent such as ethyl acetate or diethyl ether. Then, the solvent is removed by evaporation under reduced pressure to recover the product. Separation and purification into the desired highly pure compound can be achieved by filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, separation and purification methods based on activated carbon, etc., and methods based on combinations thereof, which are widely known in the art.

[0921] [Method for producing an alcoholic matrix represented by formula (1-3)]

[0922] The ketonic matrix used in the production of formula (1-3) is the ketonic matrix having the aforementioned formula (1-4).

[0923] The method for producing an alcoholic matrix represented by formula (1-3) includes:

[0924] i) A step of preparing a ketonic matrix having formula (1-4); and

[0925] j) A step of reducing the aforementioned ketonic matrix.

[0926] As the solvent that can be used in the reduction step, a variety of solvents including polar aprotic solvents and protic polar solvents are used. A single protic polar solvent or a single polar aprotic solvent can be used. Further, a mixture of polar aprotic solvents, a mixture of protic polar solvents, a mixture of polar aprotic solvents and protic polar solvents, and a mixture of aprotic or protic solvents and non-polar solvents can be used. A polar aprotic solvent or a mixture thereof is preferred. From the viewpoint of suppressing side reactions, a mixture of a polar aprotic solvent and a protic polar solvent is preferred. As the protic polar solvent, alcohol solvents such as water, methanol, ethanol, propanol, and butanol are further preferred. The solvent is effective but not an essential component. There is no limitation on suitable polar aprotic solvents, and examples include ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether, ester solvents such as ethyl acetate and γ-butyrolactone, nitrile solvents such as acetonitrile, hydrocarbon solvents such as toluene and hexane, amide solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidone, N,N-dimethylacetamide, hexamethylphosphoramide, and hexamethylphosphorous triamide, and dimethyl sulfoxide. Dimethyl sulfoxide is preferred. There is no limitation on suitable protic polar solvents, and examples include alcohol solvents such as water, methanol, ethanol, propanol, and butanol, di(propylene glycol) methyl ether, di(ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol, and n-butanol.

[0927] The amount of the solvent can be appropriately set according to the matrix, reducing agent, reaction conditions, etc. used, and there is no particular limitation. Generally, 0 to 10,000 parts by mass is appropriate relative to 100 parts by mass of the reaction raw material, and from the viewpoint of yield, 100 to 2,000 parts by mass is preferred.

[0928] As the reducing agent, various reducing agents that function under the reaction conditions of the present embodiment are used. There is no limitation on suitable reducing agents, and examples include metal hydrides, metal hydride complexes, etc., and examples include borane·dimethyl sulfide, diisobutylaluminum hydride, sodium borohydride, lithium borohydride, potassium borohydride, zinc borohydride, lithium tri-tert-butylborohydride, potassium tri-tert-butylborohydride, lithium triethylborohydride, lithium aluminum hydride, lithium tri-tert-butoxyaluminum hydride, sodium bis(methoxyethoxy)aluminum hydride, etc.

[0929] The amount of the reducing agent can be appropriately set according to the matrix, reducing agent, reaction conditions, etc. used, and there is no particular limitation. Generally, 1 to 500 parts by mass is appropriate relative to 100 parts by mass of the reaction raw material, and from the viewpoint of yield, 10 to 200 parts by mass is preferred.

[0930] As the quenching agent, various quenching agents that function under the reaction conditions of the present embodiment are used. The quenching agent has the function of inactivating the reducing agent. The quenching agent is effective but not an essential component. There is no limitation on suitable quenching agents, and examples include ethanol, aqueous ammonium chloride, water, hydrochloric acid, sulfuric acid, etc.

[0931] The amount of the quenching agent can be appropriately set according to the amount of the reducing agent used, and there is no particular limitation. Generally, 1 to 500 parts by mass is appropriate relative to 100 parts by mass of the reducing agent, and from the viewpoint of yield, 50 to 200 parts by mass is preferred.

[0932] (Reaction conditions)

[0933] The ketonic matrix having the formula (1-4), the reducing agent, and the solvent are added to a reactor to form a reaction mixture. Any suitable reactor can be used.

[0934] In addition, known methods such as batch, semi-batch, continuous, etc. can be appropriately selected to carry out the reaction.

[0935] The reaction temperature is not particularly limited. The preferred range varies depending on the concentration of the matrix, the stability of the formed product, the choice of the reducing agent, and the desired yield. Generally, a temperature of 0°C to 200°C is appropriate, and from the viewpoint of yield, a temperature of 0°C to 100°C is preferred, a temperature of 0°C to 70°C is more preferred, and a temperature of 0°C to 50°C is further preferred.

[0936] In the reaction using 4'-hydroxyacetophenone as a substrate, the preferred temperature range is 0°C to 100°C.

[0937] The reaction pressure is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of reducing agent, and the desired yield. An inert gas such as nitrogen can be used, and an aspirator pump can be additionally used to adjust the pressure. The reaction under high pressure is not limited, and conventional pressure reactors including an oscillating vessel, a rocker vessel, and a stirred autoclave can be used.

[0938] In the reaction using 4'-hydroxyacetophenone as a substrate, the preferred reaction pressure is reduced pressure to atmospheric pressure, and reduced pressure is preferred.

[0939] The reaction time is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of reducing agent, and the desired yield. However, most reactions are carried out in less than 6 hours, and the reaction time is usually 15 minutes to 600 minutes.

[0940] In the reaction using 4'-hydroxyacetophenone as a substrate, the preferred reaction time range is 15 minutes to 600 minutes.

[0941] Separation and purification can be carried out using appropriate methods known in the art after the reaction. For example, the reaction mixture is poured onto ice water and extracted in a solvent such as ethyl acetate or diethyl ether. Then, the solvent is removed by evaporation under reduced pressure to recover the product. The product can be separated and purified into the desired high-purity compound by filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, separation and purification methods based on activated carbon, etc., and methods based on combinations thereof, which are widely known in the art.

[0942] [Method for producing an iodine-containing acetylated vinyl monomer represented by formula (2)]

[0943] This embodiment is a method for producing an iodine-containing acetylated vinyl monomer having formula (2), specifically, iodine-containing acetoxystyrene.

[0944]

[0945] (In formula (2), R 16 ~R 20 are each independently H, OH, OCH 3 , OAc, a halogen, or a linear or branched alkyl group, and R 6 ~R 8 are each independently H, OH, OCH 3 , a halogen, or a cyano group, where R 16 ~R 20At least one of them is Oac, and in addition, at least one of them is iodine).

[0946] Examples of the iodine-containing acetylated vinyl monomer produced by the method of the present embodiment are not limited, and examples include 2-acetoxystyrene containing iodine, 3-acetoxystyrene containing iodine, 4-acetoxystyrene containing iodine, 3-methoxy-4-acetoxystyrene containing iodine, 3,5-dimethoxy-4-acetoxystyrene containing iodine, 2,3-acetoxystyrene containing iodine, 2,4-acetoxystyrene containing iodine, 2,5-acetoxystyrene containing iodine, 2,6-acetoxystyrene containing iodine, 3,4-acetoxystyrene containing iodine, 3,5-acetoxystyrene containing iodine, 2,3,4-triacetoxystyrene containing iodine, 2,4,6-triacetoxystyrene containing iodine, 3,4,5-triacetoxystyrene containing iodine, and α-cyano-4-acetoxystyrene containing iodine. At least one iodine is introduced, and preferably two or more are introduced. At least one OAc is introduced, and preferably two or more are introduced.

[0947] Specific examples of the iodine-containing acetylated vinyl monomer produced by the method of the present embodiment are not limited, and the following can be shown.

[0948]

[0949] (In the formula, Ac represents an acetyl group.)

[0950] The method for producing the iodine-containing acetylated vinyl monomer (iodine-containing acetoxystyrene) represented by the formula (2) includes:

[0951] k) A step of preparing an iodine-containing vinyl monomer (iodine-containing hydroxystyrene) having the formula (1); and

[0952] l) A step of acetylating the aforementioned iodine-containing hydroxystyrene.

[0953] As the solvent that can be used in the acetylation process, a variety of solvents including polar aprotic solvents and protic polar solvents are used. A single protic polar solvent or a single polar aprotic solvent can be used. Furthermore, a mixture of polar aprotic solvents, a mixture of protic polar solvents, a mixture of polar aprotic solvents and protic polar solvents, and a mixture of aprotic or protic solvents and non-polar solvents can be used, and a polar aprotic solvent or its mixture is preferred. The solvent is effective but not an essential component. There is no limitation on suitable polar aprotic solvents, and examples include ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, ester solvents such as ethyl acetate, γ-butyrolactone, nitrile solvents such as acetonitrile, hydrocarbon solvents such as toluene, hexane, amide solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidone, N,N-dimethylacetamide, hexamethylphosphoramide, hexamethylphosphorous triamide, and dimethyl sulfoxide. Dimethyl sulfoxide is preferred. There is no limitation on suitable protic polar solvents, and examples include alcohol solvents such as water, methanol, ethanol, propanol, butanol, di(propylene glycol) methyl ether, di(ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol, and n-butanol.

[0954] The amount of the solvent can be appropriately set according to the substrate, catalyst, reaction conditions, etc. used, and there is no particular limitation. Generally, 0 to 10,000 parts by mass is appropriate relative to 100 parts by mass of the reaction raw material, and from the viewpoint of yield, 100 to 2,000 parts by mass is preferred.

[0955] As the acetylating agent, a variety of acetylating agents that function under the reaction conditions of this embodiment are used.

[0956] As examples of suitable acetylating agents, there is no limitation, and for example, acetic anhydride, haloacetyl, and acetic acid can be mentioned, and acetic anhydride is preferred.

[0957] As the catalyst that can be used in the acetylation process, a variety of acetylation catalysts that function under the reaction conditions of this embodiment are used. An acid catalyst or a base catalyst is preferred.

[0958] Examples of suitable acid catalysts are not limited, and for example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid, organic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid, Lewis acids such as zinc chloride, aluminum chloride, iron(III) chloride, boron trifluoride, and solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid, or phosphomolybdic acid can be mentioned. These acid catalysts can be used alone or in combination of two or more. Among these, from the viewpoint of production, organic acids and solid acids are preferred, and from the viewpoints of availability and ease of handling in production, hydrochloric acid or sulfuric acid is preferably used.

[0959] Examples of suitable base catalysts are not limited. Examples of amine-containing catalysts are pyridine and ethylenediamine. Examples of non-amine basic catalysts preferably include metal salts and especially potassium salts or acetates. Examples of suitable catalysts are not limited, and potassium acetate, potassium carbonate, potassium hydroxide, sodium acetate, sodium carbonate, sodium hydroxide, and magnesium oxide can be mentioned.

