Compound, polymer, composition, film-forming composition, pattern forming method, insulating film forming method, and compound manufacturing method

Abstract

Provided are a compound, polymer, composition, film-forming composition, pattern formation method, method for forming insulating films, and compound production method, that yield a resist that exhibits excellent exposure sensitivity.　The compound is represented by formula (1). (In formula (1), RA is a hydrogen atom, methyl group, or trifluoromethyl group; RX is ORB or a hydrogen atom; RB is a substituted or unsubstituted C1-30 alkyl group; and P is a hydroxyl group, alkoxy group, ester group, acetal group, carboxyalkoxy group, carbonate ester group, nitro group, amino group, carboxyl group, thiol group, ether group, thioether group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, or phosphoric acid group.)

Description

[Technical Field]

[0001] The present invention relates to a compound, a polymer, a composition, a film-forming composition, a pattern-forming method, a method for forming an insulating film, and a method for producing a compound. [Background technology]

[0002] In recent years, advances in lithography technology have led to rapid advances in the miniaturization of semiconductors (patterns) and pixels in the manufacture of semiconductor elements and liquid crystal display elements. To achieve this, exposure light sources are generally being shortened in wavelength. While ultraviolet light, typically g-line and i-line, was previously used, mass production is now dominated by exposure techniques using far-ultraviolet light, such as KrF excimer lasers (248 nm) and ArF excimer lasers (193 nm). Extreme ultraviolet (EUV) lithography (13.5 nm) is also increasingly being adopted. Electron beams (EB) are also used to form fine patterns.

[0003] Conventional resist materials are polymeric resist materials capable of forming amorphous films. Examples include polymeric resist compositions such as polymethyl methacrylate, and polyhydroxystyrene or polyalkyl methacrylate having an acid-dissociable group (see, for example, Non-Patent Document 1). Conventionally, a thin resist film is prepared by applying a solution of such a resist composition onto a substrate, and then irradiating the thin resist film with ultraviolet light, far ultraviolet light, an electron beam, extreme ultraviolet light, or the like to form a line pattern of approximately 10 to 100 nm.

[0004] Furthermore, the reaction mechanism of electron beam or extreme ultraviolet (EUV) lithography differs from that of conventional optical lithography (Non-Patent Documents 2 and 3). Furthermore, electron beam or extreme ultraviolet lithography aims to form fine patterns of several nm to several tens of nm. As the dimensions of resist patterns become smaller, resist compositions with even higher sensitivity to the exposure light source are required. In particular, extreme ultraviolet (EUV) lithography is required to achieve even higher sensitivity in terms of throughput. Sensitivity to extreme ultraviolet (EUV) does not necessarily correlate with sensitivity to electron beam (EB), and it is required to exhibit particularly high sensitivity to extreme ultraviolet (EUV). As a resist material that can solve the above-mentioned problems, a resist composition containing a metal complex of titanium, tin, hafnium, zirconium, or the like has been proposed (see, for example, Patent Document 1).

[0005] Furthermore, as the dimensions of resist patterns become smaller, resist compositions with even higher sensitivity to exposure light sources are required, and iodine-containing 4-hydroxystyrene has been proposed as a raw material monomer for such compositions (see, for example, Patent Documents 2 and 3), but its effectiveness leaves room for improvement. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-108781 [Patent Document 2] US Patent Application Publication No. 2019 / 0187342 [Patent Document 3] International Publication No. 2019 / 187881 [Non-patent literature]

[0007] [Non-Patent Document 1] Shinji Okazaki and 8 others, "40 Years of Lithography Technology," S&T Publishing, December 9, 2016 [Non-patent document 2] H. Yamamoto, et al., Jpn.J.Appl.Phys.46,L142(2007) [Non-patent document 3] H. Yamamoto, et al., J.Vac.Sci.Technol.b 23,2728(2005) Summary of the Invention [Problem to be solved by the invention]

[0008] However, the film-forming compositions that have been developed so far have a problem in that they do not have a sufficiently high sensitivity to the exposure light source when forming finer patterns.

[0009] In order to solve these problems, an object of the present invention is to provide a compound, a polymer, a composition, a film-forming composition, a pattern-forming method, a method for forming an insulating film, and a method for producing a compound, which are capable of producing a resist having superior exposure sensitivity. [Means for solving the problem]

[0010] As a result of intensive research to solve the above-mentioned problems, the present inventors have found that it is possible to improve the exposure sensitivity of a resist formed using a compound having a specific structure or a polymer containing such a compound as a structural unit, and have thereby completed the present invention. That is, the present invention is as follows.

[0011] [1] A compound represented by the following formula (1): [ka] (In formula (1), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R X is OR B or a hydrogen atom, and R Bis a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group. [2] R A is a hydrogen atom or a methyl group. [3] R B is an alkyl group having 1 to 4 carbon atoms. [4] The compound according to any one of [1] to [3], wherein P is a hydroxyl group, an ester group, an acetal group, a carbonate ester group, or a carboxyalkoxy group. [5] The compound according to any one of [1] to [4], wherein P is an ester group, an acetal group, or a carbonate ester group. [6] A composition comprising a compound represented by the following formula (1A) in an amount of 1 ppm by mass or more and 10% by mass or less based on the total amount of the compound according to any one of [1] to [5]: [ka] (In formula (1A), formula (1A1), and formula (1A2), R A , R X , R B and P are the same as defined in formula (1), and R sub represents formula (1A1) or formula (1A2), and * represents the bonding site to the adjacent structural unit. [7] A composition comprising the compound according to any one of [1] to [5] and a compound represented by the following formula (1B) in an amount of 1 ppm by mass or more and 10% by mass or less based on the total amount of the compound: [ka] (In formula (1B), formula (1B1), or formula (1B2), R A , R X , R B and P are the same as defined in formula (1), n2 is an integer of 0 to 4, and R sub2 represents formula (1B1) or formula (1B2), and * represents the bonding site to the adjacent structural unit. [8] A composition comprising a compound represented by the following formula (1C) in an amount of 1 ppm by mass or more and 10% by mass or less based on the total amount of the compound according to any one of [1] to [5]: [ka] (In formula (1C), R A , R X , R B and P are defined as in formula (1). B and P do not contain I.) [9] [1] to [5], which contains the compound according to any one of [1] to [5], The composition has an elemental content of impurities containing K of 1 ppm by mass or less relative to the total amount of the compound.

[10] The composition according to [9], wherein the content of peroxide is 10 ppm by mass or less based on the total amount of the compounds.

[11] The composition according to [9] or

[10] , wherein the content of impurities containing one or more elements selected from the group consisting of Mn, Al, Si, and Li is 1 mass ppm or less, calculated as the element, based on the total amount of the compound.

[12] The composition according to any one of [9] to

[11] , wherein the content of the phosphorus-containing compound is 10 ppm by mass or less based on the total amount of the compounds.

[13] The composition according to any one of [9] to

[12] , wherein the content of maleic acid is 10 ppm by mass or less based on the total amount of the compounds.

[14] A polymer comprising a structural unit derived from the compound according to any one of [1] to [5], and represented by the following formula (1-A): [ka] (In formula (1-A), R A , R X , R B and P are defined as in formula (1), and * represents the bonding site to the adjacent structural unit.

[15] The polymer according to

[14] , further comprising a constitutional unit represented by the following formula (C0), the following formula (C1), or the following formula (C2): [ka] (In formula (C0), X's each independently represent I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 to 5 substituents selected from the group consisting of I, F, Cl, and Br; L 1 are each independently a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and 1 The ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, or phosphate group may have a substituent, Y's each independently represent a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphonic group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphonic group, urethane group, urea group, amide group, imide group, and phosphate group of Y may have a substituent, R A is the same as the definition in equation (1), A is an organic group having 1 to 30 carbon atoms, Z's each independently represent an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, or a carbonate ester group, and the alkoxy group, ester group, acetal group, carboxyalkoxy group, or carbonate ester group of Z may have a substituent; m is an integer of 0 or greater, n is an integer of 1 or greater, and r is an integer of 0 or greater. [ka] (In formula (C1), R C11 is a hydrogen atom, a methyl group, or a trifluoromethyl group, R C12 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R C13 is R C13 and the carbon atom to which they are bonded are taken together to form a cycloalkyl or heterocycloalkyl group having 4 to 20 carbon atoms, * indicates the bonding site with the adjacent structural unit. Furthermore, in formula (C2), R C21 is a hydrogen atom, a methyl group, or a trifluoromethyl group, R C22 and R C23 are each independently an alkyl group having 1 to 4 carbon atoms, R C24is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms, R C22 , R C23 , and R C24 Two or three of the R C22 , R C23 , and R C24 may form an alicyclic structure having 3 to 20 carbon atoms, formed together with carbon atoms bonding to two or three of * indicates the bonding site with the adjacent structural unit.)

[16] A film-forming composition comprising the compound according to any one of [1] to [5], the composition according to any one of [6] to

[13] , or the polymer according to

[14] or

[15] .

[17] The film-forming composition according to

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

[18] forming a resist film on a substrate using the film-forming composition according to

[16] or

[17] ; exposing the resist film to a pattern; a step of developing the resist film after exposure; A method for forming a resist pattern, comprising:

[19] forming a resist film on a substrate using the film-forming composition according to

[16] or

[17] ; exposing the resist film to a pattern; and developing the resist film after exposure.

[20] a) A general structure represented by the following formula (1-1): [ka] (In formula (1-1), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R X is OR B or a hydrogen atom, and R Bis a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7 ~R 10 are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7 ~R 10 one of which is a hydroxyl group or a methoxy group; b) a dehydration step of subjecting the iodine-containing alcoholic substrate to a dehydration treatment; A method for producing an iodine-containing vinyl monomer represented by the following formula (1): [ka] (In formula (1), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group. [twenty one] moreover, c) A general structure represented by the following formula (1-2): [ka] (In formula (1-2), R X is OR B or a hydrogen atom, and R Bis a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7 ~R 10 are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7 ~R 10 one of which is a hydroxyl group or a methoxy group; d) a reduction step of subjecting the iodine-containing ketone substrate to a reduction treatment; A method for producing an iodine-containing vinyl monomer represented by formula (1) described in

[20] , comprising: [twenty two] moreover, e) A general structure represented by the following formula (1-3): [ka] (In formula (1-3), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7 ~R 10 are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7 ~R 10 one of which is a hydroxyl group or a methoxy group; f) an iodine introduction step of introducing an iodine atom into the alcoholic substrate;

[20] A method for producing an iodine-containing vinyl monomer represented by formula (1), comprising: [twenty three] moreover, g) A general structure represented by the following formula (1-4): [ka] (In formula (1-4), R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7 ~R 10 are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7 ~R 10 wherein one of the groups is a hydroxyl group or a methoxy group; h) an iodine introduction step of introducing an iodine atom into the ketone substrate;

[20] A method for producing an iodine-containing vinyl monomer represented by formula (1), comprising: [twenty four] moreover, i) A general structure represented by the following formula (1-4): [ka] (In formula (1-4), R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R7 ~R 10 are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7 ~R 10 wherein one of the groups is a hydroxyl group or a methoxy group; j) a reduction step of subjecting the ketone substrate to a reduction treatment. [twenty five] k) A general structure represented by the following formula (1): [ka] (In formula (1), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group. providing an iodine-containing vinyl monomer having: l) an acylation step of subjecting the iodine-containing vinyl monomer to an acylation treatment; A method for producing an iodine-containing vinyl monomer represented by the following formula (2): [ka] (In formula (2), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and R C is a substituted or unsubstituted acyl group having 1 to 30 carbon atoms.

[26] c) A general structure represented by the following formula (1-2): [ka] (In formula (1-2), R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7 ~R 10 are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7 ~R 10 one of which is a hydroxyl group or a methoxy group; d) a reduction step of subjecting the iodine-containing ketone substrate to a reduction treatment; A method for producing an iodine-containing alcoholic compound represented by the following formula (1-1): [ka] (In formula (1-1), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7 ~R 10 are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7 ~R 10One of the groups is a hydroxyl group or a methoxy group.)

[27] e) A general structure represented by the following formula (1-3): [ka] (In formula (1-3), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7 ~R 10 are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7 ~R 10 one of which is a hydroxyl group or a methoxy group; f) an iodine introduction step of introducing an iodine atom into the alcoholic substrate; A method for producing an iodine-containing alcoholic compound represented by the following formula (1-1): [ka] (In formula (1-1), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7 ~R 10are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7 ~R 10 One of the groups is a hydroxyl group or a methoxy group.)

[28] g) A general structure represented by the following formula (1-4): [ka] (In formula (1-4), R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7 ~R 10 are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7 ~R 10 one of which is a hydroxyl group or a methoxy group; h) an iodine introduction step of introducing an iodine atom into the ketone substrate; A method for producing an iodine-containing ketone compound represented by the following formula (1-2): [ka] (In formula (1-2), R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7 ~R 10are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7 ~R 10 One of the groups is a hydroxyl group or a methoxy group.)

[29] i) A general structure represented by the following formula (1-4): [ka] (In formula (1-4), R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7 ~R 10 are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7 ~R 10 one of which is a hydroxyl group or a methoxy group; j) a reduction step of subjecting the ketone substrate to a reduction treatment; A method for producing an alcohol compound represented by the following formula (1-3): [ka] (In formula (1-3), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7~R 10 are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7 ~R 10 One of the groups is a hydroxyl group or a methoxy group.)

[30] a) A general structure represented by the following formula (1-5): [ka] (In formula (1-5), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphonic group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group; b) a Wittig reaction step of forming an alkene from the carbonyl moiety of the iodine-containing aldehyde substrate or the iodine-containing ketone substrate by a Wittig reaction; A method for producing an iodine-containing vinyl monomer represented by the following formula (1): [ka] (In formula (1), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group.

[31] a) A general structure represented by the following formula (1-5): [ka] (In formula (1-5), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphonic group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group; b) a malonic acid addition step of adding malonic acid to the iodine-containing aldehyde substrate or the iodine-containing ketone substrate; c) a hydrolysis step of hydrolyzing the malonic acid-added iodine-containing aldehyde substrate or the iodine-containing ketone substrate to produce an iodine-containing carboxylic acid substrate; d) a decarboxylation step of subjecting the iodine-containing carboxylic acid substrate to a decarboxylation treatment; A method for producing an iodine-containing vinyl monomer represented by the following formula (1): [ka] (In formula (1), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R X is OR B or a hydrogen atom, and R Bis a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group.

[32] The compound, polymer, composition, film-forming composition, pattern forming method, insulating film forming method, and compound manufacturing method according to any one of [1] to

[31] , which are used for extreme ultraviolet applications. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a compound, a polymer, a composition, a film-forming composition, a pattern forming method, a method for forming an insulating film, and a method for producing a compound, which are capable of obtaining a resist having superior exposure sensitivity. DETAILED DESCRIPTION OF THE INVENTION

[0013] First Embodiment A first embodiment of the present invention will be described below (hereinafter, may be referred to as "the present embodiment"). Note that the present embodiment is an example for explaining the present invention, and the present invention is not limited to only this embodiment.

[0014] In this specification, the meanings of the terms are as follows. "(Meth)acrylate" refers to at least one selected from acrylate, haloacrylate, and methacrylate. Haloacrylate refers to an acrylate in which a halogen is substituted at the methyl group position of a methacrylate. Other terms containing the term (meth) are also interpreted in the same way as (meth)acrylate. The term "(co)polymer" means at least one selected from a homopolymer and a copolymer.

[0015] [Compound (A)] The compound according to the first embodiment (hereinafter also referred to as "compound (A)" in the first embodiment) is represented by the following formula (1). [ka] (In formula (1), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group.

[0016] The compound (A) according to this embodiment can provide a compound that allows a resist having superior exposure sensitivity to be obtained.

[0017] In this embodiment, unless otherwise defined, "substituted" means that one or more hydrogen atoms in a functional group are substituted with a substituent. Examples of the "substituent" include, but are not limited to, 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 alkoxyl 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. The alkyl group may be a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, or a cyclic aliphatic hydrocarbon group.

[0018] In order to increase the sensitivity, in order to increase the hydrophilicity, R A is preferably a hydrogen atom or a methyl group.

[0019] R B is preferably an alkyl group having 1 to 4 carbon atoms.

[0020] From the viewpoint of high sensitivity, P is preferably a hydroxyl group, an ester group, an acetal group, a carbonate ester group, or a carboxyalkoxy group, and more preferably an ester group, an acetal group, or a carbonate ester group.

[0021] The above compound (A) is preferably used in combination with a compound represented by the following formula (1A). That is, the composition according to the present embodiment preferably contains compound (A) and a compound represented by formula (1A). From the viewpoint of improving exposure sensitivity and reducing residue defects, the composition is prepared so that the compound represented by formula (1A) is contained in an amount of from 1 ppm by mass to 10% by mass, more preferably from 1 ppm by mass to 5% by mass, even more preferably from 1 ppm by mass to 3% by mass, and particularly preferably from 1 ppm by mass to 1% by mass, based on the total amount of compound (A). [ka] (In formula (1A), formula (1A1), and formula (1A2), R A , R X , R B and P are the same as defined in formula (1), and R sub represents formula (1A1) or formula (1A2), and * represents the bonding site to the adjacent structural unit.

[0022] The compound (A) is preferably used in combination with a compound represented by the following formula (1B). That is, the composition according to this embodiment preferably contains the compound (A) and the compound represented by formula (1B). From the viewpoint of improving exposure sensitivity and reducing residue defects, the composition is prepared so that the compound represented by formula (1B) is contained in an amount of from 1 ppm by mass to 10% by mass, more preferably from 1 ppm by mass to 5% by mass, even more preferably from 1 ppm by mass to 3% by mass, and particularly preferably from 1 ppm by mass to 1% by mass, based on the total amount of the compound (A). [ka] (In formula (1B), formula (1B1), or formula (1B2), R A , R X , R B and P are the same as defined in formula (1), n2 is an integer of 0 to 4, and R sub2 represents formula (1B1) or formula (1B2), and * represents the bonding site to the adjacent structural unit.

[0023] The above compound (A) is preferably used in combination with the following formula (1C). That is, the composition according to this embodiment preferably contains the compound (A) and the compound represented by formula (1C). From the viewpoint of stability and reducing residual defects, the composition preferably contains the compound represented by formula (1C) in an amount of from 1 ppm by mass to 10% by mass, more preferably from 1 ppm by mass to 5% by mass, even more preferably from 1 ppm by mass to 3% by mass, and particularly preferably from 1 ppm by mass to 1% by mass, based on the total amount of the compounds (A). [ka] (In formula (1C), R A , R X , R Band P are defined as in formula (1). B and P do not contain I.)

[0024] The composition of the present embodiment contains compound (A). The composition may contain K (potassium). The content of impurities including K in the composition is, in elemental terms, preferably 1 ppm by mass or less, more preferably 0.5 ppm by mass or less, even more preferably 0.1 ppm by mass or less, and still more preferably 0.005 ppm by mass or less, based on the total amount of compound (A).

[0025] In the composition of the present embodiment, the content of peroxide is preferably 10 ppm by mass or less, more preferably 1 ppm or less, and even more preferably 0.1 ppm or less, based on the total amount of compound (A).

[0026] In the composition of the present embodiment, the content of one or more elemental impurities selected from the group consisting of Mn (manganese), Al (aluminum), Si (silicon), and Li (lithium) (preferably one or more elemental impurities selected from the group consisting of Mn and Al) is preferably 1 ppm or less, more preferably 0.5 ppm or less, and even more preferably 0.1 ppm or less, in terms of element, relative to the entire compound (A).

[0027] In the composition of the present embodiment, the content of the phosphorus-containing compound is preferably 10 ppm or less, more preferably 8 ppm or less, and even more preferably 5 ppm or less, based on the total amount of compound (A).

[0028] In the composition of the present embodiment, the content of maleic acid is preferably 10 ppm or less, more preferably 8 ppm or less, and even more preferably 5 ppm or less, based on the total amount of compound (A).

[0029] [Polymer (A)] The polymer (A) of this embodiment contains a structural unit derived from the compound (A). By including the structural unit derived from the compound (A), the polymer (A) can enhance sensitivity to an exposure light source when incorporated into a resist composition. In particular, even when extreme ultraviolet light is used as the exposure light source, the polymer (A) exhibits sufficient sensitivity and can successfully form a fine line pattern with a narrow line width.

[0030] According to the polymer (A) of this embodiment, the stability of the resist composition is improved, and even when stored for a long period of time, a decrease in sensitivity to an exposure light source is suppressed.

[0031] The polymer (A) of the present embodiment contains a structural unit derived from the compound (A). The structural unit derived from the compound (A) contained in the polymer (A) includes, for example, a structural unit represented by the following formula (1-A). [ka] (In formula (1-A), R A , R X , R B and P are defined as in formula (1), and * represents the bonding site to the adjacent structural unit.

[0032] In addition, in the polymer (A), the other monomer copolymerized with the compound (A) preferably contains a structural unit represented by the following formula (C0): That is, the polymer (A) preferably further contains a structural unit represented by the following formula (C0), (C1), or (C2), in addition to the structural unit represented by formula (1-A). [ka] (In formula (C0), X's each independently represent I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 to 5 substituents selected from the group consisting of I, F, Cl, and Br; L 1are each independently a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and 1 The ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, or phosphate group may have a substituent, Y's each independently represent a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphonic group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphonic group, urethane group, urea group, amide group, imide group, and phosphate group of Y may have a substituent, R A is the same as the definition in equation (1), A is an organic group having 1 to 30 carbon atoms, Z's each independently represent an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, or a carbonate ester group, and the alkoxy group, ester group, acetal group, carboxyalkoxy group, or carbonate ester group of Z may have a substituent; m is an integer of 0 or greater, n is an integer of 1 or greater, and r is an integer of 0 or greater. [ka] (In formula (C1), R C11 is a hydrogen atom, a methyl group, or a trifluoromethyl group, R C12 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R C13 is R C13and the carbon atom to which they are bonded are taken together to form a cycloalkyl or heterocycloalkyl group having 4 to 20 carbon atoms, * indicates the bonding site with the adjacent structural unit. Furthermore, in formula (C2), R C21 is a hydrogen atom, a methyl group, or a trifluoromethyl group, R C22 and R C23 are each independently an alkyl group having 1 to 4 carbon atoms, R C24 is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms, R C22 , R C23 , and R C24 Two or three of the R C22 , R C23 , and R C24 may form an alicyclic structure having 3 to 20 carbon atoms, formed together with carbon atoms bonding to two or three of * indicates the bonding site with the adjacent structural unit.)

