Composition, resin composition, composition for forming film, pattern forming method, and compound

Abstract

A composition containing a compound (A) represented by formula (1) and a compound (B) represented by formula (2). (In formula (1), each definition is shown in the description. ) (In formula (2), X, L1, Y, Ra, Rb, Rc, A, Z, p, m, n, and r are the same as those described in formula (1), and k represents an integer of 0-2. > # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a composition, a resin composition, a film-forming composition, a pattern forming method and a compound. Background Art

[0002] In recent years, in the manufacture of semiconductor elements and liquid crystal display elements, the miniaturization of semiconductors (patterns) and pixels has been rapidly developing due to the progress of photolithography technology. Due to the miniaturization of pixels, the wavelength of the usual exposure light source is being shortened. Specifically, although ultraviolet rays represented by g-rays and i-rays have been used in the past, the method of using far ultraviolet rays such as KrF excimer lasers (248nm) and ArF excimer lasers (193nm) for exposure has become the center of mass production, and the introduction of extreme ultraviolet (EUV: Extreme Ultraviolet) lithography (13.5nm) is being carried out. In addition, electron beams (EB: Electron Beam) are also used to form fine patterns.

[0003] So far, the common resist material is a polymer resist material that can form an amorphous film. For example, polymer resist compositions such as polymethyl methacrylate, polyhydroxystyrene or polyalkyl methacrylate having an acid dissociable group can be cited (for example, refer to non-patent document 1). In the past, a line pattern of about 10 to 100 nm was formed by coating a solution of these resist compositions on a substrate and irradiating the produced resist film with ultraviolet rays, far ultraviolet rays, electron beams, extreme ultraviolet rays, etc.

[0004] In addition, in photolithography using electron beams or extreme ultraviolet rays, the reaction mechanism is different from that of conventional photolithography (Non-patent Document 2, Non-patent Document 3). Furthermore, in photolithography using electron beams or extreme ultraviolet rays, the goal is to form a fine pattern of several nm to several tens of nm. In this way, when the size of the resist pattern becomes smaller, a highly sensitive resist composition is further sought for the exposure light source. In particular, in photolithography using extreme ultraviolet rays, further high sensitivity is sought in terms of productivity.

[0005] As a resist material for improving the above-mentioned problems, a resist composition containing a metal complex such as titanium, tin, hafnium or zirconium has been proposed (for example, refer to Patent Document 1).

[0006] In addition, when the size of the resist pattern becomes smaller, a resist composition with high sensitivity to the exposure light source is further sought, and a resist composition using 4-hydroxystyrene containing iodine as its raw material monomer has been proposed (for example, refer to Patent Documents 2 to 3). In addition, the present inventors have proposed a resist composition with excellent exposure sensitivity (for example, Patent Document 4).

[0007] Prior art literature

[0008] Patent Document

[0009] Patent Document 1: Japanese Patent Application Laid-Open No. 2015-108781

[0010] Patent Document 2: US Patent Application Publication No. 2019 / 0187342

[0011] Patent Document 3: WO Patent Application Publication No. 2019 / 187881

[0012] Patent Document 4: WO Patent Application Publication No. 2021 / 029395

[0013] Non-Patent Document

[0014] Non-Patent Document 1: Shinji Okazaki, et al., "40 Years of Lithography Technology" (in Japanese: リソグラフィ技術その40年), S&T Publishing, December 9, 2016

[0015] Non-Patent Document 2: H. Yamamoto, et al., Jpn. J. Appl. Phys. 46, L142 (2007)

[0016] Non-Patent Document 3: H. Yamamoto, et al., J. Vac. Sci. Technol. B 23, 2728 (2005) Summary of the Invention

[0017] Problems to be Solved by the Invention

[0018] However, for the film-forming compositions developed in the past, although the sensitivity to the exposure light source is good, there is a problem that defects are confirmed in the obtained film and the developed pattern over time during storage of the composition and the like.

[0019] To solve these problems, an object of the present invention is to provide a resist composition, a resist composition, a pattern forming method, and a compound capable of suppressing defects generated in the film produced and the developed pattern over time during storage and the like.

[0020] Solutions to the Problems

[0021] The inventors of the present invention conducted in-depth research to solve the above problems and found that a compound having a specific structure or a polymer containing the compound as a structural unit can suppress defects generated in the film of the resist composition and the developed pattern over time during storage and the like, thereby completing the present invention.

[0022] That is, the present invention is as described below.

[0023] [1] A composition comprising a compound (A) represented by the following formula (1) and a compound (B) represented by the following formula (2).

[0024]

[0025] (In formula (1),

[0026] X is each 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,

[0027] L 1 Each of the above L 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. 1 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

[0028] 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 thiol 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, an amide group, an imide group and a phosphoric acid group of the above Y may have a substituent,

[0029] R a , R b and R c Each is independently H, I, F, Cl, Br or an organic group having 1 to 8 carbon atoms which may have a substituent,

[0030] A is an organic group having 6 to 30 carbon atoms,

[0031] 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 above Z may have a substituent,

[0032] p is an integer greater than or equal to 1, m is an integer greater than or equal to 1, n is an integer greater than or equal to 0, and r is an integer greater than or equal to 0.)

[0033]

[0034] (In formula (2),

[0035] X, L 1 , Y, R a , Rb , R c , A, Z, p, m, n and r are the same as those described in formula (1), and k represents an integer greater than or equal to 0 and less than or equal to 2).

[0036] [2] The composition according to [1] above, wherein the formula (1) is represented by the following formula (1a).

[0037]

[0038] (In formula (1a),

[0039] X, L 1 , Y, A, Z, p, m, n and r have the same definitions as in formula (1).

[0040] [3] The composition according to [1] or [2] above, wherein formula (1) is represented by the following formula (1b).

[0041]

[0042] (In formula (1b),

[0043] X, L 1 , Y, A, Z, p, m, n and r are the same as those in formula (1),

[0044] R a1 , R b1 and R c1 Each is independently H, I, F, Cl, Br or an organic group having 1 to 8 carbon atoms which may have a substituent,

[0045] R a1 , R b1 and R c1 At least one of them is I, F, Cl, Br or an organic group having 1 to 8 carbon atoms which may have a substituent.

[0046] [4] The composition according to any one of [1] to [3] above, wherein n+r in formula (1) is an integer greater than or equal to 1.

[0047] [5] The composition according to any one of [1] to [4] above, wherein Y in formula (1) is independently a group represented by the following formula (Y-1).

[0048] -L 2 -R 2 (Y-1)

[0049] (In formula (Y-1),

[0050] L 2 is a group that is cleaved by the action of an acid or a base,

[0051] 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 heteroatoms having 1 to 30 carbon atoms, or an aromatic group containing heteroatoms having 1 to 30 carbon atoms, wherein R 2 The aliphatic group, aromatic group, aliphatic group containing a heteroatom, and aromatic group containing a heteroatom may further have a substituent.

[0052] [6] The composition according to any one of [1] to [5] above, wherein A in formula (1) is an aromatic ring.

[0053] [7] The composition according to any one of [1] to [6] above, wherein A in formula (1) is an alicyclic structure.

[0054] [8] The composition according to any one of [1] to [7] above, wherein A in formula (1) is a heterocyclic structure.

[0055] [9] The composition according to any one of [1] to [8] above, wherein n in formula (1) is 2 or more.

[0056]

[10] The composition according to any one of [1] to [9] above, wherein the compound represented by formula (1) contains a functional group that improves solubility in an alkaline developer due to the action of an acid or a base.

[0057]

[11] The composition according to any one of [1] to

[10] , wherein X in formula (1) is I, L 1 For a single key.

[0058]

[12] The composition according to any one of [1] to

[11] , wherein X in formula (1) is a group formed by introducing one or more F, Cl, Br or I into an aromatic group.

[0059]

[13] The composition according to any one of [1] to

[12] , wherein X in formula (1) is a group in which one or more F, Cl, Br or I are introduced into an alicyclic group.

[0060]

[14] The composition according to any one of [1] to

[13] above, wherein A in formula (2) is an aromatic ring.

[0061]

[15] The composition according to any one of [1] to

[14] above, wherein A in formula (2) is a benzene ring or a naphthalene ring.

[0062]

[16] The composition according to any one of [1] to

[15] above, wherein X in formula (2) is iodine or fluorine.

[0063]

[17] The composition according to any one of [1] to

[16] , wherein L in formula (2) 1 For a single key.

[0064]

[18] The composition according to any one of [1] to

[17] above, wherein Y in formula (2) is a hydroxyl group, an alkoxy group, a carbonate group or an acetal group.

[0065]

[19] The composition according to any one of [1] to

[18] , wherein the mass ratio of the content of the compound represented by formula (2) to the content of the compound represented by formula (1) is 1 ppm or more and 5 mass % or less.

[0066]

[20] The composition according to any one of [1] to

[19] above, comprising a compound represented by formula (2a), wherein the content of the compound represented by formula (2a) is 1% by mass or less relative to the compound of formula (1).

[0067]

[0068] (In formula (2a),

[0069] X, L 1 , Y, R a , R b , R c , A, Z, p, m, n and r are the same as those described in formula (1), and k represents an integer greater than 3.)

[0070]

[21] The composition according to any one of [1] to

[20] above, wherein the content of the peroxide is 10 ppm by mass or less relative to the compound of formula (1).

[0071]

[22] The composition according to any one of [1] to

[21] , wherein the amount of impurities containing one or more elements selected from the group consisting of Mn, Al, Si and Li is 1 ppm by mass or less relative to the compound of formula (1) in terms of element conversion.

[0072]

[23] The composition according to

[22] above, wherein the phosphorus-containing compound is 10 ppm by mass or less relative to the compound of formula (1).

[0073]

[24] The composition according to

[23] above, wherein the content of maleic acid is 10 ppm by mass or less based on the compound of formula (1).

[0074]

[25] The composition according to any one of [1] to

[24] , wherein in the formula (1) and the formula (2), all r are 0 and at least one n is 1 or greater.

[0075]

[26] A resin composition comprising:

[0076] A polymer comprising at least a structural unit represented by the following formula (4), wherein the number of structural units is 5 or more;

[0077] A compound (B) represented by the following formula (2) in an amount of 1% by mass or less relative to the above polymer; and

[0078] The compound (A) is represented by the following formula (1).

[0079]

[0080] (In formula (1),

[0081] X is each 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,

[0082] L 1 Each of the above L 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 phosphoric acid group. 1 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

[0083] 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 thiol 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, an amide group, an imide group and a phosphoric acid group of the above Y may have a substituent,

[0084] R a , R b and R c Each is independently H, I, F, Cl, Br or an organic group having 1 to 8 carbon atoms which may have a substituent,

[0085] A is an organic group having 6 to 30 carbon atoms,

[0086] 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 above Z may have a substituent,

[0087] p is an integer greater than or equal to 1, m is an integer greater than or equal to 1, n is an integer greater than or equal to 0, and r is an integer greater than or equal to 0.)

[0088]

[0089] (In formula (2),

[0090] X, L 1 , Y, R a , R b , R c , A, Z, p, m, n and r are the same as those described in formula (1), and k represents an integer of 0 or more and 2 or less.)

[0091]

[0092] (In formula (4), X, L 1 , Y, R a , R b , R c , A, Z, p, m, n and r have the same definitions as in formula (1),

[0093] * is the bonding site with the adjacent structural unit. )

[0094]

[27] The resin composition according to

[26] above, wherein the polymer further contains a structural unit represented by the following formula (C6).

[0095]

[0096] (In formula (C6),

[0097] X C61 is a hydroxyl group or a halogen group,

[0098] R C61 are each independently an alkyl group having 1 to 20 carbon atoms,

[0099] * is the bonding site with the adjacent structural unit. )

[0100]

[28] The resin composition according to

[26] or

[27] , wherein in the formula (1), the formula (2) and the formula (4), all r are 0 and at least one n is 1 or greater.

[0101]

[29] A film-forming composition comprising the composition described in any one of [1] to

[25] above, or the resin composition described in any one of

[26] to

[28] above.

[0102]

[30] The film-forming composition according to any one of

[26] to

[29] , further comprising an acid generator, a base generator or a base compound.

[0103]

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

[0104] A step of forming a resist film on a substrate using a film-forming composition comprising the composition described in any one of [1] to

[25] above or the resin composition described in any one of

[26] to

[28] above,

[0105] a step of exposing the resist film to a pattern, and

[0106] After the aforementioned exposure, the resist film is subjected to a development process.

[0107]

[32] A compound represented by the following formula (2).

[0108]

[0109] (In formula (2),

[0110] X is each 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,

[0111] L 1 Each of the above L 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 phosphoric acid group. 1 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

[0112] 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 thiol 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, an amide group, an imide group and a phosphoric acid group of the above Y may have a substituent,

[0113] R a , R b and R cEach is independently H, I, F, Cl, Br or an organic group having 1 to 8 carbon atoms which may have a substituent,

[0114] A is an organic group having 6 to 30 carbon atoms,

[0115] 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 above Z may have a substituent,

[0116] p is an integer greater than or equal to 1, m is an integer greater than or equal to 1, n is an integer greater than or equal to 0, r is an integer greater than or equal to 0, and k represents an integer greater than or equal to 0 and less than or equal to 2.)

[0117]

[33] The compound according to

[32] above, wherein in the formula (2), all r are 0, and at least one n is 1 or greater.

[0118] Effects of the Invention

[0119] According to the present invention, there are provided a resist composition, a resist composition, a pattern forming method, and a compound capable of obtaining a resist in which defects generated in a produced film or a pattern after development due to the passage of time due to storage or the like are suppressed. DETAILED DESCRIPTION

[0120] Hereinafter, an 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 describing the present invention, and the present invention is not limited to this embodiment.

[0121] In this specification, the meanings of each term are as follows.

[0122] "(Meth)acrylate" refers to at least one selected from acrylate, halogenated acrylate and methacrylate. Halogenated acrylate refers to acrylate in which halogen is substituted at the position of the methyl group of methacrylate. Other terms having the expression of (meth) are also interpreted in the same way as (meth)acrylate.

[0123] The "(co)polymer" refers to at least one selected from a homopolymer and a copolymer.

[0124] [Composition]

[0125] The composition of this embodiment is a composition comprising a compound (A) and a compound (B). The composition comprises a compound (A) represented by the formula (1) described below and a compound (B) represented by the formula (2) described below.

[0126] [Compound (A)]

[0127] The compound (A) of the present embodiment is preferably represented by the following formula (1). The compound (A) preferably contains a functional group that improves solubility in an alkaline developer due to the action of an acid or a base. Preferably, any one of the following Z, Y, and X contains a functional group that improves solubility in an alkaline developer due to the action of an acid or a base.

[0128]

[0129] In formula (1),

[0130] X is each 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. Among these, X is preferably each independently I, F, Cl, or Br, more preferably each independently I, F, or Br, more preferably each independently I or F, and even more preferably each independently I.

[0131] In the present embodiment, "substitution" refers to replacing one or more hydrogen atoms in a functional group with a substituent unless otherwise specified. The "substituent" is not particularly limited, and examples thereof include a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a thiol 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.

[0132] The alkyl group may be any of a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, and a cyclic aliphatic hydrocarbon group.

[0133] Examples of the alkyl group having 1 to 30 carbon atoms include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-dodecyl, and valeryl.

[0134] Examples of the aryl group having 6 to 30 carbon atoms include, but are not limited to, a phenyl group, a naphthyl group, a biphenyl group, an anthracenyl group, a pyrenyl group, and a perylenyl group.

[0135] Examples of the alkenyl group having 2 to 30 carbon atoms include, but are not limited to, ethynyl, propenyl, butynyl, and pentynyl.

[0136] Examples of the alkynyl group having 2 to 30 carbon atoms include, but are not limited to, acetylene group and ethynyl group.

[0137] Examples of the alkoxy group having 1 to 30 carbon atoms include, but are not limited to, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group.

[0138] The “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” is not particularly limited, 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,

[0139] 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, Iododihydroxyadamantyl, Iododiacetoxyadamantyl, Iodo-di-tert-butoxycarbonyladamantyl, Iodocyclohexyl, Diiodocyclohexyl, Triiodocyclohexyl, Iodohydroxycyclohexyl, Diiodohydroxynaphthyl, Iodoacetoxynaphthyl, Diiodoacetoxycyclohexyl, Iodo-tert-butoxycarbonylcyclohexyl, Diiodo-tert-butoxycarbonylcyclohexyl, Triiodo-tert-butoxycarbonylcyclohexyl, Iododihydroxycyclohexyl, Iododiacetoxycyclohexyl, Iodo-di-tert-butoxycarbonylcyclohexyl,

[0140] Monobromophenyl, dibromophenyl, tribromophenyl, tetrabromophenyl, pentabromophenyl, monobromohydroxyphenyl, dibromohydroxyphenyl, tribromohydroxyphenyl, monobromoacetoxyphenyl, dibromoacetoxyphenyl, tribromoacetoxyphenyl, monobromo-tert-butoxycarbonylphenyl, dibromo-tert-butoxycarbonylphenyl, tribromo-tert-butoxycarbonylphenyl, monobromodihydroxyphenyl, dibromodihydroxyphenyl, tribromodihydroxyphenyl, monobromodiacetoxyphenyl, dibromodiacetoxyphenyl, tribromodiacetoxyphenyl, monobromodi-tert-butoxycarbonylphenyl, dibromodi-tert-butoxycarbonylphenyl, tribromodi-tert-butoxycarbonylphenyl,

[0141] Monobromotrihydroxyphenyl, dibromotrihydroxyphenyl, monobromotriacetoxyphenyl, dibromotriacetoxyphenyl, monobromotri-tert-butoxycarbonylphenyl, dibromotri-tert-butoxycarbonylphenyl, monobromoadamantyl, dibromoadamantyl, tribromoadamantyl, monobromohydroxyadamantyl, dibromohydroxynaphthyl, monobromoacetoxynaphthyl, dibromoacetoxyadamantyl, monobromo-tert-butoxycarbonyladamantyl, dibromo-tert-butoxycarbonyladamantyl, tribromo-tert-butoxycarbonyladamantyl, monobromodihydroxyadamantyl, monobromodiacetoxyadamantyl, monobromo-di-tert-butoxycarbonyladamantyl,

[0142] Monofluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, monofluorohydroxyphenyl, difluorohydroxyphenyl, trifluorohydroxyphenyl, monofluoroacetyloxyphenyl, difluoroacetyloxyphenyl, trifluoroacetyloxyphenyl, monofluoro-tert-butoxycarbonylphenyl, difluoro-tert-butoxycarbonylphenyl, trifluoro-tert-butoxycarbonylphenyl, monofluorodihydroxyphenyl, difluorodihydroxyphenyl, trifluorodihydroxyphenyl, monofluorodiacetyloxyphenyl, difluorodiacetyloxyphenyl, trifluorodiacetyloxyphenyl, monofluorodi-tert-butoxycarbonylphenyl, difluorodi-tert-butoxycarbonylphenyl, trifluorodi-tert-butoxycarbonylbenzene yl, monofluorotrihydroxyphenyl, difluorotrihydroxyphenyl, monofluorotriacetoxyphenyl, difluorotriacetoxyphenyl, monofluorotri-tert-butoxycarbonylphenyl, difluorotri-tert-butoxycarbonylphenyl, monofluoroadamantyl, difluoroadamantyl, trifluoroadamantyl, monofluorohydroxyadamantyl, difluorohydroxynaphthyl, monofluoroacetoxynaphthyl, difluoroacetoxyadamantyl, monofluoro-tert-butoxycarbonyladamantyl, difluoro-tert-butoxycarbonyladamantyl, trifluoro-tert-butoxycarbonyladamantyl, monofluorodihydroxyadamantyl, monofluorodiacetoxyadamantyl, monofluoro-di-tert-butoxycarbonyladamantyl,

[0143] Monochlorophenyl, dichlorophenyl, trichlorophenyl, tetrachlorophenyl, pentachlorophenyl, monochlorohydroxyphenyl, dichlorohydroxyphenyl, trichlorohydroxyphenyl, monochloroacetoxyphenyl, dichloroacetoxyphenyl, trichloroacetoxyphenyl, monochloro-tert-butoxycarbonylphenyl, dichloro-tert-butoxycarbonylphenyl, trichloro-tert-butoxycarbonylphenyl, monochlorodihydroxyphenyl, dichlorodihydroxyphenyl, trichlorodihydroxyphenyl, monochlorodiacetoxyphenyl, dichlorodiacetoxyphenyl, trichlorodiacetoxyphenyl, monochloro-di-tert-butoxycarbonylphenyl, dichloro-di-tert-butoxycarbonylphenyl, trichloro-di-tert-butoxycarbonylphenyl,

[0144] Monochlorotrihydroxyphenyl, dichlorotrihydroxyphenyl, monochlorotriacetoxyphenyl, dichlorotriacetoxyphenyl, monochlorotri-tert-butoxycarbonylphenyl, dichlorotri-tert-butoxycarbonylphenyl, monochloroadamantyl, dichloroadamantyl, trichloroadamantyl, monochlorohydroxyadamantyl, dichlorohydroxynaphthyl, monochloroacetoxynaphthyl, dichloroacetoxyadamantyl, monochloro-tert-butoxycarbonyladamantyl, dichloro-tert-butoxycarbonyladamantyl, trichloro-tert-butoxycarbonyladamantyl, monochlorodihydroxyadamantyl, monochlorodiacetoxyadamantyl, monochloro-di-tert-butoxycarbonyladamantyl and the like.