[0960] All of the non-amine base catalysts of the present embodiment are sold by, for example, EMScience (Gibbstown) or Aldrich (Milwaukee).

[0961] The amount of the catalyst used can be appropriately set according to the substrate, catalyst, reaction conditions, etc. used, and there is no particular limitation. Generally, 1 to 5000 parts by mass is appropriate relative to 100 parts by mass of the reaction raw material, and from the viewpoint of yield, 50 to 3000 parts by mass is preferred.

[0962] As a polymerization inhibitor that can be used in the acetylation process, various polymerization inhibitors that function under the reaction conditions of the present embodiment are used. The polymerization inhibitor is effective but not an essential component. Examples of suitable polymerization inhibitors are not limited, and hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, phenothiazine, N-oxyl (nitroxide) inhibitors, such as Prostab (registered trademark) 5415 (bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate sold by (Ciba Specialty Chemicals, Tarrytown, NY), CAS# 2516-92-9), 4-hydroxy-TEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl sold by TCI, CAS# 2226-96-2), and Uvinul (registered trademark) 4040P (1,6-hexamethylene-bis(N-formyl-N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)amine) sold by BASF Corporation (BASF Corp., Worcester, MA)).

[0963] The amount of the polymerization inhibitor can be appropriately set according to the matrix, catalyst, reaction conditions, etc. used, and there is no particular limitation. Usually, 0.0001 to 100 parts by mass is appropriate relative to 100 parts by mass of the reaction raw materials, and preferably 0.001 to 10 parts by mass from the viewpoint of yield.

[0964] As a polymerization retarder that can be used in the acetylation process, various polymerization retarders that function under the reaction conditions of the present embodiment are used. The polymerization retarder is effective but not an essential component. It is also effective to use a polymerization retarder in combination with a polymerization inhibitor. Polymerization retarders are widely known in the art and are compounds used to delay polymerization reactions but cannot completely prevent polymerization. Common retarders are aromatic nitro compounds such as dinitro-o-cresol (DNOC) and dinitrobutylphenol (DNBP). The manufacturing method of the polymerization retarder is common and widely known in the art (for example, refer to U.S. Patent No. 6,339,177; Park et al., Polymer (Korea) (1988), 12(8), 710-19), and its use in the control of styrene polymerization is well documented (for example, refer to Bushby et al., Polymer (1998), 39(22), 5567-5571).

[0965] The amount of the polymerization inhibitor can be appropriately set according to the substrate, catalyst, reaction conditions, etc. used, and there is no particular limitation. Generally, 0.0001 to 100 parts by mass is appropriate relative to 100 parts by mass of the reaction raw materials, and from the viewpoint of yield, 0.001 to 10 parts by mass is preferred.

[0966] (Reaction conditions)

[0967] An iodine-containing hydroxystyrene having the formula (1), a catalyst, and a solvent are added to a reactor to form a reaction mixture. Any suitable reactor can be used.

[0968] In addition, known methods such as batch, semi-batch, continuous, etc. can be appropriately selected to carry out the reaction.

[0969] The reaction temperature is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. Generally, a temperature of 0°C to 200°C is appropriate, and from the viewpoint of yield, a temperature of 10°C to 190°C is preferred, more preferably a temperature of 25°C to 150°C, and further preferably a temperature of 50°C to 100°C.

[0970] In the reaction using 4-hydroxy-3,5-diiodostyrene as the substrate, the preferred temperature range is 0°C to 100°C.

[0971] The reaction pressure is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. An inert gas such as nitrogen can be used, and in addition, a suction pump, etc. can be used to adjust the pressure. The reaction under high pressure is not limited, and conventional pressure reactors including an oscillating vessel, a rocker vessel, and a stirred autoclave can be used.

[0972] In the reaction using 4-hydroxy-3,5-diiodostyrene as the substrate, the preferred reaction pressure is reduced pressure to normal pressure, and reduced pressure is preferred.

[0973] The reaction time is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. However, most reactions are carried out in less than 6 hours, and generally the reaction time is 15 minutes to 600 minutes.

[0974] In the reaction using 4-hydroxy-3,5-diiodostyrene as the substrate, the preferred reaction time range is 15 minutes to 600 minutes.

[0975] Separation and purification can be carried out using appropriate methods known in the art after the reaction. For example, the reaction mixture is poured onto ice water and extracted in a solvent such as ethyl acetate or diethyl ether. Subsequently, the solvent is removed by evaporation under reduced pressure to recover the product. The product can be separated and purified into the desired high-purity monomer by separation and purification methods based on filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, etc., which are widely known in the art, or methods based on combinations thereof.

[0976] By the production method of the present embodiment, an iodine-containing hydroxystyrene and its acetylated derivative can be produced from inexpensive raw materials under mild conditions with a high yield.

[0977] The obtained iodine-containing hydroxystyrene and its acetylated derivative are suitable for use as a raw material monomer for a resist composition for extreme ultraviolet lithography. In addition, it is useful in a variety of industrial applications including various semiconductor materials and electronic materials.

[0978] Example 1

[0979] Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited by any of these examples.

[0980] [Measurement method]

[0981] [Nuclear magnetic resonance (NMR)]

[0982] For the structure of the compound, NMR measurement was carried out using a nuclear magnetic resonance apparatus "Advance600II spectrometer" (product name, manufactured by Bruker Corporation) under the following conditions for confirmation.

[0983] 1

[0984] Frequency: 400 MHz

[0985] Solvent: CDCl 3 , or d 6 -DMSO

[0986] Internal standard: TMS

[0987] Measurement temperature: 23 °C

[0988] 13

[0989] Frequency: 500 MHz

[0990] Solvent: CDCl 3 , or d 6 -DMSO ​​​​

[0991] Internal standard: TMS

[0992] Measurement temperature: 23 °C

[0993] 〔Content of inorganic elements〕

[0994] The metal content contained in the compounds prepared in the examples and comparative examples was measured using the inorganic element analyzer (ICP-AES / ICP-MS) "AG8900" (product name, manufactured by Agilent Technologies Japan, Ltd.).

[0995] 〔Content of organic impurities〕

[0996] The content of organic impurities contained in the compounds prepared in the examples and comparative examples was calculated by gas chromatography-mass spectrometry (GC-MS), based on the area fraction of the GC chromatogram and the peak intensity ratio of the target peak to the reference peak.

[0997] Example A1: Synthesis of Compound A1 represented by Formula (M1)

[0998] Using a 200 mL glass flask as the reaction vessel, 4.96 g (40 mmol) of 4-hydroxybenzyl alcohol was dissolved using butanol as the solvent. After that, a 20 mass% aqueous iodine chloride solution (81.2 g, 100 mmol) was added dropwise over 60 minutes at 50 °C, and then the mixture was stirred at 50 °C for 2 hours to react 4-hydroxybenzyl alcohol with iodine chloride. To the reaction solution after the reaction, an aqueous sodium thiosulfate solution was added and stirred for 1 hour, and then the liquid temperature was cooled to 10 °C. The precipitate precipitated by cooling was filtered out, washed, and dried to obtain 12.1 g of a white solid. The sample of the white solid was analyzed by liquid chromatography-mass spectrometry (LC-MS), and as a result, 4-hydroxy-3,5-diiodobenzyl alcohol was confirmed.

[0999] MnO was added to the dichloromethane solvent 2 (3.4 g, 40 mmol) and stirred. Then, while dropping a 50 mass% solution prepared by dissolving all of the synthesized 4-hydroxy-3,5-diiodobenzyl alcohol in dichloromethane, the mixture was stirred for 1 hour and then stirred at room temperature for 4 hours. The reaction solution was filtered, and the solvent was distilled off to obtain 4-hydroxy-3,5-diiodobenzaldehyde.

[1000] After dissolving dimethyl malonate (5.3 g, 40 mmol) and the entire amount of 4-hydroxy-3,5-diiodobenzaldehyde synthesized above in a DMF solvent to prepare a solution, a solution prepared by dissolving ethylenediamine (0.3 g) in DMF was added dropwise, and after stirring for 1 hour, the reaction was carried out while controlling the liquid temperature to 150 °C in an oil bath and stirring for 6 hours. Thereafter, ethyl acetate and water were added, and a 2 mol / L aqueous HCl solution was added to control the pH to 4 or less, and then the organic phase was separated by liquid separation. The obtained organic phase was further washed by liquid separation in the order of 2 mol / L aqueous sodium carbonate solution, water, and brine, then purified by filtration, and the solvent was distilled off from the organic phase, whereby 8.1 g of compound A1 (4-hydroxy-3,5-diiodostyrene (the compound represented by the following formula (M1))) was obtained. By the above method, the inorganic element content and the organic impurity content were measured, and the results are shown in Table 1.

[1001]

[1002] Example A2: Synthesis of Compound A2 Represented by Formula (M2)

[1003] In a 2 L flask, 400 mL of dichloromethane, 41 g of the obtained compound A1, 16.2 g of triethylamine, and 0.7 g of N-(4-pyridyl)dimethylamine (DMAP) were dissolved in a nitrogen stream. After dissolving 33.6 g of di-tert-butyl dicarbonate in 100 mL of dichloromethane, it was added dropwise to the above 2 L flask while stirring, and then stirred at room temperature for 3 hours. Thereafter, three water washings based on liquid separation using 100 mL of water were carried out, the solvent was distilled off from the obtained organic phase, the origin component was removed by silica gel chromatography using dichloromethane / hexane, and then the solvent was distilled off, whereby 4.5 g of the BOC group-substituted product of compound A1 (the compound represented by the following formula (M2), hereinafter also referred to as "compound A2") as the target component was obtained. By the above method, the inorganic element content and the organic impurity content were measured, and the results are shown in Table 1.

[1004]

[1005] Example A3: Synthesis of Compound A3 Represented by Formula (M3)

[1006] In a 2 L flask, 400 mL of dichloromethane, 41 g of the obtained compound A1, 16.2 g of triethylamine, and 0.7 g of N-(4-pyridyl)dimethylamine (DMAP) were dissolved under a nitrogen stream. After dissolving 20.7 g of dimethyl dicarbonate in 100 mL of dichloromethane, it was added dropwise to the above 2 L flask with stirring, and then stirred at room temperature for 3 hours. Thereafter, washing with water was carried out 3 times by a liquid separation operation using 100 mL of water. The solvent was distilled off from the obtained organic phase, the origin component was removed by silica gel chromatography using dichloromethane / hexane, and then the solvent was distilled off, whereby 4.5 g of the BOC group replacement product of compound A1 as the target component (compound shown by the following formula (M3), also hereinafter referred to as "compound A3") was obtained. By the above method, the inorganic element content and the organic impurity content were measured, and the results are shown in Table 1.