[0033] [Film forming composition] The film-forming composition of this embodiment can also be used as an optical component-forming composition that applies lithography technology. Optical components are used in film and sheet form, and are useful as plastic lenses (prism lenses, lenticular lenses, microlenses, Fresnel lenses, viewing angle control lenses, contrast enhancement lenses, etc.), retardation films, electromagnetic wave shielding films, prisms, optical fibers, solder resists for flexible printed wiring, plating resists, interlayer insulating films for multilayer printed wiring boards, photosensitive optical waveguides, liquid crystal displays, organic electroluminescence (EL) displays, optical semiconductor (LED) elements, solid-state imaging elements, organic thin-film solar cells, dye-sensitized solar cells, and organic thin-film transistors (TFTs). The composition is particularly suitable for use as a filling film and planarizing film on photodiodes, planarizing films before and after color filters, microlenses, and planarizing and conformal films on microlenses, which are components of solid-state imaging elements that require a high refractive index.

[0034] The film-forming composition of this embodiment may contain the compound (A), the composition of this embodiment, or the polymer (A). The film-forming composition of this embodiment may further contain an acid generator (C), a base generator (G), or an acid diffusion controller (E) (basic compound).

[0035] [Method for forming resist pattern and insulating film] The method for forming a resist pattern of this embodiment includes: forming a resist film on a substrate using the film-forming composition of the present embodiment; exposing the resist film to a pattern; a step of developing the resist film after the exposure; may include:

[0036] The method for forming an insulating film of this embodiment may include the method for forming a resist pattern of this embodiment. That is, the method for forming an insulating film of this embodiment includes: forming a resist film on a substrate using the film-forming composition of the present embodiment; exposing the resist film to a pattern; a step of developing the resist film after the exposure; may include:

[0037] In the present embodiment, the method for producing the iodine-containing vinyl monomer represented by formula (1) is as follows: a) A general structure represented by the following formula (1-1): [ka] (In formula (1-1), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7 ~R 10 are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7 ~R 10 one of which is a hydroxyl group or a methoxy group; b) a dehydration step of subjecting the iodine-containing alcoholic substrate to a dehydration treatment; may include: [ka] (In formula (1), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R X is OR B or a hydrogen atom, and R Bis a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group.

[0038] In this embodiment, the method for producing the iodine-containing vinyl monomer represented by formula (1) further comprises: c) A general structure represented by the following formula (1-2): [ka] (In formula (1-2), R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7 ~R 10 are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7 ~R 10 one of which is a hydroxyl group or a methoxy group; d) a reduction step of subjecting the iodine-containing ketone substrate to a reduction treatment; may include:

[0039] In this embodiment, the method for producing the iodine-containing vinyl monomer represented by formula (1) further comprises: e) A general structure represented by the following formula (1-3): [ka] (In formula (1-3), R Ais a hydrogen atom, a methyl group, or a trifluoromethyl group, and R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7 ~R 10 are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7 ~R 10 one of which is a hydroxyl group or a methoxy group; f) an iodine introduction step of introducing an iodine atom into the alcoholic substrate; may include:

[0040] In the present embodiment, the method for producing the iodine-containing vinyl monomer represented by formula (1) further includes the steps of: g) A general structure represented by the following formula (1-4): [ka] (In formula (1-4), R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7 ~R 10 are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7 ~R 10 wherein one of the groups is a hydroxyl group or a methoxy group; h) an iodine introduction step of introducing an iodine atom into the ketone substrate; may include:

[0041] In this embodiment, the method for producing the iodine-containing vinyl monomer represented by formula (1) further comprises: i) A general structure represented by the following formula (1-4): [ka] (In formula (1-4), R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7 ~R 10 are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7 ~R 10 wherein one of the groups is a hydroxyl group or a methoxy group; j) a reduction step of subjecting the ketone substrate to a reduction treatment.

[0042] In the present embodiment, a method for producing an iodine-containing vinyl monomer represented by the following formula (2) is k) A general structure represented by the following formula (1): [ka] (In formula (1), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R X is OR B or a hydrogen atom, and R Bis a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group. providing an iodine-containing vinyl monomer having: l) an acylation step of subjecting the iodine-containing vinyl monomer to an acylation treatment; may include: [ka] (In formula (2), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and R C is a substituted or unsubstituted acyl group having 1 to 30 carbon atoms.

[0043] In the present embodiment, a method for producing an iodine-containing alcoholic compound represented by the following formula (1-1) is c) A general structure represented by the following formula (1-2): [ka] (In formula (1-2), R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7 ~R 10 are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7~R 10 one of which is a hydroxyl group or a methoxy group; d) a reduction step of subjecting the iodine-containing ketone substrate to a reduction treatment; may include: [ka] (In formula (1-1), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7 ~R 10 are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7 ~R 10 One of the groups is a hydroxyl group or a methoxy group.)

[0044] In the present embodiment, a method for producing an iodine-containing alcoholic compound represented by the following formula (1-1) is e) A general structure represented by the following formula (1-3): [ka] (In formula (1-3), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R X is OR B or a hydrogen atom, and R Bis a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7 ~R 10 are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7 ~R 10 one of which is a hydroxyl group or a methoxy group; f) an iodine introduction step of introducing an iodine atom into the alcoholic substrate; may include: [ka] (In formula (1-1), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7 ~R 10 are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7 ~R 10 One of the groups is a hydroxyl group or a methoxy group.)

[0045] In the present embodiment, a method for producing an iodine-containing ketone compound represented by the following formula (1-2) is g) A general structure represented by the following formula (1-4): [ka] (In formula (1-4), R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7 ~R 10 are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7 ~R 10 one of which is a hydroxyl group or a methoxy group; h) an iodine introduction step of introducing an iodine atom into the ketone substrate; may include: [ka] (In formula (1-2), R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7 ~R 10 are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7 ~R 10 One of the groups is a hydroxyl group or a methoxy group.)

[0046] In the present embodiment, a method for producing an iodine-containing vinyl monomer represented by the following formula (1) is i) A general structure represented by the following formula (1-4): [ka] (In formula (1-4), R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7 ~R 10 are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7 ~R 10 one of which is a hydroxyl group or a methoxy group; j) a reduction step of subjecting the ketone substrate to a reduction treatment; and [ka] (In formula (1-3), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7 ~R 10 are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7 ~R 10 One of the groups is a hydroxyl group or a methoxy group.)

[0047] In the present embodiment, a method for producing an iodine-containing vinyl monomer represented by the following formula (1) is a) A general structure represented by the following formula (1-5): [ka] (In formula (1-5), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphonic group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group; b) a Wittig reaction step of forming an alkene from the carbonyl moiety of the iodine-containing aldehyde substrate or the iodine-containing ketone substrate by a Wittig reaction; may include: [ka] (In formula (1), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group.

[0048] In the present embodiment, a method for producing an iodine-containing vinyl monomer represented by the following formula (1) is a) A general structure represented by the following formula (1-5): [ka] (In formula (1-5), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphonic group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group; b) a malonic acid addition step of adding malonic acid to the iodine-containing aldehyde substrate or the iodine-containing ketone substrate; c) a hydrolysis step of hydrolyzing the malonic acid-added iodine-containing aldehyde substrate or the iodine-containing ketone substrate to produce an iodine-containing carboxylic acid substrate; d) a decarboxylation step of subjecting the iodine-containing carboxylic acid substrate to a decarboxylation treatment; may include: [ka] (In formula (1), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group.

[0049] The compound, polymer, composition, film-forming composition, pattern forming method, insulating film forming method, and compound manufacturing method described above in this embodiment may be applied to extreme ultraviolet applications.

[0050] The first embodiment has been described above.

[0051] Second Embodiment The second embodiment of the present invention will be described below. The second embodiment is a compound (A) according to the first embodiment, in which R X OR B The second embodiment is an embodiment in which the above-mentioned case is satisfied. Note that the second embodiment is an example for explaining the present invention, and the present invention is not limited to only the second embodiment.

[0052] [Compound (A)] The compound according to the second embodiment (hereinafter also referred to as "compound (A)") is represented by the following formula (1).

[0053] [ka]

[0054] In formula (1), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group.

[0055] In formula (1), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group. From the viewpoint of increasing hydrophilicity for high sensitivity, R A is preferably a hydrogen atom or a methyl group. In order to increase sensitivity, in order to increase absorption of EUV, R A is preferably a trifluoromethyl group.

[0056] In formula (1), R Bis a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms. From the viewpoints of industrial production, raw material availability, high sensitivity, and enhanced hydrophilicity, R B is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms.

[0057] In the second embodiment, unless otherwise defined, "substituted" means that one or more hydrogen atoms in a functional group are substituted with a substituent. The "substituent" is not particularly limited, but 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 alkoxyl 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. The alkyl group may be any of a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, and a cyclic aliphatic hydrocarbon group.

[0058] Examples of the alkyl group having 1 to 30 carbon atoms include, but are not limited to, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-dodecyl group, and a valeric group. Examples of the aryl group having 6 to 30 carbon atoms include, but are not limited to, a phenyl group, a naphthalene group, a biphenyl group, an anthracyl group, a pyrenyl group, and a perylene group. Examples of the alkenyl group having 2 to 30 carbon atoms include, but are not limited to, an ethynyl group, a propenyl group, a butynyl group, and a pentynyl group. Examples of the alkynyl group having 2 to 30 carbon atoms include, but are not limited to, an acetylene group and an ethynyl group. 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 pentoxy group.

[0059] In formula (1), each P independently represents a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphonic group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphonic group, urethane group, urea group, amide group, imide group, and phosphate group of P may have a substituent. P can be, for example, an 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 are each independently H or a hydrocarbon group having 1 to 10 carbon atoms. 2 and R 21 may be bonded to form a cyclic ether. )], carboxyalkoxy group [* 3 -OR 22 -(C=O)-OR 2 (R 22 is a divalent hydrocarbon group having 1 to 10 carbon atoms. )], and a carbonate ester group [* 3 -O-(C=O)-OR 2 In terms of increasing sensitivity, the ester group is preferably a tertiary ester group. 3 is the binding site for A.

[0060] Among these, from the viewpoint of high sensitivity, P is preferably a hydroxyl group, an ester group, an acetal group, a carbonate ester group, or a carboxyalkoxy group, more preferably an acetal group, a carbonate ester group, or a carboxyalkoxy group, and even more preferably an acetal group or a carboxyalkoxy group. Furthermore, from the viewpoint of producing a polymer of stable quality by radical polymerization, an ester group, a carboxyalkoxy group, or a carbonate ester group is preferred. Furthermore, from the viewpoint of increasing the difference in dissolution rate before and after exposure to improve resolution, a tertiary ester group, an acetal group, a carbonate ester group, or a carboxyalkoxy group is preferred.

[0061] Preferably, each P is independently a group represented by the following formula (P-1). [ka]

[0062] In formula (P-1), L 2 is a group that is cleaved by the action of an acid or a base. Examples of groups that are 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 are each independently H or a hydrocarbon group having 1 to 10 carbon atoms. )], a carboxyalkoxy group [* 1 -OR 22 -(C=O)-O-* 2 (R 22 is a divalent hydrocarbon group having 1 to 10 carbon atoms. )], and a carbonate ester group [* 1 -O-(C=O)-O-* 2 In terms of achieving high sensitivity, the ester group is preferably a tertiary ester group. 1 is the bonding site with the benzene ring, * 2 is R 2Among these, L 2 From the viewpoint of high sensitivity, the tertiary ester group, acetal group, carbonate ester group, or carboxyalkoxy group is preferred, acetal group, carbonate ester group, or carboxyalkoxy group is more preferred, and acetal group or carboxyalkoxy group is even more preferred. Furthermore, from the viewpoint of stable quality polymer production by radical polymerization, ester group, carboxyalkoxy group, and carbonate ester group are preferred. As another effect, when the compound (A) of the second embodiment is used as a polymerization unit of a copolymer, P is preferably a group represented by formula (P-1) for the purpose of controlling the polymerizability of the resin and setting the degree of polymerization within a desired range. Since the compound (A) has iodine, it has a large effect on active species during the polymer formation reaction, making it difficult to achieve the desired control. Therefore, by having the group represented by formula (P-1) as a protecting group on the hydrophilic group in the compound (A), it is possible to suppress variations in copolymer formation and polymerization inhibition caused by the hydrophilic group.

[0063] 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 having 1 to 30 carbon atoms and containing a heteroatom, or a linear, branched or cyclic aromatic group having 1 to 30 carbon atoms and containing a heteroatom, and said R 2 The aliphatic group, aromatic group, aliphatic group containing a hetero atom, and aromatic group containing a hetero atom may or may not further have a substituent. The substituents used here are those described above, but preferred are linear, branched, or cyclic aliphatic groups having 1 to 20 carbon atoms and aromatic groups having 6 to 20 carbon atoms. R 2 Among these, an aliphatic group is preferred. 2The aliphatic group in the formula (I) is preferably a branched or cyclic aliphatic group. The number of carbon atoms in the aliphatic group is preferably 1 or more and 20 or less, more preferably 3 or more and 10 or less, and even more preferably 4 or more and 8 or less. The aliphatic group is not particularly limited, but examples thereof include a methyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a cyclohexyl group, a methylcyclohexyl group, and an adamantyl group. Among these, a tert-butyl group, a cyclohexyl group, and an adamantyl group are preferred.

[0064] L 2 but* 1 -(C=O)-O-* 2 Alternatively, if the group is a carboxyalkoxy group, when it is cleaved by the action of an acid or a base, a carboxylic acid group is formed, which increases the difference in solubility and dissolution rate between the dissociated portion and the non-dissociated portion in the development treatment, thereby improving the resolution and suppressing residues at the bottom of the pattern, particularly in fine line patterns, and is therefore preferred.

[0065] Specific examples of P include the following: P's are, for example, each independently a group represented by any of the following formulae. [ka]

[0066] Examples of alkoxy groups that can be used as P include alkoxy groups having one or more carbon atoms. From the viewpoint of the solubility of the resin after being combined with other monomers to form a resin, alkoxy groups having two or more carbon atoms are preferred, and alkoxy groups having three or more carbon atoms or having a cyclic structure are preferred. Specific examples of alkoxy groups that can be used as P include, but are not limited to, the following: [ka]

[0067] As the amino group and amido group that can be used as P, a primary amino group, a secondary amino group, a tertiary amino group, a group with a quaternary ammonium salt structure, an amide having a substituent, etc. can be appropriately used. Specific examples of usable amino groups or amido groups include, but are not limited to, the following: [ka]

[0068] The compound (A) according to the second embodiment has an iodine group and an OR group in the molecule. B By including the compound (A), when a polymer using the compound (A) is applied to a resist composition and a pattern is formed by a lithography process including film formation, exposure, and development, the iodine group and OR B By improving the solubility in a developer by the group, it is expected that it is possible to achieve a balance between development defects such as development residues, roughness, and bridges and other lithography performances such as sensitivity and resolution, and as a result, it is possible to improve the pattern quality in the formation of finer patterns. As a result, it is believed that this will be effective in improving pattern quality, particularly in patterns such as line and space patterns, where defects caused by solubility in a developer are an issue.

[0069] Examples of the compound (A) according to the second embodiment include compounds having the following structures:

[0070] [ka]

change

[0071] The above compound (A) is preferably used in combination with the compound represented by the following formula (1A). That is, the composition according to the second embodiment preferably contains the compound (A) and the compound represented by the formula (1A).

[0072] [ka] (In formula (1A), formula (1A1), and formula (1A2), R A , R B and P are the same as defined in formula (1), and R sub represents formula (1A1) or formula (1A2), and * represents the bonding site to the adjacent structural unit.

[0073] From the viewpoint of improving exposure sensitivity and reducing residual defects, the composition is preferably prepared so that the compound represented by formula (1A) is contained in the range of 1 ppm by mass to 10% by mass, more preferably 1 ppm by mass to 5% by mass, even more preferably 1 ppm by mass to 3% by mass, and particularly preferably 1 ppm by mass to 1% by mass. In the resin formed from starting materials containing the composition prepared in this manner, the high density of iodine-containing moieties and P-containing moieties in adjacent regions serves as the starting point for improving exposure sensitivity. Furthermore, the locally increased solubility in the resin leads to a reduction in residual defects after development in the lithography process.

[0074] Examples of the compound (1A) according to the second embodiment include compounds having the structure shown below. [ka]

[0075] The above compound (A) is preferably used in combination with the compound represented by the following formula (1B): That is, the composition according to the second embodiment preferably contains the compound (A) and the compound represented by the formula (1B).

[0076] [ka] (In formula (1B), formula (1B1), or formula (1B2), R A , R B and P are defined as in formula (1), n2 is an integer of 0 to 4, and R sub2 represents formula (1B1) or formula (1B2), and * represents the bonding site to the adjacent structural unit.

[0077] From the viewpoint of improving exposure sensitivity and reducing residual defects, the composition is preferably prepared so that the compound represented by formula (1B) is contained in the range of 1 ppm by mass to 10% by mass, more preferably 1 ppm by mass to 5% by mass, even more preferably 1 ppm by mass to 3% by mass, and particularly preferably 1 ppm by mass to 1% by mass. In the resin formed from starting materials containing the composition prepared in this manner, the high density of iodine-containing moieties and P-containing moieties in adjacent regions serves as the starting point for improving exposure sensitivity. Furthermore, the locally increased solubility in the resin leads to a reduction in residual defects after development in the lithography process.

[0078] Examples of the compound (1B) according to the second embodiment include compounds having the structure shown below. [ka]

[0079] The above compound (A) is preferably used in combination with the compound represented by the following formula (1C): That is, the composition according to the second embodiment preferably contains the compound (A) and the compound represented by the formula (1C).

[0080] [ka]

[0081] In formula (1C), R A , R B and P are defined as in formula (1). B and P do not contain I.

[0082] From the viewpoint of stability and reduction of residual defects, the composition preferably contains the compound represented by formula (1C) in an amount of from 1 ppm by mass to 10% by mass, more preferably from 1 ppm by mass to 5% by mass, even more preferably from 1 ppm by mass to 3% by mass, and particularly preferably from 1 ppm by mass to 1% by mass, based on the entire compound (A). The composition prepared in this way tends to be more stable. Although the reason for this is unclear, it is presumed that this is due to an equilibrium reaction of iodine atoms occurring between the iodine-containing compound (A) and the iodine-free compound (1C), resulting in stabilization. In this case, it is preferable that the composition also uses, as compound (1C), a compound having a structure in which an iodine atom has been eliminated from the compound exemplified above as compound (A). Furthermore, the composition prepared in this manner has increased stability, which not only improves storage stability but also leads to the formation of a resin with stable properties, the provision of stable resist performance, and the reduction of residue defects after development in lithography processes. The method for using the compound represented by formula (1C) in a composition containing compound (A) in an amount of 1 ppm by mass or more and 10% by mass or less, based on the total amount of compound (A), is not particularly limited, and examples thereof include a method in which compound (1C) is added to compound (A) and a method in which compound (1C) is by-produced during the production of compound (A).

[0083] Examples of the compound (1C) according to the second embodiment include compounds having the structure shown below. [ka] [ka]

[0084] [Method for producing compound (A)] The compound represented by formula (1) can be produced by various known synthesis methods.

[0085] For a compound represented by formula (1) in which P is a hydroxyl group, one example of a synthesis method is, but is not limited to, introducing a halogen group (I, F, Cl, or Br) into a hydroxyl group-containing aromatic aldehyde derivative, and then converting the aldehyde group to a vinyl group. Other examples of synthesis methods include a method of iodinating a hydroxybenzaldehyde derivative to react with iodine chloride in an organic solvent (see, for example, JP 2012-180326 A), or a method of adding iodine dropwise to an alkaline aqueous solution of phenol in the presence of β-cyclodextrin under alkaline conditions (see, for example, JP 63-101342 A and JP 2003-64012 A).

[0086] In the second embodiment, it is preferable to use an iodination reaction via iodine chloride in an organic solvent. The compound (A) of the second embodiment can be synthesized by converting the aldehyde moiety of the synthesized iodine-introduced hydroxybenzaldehyde derivative into a vinyl group. The Wittig reaction (e.g., the method described in Synthetic Communications; Vol. 22; nb4; 1992 p. 513, Synthesis; Vol. 49; nb. 23; 2017; p. 5217) can be used as appropriate to convert the aldehyde moiety into a vinyl group.

[0087] That is, the method for producing the compound (A) (iodine-containing vinyl monomer) represented by formula (1) is as follows: a) General structure represented by formula (1-5): [ka] (In formula (1-5), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R Bis a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphonic group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group; b) a Wittig reaction step of forming an alkene from the carbonyl moiety of the iodine-containing aldehyde substrate or the iodine-containing ketone substrate by a Wittig reaction; Includes:

[0088] Examples of iodine-containing aldehyde substrates or iodine-containing ketone substrates having the general structure represented by formula (1-5) include 4-hydroxy-3-iodo-5-methoxybenzaldehyde, 3-ethoxy-4-hydroxy-5-iodo-benzaldehyde, and the like. The Wittig reaction step is a step of forming an alkene by the Wittig reaction, and is a step of forming an alkene from a carbonyl moiety having an aldehyde or ketone using a phosphorus ylide, although not limited thereto. As the phosphorus ylide, a triphenylalkylphosphine bromide such as triphenylmethylphosphine bromide, which can form a stable phosphorus ylide, can be used. Alternatively, a phosphorus ylide can be formed in the reaction system by reacting a phosphonium salt with a base, and the resulting phosphorus ylide can be used in the above-mentioned reaction. As the base, a conventionally known base can be used, and for example, an alkali metal salt of an alkoxide can be used as appropriate.