[0145] For example, X may be an aromatic group and one or more F, Cl, Br or I may be introduced into the aromatic group. Examples of such aromatic groups include groups having a benzene ring such as phenyl having 1 to 5 halogens, groups having a heteroaromatic ring such as furan, thiophene, and pyridine having 1 to 5 halogens, and examples thereof include phenyl having 1 to 5 I, phenyl having 1 to 5 F, phenyl having 1 to 5 Cl, phenyl having 1 to 5 Br, naphthyl having 1 to 5 F, naphthyl having 1 to 5 Cl, and pyridine having 1 to 5 Br. naphthyl having 1 to 5 I's, phenol having 1 to 4 F's, phenol having 1 to 4 Cl's, phenol having 1 to 4 Br's, phenol having 1 to 4 I's, furanyl having 1 to 3 F's, furanyl having 1 to 3 Cl's, furanyl having 1 to 3 Br's, furanyl having 1 to 3 I's, thienyl having 1 to 3 F's, thienyl having 1 to 3 Cl's, thienyl having 1 to 3 Br's thienyl, thienyl having 1 to 3 I, pyridyl having 1 to 4 F, pyridyl having 1 to 4 Cl, pyridyl having 1 to 4 Br, pyridyl having 1 to 4 I, benzodiazolyl having 1 to 5 F, benzodiazolyl having 1 to 5 Cl, benzodiazolyl having 1 to 5 Br, benzodiazolyl having 1 to 5 I, benzimidazolyl having 1 to 4 F, benzodiazolyl having 1 to 4 Cl Imidazolyl, benzimidazolyl having 1 to 4 Br, benzimidazolyl having 1 to 4 I, benzoxazolyl having 1 to 4 F, benzoxazolyl having 1 to 4 Cl, benzoxazolyl having 1 to 4 Br, benzoxazolyl having 1 to 4 I, benzothiophenyl having 1 to 4 F, benzothiophenyl having 1 to 4 Cl, benzothiophenyl having 1 to 4 Br, benzothiophenyl having 1 to 4 I.

[0146] Furthermore, X may be an alicyclic group and one or more F, Cl, Br or I groups are introduced into the alicyclic group. Examples of such alicyclic groups include adamantyl groups having 1 to 3 halogens, adamantyl groups having 1 to 3 F, adamantyl groups having 1 to 3 Cl, adamantyl groups having 1 to 3 Br, adamantyl groups having 1 to 3 I, cyclopentyl groups having 1 to 3 F, cyclopentyl groups having 1 to 3 Cl, cyclopentyl groups having 1 to 3 Br, cyclopentyl groups having 1 to 3 I, bicycloundecyl groups having 1 to 3 F, bicycloundecyl groups having 1 to 3 Cl, bicycloundecyl groups having 1 to 3 Br, bicycloundecyl groups having 1 to 3 I, norbornyl groups having 1 to 3 F, norbornyl groups having 1 to 3 Cl, norbornyl groups having 1 to 3 Br, norbornyl groups having 1 to 3 I, and the like.

[0147] 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 carbamate group, a urea group, an amide group, an imide group or a phosphoric acid group. 1 Preferably it is a single bond. 1 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 may have a substituent. Such a substituent may be, for example, as described above.

[0148] From the viewpoint of improving exposure sensitivity, it is preferred that X in formula (1) is I, L 1 For a single key.

[0149] m is an integer of 1 or more, preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 or more and 4 or less, further preferably 1 or more and 3 or less, and further preferably 1 or 2.

[0150] 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 thiol 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, an amide group, an imide group and a phosphoric acid group of the aforementioned Y may have a substituent.

[0151] For example, Y can be selected from the group consisting of hydroxyl group, alkoxy group, 3 -OR 2 ], ester group [* 3 -O-(C=O)-R 2 or* 3 -(C=O)-OR 2 ], acetal group [* 3 -O-(C(R 21 )2)-OR 2 (R 21 Each independently represents H or a hydrocarbon group having 1 to 10 carbon atoms. )], carboxyalkoxy [* 3 -OR 22 -(C=O)-OR 2 (R 22 is a divalent hydrocarbon group having 1 to 10 carbon atoms. )], and a carbonate group [* 3 -O-(C=O)-OR 2 ] is at least one group of 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, * 3 It is the bonding site with A.

[0152] Among these, from the viewpoint of high sensitivity, as Y, preferably include any one of hydroxyl, tertiary ester group, acetal group, carbonate group or carboxy alkoxyl group, wherein, more preferably include any one of hydroxyl, acetal group, carbonate group or carboxy alkoxyl group, further preferably include any one of hydroxyl, acetal group or carboxy alkoxyl group. In addition, from the viewpoint of polymer manufacturing of stable quality based on free radical polymerization, as Y, preferably include any one of ester group, carboxy alkoxyl group and carbonate group.

[0153] Y may each independently preferably include a group represented by the following formula (Y-1).

[0154] -L 2 -R 2 (Y-1)

[0155] In formula (Y-1),

[0156] L 2 The 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 ester groups [* 1 -O-(C=O)-* 2 or *1-(C=O)-O-* 2 ], acetal group [* 1 -O-(C(R 21 )2)-O-* 2 (R 21 Each independently represents H or a hydrocarbon group having 1 to 10 carbon atoms. )], carboxyalkoxy [* 1 -OR 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 ] is at least one divalent linking group in 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 with A, * 2 For R 2 Among these, L 2 Preferably, tertiary ester group, acetal group, carbonate group or carboxyalkoxy group, more preferably acetal group, carbonate group or carboxyalkoxy group, further preferably acetal group or carboxyalkoxy group. In addition, from the viewpoint of polymer production of stable quality based on free radical polymerization, preferably ester group, carboxyalkoxy group and carbonate group.

[0157] In addition, as another effect, when the compound (A) of the present embodiment is used as a polymerization unit of a copolymer, Y is preferably a group represented by formula (Y-1) for the purpose of controlling the polymerizability of the resin and setting the degree of polymerization to a desired range. Since compound A has an X group, it has a great influence on the active species during the polymer formation reaction, and the desired control becomes difficult. Therefore, by having a group represented by formula (Y-1) as a protecting group on the hydrophilic group in compound A, the unevenness of copolymer formation and polymerization hindrance derived from the hydrophilic group can be suppressed.

[0158] 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 heteroatoms having 1 to 30 carbon atoms, or a linear, branched or cyclic aromatic group containing heteroatoms having 1 to 30 carbon atoms, wherein R 2 The aliphatic group, aromatic group, aliphatic group containing heteroatoms, and aromatic group containing heteroatoms may further have a substituent. It should be noted that the substituents mentioned above can be used as the substituents here, but preferably a linear, branched or cyclic aliphatic group having 1 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms. Among these, R 2 Preferably it is an aliphatic group. 2 The aliphatic group in is preferably a branched or cyclic aliphatic group. The carbon number 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, and adamantyl are preferred.

[0159] L 2 for* 1 -(C=O)-O-* 2 When it is a carboxylic acid alkoxy group, it is cleaved by the action of an acid or a base to form a carboxylic acid group, and the solubility difference and dissolution rate difference between the decomposed part and the non-decomposed part in the development treatment are enlarged, so the resolution is improved, and the residue at the bottom of the pattern in particular in a fine line pattern is suppressed, so it is preferred.

[0160] As Y, for example, the following specific examples can be given.

[0161]

[0162] The alkoxy group that can be used as Y includes an alkoxy group having 1 or more carbon atoms, and preferably an alkoxy group having 2 or more carbon atoms, and preferably an alkoxy group having 3 or more carbon atoms or having a cyclic structure, from the viewpoint of solubility of the resin formed by combining with other monomers.

[0163] Specific examples of the alkoxy group that can be used as Y include the following, but are not limited to these.

[0164]

[0165] As amino groups and amide groups that can be used as Y, primary amino groups, secondary amino groups, tertiary amino groups, groups with quaternary ammonium salt structures, amides having substituents, etc. can be appropriately used. Specific examples of amino groups or amide groups that can be used include the following, but are not limited thereto.

[0166]

[0167] 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, further preferably an integer of 1 or more and 3 or less, further preferably 1 or 2, and particularly preferably 2.

[0168] R a , R b and R c Each independently represents H, I, F, Cl, Br or an organic group having 1 to 8 carbon atoms which may have a substituent. a , R b and R c Combination of R a , R b and R c All are H (hydrogen atoms). As substituents of organic groups having 1 to 8 carbon atoms, there are no particular limitations, and examples thereof include I, F, Cl, Br, or other substituents. As other substituents, there are no particular limitations, and examples thereof include hydroxyl, alkoxy, ester, acetal, carbonate, nitro, amino, carboxyl, thiol, ether, thioether, phosphino, phosphonic acid, carbamate, urea, amide, imide, and phosphoric acid. Among them, alkoxy, ester, carbonate, amino, ether, thioether, phosphino, phosphonic acid, carbamate, urea, amide, imide, and phosphoric acid may also have substituents. It should be noted that as substituents herein, linear, branched, or cyclic aliphatic groups having 1 to 7 carbon atoms may be listed.

[0169] R a , R b and R c The organic group which may have a substituent in the formula (a) preferably has 1 to 6 carbon atoms.

[0170] The organic group having 1 to 8 carbon atoms which may have a substituent is not particularly limited, and examples thereof include a linear or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 4 to 8 carbon atoms, and an aromatic group having 6 to 8 carbon atoms which may contain a heteroatom.

[0171] The linear or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms is not particularly limited, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and 2-ethylhexyl.

[0172] The alicyclic hydrocarbon group is not particularly limited, and examples thereof include cyclohexyl, cycloheptyl, cyclooctyl, dicyclopentyl, etc. Furthermore, an aromatic group optionally containing a hetero atom such as benzodiazolyl, benzotriazolyl, benzothiazolyl, etc. may be appropriately selected. In addition, a combination of these organic groups may be selected.

[0173] The aromatic group having 6 to 8 carbon atoms and optionally containing a hetero atom is not particularly limited, and examples thereof include a phenyl group, a benzodiazolyl group, a benzotriazolyl group, and a benzothiazolyl group.

[0174] Among these organic groups having 1 to 8 carbon atoms which may have a substituent, a methyl group is preferred from the viewpoint of producing a polymer with stable quality.

[0175] In R a In the case of an organic group having 1 to 8 carbon atoms, or a group selected from F, Cl, and I, the total of n and r is preferably 0 or more, and r is preferably 0 and n is 1 or more.

[0176] A is an organic group having 6 to 30 carbon atoms. A may be a monocyclic organic group or a polycyclic organic group, and may have a substituent. A is preferably an aromatic ring optionally having a substituent. A preferably has 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms.

[0177] A is preferably a group represented by any one of the following formulae (A-1) to (A-4), more preferably a group represented by any one of the following formulae (A-1) to (A-2) (i.e., a benzene ring or a naphthalene ring), and still more preferably a group represented by the following formula (A-1).

[0178]

[0179] A can be an alicyclic structure optionally having a substituent. Here, "alicyclic structure" refers to a saturated or unsaturated carbon ring that does not have aromaticity. As the aforementioned alicyclic structure, for example, a saturated or unsaturated carbon ring with a carbon number of 3 to 30 can be listed, and preferably a saturated or unsaturated carbon ring with a carbon number of 3 to 20. As the aforementioned alicyclic structure, for example, a group having a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cycloeicosyl group, a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a cyclooctenyl group, a cyclopentadienyl group, a cyclooctadienyl group, an adamantyl group, a bicycloundecyl group, a decahydronaphthyl group, a norbornyl group, a norbornadienyl group, a cubane group, a basalane group, a house alkane group, etc. can be listed.

[0180] In addition, A may be a heterocyclic structure optionally having a substituent. The heterocyclic structure is not particularly limited, and examples thereof include alicyclic groups having a cyclic nitrogen-containing structure such as pyridine, piperidine, piperidone, benzodiazole, benzotriazole, triazine, cyclic carbamate structure, cyclic urea, cyclic amide, cyclic imide, furan, pyran, cyclic ether such as dioxolane, caprolactone, butyrolactone, nonanolactone, decanolactone, undecalactone, bicyclic undecalactone, phthalide, and the like.

[0181] 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.

[0182] Z is independently an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group or a carbonate group. These groups may optionally have a substituent, and as the substituent, a hydrocarbon group having 1 to 60 carbon atoms which may also have a substituent may be listed. r is an integer greater than 0, preferably an integer greater than 0 and less than 2, more preferably an integer greater than 0 and less than 1, and further preferably 0. That is, in formula (1) and formulas (2) and (4) described later, it is preferred that all r are 0 and at least one n is 1 or more.

[0183] For example, Z can be selected from alkoxy groups [* 3 -OR 2 ], ester group [* 3 -O-(C=O)-R 2 or* 3 -(C=O)-OR 2 ], acetal group [* 3 -O-(C(R 21 )2)-OR 2 (R 21 Each independently represents H or a hydrocarbon group having 1 to 10 carbon atoms. )], carboxyalkoxy [* 3 -OR 22 -(C=O)-OR 2 (R 22is a divalent hydrocarbon group having 1 to 10 carbon atoms. )], and a carbonate group [* 3 -O-(C=O)-OR 2 ] is at least one group in 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, * 3 It is the bonding site with A.

[0184] 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, further preferably an acetal group or a carboxyalkoxy group. In addition, from the viewpoint of polymer manufacturing based on the stable quality of free radical polymerization, it is preferably an ester group, a carboxyalkoxy group and a carbonate group.

[0185] As described above, n is an integer greater than or equal to 0, and r is an integer greater than or equal to 0, and at least one of n or r may be an integer greater than or equal to 1. That is, n+r in formula (1) may be an integer greater than or equal to 1.

[0186] Furthermore, from the viewpoint of suppressing etching defects, it is preferred that n in formula (1) is an integer of 2 or more.

[0187] Among the above compounds (A), the compound represented by the following formula (1a) is preferred.

[0188]

[0189] (In formula (1a),

[0190] X, L 1 , Y, A, Z, p, m, n and r have the same definitions as in formula (1).

[0191] Examples of the compound (A) according to the present embodiment (herein, a compound represented by the formula (1a)) include compounds having the structures shown below.

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201] Among the above compounds (A), from the viewpoint of further improving the sensitivity, the compound represented by the following formula (1b) is preferred.

[0202]

[0203] (In formula (1b),

[0204] X, L 1 , Y, A, Z, p, m, n and r have the same definitions, specific examples and preferred ranges as in formula (1),

[0205] R a1 , R b1 and R c1 Each is independently H, I, F, Cl, Br or an organic group having 1 to 8 carbon atoms which may have a substituent,

[0206] R a1 , R b1 and R c1 At least one of them is I, F, Cl, Br or an organic group having 1 to 8 carbon atoms which may have a substituent.

[0207] R a1 , R b1 and R c1 The organic group having 1 to 8 carbon atoms and the aforementioned R a1 , R b1 and R c1 The organic group having 1 to 8 carbon atoms which may have a substituent has the same definition. a1 It is preferably an organic group having 1 to 8 carbon atoms which may have a substituent or I, and is more preferably a methyl group or I. b1 and R c1 Preferably H.

[0208] Examples of the compound (A) according to the present embodiment (herein, a compound represented by the formula (1b)) include compounds having the structures shown below.

[0209]

[0210]

[0211]

[0212] The above compound (A) may be, for example, a compound represented by the following formula (1C). Although not particularly limited, as described below, the compound represented by the following formula (1C) is preferably used in combination with a compound (A) other than the compound.

[0213]

[0214] (In formula (1C), formula (1C1) and formula (1C2),

[0215] X, L 1 , Y, A, Z, p, m, n and r are the same as those in formula (1),

[0216] R sub Representing formula (1C1) or formula (1C2),

[0217] R a1 , R b1 and R c1 Each is independently H, I, F, Cl, Br or an organic group having 1 to 8 carbon atoms which may have a substituent,

[0218] R a1 , R b1 and R c1 At least one of is I, F, Cl, Br or an organic group having 1 to 8 carbon atoms which may have a substituent,

[0219] p-1 is an integer greater than 0,

[0220] * is the bonding part with various bonding. )

[0221] In the composition of the compound (A) of the present embodiment, when the compound shown in formula (1C) is used, the composition can be used in combination with the compound shown in the following formula (1C) and the compound (A) other than the compound. At this time, the composition is preferably prepared in a manner that the compound shown in formula (1C) is 1 mass ppm or more and 10 mass % or less relative to all compounds (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, particularly preferably 1 mass ppm or more and 1 mass % or less. In the resin form after the resin formed by the starting raw material of the composition thus made is formed, the part containing X and the part formed by Y or Z are present at a high density in the adjacent region, thereby becoming the starting point for improved sensitivity. Furthermore, the solubility in the resin is locally increased, thereby bringing about a reduction in the residue defects after development in the photolithography process.

[0222] Examples of the compound (A) according to the present embodiment (herein, a compound represented by the formula (1C)) include compounds having the structures shown below.

[0223]

[0224] Furthermore, the compound (A) of the present embodiment can be used in combination with a compound represented by the following formula (1D), for example.

[0225]

[0226] (In formula (1D), formula (1D1) or formula (1D2),

[0227] X, L 1 , Y, A, Z, p, m, n and r are the same as those in formula (1),

[0228] R sub2 Representing formula (1D1) or formula (1D2),

[0229] R a1 , R b1 and R c1 Each is independently H, I, F, Cl, Br or an organic group having 1 to 8 carbon atoms which may have a substituent,

[0230] R a1 , R b1 and R c1 At least one of is I, F, Cl, Br or an organic group having 1 to 8 carbon atoms which may have a substituent,

[0231] n2 represents an integer greater than or equal to 0 and less than or equal to 4,

[0232] p-1 is an integer greater than 0,

[0233] * is the bonding site with the adjacent structural unit. )

[0234] In the composition of the compound (A) of the present embodiment, when the compound shown in formula (1D) is used, the composition can be used in combination with the compound shown in the following formula (1D) and the compound (A) other than the compound. At this time, the composition is preferably prepared in a manner that the compound shown in formula (1D) is 1 mass ppm or more and 10 mass % or less relative to all compounds (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, particularly preferably 1 mass ppm or more and 1 mass % or less. In the resin form after the resin formed by the starting raw material of the composition thus made is formed, the site containing X and the site formed by Y or Z coexist at high density in the adjacent region, thereby becoming the starting point for improved sensitivity. Furthermore, the solubility in the resin is locally increased, thereby bringing about a reduction in the residue defects after development in the photolithography process.

[0235] Examples of the compound (A) according to the present embodiment (herein, a compound represented by the formula (1D)) include compounds having the structures shown below.

[0236]

[0237] In the composition containing the compound (A) of the present embodiment, a compound represented by the following formula (1E) may be included. When using this compound, the composition containing the compound (A) of the present embodiment preferably contains the compound represented by formula (1E) in a range of 1 mass ppm or more and 10 mass % or less relative to the total compound (A), more preferably in a range of 1 mass ppm or more and 5 mass % or less, further preferably in a range of 1 mass ppm or more and 3 mass % or less, and particularly preferably in a range of 1 mass ppm or more and 1 mass % or less.

[0238] The composition prepared in this way tends to have high stability. The reason for this is not yet determined, but it is presumed that the iodine-containing compound (A) and the iodine-free compound (1E) undergo an equilibrium reaction of iodine atoms, thereby achieving stabilization.

[0239] In this case, the composition preferably uses, as the compound (1E), a compound having a structure in which an iodine atom is removed from the compound exemplified as the above-mentioned compound (A).

[0240] Furthermore, since the composition prepared in this way has high stability, it not only improves storage stability but also forms a stable resin or imparts stable resist properties, thereby reducing residue defects after development in the photolithography process.

[0241] The method of using the compound represented by formula (1E) in a composition containing compound (A) in an amount within a range of 1 mass ppm to 10 mass % relative to compound (A) is not particularly limited, and examples thereof include a method of adding compound (1E) to compound (A).

[0242]

[0243] (In formula (1E),

[0244] X is each independently 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 F, Cl, and Br,

[0245] L 1 Each of the above L 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 phosphoric acid group. 1 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

[0246] 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 thiol 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, an amide group, an imide group and a phosphoric acid group of the above Y may have a substituent,

[0247] R a , R b and R c Each independently represents H, F, Cl, Br or an organic group having 1 to 8 carbon atoms which may have a substituent,

[0248] A is an organic group having 6 to 30 carbon atoms,

[0249] Z is each independently an alkoxy group, an ester group, an acetal group or a carbonate group,

[0250] Among them, X, L 1 , Y, R a , R b , R c , A and Z do not contain I,

[0251] p is an integer greater than or equal to 1, m' is an integer greater than or equal to 0, n is an integer greater than or equal to 0, and r is an integer greater than or equal to 0. However, m' is m'≤m-1 in the relationship with the compound (A) represented by the formula (1) used in combination (m represents m in the formula (1)).

[0252] If the compound represented by formula (1E) is contained in an amount greater than 10% by mass relative to compound (A), a polymer containing compound (A) may be formed, thereby reducing the effect of improving sensitivity when used for photolithography. On the other hand, if the amount is less than 1 ppm, the effect of improving stability over time may not be fully demonstrated.

[0253] In order to further enhance the effect of temporal stability, m' of the compound represented by formula (1E) is preferably 0.

[0254] Examples of the compound (1E) according to the present embodiment include compounds having the structures shown below.

[0255]

[0256]

[0257]

[0258]

[0259] [Method for producing compound (A)]

[0260] The compound represented by formula (1) can be manufactured by various known synthesis methods. As an example of a synthesis method, there is no particular limitation, for example, the method described in International Publication No. WO2021 / 029395 can be used. As a raw material for the synthesis of compound (A), for example, the following compounds can be used.

[0261]

[0262]

[0263]

[0264]

[0265] For the compound in this embodiment, it is preferred that after being obtained as a crude product through the above reaction, further purification is performed to remove residual metal impurities. That is, from the perspective of preventing resin deterioration over time and storage stability, and from the perspective of manufacturing yield caused by process applicability, defects, etc. when the resin is used in a semiconductor manufacturing process, it is preferred 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 mixed from the reactor or other manufacturing equipment used for manufacturing.

[0266] As the residual amount of the aforementioned metal impurities, it is preferably less than 1ppm, more preferably less than 100ppb, further preferably less than 50ppb, further preferably less than 10ppb, and most preferably less than 1ppb, respectively, relative to the resin. In particular, for various metal species including Fe, Ni, Mn, W, Al, etc., which are classified as transition metals, and alkali metals such as Li, Na, K, and Si, Sn, Sb, Pb, etc., if the metal residue is more than 1ppm, there is a concern that it will become the cause of the denaturation and degradation of the material over time through the interaction with the compound in the present embodiment. In addition, if it is more than 1ppm, there is the following concern: when using the prepared compound to make a resin for a semiconductor process, the metal residue cannot be fully reduced, which becomes the cause of the yield reduction caused by defects or performance degradation caused by the residual metal in the semiconductor manufacturing process.