[1007]

[1008] Example A4: Synthesis of compound A4 represented by formula (M4)

[1009] In a 2 L flask, 400 mL of dichloromethane, 41 g of the obtained compound A1, 16.2 g of triethylamine, and 0.7 g of N-(4-pyridyl)dimethylamine (DMAP) were dissolved under a nitrogen stream. After dissolving 20.7 g of dibenzyl dicarbonate in 100 mL of dichloromethane, it was added dropwise to the above 2 L flask with stirring, and then stirred at room temperature for 3 hours. Thereafter, washing with water was carried out 3 times by a liquid separation operation using 100 mL of water. The solvent was distilled off from the obtained organic phase, the origin component was removed by silica gel chromatography using dichloromethane / hexane, and then the solvent was distilled off, whereby 4.5 g of the BOC group replacement product of compound A1 as the target component (compound shown by the following formula (M4), also hereinafter referred to as "compound A4") was obtained. By the above method, the inorganic element content and the organic impurity content were measured, and the results are shown in Table 1.

[1010]

[1011] Example A5: Synthesis of compound A5 represented by formula (M5)

[1012] Using a 200 mL glass flask as the reaction vessel, 5.6 g (40 mmol) of 3,4-dihydroxybenzyl alcohol was dissolved using butanol as the solvent. After that, a 20 wt% aqueous solution of iodine chloride (81.2 g, 100 mmol) was added dropwise over 60 minutes at 50 °C, and then the mixture was stirred at 50 °C for 2 hours to react 3,4-dihydroxybenzyl alcohol with iodine chloride. To the reaction solution after the reaction, an aqueous solution of sodium thiosulfate was added and stirred for 1 hour, and then the liquid temperature was cooled to 10 °C. The precipitate precipitated by cooling was filtered, washed, and dried to obtain 11.3 g of a white solid. The sample of the white solid was analyzed by liquid chromatography-mass spectrometry (LC-MS), and as a result, 3,4-dihydroxy-2,5-diiodobenzyl alcohol was confirmed.

[1013] MnO was added to dichloromethane solvent 2 (3.4 g, 40 mmol) and stirred. Then, while adding dropwise a 50 wt% solution prepared by dissolving the entire amount of the synthesized 3,4-dihydroxy-2,5-diiodobenzyl alcohol in dichloromethane, the mixture was stirred for 1 hour, then stirred at room temperature for 4 hours, and then the reaction solution was filtered to remove the solvent by distillation, thereby obtaining 3,4-dihydroxy-2,5-diiodobenzaldehyde.

[1014] Dimethyl malonate (5.3 g, 40 mmol) and the entire amount of the 3,4-dihydroxy-2,5-diiodobenzaldehyde synthesized above were dissolved in DMF solvent to prepare a solution. Then, a solution prepared by dissolving ethylenediamine (0.3 g) in DMF was added dropwise and stirred for 1 hour. Then, while controlling the liquid temperature to 150 °C in an oil bath, the mixture was stirred for 6 hours to carry out the reaction. Thereafter, ethyl acetate and water were added, and then a 2 mol / L aqueous HCl solution was added to control the pH to 4 or less, and then the organic phase was separated by liquid separation. The obtained organic phase was further washed by liquid separation in the order of 2 mol / L aqueous sodium carbonate solution, water, and brine, then purified by filtration, and the solvent was distilled off from the organic phase, thereby obtaining 7.8 g of compound A5 (3,4-dihydroxy-2,5-diiodostyrene (the compound represented by the following formula (M5))). By the above method, the inorganic element content and the organic impurity content were measured, and the results are shown in Table 1.

[1015]

[1016] Example A6: Synthesis of compound A6 represented by formula (M6)

[1017] Using a 200 mL glass flask as the reaction vessel, 5.6 g (40 mmol) of 3,5-dihydroxybenzyl alcohol was dissolved using butanol as the solvent. After that, a 20 wt% aqueous solution of iodine chloride (105.6 g, 130 mmol) was added dropwise over 60 minutes at 50 °C, and then the mixture was stirred at 50 °C for 2 hours to react 3,5-dihydroxybenzyl alcohol with iodine chloride. To the reaction solution after the reaction, an aqueous solution of sodium thiosulfate was added and stirred for 1 hour, and then the liquid temperature was cooled to 10 °C. The precipitate precipitated by cooling was filtered out, washed, and dried to obtain 14.4 g of a white solid. The sample of the white solid was analyzed by liquid chromatography-mass spectrometry (LC-MS), and as a result, 3,5-dihydroxy-2,4,6-triiodobenzyl alcohol was confirmed.

[1018] MnO was added to dichloromethane solvent 2 (3.4 g, 40 mmol) and stirred. Then, while adding dropwise a 50 wt% solution prepared by dissolving the entire amount of the synthesized 3,5-dihydroxy-2,4,6-triiodobenzyl alcohol in dichloromethane, the mixture was stirred for 1 hour, and then stirred at room temperature for 4 hours. The reaction solution was filtered, and the solvent was distilled off to obtain 3,5-dihydroxy-2,4,6-triiodobenzaldehyde.

[1019] Dimethyl malonate (5.3 g, 40 mmol) and the entire amount of the 3,4-dihydroxy-2,5-diiodobenzaldehyde synthesized above were dissolved in DMF solvent to prepare a solution. Then, a solution prepared by dissolving ethylenediamine (0.3 g) in DMF was added dropwise and stirred for 1 hour. Then, while controlling the liquid temperature to 150 °C in an oil bath, the mixture was stirred for 6 hours to carry out the reaction. After that, ethyl acetate and water were added, and a 2 mol / L aqueous HCl solution was added to control the pH to 4 or less. Then, the organic phase was separated by liquid separation operation. The obtained organic phase was further washed by liquid separation operation in the order of 2 mol / L aqueous sodium carbonate solution, water, and brine, then purified by filtration, and the solvent was distilled off from the organic phase to obtain 9.8 g of compound A6 (3,5-dihydroxy-2,4,6-triiodostyrene (the compound shown in the following formula (M6))). By the above method, the inorganic element content and the organic impurity content were measured, and the results are shown in Table 1.

[1020]

[1021] Example A7: Synthesis of compound A7 shown in formula (M7)

[1022] In a 200 mL container equipped with a stirrer, a condenser tube, and a burette, 4.61 g (12.4 mmol) of the compound A1 obtained in Example A1 above and 2.42 g (12.4 mmol) of tert-butyl bromoacetate were added to 100 mL of acetone. 1.71 g (12.4 mmol) of potassium carbonate and 0.4 g of 18-crown-6 (IUPAC name: 1,4,7,10,13,16-hexaoxacyclooctadecane) were added, and the contents were stirred under reflux for 3 hours to carry out the reaction, obtaining a reaction solution. Then, the reaction solution was concentrated, 100 g of pure water was added to the concentrated solution to precipitate the reaction product, and after cooling to room temperature, filtration was carried out to separate the solid substance.

[1023] After filtering and drying the obtained solid substance, separation and purification were carried out by column chromatography, whereby 3.2 g of compound A7 (the compound shown by the following formula (M7)) was obtained. Furthermore, by the above method, the inorganic element content and the organic impurity content were measured, and the results are shown in Table 1.

[1024]

[1025] Example A8: Synthesis of compound A8 shown by formula (M8)

[1026] Through the same procedure as the method described in Example A1, 3,5-diiodo-4-hydroxybenzaldehyde was obtained. Specifically, the method described below was used.

[1027] (Step 1) Iodination reaction

[1028] Using a 200 mL glass flask as the reaction vessel, 5.52 g (40 mmol) of 4-hydroxybenzyl alcohol was dissolved using butanol as the solvent, and after dropping 20 mass% iodine chloride aqueous solution (81.2 g, 100 mmol) over 60 minutes at 50 °C, stirring was carried out at 50 °C for 2 hours to react 4-hydroxybenzyl alcohol with iodine chloride. To the reaction solution after the reaction, an aqueous solution of sodium thiosulfate was added and stirred for 1 hour, and then the liquid temperature was cooled to 10 °C. The precipitate precipitated by cooling was filtered out, washed, and dried to obtain 15.3 g of a white solid. The sample of the white solid was analyzed by liquid chromatography-mass spectrometry (LC-MS), and as a result, 4-hydroxy-3,5-diiodobenzyl alcohol was confirmed.

[1029] (Step 2) Oxidation reaction

[1030] MnO was added in dichloromethane solvent 2(3.4 g, 40 mmol) and stirred. While dropping a 50% by mass solution prepared by dissolving the entire amount of the synthesized 4-hydroxy-3,5-diiodobenzyl alcohol in dichloromethane, stirring was carried out for 1 hour, and then stirring was carried out at room temperature for 4 hours. The reaction solution was filtered, and the solvent was distilled off to obtain 14.5 g of 4-hydroxy-3,5-diiodobenzaldehyde.

[1031] (Step 3) Malonic acid addition reaction

[1032] Using a 200 mL eggplant-shaped flask equipped with a Dean-Stark trap reflux tube, 14.6 g (38 mmol) of 3,5-diiodo-4-hydroxybenzaldehyde was mixed with dimethyl malonate (10.6 g, 80 mmol), piperidine (3.4 g, 40 mmol), acetic acid (2.4 g, 40 mmol), and 40 mL of benzene. The mixture was reacted under reflux conditions for 3 hours. The obtained reaction solution was washed with 20 mL of 5% by mass HCl aqueous solution, and then washed with 5% NaHCO 3 aqueous solution. The obtained organic phase was dried with magnesium sulfate and then concentrated under reduced pressure to obtain 15.8 g of the reaction product M8-CINMe.

[1033]

[1034] (M8-CINMe)

[1035] (Step 4) Hydrolysis reaction

[1036] Using a 1 L eggplant-shaped flask equipped with a reflux tube, 38 mmol of the product M8-CINMe obtained above was added with hydrochloric acid (6 N, 131 mL) and acetic acid (131 mL), and refluxed for 48 hours. Thereafter, 6 M, 500 mL of NaOHaq. was added, and extraction was carried out with 250 mL of ethyl acetate to recover the organic phase containing ethyl acetate. The obtained organic phase was dehydrated with magnesium sulfate and then filtered. The obtained filtrate was concentrated under reduced pressure to obtain 15.2 g of the silicic acid derivative M8-CIN.