[0089] As another method for converting the aldehyde moiety into a vinyl group, a method of reacting malonic acid in the presence of a base (e.g., the methods described in Tetrahedron; Vol. 46; nb. 40; 2005; p. 6893, Tetrahedron; Vol. 63; nb. 4; 2007; p. 900, US2004 / 118673, etc.) can be appropriately used. In a second embodiment, a method for producing the compound (A) (iodine-containing vinyl monomer) represented by formula (1) includes the following steps: a) providing an iodine-containing aldehyde substrate or an iodine-containing ketone substrate having the general structure represented by formula (1-5); b) a malonic acid addition step of adding malonic acid to the iodine-containing aldehyde substrate or the iodine-containing ketone substrate; c) a hydrolysis step of hydrolyzing the malonic acid-added iodine-containing aldehyde substrate or the iodine-containing ketone substrate to produce an iodine-containing carboxylic acid substrate; d) a decarboxylation step of decarboxylating the hydrolyzed iodine-containing carboxylic acid substrate; Includes:

[0090] The malonate addition step in the second embodiment is a step of forming a malonate derivative, including but not limited to, the reaction of an aldehyde with malonic acid, a malonate ester, or malonic anhydride. The hydrolysis step in the second embodiment is a step of forming a carboxylic acid substrate by hydrolysis, and is, but is not limited to, a reaction of hydrolyzing an ester by the action of an acid or water. The decarboxylation step in the second embodiment is a step of obtaining a vinyl monomer by decarboxylating a carboxylic acid substrate, and although not limited thereto, is preferably carried out at a low temperature of 100°C or less, and more preferably uses a fluoride-based catalyst.

[0091] As a method for synthesizing the compound (A) of the second embodiment, for example, the method described in the above-mentioned reference material can be used appropriately, but is not limited thereto.

[0092] As for a compound represented by formula (1) in which P is an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, or a carbonate ester group, an example of a synthesis method is not particularly limited, and the compound can be obtained by reacting a compound represented by formula (1) in which P is a hydroxyl group with, for example, an activated carboxylic acid derivative compound such as an acid chloride, an acid anhydride, or a dicarbonate, an alkyl halide, a vinyl alkyl ether, a dihydropyran, or a halocarboxylic acid alkyl ester. For example, a compound represented by formula (1) in which P is a hydroxyl group is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran, or propylene glycol monomethyl ether acetate. Subsequently, a vinyl alkyl ether such as ethyl vinyl ether or dihydropyran is added, and the reaction is carried out at normal pressure at 20 to 60°C for 6 to 72 hours in the presence of an acid catalyst such as pyridinium p-toluenesulfonate. The reaction solution is neutralized with an alkaline compound and added to distilled water to precipitate a white solid. The separated white solid is then washed with distilled water and dried to obtain a compound represented by formula (1) in which P is an alkoxy group, ester group, acetal group, carboxyalkoxy group, or carbonate ester group. Alternatively, a compound represented by formula (1) in which P is a hydroxyl group is dissolved or suspended in an aprotic solvent such as acetone, THF, or propylene glycol monomethyl ether acetate. Subsequently, an alkyl halide such as ethyl chloromethyl ether or a halocarboxylic acid alkyl ester such as methyladamantyl bromoacetate is added, and the mixture is reacted at atmospheric pressure at 20 to 110°C for 6 to 72 hours in the presence of an alkali catalyst such as potassium carbonate. The reaction solution is neutralized with an acid such as hydrochloric acid, and added to distilled water to precipitate a white solid. The separated white solid is then washed with distilled water and dried to obtain a compound represented by formula (1) in which P is an alkoxy group, ester group, acetal group, carboxyalkoxy group, or carbonate ester group.

[0093] From the viewpoint of yield and reducing the amount of waste, the synthesis method of the compound (A) of the second embodiment preferably includes the synthesis method shown below.

[0094] [Iodine-containing alcoholic substrate] The iodine-containing alcoholic substrate used in the second embodiment may be, for example, an iodine-containing alcoholic substrate having a general structure represented by the following formula (1-1):

[0095] [ka] (In formula (1-1), R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7 ~R 10 are each independently hydrogen, a hydroxyl group, a methoxy group, a halogen, or a cyano group, provided that R 7 ~R 10 One of the groups is a hydroxyl group or a methoxy group.)

[0096] Examples of suitable iodine-containing alcoholic substrates include, but are not limited to, 1-(4-hydroxy-3-methoxy-5-iodophenyl)ethanol, 1-(3-ethoxy-4-hydroxy-5-iodophenyl)ethanol, 4-(1-hydroxyethyl)-3-methoxy-5-iodophenol, and 3-ethoxy-4-(1-hydroxyethyl)-5-iodophenol. At least one iodine atom is incorporated, and preferably two or more iodines are incorporated.

[0097] These iodine-containing alcoholic substrates can be obtained by many methods, but the methods described below are preferred from the viewpoints of availability of raw materials and yield.

[0098] The method for producing the iodine-containing vinyl monomer represented by formula (1) is as follows: a) providing an iodine-containing alcoholic substrate having the general structure represented by formula (1-1); b) a dehydration step of subjecting the iodine-containing alcoholic substrate to a dehydration treatment; Includes.

[0099] A wide variety of organic solvents can be used, including polar aprotic organic solvents and protic polar organic solvents. A single protic polar solvent or a single polar aprotic solvent can be used. Furthermore, mixtures of polar aprotic solvents, mixtures of protic polar solvents, mixtures of polar aprotic solvents and protic polar solvents, and mixtures of aprotic or protic solvents and nonpolar solvents can be used, with polar aprotic solvents or mixtures thereof being preferred. A solvent, while useful, is not a required component. Suitable polar aprotic solvents include, but are not limited to, alcoholic solvents such as methanol and ethanol; ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglyme, and triglyme; ester solvents such as ethyl acetate and γ-butyrolactone; nitrile solvents such as acetonitrile; hydrocarbon solvents such as toluene and hexane; amide solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidinone, N,N-dimethylacetamide, hexamethylphosphoramide, and hexamethylphosphite triamide; and dimethyl sulfoxide. Dimethyl sulfoxide is preferred. Suitable protic polar solvents include, but are not limited to, di(propylene glycol) methyl ether, di(ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol, and n-butanol. The amount of solvent used can be appropriately set depending on the substrate, catalyst, reaction conditions, etc. used, and is not particularly limited. Generally, however, an amount of 0 to 10,000 parts by mass per 100 parts by mass of reaction raw materials is suitable, and from the viewpoint of yield, an amount of 100 to 2,000 parts by mass is preferable.

[0100] The dehydration step is carried out using, for example, a catalyst. A wide variety of dehydration catalysts that function under the reaction conditions of the second embodiment can be used. An acid catalyst is preferred as the dehydration catalyst. Examples of suitable acid catalysts include, but are not limited to, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; organic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, and naphthalenedisulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride, and boron trifluoride; and solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid, and phosphomolybdic acid. These acid catalysts can be used alone or in combination. Among these, organic acids and solid acids are preferred from the viewpoint of production, and hydrochloric acid or sulfuric acid is preferably used from the viewpoint of production, such as ease of availability and ease of handling. The amount of catalyst used can be appropriately set depending on the substrate, catalyst, and reaction conditions used, and is not particularly limited. Generally, however, an amount of 0.0001 to 100 parts by mass per 100 parts by mass of reaction raw materials is suitable, and from the viewpoint of yield, an amount of 0.001 to 10 parts by mass is preferable.

[0101] As the polymerization inhibitor, a wide variety of polymerization inhibitors that function under the reaction conditions of the second embodiment can be used. A polymerization inhibitor is effective but not required. Examples of suitable polymerization inhibitors include, but are not limited to, hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, phenothiazine, N-oxyl (nitroxide) inhibitors, such as Prostab® 5415 (bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)sebacate, CAS# 2516-92-9, commercially available from Ciba Specialty Chemicals, Tarryton, NY), 4-hydroxy-TEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine-4-yl) sebacate, commercially available from TCI), and the like. 1-yloxy, CAS#2226-96-2) and Uvinul® 4040P (1,6-hexamethylene-bis(N-formyl-N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)amine) commercially available from BASF Corp., Worcester, MA), ammonium-N-nitrosophenylhydroxylamine (Q1300 commercially available from Fujifilm Wako Pure Chemical Industries, Ltd.), and N-nitrosophenylhydroxylamine aluminum salt (Q1301 commercially available from Fujifilm Wako Pure Chemical Industries, Ltd.). The amount of polymerization inhibitor used can be appropriately set depending on the substrate, catalyst, reaction conditions, etc. used, and is not particularly limited. Generally, however, an amount of 0.0001 to 100 parts by mass per 100 parts by mass of the reaction raw materials is suitable, and from the viewpoint of yield, an amount of 0.001 to 10 parts by mass is preferable.

[0102] A wide variety of polymerization inhibitors that function under the reaction conditions of the second embodiment can be used as the polymerization inhibitor. Polymerization inhibitors are effective but not essential. Using a polymerization retarder in combination with a polymerization inhibitor can also be effective. Polymerization retarders are well known in the art and are compounds that slow the polymerization reaction but cannot prevent it entirely. Common retarders are aromatic nitro compounds such as dinitro-ortho-cresol (DNOC) and dinitrobutylphenol (DNBP). Methods for preparing polymerization retarders are common and well known in the art (see, e.g., U.S. Pat. No. 6,339,177; Park et al., Polymer (Korea) (1988), 12(8), 710-19), and their use in controlling styrene polymerization is well documented (see, e.g., Bushby et al., Polymer (1998), 39(22), 5567-5571). The amount of polymerization inhibitor used can be appropriately set depending on the substrate, catalyst, and reaction conditions used, and is not particularly limited. Generally, however, an amount of 0.0001 to 100 parts by mass per 100 parts by mass of the reaction raw materials is suitable, and from the viewpoint of yield, an amount of 0.001 to 10 parts by mass is preferable.

[0103] Reaction conditions The iodine-containing alcoholic substrate having the formula (1-1), the catalyst, and the organic solvent are added to a reactor to form a reaction mixture. Any suitable reactor may be used. The reaction can be carried out by a known method appropriately selected from the batch method, semi-batch method, continuous method and the like.

[0104] The reaction temperature is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. Generally, a temperature of 0°C to 200°C is suitable, and from the viewpoint of yield, a temperature of 0°C to 100°C is preferred. For reactions using 1-(4-hydroxy-3-iodo-5-methoxyphenyl)ethanol as the iodine-containing alcoholic substrate, the preferred temperature range is from 0°C to 100°C.

[0105] The reaction pressure is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. The pressure can be adjusted using an inert gas such as nitrogen, or by using an air pump, etc. For reactions at high pressure, conventional pressure reactors can be used, including, but not limited to, shaker vessels, rocker vessels, and stirred autoclaves. In the reaction using 1-(4-hydroxy-3-iodo-5-methoxyphenyl)ethanol as the iodine-containing alcoholic substrate, the reaction pressure is preferably reduced pressure to atmospheric pressure, with reduced pressure being preferred.

[0106] The reaction time is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. However, most reactions are carried out in less than 6 hours, and reaction times of 15 to 600 minutes are common. For reactions using 1-(4-hydroxy-3-iodo-5-methoxyphenyl)ethanol as the substrate, the preferred reaction time range is from 15°C to 600°C.

[0107] Isolation and purification can be carried out after the completion of the reaction using a suitable method known in the art. For example, the reaction mixture can be poured onto ice water and extracted into an organic solvent such as ethyl acetate or diethyl ether. The product can then be recovered by removing the solvent using evaporation under reduced pressure. The desired high-purity monomer can be isolated and purified using separation and purification methods well known in the art, such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, etc., or a combination thereof.

[0108] [Method for producing an iodine-containing alcoholic substrate represented by formula (1-1) (I)] The iodine-containing ketonic substrate used in the production of the iodine-containing alcoholic substrate represented by formula (1-1) is, for example, an iodine-containing ketonic substrate having a general structure represented by formula (1-2).

[0109] [ka] (In formula (1-2), R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7 ~R 10 are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7 ~R 10 One of the groups is a hydroxyl group or a methoxy group.)

[0110] Examples of suitable iodine-containing ketonic substrates include, but are not limited to, 4-hydroxy-3-iodo-5-methoxyphenyl methyl ketone, 5-ethoxy-4-hydroxy-3-iodophenyl methyl ketone.

[0111] These iodine-containing ketone substrates can be obtained by many methods, but the methods described below are preferred from the viewpoints of availability of raw materials and yield.

[0112] The method for producing an iodine-containing alcoholic substrate having the general structure represented by formula (1-1) includes the steps of: c) providing an iodine-containing ketonic substrate having the general structure represented by formula (1-2); d) a reduction step of subjecting the iodine-containing ketone substrate to a reduction treatment; Includes.

[0113] The method for producing an iodine-containing vinyl monomer having the general structure represented by formula (1) may include the method for producing an iodine-containing alcoholic substrate having the general structure represented by formula (1-1). That is, the method for producing an iodine-containing vinyl monomer having the general structure represented by formula (1) may include the following steps: c) providing an iodine-containing ketonic substrate having the general structure represented by formula (1-2); d) a reduction step of subjecting the iodine-containing ketone substrate to a reduction treatment.

[0114] A wide variety of organic solvents can be used, including polar aprotic organic solvents and protic polar organic solvents. A single protic polar solvent or a single polar aprotic solvent can be used. Furthermore, mixtures of polar aprotic solvents, mixtures of protic polar solvents, mixtures of polar aprotic solvents and protic polar solvents, and mixtures of aprotic or protic solvents and nonpolar solvents can be used, with polar aprotic solvents or mixtures thereof being preferred. A solvent, while useful, is not a required component. Suitable polar aprotic solvents include, but are not limited to, alcoholic solvents such as methanol and ethanol; ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglyme, and triglyme; ester solvents such as ethyl acetate and γ-butyrolactone; nitrile solvents such as acetonitrile; hydrocarbon solvents such as toluene and hexane; amide solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidinone, N,N-dimethylacetamide, hexamethylphosphoramide, and hexamethylphosphite triamide; and dimethyl sulfoxide. Dimethyl sulfoxide is preferred. Suitable protic polar solvents include, but are not limited to, di(propylene glycol) methyl ether, di(ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol, and n-butanol. The amount of solvent used can be appropriately set depending on the substrate, catalyst, reaction conditions, etc. used, and is not particularly limited. Generally, however, an amount of 0 to 10,000 parts by mass per 100 parts by mass of reaction raw materials is suitable, and from the viewpoint of yield, an amount of 100 to 2,000 parts by mass is preferable.

[0115] The reduction step is carried out, for example, using a reducing agent. A wide variety of reducing agents that function under the reaction conditions of the second embodiment can be used. Suitable reducing agents include, but are not limited to, metal hydrides and metal hydride complex compounds, such as borane dimethyl sulfide, diisobutylaluminum hydride, sodium borohydride, lithium borohydride, potassium borohydride, zinc borohydride, lithium tri-s-butylborohydride, potassium tri-s-butylborohydride, lithium triethylborohydride, lithium aluminum hydride, lithium tri-t-butoxyaluminum hydride, and sodium bis(methoxyethoxy)aluminum hydride. The amount of catalyst used can be appropriately set depending on the substrate, catalyst, and reaction conditions used, and is not particularly limited. Generally, however, an amount of 1 to 500 parts by mass per 100 parts by mass of reaction raw materials is suitable, and from the viewpoint of yield, an amount of 10 to 200 parts by mass is preferable.

[0116] A wide variety of quenching agents that function under the reaction conditions of the second embodiment can be used. The quenching agent has the function of deactivating the reducing agent. While effective, the quenching agent is not a required component. Suitable quenching agents include, but are not limited to, ethanol, aqueous ammonium chloride, water, hydrochloric acid, sulfuric acid, and the like. The amount of the quenching agent used can be appropriately set depending on the amount of the reducing agent used and is not particularly limited, but generally, 1 to 500 parts by mass per 100 parts by mass of the reducing agent is suitable, and from the viewpoint of yield, 50 to 200 parts by mass is preferable.

[0117] Reaction conditions The iodine-containing ketonic substrate having formula (1-2), the catalyst, and the organic solvent are added to a reactor to form a reaction mixture. Any suitable reactor may be used. The reaction can be carried out by a known method appropriately selected from the batch method, semi-batch method, continuous method and the like.

[0118] The reaction temperature is not particularly limited. The preferred range varies depending on the concentration of the iodine-containing ketone substrate, the stability of the formed product, the catalyst selected, and the desired yield. Generally, a temperature of 0°C to 200°C is suitable, and from the viewpoint of yield, a temperature of 0°C to 100°C is preferred. For reactions using 4'-hydroxy-3'-iodo-5'-methoxyacetophenone as the iodine-containing ketonic substrate, the preferred temperature range is 0°C to 100°C.

[0119] The reaction pressure is not particularly limited. The preferred range varies depending on the concentration of the iodine-containing ketone substrate, the stability of the formed product, the choice of catalyst, and the desired yield. The pressure can be adjusted using an inert gas such as nitrogen or an air pump. For reactions at high pressure, conventional pressure reactors can be used, including, but not limited to, shaker vessels, rocker vessels, and stirred autoclaves. In the reaction using 4'-hydroxy-3'-iodo-5'-methoxyacetophenone as the iodine-containing ketone substrate, the reaction pressure is preferably reduced pressure to atmospheric pressure, with reduced pressure being preferred.

[0120] The reaction time is not particularly limited. The preferred range varies depending on the concentration of the iodine-containing ketone substrate, the stability of the formed product, the choice of catalyst, and the desired yield. However, most reactions are carried out in less than 6 hours, with reaction times of 15 to 600 minutes being typical. For reactions using 4'-hydroxy-3'-iodo-5'-methoxyacetophenone as the iodine-containing ketonic substrate, the preferred reaction time range is from 15°C to 600°C.

[0121] Isolation and purification can be carried out after the completion of the reaction using a suitable method known in the art. For example, the reaction mixture can be poured onto ice water and extracted into an organic solvent such as ethyl acetate or diethyl ether. The product can then be recovered by removing the solvent using evaporation under reduced pressure. The desired high-purity monomer can be isolated and purified using separation and purification methods well known in the art, such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, etc., or a combination thereof.

[0122] [Method for producing an iodine-containing alcoholic substrate represented by formula (1-1) (II)] The alcoholic substrate used in the production of the iodine-containing alcoholic substrate represented by formula (1-1) is, for example, an alcoholic substrate having a general structure represented by formula (1-3).

[0123] [ka] (In formula (1-3), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7 ~R 10 are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7 ~R 10 One of the groups is a hydroxyl group or a methoxy group.

[0124] Examples of suitable alcoholic substrates include, but are not limited to, 1-(4-hydroxy-3-methoxyphenyl)ethanol, 1-(3-ethoxy-4-hydroxyphenyl)ethanol, 4-(1-hydroxyethyl)-3-methoxyphenol, and 3-ethoxy-4-(1-hydroxyethyl)phenol.

[0125] These alcoholic substrates can be obtained by many methods, but the methods described below are preferred from the viewpoints of availability of raw materials and yield.

[0126] The method for producing an iodine-containing alcoholic substrate having the general structure represented by formula (1-1) includes the steps of: e) providing an alcoholic substrate having the general structure represented by formula (1-3); f) an iodine introduction step of introducing an iodine atom into the alcoholic substrate; Includes. The iodine introduction step in the second embodiment is not particularly limited, and may be appropriately selected from, for example, a method of reacting an iodinating agent in a solvent (e.g., JP 2012-180326 A), or a method of adding iodine dropwise to an alkaline aqueous solution of phenol in the presence of β-cyclodextrin under alkaline conditions (JP 63-101342 A, JP 2003-64012 A). The iodinating agent is not particularly limited, and examples thereof include iodine chloride, iodine, and N-iodosuccinimide. Among these, iodine chloride is preferred. In the second embodiment, particularly when the purpose is to introduce multiple iodines, it is preferable to use an iodination reaction via iodine chloride in an organic solvent. As a method for synthesizing compound (A) in the second embodiment, for example, the method described in the above-mentioned reference material can be appropriately used, but is not limited thereto.

[0127] The method for producing an iodine-containing vinyl monomer having the general structure represented by formula (1) may include the method for producing an iodine-containing alcoholic substrate having the general structure represented by formula (1-1). That is, the method for producing an iodine-containing vinyl monomer having the general structure represented by formula (1) may include the following steps: e) providing an alcoholic substrate having the general structure represented by formula (1-3); f) Iodine introduction step; may include:

[0128] A wide variety of organic solvents can be used, including polar aprotic organic solvents and protic polar organic solvents. A single protic polar solvent or a single polar aprotic solvent can be used. Furthermore, mixtures of polar aprotic solvents, mixtures of protic polar solvents, mixtures of polar aprotic solvents and protic polar solvents, and mixtures of aprotic or protic solvents and nonpolar solvents can be used, with polar aprotic solvents or mixtures thereof being preferred. A solvent, while useful, is not a required component. Suitable polar aprotic solvents include, but are not limited to, alcoholic solvents such as methanol and ethanol; ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglyme, and triglyme; ester solvents such as ethyl acetate and γ-butyrolactone; nitrile solvents such as acetonitrile; hydrocarbon solvents such as toluene and hexane; amide solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidinone, N,N-dimethylacetamide, hexamethylphosphoramide, and hexamethylphosphite triamide; and dimethyl sulfoxide. Dimethyl sulfoxide is preferred. Suitable protic polar solvents include, but are not limited to, di(propylene glycol) methyl ether, di(ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol, and n-butanol. The amount of solvent used can be appropriately set depending on the substrate, catalyst, reaction conditions, etc. used, and is not particularly limited. Generally, however, an amount of 0 to 10,000 parts by mass per 100 parts by mass of reaction raw materials is suitable, and from the viewpoint of yield, an amount of 100 to 2,000 parts by mass is preferable.