[0267] The purification method is not particularly limited, and for example, the method described in International Publication No. WO2021 / 029395 can be used.

[0268] [Uses of Compound (A)]

[0269] The compound (A) of this embodiment can be added to the film-forming composition directly or in the form of a polymer described later to improve the sensitivity to the exposure light source. The compound (A) or its polymer is preferably used in a photoresist.

[0270] [Compound (B)]

[0271] The compound (B) of the present embodiment is a compound different from the compound (A), and is a compound shown in the following formula (2), having two or more halogens and an unsaturated double bond in the molecule that is not a terminal. The compound (B) shown in formula (2) can be any one of cis and trans. In addition, the composition of the present embodiment can contain only any one of the cis and trans of the compound shown in formula (2) as compound (B), or can contain both cis and trans as compound (B).

[0272]

[0273] (In formula (2),

[0274] X, L 1 , Y, R a , R b , R c , A, Z, p, m, n and r are the same as those described in formula (1), and k represents an integer of 0 or more and 2 or less.)

[0275] In formula (2), X, L 1 , Y, R a , R b , R c , A, Z, p, m, n and r have the same definitions, specific examples and preferred ranges as those in formula (1). 1 , Y, R a , R b , R c A, Z, p, m, n and r within their definitions may be X, L and 1 , Y, R a , R b , R c , A, Z, p, m, n and r are the same group or different groups. 1 , Y, R a , R b , R c A, Z, p, m, n and r are within their definitions and may be used in combination with X, L and 1 , Y, R a , R b , R c , A, Z, p, m, n and r may be bonded at the same position or at different positions.

[0276] Compound (B) may further have one or more hydrophilic groups or one decomposable group as Y. From the viewpoint of the roughness of the pattern, as Y, it is preferred to have one or more hydrophilic groups or one decomposable group. That is, compound (B) of the present embodiment preferably has two or more halogens, and one or more hydrophilic groups or one decomposable group, and an unsaturated double bond in the molecule that is not a terminal. In addition, compound (B) may further have one or more hydrophilic groups or one decomposable group.

[0277] As the halogen represented by X, preferably I, F, Cl, and Br can be mentioned. Among these, from the viewpoint of the sensitization effect due to 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 2 to 10, more preferably an integer of 2 to 8, and further preferably 2 to 6.

[0278] "Hydrophilic group" refers to a group that improves the affinity of the organic compound to water by bonding to an organic compound. As hydrophilic groups, hydroxyl, nitro, amino, carboxyl, thiol, phosphino, phosphonic acid, phosphoric acid, ether, thioether, carbamate, urea, amide, and imide groups in Y can be cited. Among these, hydroxyl is preferred from the viewpoint of the sensitization effect caused by EUV and the reduction of the roughness of the pattern. The number of hydrophilic groups is preferably an integer of 1 or more and 10 or less, more preferably an integer of 1 or more and 6 or less, further preferably 1 or more and 4 or less, and particularly preferably 2 or more and 4 or less.

[0279] "Decomposable group" refers to a group that decomposes in the presence of an acid or a base, or by irradiation from a light source such as radiation, an electron beam, extreme ultraviolet light (EUV), or ArF, KrF, etc. The decomposable group is not particularly limited, and for example, the acid dissociable functional group described in International Publication No. WO2013 / 024778 can be used. Among the decomposable groups, a hydrolyzable group is preferred. "Hydrolyzable group" refers to a group that hydrolyzes in the presence of an acid or a base. As hydrolyzable groups, for example, alkoxy groups, ester groups, acetal groups, and carbonate groups in Y can be listed. The number of decomposable groups is preferably an integer of 1 or more and 10 or less, more preferably an integer of 1 or more and 6 or less, further preferably 1 or more and 4 or less, and particularly preferably 2 or more and 4 or less.

[0280] The unsaturated double bond in formula (2) is preferably a polymerizable unsaturated double bond. a , R b The group having an unsaturated double bond formed together is not particularly limited, and examples thereof include vinyl, isopropenyl, (meth)acryloyl, and halogenated acryloyl. Examples of halogenated acryloyl include α-fluoroacryloyl, α-chloroacryloyl, α-bromoacryloyl, α-iodinated acryloyl, α,β-dichloroacryloyl, and α,β-diiodinated acryloyl. Among these unsaturated double bonds, isopropenyl and vinyl are preferred. The number of unsaturated double bonds is preferably an integer of 1 to 6, more preferably an integer of 1 to 4, and further preferably 1 to 2.

[0281] From the viewpoint of suppressing etching residues, compound (B) preferably contains a functional group that improves solubility in an alkaline developer due to the action of an acid or a base, and preferably contains a functional group that improves solubility in an alkaline developer due to the action of an acid or a base in either Y or X. Examples of the functional group include a carbonyloxy group (e.g., an acetyl group, an ester group), an acetal group, a carbonate group, and a tertiary alkoxy group.

[0282] In the composition of the compound (A) of the present embodiment, when the compound (B) shown in formula (2) is used, the composition can be used in combination with the compound (B) shown in formula (2) and the compound (A) other than the compound. At this time, the composition is preferably prepared in a manner that the compound (B) shown in formula (2) is 1 mass ppm or more and 10 mass % or less relative to all compounds (A), more preferably 1 mass ppm or more and 10 mass % or less, further preferably 1 mass ppm or more and 3 mass % or less, particularly preferably 1 mass ppm or more and 1 mass % or less. In the resin form after the resin formed by the starting raw material of the composition thus made is formed, the part containing X and the part formed by Y or Z are present at a high density in the adjacent region, thereby becoming the starting point for improved sensitivity. Furthermore, the solubility in the resin is locally increased, thereby bringing about a reduction in the residue defects after development in the photolithography process.

[0283] In addition, as another effect, the temporal stability of compound (A) can be improved by allowing compound (A) and compound (B) to coexist. The mechanism of the effect of improving the temporal stability of compound (A) has not yet been determined, but it is believed that: when the resin containing a composition containing compound (A) as a starting material is applied to a photolithography process, the temporal increase of defects in which polymer impurities become base points caused by compound (A) is greatly suppressed, and the performance in the photolithography process can be maintained.

[0284] The method of using compound (B) in a composition containing compound (A) in an amount of 1 mass ppm or more and 10 mass % or less relative to compound (A) is not particularly limited, and examples thereof include a method of adding compound (B) to compound (A). For example, it is preferred that the types of substituents (Y, X, etc.) and bonding positions common to compound (A) and compound (B) in each formula are the same.

[0285] Examples of the compound (B) or the mixture of compounds (B) according to the present embodiment include the structures shown below. The structures shown below may be either a cis isomer or a trans isomer, and are preferably a trans isomer.

[0286]

[0287] (The compound containing n in the formula refers to a mixture of n=1 to 4).

[0288] From the viewpoint of solubility, A in formula (2) is more preferably a benzene ring or a naphthalene ring.

[0289] From the viewpoint of exposure sensitivity, X in formula (2) is preferably iodine or fluorine.

[0290] From the viewpoint of compound stability, L in formula (2) 1 Preferred is a single bond.

[0291] From the viewpoint of suppressing pattern defects, Y in formula (2) is preferably a hydroxyl group, an alkoxy group, an ester group, a carbonate group or an acetal group.

[0292] In this embodiment, the composition may include a compound (Ba) represented by the following formula (2a) in addition to the compound (A) and the compound (B). The compound represented by the formula (2a) may be either a cis-isomer or a trans-isomer. In addition, the composition of this embodiment may include only either a cis-isomer or a trans-isomer of the compound represented by the formula (2a) as the compound (Ba), or may include both a cis-isomer and a trans-isomer as the compound (Ba).

[0293]

[0294] (In formula (2a),

[0295] X, L 1 , Y, R a , R b , R c , A, Z, p, m, n and r are the same as those in formula (1), and k represents an integer greater than 3).

[0296] In formula (2a), X, L 1 , Y, R a , R b , R c , A, Z, p, m, n and r have the same definitions, specific examples and preferred ranges as in formula (1). From the viewpoint of solubility, k in formula (2a) is preferably 3 or more and 5 or less, and more preferably 3.

[0297] [Method for producing compound (B)]

[0298] The compound (B) represented by formula (2) can be manufactured by various synthesis methods. As an example of a preferred synthesis method of compound (B), it is not particularly limited, for example, it can be manufactured by adjusting the reaction temperature in the synthesis method of compound (A) represented by formula (1). A higher reaction temperature improves the selectivity of compound (B) represented by formula (2) compared with compound (A) represented by formula (1). It is not particularly limited, for example, the reaction is carried out at a temperature above 50°C and below the boiling point of the solvent used. From the perspective of the selectivity of compound (B), it is preferably carried out at a temperature above 60°C and below the boiling point of the solvent. In addition, from the perspective of reaction temperature control, it is more preferred to carry out the reaction at the boiling point of the solvent.

[0299] For the compound manufactured in the present embodiment, it is preferred that after being obtained as a crude product by the above-mentioned reaction, further purification is performed to remove residual metal impurities. As an example of a purification method, it is not particularly limited, for example, the same purification method as the aforementioned purification method of the compound (A) shown in formula (1) can be used for purification.

[0300] As the residual amount of the aforementioned metal impurities, it is preferably less than 1ppm, more preferably less than 100ppb, further preferably less than 50ppb, further preferably less than 10ppb, and most preferably less than 1ppb, respectively, relative to the resin. In particular, for various metal species including Fe, Ni, Mn, W, Al, etc., which are classified as transition metals, and alkali metals such as Li, Na, K, and Si, Sn, Sb, Pb, etc., if the metal residue is more than 1ppm, there is a concern that it will become the cause of the denaturation and degradation of the material over time through the interaction with the compound in this embodiment. In addition, if it is more than 1ppm, there is the following concern: when using the prepared compound to make a resin for a semiconductor process, the metal residue cannot be fully reduced, which becomes the cause of the yield reduction caused by defects or performance degradation caused by the residual metal in the semiconductor manufacturing process.

[0301] [Uses of Compound (B)]

[0302] The compound (B) of this embodiment can improve the sensitivity to the exposure light source by adding it to the film-forming composition directly or as a polymer described later. The compound (B) or its polymer is preferably used in a photoresist.

[0303] [Method for producing compound (Ba)]

[0304] The compound (Ba) shown in formula (2a) can be manufactured by various synthesis methods. As an example of a preferred synthesis method of the compound, it is not particularly limited, for example, it can be manufactured by adjusting the reaction temperature in the synthesis method of the compound (A) shown in formula (1). The higher the reaction temperature, the higher the selectivity of the compound (Ba). It is not particularly limited, for example, from the viewpoint of improving the selectivity of the compound (Ba), it is preferred to dissolve the raw materials with a solvent with a high boiling point and react at a boiling reaction temperature. In order to increase the reaction temperature, a high boiling point solvent can be used under reflux.

[0305] [Uses of Compound (Ba)]

[0306] The compound (Ba) represented by the formula (2a) of the present embodiment can improve the sensitivity to the exposure light source by being added to the film-forming composition directly or as a polymer described later. The compound (Ba) or its polymer is preferably used in a photoresist.

[0307] [Composition]

[0308] The composition of the present embodiment contains compound (A) and compound (B). The content of compound (A) in the present embodiment is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 99% by mass or more.

[0309] As another preferred embodiment of the composition of the present embodiment, the content of the compound (B) represented by the formula (2) relative to the content of the compound (A) represented by the formula (1) preferably comprises a small amount of greater than 1 mass ppm and less than 10 mass %, more preferably greater than 1 mass ppm and less than 5 mass %, further preferably greater than 20 mass ppm and less than 2 mass %, and particularly preferably greater than 50 mass ppm and less than 1 mass %.

[0310] By setting the content of the compound (B) represented by formula (2) to the above range, the interaction between the resins during resinification can be reduced, and the crystallinity caused by the interaction between the resins after film formation using the resin can be suppressed. As a result, the local solubility in the developer during development at the molecular level from several nanometers to tens of nanometers is reduced, and the reduction in pattern quality such as line edge roughness and residue defects of the pattern formed by the pattern forming process in a series of photolithography processes such as exposure, post-exposure baking, and development is suppressed, and the resolution is further improved. Furthermore, the mechanism has not yet been determined, but the compound (B) represented by formula (2) effectively and actively captures free radicals generated by heat, etc., suppresses the deterioration of the compound (A) represented by formula (1) in the composition, and suppresses the generation of trace amounts of particulate foreign matter, and suppresses the defects of the obtained film and the pattern after development caused by time.

[0311] Regarding the effects of these lithographic properties, the compound represented by formula (2) having a mother nucleus A introduced with a halogen element, especially iodine, fluorine, etc., has a further increased affinity for the compound represented by formula (1) compared to the compound having a hydroxystyrene skeleton without the introduction of iodine, etc., and the polarization of the polar part is increased, thereby utilizing the compound represented by formula (2) to increase the effect of improving resolution by suppressing the crystallinity caused by the interaction between resins.

[0312] The composition of the present embodiment may also contain a compound (Ba) represented by formula (2a) on the basis of containing compound (A) and compound (B), as described above. From the viewpoint of etching defect suppression, the content of compound (Ba) in the composition of the present embodiment is preferably 1% by mass or less, more preferably 0.1% by mass or less, and further preferably 0.01% by mass or more and 0.1% by mass or less relative to the content of compound (A).

[0313] In the composition of the present embodiment, the amount of impurities including K (potassium) relative to the total amount of compound (A) and compound (B) when converted to element is preferably 1 mass ppm or less, more preferably 0.5 mass ppm or less, further preferably 0.1 mass ppm or less, and further preferably 0.005 mass ppm or less.

[0314] In the composition of the present embodiment, the content of one or more element impurities selected from the group consisting of Fe (iron), Ni (nickel), Mn (manganese), W (tungsten), Al (aluminum), Li (lithium), Na (sodium), K (potassium), Si (silicon), Sn (tin), Sb (antimony), Zn (zinc), Co (cobalt), Cr (chromium), Zr (zirconium), Mo (molybdenum) and Pb (lead) (preferably one or more element impurities selected from the group consisting of Mn and Al) is preferably 1 mass ppm or less, more preferably 0.5 mass ppm or less, and even more preferably 0.1 mass ppm or less, when calculated on an element basis, relative to compound (A) (or relative to compound (A) and compound (B)) from the viewpoint of suppressing pattern defects.

[0315] The amounts of K, Mn, Al, etc. can be measured by inorganic element analysis (IPC-AES / IPC-MS). Examples of inorganic element analysis apparatus include "AG8900" manufactured by Agilent Technologies.

[0316] In the composition of the present embodiment, the phosphorus-containing compound is preferably 10 ppm by mass or less, more preferably 8 ppm by mass or less, and even more preferably 5 ppm by mass or less relative to compound (A) (or relative to compound (A) and compound (B)) from the viewpoint of pattern shape.

[0317] In the composition of the present embodiment, the content of maleic acid relative to compound (A) (or relative to compound (A) and compound (B)) is preferably 10 mass ppm or less, more preferably 8 mass ppm or less, and even more preferably 5 mass ppm or less, from the viewpoint of pattern shape.

[0318] The amounts of the phosphorus-containing compound and maleic acid were calculated by gas chromatography-mass spectrometry (GC-MS) from the area fraction of the GC chart and the peak intensity ratio between the target peak and the reference peak.

[0319] In the composition of the present embodiment, the content of the peroxide relative to compound (A) (or relative to compound (A) and compound (B)) is preferably 10 mass ppm or less, more preferably 1 mass ppm or less, and even more preferably 0.1 mass ppm or less, from the viewpoint of reactivity.

[0320] The amount of peroxide is determined by the ammonium ferrothiocyanate method (hereinafter referred to as the AFTA method), in which trichloroacetic acid is added to the sample, and then ammonium ferrous (II) sulfate and potassium thiocyanate are added to obtain a standard curve of peroxides known as standard substances, and the absorbance at a wavelength of 480 μm is measured for quantification.

[0321] In the composition of the present embodiment, the water content is preferably 100,000 mass ppm or less, more preferably 20,000 mass ppm or less, further preferably 1,000 mass ppm or less, further preferably 500 mass ppm or less, further preferably 100 mass ppm or less, relative to compound (A) and compound (B). The water content can be measured by the Karl Fischer method (Karl Fischer water content measuring device).

[0322] [Polymer (A)]

[0323] The polymer (A) of the present embodiment includes a structural unit derived from the above-mentioned compound (A). When the polymer (A) includes a structural unit derived from the compound (A), the sensitivity to the exposure light source can be improved when the polymer (A) is mixed with the resist composition. In particular, even when extreme ultraviolet rays are used as the exposure light source, sufficient sensitivity can be exhibited, and a fine line pattern with a narrow line width can be well formed.

[0324] In addition, the sensitivity of conventional resist compositions to exposure light sources sometimes decreases over time due to storage, making it difficult to expand to actual semiconductor manufacturing. However, according to the polymer (A) of this embodiment, the stability of the resist composition is improved, and even in the case of long-term storage, the decrease in sensitivity to exposure light sources is suppressed.

[0325] The polymer (A) according to the present embodiment includes a structural unit derived from the compound (A).

[0326] The structural unit derived from the compound (A) is a structural unit represented by the following formula (4).

[0327]

[0328] In formula (4), X, L 1 , Y, R a , R b , R c , A, Z, p, m, n and r have the same definitions, specific examples and preferred ranges as in formula (1).

[0329] The polymer (A) is obtained by polymerizing the compound (A) of this 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 photolithography.

[0330] As the structural unit derived from the compound (A), a structural unit represented by the following formula (5) is preferred.

[0331]

[0332] In formula (5), X, L 1 , Y, A, p, m and n have the same definitions, specific examples and preferred ranges as in formula (1).

[0333] As the structural unit derived from the compound (A), a structural unit represented by the following formula (6) is more preferred.

[0334]

[0335] In formula (6), X, L 1 , Y, R a1 , R b1 , R c1 , A, Z, p, m, n and r have the same definitions, specific examples and preferred ranges as in formula (1b).

[0336] The amount of the structural unit derived from the compound (A) is preferably 5 mol% or more, more preferably 8 mol% or more, and further preferably 10 mol% or more relative to the total amount of the monomer components of the polymer (A). In addition, the amount of the structural unit derived from the compound (A) is 100 mol% or less, preferably 80 mol% or less, more preferably 70 mol% or less, and further preferably 30 mol% or less relative to the total amount of the monomer components of the polymer (A).

[0337] As one of the preferred modes of the polymer of the present embodiment, as the structural unit of the polymer (A), it is preferred to include at least a compound represented by formula (1) other than formula (1C) as the monomer represented by compound (A) and a compound represented by formula (1C). As the ratio of the monomer represented by formula (1C), it is preferred to include a small amount of 10 ppm or more and 10% by mass or less, more preferably 20 ppm or more and 2% by mass or less, and further preferably 50 ppm or more and 1% by mass or less, relative to the monomer represented by formula (1).

[0338] By setting the content of the compound represented by formula (1C) to the range described above, the interaction between resins during resinification can be reduced, and the crystallinity caused by the interaction between resins after film formation using the resin can be suppressed, thereby reducing the local solubility in the developer during development at the molecular level from several nanometers to tens of nanometers, and suppressing the reduction in pattern quality such as line edge roughness and residue defects of the pattern formed by the pattern forming process in a series of photolithography processes such as exposure, post-exposure baking, and development, thereby further improving the resolution.

[0339] Regarding the effects of these lithography properties, the compounds represented by formula (1) and the compounds represented by formula (1C) having a parent core A introduced with a halogen element, especially iodine or fluorine, have a shifted hydrophilicity and a greater polarization of the polar parts compared to the compounds having a hydroxystyrene skeleton without the introduction of iodine, etc., thereby increasing the effect in the monomer represented by formula (1C).

[0340] As other monomers copolymerized with the compound (A), it is preferred that the monomers contain, as polymerized units, an aromatic compound having an unsaturated double bond as a substituent and contain polymerized units having a functional group that improves solubility in an alkaline developer by the action of an acid or a base.

[0341] As other monomers, there is no particular limitation, and examples thereof include International Publication WO2016 / 125782, International Publication WO2015 / 115613, Japanese Patent Publication 2015 / 117305, International Publication WO2014 / 175275, Japanese Patent Publication 2012 / 162498, Japanese Patent Publication 2015-161823, paragraphs 0015 to 0131, paragraphs 0050 to 0059 of Japanese Patent Publication 7044011, paragraphs 0096 to 0125 of Japanese Patent Publication 2022-123839, or compounds represented by the following formula (C1) or formula (C2). Among these, compounds represented by the following formula (C1) or formula (C2) are preferred.

[0342] From the perspective of the quality of the pattern shape after exposure and development in the photolithography process, especially the roughness and pattern collapse suppression, the dissolution rate R of the resin in the alkaline developer, which is the unexposed part during exposure and becomes the pattern convex part during alkali development, is min The dissolution rate R of the resin in the alkaline developer is the same as the dissolution rate R of the resin in the exposed part during exposure, which becomes the concave part of the pattern during alkali development. max The difference is preferably greater than 3 orders of magnitude, preferably, the difference in dissolution rate caused by the presence or absence of the protecting group is large, and the rate of separation of the protecting group in post-exposure baking (PEB) and development is large. From these viewpoints, the other monomers copolymerized with the compound (A) in the polymer (A) preferably have a structural unit represented by the following formula (C1).

[0343]

[0344] In formula (C1),

[0345] R C11 is H or methyl,

[0346] R C12 is H or an alkyl group having 1 to 4 carbon atoms,

[0347] R C13 For R C13 The carbon atoms to which the bonding is applied together form a cycloalkyl or heterocycloalkyl group having 4 to 20 carbon atoms,

[0348] * is a bonding site to an adjacent structural unit.

[0349] R C12 Preferably, H or an alkyl group having 1 to 3 carbon atoms, R C13 Preferably with R C13 The carbon atoms to which they are bonded together form a cycloalkyl or heterocycloalkyl group having 4 to 10 carbon atoms. C13 The cycloalkyl group or heterocycloalkyl group optionally has a substituent (eg, an oxo group).