[1037]

[1038] (Step 5) Decarboxylation reaction

[1039] Using a 1 L eggplant-shaped flask, a solution prepared by dissolving 40 mmol of the previously prepared silyl acid derivative M8-CIN in 40 mL of dimethyl sulfoxide was slowly added at 10 °C with a solution prepared by dissolving 0.13 g (0.4 mmol) of tetrabutylammonium fluoride trihydrate in 20 mL of dimethyl sulfoxide, and after stirring, the temperature was raised to 40 °C and stirred for 12 hours. The resulting reaction solution was washed three times with 20 mL of pure water, dried over magnesium sulfate, filtered, and the resulting filtrate was concentrated under reduced pressure to obtain 14.4 g of the compound (M8-OH) represented by the formula (M8-OH).

[1040]

[1041] (Step 6) Acetyl protecting group introduction reaction

[1042] Using a 1 L eggplant-shaped flask, 6.1 g (60 mmol) of acetic anhydride, 6.0 g (60 mmol) of triethylamine, 0.8 g (6 mmol) of DMAP, and 350 mL of a solvent (dichloromethane) were placed and stirred to dissolve under a state cooled to 4 °C with ice water to prepare a reaction solution. Under a state cooled to 4 °C, 14.4 g (37 mmol) of the compound M8-OH prepared in the previous step was dissolved in 50 mL of dichloromethane to prepare a solution of the compound M8-OH, and it was added to the solution prepared in the 1 L eggplant-shaped flask over 30 minutes. Thereafter, stirring was carried out at 4 °C for 2 hours to allow the reaction to proceed sufficiently, and after thoroughly washing with 400 mL of ice water and 400 mL of brine, the resulting organic phase was dried over magnesium sulfate, and the filtrate after filtration was concentrated under reduced pressure to obtain a reaction product. Further purification was carried out using a column, and the developing solvent was distilled off to fractionate 14.8 g of the target compound A8 represented by the formula (M8). The yield was 90% by mass.

[1043] In addition, 1 1H-NMR measurement was carried out under the above-mentioned measurement conditions, and the following peaks were observed, confirming the presence of the above chemical structure.

[1044] δ (ppm) (d6-DMSO): 2.3 (3H, -CH3), 7.7 (2H, Ph), 6.7 (1H, -CH=), 5.3 (1H, =CH2), 5.7 (1H, =CH2)

[1045]

[1046] Example A9: Synthesis of compound A9 represented by the formula (M9)

[1047] Compound A9 represented by the formula (M9) was synthesized by the method described below.

[1048]

[1049] (Process 1)

[1050] Using a 200 mL glass flask as the reaction vessel, dissolve 5.52 g (40 mmol) of 3,4-dihydroxybenzaldehyde in methanol as the solvent, and then dropwise add a 20% by mass aqueous iodine chloride solution (81.2 g, 100 mmol) over 60 minutes under ice-cooling conditions. Further, dropwise add 4.90 g (20 mmol) of a 71.9% by mass aqueous iodic acid solution over 30 minutes under ice-cooling conditions within the range where the liquid temperature is 8 °C or lower. Thereafter, stir at 40 °C for 3 hours to react 3,4-dihydroxybenzaldehyde with iodine chloride. To the reaction solution after the reaction, add an aqueous sodium thiosulfate solution and stir for 1 hour, and then cool the liquid temperature to 10 °C. Filter, wash, and dry the precipitate precipitated by cooling to obtain 15.3 g of a white solid. Analyze the sample of the white solid by liquid chromatography-mass spectrometry (LC-MS), and as a result, 2,5-diiodo-3,4-dihydroxybenzaldehyde was confirmed.

[1051] (Process 2)

[1052] Using a 200 mL eggplant-shaped flask equipped with a Dean-Stark trap reflux tube, mix 15.3 g (39 mmol) of 2,5-diiodo-3,4-dihydroxybenzaldehyde, malononitrile (3.97 g, 60 mmol), piperidine (3.4 g, 40 mmol), acetic acid (2.4 g, 40 mmol), and 40 mL of benzene, and react under reflux conditions for 3 hours. Wash the obtained reaction solution with 20 mL of a 5% by mass HCl aqueous solution, and then wash with a 5% NaHCO 3 aqueous solution. Dry the obtained organic phase with magnesium sulfate, and then concentrate under reduced pressure to obtain a reaction product represented by the following formula M9-CN.

[1053]

[1054] (Process 3)

[1055] Using a 1 L eggplant-shaped flask equipped with a reflux tube, add hydrochloric acid (6N, 131 mL) and acetic acid (131 mL) to 39 mmol of the product M9-CN obtained above, and reflux for 48 hours. Thereafter, add 6M, 500 mL of NaOHaq., extract with 250 mL of ethyl acetate, and recover the organic phase containing ethyl acetate. Dehydrate the obtained organic phase with magnesium sulfate and then filter, and concentrate the obtained filtrate under reduced pressure to obtain 16.4 g (38 mmol) of a silicic acid derivative represented by the following (M9-CA).

[1056]

[1057] (Process 4) Decarbonation reaction

[1058] Using a 1 L eggplant-shaped flask, to a solution prepared by dissolving 38 mmol of the previously prepared silyl acid derivative M9-CA in 40 mL of dimethyl sulfoxide, a solution prepared by dissolving 0.13 g (0.4 mmol) of tetrabutylammonium fluoride trihydrate in 20 mL of dimethyl sulfoxide was slowly added at 10 °C and stirred. Then, the temperature was raised to 40 °C and stirred for 12 hours. The resulting reaction solution was washed three times with 20 mL of pure water, dried with magnesium sulfate, filtered, and the obtained filtrate was concentrated under reduced pressure to obtain 14.4 g (37 mmol) of the compound (M9-OH) represented by the formula (M9-OH).

[1059]

[1060] (Process 5) Acetyl protecting group introduction reaction

[1061] Using a 1 L eggplant-shaped flask, 6.1 g (60 mmol) of acetic anhydride, 6.0 g (60 mmol) of triethylamine, 0.8 g (6 mmol) of DMAP, and 350 mL of a solvent (dichloromethane) were placed and stirred and dissolved under the condition of being set to 4 °C with ice water to prepare a reaction solution. Under the condition of being cooled to 4 °C, 14.4 g (37 mmol) of the compound M9-OH prepared in the previous step was dissolved in 50 mL of dichloromethane to prepare a solution of the compound M9-OH, and it was added to the solution prepared in the 1 L eggplant-shaped flask over 30 minutes. Thereafter, it was stirred at 4 °C for 2 hours to allow the reaction to proceed sufficiently. Then, it was washed thoroughly with 400 mL of ice water and 400 mL of brine, the obtained organic phase was dried with magnesium sulfate, and the filtered filtrate was concentrated under reduced pressure to obtain a reaction product. Further, it was purified by column chromatography, and the developing solvent was distilled off to fractionate 16.5 g of the target compound A9 represented by the formula (M9). The yield was 88% by mass.

[1062] In addition, under the aforementioned measurement conditions, 1 1H-NMR measurement was carried out, and the following peaks were observed, confirming that it has the following chemical structure.

[1063] δ (ppm) (d6-DMSO): 2.3 (6H, -CH3), 7.4 (1H, Ph), 7.4 (1H, -CH=), 5.6 (1H, =CH2), 5.7 (1H, =CH2)

[1064]

[1065] Example A10: Synthesis of the compound A10 represented by the formula (M10)

[1066] Compound A10 represented by formula (M10) was synthesized by the method described below.

[1067]

[1068] (Step 1)

[1069] Using a 200 mL glass flask as the reaction vessel, 5.52 g (40 mmol) of 3,5-dihydroxybenzaldehyde was dissolved using methanol as the solvent, and then a 20% by mass aqueous solution of iodine chloride (121.8 g, 150 mmol) was added dropwise over 90 minutes under ice-cooling conditions. Further, a 71.9% by mass aqueous solution of iodic acid (7.45 g, 30 mmol) was added dropwise over 30 minutes under ice-cooling conditions in a temperature range where the liquid temperature was 8 °C or lower. Thereafter, the mixture was stirred at 40 °C for 3 hours to react 3,5-dihydroxybenzaldehyde with iodine chloride. To the reaction solution after the reaction, an aqueous solution of sodium thiosulfate was added and stirred for 1 hour, and then the liquid temperature was cooled to 10 °C. The precipitate precipitated by cooling was filtered, washed, and dried to obtain 20.1 g of a white solid. The sample of the white solid was analyzed by liquid chromatography-mass spectrometry (LC-MS), and as a result, 2,4,6-triiodo-3,5-dihydroxybenzaldehyde was confirmed.

[1070] (Step 2)

[1071] Using a 200 mL eggplant-shaped flask equipped with a Dean-Stark trap reflux tube, 20.1 g (39 mmol) of 2,4,6-triiodo-3,5-dihydroxybenzaldehyde was mixed with malonic acid (15.6 g, 150 mmol), piperidine (12.8 g, 150 mmol), acetic acid (90 g, 150 mmol), and 40 mL of benzene, and the reaction was carried out under reflux conditions for 3 hours. The obtained reaction solution was washed with 20 mL of a 5% by mass aqueous solution of HCl, and then washed with a 5% aqueous solution of NaHCO 3 The obtained organic phase was dried with magnesium sulfate and then concentrated under reduced pressure to obtain 20.6 g of a silyl acid derivative (M10-CA).

[1072]

[1073] (Step 3) Decarboxylation reaction

[1074] Using a 1 L eggplant-shaped flask, a solution prepared by dissolving 20.6 g (37 mmol) of the previously prepared silyl acid derivative M10-CA in 40 mL of dimethyl sulfoxide was slowly added with a solution prepared by dissolving 0.13 g (0.4 mmol) of tetrabutylammonium fluoride trihydrate in 20 mL of dimethyl sulfoxide at 10 °C and stirred. Then, the temperature was raised to 40 °C and stirred for 12 hours. The resulting reaction solution was washed three times with 20 mL of pure water, dried over magnesium sulfate, filtered, and the obtained filtrate was concentrated under reduced pressure to obtain 18.0 g (35 mmol) of the compound (M10-OH) represented by the formula (M10-OH).