[0129] A wide variety of dehydration catalysts that function under the reaction conditions of the second embodiment can be used as the catalyst. An acid catalyst is preferred. Examples of suitable acid catalysts include, but are not limited to, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; organic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, and naphthalenedisulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride, and boron trifluoride; and solid acids such as tungstosilicic acid, tungstophosphoric acid, molybdic silicic acid, and molybdic phosphonic acid. These acid catalysts can be used alone or in combination. Among these, organic acids and solid acids are preferred from the viewpoint of production, and hydrochloric acid or sulfuric acid is preferably used from the viewpoint of production, such as ease of availability and ease of handling. The amount of catalyst used can be appropriately set depending on the substrate, catalyst, and reaction conditions used, and is not particularly limited. Generally, however, an amount of 0.0001 to 100 parts by mass per 100 parts by mass of reaction raw materials is suitable, and from the viewpoint of yield, an amount of 0.001 to 10 parts by mass is preferable.

[0130] Reaction conditions The alcoholic substrate having formula (1-3), the catalyst, and the organic solvent are added to a reactor to form a reaction mixture. Any suitable reactor may be used. The reaction can be carried out by a known method appropriately selected from the batch method, semi-batch method, continuous method and the like.

[0131] The reaction temperature is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. Generally, a temperature of 0°C to 200°C is suitable, and from the viewpoint of yield, a temperature of 0°C to 100°C is preferred. For reactions using 1-(4-hydroxy-3-methoxyphenyl)ethanol as the substrate, the preferred temperature range is 0°C to 100°C.

[0132] The reaction pressure is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. The pressure can be adjusted using an inert gas such as nitrogen, or by using an air pump, etc. For reactions at high pressure, conventional pressure reactors can be used, including, but not limited to, shaker vessels, rocker vessels, and stirred autoclaves. In the reaction using 1-(4-hydroxy-3-methoxyphenyl)ethanol as a substrate, the reaction pressure is preferably from reduced pressure to atmospheric pressure, with reduced pressure being preferred.

[0133] The reaction time is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. However, most reactions are carried out in less than 6 hours, and reaction times of 15 to 600 minutes are common. For reactions using 1-(4-hydroxy-3-methoxyphenyl)ethanol as the substrate, the preferred reaction time range is from 15°C to 600°C.

[0134] Isolation and purification can be carried out after the completion of the reaction using a suitable method known in the art. For example, the reaction mixture can be poured onto ice water and extracted into an organic solvent such as ethyl acetate or diethyl ether. The product can then be recovered by removing the solvent using evaporation under reduced pressure. The desired high-purity monomer can be isolated and purified using separation and purification methods well known in the art, such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, etc., or a combination thereof.

[0135] [Method for producing an iodine-containing ketone substrate represented by formula (1-2)] The ketonic substrate used in the production of the iodine-containing ketonic substrate represented by formula (1-2) is, for example, a ketonic substrate having the general structure represented by formula (1-4).

[0136] [ka] (In formula (1-4), R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7 ~R 10 are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7 ~R 10 One of the groups is a hydroxyl group or a methoxy group.)

[0137] Examples of suitable ketonic substrates include, but are not limited to, 4-hydroxy-5-methoxyphenyl methyl ketone, 5-ethoxy-4-hydroxyphenyl methyl ketone.

[0138] These ketonic substrates can be obtained in a number of ways.

[0139] A method for producing an iodine-containing ketonic substrate having the general structure represented by formula (1-2) includes: g) providing a ketonic substrate having the general structure represented by formula (1-4); h) an iodine introduction step of introducing an iodine atom into the ketone substrate; may include:

[0140] The method for producing an iodine-containing vinyl monomer having the general structure represented by formula (1) may include the method for producing an iodine-containing ketonic substrate having the general structure represented by formula (1-2). That is, the method for producing an iodine-containing vinyl monomer having the general structure represented by formula (1) may include the method for producing an iodine-containing ketonic substrate having the general structure represented by formula (1-2): g) providing a ketonic substrate having the general structure represented by formula (1-4); h) an iodine introduction step of introducing an iodine atom into the ketone substrate; may include:

[0141] A wide variety of organic solvents can be used, including polar aprotic organic solvents and protic polar organic solvents. A single protic polar solvent or a single polar aprotic solvent can be used. Furthermore, mixtures of polar aprotic solvents, mixtures of protic polar solvents, mixtures of polar aprotic solvents and protic polar solvents, and mixtures of aprotic or protic solvents and nonpolar solvents can be used, with polar aprotic solvents or mixtures thereof being preferred. A solvent, while useful, is not a required component. Suitable polar aprotic solvents include, but are not limited to, alcoholic solvents such as methanol and ethanol; ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglyme, and triglyme; ester solvents such as ethyl acetate and γ-butyrolactone; nitrile solvents such as acetonitrile; hydrocarbon solvents such as toluene and hexane; amide solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidinone, N,N-dimethylacetamide, hexamethylphosphoramide, and hexamethylphosphite triamide; and dimethyl sulfoxide. Dimethyl sulfoxide is preferred. Suitable protic polar solvents include, but are not limited to, di(propylene glycol) methyl ether, di(ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol, and n-butanol. The amount of solvent used can be appropriately set depending on the substrate, catalyst, reaction conditions, etc. used, and is not particularly limited. Generally, however, an amount of 0 to 10,000 parts by mass per 100 parts by mass of reaction raw materials is suitable, and from the viewpoint of yield, an amount of 100 to 2,000 parts by mass is preferable.

[0142] A wide variety of dehydration catalysts that function under the reaction conditions of the second embodiment can be used as the catalyst. An acid catalyst is preferred. Examples of suitable acid catalysts include, but are not limited to, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; organic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, and naphthalenedisulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride, and boron trifluoride; and solid acids such as tungstosilicic acid, tungstophosphoric acid, molybdic silicic acid, and molybdic phosphonic acid. These acid catalysts can be used alone or in combination. Among these, organic acids and solid acids are preferred from the viewpoint of production, and hydrochloric acid or sulfuric acid is preferably used from the viewpoint of production, such as ease of availability and ease of handling. The amount of catalyst used can be appropriately set depending on the substrate, catalyst, and reaction conditions used, and is not particularly limited. Generally, however, an amount of 0.0001 to 100 parts by mass per 100 parts by mass of reaction raw materials is suitable, and from the viewpoint of yield, an amount of 0.001 to 10 parts by mass is preferable.

[0143] Reaction conditions The ketonic substrate having formula (1-4), the catalyst, and the organic solvent are added to a reactor to form a reaction mixture. Any suitable reactor may be used. The reaction can be carried out by a known method appropriately selected from the batch method, semi-batch method, continuous method and the like.

[0144] The reaction temperature is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. Generally, a temperature of 0°C to 200°C is suitable, and from the viewpoint of yield, a temperature of 0°C to 100°C is preferred. For reactions using 4'-hydroxy-3'-methoxyacetophenone as the substrate, the preferred temperature range is 0°C to 100°C.

[0145] The reaction pressure is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. The pressure can be adjusted using an inert gas such as nitrogen, or by using an air pump, etc. For reactions at high pressure, conventional pressure reactors can be used, including, but not limited to, shaker vessels, rocker vessels, and stirred autoclaves. In the reaction using 4'-hydroxy-3'-methoxyacetophenone as the substrate, the reaction pressure is preferably reduced pressure to atmospheric pressure, with reduced pressure being preferred.

[0146] The reaction time is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. However, most reactions are carried out in less than 6 hours, and reaction times of 15 to 600 minutes are common. For reactions using 4'-hydroxy-3'-methoxyacetophenone as the substrate, the preferred reaction time range is from 15°C to 600°C.

[0147] Isolation and purification can be carried out after the completion of the reaction using a suitable method known in the art. For example, the reaction mixture can be poured onto ice water and extracted into an organic solvent such as ethyl acetate or diethyl ether. The product can then be recovered by removing the solvent using evaporation under reduced pressure. The desired high-purity monomer can be isolated and purified using separation and purification methods well known in the art, such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, etc., or a combination thereof.

[0148] [Method for producing an alcoholic substrate represented by formula (1-3)] The ketone substrate used in the production of the alcoholic substrate having the general structure represented by formula (1-3) is, for example, a ketone substrate having the general structure represented by the above formula (1-4).

[0149] A method for producing an alcoholic substrate having the general structure represented by formula (1-3) is i) providing a ketonic substrate having the general structure represented by formula (1-4); j) a reduction step of subjecting the ketone substrate to a reduction treatment; may include:

[0150] The method for producing an iodine-containing vinyl monomer having the general structure represented by formula (1) may include the method for producing an alcoholic substrate having the general structure represented by formula (1-3), that is, the method for producing an iodine-containing vinyl monomer having the general structure represented by formula (1) may include the method for producing an alcoholic substrate having the general structure represented by formula (1-3), i) providing a ketonic substrate having the general structure represented by formula (1-4); j) a reduction step of subjecting the ketone substrate to a reduction treatment; may include:

[0151] A wide variety of organic solvents can be used, including polar aprotic organic solvents and protic polar organic solvents. A single protic polar solvent or a single polar aprotic solvent can be used. Furthermore, mixtures of polar aprotic solvents, mixtures of protic polar solvents, mixtures of polar aprotic solvents and protic polar solvents, and mixtures of aprotic or protic solvents and nonpolar solvents can be used, with polar aprotic solvents or mixtures thereof being preferred. A solvent, while useful, is not a required component. Suitable polar aprotic solvents include, but are not limited to, alcoholic solvents such as methanol and ethanol; ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglyme, and triglyme; ester solvents such as ethyl acetate and γ-butyrolactone; nitrile solvents such as acetonitrile; hydrocarbon solvents such as toluene and hexane; amide solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidinone, N,N-dimethylacetamide, hexamethylphosphoramide, and hexamethylphosphite triamide; and dimethyl sulfoxide. Dimethyl sulfoxide is preferred. Suitable protic polar solvents include, but are not limited to, di(propylene glycol) methyl ether, di(ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol, and n-butanol. The amount of solvent used can be appropriately set depending on the substrate, catalyst, reaction conditions, etc. used, and is not particularly limited. Generally, however, an amount of 0 to 10,000 parts by mass per 100 parts by mass of reaction raw materials is suitable, and from the viewpoint of yield, an amount of 100 to 2,000 parts by mass is preferable.

[0152] In the reduction step, for example, a reducing agent is used to reduce the ketone substrate. A wide variety of reducing agents that function under the reaction conditions of the second embodiment can be used. Suitable reducing agents include, but are not limited to, metal hydrides and metal hydride complexes, such as borane dimethyl sulfide, diisobutylaluminum hydride, sodium borohydride, lithium borohydride, potassium borohydride, zinc borohydride, lithium tri-s-butylborohydride, potassium tri-s-butylborohydride, lithium triethylborohydride, lithium aluminum hydride, lithium tri-t-butoxyaluminum hydride, and sodium bis(methoxyethoxy)aluminum hydride. The amount of catalyst used can be appropriately set depending on the substrate, catalyst, and reaction conditions used, and is not particularly limited. Generally, however, an amount of 1 to 500 parts by mass per 100 parts by mass of reaction raw materials is suitable, and from the viewpoint of yield, an amount of 10 to 200 parts by mass is preferable.

[0153] A wide variety of quenching agents that function under the reaction conditions of the second embodiment can be used. The quenching agent has the function of deactivating the reducing agent. While effective, the quenching agent is not a required component. Suitable quenching agents include, but are not limited to, ethanol, aqueous ammonium chloride, water, hydrochloric acid, sulfuric acid, and the like. The amount of the quenching agent used can be appropriately set depending on the amount of the reducing agent used and is not particularly limited, but generally, 1 to 500 parts by mass per 100 parts by mass of the reducing agent is suitable, and from the viewpoint of yield, 50 to 200 parts by mass is preferable.

[0154] Reaction conditions The ketonic substrate having formula (1-4), the catalyst, and the organic solvent are added to a reactor to form a reaction mixture. Any suitable reactor may be used. The reaction can be carried out by a known method appropriately selected from the batch method, semi-batch method, continuous method and the like.

[0155] The reaction temperature is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. Generally, a temperature of 0°C to 200°C is suitable, and from the viewpoint of yield, a temperature of 0°C to 100°C is preferred. For reactions using 4'-hydroxy-3'-methoxyacetophenone as the substrate, the preferred temperature range is 0°C to 100°C.

[0156] The reaction pressure is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. The pressure can be adjusted using an inert gas such as nitrogen, or by using an air pump, etc. For reactions at high pressure, conventional pressure reactors can be used, including, but not limited to, shaker vessels, rocker vessels, and stirred autoclaves. In the reaction using 4'-hydroxy-3'-methoxyacetophenone as the substrate, the reaction pressure is preferably reduced pressure to atmospheric pressure, with reduced pressure being preferred.

[0157] The reaction time is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. However, most reactions are carried out in less than 6 hours, and reaction times of 15 to 600 minutes are common. For reactions using 4'-hydroxy-3'-methoxyacetophenone as the substrate, the preferred reaction time range is from 15°C to 600°C.

[0158] Isolation and purification can be carried out after the completion of the reaction using a suitable method known in the art. For example, the reaction mixture can be poured onto ice water and extracted into an organic solvent such as ethyl acetate or diethyl ether. The product can then be recovered by removing the solvent using evaporation under reduced pressure. The desired high-purity monomer can be isolated and purified using separation and purification methods well known in the art, such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, etc., or a combination thereof.

[0159] [Method for producing an iodine-containing vinyl monomer represented by formula (2)] The method for producing an iodine-containing vinyl monomer according to the second embodiment may be a method for producing an iodine-containing vinyl monomer represented by formula (2), and specifically, may be a method for producing an iodine-containing alkoxystyrene.

[0160] [ka] (In formula (2), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and R C is a substituted or unsubstituted acyl group having 1 to 30 carbon atoms.

[0161] Examples of acetoxystyrenes produced by the method of the second embodiment include, but are not limited to, 4-acetoxy-3-iodo-5-methoxystyrene, 4-acetoxy-5-ethoxy-3-iodostyrene.

[0162] [Iodine-containing vinyl monomers] The iodine-containing vinyl monomer used in the second embodiment is, for example, an iodine-containing vinyl monomer having a general structure represented by the above formula (1).

[0163] Iodine-containing vinyl monomers having the general structure represented by formula (2) are k) providing an iodine-containing vinyl monomer having the general structure represented by formula (1); l) an acylation step of subjecting the iodine-containing vinyl monomer to an acylation treatment; may include:

[0164] A wide variety of organic solvents can be used, including polar aprotic organic solvents and protic polar organic solvents. A single protic polar solvent or a single polar aprotic solvent can be used. Furthermore, mixtures of polar aprotic solvents, mixtures of protic polar solvents, mixtures of polar aprotic solvents and protic polar solvents, and mixtures of aprotic or protic solvents and nonpolar solvents can be used, with polar aprotic solvents or mixtures thereof being preferred. A solvent, while useful, is not a required component. Suitable polar aprotic solvents include, but are not limited to, alcoholic solvents such as methanol and ethanol; ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglyme, and triglyme; ester solvents such as ethyl acetate and γ-butyrolactone; nitrile solvents such as acetonitrile; hydrocarbon solvents such as toluene and hexane; amide solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidinone, N,N-dimethylacetamide, hexamethylphosphoramide, and hexamethylphosphite triamide; and dimethyl sulfoxide. Dimethyl sulfoxide is preferred. Suitable protic polar solvents include, but are not limited to, di(propylene glycol) methyl ether, di(ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol, and n-butanol. The amount of solvent used can be appropriately set depending on the substrate, catalyst, reaction conditions, etc. used, and is not particularly limited. Generally, however, an amount of 0 to 10,000 parts by mass per 100 parts by mass of reaction raw materials is suitable, and from the viewpoint of yield, an amount of 100 to 2,000 parts by mass is preferable.

[0165] The acylation step is carried out, for example, using a catalyst. A wide variety of acylation catalysts that function under the reaction conditions of the second embodiment can be used as the catalyst. A base catalyst is preferred. Examples of suitable base catalysts include, but are not limited to, amine-containing catalysts such as pyridine and ethylenediamine, and non-amine basic catalysts such as metal salts, particularly potassium salts or acetate salts. Suitable catalysts include, but are not limited to, potassium acetate, potassium carbonate, potassium hydroxide, sodium acetate, sodium carbonate, sodium hydroxide, and magnesium oxide. All of the non-amine base catalysts of the second embodiment are commercially available, for example, from EM Science (Gibbstown) or Aldrich (Milwaukee). The amount of catalyst used can be appropriately set depending on the substrate, catalyst, and reaction conditions used, and is not particularly limited. Generally, however, an amount of 1 to 5,000 parts by mass per 100 parts by mass of reaction raw materials is suitable, and from the viewpoint of yield, an amount of 50 to 3,000 parts by mass is preferable.

[0166] As the polymerization inhibitor, a wide variety of polymerization inhibitors that function under the reaction conditions of the second embodiment can be used. A polymerization inhibitor is effective but not required. Examples of suitable polymerization inhibitors include, but are not limited to, hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, phenothiazine, N-oxyl (nitroxide) inhibitors, such as Prostab® 5415 (bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)sebacate, CAS# 2516-92-9, commercially available from Ciba Specialty Chemicals, Tarryton, NY), 4-hydroxy-TEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine-4-yl) sebacate, commercially available from TCI), and the like. 1-yloxy, CAS#2226-96-2) and Uvinul® 4040P (1,6-hexamethylene-bis(N-formyl-N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)amine) commercially available from BASF Corp., Worcester, MA), ammonium-N-nitrosophenylhydroxylamine (Q1300 commercially available from Fujifilm Wako Pure Chemical Industries, Ltd.), and N-nitrosophenylhydroxylamine aluminum salt (Q1301 commercially available from Fujifilm Wako Pure Chemical Industries, Ltd.). The amount of polymerization inhibitor used can be appropriately set depending on the substrate, catalyst, reaction conditions, etc. used, and is not particularly limited. Generally, however, an amount of 0.0001 to 100 parts by mass per 100 parts by mass of the reaction raw materials is suitable, and from the viewpoint of yield, an amount of 0.001 to 10 parts by mass is preferable.

[0167] A wide variety of polymerization inhibitors that function under the reaction conditions of the second embodiment can be used as the polymerization inhibitor. Polymerization inhibitors are effective but not essential. Using a polymerization retarder in combination with a polymerization inhibitor can also be effective. Polymerization retarders are well known in the art and are compounds that slow the polymerization reaction but cannot prevent it entirely. Common retarders are aromatic nitro compounds such as dinitro-ortho-cresol (DNOC) and dinitrobutylphenol (DNBP). Methods for preparing polymerization retarders are common and well known in the art (see, e.g., U.S. Pat. No. 6,339,177; Park et al., Polymer (Korea) (1988), 12(8), 710-19), and their use in controlling styrene polymerization is well documented (see, e.g., Bushby et al., Polymer (1998), 39(22), 5567-5571). The amount of polymerization inhibitor used can be appropriately set depending on the substrate, catalyst, and reaction conditions used, and is not particularly limited. Generally, however, an amount of 0.0001 to 100 parts by mass per 100 parts by mass of the reaction raw materials is suitable, and from the viewpoint of yield, an amount of 0.001 to 10 parts by mass is preferable.

[0168] Reaction conditions The iodine-containing vinyl monomer having formula (1), the catalyst, and the organic solvent are added to a reactor to form a reaction mixture. Any suitable reactor may be used. The reaction can be carried out by a known method appropriately selected from the batch method, semi-batch method, continuous method and the like.

[0169] The reaction temperature is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. Generally, a temperature of 0°C to 200°C is suitable, and from the viewpoint of yield, a temperature of 0°C to 100°C is preferred. For reactions using 4-hydroxy-3-iodo-5-methoxystyrene as the substrate, the preferred temperature range is 0°C to 100°C.

[0170] The reaction pressure is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. The pressure can be adjusted using an inert gas such as nitrogen, or by using an air pump, etc. For reactions at high pressure, conventional pressure reactors can be used, including, but not limited to, shaker vessels, rocker vessels, and stirred autoclaves. In the reaction using 4-hydroxy-3-iodo-5-methoxystyrene as the substrate, the reaction pressure is preferably reduced pressure to atmospheric pressure, with reduced pressure being preferred.

[0171] The reaction time is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. However, most reactions are carried out in less than 6 hours, and reaction times of 15 to 600 minutes are common. For reactions using 4-hydroxy-3-iodo-5-methoxystyrene as the substrate, the preferred reaction time range is from 15°C to 600°C.

[0172] Isolation and purification can be carried out after the completion of the reaction using a suitable method known in the art. For example, the reaction mixture can be poured onto ice water and extracted into an organic solvent such as ethyl acetate or diethyl ether. The product can then be recovered by removing the solvent using evaporation under reduced pressure. The desired high-purity monomer can be isolated and purified using separation and purification methods well known in the art, such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, etc., or a combination thereof.

[0173] It is preferable that the compound in the second embodiment is obtained as a crude product by the above-described reaction, and then further purified to remove remaining metal impurities. That is, from the viewpoint of preventing deterioration of the resin over time and storage stability, and further from the viewpoint of process suitability and production yield due to defects when the resin is applied to a semiconductor manufacturing process, it is preferable to avoid the remaining metal impurities resulting from the contamination of metal components used as reaction aids in the compound manufacturing process or coming from the manufacturing reactor or other manufacturing equipment.

[0174] The residual amounts of the above-mentioned metal impurities are preferably less than 1 ppm, more preferably less than 100 ppb, even more preferably less than 50 ppb, even more preferably less than 10 ppb, and most preferably less than 1 ppb, relative to the resin. In particular, for transition metals such as Fe, Ni, Sb, W, and Al, if the residual metal amount is 1 ppm or more, there is a concern that interaction with the compound of the second embodiment may cause denaturation or deterioration of the material over time. Furthermore, if the residual metal amount is 1 ppm or more, the residual metal amount cannot be sufficiently reduced when the compound is used to produce a resin for semiconductor processing, which may result in defects or performance degradation due to the residual metal in the semiconductor manufacturing process, resulting in a decrease in yield.