[0350] The amount of the structural unit represented by formula (C1) is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 20 mol% or more relative to the total amount of the monomer components of the polymer (A). In addition, the amount of the structural unit represented by formula (C1) is preferably 90 mol% or less, more preferably 80 mol% or less, and further preferably 70 mol% or less relative to the total amount of the monomer components of the polymer (A).

[0351] The other monomer copolymerized with the compound (A) in the polymer (A) is preferably a structural unit represented by the following formula (C2) from the viewpoint of the quality of the pattern shape after exposure and development in the photolithography process, particularly the roughness and suppression of pattern collapse.

[0352]

[0353] In formula (C2),

[0354] R C21 is H or methyl,

[0355] R C22 and R C23 are each independently an alkyl group having 1 to 4 carbon atoms,

[0356] R C24 is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms,

[0357] R C22 , R C23 and R C24 Two or three of them may form an alicyclic structure with 3 to 20 carbon atoms together with the carbon atoms to which they are bonded.

[0358] * is a bonding site to an adjacent structural unit.

[0359] R C22 Preferably, it is an alkyl group having 1 to 3 carbon atoms, C24 is a cycloalkyl group having 5 to 10 carbon atoms. C22 , R C23 and R C24 The alicyclic structure formed may include a plurality of rings, such as adamantyl group, etc. In addition, the alicyclic structure may have a substituent (such as a hydroxyl group or an alkyl group).

[0360] The amount of the structural unit represented by formula (C2) is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 20 mol% or more relative to the total amount of the monomer components of the polymer (A). In addition, the amount of the structural unit represented by formula (C2) is preferably 80 mol% or less, more preferably 60 mol% or less, and further preferably 40 mol% or less relative to the total amount of the monomer components of the polymer (A).

[0361] The monomer raw material of the structural unit represented by formula (C2) is not limited, 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)acryloyloxydecahydro-1,4:5,8-dimethylnaphthalene, 2-ethyl-2-(meth)acryloyloxynorbornane. Commercially available products can be used as these monomers.

[0362] The other monomer copolymerized with the compound (A) in the polymer (A) preferably has a structural unit represented by the following formula (C3).

[0363]

[0364] In formula (C3), R C31 is H or methyl, and m, A, and * are as defined in the above formula (4).

[0365] The other monomer copolymerized with the compound (A) in the polymer (A) preferably has a structural unit represented by the following formula (C4).

[0366]

[0367] In formula (C4), B represents an organic group having 5 to 30 carbon atoms and containing an aromatic ring, and R C31 , m, and * are as defined in the above formula (C3).

[0368] The other monomer copolymerized with the compound (A) in the polymer (A) preferably has a structural unit represented by the following formula (C5).

[0369]

[0370] In formula (C5), B' represents an organic group having 5 to 30 carbon atoms and containing an aromatic ring, and R C31 , m, and * are as defined in the above formula (C3).

[0371] Regarding other monomers copolymerized with compound (A) in polymer (A), from the viewpoint of exposure sensitivity of pattern formation after exposure and development in a photolithography process, quality of pattern shape, especially roughness or suppression of pattern collapse, preferably a structural unit represented by the following formula (C6).

[0372]

[0373] In formula (C6),

[0374] X C61 is a hydroxyl group or a halogen group,

[0375] R C61 are each independently an alkyl group having 1 to 20 carbon atoms,

[0376] * is a bonding site to an adjacent structural unit.

[0377] X C61 It is preferably F, Cl, Br or I, more preferably Cl or I, and even more preferably I. C61 An alkyl group having 1 to 4 carbon atoms is preferred, and a methyl group is more preferred.

[0378] The amount of the structural unit represented by formula (C6) is preferably 20 mol% or more, more preferably 30 mol% or more, and further preferably 40 mol% or more relative to the total amount of the monomer components of the 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 further preferably 60 mol% or less relative to the total amount of the monomer components of the polymer (A).

[0379] The monomer raw material of the structural unit represented by formula (C6) is not limited, and examples thereof include 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. Commercially available products can be used as these monomers.

[0380] Next, the method for producing the polymer (A) is described. Regarding the polymerization reaction, the monomers that will become the structural units are dissolved in a solvent, a polymerization initiator is added, and the polymerization is carried out while heating or cooling. The reaction conditions can be arbitrarily set according to the type of polymerization initiator, the initiation method such as heat or light, temperature, pressure, concentration, solvent, additives, etc. As the polymerization initiator, free radical polymerization initiators such as azoisobutyronitrile and peroxides, anionic polymerization initiators such as alkyl lithium and Grignard reagents can be listed.

[0381] As the solvent used in the polymerization reaction, a commercially available product that is generally available can be used. For example, various solvents such as alcohols, ethers, hydrocarbons, and halogen-based solvents can be used appropriately within the range that does not hinder the reaction. A variety of solvents can also be mixed and used within the range that does not hinder the above reaction.

[0382] The polymer (A) obtained by the polymerization reaction can be purified by a known method, specifically, by combining ultrafiltration, crystallization, microfiltration, acid washing, washing with water having an electrical conductivity of 10 mS / m or less, and extraction.

[0383] [Resin composition]

[0384] The resin composition of the present embodiment may include, for example, a polymer containing at least a structural unit represented by formula (4), a compound (B) represented by formula (2), and a compound (A) represented by formula (1). The number of structural units (number of monomer units) contained in the above-mentioned polymer is preferably 5 or more. The content of the compound (B) contained in the above-mentioned resin composition is preferably 1% by mass or less, more preferably 0.1% by mass or less, and further preferably 0.05% by mass or less relative to the above-mentioned polymer. The above-mentioned polymer may also be the above-mentioned polymer (A).

[0385] The above-mentioned polymer (polymer (A)) included in the resin composition of the present embodiment can be obtained by copolymerization of compound (A) and other monomers. The other monomers are not particularly limited, for example, can be International Publication WO2016 / 125782, International Publication WO2015 / 115613, Japanese Patent Publication 2015 / 117305, International Publication WO2014 / 175275 and Japanese Patent Publication 2012 / 162498, Japanese Patent Publication 2015-161823 Communique, Japanese Patent Publication 7044011 Communique, paragraphs 0050 to 0059, Japanese Patent Publication 2022-123839, paragraphs 0096 to 0125, at least a portion of the monomers recorded. In addition, the other monomer is not particularly limited, and may be, for example, a compound having a structural unit represented by formula (C1), formula (C2), formula (C3), formula (C4), formula (C5) or formula (C6).

[0386] The above-mentioned polymer contained in the resin composition of this embodiment is preferably obtained by copolymerization of compound (A) and a compound having a structural unit represented by formula (C6) from the viewpoint of pattern shape. That is, the above-mentioned polymer contained in the resin composition of this embodiment may further contain a structural unit represented by formula (C6).

[0387] [Film-forming composition]

[0388] The film-forming composition of the present embodiment may include compound (A) or polymer (A) and compound (B), and is particularly suitable for photolithography. In addition, the film-forming composition of the present embodiment may contain the above-mentioned composition of the present embodiment, or the above-mentioned resin composition of the present embodiment. Although not particularly limited, the above-mentioned composition can be used for photolithography film formation purposes, such as anti-etching film formation purposes (i.e., "anti-etching composition"). Furthermore, the above-mentioned composition can be used for upper film formation purposes (i.e., "upper film forming composition"), middle layer formation purposes (i.e., "middle layer forming composition"), lower film formation purposes (i.e., "lower film forming composition"), etc. According to the composition of the present embodiment, a film with high sensitivity can be formed, and a good anti-etching pattern shape can also be given.

[0389] The film-forming composition of the present embodiment can also be used as an optical component forming composition for applying photolithography. The optical component can be used not only in a film-like or sheet-like form, but also as a plastic lens (prism lens, cylindrical lens, microlens, Fresnel lens, field angle control lens, contrast enhancement lens, etc.), a phase difference film, an electromagnetic shielding film, a prism, an optical fiber, a solder resist for flexible printed wiring, a plating resist, an interlayer insulating film for a multilayer printed circuit board, a photosensitive optical waveguide, a liquid crystal display, an organic electroluminescent (EL) display, a light semiconductor (LED) element, a solid-state imaging element, an organic thin film solar cell, a dye-sensitized solar cell, and an organic thin film transistor (TFT). The aforementioned composition can be suitably used as a member of a solid-state imaging element that particularly requires a high refractive index, a buried film on a photodiode and a flattening film, a flattening film before and after a color filter, a microlens, a flattening film on a microlens, and a conformal film.

[0390] As another preferred embodiment of the composition of this embodiment, the compound (B) preferably contains a small amount of more than 1 mass ppm and less than 10 mass %, more preferably more than 20 mass ppm and less than 2 mass %, and preferably more than 50 mass ppm and less than 1 mass %, relative to the compound (A) or the polymer (A).

[0391] By setting the content of compound (B) to the described range, the mechanism has not yet been determined, but compound (B) effectively and actively captures free radicals generated by heat, etc., inhibits the deterioration of compound (A) or the compound represented by polymer (A) in the composition, and inhibits the generation of trace amounts of particulate foreign matter, thereby inhibiting defects in the obtained film and the pattern after development caused by time.

[0392] The film-forming composition of the present embodiment may further include an acid generator (C), a base generator (G) or a base compound (H). In addition, the film-forming composition of the present embodiment includes the compound (A) or the polymer (A) and the compound (B), and may also include other components such as a base material (D), a solvent (S) or an acid diffusion controller (E) as required. Each component is described below.

[0393] [Base material (D)]

[0394] In the present embodiment, "substrate (D)" refers to a compound (including resin) other than compound (A) or polymer (A), and is suitable for use as a substrate (for example, a substrate for lithography, a substrate for resist) for g-rays, i-rays, KrF excimer lasers (248nm), ArF excimer lasers (193nm), extreme ultraviolet (EUV) lithography (13.5nm) or electron beam (EB) resists. If these substrates, then there is no particular limitation and can be used as the substrate (D) in the present embodiment. As substrate (D), for example, phenol novolac resin, cresol phenol novolac resin, hydroxystyrene resin, (methyl) acrylic resin, hydroxystyrene-(methyl) acrylic copolymer, cycloolefin-maleic anhydride copolymer, cycloolefin, vinyl ether-maleic anhydride copolymer, and inorganic resist materials with metal elements such as titanium, tin, hafnium, zirconium, and their derivatives. Among them, from the viewpoint of the shape of the obtained resist pattern, preferred are phenol novolac resins, cresol phenol novolac resins, hydroxystyrene resins, (meth)acrylic resins, hydroxystyrene-(meth)acrylic copolymers, and inorganic resist materials having metal elements such as titanium, tin, hafnium or zirconium, and their derivatives.

[0395] The derivative is not particularly limited, and examples thereof include derivatives into which a dissociative group is introduced, derivatives into which a crosslinking group is introduced, etc. The derivatives into which a dissociative group or a crosslinking group is introduced can undergo a dissociation reaction or a crosslinking reaction by the action of light, acid, or the like.

[0396] The "dissociative group" refers to a characteristic group that is cleaved to generate a functional group such as an alkali-soluble group that changes solubility. The alkali-soluble group is not particularly limited, and examples thereof include a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, and a hexafluoroisopropanol group. Phenolic hydroxyl groups and carboxyl groups are preferred, and phenolic hydroxyl groups are particularly preferred.

[0397] The "crosslinkable group" refers to a group that undergoes crosslinking in the presence of a catalyst or in the absence of a catalyst. The crosslinkable group is not particularly limited, and examples thereof include 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 carbamate (meth)acryloyl group, a group having a glycidyl group, and a group having a vinylphenylmethyl group.

[0398] [Solvent (S)]

[0399] As the solvent in the present embodiment, any known solvent can be appropriately used as long as it can dissolve at least the compound (A) or the polymer (A). The solvent is not particularly limited, and examples thereof include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol mono-n-butyl ether acetate; 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 mono-n-propyl ether acetate, and propylene glycol mono-n-butyl ether acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether; lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, and n-pentyl lactate; methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-pentyl acetate, n-hexyl acetate, methyl propionate; 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, ethyl pyruvate and other esters; aromatic hydrocarbons such as toluene and xylene; ketones such as acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone (CPN), cyclohexanone (CHN); amides such as N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone and the like; 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 further preferably at least one selected from PGMEA, PGME, CHN, CPN and ethyl lactate.

[0400] In the film-forming composition of this embodiment, the solid content concentration is not particularly limited, but is preferably 1 to 80 mass %, more preferably 1 to 50 mass %, further preferably 2 to 40 mass %, and further preferably 2 to 10 mass % relative to the total mass of the film-forming composition.

[0401] [Acid generator (C)]

[0402] In the film-forming composition of the present embodiment, it is preferred to include one or more acid generators (C) that directly or indirectly generate acid by 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 light (EUV), X-ray and ion beam. The acid generator (C) is not particularly limited, and for example, the acid generator described in International Publication No. WO2013 / 024778 can be used. The acid generator (C) can be used alone or in combination of two or more.

[0403] The amount of the acid generator (C) is preferably 0.001 to 49% by mass, more preferably 1 to 40% by mass, further preferably 3 to 30% by mass, and further preferably 10 to 25% by mass relative to the total mass of the solid component. By using the acid generator (C) within the aforementioned range, there is a tendency to obtain a pattern profile with high sensitivity and low edge roughness. In the present embodiment, as long as 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, more fine processing can be performed. In addition, if electron beams, extreme ultraviolet rays, X-rays, and ion beams are used as high-energy rays, further fine processing can be performed.

[0404] [Acid diffusion controller (E)]

[0405] The film-forming composition of the present embodiment may contain an acid diffusion controller (E). The acid diffusion controller (E) controls the diffusion of the acid generated by the acid generator by radiation irradiation in the resist film, preventing undesired chemical reactions from occurring in the unexposed area. By using the acid diffusion controller (E), there is a tendency to improve the storage stability of the composition of the present embodiment. In addition, by using the acid diffusion controller (E), there is a tendency to improve the resolution of the film formed using the composition of the present embodiment, and the line width change of the resist pattern caused by the change of the standby time before the radiation irradiation and the standby time after the radiation irradiation can be suppressed, and the process stability becomes excellent. As the acid diffusion controller (E), it is not particularly limited, and radiation-decomposable basic compounds such as basic compounds containing nitrogen atoms, basic sulfonium compounds, and basic iodonium compounds can be listed.

[0406] The acid diffusion controller (E) is not particularly limited, and for example, the acid diffusion controllers described in International Publication No. WO2013 / 024778 can be used. The acid diffusion controller (E) can be used alone or in combination of two or more.

[0407] The amount of the acid diffusion controller (E) is preferably 0.001 to 49% by mass, more preferably 0.01 to 10% by mass, further preferably 0.01 to 5% by mass, and further preferably 0.01 to 3% by mass relative to the total mass of the solid component. When the amount of the acid diffusion controller (E) is within the above range, there is a tendency to prevent degradation of the resolution, pattern shape, dimensional fidelity, etc. Furthermore, even if the waiting time from electron beam irradiation to heating after radiation irradiation is long, the shape degradation of the upper layer of the pattern can be suppressed. In addition, when the amount of the acid diffusion controller (E) is less than 10% by mass, there is a tendency to prevent the sensitivity, the developability of the unexposed part, etc. from being reduced. In addition, by using this acid diffusion controller, there is a tendency that the storage stability of the resist composition is improved, and the resolution is improved, and the line width change of the resist pattern caused by the change of the waiting time before radiation irradiation and the waiting time after radiation irradiation can be suppressed, and the process stability becomes excellent.

[0408] [Alkali generating agent (G)]

[0409] The case where the base generator (G) is a photobase generator will be described.

[0410] The photobase generator is a substance that generates a base by exposure to light, and is not particularly limited as long as it is inactive under normal conditions of room temperature and pressure but generates a base (alkaline substance) when irradiated with electromagnetic waves or heated as external stimuli.

[0411] The photobase generator that can be used in the present embodiment is not particularly limited and any known photobase generator can be used. Examples thereof include carbamate derivatives, amide derivatives, imide derivatives, α-cobalt complexes, imidazole derivatives, cinnamamide derivatives, and oxime derivatives.

[0412] The basic substance generated by the photobase generator is not particularly limited, and examples thereof include compounds having an amino group, particularly polyamines such as monoamines and diamines, and amidines, etc. The generated basic substance is preferably a compound having an amino group with a higher basicity (higher pKa value of the conjugate acid) from the viewpoint of sensitivity and resolution.

[0413] Examples of the photobase generator include base generators having a cinnamamide structure as disclosed in Japanese Unexamined Patent Application Publication No. 2009-80452 and International Publication No. 2009 / 123122, base generators having a carbamate structure as disclosed in Japanese Unexamined Patent Application Publication No. 2006-189591 and Japanese Unexamined Patent Application Publication No. 2008-247747, base generators having an oxime structure or a carbamoyl oxime structure as disclosed in Japanese Unexamined Patent Application Publication No. 2007-249013 and Japanese Unexamined Patent Application Publication No. 2008-003581, and compounds described in Japanese Unexamined Patent Application Publication No. 2010-243773, but the present invention is not limited to these, and other known base generator structures may also be used.

[0414] The photobase generator may be used alone or in combination of two or more.

[0415] The preferred content of the photobase generator in the active light-sensitive or radiation-sensitive resin composition is the same as the preferred content of the aforementioned photoacid generator in the active light-sensitive or radiation-sensitive resin composition.

[0416] [Basic compound (H)]

[0417] The basic compound (H) is not particularly limited, and the basic compounds described in International Publication No. WO2013 / 024778 can be used. The basic compound (H) can be used alone or in combination of two or more.

[0418] The amount of the alkali compound (H) to be added is preferably 0.001 to 49% by mass, more preferably 0.01 to 5% by mass, and even more preferably 0.01 to 3% by mass, based on the total mass of the solid content.

[0419] [Other ingredients (F)]

[0420] In the film-forming composition of the present embodiment, as other components (F), one or more of various additives such as a crosslinking agent, a dissolution accelerator, a dissolution control agent, a sensitizer, a surfactant, and an organic carboxylic acid or an oxyacid of phosphorus or a derivative thereof may be added as necessary.

[0421] (Crosslinking agent)

[0422] 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 (D). As the crosslinking agent, it is preferably an acid crosslinking agent that can crosslink the substrate (D) intramolecularly or intermolecularly in the presence of an acid generated by the acid generator (C). As such an acid crosslinking agent, for example, a compound having one or more groups (hereinafter referred to as "crosslinking groups") that can crosslink the substrate (D) can be cited.

[0423] Examples of the crosslinking group include (i) hydroxyalkyl groups such as 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), and acetoxy groups (alkyl groups having 1 to 6 carbon atoms), 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 having a nitrogen-containing group such as dimethylaminomethyl groups, diethylaminomethyl groups, dihydroxymethylaminomethyl groups, dihydroxyethylaminomethyl groups, and morpholinomethyl groups; (iv) groups containing a glycidyl group such as a glycidyl ether group, a glycidyl ester group, and a glycidylamino group; (v) groups derived from aromatic groups such as a benzyloxymethyl group, a benzoyloxymethyl group, and an allyloxy group having 1 to 6 carbon atoms (alkyl groups having 1 to 6 carbon atoms), and an aralkyloxy group having 1 to 6 carbon atoms (alkyl groups having 1 to 6 carbon atoms); and (vi) groups containing a polymerizable multiple bond such as a vinyl group and an isopropenyl group. As the crosslinkable group of the crosslinking agent in the present embodiment, a hydroxyalkyl group, an alkoxyalkyl group, and the like are preferred, and an alkoxymethyl group is particularly preferred.

[0424] The crosslinking agent having a crosslinkable group is not particularly limited, and for example, an acid crosslinking agent described in International Publication No. WO2013 / 024778 can be used. The crosslinking agent can be used alone or in combination of two or more.

[0425] In the present embodiment, the amount of the crosslinking agent blended is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and further preferably 20% by mass or less, based on the total mass of the solid content.

[0426] (Dissolution accelerator)

[0427] The dissolution promoter is a component that has the effect of improving the solubility of the solid component in the developer when the solubility is too low, and appropriately increasing the dissolution rate of the aforementioned compound during development. As the dissolution promoter, preferably a low molecular weight one, for example, a low molecular weight phenolic compound can be listed. As the low molecular weight phenolic compound, for example, bisphenols, tris (hydroxyphenyl) methane, etc. can be listed. These dissolution promoters can be used alone or in combination of two or more.

[0428] The amount of the dissolution promoter added is appropriately adjusted depending on the type of the solid component 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, based on the total mass of the solid component.

[0429] (Dissolution Control Agent)

[0430] The dissolution control agent is a component that has the function of controlling the solubility of the solid component in the developer when the solubility is too high, and appropriately reducing the dissolution rate during development. As such a dissolution control agent, it is preferred that the material does not undergo chemical changes during the steps of baking, radiation irradiation, and development of the resist film.

[0431] The dissolution control agent is not particularly limited, and examples thereof include aromatic hydrocarbons such as phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenylnaphthyl ketone; sulfones such as methyl phenyl sulfone, diphenyl sulfone, and dinaphthyl sulfone, etc. These dissolution control agents may be used alone or in combination of two or more.

[0432] The amount of the dissolution control agent is appropriately adjusted depending on the type of the 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, based on the total mass of the solid content.

[0433] (Sensitizer)

[0434] The sensitizer is a component that absorbs the energy of the irradiated radiation and transfers the energy to the acid generator (C), thereby increasing the amount of acid generated and improving the apparent sensitivity of the resist. Examples of such sensitizers include benzophenones, diacetyl groups, pyrenes, phenothiazines, fluorenes, etc., but are not particularly limited. These sensitizers can be used alone or in combination of two or more.

[0435] The amount of the sensitizer added is appropriately adjusted depending on the type of the 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, based on the total mass of the solid content.