[1075] (Step 4) Acetyl protecting group introduction reaction

[1076] Using a 1 L eggplant-shaped flask, 6.1 g (60 mmol) of acetic anhydride, 6.0 g (60 mmol) of triethylamine, 0.8 g (6 mmol) of DMAP, and 350 mL of a solvent (dichloromethane) were placed and stirred to dissolve under a condition set to 4 °C with ice water to prepare a reaction solution. Under a condition of being cooled to 4 °C, a solution of the compound M10-OH prepared in the previous step, 18.0 g (35 mmol), dissolved in 50 mL of dichloromethane was added to the solution prepared in the 1 L eggplant-shaped flask over 30 minutes. Thereafter, the mixture was stirred at 4 °C for 2 hours to allow the reaction to proceed sufficiently, then washed thoroughly with 400 mL of ice water and 400 mL of brine, the obtained organic phase was dried over magnesium sulfate, and the filtrate after filtration was concentrated under reduced pressure to obtain a reaction product. Further, purification was carried out using a column, and the developing solvent was distilled off to fractionate 20.3 g of the target compound M10. The yield was 85% by mass.

[1077] In addition, under the aforementioned measurement conditions, 1 1H-NMR measurement was carried out, and the following peaks were observed, confirming the presence of the following chemical structure.

[1078] δ (ppm) (d6-DMSO): 2.3 (6H, -CH3), 7.4 (1H, -CH=), 5.6 (1H, =CH2), 5.7 (1H, =CH2)

[1079]

[1080] Example A11 and Example A12: Synthesis of the compound A11 represented by the formula (M11) and the compound A12 represented by the formula (M12)

[1081] The compound A11 represented by the formula (M11) and the compound A12 represented by the formula (12) were synthesized by the method described below.

[1082]

[1083] (Process 1) Iodination reaction

[1084] Using a 200 mL glass flask as the reaction vessel, dissolve 5.45 g (40 mmol) of 4-hydroxybenzyl alcohol in butanol as the solvent. After that, add dropwise a 20 wt% iodine chloride aqueous solution (40.6 g, 50 mmol) over 60 minutes at 50 °C, and then stir for 2 hours at 50 °C to react 4-hydroxybenzaldehyde with iodine chloride. After the reaction, add an aqueous sodium thiosulfate solution to the reaction solution and stir for 1 hour, and then cool the liquid temperature to 10 °C. Filter, wash, and dry the precipitate precipitated by cooling to obtain 10.3 g of a white solid. Analyze the sample of the white solid by liquid chromatography-mass spectrometry (LC-MS), and as a result, 4-hydroxy-3-iodobenzyl alcohol was confirmed.

[1085] (Process 2) Oxidation reaction

[1086] Add MnO 2 (3.4 g, 40 mmol) to dichloromethane solvent and stir. Then, while adding dropwise a 50 wt% solution prepared by dissolving all of the synthesized 4-hydroxy-3-iodobenzyl alcohol in dichloromethane, stir for 1 hour, and then stir for 4 hours at room temperature. Filter the reaction solution and distill off the solvent to obtain 14.5 g of 4-hydroxy-3-iodobenzaldehyde.

[1087] (Process 3) Malonic acid addition reaction

[1088] Use a 200 mL eggplant-shaped flask equipped with a Dean-Stark trap. Mix 14.6 g (38 mmol) of 4-iodo-3-hydroxybenzaldehyde, dimethyl malonate (10.6 g, 80 mmol), piperidine (3.4 g, 40 mmol), acetic acid (2.4 g, 40 mmol), and 40 mL of benzene, and react under reflux conditions for 3 hours. Wash the obtained reaction solution with 20 mL of a 5 wt% HCl aqueous solution, and then wash it with a 5% NaHCO 3 aqueous solution. Dry the obtained organic phase with magnesium sulfate, and then concentrate it under reduced pressure to obtain 13.4 g of the reaction product M11-CINMe.

[1089]

[1090] (Process 4) Hydrolysis reaction

[1091] Using a 1 L eggplant-shaped flask, to the product M11-CINMe13.4 (37 mmol) obtained above, hydrochloric acid (6 N, 131 mL) and acetic acid (131 mL) were added, and reflux was carried out for 48 hours. Thereafter, 6 M, 500 mL of NaOHaq. was added, and extraction was carried out with 250 mL of ethyl acetate, and the organic phase containing ethyl acetate was recovered. After dehydrating the obtained organic phase with magnesium sulfate and then filtering, the obtained filtrate was concentrated under reduced pressure to obtain 10.4 g of the silyl acid derivative MA11-CA.

[1092]

[1093] (Step 5) Decarboxylation reaction

[1094] Using a 1 L eggplant-shaped flask, to a solution prepared by dissolving 10.4 (36 mmol) of the silyl acid derivative MA11-CA prepared above in 40 mL of dimethyl sulfoxide, a solution prepared by dissolving 0.13 g (0.4 mmol) of tetrabutylammonium fluoride trihydrate in 20 mL of dimethyl sulfoxide was slowly added at 10 °C and stirred, and then the temperature was raised to 40 °C and stirred for 12 hours. The obtained reaction solution was washed 3 times with 20 mL of pure water, dried with magnesium sulfate, filtered, and the obtained filtrate was concentrated under reduced pressure to obtain 8.6 g of the compound (A11) represented by the formula (M11).

[1095] In addition, under the aforementioned measurement conditions, 1 1H-NMR measurement was carried out, and as a result, the following peaks were observed, and it was confirmed that it has the following chemical structure.

[1096] δ (ppm) (d6-DMSO): 2.3 (3H, -CH3), 7.7 (2H, Ph), 6.7 (1H, -CH=), 5.3 (1H, =CH2), 5.7 (1H, =CH2)

[1097]

[1098] (Step 6) Acetyl protecting group introduction reaction

[1099] Using a 1 L eggplant-shaped flask, 6.1 g (60 mmol) of acetic anhydride, 6.0 g (60 mmol) of triethylamine, 0.8 g (6 mmol) of DMAP, and 350 mL of a solvent (dichloromethane) were placed and stirred to dissolve under a condition set to 4 °C using ice water to prepare a reaction solution. While being cooled to 4 °C, 8.6 g (36 mmol) of the compound A11 prepared in the previous step was dissolved in 50 mL of dichloromethane to prepare a solution of the compound A11, and this was added to the solution prepared in the 1 L eggplant-shaped flask over 30 minutes. Thereafter, stirring was carried out at 4 °C for 2 hours to allow the reaction to proceed sufficiently, followed by thorough washing with 400 mL of ice water and 400 mL of brine. The resulting organic phase was dried with magnesium sulfate, and the filtered filtrate was concentrated under reduced pressure to obtain a reaction product. Furthermore, purification was carried out using a column, and the developing solvent was distilled off to fractionate 10.0 g of the target compound A12 represented by the formula (M12). The yield was 88% by mass.

[1100] In addition, under the aforementioned measurement conditions, 1 1H-NMR measurement was carried out, and as a result, the following peaks were observed, confirming that it has the following chemical structure.

[1101] δ (ppm) (d6-DMSO): 2.3 (3H, -CH3), 7.7 (2H, Ph), 6.7 (1H, -CH=), 5.3 (1H, =CH2), 5.7 (1H, =CH2)

[1102]

[1103] Examples A13 and A14: Synthesis of Compound A13 and Compound A14 Represented by Formula (M13) and Formula (M14)

[1104] Compound A13 represented by formula (M13) and compound A14 represented by formula (M14) were synthesized by the method described below.

[1105]

[1106] (Step 1)

[1107] A 200 mL glass flask was used as the reaction vessel. 5.52 g (40 mmol) of 3,4-dihydroxybenzaldehyde was dissolved using methanol as the solvent, and then a 20% by mass aqueous solution of iodine chloride (40.6 g, 50 mmol) was added dropwise over 60 minutes under ice-cooling conditions. Further, a 71.9% by mass aqueous solution of iodic acid (2.45 g, 10 mmol) was added dropwise over 30 minutes under ice-cooling conditions within the range where the liquid temperature was 8 °C or lower. Thereafter, the mixture was stirred at 40 °C for 3 hours to react 3,4-dihydroxybenzaldehyde with iodine chloride. To the reaction solution after the reaction, an aqueous solution of sodium thiosulfate was added and stirred for 1 hour, and then the liquid temperature was cooled to 10 °C. The precipitate precipitated by cooling was filtered, washed, and dried to obtain 10.2 g of a white solid. Further, the sample of the white solid was analyzed by liquid chromatography-mass spectrometry (LC-MS) using silica gel chromatography, and as a result, 2-iodo-3,4-dihydroxybenzaldehyde was confirmed.

[1108] (Step 2)

[1109] Using a 200 mL eggplant-shaped flask equipped with a Dean-Stark trap reflux condenser, 10.3 g (39 mmol) of 2-iodo-3,4-dihydroxybenzaldehyde was mixed with malononitrile (3.97 g, 60 mmol), piperidine (3.4 g, 40 mmol), acetic acid (2.4 g, 40 mmol), and 40 mL of benzene, and the reaction was carried out under reflux conditions for 3 hours. The resulting reaction solution was washed with 20 mL of a 5% by mass aqueous HCl solution, and then washed with a 5% by mass aqueous NaHCO 3 aqueous solution. The obtained organic phase was dried with magnesium sulfate and then concentrated under reduced pressure to obtain 11.9 g of the reaction product (M13-CINMe).

[1110]

[1111] (Step 3)

[1112] Using a 1 L eggplant-shaped flask equipped with a reflux condenser, to the product 11.9 (38 mmol) obtained above, hydrochloric acid (6 N, 131 mL) and acetic acid (131 mL) were added, and the mixture was refluxed for 48 hours. Thereafter, 6 M, 500 mL of NaOH aq. was added, and then extraction was carried out with 250 mL of ethyl acetate to recover the organic phase containing ethyl acetate. The obtained organic phase was dehydrated with magnesium sulfate and then filtered, and the resulting filtrate was concentrated under reduced pressure to obtain 11.6 g of the silyl acid derivative (M13-CA).

[1113]

[1114] (Step 4) Decarboxylation reaction

[1115] Using a 1L eggplant flask, a solution prepared by dissolving 11.6 g (38 mmol) of the carnosic acid derivative prepared above in 40 mL of dimethyl sulfoxide was slowly added at 10°C to a solution prepared by dissolving 0.023 g (0.4 mmol) of potassium fluoride trihydrate in 4 mL of acetic acid and 16 mL of dimethyl sulfoxide, and stirred, and then the mixture was heated to 40°C and stirred for 12 hours. The obtained reaction solution was washed three times with 20 mL of pure water, dried with magnesium sulfate, filtered, and the obtained filtrate was concentrated under reduced pressure to obtain 9.1 g of compound A13 represented by formula (M13).

[1116] In addition, the above-mentioned measurement conditions were carried out 1 As a result of H-NMR measurement, the following peaks were observed, confirming that the compound had the chemical structure of Compound A13.