[0175] The purification method is not particularly limited, but includes a step of dissolving the compound of the second embodiment in a solvent to obtain a solution (S), and a step (first extraction step) of contacting the obtained solution (S) with an acidic aqueous solution to extract impurities in the compound of the second embodiment, wherein the solvent used in the step of obtaining the solution (S) includes an organic solvent that is arbitrarily immiscible with water. According to the purification method, it is possible to reduce the content of various metals that may be contained as impurities in the resin. More specifically, the compound according to the second embodiment can be dissolved in an organic solvent that is immiscible with water to obtain a solution (S), which can then be subjected to extraction treatment by contacting the solution (S) with an acidic aqueous solution, thereby transferring the metals contained in the solution (S) to the aqueous phase, and then separating the organic and aqueous phases to obtain a resin with a reduced metal content.

[0176] The water-immiscible solvent used in the purification method is not particularly limited, but is preferably an organic solvent that can be safely used in semiconductor manufacturing processes, specifically an organic solvent whose solubility in water at room temperature is less than 30%, more preferably less than 20%, and particularly preferably less than 10%. The amount of the organic solvent used is preferably 1 to 100 times by mass the total amount of the resin used.

[0177] Specific examples of solvents that are arbitrarily immiscible with water include, but are not limited to, ethers such as diethyl ether and diisopropyl ether; esters such as ethyl acetate, n-butyl acetate, and isoamyl acetate; ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 2-pentanone; glycol ether acetates such as ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol monoethyl ether acetate; aliphatic hydrocarbons such as n-hexane and n-heptane; aromatic hydrocarbons such as toluene and xylene; and halogenated hydrocarbons such as methylene chloride and chloroform. Among these, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethyl acetate, etc. are preferred, with methyl isobutyl ketone, ethyl acetate, cyclohexanone, and propylene glycol monomethyl ether acetate being more preferred, and methyl isobutyl ketone and ethyl acetate being even more preferred. Methyl isobutyl ketone, ethyl acetate, etc. have a relatively high saturated solubility of the compound in the second embodiment and a relatively low boiling point, making it possible to reduce the load in industrially removing the solvent by distillation or in the process of removing it by drying. These solvents can be used alone or in combination of two or more.

[0178] The acidic aqueous solution used in the purification method is appropriately selected from aqueous solutions prepared by dissolving commonly known organic or inorganic compounds in water. Examples include, but are not limited to, mineral acid aqueous solutions prepared by dissolving mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid in water, and organic acid aqueous solutions prepared by dissolving organic acids such as acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid in water. These acidic aqueous solutions can be used alone or in combination of two or more. Among these acidic aqueous solutions, preferred are aqueous solutions of one or more mineral acids selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, or aqueous solutions of one or more organic acids selected from the group consisting of acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid. Sulfuric acid, nitric acid, and aqueous solutions of carboxylic acids such as acetic acid, oxalic acid, tartaric acid, and citric acid are more preferred, and aqueous solutions of oxalic acid are even more preferred. Polycarboxylic acids such as oxalic acid, tartaric acid, and citric acid coordinate with metal ions, creating a chelating effect, which is thought to tend to more effectively remove metals. Furthermore, in accordance with the purpose of the purification method of the second embodiment, it is preferable to use water with a low metal content, such as ion-exchanged water.

[0179] Although the pH of the acidic aqueous solution used in the purification method is not particularly limited, it is preferable to adjust the acidity of the aqueous solution in consideration of the effect on the compound. The pH range is usually about 0 to 5, and preferably about 0 to 3.

[0180] The amount of the acidic aqueous solution used in the purification method is not particularly limited, but it is preferable to adjust the amount used from the viewpoint of reducing the number of extractions for metal removal and ensuring operability in consideration of the total liquid volume. From these viewpoints, the amount of the acidic aqueous solution used is preferably 10 to 200% by mass, more preferably 20 to 100% by mass, relative to 100% by mass of the solution (S).

[0181] In the purification method, the acidic aqueous solution is brought into contact with the solution (S), thereby making it possible to extract metal components from the compound in the solution (S).

[0182] In the purification method, the solution (S) may further contain an organic solvent that is optionally miscible with water. When the solution (S) contains an organic solvent that is optionally miscible with water, the amount of the compound charged can be increased, and separation properties are improved, tending to enable purification with high purification efficiency. The method for adding the organic solvent that is optionally miscible with water is not particularly limited. For example, any of a method in which the organic solvent is added to a solution containing the organic solvent in advance, a method in which the organic solvent is added to water or an acidic aqueous solution in advance, and a method in which the organic solvent is added after contacting the solution containing the organic solvent with water or an acidic aqueous solution may be used. Among these, the method of adding the organic solvent in advance to a solution containing the organic solvent is preferred in terms of ease of operation and ease of control of the charged amount.

[0183] The water-miscible organic solvent used in the purification method is not particularly limited, but is preferably an organic solvent that can be safely used in semiconductor manufacturing processes. The amount of the water-miscible organic solvent used is not particularly limited as long as it is within a range that allows separation of the solution phase and the aqueous phase, but is preferably 0.1 to 100 times by mass, more preferably 0.1 to 50 times by mass, and even more preferably 0.1 to 20 times by mass, relative to the total amount of the compounds used.

[0184] Specific examples of the organic solvent that is miscible with water and used in the purification method include, but are not limited to, ethers such as tetrahydrofuran and 1,3-dioxolane; alcohols such as methanol, ethanol, and isopropanol; ketones such as acetone and N-methylpyrrolidone; and aliphatic hydrocarbons such as glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), and propylene glycol monoethyl ether. Among these, N-methylpyrrolidone and propylene glycol monomethyl ether are preferred, with N-methylpyrrolidone and propylene glycol monomethyl ether being more preferred. These solvents can be used alone or in combination of two or more.

[0185] The temperature during the extraction treatment is usually 20 to 90°C, preferably in the range of 30 to 80°C. The extraction operation is carried out, for example, by thoroughly mixing the solution by stirring or the like, and then allowing it to stand. This allows the metal components contained in the solution (S) to migrate to the aqueous phase. This operation also reduces the acidity of the solution, making it possible to suppress the deterioration of the compounds.

[0186] The mixed solution separates into a solution phase containing the compound and the solvent and an aqueous phase upon standing, and the solution phase is recovered by decantation or the like. The standing time is not particularly limited, but it is preferable to adjust the standing time from the viewpoint of improving the separation of the solution phase containing the solvent and the aqueous phase. The standing time is usually 1 minute or more, preferably 10 minutes or more, and more preferably 30 minutes or more. Furthermore, the extraction treatment may be performed only once, but it is also effective to repeat the operations of mixing, standing, and separation multiple times.

[0187] The purification method preferably includes, after the first extraction step, a step (second extraction step) of further contacting the solution phase containing the compound with water to extract impurities in the resin. Specifically, for example, after the extraction treatment using an acidic aqueous solution, the solution phase containing the resin and solvent extracted and recovered from the aqueous solution is preferably subjected to a further extraction treatment with water. The extraction treatment with water is not particularly limited, but can be carried out, for example, by thoroughly mixing the solution phase and water by stirring or the like, and then allowing the resulting mixed solution to stand. After standing, the mixed solution separates into a solution phase containing the compound and solvent and an aqueous phase, and the solution phase can be recovered by decantation or the like. In addition, in accordance with the object of the second embodiment, the water used here is preferably water with a low metal content, such as ion-exchanged water. The extraction treatment may be performed only once, but it is also effective to repeat the steps of mixing, leaving, and separating multiple times. In addition, the conditions for the extraction treatment, such as the ratio of the two components used, temperature, and time, are not particularly limited, but may be the same as those for the contact treatment with the acidic aqueous solution.

[0188] Water that may be mixed into the solution containing the compound and the solvent thus obtained can be easily removed by performing an operation such as distillation under reduced pressure. If necessary, a solvent can be added to the solution to adjust the concentration of the compound to a desired concentration.

[0189] In the method for purifying the compound according to the second embodiment, the compound can also be purified by passing a solution obtained by dissolving the resin in a solvent through a filter. According to the method for purifying a substance according to the second embodiment, the content of various metals in the resin can be effectively and significantly reduced. The amount of these metal components can be measured by the method described in the Examples below. In the second embodiment, "passing" means that the solution moves from the outside of the filter through the inside of the filter and then back to the outside of the filter, and excludes, for example, a case in which the solution is simply brought into contact with the surface of the filter, or a case in which the solution is brought into contact with the surface of the filter and moves outside the ion exchange resin (i.e., a case in which the solution simply comes into contact).

[0190] [Filter purification process (liquid passing process)] In the filter passing step of the second embodiment, the filter used to remove metals from the solution containing the compound and solvent can typically be a commercially available filter for liquid filtration. While the filtration accuracy of the filter is not particularly limited, the nominal pore size of the filter is preferably 0.2 μm or less, more preferably less than 0.2 μm, even more preferably less than 0.1 μm, even more preferably less than 0.1 μm, and even more preferably 0.05 μm or less. The lower limit of the nominal pore size of the filter is not particularly limited, but is typically 0.005 μm. The nominal pore size here refers to the nominal pore size that indicates the separation performance of the filter, and is determined by a test method specified by the filter manufacturer, such as a bubble point test, a mercury intrusion porosimetry test, or a standard particle capture test. When a commercially available product is used, the value is the value listed in the manufacturer's catalog data. By setting the nominal pore size to 0.2 μm or less, the metal content after a single pass of the solution through the filter can be effectively reduced. In the second embodiment, the filter passing step may be carried out two or more times in order to further reduce the content of each metal in the solution.

[0191] The filter may be in the form of a hollow fiber membrane filter, a membrane filter, a pleated membrane filter, or a filter filled with a filter material such as a nonwoven fabric, cellulose, or diatomaceous earth. Among these, the filter is preferably one or more selected from the group consisting of a hollow fiber membrane filter, a membrane filter, and a pleated membrane filter. Furthermore, it is particularly preferred to use a hollow fiber membrane filter because of its particularly high filtration accuracy and a larger filtration area compared to other forms.

[0192] Examples of the filter material include polyolefins such as polyethylene and polypropylene, polyethylene-based resins to which functional groups having ion exchange capacity have been added by graft polymerization, polar group-containing resins such as polyamide, polyester, and polyacrylonitrile, and fluorine-containing resins such as fluorinated polyethylene (PTFE). Among these, the filter material is preferably one or more selected from the group consisting of polyamide, polyolefin resin, and fluororesin. Furthermore, polyamide is particularly preferred from the viewpoint of reducing heavy metals such as chromium. Furthermore, from the viewpoint of preventing metal elution from the filter material, it is preferable to use a filter made of a material other than sintered metal.

[0193] Examples of polyamide filters (hereinafter referred to as trademarks) include, but are not limited to, the Polyfix Nylon series manufactured by Kitz Microfilter Co., Ltd., Ultipleat P-Nylon 66 and Ultipore N66 manufactured by Nippon Pall Co., Ltd., and the LifeAsure PSN series and LifeAsure EF series manufactured by 3M Limited. Examples of polyolefin filters include, but are not limited to, Ultipleat PE Clean and Ion Clean manufactured by Nippon Pall Co., Ltd., and Protego series, Microguard Plus HC10, and Optimizer D manufactured by Nippon Entegris Co., Ltd. Examples of polyester filters include, but are not limited to, Gelaflow DFE manufactured by Central Filter Kogyo Co., Ltd. and Breeze Type PMC manufactured by Nippon Filter Co., Ltd. Examples of polyacrylonitrile filters include, but are not limited to, Ultrafilters AIP-0013D, ACP-0013D, and ACP-0053D manufactured by Advantech Toyo Co., Ltd. Examples of fluororesin filters include, but are not limited to, Enflon HTPFR manufactured by Nippon Pall Co., Ltd., and Lifesure FA series manufactured by 3M Limited. These filters may be used alone or in combination of two or more.

[0194] The filter may also contain an ion exchanger such as a cation exchange resin, or a cationic charge regulator that generates a zeta potential in the organic solvent solution to be filtered. Examples of filters containing an ion exchanger include, but are not limited to, the Protego series manufactured by Nippon Entegris Co., Ltd. and Clangraft manufactured by Kurashiki Seni Kako Co., Ltd. Furthermore, examples of filters containing substances with a positive zeta potential, such as polyamide polyamine epichlorohydrin cationic resin (hereinafter referred to as "trademarks"), include, but are not limited to, Zeta Plus 40QSH and Zeta Plus 020GN manufactured by 3M Limited, and the Life Asure EF series.

[0195] The compound according to the second embodiment can also be purified by distilling the compound itself. The distillation method is not particularly limited, and known methods such as atmospheric distillation, reduced pressure distillation, molecular distillation, and steam distillation can be used.

[0196] [Use of compound (A)] The compound (A) according to the second embodiment can be added to a film-forming composition as it is or as a polymer described later, thereby increasing the sensitivity to an exposure light source. The compound (A) or its polymer is preferably used in a photoresist.

[0197] [Composition] The composition of the second embodiment contains compound (A). The content of compound (A) in the second embodiment is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 99% by mass or more.

[0198] In another preferred embodiment of the composition of the second embodiment, the compound (A) preferably contains at least a compound represented by formula (1) other than formula (1C) and a compound represented by formula (1C). The proportion of the monomer represented by formula (1C) is preferably a small amount of 1 ppm by mass or more and 10% by mass or less, more preferably 20 ppm by mass or more and 2% by mass or less, and more preferably 50 ppm by mass or more and 1% by mass or less, based on the total amount of the monomer represented by formula (1).

[0199] By setting the content of the compound represented by formula (1C) within the range described above, it is possible to reduce interactions between resins during resinification, and by suppressing crystallinity resulting from interactions between resins after a film is formed using the resin, it is possible to reduce the locality of solubility in a developer during development at a molecular level of several nanometers to several tens of nanometers, and to suppress deterioration in pattern quality such as line edge roughness and residual defects in a pattern formed in a pattern formation process in a series of lithography processes including exposure, post-exposure baking, and development, thereby enabling further improvement in resolution.

[0200] These effects on lithography performance are greater in the compound represented by formula (1C) having a mother nucleus A into which a halogen element, particularly iodine or fluorine, has been introduced, because the hydrophilicity / hydrophobicity of the compound represented by formula (1) and the compound represented by formula (1C) are shifted compared to a compound having a hydroxystyrene skeleton without iodine or the like introduced therein, and polarization at the polar moiety is increased.

[0201] The composition of the second embodiment contains compound (A). The content of impurities including K (potassium) in the composition is preferably 1 ppm by mass or less, more preferably 0.5 ppm by mass or less, even more preferably 0.1 ppm by mass or less, and still more preferably 0.005 ppm by mass or less, in elemental terms, relative to the total amount of compound (A).

[0202] In the composition of the second embodiment, the content of one or more elemental impurities selected from the group consisting of Mn (manganese), Al (aluminum), Si (silicon), and Li (lithium) (preferably one or more elemental impurities selected from the group consisting of Mn and Al) is preferably 1 ppm or less, more preferably 0.5 ppm or less, and even more preferably 0.1 ppm or less, in terms of element, relative to the entire compound (A). The amounts of K, Mn, Al, Si, Li, etc. are measured by inorganic elemental analysis (IPC-AES / IPC-MS). An example of an inorganic elemental analyzer is the "AG8900" manufactured by Agilent Technologies.

[0203] In the composition of the second embodiment, the content of the phosphorus-containing compound is preferably 10 ppm or less, more preferably 8 ppm or less, and even more preferably 5 ppm or less, based on the total amount of compound (A).

[0204] In the composition of the second embodiment, the content of maleic acid is preferably 10 ppm or less, more preferably 8 ppm or less, and even more preferably 5 ppm or less, based on the total amount of compound (A). The amounts of phosphorus-containing compounds and maleic acid are calculated by gas chromatography-mass spectrometry (GC-MS) from the area fractions in the GC chart and the peak intensity ratios between the target peak and the reference peak.

[0205] In the composition of the second embodiment, the content of peroxide is preferably 10 ppm by mass or less, more preferably 1 ppm or less, and even more preferably 0.1 ppm or less, based on the total amount of compound (A). The peroxide content is determined by the ammonium ferrothiocyanate acid method (hereinafter referred to as the AFTA method) by adding trichloroacetic acid to the sample, then adding ammonium iron sulfate (II) and potassium thiocyanate, obtaining a calibration curve for a known peroxide as a standard substance, and measuring the absorbance at a wavelength of 480 μm to quantify it.

[0206] In the composition of the second embodiment, the water content is preferably 100,000 ppm or less, more preferably 20,000 ppm or less, even more preferably 1,000 ppm or less, still more preferably 500 ppm or less, and even more preferably 100 ppm or less, based on the total amount of compound (A). The water content is measured by the Karl Fischer method (Karl Fischer water content analyzer).

[0207] [Polymer (A)] The polymer (A) of the second embodiment contains a structural unit derived from the compound (A). By containing the structural unit derived from the compound (A), the polymer (A) can enhance the sensitivity to the exposure light source when incorporated into a resist composition. In particular, even when extreme ultraviolet light is used as the exposure light source, the polymer (A) exhibits sufficient sensitivity and can successfully form a fine line pattern with a narrow line width.

[0208] Furthermore, conventional resist compositions can lose their sensitivity to an exposure light source over time due to storage, etc., making it difficult to apply them to actual semiconductor manufacturing. However, the polymer (A) of the second embodiment improves the stability of the resist composition, and even after long-term storage, the loss of sensitivity to an exposure light source is suppressed.

[0209] The polymer (A) of the second embodiment contains a structural unit derived from the compound (A).

[0210] The structural unit derived from the compound (A) contained in the polymer (A) includes, for example, a structural unit represented by the following formula (1-A). [ka]

[0211] In formula (1-A), R A , R B and P are defined as in formula (1), and * is the bonding site to the adjacent structural unit. R A is preferably a hydrogen atom or a methyl group. Also, R B is preferably an alkyl group having 1 to 4 carbon atoms. Furthermore, P is preferably a hydroxyl group, a tertiary ester group, an acetal group, a carbonate ester group, or a carboxyalkoxy group.

[0212] The polymer (A) can be obtained by polymerizing the compound (A) of the second embodiment or by copolymerizing the compound (A) with another monomer. The polymer (A) can be used, for example, as a film-forming material for lithography.

[0213] The amount of the structural units derived from the compound (A) is preferably 5 mol% or more, more preferably 8 mol% or more, and even more preferably 10 mol% or more, based on the total amount of the monomer components of the polymer (A). The amount of the structural units derived from the compound (A) is 100 mol% or less, preferably 80 mol% or less, more preferably 50 mol% or less, and even more preferably 30 mol% or less, based on the total amount of the monomer components of the polymer (A).

[0214] In one preferred embodiment of the polymer of the second embodiment, the polymer preferably contains at least a compound represented by formula (1) and a compound represented by formula (1C) as monomers represented by compound (A) as constituent units of polymer (A). The content of the monomer represented by formula (1C) is preferably 10 ppm to 10 mass %, more preferably 20 ppm to 2 mass %, and even more preferably 50 ppm to 1 mass %, based on the total amount of the monomers represented by formula (1). By setting the content of the compound represented by formula (1C) within the above range, interactions between resins during resinification can be reduced. Furthermore, by suppressing crystallinity resulting from interactions between resins after film formation using the resin, the locality of solubility in the developer during development can be reduced at the molecular level of several nanometers to several tens of nanometers. As a result, degradation of pattern quality, such as line edge roughness and residue defects, can be suppressed in patterns formed in a pattern formation process in a series of lithography processes including exposure, post-exposure baking, and development, and resolution can be further improved. These effects on lithography performance are greater in the monomer represented by formula (1C) because the compounds represented by formula (1) and formula (1C) having a mother nucleus into which a halogen element, particularly iodine, has been introduced exhibit a shift in hydrophilicity to hydrophobicity compared to compounds having a hydroxystyrene skeleton without iodine or the like introduced therein, and the polarization at the polar moiety is increased.

[0215] In the polymer (A), the other monomer to be copolymerized with the compound (A) preferably contains, as a polymerized unit, an aromatic compound having an unsaturated double bond as a substituent, and a polymerized unit having a functional group that improves the solubility in an alkaline developer by the action of an acid or a base.

[0216] In the polymer (A), the other monomer to be copolymerized with the compound (A) is not particularly limited, but examples thereof include those described in International Publication WO2016 / 125782, International Publication WO2015 / 115613, JP2015 / 117305, International Publication WO2014 / 175275, and JP2012 / 162498, 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. Furthermore, in the polymer (A), the other monomer to be copolymerized with the compound (A) preferably contains a structural unit represented by the following formula (C0). That is, the polymer (A) preferably further contains a structural unit represented by the following formula (C0), (C1) or (C2) in addition to the structural unit represented by formula (1-A).

[0217] From the viewpoint of the quality of the pattern shape after exposure and development in the lithography process, especially the prevention of roughness and pattern collapse, the dissolution rate R of the resin in the alkaline developer in the unexposed area during exposure that becomes the pattern convex part during alkaline development is min and the dissolution rate R of the resin in the alkaline developer that becomes a recessed pattern in the exposed area during alkaline development. max It is preferable that the difference between the dissolution rates is greater by three orders of magnitude or more, that the difference in dissolution rate between the presence and absence of a protecting group is greater, and that the rate at which the protecting group is removed during post-exposure baking (PEB) and development is greater. From these viewpoints, it is preferable that the other monomer to be copolymerized with compound (A) in polymer (A) has a constituent unit represented by the following formula (C1): [ka]

[0218] In formula (C1), R C11 is a hydrogen atom, a methyl group, or a trifluoromethyl group, R C12 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R C13 is R C13 and a carbon atom to which they are bonded, together with a cycloalkyl group or heterocycloalkyl group having 4 to 20 carbon atoms, * indicates the bonding site with the adjacent structural unit.

[0219] R C12 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. C13 is preferably R C13 R is a cycloalkyl group or heterocycloalkyl group having 4 to 10 carbon atoms, formed together with the carbon atom to which it is bonded. C13 The cycloalkyl group or heterocycloalkyl group may have a substituent (for example, an oxo group).

[0220] The amount of the structural unit represented by formula (C1) is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more, based on the total amount of the monomer components of polymer (A). The amount of the structural unit represented by formula (C1) is preferably 90 mol% or less, more preferably 80 mol% or less, and even more preferably 70 mol% or less, based on the total amount of the monomer components of polymer (A).

[0221] The other monomer to be 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 lithography process, in particular, suppression of roughness and pattern collapse.