[0436] (Surfactant)

[0437] Surfactant is a component that has the effect of improving the coating property, stripe (striation), and the developability of the resist of the composition of the present embodiment. Surfactant can be any one of anionic surfactant, cationic surfactant, nonionic surfactant or amphoteric surfactant. As a preferred surfactant, nonionic surfactant can be listed. The nonionic surfactant has good affinity with the solvent used in the manufacture of the composition of the present embodiment, which can further improve the effect of the composition of the present embodiment. As an example of nonionic surfactant, polyoxyethylene high alkyl ethers, polyoxyethylene high alkyl phenyl ethers, and high fatty acid diesters of polyethylene glycol can be listed, without particular limitation. As commercial products of these surfactants, the following trade names Eftop (manufactured by JEMCO), MEGAFAC (manufactured by Dainippon Ink and Chemicals), FLUORAD (manufactured by Sumitomo 3M), AsahiGuard, Surflon (manufactured by Asahi Glass Co., Ltd.), Pepol (manufactured by Toho Chemical Industry Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), Polyflow (manufactured by Kyoeisha Oil and Fat Chemical Industry Co., Ltd.), etc. can be listed.

[0438] The amount of the surfactant added is appropriately adjusted depending on the type of the solid component 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, based on the total mass of the solid component.

[0439] (Organic carboxylic acid or phosphorus oxygen acid or its derivative)

[0440] In order to prevent sensitivity degradation or improve the purpose of resist pattern shape, standby stability, etc., organic carboxylic acid or oxyacid of phosphorus or its derivatives can also be contained as arbitrary components. It should be noted that organic carboxylic acid or oxyacid of phosphorus or its derivatives can be used in combination with acid diffusion control agent, or can be used alone. As organic carboxylic acid, for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, etc. are suitable. As oxyacid of phosphorus or its derivatives, derivatives such as phosphoric acid or their esters such as phosphoric acid, di-n-butyl phosphate, diphenyl phosphate, phosphonic acid, dimethyl phosphonate, di-n-butyl phosphonate, phenylphosphonic acid, diphenyl phosphonate, phosphonic acid or their esters such as phosphinic acid, phenylphosphinic acid and their esters can be listed. Among these, phosphonic acid is particularly preferred.

[0441] The organic carboxylic acid or the oxyacid of phosphorus or its derivatives can be used alone or in combination of two or more. The amount of the organic carboxylic acid or the oxyacid of phosphorus or its derivatives is appropriately adjusted according to the type of the aforementioned compound used, preferably 0 to 49% by mass of the total mass of the solid content, more preferably 0 to 5% by mass, further preferably 0 to 1% by mass, and particularly preferably 0% by mass.

[0442] [Other additives]

[0443] Furthermore, in the composition of the present embodiment, one or more additives other than the above-mentioned components can be mixed as needed. As such additives, for example, dyes, pigments and bonding aids can be listed. For example, when a dye or a pigment is mixed, the latent image of the exposure portion is visualized, and the influence of the halo during exposure can be alleviated, so it is preferred. In addition, when a bonding aid is mixed, the adhesion to the substrate can be improved, so it is preferred. Furthermore, as other additives, halo preventers, storage stabilizers, defoamers, shape modifiers, etc. can be listed, specifically 4-hydroxy-4'-methyl chalcone, etc.

[0444] In the composition of this embodiment, the total amount of the optional component (F) can be set to 0 to 99 mass % of the total mass of the solid content, preferably 0 to 49 mass %, more preferably 0 to 10 mass %, further preferably 0 to 5 mass %, further preferably 0 to 1 mass %, and particularly preferably 0 mass %.

[0445] [Method for forming resist pattern]

[0446] The method for forming the resist pattern of the present embodiment includes:

[0447] a step of forming a resist film on a substrate using the film-forming composition of the present embodiment;

[0448] A step of exposing the resist film pattern; and

[0449] A step of developing the resist film after the exposure.

[0450] The film-forming composition of the present embodiment contains, for example, the compound (A) or the polymer (A) and the compound (B), as described above.

[0451] There is no particular limitation on the coating method in the process of forming the resist film, and examples thereof include a spin coater, a dip coater, and a roll coater. There is no particular limitation on the substrate, and examples thereof include a silicon wafer, a metal, a plastic, a glass, and a ceramic. After the resist film is formed, a heat treatment may be performed at a temperature of about 50° C. to 200° C. The film thickness of the resist film is not particularly limited, and examples thereof include 50 nm to 1 μm.

[0452] In the exposure process, exposure can be performed across a prescribed mask pattern, or unit (shot) exposure can be performed without a mask. The thickness of the coating is, for example, 0.1 to 20 μm, preferably about 0.3 to 2 μm. Light of various wavelengths, such as ultraviolet rays, X-rays, etc., can be used in the exposure. For example, as a light source, far ultraviolet rays, extreme ultraviolet rays (wavelength 13n), X-rays, electron beams, etc. such as F2 excimer lasers (wavelength 157nm), ArF excimer lasers (wavelength 193nm), and KrF excimer lasers (wavelength 248nm) are appropriately selected. Among these, extreme ultraviolet rays are preferred. In addition, exposure conditions such as exposure amount are appropriately selected according to the compounding composition of the above-mentioned resins and / or compounds, the types of various additives, etc.

[0453] In this embodiment, in order to stably form a fine pattern with high precision, it is preferred to perform a heat treatment at a temperature of 50 to 200° C. for more than 30 seconds after exposure. At this time, when the temperature is less than 50° C., there is a concern that the sensitivity unevenness caused by the type of substrate will expand. Then, the alkali developer is used to develop under the conditions of usually 10 to 50° C. for 10 to 200 seconds, preferably 20 to 25° C. for 15 to 90 seconds, thereby forming a predetermined resist pattern.

[0454] As the above-mentioned alkaline developer, for example, an alkaline aqueous solution obtained by dissolving alkaline compounds such as alkali metal hydroxides, 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 in a concentration of usually 1 to 10% by mass, preferably 1 to 3% by mass, is used. In addition, a water-soluble organic solvent or a surfactant may be appropriately added to the developer formed by the above-mentioned alkaline aqueous solution.

[0455] The composition of the present embodiment can also be used as an optical component forming composition for applying photolithography. The optical component can be used not only in a film-like or sheet-like form, but also as a plastic lens (prism lens, cylindrical lens, microlens, Fresnel lens, field angle control lens, contrast enhancement lens, etc.), a phase difference film, an electromagnetic shielding film, a prism, an optical fiber, a solder resist for flexible printed wiring, a plating resist, an interlayer insulating film for a multilayer printed circuit board, a photosensitive optical waveguide, a liquid crystal display, an organic electroluminescent (EL) display, a light semiconductor (LED) element, a solid-state imaging element, an organic thin film solar cell, a dye-sensitized solar cell, and an organic thin film transistor (TFT). The aforementioned composition can be suitably used as a member of a solid-state imaging element particularly requiring a high refractive index, a buried film on a photodiode and a flattening film, a flattening film before and after a color filter, a microlens, a flattening film on a microlens, and a conformal film.

[0456] In addition, the composition of the present embodiment can be used as a patterning material for photolithography purposes. As the purpose of photolithography, it can be used for various purposes such as semiconductors, liquid crystal display panels, display panels using OLED, power devices, CCD or other sensors. When facing the integrated circuit of semiconductors and devices in particular, the composition of the present embodiment can be suitably used for the following purposes: forming device elements on silicon wafers, based on the pattern formed by the composition of the present embodiment on the upper surface side of insulating layers such as silicon oxide films and other oxide films, by etching the insulating film on the substrate side to form a pattern, and then based on the insulating film pattern formed, stacking metal films and semiconductor materials, forming a circuit pattern, thereby constructing semiconductor elements or other devices.

[0457] Example

[0458] Hereinafter, the present invention will be described in further detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples at all.

[0459] [Measurement method]

[0460] [Nuclear Magnetic Resonance (NMR)]

[0461] The structure of the compound was confirmed by NMR measurement under the following conditions using a nuclear magnetic resonance apparatus "Advance 600II spectrometer" (product name, manufactured by Bruker Corporation).

[0462] [ 1 H-NMR measurement]

[0463] Frequency: 400MHz

[0464] Solvent: CDCl3 or d6-DMSO

[0465] Internal standard: TMS

[0466] Measurement temperature: 23°C

[0467] [ 13 C-NMR measurement]

[0468] Frequency: 500MHz

[0469] Solvent: CDCl3 or d6-DMSO

[0470] Internal standard: TMS

[0471] Measurement temperature: 23°C

[0472] [Inorganic element content]

[0473] The metal contents contained in the compounds prepared in Examples and Comparative Examples were measured using an inorganic element analysis (ICP-AES / ICP-MS) apparatus “AG8900” (product name, manufactured by Agilent Technologies, Inc.).

[0474] [Organic impurity content]

[0475] The content of organic impurities contained in the compounds prepared in Examples and Comparative Examples was calculated from the area fraction of the GC chart and the peak intensity ratio between the target peak and the reference peak by gas chromatography-mass spectrometry (GC-MS).

[0476] (Synthesis Example BP1) Synthesis of Compound BP1 Represented by Formula (BP1)

[0477] The compound BP1 (trans isomer) represented by the formula (BP1) was synthesized by the method described below.

[0478]

[0479] 15.6 g of 1-(4-hydroxy-3,5-diiodophenyl)ethanol, 0.15 g of methanesulfonic acid, 0.04 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical, and 60 mL of DMSO (dimethyl sulfoxide) were added to the reaction vessel and stirring was started. Next, the decompression conditions of reflux at 120 ° C using Dean-Stark and a condenser were adjusted, and air at a flow rate of 1 mL / min was blown into the reaction solution. It should be noted that the water recovered in the Dean-Stark was appropriately discharged to the outside of the system. Next, the reaction vessel was immersed in a 90 ° C water bath and continued to stir for 30 hours. Next, the reaction vessel was immersed in a 25 ° C water bath and the reaction solution was cooled. Next, the reaction solution was slowly added to 500 g of a 0.1% by mass sodium bisulfite aqueous solution while vigorously stirring and mixing. Next, the precipitate was filtered by suction filtration, squeezed, and washed with 200 mL of a 33.3% by volume methanol aqueous solution. The obtained precipitate was separated into only the main component (trans isomer) by column generation, and the solvent was distilled off by evaporation. The obtained solid was vacuum dried at 40° C. to obtain 8.1 g of a white solid. The yield was 26%.

[0480] As a result of liquid chromatography-mass spectrometry (LC-MS) analysis, the molecular weight was confirmed to be 743.9, and it was confirmed to be compound BP1 represented by formula (BP1).

[0481] In addition, under the above-mentioned measurement conditions 1 As a result of H-NMR measurement, the following peaks were observed, confirming that the compound had a chemical structure of Compound BP1.

[0482] δ (ppm) (d6-DMSO): 9.6 (2H, OH), 7.5 (2H, Ph), 7.8 (2H, Ph), 3.6 (1H, -CH-), 1.3 (3H, -CH3), 6.4~6.7 (2H, -CH=CH-)

[0483] (Synthesis Example BP2) Synthesis of Compound BP2 Represented by Formula (BP2)

[0484] The compound BP2 (trans isomer) represented by the formula (BP2) was synthesized by the method described below.

[0485]

[0486] 1-(4-hydroxy-3-methoxy-5-iodophenyl)ethanol 11.8g, methanesulfonic acid 0.2g, 4-methoxyphenol 0.15g, toluene 60mL were added to the reaction vessel and stirring was started. Then, using Dean-Stark and condenser at 113°C reflux conditions, air at a flow rate of 1mL / minute was blown into the reaction solution. It should be noted that the water recovered in the Dean-Stark was appropriately discharged to the outside of the system. Then, the reaction vessel was immersed in a 90°C water bath and continued to stir for 30 hours. Then, the reaction vessel was immersed in a 25°C water bath and the reaction solution was cooled. Then, the reaction solution was slowly added to 500g of a 0.1% by mass sodium bisulfite aqueous solution while vigorously stirring and mixing. Then, the precipitate was filtered and squeezed by suction filtration, and washed with 200mL of a 33.3% by volume methanol aqueous solution. The obtained precipitate was passed through a column to separate only the main component (trans isomer), and then the solvent was distilled off by evaporation, and the obtained solid was vacuum dried at 40°C to obtain 10.2 g of a white solid. The yield was 43%.

[0487] As a result of liquid chromatography-mass spectrometry (LC-MS) analysis, a molecular weight of 552.2 was confirmed, and it was confirmed to be compound BP2 represented by formula (BP2).

[0488] In addition, under the above-mentioned measurement conditions 1 As a result of H-NMR measurement, the following peaks were observed, confirming that the compound had a chemical structure of BP2.

[0489] δ (ppm) (d6-DMSO): 9.6 (2H, OH), 7.0~7.2 (2H, Ph), 6.7 (1H, Ph), 7.5 (1H, Ph), 3.6 (1H, -CH-), 1.3 (3H, -CH3), 6.4~6.7 (2H, -CH=CH-), 3.8 (6H, -CH3)

[0490] (Synthesis Example BP3) Synthesis of Compound BP3 Represented by Formula (BP3)

[0491] The compound BP3 represented by the formula (BP3) was synthesized by the method described below.

[0492]

[0493] The following steps were carried out using the compound BP1 synthesized above.

[0494] Using a 1L eggplant flask, add 1.57g of acetic anhydride, 1.53g of triethylamine, 0.19g of DMAP, and 35mL of solvent (dichloromethane) at 4°C with ice water, and stir to dissolve to prepare a reaction solution. Under a state cooled to 4°C, 7.43g10mmol of the compound BP1 (trans isomer) prepared in the previous step is dissolved in 10mL of dichloromethane to prepare a solution of compound BP1, and the prepared solution is added to a 1L eggplant flask over 30 minutes. Then stir at 4°C for 2 hours, and after sufficient reaction, wash with 40mL of ice water and 40mL of brine, dry the obtained organic phase with magnesium sulfate, and concentrate the filtered filtrate under reduced pressure to obtain a reaction product. Furthermore, 6.7g of the target compound BP3 is prepared by purifying using a column and distilling off the developing solvent.

[0495] In addition, under the above-mentioned measurement conditions 1 As a result of H-NMR measurement, the following peaks were observed, confirming that the compound had a chemical structure of BP3.

[0496] δ (ppm) (d6-DMSO): 2.3 (6H, -CH3), 7.7 (2H, Ph), 8.0 (2H, Ph), 1.3 (3H, -CH3), 3.6 (1H, -CH-), 6.4~6.7 (2H, -CH=CH-)

[0497] (Synthesis Example BP4) Synthesis of Compound BP4 Represented by Formula (BP4)

[0498] The compound BP4 represented by the formula (BP4) was synthesized by the method described below.

[0499]

[0500] The following steps were carried out using the compound BP2 (trans isomer) synthesized above.

[0501] Using a 1L eggplant flask, add 1.57g of acetic anhydride, 1.53g of triethylamine, 0.19g of DMAP (4-dimethylaminopyridine), and 35mL of solvent (dichloromethane) at 4°C with ice water, and stir to dissolve to prepare a reaction solution. Under a state cooled to 4°C, 7.43g (10mmol) of the compound BP2 prepared in the previous step is dissolved in 10mL of dichloromethane to prepare a solution of compound BP2, and the prepared solution is added to a 1L eggplant flask over 30 minutes. Then stir at 4°C for 2 hours, and after sufficient reaction, wash with 40mL of ice water and 40mL of brine, dry the obtained organic phase with magnesium sulfate, and concentrate the filtered filtrate under reduced pressure to obtain a reaction product. Furthermore, 7.1g of the target compound BP4 is prepared by column purification and distilling off the developing solvent.

[0502] In addition, under the above-mentioned measurement conditions 1 As a result of H-NMR measurement, the following peaks were observed, confirming that the compound had a chemical structure of BP4.

[0503] δ (ppm) (d6-DMSO): 2.3 (6H, -CH3), 6.9~7.7 (4H, Ph), 1.3 (3H, -CH3), 3.6 (1H, -CH-), 6.3~6.7 (2H, -CH=CH-), 3.8 (6H, -CH3)

[0504] (Synthesis Example BP11) Synthesis of Compound BP11 Represented by Formula (BP11)

[0505] Compound BP11 represented by formula (BP11) was synthesized by the method described below.

[0506]

[0507] 15.6 g of 1-(4-hydroxy-3,5-diiodophenyl)ethanol, 0.15 g of methanesulfonic acid, 0.04 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical, and 60 mL of DMSO were added to the reaction vessel and stirring was started. Next, the decompression conditions of reflux at 120 ° C using Dean-Stark and a condenser were adjusted, and air at a flow rate of 1 mL / min was blown into the reaction solution. It should be noted that the water recovered in the Dean-Stark was appropriately discharged to the outside of the system. Next, the reaction vessel was immersed in a 90 ° C water bath and continued to stir for 30 hours. Next, the reaction vessel was immersed in a 25 ° C water bath and the reaction solution was cooled. Next, the reaction solution was slowly added to 500 g of a 0.1 mass% concentration of sodium bisulfite aqueous solution while vigorously stirring and mixing. Next, the precipitate was filtered and squeezed by suction filtration and washed with 200 mL of a 33.3 volume% concentration of methanol aqueous solution. The obtained precipitate was passed through a column to separate and prepare the oligomer component, and then the solvent was distilled off by evaporation, and the obtained solid was vacuum dried at 40° C. to obtain 11.2 g of a white solid. The yield was 36%.

[0508] The molecular weights were confirmed to be 743.9, 1115.8, 1487.7, and 1859.6 by mass spectrometry (FD-MS) analysis, and liquid chromatography-mass spectrometry (LC-MS) confirmed that the compound contained the same components as BP11. These analysis results confirmed that the compound was BP11 represented by the formula (BP11).

[0509] (Synthesis Example BP12) Synthesis of Compound BP12 Represented by Formula (BP12)

[0510] Compound BP12 represented by formula (BP12) was synthesized by the method described below.

[0511]

[0512] 1-(4-hydroxy-3-methoxy-5-iodophenyl)ethanol 11.8g, methanesulfonic acid 0.2g, 4-methoxyphenol 0.15g, toluene 60mL were added to the reaction vessel and stirring was started. Then, using Dean-Stark and a condenser, air at a flow rate of 1mL / minute was blown into the reaction solution under reflux conditions at 113°C. It should be noted that the water recovered in the Dean-Stark was appropriately discharged to the outside of the system. Then, the reaction vessel was immersed in a 90°C water bath and continued to stir for 30 hours. Then, the reaction vessel was immersed in a 25°C water bath and the reaction solution was cooled. Then, the reaction solution was slowly added to 500g of a 0.1% by mass sodium bisulfite aqueous solution while vigorously stirring and mixed. Then, the precipitate was filtered and squeezed by suction filtration and washed with 200mL of a 33.3% by volume methanol aqueous solution. The obtained precipitate was passed through a column to separate and prepare the oligomer component, and then the solvent was distilled off by evaporation. The obtained solid was vacuum dried at 40°C to obtain 12.3 g of a white solid. The yield was 52%.

[0513] The results of mass spectrometry (FD-MS) analysis confirmed molecular weights of 552.2, 828.2, 1104.2, and 1380.2. In addition, the results of LC-MS analysis confirmed that the same components as BP12 were contained. From the above analysis results, it was confirmed that it was the compound BP12 represented by the formula (BP12).

[0514] (Synthesis Examples A1 to A16, ACL1, AMD3 to AMD4, AH2, AR1 to AR-2) Synthesis of Compounds A1 to A16, ACL1, AMD3 to AMD4, AH2, AR1 to AR-2 Represented by Formulas (A1) to (A16), (ACL1), (AMD3) to (AMD4), (AH2), and (AR-1) to (AR-2)

[0515] The compounds represented by formulas (M1) to (M16), (MCL1), (MD3) to (MD4), (MH2), and (MR-1) to (MR-2) described in International Publication No. WO2021 / 029395 (hereinafter referred to as (compounds A1 to A16, ACL1, AMD3 to AMD4, AH2, AR1 to AR-2) were synthesized according to the description of International Publication No. WO2021 / 029395).

[0516]

[0517]

[0518]

[0519] (Synthesis Example Aa1) Synthesis of Compound Ma1 Represented by Formula (Ma1)

[0520] A 3L glass flask was used as a reaction vessel, and 283g (792mmol) of methyltriphenylphosphine bromide, 7mg of methylhydroquinone, and 1470mL of dehydrated THF were placed therein and dissolved. After adding 148g (1320mmol) of potassium tert-butoxide to the THF solution in an ice bath while adjusting to below 15°C, the mixture was stirred for 30 minutes in this state. Furthermore, after adding 147g (529mmol) of 4-hydroxy-3-iodo-5-methoxybenzaldehyde in portions while adjusting to below 25°C, the mixture was stirred for 30 minutes in this state. Then, the reaction solution was added to 4000mL of 3N HCl aqueous solution, and then further washed with 1L of toluene and 2L of water in sequence. 128g of 4-hydroxy-3-iodo-5-methoxystyrene shown as the target substance of formula (Ma1) was separated by a silica gel column.

[0521] As a result of liquid chromatography-mass spectrometry (LC-MS) analysis, a molecular weight of 276 was confirmed.

[0522] In addition, under the above-mentioned measurement conditions 1 As a result of H-NMR measurement, the following peaks were observed, confirming that the compound Ma1 had the chemical structure represented by the formula (Ma1).

[0523] δ (ppm) (d6-DMSO): 3.8 (3H, -CH3), 7.7 (2H, Ph), 6.7 (1H, -CH=), 5.3 (1H, =CH2), 5.7 (1H, =CH2), 9.5 (1H, -OH)

[0524]

[0525] (Synthesis Example Aa1a) Synthesis of Compound A1a Represented by Formula (Ma1a) (Synthesis of 4-acetoxy-3-iodo-5-methoxystyrene)

[0526] A 100 mL glass flask was used as a reaction container. 16.7 g (45 mmol) of 4-hydroxy-3-iodo-5-methoxystyrene was dissolved in dimethyl sulfoxide as a solvent, and then 2 eq. of acetic anhydride and 1 eq. of sulfuric acid were added, and the mixture was heated to 80° C. and stirred for 3 hours. Then, the stirred solution was cooled, and the precipitate was filtered, washed, and dried to obtain 9.0 g of a white solid. The sample of the white solid was analyzed by liquid chromatography-mass spectrometry (LC-MS), and the molecular weight was confirmed to be 414, which was confirmed to be 4-acetoxy-3-iodo-5-methoxystyrene.