[1117] δ (ppm) (d6-DMSO): 9.5 (1H, OH), 9.6 (1H, OH), 7.0 (2H, Ph), 6.7 (1H, -CH=), 5.3 (1H, =CH2), 5.7 (1H, =CH2)

[1118] (Step 5) Acetyl Protecting Group Introduction Reaction

[1119] Using a 1L eggplant flask, 6.1g (60mmol) of acetic anhydride, 6.0g (60mmol) of triethylamine, 0.8g (6mmol) of DMAP, and 350mL of solvent (dichloromethane) were placed in a state of 4°C with ice water and stirred to dissolve to prepare a reaction solution. Under ice-cooled conditions of 4°C, 9.1g (35mmol) of compound A13 prepared in the process was dissolved in 50mL of dichloromethane to prepare a solution of compound A13, which was added to the solution prepared in a 1L eggplant flask over 30 minutes. After stirring at 4°C for 2 hours to allow the reaction to proceed fully, the organic phase was dried with magnesium sulfate after being fully washed with 400mL of ice water and 400mL of saline solution, and the filtered filtrate was concentrated under reduced pressure to obtain a reaction product. Further, the column was used for purification, and the developing solvent was distilled off, thereby extracting 12.1g of the target compound A14 shown in formula (M14).

[1120] In addition, the above-mentioned measurement conditions were carried out 1 As a result of H-NMR measurement, the following peaks were observed, confirming that the compound had the chemical structure of Compound A14.

[1121] δ (ppm) (d6-DMSO): 2.3 (6H, -CH3), 7.7 (2H, Ph), 6.7 (1H, -CH=), 5.3 (1H, =CH2), 5.7 (1H, =CH2)

[1122] Examples A15 and A16: Synthesis of Compound A15 and Compound A16 Represented by Formula (M15) and Formula (M16)

[1123] Compound A15 represented by formula (M15) and compound A16 represented by formula (M16) were synthesized by the method described below.

[1124] (Step 1) Formation of 4-Iodo-3,5-dihydroxybenzaldehyde

[1125] Using a 200 mL glass flask as a reaction vessel, 5.52 g (40 mmol) of 3,5-dihydroxybenzaldehyde was dissolved using methanol as a solvent, and then a 20% by mass aqueous iodine chloride solution (40.6 g, 50 mmol) was added dropwise over 60 minutes under ice-cooling conditions. Further, 2.45 g (10 mmol) of a 71.9% by mass aqueous iodic acid solution was added dropwise over 30 minutes under ice-cooling conditions within the range where the liquid temperature was 8°C or lower. Thereafter, the mixture was stirred at 40°C for 3 hours to react 3,5-dihydroxybenzaldehyde with iodine chloride. To the reaction solution after the reaction, an aqueous sodium thiosulfate solution was added and stirred for 1 hour, and then the liquid temperature was cooled to 10°C. The precipitate precipitated by cooling was filtered, washed, and dried to obtain 10.2 g of a white solid. The sample of the white solid was analyzed by liquid chromatography-mass spectrometry (LC-MS), and as a result, 4-iodo-3,5-dihydroxybenzaldehyde was confirmed.

[1126] (Step 2) Formation of the Structure of the Malonic Acid Derivative

[1127] Using a 200 mL eggplant-shaped flask equipped with a Dean-Stark trap, 10.3 g (39 mmol) of 4-iodo-3,5-dihydroxybenzaldehyde was mixed with malonic acid (6.24 g, 60 mmol), piperidine (3.4 g, 40 mmol), acetic acid (2.4 g, 40 mmol), and 40 mL of benzene, and the mixture was reacted under reflux conditions for 3 hours. The obtained reaction solution was washed with 20 mL of a 5% by mass HCl aqueous solution, and then washed with a 5% NaHCO 3 aqueous solution. The obtained organic phase was dried with magnesium sulfate and then concentrated under reduced pressure to obtain 11.7 g of a reaction product (M15-CA) formed from the malonic acid derivative.

[1128]

[1129] (Step 3) Decarboxylation Reaction

[1130] Using a 1 L eggplant-shaped flask, a solution prepared by dissolving 11.7 g (38 mmol) of the above-prepared silicic acid derivative (M15-CA) in 40 mL of dimethyl sulfoxide was slowly added with a solution prepared by dissolving 0.13 g (0.4 mmol) of tetrabutylammonium fluoride trihydrate in 20 mL of dimethyl sulfoxide at 10 °C and stirred. Then, the temperature was raised to 40 °C and stirred for 12 hours. The obtained reaction solution was washed three times with 20 mL of pure water, dried over magnesium sulfate, filtered, and the obtained filtrate was concentrated under reduced pressure to obtain 9.4 g of the compound (A15) represented by the formula (M15).

[1131] In addition, under the above measurement conditions, 1 1H-NMR measurement was carried out, and the following peaks were observed, confirming the following chemical structure.

[1132] δ (ppm) (d6-DMSO): 11.6 (2H, OH), 6.0 (2H, Ph), 6.7 (1H, -CH=), 5.3 (1H, =CH2), 5.7 (1H, =CH2)

[1133]

[1134] (Step 4) Acetyl protecting group introduction reaction

[1135] Using a 1 L eggplant-shaped flask, 6.1 g (60 mmol) of acetic anhydride, 6.0 g (60 mmol) of triethylamine, 0.8 g (6 mmol) of DMAP, and 350 mL of a solvent (dichloromethane) were placed and stirred and dissolved under the condition of being set to 4 °C with ice water to prepare a reaction solution. Under the condition of being cooled to 4 °C, 9.4 g (36 mmol) of the compound A15 prepared in the previous step was dissolved in 50 mL of dichloromethane to prepare a solution of compound A15, and it was added to the solution prepared in the 1 L eggplant-shaped flask over 30 minutes. Then, after stirring at 4 °C for 2 hours to allow the reaction to proceed sufficiently, it was washed thoroughly with 400 mL of ice water and 400 mL of brine, the obtained organic phase was dried over magnesium sulfate, and the obtained filtrate was concentrated under reduced pressure to obtain a reaction product. Furthermore, it was purified by column chromatography, and the developing solvent was distilled off to fractionate 12.3 g of the target compound A16.

[1136] In addition, under the above measurement conditions, 1 1H-NMR measurement was carried out, and the following peaks were observed, confirming the chemical structure of compound A16.

[1137] δ (ppm) (d6-DMSO): 2.3 (6H, -CH3), 6.7 (2H, Ph), 6.7 (1H, -CH=), 5.3 (1H, =CH2), 5.7 (1H, =CH2)

[1138] Synthesis Example ACL1: Synthesis of Compound MCL1 Represented by Formula (MCL1)

[1139] Compound MCL1 represented by formula (MCL1) was synthesized by the method described below.

[1140] (Step 1) Diiodination of 4-Hydroxyacetophenone

[1141] Using a 200 mL glass flask as a reaction vessel, 6.1 g (45 mmol) of 4-hydroxyacetophenone was dissolved using butanol as a solvent, and then a 20% by mass aqueous iodine chloride solution (81.2 g, 100 mmol) was added dropwise at 50°C over 60 minutes. After that, the mixture was stirred at 50°C for 2 hours to react 4-hydroxyacetophenone with iodine chloride. To the reaction solution after the reaction, an aqueous sodium thiosulfate solution was added and stirred for 1 hour, and then the liquid temperature was cooled to 10°C. The precipitate precipitated by cooling was filtered, washed, and dried to obtain 16.3 g of a white solid. The sample of the white solid was analyzed by liquid chromatography-mass spectrometry (LC-MS), and as a result, 4-hydroxy-3,5-diiodoacetophenone was confirmed.

[1142]

[1143] (Starting Acetophenone Derivative) Mw 387.94

[1144] (Step 2) α-Amino Group Introduction

[1145] In a flask, 0.6 g (6.1 mmol) of CuCl, 1.3 g (13 mmol) of triethylamine, 5.2 g (34 mmol) of POCl 3 (Phosphorus Oxychloride (V)), and 15 mL of heptane were stirred, and 16.3 g (42 mmol) of 4-hydroxy-3,5-diiodoacetophenone prepared in Step 1 was added and dissolved. After heating the solution temperature to 100°C, the reaction was carried out for 20 hours, then cooled to 45°C, and 25 mL of pure water was added dropwise to terminate the reaction. After removing the aqueous layer by liquid separation, it was washed with pure water (10 mL) and saturated brine (10 mL), and then magnesium sulfate was added for dehydration treatment. The filtered filtrate was concentrated to obtain the compound described in formula (MCL1).

[1146] In addition, 1 1H-NMR measurement was carried out under the above measurement conditions, and as a result, the following peaks were observed, and it was confirmed that it had the following chemical structure.

[1147] δ (ppm) (d6-DMSO): 9.6 (1H, -OH), 7.5 (2H, Ph), 5.4 (1H, =CH2), 5.7 (1H, =CH2)

[1148]

[1149] (Target compound) Mw 406.39

[1150] Synthesis Example AD1: Synthesis of Compound MD1 represented by formula (MD1)

[1151] Compound MD1 represented by formula (MD1) was synthesized by the method described below.

[1152]

[1153] 15.6 g of 1-(4-hydroxy-3,5-diiodophenyl)ethanol, 0.12 g of concentrated sulfuric acid, 0.04 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical, and 1.60 mL of DMSO were placed in a reactor and stirred. Then, under reduced pressure conditions adjusted for reflux at 120 °C using a Dean-Stark trap and condenser, air was blown into the reaction solution at a flow rate of 1 mL / min. The water recovered in the Dean-Stark trap was appropriately discharged out of the system. Then, the reactor was immersed in a water bath at 90 °C and stirring was continued for 30 hours. Then, the reactor was immersed in a water bath at 25 °C to cool the reaction solution. Then, the reaction solution was slowly added to 400 g of an aqueous sodium bisulfite solution with a concentration of 0.1 mass% while stirring vigorously and mixed. Then, the precipitate was filtered out and compressed with a suction filter and washed with 200 mL of an aqueous methanol solution with a concentration of 33.3 volume%. After separating only the main component by column generation for the obtained precipitate, the solvent was distilled off by evaporation, and the obtained solid was vacuum dried at 40 °C to obtain 9.7 g of a white solid. The yield was 66%.

[1154] Analysis was performed by liquid chromatography - mass spectrometry (LC-MS), and as a result, the molecular weight was confirmed to be 743.9, and it was confirmed to be Compound MD1 represented by formula (MD1).