[0222] [ka]

[0223] In formula (C2), R C21 is a hydrogen atom, a methyl group, or a trifluoromethyl group, R C22 and R C23 are each independently an alkyl group having 1 to 4 carbon atoms, R C24 is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms, R C22 , R C23 , and R C24 Two or three of the R C22 , R C23 , and R C24 may form an alicyclic structure having 3 to 20 carbon atoms, formed together with carbon atoms bonding to two or three of * indicates the bonding site with the adjacent structural unit.

[0224] R C22 is preferably an alkyl group having 1 to 3 carbon atoms, and R C24 is a cycloalkyl group having 5 to 10 carbon atoms.C22 , R C23 , and R C24 The alicyclic structure formed by may contain a plurality of rings such as adamantyl groups, etc. The alicyclic structure may have a substituent (for example, a hydroxyl group, an alkyl group).

[0225] The amount of the structural unit represented by formula (C2) is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more, based on the total amount of the monomer components of polymer (A). Also, the amount of the structural unit represented by formula (C2) is preferably 80 mol% or less, more preferably 60 mol% or less, and even more preferably 40 mol% or less, based on the total amount of the monomer components of polymer (A).

[0226] Examples of monomer raw materials for the constituent unit represented by formula (C2) include, but are not limited to, 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-dimethanonaphthalene, 2-ethyl-2-(meth)acryloyloxynorbornane. Commercially available products can be used as these monomers.

[0227] The other monomer to be copolymerized with the compound (A) in the polymer (A) is preferably a structural unit represented by the following formula (C0), from the viewpoints of exposure in the lithography process, the quality of the pattern shape after development, sensitization, and particularly suppression of roughness and pattern collapse.

[0228] [ka]

[0229] In formula (C0), X's each independently represent I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 to 5 substituents selected from the group consisting of I, F, Cl, and Br; L 1 are each independently a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and 1 The ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, or phosphate group may have a substituent, Y's each independently represent a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphonic group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphonic group, urethane group, urea group, amide group, imide group, and phosphate group of Y may have a substituent, R A is the same as the definition in equation (1), A is an organic group having 1 to 30 carbon atoms, Z's each independently represent an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, or a carbonate ester group, and the alkoxy group, ester group, acetal group, carboxyalkoxy group, or carbonate ester group of Z may have a substituent; m is an integer of 0 or greater, n is an integer of 1 or greater, and r is an integer of 0 or greater.

[0230] Examples of the "organic group having 1 to 30 carbon atoms and having 1 to 5 substituents selected from the group consisting of I, F, Cl, and Br" include, but are not limited to, a monoiodophenyl group, a diiodophenyl group, a triiodophenyl group, a tetraiodophenyl group, a pentaiodophenyl group, a monoiodohydroxyphenyl group, a diiodohydroxyphenyl group, a triiodohydroxyphenyl group, a monoiodoacetoxyphenyl group, a diiodoacetoxyphenyl group, a triiodoacetoxyphenyl group, a monoiodo-t-butoxycarbonylphenyl group, a diiodo-t-butoxycarbonylphenyl group, a -butoxycarbonylphenyl group, triiodo-t-butoxycarbonylphenyl group, monoiododihydroxyphenyl group, diiododihydroxyphenyl group, triiododihydroxyphenyl group, monoiododiacetoxyphenyl group, diiododiacetoxyphenyl group, triiododiacetoxyphenyl group, monoiodo-di-t-butoxycarbonylphenyl group, diiodo-di-t-butoxycarbonylphenyl group, triiodo-di-t-butoxycarbonylphenyl group, monoiodotrihydroxyphenyl group, diiodotrihydroxy Phenyl group, monoiodotriacetoxyphenyl group, diiodotriacetoxyphenyl group, monoiodo-tri-t-butoxycarbonylphenyl group, diiodo-tri-t-butoxycarbonylphenyl group, monoiodonaphthyl group, diiodonaphthyl group, triiodonaphthyl group, tetraiodonaphthyl group, pentaiodonaphthyl group, monoiodohydroxynaphthyl group, diiodohydroxynaphthyl group, triiodohydroxynaphthyl group, monoiodoacetoxynaphthyl group, diiodoacetoxynaphthyl group, triiodoacetoxynaphthyl group, monoiodo-t-butoxycarbonylnaphthyl group, diiodo-t-butoxycarbonylnaphthyl group, triiodo-t-butoxycarbonylnaphthyl group, monoiododihydroxynaphthyl group, diiododihydroxynaphthyl group, triiododihydroxynaphthyl group, monoiododiacetoxynaphthyl group, diiododiacetoxynaphthyl group, triiododiacetoxynaphthyl group, monoiodo-di-t-butoxycarbonylnaphthyl group, diiodo-di-t-butoxycarbonylnaphthyl group, triiodo-di-t-butoxycarbonylnaphthyl group,

[0231] Monoiodotrihydroxynaphthyl group, diiodotrihydroxynaphthyl group, monoiodotriacetoxynaphthyl group, diiodotriacetoxynaphthyl group, monoiodo-tri-t-butoxycarbonylnaphthyl group, diiodo-tri-t-butoxycarbonylnaphthyl group, monoiodoadamantyl group, diiodoadamantyl group, triiodoadamantyl group, monoiodohydroxyadamantyl group, diiodohydroxynaphthyl group, monoiodoacetoxynaphthyl group, diiodoacetoxyadamantyl group, monoiodo-t-butoxycarbonyladamantyl group, diiodo-t-butoxycarbonyladamantyl group, triiodo-t-butoxycarbonyladamantyl group, monoiododihydroxy siadamantyl group, monoiododiacetoxyadamantyl group, monoiodo-di-t-butoxycarbonyladamantyl group, monoiodocyclohexyl group, diiodocyclohexyl group, triiodocyclohexyl group, monoiodohydroxycyclohexyl group, diiodohydroxynaphthyl group, monoiodoacetoxynaphthyl group, diiodoacetoxycyclohexyl group, monoiodo-t-butoxycarbonylcyclohexyl group, diiodo-t-butoxycarbonylcyclohexyl group, triiodo-t-butoxycarbonylcyclohexyl group, monoiododihydroxycyclohexyl group, monoiododiacetoxycyclohexyl group, monoiodo-di-t-butoxycarbonylcyclohexyl group,

[0232] a monobromophenyl group, a dibromophenyl group, a tribromophenyl group, a tetrabromophenyl group, a pentabromophenyl group, a monobromohydroxyphenyl group, a dibromohydroxyphenyl group, a tribromohydroxyphenyl group, a monobromoacetoxyphenyl group, a dibromoacetoxyphenyl group, a tribromoacetoxyphenyl group, a monobromo-t-butoxycarbonylphenyl group, a dibromo-t-butoxycarbonylphenyl group, a tribromo-t-butoxycarbonylphenyl group, a monobromodihydroxyphenyl group, a dibromodihydroxyphenyl group, a tribromodihydroxyphenyl group, a monobromodiacetoxyphenyl group, a dibromodiacetoxyphenyl group, a monobromodi-t-butoxycarbonylphenyl group, a dibromodi-t-butoxycarbonylphenyl group, a tribromodi-t-butoxycarbonylphenyl group,

[0233] a monobromotrihydroxyphenyl group, a dibromotrihydroxyphenyl group, a monobromotriacetoxyphenyl group, a dibromotriacetoxyphenyl group, a monobromotri-t-butoxycarbonylphenyl group, a dibromotri-t-butoxycarbonylphenyl group, a monobromoadamantyl group, a dibromoadamantyl group, a tribromoadamantyl group, a monobromohydroxyadamantyl group, a dibromohydroxynaphthyl group, a monobromoacetoxynaphthyl group, a dibromoacetoxyadamantyl group, a monobromo-t-butoxycarbonyladamantyl group, a dibromo-t-butoxycarbonyladamantyl group, a tribromo-t-butoxycarbonyladamantyl group, a monobromodihydroxyadamantyl group, a monobromodiacetoxyadamantyl group, a monobromo-di-t-butoxycarbonyladamantyl group,

[0234] Monofluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, monofluorohydroxyphenyl group, difluorohydroxyphenyl group, trifluorohydroxyphenyl group, monofluoroacetoxyphenyl group, difluoroacetoxyphenyl group, trifluoroacetoxyphenyl group, monofluoro t-butoxycarbonylphenyl group, difluoro t-butoxycarbonylphenyl group, trifluoro t-butoxycarbonylphenyl group, monofluorodihydroxyphenyl group, difluorodihydroxyphenyl group, trifluorodihydroxyphenyl group, monofluorodiacetoxyphenyl group, difluorodiacetoxyphenyl group, trifluorodiacetoxyphenyl group, monofluorodi-t-butoxycarbonylphenyl group, difluorodi-t-butoxycarbonylphenyl group, trifluorodi-t -butoxycarbonylphenyl group, monofluorotrihydroxyphenyl group, difluorotrihydroxyphenyl group, monofluorotriacetoxyphenyl group, difluorotriacetoxyphenyl group, monofluorotri-t-butoxycarbonylphenyl group, difluorotri-t-butoxycarbonylphenyl group, monofluoroadamantyl group, difluoroadamantyl group, trifluoroadamantyl group, monofluorohydroxyadamantyl group, difluorohydroxynaphthyl group, monofluoroacetoxynaphthyl group, difluoroacetoxyadamantyl group, monofluoro-t-butoxycarbonyladamantyl group, difluoro-t-butoxycarbonyladamantyl group, trifluoro-t-butoxycarbonyladamantyl group, monofluorodihydroxyadamantyl group, monofluorodiacetoxyadamantyl group, monofluoro-di-t-butoxycarbonyladamantyl group,

[0235] Monochlorophenyl group, dichlorophenyl group, trichlorophenyl group, tetrachlorophenyl group, pentachlorophenyl group, monochlorohydroxyphenyl group, dichlorohydroxyphenyl group, trichlorohydroxyphenyl group, monochloroacetoxyphenyl group, dichloroacetoxyphenyl group, trichloroacetoxyphenyl group, monochloro-t-butoxycarbonylphenyl group, dichloro-t-butoxycarbonylphenyl group, trichloro-t-butoxycarbonylphenyl group, monochlorodihydroxyphenyl group, dichlorodihydroxyphenyl group, trichlorodihydroxyphenyl group, monochlorodiacetoxyphenyl group, dichlorodiacetoxyphenyl group, trichlorodiacetoxyphenyl group, monochlorodi-t-butoxycarbonylphenyl group, dichlorodi-t-butoxycarbonylphenyl group, trichlorodi-t-butoxycarbonylphenyl group,

[0236] Examples thereof include a monochlorotrihydroxyphenyl group, a dichlorotrihydroxyphenyl group, a monochlorotriacetoxyphenyl group, a dichlorotriacetoxyphenyl group, a monochlorotri-t-butoxycarbonylphenyl group, a dichlorotri-t-butoxycarbonylphenyl group, a monochloroadamantyl group, a dichloroadamantyl group, a trichloroadamantyl group, a monochlorohydroxyadamantyl group, a dichlorohydroxynaphthyl group, a monochloroacetoxynaphthyl group, a dichloroacetoxyadamantyl group, a monochloro-t-butoxycarbonyladamantyl group, a dichloro-t-butoxycarbonyladamantyl group, a trichloro-t-butoxycarbonyladamantyl group, a monochlorodihydroxyadamantyl group, a monochlorodiacetoxyadamantyl group, and a monochlorodi-t-butoxycarbonyladamantyl group.

[0237] For example, X may be an aromatic group having one or more F, Cl, Br, or I introduced therein. Examples of such aromatic groups include groups having a benzene ring, such as a phenyl group having 1 to 5 halogens, and groups having a heteroaromatic ring, such as furan, thiophene, or pyridine, each having 1 to 5 halogens, and examples thereof include a phenyl group having 1 to 5 I, a phenyl group having 1 to 5 F, a phenyl group having 1 to 5 Cl, a phenyl group having 1 to 5 Br, a naphthyl group having 1 to 5 F, a naphthyl group having 1 to 5 Cl, and a phenyl group having 1 to 5 Br. naphthyl groups having 1 to 5 I's, naphthyl groups having 1 to 5 I's, phenol groups having 1 to 4 F's, phenol groups having 1 to 4 Cl's, phenol groups having 1 to 4 Br's, phenol groups having 1 to 4 I's, furan groups having 1 to 3 F's, furan groups having 1 to 3 Cl's, furan groups having 1 to 3 Br's, furan groups having 1 to 3 I's, thiophene groups having 1 to 3 F's, thiophene groups having 1 to 3 Cl's, thiophene groups having 1 to 3 Br's, a thiophene group having 3 F, a pyridine group having 1 to 4 Cl, a pyridine group having 1 to 4 Br, a pyridine group having 1 to 4 I, a benzodiazole group having 1 to 5 F, a benzodiazole group having 1 to 5 Cl, a benzodiazole group having 1 to 5 Br, a benzodiazole group having 1 to 5 I, a benzimidazole group having 1 to 4 F, a benzimidazole group having 1 to 4 Cl, a Examples of the benzothiophene group include a benzimidazole group having one to four F atoms, a benzimidazole group having one to four I atoms, a benzoxazole group having one to four Cl atoms, a benzoxazole group having one to four Br atoms, a benzoxazole group having one to four I atoms, a benzothiophene group having one to four F atoms, a benzothiophene group having one to four Cl atoms, a benzothiophene group having one to four Br atoms, and a benzothiophene group having one to four I atoms. X may also be an alicyclic group having one or more F, Cl, Br, or I atoms introduced into the alicyclic group.Examples of such alicyclic groups include an adamantyl group having 1 to 3 halogens, an adamantyl group having 1 to 3 F, an adamantyl group having 1 to 3 Cl, an adamantyl group having 1 to 3 Br, an adamantyl group having 1 to 3 I, a cyclopentyl group having 1 to 3 F, a cyclopentyl group having 1 to 3 Cl, a cyclopentyl group having 1 to 3 Br, a cyclopentyl group having 1 to 3 I, a bicycloundecyl group having 1 to 3 F, a bicycloundecyl group having 1 to 3 Cl, a bicycloundecyl group having 1 to 3 Br, a bicycloundecyl group having 1 to 3 I, a norbornyl group having 1 to 3 F, a norbornyl group having 1 to 3 Cl, a norbornyl group having 1 to 3 Br, and a norbornyl group having 1 to 3 I.

[0238] L 1 is a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group. 1 is preferably a single bond. 1 The ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, or phosphate group may have a substituent. Examples of such a substituent are as described above.

[0239] m is an integer of 0 or more, preferably an integer of 0 or more and 5 or less, more preferably an integer of 0 or more and 2 or less, even more preferably 0 or 1, and particularly preferably 0.

[0240] Each Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphonic group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphonic group, urethane group, urea group, amide group, imide group, and phosphate group of Y may have a substituent. Y is, for example, an 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 are each independently H or a hydrocarbon group having 1 to 10 carbon atoms. )], a carboxyalkoxy group [* 3 -OR 22 -(C=O)-OR 2 (R 22 is a divalent hydrocarbon group having 1 to 10 carbon atoms. )], and a carbonate ester group [* 3 -O-(C=O)-OR 2 In terms of increasing sensitivity, the ester group is preferably a tertiary ester group. 3 is the binding site for A. Among these, from the viewpoint of high sensitivity, Y is preferably a tertiary ester group, an acetal group, a carbonate ester group, or a carboxyalkoxy group, more preferably an acetal group, a carbonate ester group, or a carboxyalkoxy group, and even more preferably an acetal group or a carboxyalkoxy group. Furthermore, from the viewpoint of producing a polymer of stable quality by radical polymerization, an ester group, a carboxyalkoxy group, or a carbonate ester group is preferred.

[0241] Preferably, each Y is independently a group represented by the following formula (Y-1). [ka]

[0242] In formula (Y-1), L 2 is a group that is cleaved by the action of an acid or a base. Examples of groups that are 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 are each independently H or a hydrocarbon group having 1 to 10 carbon atoms. )], a carboxyalkoxy group [* 1 -OR 22 -(C=O)-O-* 2 (R 22 is a divalent hydrocarbon group having 1 to 10 carbon atoms. )], and a carbonate ester group [* 1 -O-(C=O)-O-* 2 In terms of achieving high sensitivity, the ester group is preferably a tertiary ester group. 1 is the binding site for A, * 2 is R 2 Among these, L 2 From the viewpoint of high sensitivity, the tertiary ester group, acetal group, carbonate ester group, or carboxyalkoxy group is preferred, acetal group, carbonate ester group, or carboxyalkoxy group is more preferred, and acetal group or carboxyalkoxy group is even more preferred. Furthermore, from the viewpoint of stable quality polymer production by radical polymerization, ester group, carboxyalkoxy group, and carbonate ester group are preferred. As another effect, when compound (A) of the second 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 within a desired range. Since compound (A) has a X group, it has a large effect on active species during the polymer formation reaction, making it difficult to achieve the desired control. Therefore, by having a group represented by formula (Y-1) as a protecting group on the hydrophilic group in compound (A), it is possible to suppress variations in copolymer formation and polymerization inhibition caused by the hydrophilic group.

[0243] 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 having 1 to 30 carbon atoms and containing a heteroatom, or a linear, branched or cyclic aromatic group having 1 to 30 carbon atoms and containing a heteroatom, and said R 2 The aliphatic group, aromatic group, aliphatic group containing a hetero atom, and aromatic group containing a hetero atom may further have a substituent. The substituents used here are those mentioned above, but a linear, branched, or cyclic aliphatic group having 1 to 20 carbon atoms and an aromatic group having 6 to 20 carbon atoms are preferred. R 2 Among these, an aliphatic group is preferred. 2 The aliphatic group in the formula (I) is preferably a branched or cyclic aliphatic group. The number of carbon atoms in the aliphatic group is preferably 1 or more and 20 or less, more preferably 3 or more and 10 or less, and even more preferably 4 or more and 8 or less. The aliphatic group is not particularly limited, but examples thereof include a methyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a cyclohexyl group, a methylcyclohexyl group, and an adamantyl group. Among these, a tert-butyl group, a cyclohexyl group, and an adamantyl group are preferred.

[0244] L 2 but* 1 -(C=O)-O-* 2Alternatively, if the group is a carboxyalkoxy group, when it is cleaved by the action of an acid or a base, a carboxylic acid group is formed, which increases the difference in solubility and dissolution rate between the dissociated portion and the non-dissociated portion in the development treatment, thereby improving the resolution and suppressing residues at the bottom of the pattern, particularly in fine line patterns, and is therefore preferred.

[0245] Specific examples of Y include the following: Each Y is independently a group represented by any one of the following formulae. [ka]

[0246] Examples of alkoxy groups that can be used as Y include alkoxy groups having one or more carbon atoms. From the viewpoint of the solubility of the resin after being combined with other monomers to form a resin, alkoxy groups having two or more carbon atoms are preferred, and alkoxy groups having three or more carbon atoms or having a cyclic structure are preferred. Specific examples of alkoxy groups that can be used as Y include, but are not limited to, the following: [ka]

[0247] As the amino group and amido group that can be used as Y, a primary amino group, a secondary amino group, a tertiary amino group, a group having a quaternary ammonium salt structure, an amide having a substituent, etc. can be appropriately used. Specific examples of usable amino groups or amido groups include, but are not limited to, the following: [ka]

[0248] n 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, even more preferably an integer of 1 or more and 3 or less, even more preferably 1 or 2, and particularly preferably 1.

[0249] R A are each independently H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent. The substituent on the organic group having 1 to 60 carbon atoms is not particularly limited, but examples thereof include I, F, Cl, Br, and other substituents. The other substituents are not particularly limited, but examples thereof include a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphonic group, a urethane group, a urea group, an amide group, an imide group, and a phosphate group. Of these, the alkoxy group, the ester group, the carbonate ester group, the amino group, the ether group, the thioether group, the phosphine group, the phosphonic group, the urethane group, the urea group, the amide group, the imide group, and the phosphate group may further have a substituent. Examples of the substituent include a linear, branched, or cyclic aliphatic group having 1 to 20 carbon atoms, and an aromatic group having 6 to 20 carbon atoms.

[0250] R A The organic group, which may have a substituent, preferably has 1 to 30 carbon atoms.

[0251] The organic group having 1 to 60 carbon atoms which may have a substituent is not particularly limited, but examples thereof include a linear or branched aliphatic hydrocarbon group having 1 to 60 carbon atoms, an alicyclic hydrocarbon group having 4 to 60 carbon atoms, and an aromatic group having 6 to 60 carbon atoms which may contain a heteroatom. The linear or branched aliphatic hydrocarbon group having 1 to 60 carbon atoms is not particularly limited, but examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-dodecyl group, a valerate group, and a 2-ethylhexyl group.

[0252] The alicyclic hydrocarbon group is not particularly limited, but examples thereof include a cyclohexyl group, a cyclododecyl group, a dicyclopentyl group, a tricyclodecyl group, and an adamantyl group. Furthermore, aromatic groups that may contain heteroatoms, such as a benzodiazole group, a benzotriazole group, and a benzothiadiazole group, can also be appropriately selected. Furthermore, a combination of these organic groups can also be selected.

[0253] The aromatic group having 6 to 60 carbon atoms and optionally containing a heteroatom is not particularly limited, but examples thereof include a phenyl group, a naphthalene group, a biphenyl group, an anthracyl group, a pyrenyl group, a benzodiazole group, a benzotriazole group, and a benzothiadiazole group.

[0254] Among these organic groups having 1 to 60 carbon atoms which may have a substituent, a methyl group is preferred from the viewpoint of producing a polymer of stable quality.

[0255] A is an organic group having 1 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 which may have a substituent. The number of carbon atoms in A is preferably 6 to 14, and more preferably 6 to 10. A is preferably a group represented by any of the following formulae, more preferably a group represented by the following formulae (A-1) to (A-2), and even more preferably a group represented by the following formula (A-1).