[0527] In addition, under the above-mentioned measurement conditions 1H-NMR measurement revealed the following peaks, confirming the chemical structure of 4-acetoxy-3-iodo-5-methoxystyrene having the compound A1a represented by the formula (Ma1a). δ (ppm) (d6-DMSO): 7.9 (2H, Ph), 6.6 (1H, -CH2-), 5.7 (1H, =CH2), 5.1 (1H, =CH2), 3.8 (3H, -CH3), 2.3 (3H, -CH3)

[0528]

[0529] (Synthesis Example Aa2) Synthesis of Compound Ma2 Represented by Formula (Ma2)

[0530] The reaction was carried out in the same manner as in Example A1 except that 4-hydroxy-3-iodo-5-methoxybenzaldehyde in Synthesis Example Aa1 was changed to 3-ethoxy-4-hydroxy-5-iodobenzaldehyde, thereby isolating 132 g of the target product 3-ethoxy-4-hydroxy-5-iodostyrene represented by formula (Ma2).

[0531] As a result of liquid chromatography-mass spectrometry (LC-MS) analysis, a molecular weight of 290 was confirmed.

[0532] In addition, under the above-mentioned measurement conditions 1 As a result of H-NMR measurement, the following peaks were observed, confirming that the compound Ma2 had a chemical structure represented by the formula (Ma2).

[0533] δ (ppm) (d6-DMSO): 9.5 (1H, -OH), 7.7 (2H, Ph), 6.7 (1H, -CH=), 5.7 (1H, =CH2), 5.3 (1H, =CH2), 4.1 (2H, -CH2-), 1.4 (3H, -CH3)

[0534]

[0535] (Synthesis Example Aa2a) Synthesis of Compound A2a Represented by Formula (Ma2a)

[0536] The reaction was carried out in the same manner as in Synthesis Example 1: Example A1a except that 4-hydroxy-3-iodo-5-methoxystyrene in Synthesis Example Aa1a was replaced with 3-ethoxy-4-hydroxy-5-iodostyrene, and 9.1 g of a white solid was isolated. The sample of the white solid was analyzed by liquid chromatography-mass spectrometry (LC-MS), and the molecular weight was confirmed to be 332, confirming that it was 4-acetoxy-3-ethoxy-5-iodostyrene.

[0537] In addition, under the above-mentioned measurement conditions 1As a result of H-NMR measurement, the following peaks were observed, confirming that compound A2a having the chemical structure of 4-acetoxy-3-ethoxy-5-iodostyrene represented by formula (Ma2a) was obtained.

[0538] δ (ppm) (d6-DMSO): 7.7 (2H, Ph), 6.7 (1H, -CH=), 5.7 (1H, =CH2), 5.3 (1H, =CH2), 4.1 (2H, -CH2-), 2.3 (3H, -CH3) 1.4 (3H, -CH3)

[0539]

[0540] (Synthesis Example Aa3) Synthesis of Compound Aa3 Represented by Formula (Ma3)

[0541] In a 2L flask, 400mL of dichloromethane, 41g of the compound Ma1 obtained in Synthesis Example Aa1, 16.2g of triethylamine, and 0.7g of N-(4-pyridyl)dimethylamine (DMAP) were dissolved in a nitrogen stream. After 33.6g of di-tert-butyl dicarbonate was dissolved in 100mL of dichloromethane, it was added dropwise to the above-mentioned 2L flask while stirring, and stirred at room temperature for 3 hours. Then, 3 times of water washing was performed by a liquid separation operation using 100mL of water, and the solvent was distilled off from the obtained organic phase, and the origin component was removed by silica gel chromatography with dichloromethane / hexane, and the solvent was further distilled off, thereby obtaining 4.5g of the BOC-substituted compound Ma1 as the target component (the compound shown in the following formula (Ma3), hereinafter also referred to as "compound Aa3").

[0542] As a result of liquid chromatography-mass spectrometry (LC-MS) analysis, a molecular weight of 376 was confirmed.

[0543] In addition, under the above-mentioned measurement conditions 1 As a result of H-NMR measurement, the following peaks were observed, confirming that the compound had the chemical structure represented by formula (Ma3).

[0544] δ (ppm) (d6-DMSO): 7.7 (2H, Ph), 6.7 (1H, -CH=), 5.7 (1H, =CH2), 5.3 (1H, =CH2), 3.8 (3H, -CH3), 1.4 (9H, -C-(CH3)3)

[0545]

[0546] (Synthesis Example Aa4) Synthesis of Compound Aa4 Represented by Formula (Ma4)

[0547] In a container with a volume of 200 mL equipped with a stirrer, a cooling tube and a burette, 4.61 g (12.4 mmol) of the compound Ma1 obtained in the above-mentioned Synthesis Example Aa1 and 2.42 g (12.4 mmol) of ethyl vinyl ether were added to 100 mL of acetone, 2.5 g of pyridinium p-toluenesulfonate was added, and the contents were stirred at room temperature for 24 hours to react to obtain a reaction solution. Then, the reaction solution was concentrated and filtered to separate the solid matter.

[0548] The obtained solid matter was filtered and dried, and then separated and purified by column chromatography to obtain 3.2 g of compound Aa4 (a compound represented by the following formula (Ma4)).

[0549] As a result of liquid chromatography-mass spectrometry (LC-MS) analysis, a molecular weight of 348 was confirmed.

[0550] In addition, under the above-mentioned measurement conditions 1 As a result of H-NMR measurement, the following peaks were observed, confirming that the compound had the chemical structure represented by formula (Ma4).

[0551] δ (ppm) (d6-DMSO): 7.7 (2H, Ph), 6.7 (1H, -CH=), 5.7 (1H, =CH2), 5.6 (1H, CH3C H -), 5.3 (1H, =CH2), 3.8 (3H, -CH3), 3.9 (2H, CH3C H 2-), 1.6(3H, C H 3CH-), 1.2(3H, C H 3CH2-)

[0552]

[0553] (Synthesis Example Aa5) Synthesis of Compound Aa5 Represented by Formula (Ma5)

[0554] In a container with a volume of 200 mL equipped with a stirrer, a cooling tube and a burette, 4.61 g (12.4 mmol) of the compound Ma1 obtained in the above-mentioned Synthesis Example Aa1 and 2.42 g (12.4 mmol) of tetrahydropyran were added to 100 mL of acetone, 2.5 g of pyridinium p-toluenesulfonate was added, and the contents were stirred at room temperature for 24 hours to react to obtain a reaction solution. Then, the reaction solution was concentrated and filtered to separate the solid matter.

[0555] The obtained solid matter was filtered and dried, and then separated and purified by column chromatography to obtain 3.2 g of compound Aa5 (a compound represented by the following formula (Ma5)).

[0556] In addition, under the above-mentioned measurement conditions 1 As a result of H-NMR measurement, the following peaks were observed, confirming that the compound had the chemical structure represented by formula (Ma5).

[0557] As a result of liquid chromatography-mass spectrometry (LC-MS) analysis, a molecular weight of 360 was confirmed.

[0558] δ (ppm) (d6-DMSO): 7.7 (2H, Ph), 6.7 (1H, -CH=), 5.8 (1H, proton of tetrahydropyranyl group = CH-), 5.7 (1H, = CH2), 5.3 (1H, = CH2), 3.8 (3H, -CH3), 1.6 to 3.7 (8H, proton of tetrahydropyranyl group -CH2-)

[0559]

[0560] (Synthesis Example Aa6) Synthesis of Compound Aa6 Represented by Formula (Ma6)

[0561] In a container with a stirring machine, a cooling tube and a burette having an internal volume of 200 mL, 4.61 g (12.4 mmol) of the compound Ma1 obtained in the above-mentioned Synthesis Example Aa1 and 2.42 g (12.4 mmol) of tert-butyl bromoacetate were added to 100 mL of acetone, and 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 react to obtain 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, the solution was filtered to separate the solid matter.

[0562] The obtained solid matter was filtered and dried, and then separated and purified by column chromatography to obtain 3.2 g of compound Aa6 (a compound represented by the following formula (Ma6)).

[0563] As a result of liquid chromatography-mass spectrometry (LC-MS) analysis, a molecular weight of 390 was confirmed.

[0564] In addition, under the above-mentioned measurement conditions 1 As a result of H-NMR measurement, the following peaks were observed, confirming the chemical structure of the compound represented by formula (Ma6).

[0565] δ (ppm) (d6-DMSO): 7.7 (2H, Ph), 6.7 (1H, -CH=), 5.7 (1H, =CH2), 5.3 (1H, =CH2), 5.0 (2H, -CH2-), 3.8 (3H, -CH3), 1.4 (9H, -C-(CH3)3)

[0566]

[0567] (Synthesis Example Aa7) Synthesis of Compound Aa7 Represented by Formula (Ma7)

[0568] In a container with a volume of 200 mL equipped with a stirrer, a cooling tube and a burette, 4.61 g (12.4 mmol) of the compound Ma1 obtained in the above-mentioned Synthesis Example Aa1 and 2.42 g (12.4 mmol) of 2-methyl-2-adamantyl bromoacetate were added to 100 mL of acetone, and 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 react to obtain 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, it was filtered to separate the solid matter.

[0569] The obtained solid matter was filtered and dried, and then separated and purified by column chromatography to obtain 3.2 g of compound Aa7 (a compound represented by the following formula (Ma7)).

[0570] In addition, under the above-mentioned measurement conditions 1 As a result of H-NMR measurement, the following peaks were observed, confirming that the compound had the chemical structure represented by formula (Ma7).

[0571] As a result of liquid chromatography-mass spectrometry (LC-MS) analysis, a molecular weight of 482 was confirmed.

[0572] δ (ppm) (d6-DMSO): 7.7 (2H, Ph), 6.7 (1H, -CH=), 5.7 (1H, =CH2), 5.3 (1H, =CH2), 5.0 (2H, -CH2-), 3.8 (3H, -CH3), 0.8 to 2.4 (17H, proton of 2-methyl-2-adamantyl)

[0573]

[0574] (Synthesis Example Aa8) Synthesis of Compound Aa8 Represented by Formula (Ma8)

[0575] In a container with a stirring machine, a cooling tube and a burette having an internal volume of 200 mL, 4.61 g (12.4 mmol) of the compound Ma1 obtained in the above-mentioned Synthesis Example Aa1 and 1.70 g (12.4 mmol) of tert-butyl bromide were added to 100 mL of acetone, and 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 react to obtain a reaction liquid. Then, the reaction liquid was concentrated, 100 g of pure water was added to the concentrated liquid to precipitate the reaction product, and after cooling to room temperature, it was filtered to separate the solid matter.

[0576] The obtained solid matter was filtered and dried, and then separated and purified by column chromatography to obtain 0.5 g of compound Aa8 (a compound represented by the following formula (Ma8)).

[0577] In addition, under the above-mentioned measurement conditions 1 As a result of H-NMR measurement, the following peaks were observed, confirming that the compound had the chemical structure represented by formula (Ma8).

[0578] As a result of liquid chromatography-mass spectrometry (LC-MS) analysis, a molecular weight of 332 was confirmed.

[0579] δ (ppm) (d6-DMSO): 7.7 (2H, Ph), 6.7 (1H, -CH=), 5.7 (1H, =CH2), 5.3 (1H, =CH2), 3.8 (3H, -CH3), 1.4 (9H, -C-(CH3)3)

[0580]

[0581] (Synthesis Example Aa9) Synthesis of Compound Aa9 Represented by Formula (Ma9)

[0582] In synthesis example Aa3, 4-hydroxy-3-iodo-5-methoxystyrene (compound Ma1) is changed to 3-ethoxy-4-hydroxy-5-iodostyrene, and the reaction is carried out in the same manner as in example Aa3 to obtain 4.6 g of a BOC-substituted compound A2 represented by formula (Ma9) as the target product (the compound represented by the following formula (Ma9), hereinafter also referred to as "compound Aa9") .

[0583] As a result of liquid chromatography-mass spectrometry (LC-MS) analysis, a molecular weight of 390 was confirmed.

[0584] In addition, under the above-mentioned measurement conditions 1 As a result of H-NMR measurement, the following peaks were observed, confirming that the compound had the chemical structure represented by formula (Ma9).

[0585] δ (ppm) (d6-DMSO): 7.7 (2H, Ph), 6.7 (1H, -CH=), 5.7 (1H, =CH2), 5.3 (1H, =CH2), 4.1 (2H, -CH2-), 1.4 (3H, -CH3), 1.3 (H, -C-(CH3)3)

[0586]

[0587] (Synthesis Example Aa10) Synthesis of Compound Aa10 Represented by Formula (Ma10)

[0588] In Synthesis Example A4, 4-hydroxy-3-iodo-5-methoxystyrene (Compound Ma1) is changed to 3-ethoxy-4-hydroxy-5-iodostyrene, and the reaction is carried out in the same manner as in Example Aa4 to obtain 3.5 g of the target compound represented by formula (Ma10, hereinafter also referred to as "Compound Aa10").

[0589] As a result of liquid chromatography-mass spectrometry (LC-MS) analysis, a molecular weight of 362 was confirmed.

[0590] In addition, under the above-mentioned measurement conditions 1 As a result of H-NMR measurement, the following peaks were observed, confirming that the compound had the chemical structure represented by formula (Ma10).

[0591] δ (ppm) (d6-DMSO): 7.7 (2H, Ph), 6.7 (1H, -CH=), 5.7 (1H, =CH2), 5.6 (1H, CH3C H -), 5.3 (1H, =CH2), 4.1 (2H, -CH2-), 3.9 (2H, CH3C H 2-), 1.6(3H, C H 3CH-), 1.4(3H, -CH3), 1.2(3H, C H 3CH2-)

[0592]

[0593] (Synthesis Example Aa11) Synthesis of Compound Aa11 Represented by Formula (Ma11)

[0594] In Synthesis Example A5, 4-hydroxy-3-iodo-5-methoxystyrene (Compound Ma1) is changed to 3-ethoxy-4-hydroxy-5-iodostyrene, and the reaction is carried out in the same manner as in Example Aa5 to obtain 3.6 g of the target compound represented by formula (Ma11, hereinafter also referred to as "Compound Aa11").

[0595] As a result of liquid chromatography-mass spectrometry (LC-MS) analysis, a molecular weight of 374 was confirmed.

[0596] In addition, under the above-mentioned measurement conditions 1 As a result of H-NMR measurement, the following peaks were observed, confirming that the compound had the chemical structure represented by formula (Ma11).

[0597] δ (ppm) (d6-DMSO): 7.7 (2H, Ph), 6.7 (1H, -CH=), 5.8 (1H, proton of tetrahydropyranyl group = CH-), 5.7 (1H, = CH2), 5.3 (1H, = CH2), 4.1 (2H, -CH2-), 1.6-3.7 (8H, proton of tetrahydropyranyl group -CH2-), 1.4 (3H, -CH3)

[0598]

[0599] (Synthesis Example Aa12) Synthesis of Compound Aa12 Represented by Formula (Ma12)

[0600] In synthesis example Aa6, 4-hydroxy-3-iodo-5-methoxystyrene (compound Ma1) is changed to 3-ethoxy-4-hydroxy-5-iodostyrene, and the reaction is carried out in the same manner as in example Aa6 to obtain 3.8 g of the target compound represented by formula (Ma12, hereinafter also referred to as "compound Aa12").

[0601] As a result of liquid chromatography-mass spectrometry (LC-MS) analysis, a molecular weight of 404 was confirmed.

[0602] In addition, under the above-mentioned measurement conditions 1 As a result of H-NMR measurement, the following peaks were observed, confirming that the compound had the chemical structure represented by formula (Ma12).

[0603] δ (ppm) (d6-DMSO): 7.7 (2H, Ph), 6.7 (1H, -CH=), 5.7 (1H, =CH2), 5.3 (1H, =CH2), 5.0 (2H, -CH2-), 4.1 (2H, -CH2-), 1.4 (9H, -C-(CH3)3), 1.3 (3H, -CH3)

[0604]

[0605] (Synthesis Example Aa13) Synthesis of Compound Aa13 Represented by Formula (Ma13)

[0606] In Synthesis Example Aa7, 4-hydroxy-3-iodo-5-methoxystyrene (Compound Ma1) is changed to 3-ethoxy-4-hydroxy-5-iodostyrene, and the other reactions are carried out in the same manner as in Synthesis Example Aa7 to obtain 4.1 g of the target compound represented by formula (Ma13, hereinafter also referred to as "Compound Aa13").

[0607] As a result of liquid chromatography-mass spectrometry (LC-MS) analysis, a molecular weight of 496 was confirmed.

[0608] In addition, under the above-mentioned measurement conditions 1 As a result of H-NMR measurement, the following peaks were observed, confirming that the compound had the chemical structure represented by formula (Ma13).

[0609] δ (ppm) (d6-DMSO): 7.7 (2H, Ph), 6.7 (1H, -CH=), 5.7 (1H, =CH2), 5.3 (1H, =CH2), 5.0 (2H, -CH2-), 4.1 (2H, -CH2-), 0.8 to 2.4 (17H, proton of 2-methyl-2-adamantyl + 3H, -CH3)

[0610]

[0611] (Synthesis Example Aa14) Synthesis of Compound Aa14 Represented by Formula (Ma14)

[0612] In synthesis example Aa8, 4-hydroxy-3-iodo-5-methoxystyrene (compound Ma1) is changed to 3-ethoxy-4-hydroxy-5-iodostyrene, and the other reactions are carried out in the same manner as in example Aa8 to obtain 3.5 g of the compound represented by formula (Ma14) as the target product, hereinafter also referred to as "compound Aa14".

[0613] As a result of liquid chromatography-mass spectrometry (LC-MS) analysis, a molecular weight of 346 was confirmed.

[0614] In addition, under the above-mentioned measurement conditions 1 As a result of H-NMR measurement, the following peaks were observed, confirming that the compound had the chemical structure represented by formula (Ma14).

[0615] δ(ppm)(d6-DMSO): 7.7(2H,Ph), 6.7(1H,-CH=), 5.7(1H,=CH2), 5.3(1H,=CH2), 4.1(2H,-CH2-), 1.4(9H,-C-(CH3)3), 1.3(3H,-CH3)

[0616]

[0617] (Synthesis Example BP5) Synthesis of Compound BP5 Represented by Formula (BP5)

[0618] The compound BP5 (trans isomer) represented by the formula (BP5) was synthesized by the method described below.

[0619]

[0620] 15.6 g of 1-(2-hydroxy-3,5-diiodophenyl)ethanol, 0.15 g of methanesulfonic acid, 0.04 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical, and 60 mL of DMSO (dimethyl sulfoxide) were added to the reaction vessel and stirring was started. Next, the decompression conditions of reflux at 120 ° C using Dean-Stark and a condenser were adjusted, and air at a flow rate of 1 mL / min was blown into the reaction solution. It should be noted that the water recovered in the Dean-Stark was appropriately discharged to the outside of the system. Next, the reaction vessel was immersed in a 90 ° C water bath and continued to stir for 30 hours. Next, the reaction vessel was immersed in a 25 ° C water bath and the reaction solution was cooled. Next, the reaction solution was slowly added to 500 g of a 0.1 mass% sodium bisulfite aqueous solution while vigorously stirring and mixing. Next, the precipitate was filtered by suction filtration, squeezed, and washed with 200 mL of a 33.3% by volume methanol aqueous solution. The obtained precipitate was separated into only the main component (trans isomer) by column generation, and the solvent was distilled off by evaporation. The obtained solid was vacuum dried at 40° C. to obtain 7.1 g of a white solid. The yield was 23%.

[0621] As a result of liquid chromatography-mass spectrometry (LC-MS) analysis, the molecular weight was confirmed to be 743.9, and it was confirmed to be compound BP5 represented by formula (BP5).

[0622] In addition, under the above-mentioned measurement conditions 1 As a result of H-NMR measurement, the following peaks were observed, confirming that the compound had a chemical structure of BP5.

[0623] δ (ppm) (d6-DMSO): 10.2 (1H, OH), 9.6 (1H, OH), 7.8 (2H, Ph), 7.7 (1H, Ph), 7.5 (1H, Ph), 3.6 (1H, -CH-), 1.3 (3H, -CH3), 6.5~6.7 (2H, -CH=CH-)

[0624] (Synthesis Example BP6) Synthesis of Compound BP6 Represented by Formula (BP6)

[0625] The compound BP6 (trans isomer) represented by the formula (BP6) was synthesized by the method described below.

[0626]

[0627] 1-(3,5-dihydroxy-4-iodophenyl)ethanol 11.2g, methanesulfonic acid 0.15g, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical 0.04g, DMSO (dimethyl sulfoxide) 60mL were added to the reaction vessel and stirring was started. Next, the decompression conditions of reflux at 120°C using Dean-Stark and a condenser were adjusted, and air at a flow rate of 1mL / min was blown into the reaction solution. It should be noted that the water recovered in the Dean-Stark was appropriately discharged to the outside of the system. Next, the reaction vessel was immersed in a 90°C water bath and continued to stir for 30 hours. Next, the reaction vessel was immersed in a 25°C water bath and the reaction solution was cooled. Next, the reaction solution was slowly added to 500g of a 0.1% by mass sodium bisulfite aqueous solution while vigorously stirring and mixing. Next, the precipitate was filtered and squeezed by suction filtration, and washed with 200 mL of a 33.3% by volume methanol aqueous solution. The obtained precipitate was separated into only the main component (trans isomer) by column generation, and the solvent was distilled off by evaporation. The obtained solid was vacuum dried at 40° C. to obtain 5.0 g of a white solid. The yield was 23%.

[0628] As a result of liquid chromatography-mass spectrometry (LC-MS) analysis, the molecular weight was confirmed to be 524.1, and it was confirmed to be compound BP5 represented by formula (BP6).

[0629] In addition, under the above-mentioned measurement conditions 1 As a result of H-NMR measurement, the following peaks were observed, confirming that the compound had a chemical structure of BP6.