[1155] In addition, 1 1H-NMR measurement was performed under the above measurement conditions, and as a result, the following peaks were observed, and the chemical structure of Compound MD1 was confirmed.

[1156] δ (ppm) (d6-DMSO): 9.6 (2H, OH), 7.5 (2H, Ph), 7.9 (2H, Ph), 3.5 (1H, -CH-), 1.3 (3H, -CH3), 4.9 (1H, =CH2), 5.3 (1H, =CH2)

[1157] Synthesis Example AD2: Synthesis of Compound MD2 Represented by Formula (MD2)

[1158] Compound MD2 represented by formula (MD2) was synthesized by the method described below.

[1159]

[1160] 15.6 g of 1-(4-hydroxy-3,5-diiodophenyl)ethanol, 0.12 g of concentrated sulfuric acid, 0.2 g of 4-methoxyphenol, and 150 mL of toluene were placed in a reactor and stirring was started. Subsequently, using a Dean-Stark trap and a condenser, air was blown into the reaction solution at a flow rate of 1 mL / min under reflux conditions at 113°C. It should be noted that the water recovered in the Dean-Stark trap was appropriately discharged outside the system. Subsequently, the reactor was immersed in a water bath at 90°C and stirring was continued for 30 hours. Then, the reactor was immersed in a water bath at 25°C to cool the reaction solution. Then, while stirring vigorously, the reaction solution was slowly added to 400 g of an aqueous sodium bisulfite solution with a concentration of 0.1 mass percentage and mixed. Then, the precipitate was filtered out and compressed with a suction filter, and washed with 200 mL of an aqueous methanol solution with a concentration of 33.3 volume percentage. After separating only the main component of the obtained precipitate by column generation, the solvent was distilled off by evaporation, and the obtained solid was vacuum dried at 40°C to obtain 5.9 g of a white solid. The yield was 41%.

[1161] Analysis was performed by liquid chromatography-mass spectrometry (LC-MS), and as a result, the molecular weight was confirmed to be 743.89, and it was confirmed to be Compound MD2 represented by formula (MD2).

[1162] In addition, 1 1H-NMR measurement was performed under the above-described measurement conditions, and as a result, the following peaks were observed, and the chemical structure of Compound MD2 was confirmed.

[1163] δ (ppm) (d6-DMSO): 9.6 (2H, O...

Claims

1. A compound having an unsaturated double bond and more than one halogen, represented by the following formula (1), and having more than one hydrophilic group or one decomposable group, In formula (1), Each X is independently I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having more than one and 5 or less substituents selected from the group consisting of I, F, Cl, and Br. L 1 each independently represents a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphino group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphoric acid group, and the L 1 of the ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphino group, phosphonic acid group, carbamate group, urea group, amide group, imide group, or phosphoric acid group optionally has a substituent Each Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate group, a nitro group, an amino group, a carboxyl group, a mercapto group, an ether group, a thioether group, a phosphino group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphoric acid group. The alkoxy group, ester group, carbonate group, amino group, ether group, thioether group, phosphino group, phosphonic acid group, carbamate group, urea group, amide group, imide group, and phosphoric acid group of Y may optionally have substituents. R a 、R b 、and R c each independently represents H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms optionally with substituents. A is a heterocyclic structure having 4 to 5 carbon atoms. Each Z is independently an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, or a carbonate group. The alkoxy group, ester group, acetal group, carboxyalkoxy group, or carbonate group of Z may optionally have substituents. p is an integer of 1 or more, m is an integer of 1 or more, n is an integer of 0 or more, and r is an integer of 0 or more.

2. The compound according to claim 1, wherein, n is 2 or more.

3. The compound according to claim 1, which contains a functional group capable of increasing its solubility in an alkaline developer by the action of an acid or a base.

4. The compound according to claim 1, wherein, X is I, L 1 is a single bond.

5. The compound according to claim 1, wherein, X is an aromatic group and is a group formed by introducing one or more of F, Cl, Br, or I into the aromatic group.

6. The compound according to claim 1, wherein, X is an alicyclic group and is a group formed by introducing one or more of F, Cl, Br, or I into the alicyclic group.

7. A composition containing 1 mass ppm or more and 10 mass% or less of the compound represented by formula (1C) with respect to the total amount of the compound according to any one of claims 1 to 6. In formula (1C), formula (1C1), and formula (1C2), L 1 , Z, p, m, and r are the same as defined in formula (1). Each X is independently I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having more than one and 5 or less substituents selected from the group consisting of I, F, Cl, and Br. Each Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate group, a nitro group, an amino group, a carboxyl group, a mercapto group, an ether group, a thioether group, a phosphino group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphoric acid group. The alkoxy group, ester group, carbonate group, amino group, ether group, thioether group, phosphino group, phosphonic acid group, carbamate group, urea group, amide group, imide group, and phosphoric acid group of Y may optionally have substituents. A is an organic group having 1 to 30 carbon atoms. n is an integer of 0 or more. R sub Expression (1C1) or Expression (1C2), R a1 、R b1 、and R c1 each independently represents H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms optionally with substituents, R a1 、R b1 、and R c1 at least any one of them is I, F, Cl, Br, or an optionally substituted organic group having 1 to 60 carbon atoms, p - 1 is an integer of 0 or more. * is a bonding site with an adjacent structural unit.

8. A composition, characterized in that, Comprising the compound according to any one of claims 1 to 6 and a compound represented by formula (1D) in an amount of 1 mass ppm or more and 10 mass% or less relative to the compound, In formula (1D), formula (1D1), or formula (1D2), L 1 , Z, p, m, and r are the same as defined in formula (1), X is each independently I, F, Cl, Br, or an organic group having 1 to 5 substituents selected from the group consisting of I, F, Cl, and Br and having 1 to 30 carbon atoms, Y is each independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate group, a nitro group, an amino group, a carboxyl group, a mercapto group, an ether group, a thioether group, a phosphino group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphoric acid group, and the alkoxy group, ester group, carbonate group, amino group, ether group, thioether group, phosphino group, phosphonic acid group, carbamate group, urea group, amide group, imide group, and phosphoric acid group of Y may optionally have substituents, A is an organic group having 1 to 30 carbon atoms, n is an integer of 0 or more, R sub2 Expression (1D1) or Expression (1D2) R a1 、R b1 、and R c1 each independently represents H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms optionally with substituents, R a1 、R b1 、and R c1 、and at least any one of R c1 is I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms optionally having substituents, n2 represents an integer of 0 or more and 4 or less, p - 1 is an integer of 0 or more, * is a bonding site to an adjacent structural unit.

9. A composition comprising a compound represented by formula (1E) in an amount of 1 mass ppm or more and 10 mass% or less relative to the compound according to any one of claims 1 to 6, In formula (1E), X is each independently F, Cl, Br, or an organic group having 1 to 5 substituents selected from the group consisting of F, Cl, and Br and having 1 to 30 carbon atoms, L 1 each independently is a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphate group, and the L 1 of the ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphine group, phosphonic acid group, carbamate group, urea group, amide group, imide group, or phosphate group optionally has a substituent Y is each independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate group, a nitro group, an amino group, a carboxyl group, a mercapto group, an ether group, a thioether group, a phosphino group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphoric acid group, and the alkoxy group, ester group, carbonate group, amino group, ether group, thioether group, phosphino group, phosphonic acid group, carbamate group, urea group, amide group, imide group, and phosphoric acid group of Y may optionally have substituents, R a 、R b 、and R c each independently represents H, F, Cl, Br, or an organic group having 1 to 60 carbon atoms optionally with substituents. A is an organic group having 1 to 30 carbon atoms, Z is each independently an alkoxy group, an ester group, an acetal group, or a carbonate group, wherein, X, L 1 , Y, R a , R b , R c , A and Z do not contain I, p is an integer of 1 or more, m' is an integer of 0 or more, n is an integer of 0 or more, and r is an integer of 0 or more.

10. A composition comprising the compound according to any one of claims 1 to 6, The impurity containing K is 1 mass ppm or less in terms of element relative to the compound.

11. The composition according to claim 10, wherein, The peroxide is 10 mass ppm or less relative to the compound.

12. The composition according to claim 10, wherein, The impurity containing one or more elements selected from the group consisting of Mn, Al, Si, and Li is 1 mass ppm or less in terms of element relative to the compound.

13. The composition according to claim 10, wherein, The phosphorus-containing compound is 10 mass ppm or less relative to the compound.

14. The composition according to claim 10, wherein, Maleic acid is 10 mass ppm or less relative to the compound.

15. A polymer comprising a structural unit derived from the compound according to any one of claims 1 to 6.

16. The polymer according to claim 15, further comprising a structural unit represented by the following formula (C6), In formula (C6), X C61 is a hydroxyl or halogen group, R C61 each independently represents an alkyl group having 1 to 20 carbon atoms, * is a bonding site with an adjacent structural unit.

17. A film-forming composition containing the compound according to any one of claims 1 to 6 or the polymer according to claim 15 or 16.

18. The film-forming composition according to claim 17, further comprising an acid generator, a base generator, or a base compound.

19. A method for forming a resist pattern, which comprises: a step of forming a resist film on a substrate using the film-forming composition, the film-forming composition containing the compound according to any one of claims 1 to 6 or the polymer according to claim 15 or 16; a step of pattern-exposing the resist film; and a step of developing the resist film after the exposure.

20. A method for forming an insulating film, comprising the method according to claim 19.

21. A method for producing a compound represented by the following formula (0), comprising a double bond introduction step of introducing an unsaturated double bond into a substituent Q of a compound represented by the following formula (S1), In formula (S1) and formula (0), A is a heterocyclic structure, the compound represented by formula (0) has an unsaturated double bond and one or more halogens, and has one or more hydrophilic groups or one decomposable group, In formula (S1), X 0 is an organic group having 1 to 30 carbon atoms, L 1 each independently is a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphate group Y are each independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate group, a nitro group, an amino group, a carboxyl group, a mercapto group, an ether group, a thioether group, a phosphino group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphoric acid group, and the alkoxy group, ester group, carbonate group, amino group, ether group, thioether group, phosphino group, phosphonic acid group, carbamate group, urea group, amide group, imide group, and phosphoric acid group of Y may optionally have a substituent, A is a heterocyclic structure having 4 to 5 carbon atoms, Z are each independently an alkoxy group, an ester group, an acetal group, or a carbonate group, Q is an organic group having 1 to 30 carbon atoms and having a hydroxyl group, an aldehyde group, a carboxyl group, or a ketone group, p is an integer of 1 or more, m' is an integer of 0 or more, n is an integer of 0 or more, m'+n is 3 or more, and r is an integer of 0 or more, In formula (0), X are each independently I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 or more and 5 or less substituents selected from the group consisting of I, F, Cl, and Br, L 1 each independently represents a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphoric acid group Y are each independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate group, a nitro group, an amino group, a carboxyl group, a mercapto group, an ether group, a thioether group, a phosphino group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphoric acid group, and the alkoxy group, ester group, carbonate group, amino group, ether group, thioether group, phosphino group, phosphonic acid group, carbamate group, urea group, amide group, imide group, and phosphoric acid group of Y may optionally have a substituent, R a 、R b 、and R c each independently represents H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms optionally with substituents. A is a heterocyclic structure having 4 to 5 carbon atoms, Z are each independently an alkoxy group, an ester group, an acetal group, or a carbonate group, p is an integer of 1 or more, m' is an integer of 0 or more, n is an integer of 0 or more, m'+n is 3 or more, and r is an integer of 0 or more.