[0256] [ka]

[0257] A may be an alicyclic structure which may have a substituent. Here, the "alicyclic structure" refers to a saturated or unsaturated carbocyclic ring which does not have aromaticity. Examples of the alicyclic structure include saturated or unsaturated carbocyclic rings having 3 to 30 carbon atoms, and preferably saturated or unsaturated carbocyclic rings having 3 to 20 carbon atoms. Examples of the alicyclic structure include groups having cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloicosyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclopentadienyl, cyclooctadienyl, adamantyl, bicycloundecyl, decahydronaphthyl, norbornyl, norbornadienyl, cubane, basketane, or hasan. Furthermore, A may be a heterocyclic structure which may have a substituent. The heterocyclic structure is not particularly limited, and examples thereof include cyclic nitrogen-containing structures such as pyridine, piperidine, piperidone, benzodiazole, and benzotriazole, triazine, cyclic urethane structure, cyclic urea, cyclic amide, cyclic imide, cyclic ethers such as furan, pyran, and dioxolane, and alicyclic groups having a lactone structure such as caprolactone, butyrolactone, nonalactone, decalactone, undecalactone, bicycloundecalactone, and phthalide.

[0258] Each Z is independently an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, or a carbonate ester group. These groups may have a substituent, and the substituent may be a hydrocarbon group having 1 to 60 carbon atoms which may further have a substituent. r is an integer of 0 or more, preferably an integer of 0 to 2, more preferably an integer of 0 to 1, and even more preferably 0.

[0259] Z is, for example, an alkoxy group [* 3 -OR 2 ], ester group [* 3 -O-(C=O)-R 2 or * 3 -(C=O)-OR2 ], acetal group [* 3 -O-(C(R 21 )2)-OR 2 (R 21 are each independently H or a hydrocarbon group having 1 to 10 carbon atoms. )], a carboxyalkoxy group [* 3 -OR 22 -(C=O)-OR 2 (R 22 is a divalent hydrocarbon group having 1 to 10 carbon atoms. )], and a carbonate ester group [* 3 -O-(C=O)-OR 2 In terms of increasing sensitivity, the ester group is preferably a tertiary ester group. 3 is the binding site for A. Among these, from the viewpoint of high sensitivity, Z is preferably a tertiary ester group, an acetal group, a carbonate ester group, or a carboxyalkoxy group, more preferably an acetal group, a carbonate ester group, or a carboxyalkoxy group, and even more preferably an acetal group or a carboxyalkoxy group. Furthermore, from the viewpoint of producing a polymer of stable quality by radical polymerization, an ester group, a carboxyalkoxy group, or a carbonate ester group is preferred.

[0260] In the polymer (A), the other monomer to be copolymerized with the compound (A) preferably has a structural unit represented by the following formula (C3).

[0261] [ka]

[0262] In formula (C3), R C31 represents a hydrogen atom, a methyl group or a trifluoromethyl group, and m, A and * are as defined in the formula (C0) above.

[0263] Next, a method for producing polymer (A) will be described. The polymerization reaction is carried out by dissolving the monomers that will become the constituent units in a solvent, adding a polymerization initiator, and heating or cooling the mixture. The reaction conditions can be set as desired depending on the type of polymerization initiator, the initiation method (heat or light, etc.), temperature, pressure, concentration, solvent, additives, etc. Examples of polymerization initiators include radical polymerization initiators such as azoisobutyronitrile and peroxides, and anionic polymerization initiators such as alkyllithium and Grignard reagents.

[0264] As the solvent used in the polymerization reaction, commercially available products that are generally available can be used. For example, various solvents such as alcohols, ethers, hydrocarbons, and halogenated solvents can be used as appropriate within the range that does not inhibit the reaction. A mixture of multiple solvents can also be used within the range that does not inhibit the reaction.

[0265] The polymer (A) obtained by the polymerization reaction can be purified by a known method, specifically by a combination of ultrafiltration, crystallization, microfiltration, acid washing, washing with water having an electrical conductivity of 10 mS / m or less, and extraction.

[0266] [Composition and film-forming composition] The composition or film-forming composition of the second embodiment contains a compound (A) or a polymer (A) and is particularly suitable for lithography. While not particularly limited, the composition or film-forming composition can be used for lithography film formation, for example, for resist film formation (i.e., a "resist composition"). Furthermore, the composition or film-forming composition can be used for forming an upper layer film (i.e., a "composition for forming an upper layer film"), an intermediate layer (i.e., a "composition for forming an intermediate layer"), an underlayer film (i.e., a "composition for forming an underlayer film"), etc. The composition of the second embodiment can form a film with high sensitivity and can also impart a good resist pattern shape.

[0267] The film-forming composition of the second embodiment can also be used as an optical component-forming composition that applies lithography technology. Optical components are used in film and sheet form, and are useful as plastic lenses (prism lenses, lenticular lenses, microlenses, Fresnel lenses, viewing angle control lenses, contrast enhancement lenses, etc.), retardation films, electromagnetic wave shielding films, prisms, optical fibers, solder resists for flexible printed wiring, plating resists, interlayer insulating films for multilayer printed wiring boards, photosensitive optical waveguides, liquid crystal displays, organic electroluminescence (EL) displays, optical semiconductor (LED) elements, solid-state imaging elements, organic thin-film solar cells, dye-sensitized solar cells, and organic thin-film transistors (TFTs). The composition is particularly suitable for use as a filling film and planarizing film on photodiodes, planarizing films before and after color filters, microlenses, and planarizing and conformal films on microlenses, which are components of solid-state imaging elements that require a high refractive index.

[0268] The film-forming composition of the second embodiment may contain a compound (A), the composition of the second embodiment, or a polymer (A). The film-forming composition of the second embodiment may further contain an acid generator (C), a base generator (G), or an acid diffusion controller (E) (basic compound). The film-forming composition of the second embodiment may further contain other components such as a base material (B) and a solvent (S), as needed. Each component will be described below.

[0269] [Base material (B)] In the second embodiment, the term "substrate (B)" refers to a compound (including a resin) other than the compound (A) or the polymer (A) and is used as a resist for g-line, i-line, KrF excimer laser (248 nm), ArF excimer laser (193 nm), extreme ultraviolet (EUV) lithography (13.5 nm), or electron beam (EB) lithography (e.g., a substrate for lithography or a substrate for resist). Any of these substrates can be used as the substrate (B) in the second embodiment without any particular limitations. Examples of the substrate (B) include phenol novolac resin, cresol novolac resin, hydroxystyrene resin, (meth)acrylic resin, hydroxystyrene-(meth)acrylic copolymer, cycloolefin-maleic anhydride copolymer, cycloolefin, vinyl ether-maleic anhydride copolymer, inorganic resist materials containing metal elements such as titanium, tin, hafnium, and zirconium, and derivatives thereof. Among these, from the viewpoint of the shape of the resist pattern to be obtained, preferred are phenol novolac resins, cresol novolac resins, hydroxystyrene resins, (meth)acrylic resins, hydroxystyrene-(meth)acrylic copolymers, and inorganic resist materials containing metal elements such as titanium, tin, hafnium, and zirconium, as well as derivatives of these.

[0270] The derivative is not particularly limited, but examples thereof include those into which a dissociable group has been introduced, those into which a crosslinkable group has been introduced, etc. The derivative into which a dissociable group or a crosslinkable group has been introduced can undergo a dissociation reaction or a crosslinking reaction by the action of light, acid, etc.

[0271] The term "dissociable group" refers to a characteristic group that cleaves to generate a functional group such as an alkali-soluble group that changes solubility. The alkali-soluble group is not particularly limited, but examples thereof include a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, and a hexafluoroisopropanol group. The phenolic hydroxyl group and the carboxyl group are preferred, and the phenolic hydroxyl group is particularly preferred.

[0272] The term "crosslinkable group" refers to a group that crosslinks in the presence or absence of a catalyst. The crosslinkable group is not particularly limited, but 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 urethane(meth)acryloyl group, a group having a glycidyl group, and a group having a vinyl-containing phenylmethyl group.

[0273] [Solvent (S)] The solvent in the second embodiment may be any known solvent that can dissolve at least the compound (A) or 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; methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, and n-amino lactate. lactic acid esters such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate, etc.; aliphatic carboxylic acid 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, 3-methoxy-3-methylpropionate Examples of suitable esters include butyl butyrate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate, and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; ketones such as acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone (CPN), and cyclohexanone (CHN); amides such as N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpyrrolidone; and lactones such as γ-lactone.The solvent used in the second 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 even more preferably at least one selected from PGMEA, PGME, CHN, CPN, and ethyl lactate.

[0274] The solid component concentration in the film-forming composition of the second embodiment is not particularly limited, but is preferably 1 to 80 mass %, more preferably 1 to 50 mass %, even more preferably 2 to 40 mass %, and even more preferably 2 to 10 mass %, relative to the total mass of the film-forming composition.

[0275] [Acid generator (C)] The film-forming composition of the second embodiment preferably contains one or more acid generators (C) that generate acid directly or indirectly upon irradiation with radiation. The radiation is at least one selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), X-ray, and ion beam. The acid generator (C) is not particularly limited, but for example, those described in International Publication WO2013 / 024778 can be used. The acid generators (C) can be used alone or in combination of two or more.

[0276] The amount of the acid generator (C) blended is preferably 0.001 to 49% by mass, more preferably 1 to 40% by mass, even more preferably 3 to 30% by mass, and even more preferably 10 to 25% by mass, based on the total mass of the solid components. Using the acid generator (C) within the above range tends to result in a pattern profile with high sensitivity and low edge roughness. In the second embodiment, the method for generating acid is not particularly limited as long as an acid is generated in the system. Using an excimer laser instead of ultraviolet light such as g-rays or i-rays enables finer processing, and using an electron beam, extreme ultraviolet light, X-rays, or ion beam as a high-energy beam enables even finer processing.

[0277] Base generator (G) The case where the base generator (G) is a photobase generator will be described. The photobase generator is a substance that generates a base upon exposure to light, and is not particularly limited as long as it is inactive under normal conditions of room temperature and normal pressure, but generates a base (basic substance) upon exposure to electromagnetic waves and heating as external stimuli.

[0278] The photobase generator that can be used in the second embodiment is not particularly limited, and known ones can be used, such as carbamate derivatives, amide derivatives, imide derivatives, α-cobalt complexes, imidazole derivatives, cinnamic acid amide derivatives, and oxime derivatives.

[0279] The basic substance generated from the photobase generator is not particularly limited, but examples thereof include compounds having an amino group, particularly monoamines, polyamines such as diamines, and amidines. From the viewpoint of sensitivity and resolution, the generated basic substance is preferably a compound having an amino group with a higher basicity (higher pKa value of the conjugate acid). Examples of photobase generators include base generators having a cinnamic acid amide structure as disclosed in JP 2009-80452 A and WO 2009 / 123122 A, base generators having a carbamate structure as disclosed in JP 2006-189591 A and JP 2008-247747 A, base generators having an oxime structure or a carbamoyloxime structure as disclosed in JP 2007-249013 A and JP 2008-003581 A, and compounds described in JP 2010-243773 A, but are not limited to these, and other known base generator structures can also be used.

[0280] The photobase generators can be used alone or in combination of two or more. The preferred content of the photobase generator in the actinic ray-sensitive or radiation-sensitive resin composition is the same as the preferred content of the photoacid generator in the actinic ray-sensitive or radiation-sensitive resin composition described above.

[0281] [Acid diffusion controller (E)] The film-forming composition of the second embodiment may contain an acid diffusion controller (E) as a basic compound. The acid diffusion controller (E) controls the diffusion of the acid generated from the acid generator upon irradiation in the resist film, thereby preventing undesirable chemical reactions in unexposed areas. The use of the acid diffusion controller (E) tends to improve the storage stability of the composition of the second embodiment. Furthermore, the use of the acid diffusion controller (E) tends to improve the resolution of the film formed using the composition of the second embodiment, and also tends to suppress changes in the line width of the resist pattern due to variations in the exposure time before and after radiation exposure, thereby resulting in excellent process stability. The acid diffusion controller (E) is not particularly limited, and examples thereof include radiation-decomposable basic compounds such as nitrogen-containing basic compounds, basic sulfonium compounds, and basic iodonium compounds.

[0282] The acid diffusion controller (E) is not particularly limited, but for example, those described in International Publication WO 2013 / 024778 can be used. The acid diffusion controller (E) can be used alone or in combination of two or more.

[0283] The amount of the acid diffusion controller (E) is preferably 0.001 to 49% by mass, more preferably 0.01 to 10% by mass, even 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 components. When the amount of the acid diffusion controller (E) is within this range, it tends to be possible to prevent a decrease in resolution and deterioration of the pattern shape and dimensional fidelity. Furthermore, even if the exposure time between electron beam irradiation and post-exposure heating is long, it is possible to suppress deterioration of the shape of the upper layer of the pattern. Furthermore, when the amount of the acid diffusion controller (E) is 10% by mass or less, it tends to be possible to prevent a decrease in sensitivity, developability of unexposed areas, and the like. Furthermore, the use of such an acid diffusion controller improves the storage stability and resolution of the resist composition, and also suppresses changes in the line width of the resist pattern due to variations in the exposure time before and after radiation exposure, tending to result in excellent process stability.

[0284] [Other ingredients (F)] To the film-forming composition of the second embodiment, one or more of various additives such as a crosslinking agent, a dissolution promoter, a dissolution control agent, a sensitizer, a surfactant, and an organic carboxylic acid or a phosphorus oxoacid or a derivative thereof can be added as other component (F), if necessary.

[0285] (Crosslinking agent) The film-forming composition of the second embodiment may contain a crosslinking agent. The crosslinking agent can crosslink at least one of the compound (A), the polymer (A), and the base material (B). The crosslinking agent is preferably an acid crosslinking agent that can intramolecularly or intermolecularly crosslink the base material (B) in the presence of an acid generated from the acid generator (C). Examples of such acid crosslinking agents include compounds having one or more groups (hereinafter referred to as "crosslinkable groups") that can crosslink the base material (B).

[0286] Examples of the crosslinkable group include (i) hydroxyalkyl groups such as a hydroxy group, a hydroxyalkyl group (an alkyl group having 1 to 6 carbon atoms), an alkoxy group having 1 to 6 carbon atoms (an alkyl group having 1 to 6 carbon atoms), and an acetoxy group (an alkyl group having 1 to 6 carbon atoms), or groups derived therefrom; (ii) carbonyl groups such as a formyl group and a carboxy group (an alkyl group having 1 to 6 carbon atoms), or groups derived therefrom; (iii) dimethylaminomethyl groups, diethylaminomethyl groups, dimethylolaminomethyl groups, diethylaminomethyl groups, and the like; Examples of the crosslinkable group include nitrogen-containing groups such as arylaminomethyl and morpholinomethyl groups; (iv) glycidyl group-containing groups such as glycidyl ether, glycidyl ester and glycidylamino groups; (v) groups derived from aromatic groups such as allyloxy (alkyl groups having 1 to 6 carbon atoms) and aralkyloxy (alkyl groups having 1 to 6 carbon atoms) having 1 to 6 carbon atoms, such as benzyloxymethyl and benzoyloxymethyl groups; and (vi) polymerizable multiple bond-containing groups such as vinyl and isopropenyl groups. The crosslinkable group of the crosslinking agent in the second embodiment is preferably a hydroxyalkyl group or an alkoxyalkyl group, with an alkoxymethyl group being particularly preferred.

[0287] The crosslinking agent having a crosslinkable group is not particularly limited, and for example, the acid crosslinking agents described in International Publication No. WO 2013 / 024778 can be used. The crosslinking agents can be used alone or in combination of two or more.

[0288] In the second embodiment, the amount of the crosslinking agent is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and even more preferably 20% by mass or less, based on the total mass of the solid components.

[0289] (solubility enhancer) The dissolution promoter is a component that has the effect of increasing the solubility of a solid component in a developer when the solubility of the solid component is too low, thereby appropriately increasing the dissolution rate of the compound during development. The dissolution promoter is preferably a low-molecular-weight compound, and examples thereof include low-molecular-weight phenolic compounds. Examples of low-molecular-weight phenolic compounds include bisphenols and tris(hydroxyphenyl)methane. These dissolution promoters can be used alone or in combination of two or more.

[0290] The amount of the dissolution promoter to be added is adjusted appropriately depending on the type of the solid component used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass, of the total mass of the solid components.

[0291] (dissolution regulator) The dissolution controller is a component that has the effect of controlling the solubility of a solid component in a developer when the solubility of the solid component is too high, thereby appropriately reducing the dissolution rate during development. Such a dissolution controller is preferably one that does not undergo chemical changes during processes such as baking, irradiation, and development of the resist film.

[0292] The dissolution controller is not particularly limited, but examples thereof include aromatic hydrocarbons such as phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenyl naphthyl ketone; and sulfones such as methyl phenyl sulfone, diphenyl sulfone, and dinaphthyl sulfone. These dissolution controllers can be used alone or in combination of two or more.

[0293] The amount of the dissolution controller is adjusted appropriately depending on the type of the compound used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass, of the total mass of the solid components.

[0294] (sensitizer) The sensitizer is a component that absorbs the energy of irradiated radiation and transfers that energy to the acid generator (C), thereby increasing the amount of acid produced and improving the apparent sensitivity of the resist. Examples of such sensitizers include, but are not limited to, benzophenones, biacetyls, pyrenes, phenothiazines, and fluorenes. These sensitizers can be used alone or in combination of two or more.

[0295] The amount of the sensitizer to be added is adjusted appropriately depending on the type of the compound used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass, of the total mass of the solid components.

[0296] (surfactant) The surfactant is a component that has the effect of improving the coatability and striation of the composition of the second embodiment, the developability of the resist, etc. The surfactant may be any of anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. Preferred surfactants include nonionic surfactants. Nonionic surfactants have good affinity with the solvent used in producing the composition of the second embodiment, and can further enhance the effects of the composition of the second embodiment. Examples of nonionic surfactants include, but are not limited to, polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, and higher fatty acid diesters of polyethylene glycol. Commercially available surfactants include, under the trade names below, F-Top (manufactured by Gemco), Megafac (manufactured by Dainippon Ink and Chemicals, Inc.), Fluorad (manufactured by Sumitomo ThreeM), Asahi Guard, Surflon (all manufactured by Asahi Glass Co., Ltd.), Pepol (manufactured by Toho Chemical Industry Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), and Polyflo (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.).

[0297] The amount of surfactant to be added is adjusted appropriately depending on the type of solid component used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass, of the total mass of the solid components.

[0298] (organic carboxylic acid or phosphorus oxoacid or its derivative) For the purpose of preventing sensitivity degradation or improving resist pattern shape and deposition stability, an organic carboxylic acid or a phosphorus oxo acid or a derivative thereof can be further contained as an optional component. The organic carboxylic acid or the phosphorus oxo acid or a derivative thereof can be used in combination with an acid diffusion controller or alone. Suitable organic carboxylic acids include malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid. Examples of phosphorus oxo acids or derivatives thereof include phosphoric acid, di-n-butyl phosphate, diphenyl phosphate, and other phosphoric acid or ester derivatives thereof; phosphonic acid, dimethyl phosphonate, di-n-butyl phosphonate, phenylphosphonic acid, diphenyl phosphonate, and other phosphonic acid or ester derivatives thereof; and phosphinic acid, phenylphosphinic acid, and other ester derivatives thereof. Among these, phosphonic acid is particularly preferred.

[0299] The organic carboxylic acid, phosphorus oxo acid, or derivative thereof may be used alone or in combination of two or more. The amount of the organic carboxylic acid, phosphorus oxo acid, or derivative thereof is adjusted appropriately depending on the type of compound used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass, of the total mass of the solid components.

[0300] [Other additives] Furthermore, the composition of the second embodiment may contain one or more additives other than the above-mentioned components, as needed. Examples of such additives include dyes, pigments, and adhesion promoters. For example, the incorporation of a dye or pigment is preferred because it can visualize the latent image in the exposed area and mitigate the effects of halation during exposure. Furthermore, the incorporation of an adhesion promoter is preferred because it can improve adhesion to the substrate. Other additives include antihalation agents, storage stabilizers, antifoaming agents, shape modifiers, and the like, specifically 4-hydroxy-4'-methylchalcone.

[0301] In the composition of the second embodiment, the total amount of optional component (F) can be 0 to 99 mass% of the total mass of the solid components, preferably 0 to 49 mass%, more preferably 0 to 10 mass%, even more preferably 0 to 5 mass%, even more preferably 0 to 1 mass%, and particularly preferably 0 mass%.

[0302] [Method for forming resist pattern and insulating film] The method for forming a resist pattern according to the second embodiment includes the steps of: forming a resist film on a substrate using the film-forming composition of the second embodiment; exposing the resist film to a pattern; a step of developing the resist film after the exposure; Includes.

[0303] The method for forming an insulating film according to the second embodiment may include the method for forming a resist pattern according to the second embodiment. That is, the method for forming an insulating film according to the second embodiment includes: forming a resist film on a substrate using the film-forming composition of the second embodiment; exposing the resist film to a pattern; a step of developing the resist film after the exposure; may include:

[0304] The film-forming composition of the second embodiment contains, for example, the compound (A), the composition of the second embodiment, or the polymer (A). The coating method in the step of forming the resist film is not particularly limited, but examples thereof include a spin coater, a dip coater, and a roller coater. The substrate is not particularly limited, but examples thereof include a silicon wafer, metal, plastic, glass, and ceramic. After forming the resist film, a heat treatment may be performed at a temperature of about 50°C to 200°C. The thickness of the resist film is not particularly limited, but is, for example, 50 nm to 1 μm.

[0305] In the exposure step, exposure may be performed through a predetermined mask pattern, or shot exposure without a mask may be performed. The thickness of the coating film is, for example, 0.1 to 20 μm, preferably about 0.3 to 2 μm. Light rays of various wavelengths, such as ultraviolet rays and X-rays, can be used for exposure. For example, as a light source, far ultraviolet rays such as F2 excimer laser (wavelength 157 nm), ArF excimer laser (wavelength 193 nm), and KrF excimer laser (wavelength 248 nm), extreme ultraviolet rays (wavelength 13 nm), X-rays, electron beams, etc. are appropriately selected and used. Among these, extreme ultraviolet rays are preferred. In addition, exposure conditions such as exposure dose are appropriately selected depending on the blending composition of the above-mentioned resins and / or compounds, the types of each additive, etc.