[0630] δ (ppm) (d6-DMSO): 10.8 (4H, OH), 6.7 (1H, -CH=CH-), 6.4 (1H, -CH=CH-), 6.3 (2H, Ph), 6.0 (2H, Ph), 3.6 (1H, -CH-), 1.3 (3H, -CH3)

[0631] (Synthesis Example Aa15) Synthesis of Compound Aa15 Represented by Formula (Ma15)

[0632] (Step 1) Synthesis of 1-(4-hydroxy-3,5-diiodophenyl)ethanol

[0633] 1-(4-hydroxyphenyl)ethanol 120g, iodine 177g, methanol 1400mL, pure water 200mL were added to the reaction container, and the reaction container was immersed in an ice bath and stirring was started. Then, 87g of iodic acid aqueous solution with a concentration of 70% by mass was added dropwise over 30 minutes. Then, the reaction container was immersed in a water bath at 25°C and continued to stir for 3.5 hours. Then, 18mL of sodium bisulfite aqueous solution with a concentration of 35% by mass was added to quench the reaction. Then, the reaction solution was slowly added to 3.5L of pure water while vigorously stirring and mixed. Then, the precipitate was filtered and squeezed by suction filtration, and washed with a methanol aqueous solution with a concentration of 33.3% by volume. Then, the precipitate was vacuum dried at 40°C to obtain 310g of a mixture of 1-(4-hydroxy-3,5-diiodophenyl)ethanol and 2,6-diiodo-4-(1-methoxyethyl)phenol. As a result of HPLC analysis using a UV detector at a measurement wavelength of 254 nm, the ratio of 1-(4-hydroxy-3,5-diiodophenyl)ethanol to 2,6-diiodo-4-(1-methoxyethyl)phenol was 50.88:47.15.

[0634] As a result of liquid chromatography-mass spectrometry (LC-MS) analysis, molecular weights of 390 and 404 were confirmed, indicating that the product was a mixture of 1-(4-hydroxy-3,5-diiodophenyl)ethanol and 2,6-diiodo-4-(1-methoxyethyl)phenol.

[0635] In addition, under the above-mentioned measurement conditions 1 As a result of H-NMR measurement, the following peaks were observed, confirming that the chemical structure existed.

[0636] δ (ppm) (d6-DMSO): 9.4 (1H, -OH), 7.7 (2H, Ph), 5.2 (0.5H, -CH-OH), 4.6~4.3 (1H, -CH-OH), 3.0 (1.5H, -O-CH3), 1.3 (3H, -CH3)

[0637]

[0638] (Step 2) Synthesis of 4-hydroxy-3,5-diiodostyrene

[0639] Into a reaction vessel connected to a reflux tube and Dean-Stark, 200 g of a mixture of 1-(4-hydroxy-3,5-diiodophenyl)ethanol and 2,6-diiodo-4-(1-methoxyethyl)phenol obtained in the above (step 1), 29 mL of concentrated sulfuric acid, 0.2 g of 4-hydroxy-2,2,6,6-tetramethylpiperidinyl 1-oxyl radical, 0.2 g of 4-methoxyphenol, 2.5 L of dimethyl sulfoxide, and 0.5 L of toluene were added, and stirring was started. Next, the reaction vessel was depressurized to 30 hPa, and air at a flow rate of 1 mL / min was started to be blown into the reaction solution. Next, the reaction vessel was immersed in a 90°C water bath and stirring was continued for 3 hours. Next, the reaction vessel was immersed in a 25°C water bath and the reaction solution was cooled. Next, 30 g of a 0.1% by mass sodium bisulfite aqueous solution was slowly added and mixed while the reaction solution was vigorously stirred. Next, the precipitate was filtered by suction, squeezed, and washed with 15 mL of a 33.3% by volume methanol aqueous solution. Next, the precipitate was vacuum dried at 40° C. to obtain 181 g of 4-hydroxy-3,5-diiodostyrene. The yield was 94.9%.

[0640] As a result of liquid chromatography-mass spectrometry (LC-MS) analysis, a molecular weight of 372 was confirmed, and the compound was identified as compound Aa15 (4-hydroxy-3,5-diiodostyrene) represented by formula (Ma15).

[0641] In addition, under the above-mentioned measurement conditions 1 As a result of H-NMR measurement, the following peaks were observed, confirming that the chemical structure existed.

[0642] δ (ppm) (d6-DMSO): 9.6 (1H, OH), 7.9 (2H, Ph), 6.6 (1H, -CH2-), 5.7 (1H, =CH2), 5.1 (1H, =CH2)

[0643]

[0644] (Synthesis Example Aa16) Synthesis of Compound Aa16 Represented by Formula (Ma16) (Synthesis of 4-acetoxy-3,5-diiodostyrene)

[0645] A 100 mL glass flask was used as a reaction container. 16.7 g (45 mmol) of 4-hydroxy-3,5-diiodostyrene obtained in (Synthesis Example Aa15) was dissolved in dimethyl sulfoxide as a solvent, and then 2 eq. of acetic anhydride and 1 eq. of sulfuric acid were added, and the mixture was heated to 80°C and stirred for 3 hours. Then, the stirred solution was cooled, and the precipitate was filtered, washed, and dried to obtain 9.0 g of a white solid. The sample of the white solid was analyzed by liquid chromatography-mass spectrometry (LC-MS), and the molecular weight was confirmed to be 414, which was confirmed to be compound Aa16 (4-acetoxy-3,5-diiodostyrene) shown in formula (Ma16).

[0646] In addition, under the above-mentioned measurement conditions 1 As a result of H-NMR measurement, the following peaks were observed, confirming that the chemical structure existed.

[0647] δ (ppm) (d6-DMSO): 7.9 (2H, Ph), 6.6 (1H, -CH2-), 5.7 (1H, =CH2), 5.1 (1H, =CH2), 2.3 (3H, -CH3)

[0648]

[0649] (Synthesis Example Aa17) Synthesis of Compound Aa17 (4-hydroxy-3,5-diiodostyrene) Represented by Formula (Ma17)

[0650] Except for using 1-(2-hydroxyphenyl)ethanol instead of 1-(4-hydroxyphenyl)ethanol, the same method as the above-mentioned synthesis example Aa15 is carried out to carry out (step 1) and (step 2) to obtain compound Aa17 (2-hydroxy-3,5-diiodostyrene) represented by formula (Ma17).

[0651]

[0652] (Synthesis Example Aa18) Synthesis of Compound Aa18 (4-acetoxy-3,5-diiodostyrene) Represented by Formula (Ma18)

[0653] Compound Aa18 (2-acetoxy-3,5-diiodostyrene) represented by the formula (Ma18) was obtained by the same method as in Synthesis Example Aa15 except that 2-hydroxy-3,5-diiodostyrene was used instead of 4-hydroxy-3,5-diiodostyrene.

[0654]

[0655] (Synthesis Example Aa19) Synthesis of Compound Aa19 (3,5-dihydroxy-4-iodostyrene) Represented by Formula (Ma19)

[0656] (Synthesis Example Aa19-1) Synthesis of 3',5'-dihydroxy-4'-iodoacetophenone

[0657] A 500 mL glass flask was used as a reaction vessel, 8.00 g (52.6 mmol) of 3',5'-dihydroxyacetophenone, 146 mL of methanol, and 12.9 mL of ion exchange water were added, and stirring was started at room temperature of 20°C. Next, nitrogen gas was blown in at a flow rate of 10 mL / min. After adding 5.34 g (21.0 mmol) of iodine, 6.12 g (10.5 mmol) of an aqueous solution of iodic acid with a concentration of 30% by mass% was added while adjusting the temperature to be below 30°C. After stirring for 1 hour, 3 g of an aqueous solution of sodium bisulfite with a concentration of 5% by mass% was added, the solution was concentrated and added dropwise to 100 g of water. The obtained precipitate was recovered by suction filtration and vacuum dried at 40°C to obtain 12.6 g of a white solid. The yield was 86%.

[0658] As a result of liquid chromatography-mass spectrometry (LC-MS) analysis, a molecular weight of 278 was confirmed.

[0659] In addition, under the above-mentioned measurement conditions 1 As a result of H-NMR measurement, the following peaks were observed, confirming that the chemical structure was 3',5'-dihydroxy-4'-iodoacetophenone.

[0660] δ(ppm)(d6-DMSO): 10.5(2H, OH), 6.5(2H, ArH), 2.5(3H, -CH3)

[0661]

[0662] (Synthesis Example Aa19-2) Synthesis of 1-(3,5-hydroxy-4-iodophenyl)ethanol

[0663] A 500 mL glass flask was used as a reaction vessel, 12.0 g (43.2 mmol) of 3',5'-dihydroxy-4'-iodoacetophenone and 129 mL of methanol of Synthesis Example Aa19-1 were added, and stirring was started at 0°C. Next, nitrogen gas at a flow rate of 10 mL / min was started. While adjusting to below 10°C, 1.63 g (43.2 mmol) of sodium borohydride was added in portions and stirred for 1 hour. After adding 2M hydrochloric acid until the reaction solution became acidic, 50 g of ion exchange water was added. Next, the reaction vessel was depressurized to 50 hPa, immersed in a water bath at 20°C, and the reaction solution was concentrated. 30 g of saturated brine and 100 g of ethyl acetate were added to the concentrated solution and stirred. The organic layer was washed with ion exchange water and saturated brine, concentrated to dryness, and the crude product was recovered. The crude product was vacuum dried at 40°C to obtain 9.0 g of a white solid. The yield was 75%.

[0664] As a result of liquid chromatography-mass spectrometry (LC-MS) analysis, a molecular weight of 280 was confirmed.

[0665] In addition, under the above-mentioned measurement conditions 1 As a result of H-NMR measurement, the following peaks were observed, confirming that the chemical structure of 1-(3,5-hydroxy-4-iodophenyl)ethanol was present.

[0666] δ (ppm) (d6-DMSO): 11.6 (2H, ArOH), 6.2 (2H, ArH), 5.2 (1H, -CHOH-), 5.0 (1H, -CHOH-), 1.5 (3H, -CH3)

[0667]

[0668] (Synthesis Example Aa19-3) Synthesis of Compound Aa19 Represented by Formula (Ma19) (Synthesis of 3,5-Dihydroxy-4-iodostyrene)

[0669] A 300 mL glass flask was used as a reaction vessel, and 8.5 g of 1-(3,5-hydroxy-4-iodophenyl)ethanol, 0.40 g of concentrated sulfuric acid, 0.015 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical, and 76 mL of dimethyl sulfoxide of Synthesis Example Aa19-2 were added and stirring was started. Next, the reaction vessel was depressurized to 30 hPa, and air at a flow rate of 9 mL / min was blown into the reaction solution. Next, the reaction vessel was immersed in a 90°C water bath and continued to stir for 5 hours. Next, the reaction vessel was immersed in a 25°C water bath and the reaction solution was cooled. Next, the reaction solution was slowly added to 153 g of a 0.1% mass% concentration of sodium bisulfite aqueous solution while vigorously stirring and mixed. Next, the precipitate was filtered and squeezed by suction filtration, and washed with 76 mL of a 33.3% volume% methanol aqueous solution. Next, the precipitate was dried in vacuum at 25°C to obtain 7.6 g of a white solid with a yield of 96%.

[0670] As a result of liquid chromatography-mass spectrometry (LC-MS) analysis, a molecular weight of 262 was confirmed, and the compound was identified as compound Aa19 (3,5-dihydroxy-4-iodostyrene) represented by formula (Ma19).

[0671] In addition, under the above-mentioned measurement conditions 1 As a result of H-NMR measurement, the following peaks were observed, and it was confirmed that the compound had the following chemical structure.

[0672] δ (ppm) (d6-DMSO): 11.6 (2H, OH), 6.7 (1H, -CH=), 6.0 (2H, ArH), 5.7 (1H, =CH2), 5.3 (1H, =CH2)

[0673]

[0674] (Synthesis Example Aa19-4) Synthesis of Compound Aa20 Represented by Formula (Ma20)

[0675] A 300 mL glass flask was used as a reaction vessel. After dissolving 7.0 g (0.027 mol) of 3,5-dihydroxy-4-iodostyrene obtained in Synthesis Example Aa19-3 using 74 mL of chloroform as a solvent, 8.2 g (0.080 mol) of triethylamine and 0.98 g (0.0080 mol) of 4-dimethylaminopyridine were added, and the mixture was immersed in ice water and stirred while cooling to 0°C. 8.2 g (0.080 mol) of acetic anhydride was added over 20 minutes, and after stirring for 2 hours under cooling, 64 g of 0.2 M hydrochloric acid was added dropwise over 20 minutes. 5.3 mL of chloroform was added for liquid separation, and the organic layer was washed with a 5% sodium bicarbonate aqueous solution and water. After concentrating the solution, an excess of heptane was added, the solution was cooled, and the obtained precipitate was recovered by suction filtration and vacuum dried at 25°C to obtain 8.3 g of a white solid. The yield was 90%.

[0676] As a result of liquid chromatography-mass spectrometry (LC-MS) analysis, a molecular weight of 346 was confirmed, and the compound was identified as compound Aa20 (3,5-diacetoxy-4-iodostyrene) represented by formula (Ma20).

[0677] In addition, under the above-mentioned measurement conditions 1 As a result of H-NMR measurement, the following peaks were observed, and it was confirmed that the compound had the following chemical structure.

[0678] δ (ppm) (d6-DMSO): 6.8 (2H, ArH), 6.7 (1H, -CH=), 5.8 (1H, =CH2), 5.3 (1H, =CH2), 2.3 (6H, -CH3)

[0679]

[0680] (Synthesis Example Aa19-5) Synthesis of 3',5'-diacetoxy-4'-iodoacetophenone

[0681] A 500 mL glass flask was used as a reaction vessel. 12.0 g (0.043 mol) of 3',5'-dihydroxy-4'-iodoacetophenone obtained in Synthesis Example Aa19-1 was dissolved in 156 g of ethyl acetate as a solvent, and then 13 g (0.13 mol) of triethylamine and 1.6 g (0.013 mol) of 4-dimethylaminopyridine were added. The mixture was cooled to 0°C and stirred in ice water. 13 g (0.13 mol) of acetic anhydride was added over 20 minutes, and after stirring for 2 hours under ice cooling, 206 g of 0.2 M hydrochloric acid was added dropwise over 20 minutes. After adding hexane to confirm the separation of the layers, the organic layer was washed with a 5% sodium bicarbonate aqueous solution and water. After concentrating the solution, an excess of a 2-propanol / water mixture was added, and the solution was cooled. The obtained precipitate was recovered by suction filtration and vacuum dried at 25°C to obtain 14 g of a white solid. The yield was 92%.

[0682] As a result of liquid chromatography-mass spectrometry (LC-MS) analysis, the molecular weight was confirmed to be 362, and it was confirmed to be 3',5'-diacetoxy-4'-iodoacetophenone.

[0683] In addition, under the above-mentioned measurement conditions 1 As a result of H-NMR measurement, the following peaks were observed, and it was confirmed that the compound had the following chemical structure.

[0684] δ(ppm)(d6-DMSO): 7.3(2H, ArH), 2.5(3H, -CH3), 2.3(6H, -CH3)

[0685]

[0686] (Synthesis Example Aa19-6) Synthesis of 1-(3,5-diacetoxy-4-iodophenyl)ethanol

[0687] A 500 mL glass flask was used as a reaction vessel, 13.5 g (37.2 mmol) of 3',5'-diacetoxy-4'-iodoacetophenone and 111 mL of methanol of Synthesis Example Aa19-5 were added, and stirring was started at 0°C. Next, nitrogen gas was blown in at a flow rate of 10 mL / min. After adding 1.41 g (37.2 mmol) of sodium borohydride in portions while adjusting the temperature to below 10°C, the mixture was stirred for 1 hour. The reaction solution was added dropwise to 100 g of 0.5 M hydrochloric acid. Next, the reaction vessel was depressurized to 50 hPa, immersed in a water bath at 20°C, and the reaction solution was concentrated. 30 g of saturated brine and 100 g of ethyl acetate were added to the concentrated solution and stirred. The organic layer was washed with ion exchange water and saturated brine, concentrated to dryness, and the crude product was recovered. The crude product was vacuum dried at 40°C to obtain 11.9 g of a white solid. The yield was 88%.

[0688] As a result of liquid chromatography-mass spectrometry (LC-MS) analysis, a molecular weight of 364 was confirmed.

[0689] In addition, under the above-mentioned measurement conditions 1 As a result of H-NMR measurement, the following peaks were observed, confirming that the chemical structure of 1-(3,5-diacetoxy-4-iodophenyl)ethanol was obtained.

[0690] δ (ppm) (d6-DMSO): 6.9 (2H, ArH), 5.2 (1H, -CHOH-), 5.0 (1H, -CHOH-), 2.3 (6H, -CH3), 1.5 (3H, -CH3)

[0691]

[0692] (Synthesis Example Aa19-7) Synthesis of Compound Aa20 Represented by Formula (Ma20) (3,5-Dihydroxy-4-iodostyrene)

[0693] A 300 mL glass flask was used as a reaction vessel, and 11.5 g of 1-(3,5-diacetoxy-4-iodophenyl)ethanol, 0.42 g of concentrated sulfuric acid, 0.016 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical, and 79 mL of dimethyl sulfoxide of Synthesis Example Aa19-6 were added, and stirring was started. Next, the reaction vessel was depressurized to 30 hPa, and air at a flow rate of 9 mL / min was blown into the reaction solution. Next, the reaction vessel was immersed in a 90°C water bath and continued to stir for 5 hours. Next, the reaction vessel was immersed in a 25°C water bath and the reaction solution was cooled. Next, the reaction solution was slowly added to 159 g of a 0.1% mass% sodium bisulfite aqueous solution while vigorously stirring and mixed. Next, the precipitate was filtered and squeezed by suction filtration, and washed with 79 mL of a 33.3% volume% methanol aqueous solution. Next, the precipitate was vacuum dried at 25°C to obtain 10.6 g of a white solid with a yield of 97%.

[0694] As a result of liquid chromatography-mass spectrometry (LC-MS) analysis, a molecular weight of 346 was confirmed, and the compound was identified as compound Aa20 (3,5-dihydroxy-4-iodostyrene) represented by formula (Ma20).

[0695] In addition, under the above-mentioned measurement conditions 1 As a result of H-NMR measurement, the following peaks were observed, confirming that the chemical structure existed.

[0696] δ (ppm) (d6-DMSO): 6.8 (2H, ArH), 6.7 (1H, -CH=), 5.8 (1H, =CH2), 5.3 (1H, =CH2), 2.3 (6H, -CH3)

[0697]

[0698] (Synthesis Examples Aa20-1 to 10) Synthesis of Compounds Represented by Formula (Ma21) to (Ma30)

[0699] Compounds Aa21 to Aa30 represented by formula (Ma21) to (Ma30) were synthesized according to the following routes. The respective raw materials were obtained from the market.

[0700]

[0701]

[0702]

[0703] [Table 1A]

[0704]

[0705] (Synthesis Example B1) Synthesis of polymer B1 represented by formula (MA1)

[0706] 1.5 g of compound A1 obtained in Synthesis Example A1, 4.0 g of 2-methyl-2-adamantyl methacrylate, 0.9 g of γ-butyrolactone methacrylate and 1.5 g of hydroxyadamantyl methacrylate were dissolved in 45 mL of tetrahydrofuran, and 0.20 g of azobisisobutyronitrile was added. After refluxing for 12 hours, the reaction solution was added dropwise to 2 L of n-heptane. The precipitated polymer was filtered and dried under reduced pressure to obtain a white powder of polymer B1 represented by the following formula (MA1). The weight average molecular weight (Mw) of the polymer is 12,000, and the degree of dispersion (Mw / Mn) is 1.90. In addition, the determination 13 According to the result of C-NMR, the composition ratio (molar ratio) in the following formula (MA1) is a:b:c:d=60:10:15:15. It should be noted that the following formula (MA1) is briefly described in order to show the ratio of each structural unit, but the arrangement order of each structural unit is random, and it is not a block copolymer in which each structural unit forms independent blocks. The molar ratio of the polystyrene monomer (compound A1) is based on the carbon of the basic structure of the benzene ring, and the methacrylate monomer (2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate and hydroxyadamantyl methacrylate) is based on the carbonyl carbon of the ester bond. The types of monomers in the polymer obtained in Synthesis Example B1, their ratios, and the composition ratio are shown in Table 1. The types of monomers in the polymers obtained in the examples described below, their ratios, and the composition ratios are also shown in Table 1.

[0707]

[0708] (Synthesis Examples B2 to B42, Comparative Examples B1 to B2)

[0709] 1.5 g of compound A1 was set to the type and amount shown in Table 1. In addition, polymers B2 to B52 and polymers BR1 to BR2 represented by formulas (MA1a) to (MA2a), (MA2) to (MA50), and (MAR1) to (MAR2) were obtained by the method described in Synthesis Example B1.

[0710]

[0711]

[0712]

[0713]

[0714]

[0715]

[0716]

[0717]

[0718]

[0719]

[0720]

[0721]

[0722]

[0723] [Table 1]

[0724]

[0725] (Synthesis Examples C1 to C76)

[0726] Each polymer described in Tables 2 to 4 was obtained by the same method as described in Synthesis Example B1, except that 1.5 g of Compound A1 used in Synthesis Example B1 was used as a composition having the types and amounts of the compounds shown in Tables 2 to 4.

[0727] [Table 2]

[0728]

[0729] [Table 3]

[0730]

[0731] [Table 4]

[0732]

[0733] The meanings of the abbreviations in Tables 2 to 4 are as follows.

[0734] MAMA: 2-methyl-2-adamantyl methacrylate

[0735] BLMA: gamma-butyrolactone methacrylate

[0736] HAMA: Hydroxyadamantyl Methacrylate

[0737] (Inorganic element content and organic impurity content)

[0738] The inorganic element content and the organic impurity content of the polymers obtained in the synthesis examples described in Tables 2 to 4 were measured by the above-mentioned methods. The results are shown in Table 4-1.