22. The method for producing the compound according to claim 21, wherein, the compound represented by the formula (S1) is the compound represented by the following formula (SA1), the production method includes the step shown in A1 below and the step shown in A2 below: A1) A step of using the compound represented by the formula (SA1) and using the compound represented by the following formula (RM1) or malononitrile to obtain the compound represented by the following formula (SA2); A2) A step of using the formula (SA2) and a fluorine source to form the formula (0), In the formulas (SA1), (RM1) and (SA2), X 0 、L 1 、Y, A, Z, p, m’, n, r are the same as defined in formula (S1), (0), Q 1 is an aldehyde or a ketone, LG is a group selected from a hydroxyl group, an alkoxy group, a carbonate group, an acetal group, and a carboxyl group, and the alkoxy group, the carbonate group, the acetal group, and the carboxyl group include an optionally substituted aliphatic group or aromatic group having 1 to 60 carbon atoms, R 3 is a hydrogen group, or a carboxyl group or an ester group having 1 to 60 carbon atoms which may optionally have substituents. R 4 is a hydrogen group, R 5 、R 6 are each independently H, F, Cl, Br, or an organic group having 1 to 60 carbon atoms optionally having substituents. XA is a group selected from a hydrogen group and a halogen group.

23. The method for producing the compound according to claim 22, wherein, in the step shown in A2, a decarbonation reaction of the compound represented by the formula (SA2) is carried out using the fluorine source at 100°C or lower.

24. The method for producing the compound according to claim 22, wherein, in the step shown in A1, a reducing agent is also used to obtain the compound represented by the formula (SA2).

25. The method for producing the compound according to claim 21, wherein, in the formula (S1), A is a heteroaromatic ring.

26. The method for producing the compound represented by the following formula (1), which includes: the step shown in B1A below; a step of forming the compound represented by the following formula (SB1) using at least one of the compounds represented by the following formulas (SB2A) and (SB3A) obtained through at least one of the steps shown in B2A and B3A below; and a double bond introduction step of introducing an unsaturated double bond into the substituent Qb of the compound represented by the formula (SB1), in the formulas (SB1A) to (SB3A), the formula (SB1) and the formula (1), A is a heterocyclic structure, the compound represented by the formula (1) has an unsaturated double bond and one or more halogens, and has one or more hydrophilic groups or one decomposable group, B1A) A step of preparing the following substrate SB1A, the substrate SB1A containing one or more amino groups and containing a parent nucleus B having an aldehyde group or a ketone group, B2A) A step of introducing iodine into the parent nucleus B to obtain the compound represented by the following formula (SB2A), B3A) A step of replacing the amino group with a halogen group by a Sandmeyer reaction to obtain the compound represented by the formula (SB3A), in the formula (1), each X is independently I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms having one or more and five or less substituents selected from the group consisting of I, F, Cl, and Br L 1 each independently represents a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphate group, and the L 1 of the ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphine group, phosphonic acid group, carbamate group, urea group, amide group, imide group, or phosphate group may optionally have a substituent, Y is each independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate group, a nitro group, an amino group, a carboxyl group, a mercapto group, an ether group, a thioether group, a phosphino group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphoric acid group, and the alkoxy group, ester group, carbonate group, amino group, ether group, thioether group, phosphino group, phosphonic acid group, carbamate group, urea group, amide group, imide group, and phosphoric acid group of Y may optionally have substituents, R a 、R b 、and R c each independently represents H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms optionally with substituents, A is a heterocyclic structure having 4 to 5 carbon atoms, Z is each independently an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, or a carbonate group, and the alkoxy group, ester group, acetal group, carboxyalkoxy group, or carbonate group of Z may optionally have substituents, p is an integer of 1 or more, m is an integer of 1 or more, n is an integer of 0 or more, m + n is 3 or more, and r is an integer of 0 or more, In formulae (SB1A), (SB2A), (SB3A), and (SB1), Zb represents a hydrogen group or an optionally substituted amino group, the substituent of which contains an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, rb represents an integer of 1 or more, L 1b , X b1 , B, pb, mb’ respectively have the same meanings as L 1 , X, A, p, m in formula (1), X b2 represents I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 or more and 5 or less substituents selected from the group consisting of I, F, Cl, and Br, and Qb is an organic group having 1 to 30 carbon atoms and having a hydroxyl group, an aldehyde group, a carboxyl group, or a ketone group.

27. The method for producing the compound according to claim 26, characterized in that, an organophosphorus compound and a base are used in the step of introducing a double bond.

28. The method for producing the compound according to claim 21, which includes a halogen-introducing step of reacting a halogenating agent with the compound represented by the formula (S1) to introduce a halogen atom.

29. The method for producing the compound according to claim 22, wherein, the compound represented by the formula (SA1) is at least one of the compounds represented by the following formula (SB2A) and the following formula (SB3A) obtained through the step shown by the following B1A and at least one of the steps shown by the following B2A and B3A, B1A) A step of preparing the following substrate SB1A, which contains one or more amino groups and a mother nucleus B having an aldehyde group or a ketone group, B2A) A step of introducing iodine into the mother nucleus B to obtain the compound represented by the following formula (SB2A), B3A) A step of replacing the amino group with a halogen group by the Sandmeyer reaction to obtain the compound represented by the formula (SB3A), In formulae (SB1A), (SB2A), and (SB3A), Zb represents a hydrogen group or an optionally substituted amino group, the substituent of which comprises an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, rb represents an integer of 1 or more, Qb, L 1b , X b1 , B, pb, mb’ have the same meanings as Q, L 1 , X 0 , A, p, m’ in formula (S1), respectively, and X b2 represents I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms with 1 or more and 5 or less substituents selected from the group consisting of I, F, Cl, and Br.

30. The method for producing the compound according to claim 27, wherein, in the step shown by B2A, at least an iodine source and an oxidizing agent are used to introduce iodine into the mother nucleus B.

31. The method for producing the compound according to claim 22, wherein, the compound represented by the formula (SA1) is a compound produced through the step shown by the following B1B and at least any one of the steps shown by the following B2B and B3B, B1B) A step of preparing the following substrate SB1B, which contains one or more amino groups and a mother nucleus B having an aldehyde group or a ketone group, B2B) A step of introducing iodine into the mother nucleus B to obtain the compound represented by the formula (SB2B), B3B) A step of replacing the amino group with a halogen group to obtain the compound represented by the formula (SB3B), In formulae (SB1B), (SB2B), and (SB3B), Zb represents a hydrogen group or an optionally substituted amino group, the substituent of which contains an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, rb represents an integer of 1 or more, Qb, L 1b , X b1 , B, pb, mb’ respectively have the same meanings as Q, L 1 , X 0 , A, p, m’ in formula (S1), and X b2 represents I, F, Cl, Br, or an organic group having 1 or more and 5 or less substituents selected from the group consisting of I, F, Cl, and Br and having 1 to 30 carbon atoms.

32. The method for producing the compound according to claim 31, wherein, it further includes the step shown by the following B4a, B4a) Wittig reaction.

33. The method for producing the compound according to claim 29, wherein, in the process represented by B2B, at least an iodine source and an oxidizing agent are used to introduce iodine into the mother nucleus B.

34. The method for producing the compound according to claim 31, wherein, the mother nucleus B contains an aromatic ring structure optionally having a heteroatom.

35. The method for producing the compound represented by the following formula (1), characterized in that, it includes: a halogen-introducing step of reacting a halogenating agent with the compound represented by the following formula (S1) to introduce a halogen atom; and a double-bond introducing step of introducing an unsaturated double bond into the substituent Q, wherein, an organic phosphorus compound and a base are used in the step of introducing the double bond, in formula (S1) and formula (1), A is a heterocyclic structure, the compound represented by formula (1) has an unsaturated double bond and one or more halogens, and has one or more hydrophilic groups or one decomposable group, in formula (S1), X 0 is an organic group having 1 to 30 carbon atoms, L 1 each independently is a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphoric acid group Y are each independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate group, a nitro group, an amino group, a carboxyl group, a mercapto group, an ether group, a thioether group, a phosphino group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphoric acid group, and the alkoxy group, ester group, carbonate group, amino group, ether group, thioether group, phosphino group, phosphonic acid group, carbamate group, urea group, amide group, imide group, and phosphoric acid group of Y optionally have substituents, A is a heterocyclic structure having 4 to 5 carbon atoms, Z are each independently an alkoxy group, an ester group, an acetal group, or a carbonate group, Q is an organic group having 1 to 30 carbon atoms and having a hydroxyl group, an aldehyde group, a carboxyl group, or a ketone group, p is an integer of 1 or more, m' is an integer of 0 or more, n is an integer of 0 or more, m'+n is 3 or more, r is an integer of 0 or more, in formula (1), X are each independently I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 or more and 5 or less substituents selected from the group consisting of I, F, Cl, and Br, L 1 each independently represents a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphate group Y are each independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate group, a nitro group, an amino group, a carboxyl group, a mercapto group, an ether group, a thioether group, a phosphino group, a phosphonic acid group, a carbamate group, a urea group, an amide group, an imide group, or a phosphoric acid group, and the alkoxy group, ester group, carbonate group, amino group, ether group, thioether group, phosphino group, phosphonic acid group, carbamate group, urea group, amide group, imide group, and phosphoric acid group of Y optionally have substituents, R a 、R b 、and R c each independently represents H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms optionally with substituents, A is a heterocyclic structure having 4 to 5 carbon atoms, Z are each independently an alkoxy group, an ester group, an acetal group, or a carbonate group, p is an integer of 1 or more, m is an integer of 1 or more, n is an integer of 0 or more, m+n is 3 or more, r is an integer of 0 or more.

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