[0739] [Table 4-1]

[0740]

[0741] (Synthesis Examples C1P to C76P, Comparative Examples B1 to B2)

[0742] For the synthesized compound A1, the purification treatment of each raw material is additionally implemented before the synthesis of the polymer. Using ethyl acetate (PrimePure manufactured by Kanto Chemical Co., Ltd.) as a solvent, an ethyl acetate solution of 10% by mass of the compound class of compound A1 is obtained. For the purpose of removing metal impurities, the ion exchange resin "AMBERLYST MSPS2-1·DRY" (product name, manufactured by ORGANO) is immersed in ethyl acetate (Kanto Chemical Co., Ltd., PrimePure) and the solvent is removed after stirring for 1 hour. Repeat 10 times to wash, thereby washing the ion exchange resin. For the ethyl acetate solution of the above-mentioned compound A1, the ion exchange treatment is repeated 3 times by adding the washed ion exchange resin in a manner that is the same mass as the resin solid component and stirring at room temperature for one day and filtering out the ion exchange resin to obtain an ethyl acetate solution of the compound A1 that has completed the ion exchange. Furthermore, the same treatment is performed on other monomers to obtain an ethyl acetate solution containing monomers that has completed the ion exchange. The obtained ethyl acetate solution containing monomers after ion exchange treatment was used, and Pruimepure manufactured by Kanto Chemical Co., Ltd. of electronic grade was used as a solvent such as n-heptane and tetrahydrofuran, and then the reaction containers such as flasks were all immersed in nitric acid for 1 day and then washed with ultrapure water. The polymer B1 was synthesized by the same route as the synthesis of the composition of Synthesis Example B1. Furthermore, in the post-synthesis post-treatment, a 5nm nylon filter (manufactured by Pall) and a 15nm PTFE filter (manufactured by Entegris) were used in sequence for purification, and the polymer C1P in the form of a white powder was obtained by reduced pressure drying. For the polymer, the inorganic element content and the organic impurity content were determined by the above method, and are shown in Table 4-2.

[0743] Polymers C2P to C76P were obtained by the same method as C1P except that 1.5 g of compound A1 was used in the types and amounts shown in Tables 2 and 3. In addition, the inorganic element content and organic impurity content of the obtained polymers were measured by the above methods and are shown in Table 4-2.

[0744] [Table 4-2]

[0745]

[0746] [evaluate]

[0747] The evaluation of each polymer obtained in the above-mentioned synthesis example and comparative example was performed as follows. The results are shown in Table 4-3, Table 5 and Table 6.

[0748] (EUV sensitivity - TMAH aqueous solution development)

[0749] 5 parts by mass of the polymer obtained in the examples or comparative examples, 1 part by mass of triphenylsulfonium nonafluorobutanesulfonate, 0.2 parts by mass of tributylamine, 80 parts by mass of PGMEA, and 12 parts by mass of PGME were mixed to prepare a solution.

[0750] The solution was applied on a silicon wafer and baked at 110° C. for 60 seconds to form a photoresist layer with a film thickness of 100 nm.

[0751] Next, an extreme ultraviolet (EUV) exposure device "EUVES-7000" (product name, manufactured by Litho Tech Japan Corporation) was used to increase the exposure dose from 1 mJ / cm 2 Increase by 1mJ / cm 2 Up to 80mJ / cm 2 After unit exposure under maskless conditions up to 100%, baking (PEB) was performed at 110°C for 90 seconds, and development was performed with a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, to obtain a wafer with 80 units of unit exposure on the wafer. For each unit exposure area obtained, the film thickness was measured using an optical interference film thickness meter "VM3200" (product name, manufactured by SCREEN Semiconductor Solutions Co., Ltd.), and the profile data of the film thickness relative to the exposure amount was obtained. The exposure amount at which the slope of the film thickness change relative to the exposure amount becomes the largest was calculated as the sensitivity value (mJ / cm 2 ), as an indicator of the EUV sensitivity of the resist.

[0752] (Temporal sensitivity evaluation)

[0753] For the solution prepared in the above-mentioned EUV sensitivity evaluation, a forced time treatment was carried out under light-shielding conditions at 40°C / 240 hours, and the liquid after the time treatment was similarly subjected to EUV sensitivity evaluation, and an evaluation was performed based on the sensitivity change. As a specific evaluation method, in the EUV sensitivity evaluation, the sensitivity value at which the slope of the film thickness-sensitivity curve after development is the maximum when the horizontal axis is set to sensitivity and the vertical axis is set to film thickness is measured as the standard sensitivity. The standard sensitivity of the solution before and after the forced time treatment is respectively calculated, and the sensitivity shift caused by the time treatment is evaluated based on the numerical value obtained by the following calculation formula. The evaluation criteria are as follows.

[0754] [Sensitivity shift] = 1 - ([Standard sensitivity of the solution after time] ÷ [Standard sensitivity of the solution before time])

[0755] (Evaluation Criteria)

[0756] A: [Sensitivity offset] ≤ 0.005

[0757] B: 0.005<[Sensitivity offset]≤0.02

[0758] C: 0.02<[Sensitivity offset]≤0.05

[0759] D: 0.05<[Sensitivity offset]

[0760] (EB pattern-TMAH aqueous solution development)

[0761] A solution was prepared by mixing 5 parts by mass of the compound or polymer obtained in the examples or comparative examples, 1 part by mass of triphenylsulfonium nonafluorobutane sulfonate, 0.1 parts by mass of tributylamine and 92 parts by mass of PGMEA. The solution was applied on a silicon wafer and baked at 110 to 130° C. for 60 seconds to form a resist film with a film thickness of 100 nm.

[0762] Next, the pattern was exposed using an electron beam lithography apparatus "ELS-7500" (product name, manufactured by ELIONIX INC., 50 keV), baked (PEB) at 115°C for 90 seconds, and developed for 60 seconds using a 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution to obtain a positive pattern. It should be noted that the exposure amount was adjusted so as to obtain a half-pitch 50 nm line and space.

[0763] The obtained resist pattern was imaged with a scanning electron microscope "S-4800" (product name, manufactured by Hitachi, Ltd.) at a magnification of 100,000 times to obtain 80 pattern images, and the number of residues in the space between the resist patterns was counted and evaluated based on the total amount of residues. The evaluation criteria are as follows.

[0764] (Evaluation Criteria)

[0765] A: The number of residues ≤ 10

[0766] B: 10 < Number of residues ≤ 80

[0767] C: 80 <Number of residues ≤ 400

[0768] D: 400 < the number of residues

[0769] (Etching defect evaluation)

[0770] 5 parts by mass of the polymer obtained in the examples or comparative examples, 1 part by mass of triphenylsulfonium nonafluorobutanesulfonate, 0.2 parts by mass of tributylamine, 80 parts by mass of PGMEA, and 12 parts by mass of PGME were mixed to prepare a solution.

[0771] This solution was applied on an 8-inch silicon wafer having an oxide film with a thickness of 100 nm formed on the outermost layer, and baked at 110° C. for 60 seconds to form a photoresist layer with a thickness of 100 nm.

[0772] Next, the entire surface of the wafer was subjected to unit exposure using an extreme ultraviolet (EUV) exposure device "EUVES-7000" (product name, manufactured by Litho Tech Japan Corporation) with an exposure amount that was 10% less than the EUV sensitivity value obtained in the above EUV sensitivity evaluation, and then baked (PEB) at 110°C for 90 seconds and developed with a 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, thereby obtaining a wafer with 80 unit exposures on the entire surface.

[0773] The wafers that have been exposed are etched using an etching device "Telius SCCM" (product name, manufactured by Tokyo Electron Ltd.) using CF4 / Ar gas until the oxide film is etched to 50 nm. The wafers produced by etching are evaluated for defects using a defect inspection device "Surfscan SP5" (product name, manufactured by KLA), and the number of pyramidal defects larger than 19 nm is determined as an indicator of etching defects.

[0774] (Evaluation Criteria)

[0775] A: The number of cone defects is ≤ 10

[0776] B: 10 <Number of cone defects ≤ 80

[0777] C: 80 < the number of cone defects ≤ 400

[0778] D: 400 < the number of cone defects

[0779] (Evaluation of Etching Defect Changes over Time)

[0780] The solution prepared in the above etching defect evaluation was placed at room temperature under light-shielding conditions for 7 days, and the etching defect evaluation was performed on the liquid after placement in the same manner, and the evaluation was implemented based on the change in the number of defects. As a specific evaluation method, the case where the change in EUV sensitivity before and after placement was less than 6% was evaluated as "G", and the case where it was more than 6% was evaluated as "N".

[0781] [Table 4-3]

[0782]

[0783] [Table 5]

[0784]

[0785] [Table 6]

[0786]

[0787] From Table 4-3 and Table 5, it was confirmed that the stability of etching defects over time was improved when compound A contained a small amount of compound B such as BP1 to BP-4, BP11, and BP12.

[0788] According to Tables 4-3, 5 and 6, by containing a trace amount of compound B such as BP1 to BP6, BP11, BP12 in compound A of the present invention, the temporal stability of etching defects is improved. In addition, if the impurities of metals, maleic acid, and phosphorus-containing compounds are small, the temporal change of EUV sensitivity is suppressed, the residue is reduced, and the temporal stability of etching defects is improved.

[0789] (Time-dependent changes in etching defects due to addition of compound B)

[0790] Compositions were prepared using 5 parts by mass of polymers B1 to B52 obtained in Synthesis Examples B1 to B52 and BP1 to BP6, BP11, and BP12 as shown in Table 7, and the compositions were evaluated in the same manner as the above-mentioned evaluation of the change in etching defects over time.

[0791] [Table 7]

[0792]

[0793] From Table 4-3 and Table 7, it was confirmed that the polymer of the present invention contains a small amount of compound B such as BP1 to BP6, BP11, and BP12, and thus the temporal stability of etching defects is improved.

[0794] (Evaluation in organic solvent development)

[0795] Polymers B1, C3, C5, C3P, C5P, BR1, and BR2 were developed with an organic solvent by the following method and evaluated in the same manner as in Comparative Examples B1, B2, B37, and B38 and Examples C1, C2, C1P, and C2P. The evaluation results are shown in Table 8.

[0796] (EUV sensitivity-organic solvent development)

[0797] A solution containing the polymer obtained in the example or comparative example was prepared by the same method as EUV sensitivity-TMAH aqueous solution development, coated on a silicon wafer, and baked at 110° C. for 60 seconds to form a photoresist layer with a film thickness of 100 nm.

[0798] Next, an extreme ultraviolet (EUV) exposure device "EUVES-7000" (product name, manufactured by Litho Tech Japan Corporation) was used to increase the exposure dose from 1 mJ / cm 2 Increase by 1mJ / cm 2Up to 80mJ / cm 2 After unit exposure under maskless conditions up to 100°C, baking (PEB) was performed at 110°C for 90 seconds, and development was performed with butyl acetate for 30 seconds, to obtain a wafer with 80 units of unit exposure on the wafer. For each unit exposure area obtained, the film thickness was measured using an optical interference film thickness meter "VM3200" (product name, manufactured by SCREEN Semiconductor Solutions Co., Ltd.), and the profile data of the film thickness relative to the exposure amount was obtained. The exposure amount at which the slope of the film thickness change relative to the exposure amount became the maximum was calculated as the sensitivity value (mJ / cm 2 ), as an indicator of the EUV sensitivity of the resist.

[0799] The sensitivity over time was evaluated by the same method as EUV sensitivity-TMAH aqueous solution development. The evaluation results are shown in Table 8.

[0800] (EB pattern-organic solvent development)

[0801] The compound or polymer obtained in the example or comparative example was prepared by the same method as the EB pattern-TMAH aqueous solution development, coated on a silicon wafer, and baked at 110-130° C. for 60 seconds to form a resist film with a film thickness of 100 nm.

[0802] Next, the pattern was exposed using an electron beam lithography apparatus "ELS-7500" (product name, manufactured by ELIONIX INC., 50 keV), baked (PEB) at 115°C for 90 seconds, and developed using a 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds to obtain a negative pattern. It should be noted that the exposure amount was adjusted so as to obtain a half-pitch 50 nm line and space.

[0803] The obtained resist pattern was imaged with a scanning electron microscope "S-4800" (product name, manufactured by Hitachi, Ltd.) at a magnification of 100,000 times to obtain 80 pattern images, and the number of residues in the space between the resist patterns was counted and evaluated based on the total amount of residues. The evaluation criteria are as follows.

[0804] (Evaluation Criteria)

[0805] A: The number of residues ≤ 10

[0806] B: 10 < Number of residues ≤ 80

[0807] C: 80 <Number of residues ≤ 400

[0808] D: 400 < the number of residues

[0809] The same method as EUV sensitivity-TMAH aqueous solution development was used to evaluate etching defects and the change in etching defects over time. The evaluation results are shown in Table 8.

[0810] [Table 8]

[0811]

[0812] According to Table 8, even in the organic solvent development, it was confirmed that the stability of etching defects over time was improved.

[0813] (Resin Synthesis Example D1) Synthesis of P-MA8 Resin

[0814] 3.00 g of MA8, 4.5 g of EADMA, 0.62 g of methacrylate γ-butyrolactone and 0.87 g of 4-vinylphenol were dissolved in 50 mL of tetrahydrofuran, and 0.20 g of azobisisobutyronitrile was added. After refluxing for 12 hours, the reaction solution was added dropwise to 2 L of n-heptane. The precipitated resin was filtered and dried under reduced pressure to obtain a white powdery resin represented by the following chemical formula (P-MA8). The molecular weight (Mw) of the resin is 11,000, and the dispersion degree (Mw / Mn) is 1.93. In addition, the determination 13 The results of C-NMR showed that the composition ratio (molar ratio) in the following chemical formula (P-MA8) was a:b:c=10:20:50:20. It should be noted that the following chemical formula (P-MA-8) is simply recorded to show the ratio of each structural unit, and P-MA8 is not a block copolymer in which each structural unit forms a block independent of each other.

[0815]

[0816] Resin Synthesis Examples D2 to A10 were carried out in the same manner as in Resin Synthesis Example D1, except that P-MA8 was used in the following type and amount among the monomers used.

[0817] The Mw, dispersion degree, and monomer composition ratio a:b:c:d of the obtained resin are shown in the following table.

[0818] [Table 9]

[0819]

[0820] For the above-mentioned Synthesis Examples D1 to D10, D1P to D10P synthesized by performing the same purification treatment as Synthesis Example C1P were synthesized. The impurity content of the obtained polymers was evaluated in the same manner.

[0821] [Table 10]

[0822]

[0823] Furthermore, EUV sensitivity (TMAH aqueous solution development), sensitivity change over time, EB pattern (TMAH aqueous solution development), etching defects, and etching defect change over time were evaluated by the same method as C1P.

[0824] [Table 11]

[0825]

[0826] From the results of the above examples and comparative examples, it is understood that according to the composition of the present embodiment, a film-forming composition having excellent sensitivity to an exposure light source can be obtained, and the temporal stability of defects is improved.

[0827] Industrial Applicability

[0828] The present invention provides a composition, a film-forming composition, a pattern-forming method, and a compound that are excellent in sensitivity to exposure light sources and can suppress defects generated over time in a film or a pattern after development. The composition, the film-forming composition, the pattern-forming method, and the compound can be used as a photoresist used in photolithography in the manufacture of semiconductor elements and liquid crystal display elements.

Claims

1. A composition comprising a compound (A) represented by the following formula (1) and a compound (B) represented by the following formula (2), In formula (1), X is each 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, 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 phosphoric acid group, wherein L 1 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 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 thiol 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, an amide group, an imide group and a phosphoric acid group of Y may have a substituent, R a , R b and R c Each is independently H, I, F, Cl, Br or an organic group having 1 to 8 carbon atoms which may have a substituent, A is an organic group having 6 to 30 carbon atoms, 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 Z may have a substituent, p is an integer greater than or equal to 1, m is an integer greater than or equal to 1, n is an integer greater than or equal to 0, r is an integer greater than or equal to 0, In formula (2), X, L 1 , Y, R a , R b , R c , A, Z, p, m, n and r are the same as those described in formula (1), and k represents an integer of 0 to 2.

2. The composition according to claim 1, wherein Formula (1) is represented by the following formula (1a), In formula (1a), X, L 1 , Y, A, Z, p, m, n and r have the same definitions as in formula (1).

3. The composition according to claim 1, wherein Formula (1) is represented by the following formula (1b), In formula (1b), X, L 1 , Y, A, Z, p, m, n and r are the same as those in formula (1), R a1 , R b1 and R c1 Each is independently H, I, F, Cl, Br or an organic group having 1 to 8 carbon atoms which may have a substituent, R a1 , R b1 and R c1 At least one of them is I, F, Cl, Br or an organic group having 1 to 8 carbon atoms which may have a substituent.

4. The composition according to claim 1, wherein In the formula (1), n+r is an integer greater than or equal to 1.

5. The composition according to claim 1, wherein Each Y in formula (1) is independently a group represented by the following formula (Y-1), —L 2 ——R 2 (Y-1) In formula (Y-1), L 2 is a group that is cleaved by the action of an acid or a base, 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 heteroatoms having 1 to 30 carbon atoms, or an aromatic group containing heteroatoms having 1 to 30 carbon atoms, wherein R 2 The aliphatic group, aromatic group, heteroatom-containing aliphatic group, and heteroatom-containing aromatic group may further have a substituent.

6. The composition according to claim 1, wherein A in formula (1) is an aromatic ring.

7. The composition according to claim 1, wherein A in formula (1) is an alicyclic structure.

8. The composition according to claim 1, wherein A in formula (1) is a heterocyclic structure.

9. The composition according to claim 1, wherein In the formula (1), n ​​is 2 or more.

10. The composition according to claim 1, wherein The compound represented by formula (1) contains a functional group that improves solubility in an alkaline developer due to the action of an acid or a base.

11. The composition according to claim 1, wherein In formula (1), X is I, L 1 For a single key.

12. The composition according to claim 1, wherein X in the formula (1) is a group in which one or more F, Cl, Br or I are introduced into an aromatic group.

13. The composition according to claim 1, wherein X in the formula (1) is a group in which one or more F, Cl, Br or I are introduced into an alicyclic group.

14. The composition according to claim 1, wherein A in formula (2) is an aromatic ring.

15. The composition according to claim 14, wherein A in formula (2) is a benzene ring or a naphthalene ring.

16. The composition according to claim 1, wherein X in formula (2) is iodine or fluorine.

17. The composition according to claim 1, wherein L in formula (2) 1 For a single key.

18. The composition according to claim 1, wherein Y in formula (2) is a hydroxyl group, an alkoxy group, a carbonate group or an acetal group.

19. The composition according to claim 1, wherein The mass ratio of the content of the compound represented by formula (2) to the content of the compound represented by formula (1) is 1 ppm or more and 5 mass % or less.

20. The composition according to claim 1, comprising a compound represented by formula (2a), wherein the content of the compound represented by formula (2a) is 1% by mass or less relative to the compound represented by formula (1), In formula (2a), X, L 1 , Y, R a , R b , R c , A, Z, p, m, n and r are the same as those described in formula (1), and k represents an integer greater than 3.

21. The composition according to claim 20, wherein The amount of the peroxide is 10 ppm by mass or less based on the compound of formula (1).

22. The composition according to claim 20, wherein The 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 element conversion with respect to the compound of formula (1).

23. The composition according to claim 20, wherein The phosphorus-containing compound is contained in an amount of 10 ppm by mass or less based on the compound of formula (1).

24. The composition according to claim 20, wherein The content of maleic acid is 10 ppm by mass or less based on the compound of formula (1).

25. The composition according to claim 1, wherein In the formula (1) and the formula (2), all r are 0, and at least one n is 1 or more.

26. A resin composition comprising: A polymer comprising at least a structural unit represented by the following formula (4), wherein the number of structural units is 5 or more; A compound (B) represented by the following formula (2) in an amount of 1% by mass or less based on the polymer; and A compound (A) represented by the following formula (1), In formula (1), X is each 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, 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 phosphoric acid group, wherein L 1 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 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 thiol 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, an amide group, an imide group and a phosphoric acid group of Y may have a substituent, R a , R b and R c Each is independently H, I, F, Cl, Br or an organic group having 1 to 8 carbon atoms which may have a substituent, A is an organic group having 6 to 30 carbon atoms, 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 Z may have a substituent, p is an integer greater than or equal to 1, m is an integer greater than or equal to 1, n is an integer greater than or equal to 0, r is an integer greater than or equal to 0, In formula (2), X, L 1 , Y, R a , R b , R c , A, Z, p, m, n and r are the same as those described in formula (1), k represents an integer of 0 to 2, In formula (4), X, L 1 , Y, R a , R b , R c , A, Z, p, m, n and r have the same definitions as in formula (1), * is a bonding site to an adjacent structural unit.

27. The resin composition according to claim 26, wherein The polymer further comprises a structural unit represented by the following formula (C6), In formula (C6), X C61 is a hydroxyl group or a halogen group, R C61 are each independently an alkyl group having 1 to 20 carbon atoms, * is a bonding site to an adjacent structural unit.

28. The resin composition according to claim 26, wherein In the above formula (1), the above formula (2) and the above formula (4), all r are 0, and at least one n is 1 or more. 29 . A film-forming composition comprising the composition according to claim 1 , or the resin composition according to claim 26 . 30 . The film-forming composition according to claim 29 , further comprising an acid generator, a base generator or a base compound.

31. A method for forming a resist pattern, comprising: A step of forming a resist film on a substrate using a film-forming composition comprising the composition according to any one of claims 1 to 24 or the resin composition according to any one of claims 26 to 28, a step of exposing the resist film to a pattern, and After the exposure, the resist film is subjected to a development process.

32. A compound represented by the following formula (2), In formula (2), X is each 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, 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 phosphoric acid group, wherein L 1 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 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 thiol 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, an amide group, an imide group and a phosphoric acid group of Y may have a substituent, R a , R b and R c Each is independently H, I, F, Cl, Br or an organic group having 1 to 8 carbon atoms which may have a substituent, A is an organic group having 6 to 30 carbon atoms, 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 Z may have a substituent, p is an integer greater than or equal to 1, m is an integer greater than or equal to 1, n is an integer greater than or equal to 0, r is an integer greater than or equal to 0, k represents an integer of 0 or more and 2 or less.

33. The compound according to claim 32, wherein In the formula (2), all r's are 0, and at least one n is 1 or greater.

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