[0306] In the second embodiment, in order to stably form a highly accurate fine pattern, it is preferable to perform a heat treatment at a temperature of 50 to 200°C for 30 seconds or more after exposure. In this case, if the temperature is less than 50°C, there is a risk of widening the variation in sensitivity depending on the type of substrate. Thereafter, the resist is developed with an alkaline developer typically at 10 to 50°C for 10 to 200 seconds, preferably at 20 to 25°C for 15 to 90 seconds, to form a predetermined resist pattern.

[0307] The alkaline developer is typically an alkaline aqueous solution prepared by dissolving an alkaline compound, such as an alkali metal hydroxide, aqueous ammonia, alkylamines, alkanolamines, heterocyclic amines, tetraalkylammonium hydroxides, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, or 1,5-diazabicyclo-[4.3.0]-5-nonene, at a concentration of typically 1 to 10% by mass, preferably 1 to 3% by mass. A water-soluble organic solvent or a surfactant may also be added to the alkaline aqueous developer.

[0308] A solvent can also be used as the developer. It is preferable to select a solvent with a solubility parameter (SP value) close to that of the compound or resin according to the second embodiment to be used as the developer. Polar solvents such as ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents, hydrocarbon-based solvents, or alkaline aqueous solutions can be used. Depending on the type of developer, either a positive or negative resist pattern can be produced. Generally, polar solvents such as ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents, and hydrocarbon-based solvents produce negative resist patterns, while alkaline aqueous solutions produce positive resist patterns. Examples of ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, hydrocarbon-based solvents, and alkaline aqueous solutions include those disclosed in International Publication No. WO 2017 / 033943.

[0309] The solvents may be mixed in plural, or may be mixed with other solvents or water within the range of performance. However, to fully achieve the effects of the second embodiment, the water content of the developer as a whole is preferably less than 70% by mass, more preferably less than 50% by mass, more preferably less than 30% by mass, even more preferably less than 10% by mass, and particularly preferably substantially free of water. That is, the content of the organic solvent in the developer is not particularly limited, and is preferably 30% by mass or more and 100% by mass or less, more preferably 50% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 100% by mass or less, even more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less, based on the total amount of the developer.

[0310] In particular, a developer containing at least one solvent selected from a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, an amide-based solvent, and an ether-based solvent is preferred, as this improves resist performance such as the resolution and roughness of the resist pattern.

[0311] The vapor pressure of the developer is not particularly limited, and is preferably 5 kPa or less at 20°C, more preferably 3 kPa or less, and particularly preferably 2 kPa or less. By setting the vapor pressure of the developer to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, improving temperature uniformity within the wafer surface and, as a result, improving dimensional uniformity within the wafer surface. Examples of developers having such a vapor pressure include the developers disclosed in International Publication No. 2017 / 033943.

[0312] If necessary, an appropriate amount of a surfactant may be added to the developer. The surfactant is not particularly limited, but for example, an ionic or nonionic fluorine-based or silicon-based surfactant may be used. Examples of these fluorine- or silicon-based surfactants include those described in JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, U.S. Pat. Nos. 5,405,720, 5,360,692, 5,529,881, 5,296,330, 5,436,098, 5,576,143, 5,294,511, and 5,824,451, and preferably nonionic surfactants. The nonionic surfactant is not particularly limited, but it is more preferable to use a fluorine-based surfactant or a silicon-based surfactant.

[0313] The amount of the surfactant used is usually from 0.001 to 5% by mass, preferably from 0.005 to 2% by mass, and more preferably from 0.01 to 0.5% by mass, based on the total amount of the developer.

[0314] Examples of development methods that can be applied include a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which a developer is piled up on the surface of the substrate by surface tension and left standing for a certain period of time (puddle method), a method in which a developer is sprayed onto the surface of the substrate (spray method), and a method in which a developer is continuously dispensed onto a substrate rotating at a constant speed while a developer dispensing nozzle is scanned at a constant speed (dynamic dispense method). There are no particular restrictions on the time for developing the pattern, but it is preferably 10 to 90 seconds.

[0315] After the development step, a step of stopping the development while replacing the solvent with another solvent may be carried out.

[0316] After the development, it is preferable to include a step of washing with a rinse liquid containing an organic solvent.

[0317] The rinse liquid used in the rinsing step after development is not particularly limited as long as it does not dissolve the resist pattern hardened by crosslinking, and a solution containing a common organic solvent or water can be used. The rinse liquid preferably contains at least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. More preferably, after development, a cleaning step is performed using a rinse liquid containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, and amide solvents. Even more preferably, after development, a cleaning step is performed using a rinse liquid containing an alcohol solvent or an ester solvent. Even more preferably, after development, a cleaning step is performed using a rinse liquid containing a monohydric alcohol. Particularly preferably, after development, a cleaning step is performed using a rinse liquid containing a monohydric alcohol having 5 or more carbon atoms. The time for rinsing the pattern is not particularly limited, but is preferably 10 to 90 seconds.

[0318] Here, the monohydric alcohol used in the rinsing step after development is not particularly limited, and examples thereof include linear, branched, and cyclic monohydric alcohols. Specific examples include 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, and 4-octanol. Particularly preferred monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, and 3-methyl-1-butanol.

[0319] The above-mentioned components may be mixed in plural, or may be mixed with an organic solvent other than those mentioned above.

[0320] The water content in the rinse solution is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By keeping the water content at 10% by mass or less, better development characteristics can be obtained.

[0321] The vapor pressure of the rinse liquid used after development is preferably 0.05 kPa to 5 kPa, more preferably 0.1 kPa to 5 kPa, and even more preferably 0.12 kPa to 3 kPa at 20° C. By setting the vapor pressure of the rinse liquid to 0.05 kPa to 5 kPa, the temperature uniformity within the wafer surface is further improved, and swelling due to penetration of the rinse liquid is further suppressed, resulting in improved dimensional uniformity within the wafer surface.

[0322] The rinse solution may contain an appropriate amount of a surfactant.

[0323] In the rinsing step, the developed wafer is cleaned using a rinse solution containing the organic solvent. The cleaning method is not particularly limited, but may be, for example, a method in which the rinse solution is continuously applied to a substrate rotating at a constant speed (spin coating method), a method in which the substrate is immersed in a tank filled with the rinse solution for a certain period of time (dip method), or a method in which the rinse solution is sprayed onto the surface of the substrate (spray method). Among these, it is preferable to perform the cleaning by the spin coating method, and then rotate the substrate at a rotation speed of 2000 rpm to 4000 rpm after cleaning to remove the rinse solution from the substrate.

[0324] The composition of the second embodiment can also be used as a composition for forming optical components using lithography technology. Optical components are used in film and sheet form, and are useful as plastic lenses (prism lenses, lenticular lenses, microlenses, Fresnel lenses, viewing angle control lenses, contrast enhancement lenses, etc.), retardation films, electromagnetic wave shielding films, prisms, optical fibers, solder resists for flexible printed wiring, plating resists, interlayer insulating films for multilayer printed wiring boards, photosensitive optical waveguides, liquid crystal displays, organic electroluminescence (EL) displays, optical semiconductor (LED) elements, solid-state imaging elements, organic thin-film solar cells, dye-sensitized solar cells, and organic thin-film transistors (TFTs). The composition is particularly suitable for use as a filling film and planarizing film on photodiodes, planarizing films before and after color filters, microlenses, and planarizing and conformal films on microlenses, which are components of solid-state imaging elements that require a high refractive index.

[0325] The composition of the second embodiment can also be used as a patterning material for lithography applications. Lithography processes can be used in a variety of applications, including semiconductors, liquid crystal display panels and display panels using OLEDs, power devices, CCDs and other sensors, and the like. In particular, for integrated circuits of semiconductors and devices, in the process of forming device elements on a silicon wafer, a pattern is formed on the upper surface of an insulating layer, such as a silicon oxide film or other oxide film, using the composition of the second embodiment to form a pattern on an insulating film on the substrate side by etching, and then a metal film or semiconductor material is laminated based on the formed insulating film pattern to form a circuit pattern, thereby constructing a semiconductor element or other device. The composition of the second embodiment can be suitably used.

[0326] This concludes the description of the second embodiment.

[0327] Third Embodiment The third embodiment of the present invention will be described below. The third embodiment is a compound (A) according to the first embodiment, in which RX is a hydrogen atom. In the following description of the third embodiment, the description of the same content as in the second embodiment may be simplified or omitted. Note that the third embodiment is an example for explaining the present invention, and the present invention is not limited to only the second embodiment.

[0328] [Compound (A)] The compound according to the third embodiment (hereinafter also referred to as "compound (A)") is represented by the following formula (1).

[0329] [ka]

[0330] By using a compound, polymer, composition, or film-forming composition containing compound (A), a resist having extremely excellent exposure sensitivity can be obtained. Furthermore, a pattern-forming method, an insulating film-forming method, or a compound-producing method using compound (A) can provide a resist having extremely excellent exposure sensitivity. That is, it is possible to provide a compound, polymer, composition, film-forming composition, pattern-forming method, insulating film-forming method, and compound-producing method that can provide a resist having extremely excellent exposure sensitivity by using compound (A).

[0331] Although it is not clear why the use of compound (A) results in a resist with extremely excellent exposure sensitivity, it is presumed that this is due to a combination of the following: the high absorption effect of the iodine atom against EUV; the presence of the substituent P immediately adjacent to the iodine atom, which is susceptible to the absorption effect and therefore likely to produce a sensitizing effect from the substituent P; and the fact that the iodine atom of the substituent P is unsubstituted on the opposite side, which is likely to result in the sensitizing effect of P.

[0332] In formula (1), R Ais a hydrogen atom, a methyl group, or a trifluoromethyl group, and P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group.

[0333] In formula (1), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group. From the viewpoint of increasing hydrophilicity for high sensitivity, R A is preferably a hydrogen atom or a methyl group. In order to increase sensitivity, in order to increase absorption of EUV, R A is preferably a trifluoromethyl group.

[0334] In the third embodiment, unless otherwise defined, "substituted" means that one or more hydrogen atoms in a functional group are substituted with a substituent. The "substituent" is not particularly limited, but 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 alkoxyl 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. The alkyl group may be any of a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, and a cyclic aliphatic hydrocarbon group.

[0335] Examples of the alkyl group having 1 to 30 carbon atoms include, but are not limited to, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-dodecyl group, and a valeric group. Examples of the aryl group having 6 to 30 carbon atoms include, but are not limited to, a phenyl group, a naphthalene group, a biphenyl group, an anthracyl group, a pyrenyl group, and a perylene group. Examples of the alkenyl group having 2 to 30 carbon atoms include, but are not limited to, an ethynyl group, a propenyl group, a butynyl group, and a pentynyl group. Examples of the alkynyl group having 2 to 30 carbon atoms include, but are not limited to, an acetylene group and an ethynyl group. 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 pentoxy group.

[0336] In formula (1), each P independently represents a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphonic group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphonic group, urethane group, urea group, amide group, imide group, and phosphate group of P may have a substituent. P can be, for example, an 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 are each independently H or a hydrocarbon group having 1 to 10 carbon atoms. 2 and R 21 may be bonded to form a cyclic ether. )], carboxyalkoxy group [* 3 -OR 22 -(C=O)-OR 2 (R 22 is a divalent hydrocarbon group having 1 to 10 carbon atoms. )], and a carbonate ester group [* 3 -O-(C=O)-OR 2In terms of increasing sensitivity, the ester group is preferably a tertiary ester group. 3 is the binding site for A.

[0337] Among these, from the viewpoint of high sensitivity, P is preferably a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphonic group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group; more preferably a hydroxyl group, an ester group, an acetal group, a carbonate ester group, or a carboxyalkoxy group; still more preferably an acetal group, a carbonate ester group, or a carboxyalkoxy group; and particularly preferably an acetal group or a carboxyalkoxy group. Furthermore, from the viewpoint of producing a polymer of stable quality by radical polymerization, an ester group, a carboxyalkoxy group, and a carbonate ester group are preferred. Furthermore, from the viewpoint of increasing the difference in dissolution rate before and after exposure to improve resolution, a tertiary ester group, an acetal group, a carbonate ester group, or a carboxyalkoxy group is preferred. From the viewpoint of achieving high sensitivity without adversely affecting other properties, P is preferably an ester group, an acetal group, or a carbonate ester group.

[0338] Preferably, each P is independently a group represented by the following formula (P-1). [ka]

[0339] In formula (P-1), L 2 is a group that is cleaved by the action of an acid or a base. Examples of groups that are 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 21are each independently H or a hydrocarbon group having 1 to 10 carbon atoms. )], a carboxyalkoxy group [* 1 -OR 22 -(C=O)-O-* 2 (R 22 is a divalent hydrocarbon group having 1 to 10 carbon atoms. )], and a carbonate ester group [* 1 -O-(C=O)-O-* 2 In terms of achieving high sensitivity, the ester group is preferably a tertiary ester group. 1 is the bonding site with the benzene ring, * 2 is R 2 Among these, L 2 From the viewpoint of high sensitivity, the tertiary ester group, acetal group, carbonate ester group, or carboxyalkoxy group is preferred, acetal group, carbonate ester group, or carboxyalkoxy group is more preferred, and acetal group or carboxyalkoxy group is even more preferred. Furthermore, from the viewpoint of stable quality polymer production by radical polymerization, ester group, carboxyalkoxy group, and carbonate ester group are preferred. As another effect, when the compound (A) of the third embodiment is used as a polymerization unit of a copolymer, P is preferably a group represented by formula (P-1) for the purpose of controlling the polymerizability of the resin and setting the degree of polymerization within a desired range. Since the compound (A) has iodine, it has a large effect on active species during the polymer formation reaction, making it difficult to achieve the desired control. Therefore, by having the group represented by formula (P-1) as a protecting group on the hydrophilic group in the compound (A), it is possible to suppress variations in copolymer formation and polymerization inhibition due to the hydrophilic group.

[0340] 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 having 1 to 30 carbon atoms and containing a heteroatom, or a linear, branched or cyclic aromatic group having 1 to 30 carbon atoms and containing a heteroatom, and said R 2The aliphatic group, aromatic group, aliphatic group containing a hetero atom, and aromatic group containing a hetero atom may or may not further have a substituent. The substituents used here are those described above, but preferred are linear, branched, or cyclic aliphatic groups having 1 to 20 carbon atoms and aromatic groups having 6 to 20 carbon atoms. R 2 Among these, an aliphatic group is preferred. 2 The aliphatic group in the formula (I) is preferably a branched or cyclic aliphatic group. The number of carbon atoms in the aliphatic group is preferably 1 or more and 20 or less, more preferably 3 or more and 10 or less, and even more preferably 4 or more and 8 or less. The aliphatic group is not particularly limited, but examples thereof include a methyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a cyclohexyl group, a methylcyclohexyl group, and an adamantyl group. Among these, a tert-butyl group, a cyclohexyl group, and an adamantyl group are preferred.

[0341] L 2 but* 1 -(C=O)-O-* 2 Alternatively, if the group is a carboxyalkoxy group, when it is cleaved by the action of an acid or a base, a carboxylic acid group is formed, which increases the difference in solubility and dissolution rate between the dissociated portion and the non-dissociated portion in the development treatment, thereby improving the resolution and suppressing residues at the bottom of the pattern, particularly in fine line patterns, and is therefore preferred.

[0342] Specific examples of P include the following: P's are, for example, each independently a group represented by any of the following formulae. [ka]

[0343] Examples of alkoxy groups that can be used as P include alkoxy groups having one or more carbon atoms. From the viewpoint of the solubility of the resin after being combined with other monomers to form a resin, alkoxy groups having two or more carbon atoms are preferred, and alkoxy groups having three or more carbon atoms or having a cyclic structure are preferred. Specific examples of alkoxy groups that can be used as P include, but are not limited to, the following: [ka]

[0344] As the amino group and amido group that can be used as P, a primary amino group, a secondary amino group, a tertiary amino group, a group with a quaternary ammonium salt structure, an amide having a substituent, etc. can be appropriately used. Specific examples of usable amino groups or amido groups include, but are not limited to, the following: [ka]

[0345] Compound (A) according to the third embodiment has a hydrogen group serving as a proton source at the ortho position of the phenolic hydroxyl group, which is thought to contribute to improving the efficiency of the proton generation mechanism after exposure. When a polymer using compound (A) is applied to a resist composition and a pattern is formed by a lithography process consisting of film formation, exposure, and development, improving the efficiency of proton generation after exposure makes up for a shortage of generated protons that cause development residues, roughness, bridges, etc., and makes it possible to achieve both development defects and other lithography performance such as sensitivity and resolution. As a result, it is expected that pattern quality can be improved in the formation of finer patterns. As a result, it is believed that this will be effective in improving the pattern quality, particularly in patterns with low aperture ratios such as hole patterns.

[0346] Examples of the compound (A) according to the third embodiment include compounds having the following structures:

[0347] [ka]

[0348] [ka]

[0349] The above compound (A) is preferably used in combination with the compound represented by the following formula (1A). That is, the composition according to the third embodiment preferably contains the compound (A) and the compound represented by the formula (1A).

[0350] [ka] (In formula (1A), formula (1A1), and formula (1A2), R A and P are the same as defined in formula (1), and R sub represents formula (1A1) or formula (1A2), and * represents the bonding site to the adjacent structural unit.

[0351] From the viewpoint of improving exposure sensitivity and reducing residual defects, the composition is preferably prepared so that the compound represented by formula (1A) is contained in the range of 1 ppm by mass to 10% by mass, more preferably 1 ppm by mass to 5% by mass, even more preferably 1 ppm by mass to 3% by mass, and particularly preferably 1 ppm by mass to 1% by mass. In the resin formed from starting materials containing the composition prepared in this manner, the high density of iodine-containing moieties and P-containing moieties in adjacent regions serves as the starting point for improving exposure sensitivity. Furthermore, the locally increased solubility in the resin leads to a reduction in residual defects after development in the lithography process.

[0352] Examples of the compound (1A) according to the third embodiment include compounds having the following structures:

[0353] [ka]

[0354] The above compound (A) is preferably used in combination with the compound represented by the following formula (1B): That is, the composition according to the third embodiment preferably contains the compound (A) and the compound represented by the formula (1B).

[0355] [ka] (In formula (1B), formula (1B1), or formula (1B2), R A and P are defined as in formula (1), n2 is an integer of 0 to 4, and R sub2 represents formula (1B1) or formula (1B2), and * represents the bonding site to the adjacent structural unit.

[0356] From the viewpoint of improving exposure sensitivity and reducing residual defects, the composition is preferably prepared so that the compound represented by formula (1B) is contained in the range of 1 ppm by mass to 10% by mass, more preferably 1 ppm by mass to 5% by mass, even more preferably 1 ppm by mass to 3% by mass, and particularly preferably 1 ppm by mass to 1% by mass. In the resin formed from starting materials containing the composition prepared in this manner, the high density of iodine-containing moieties and P-containing moieties in adjacent regions serves as the starting point for improving exposure sensitivity. Furthermore, the locally increased solubility in the resin leads to a reduction in residual defects after development in the lithography process.

[0357] Examples of the compound (1B) according to the third embodiment include compounds having the following structure.

[0358] [ka]

[0359] The above compound (A) is preferably used in combination with the compound represented by the following formula (1C): That is, the composition according to the third embodiment preferably contains the compound (A) and the compound represented by the formula (1C).

[0360] [ka]

[0361] In formula (1C), R A and P are defined as in formula (1), provided that P does not include I.

[0362] From the viewpoint of stability and reduction of residual defects, the composition preferably contains the compound represented by formula (1C) in an amount of from 1 ppm by mass to 10% by mass, more preferably from 1 ppm by mass to 5% by mass, even more preferably from 1 ppm by mass to 3% by mass, and particularly preferably from 1 ppm by mass to 1% by mass, based on the entire compound (A). The composition prepared in this way tends to be more stable. Although the reason for this is unclear, it is presumed that this is due to an equilibrium reaction of iodine atoms occurring between the iodine-containing compound (A) and the iodine-free compound (1C), resulting in stabilization. In this case, it is preferable that the composition also uses, as compound (1C), a compound having a structure in which an iodine atom has been eliminated from the compound exemplified above as compound (A). Furthermore, the composition prepared in this manner has increased stability, which not only improves storage stability but also leads to the formation of a resin with stable properties, the provision of stable resist performance, and the reduction of residue defects after development in lithography processes. The method for using the compound represented by formula (1C) in a composition containing compound (A) in an amount of 1 ppm by mass or more and 10% by mass or less, based on the total amount of compound (A), is not particularly limited, and examples thereof include a method in which compound (1C) is added to compound (A) and a method in which compound (1C) is by-produced during the production of compound (A).

[0363] Examples of the compound (1C) according to the third embodiment include compounds having the following structures: [ka] [ka]

[0364] [Method for producing compound (A)] The compound represented by formula (1) can be produced by various known synthesis methods.

[0365] For a compound represented by formula (1) in which P is a hydroxyl group, one example of a synthesis method is, but is not limited to, introducing a halogen group (I, F, Cl, or Br) into a hydroxyl group-containing aromatic aldehyde derivative, and then converting the aldehyde group to a vinyl group. Other examples of synthesis methods include a method of iodinating a hydroxybenzaldehyde derivative to react with iodine chloride in an organic solvent (see, for example, JP 2012-180326 A), or a method of adding iodine dropwise to an alkaline aqueous solution of phenol in the presence of β-cyclodextrin under alkaline conditions (see, for example, JP 63-101342 A and JP 2003-64012 A).

[0366] In the third embodiment, it is preferable to use an iodination reaction via iodine chloride in an organic solvent. The compound (A) of the third embodiment can be synthesized by converting the aldehyde moiety of the synthesized iodine-introduced hydroxybenzaldehyde derivative into a vinyl group. The Wittig reaction (e.g., the method described in Synthetic Communications; Vol. 22; nb4; 1992 p. 513, Synthesis; Vol. 49; nb. 23; 2017; p. 5217) can be used as appropriate to convert the aldehyde moiety into a vinyl group.

[0367] That is, the method for producing the compound (A) (iodine-containing vinyl monomer) represented by formula (1) is as follows: a) General structure represented by formula (1-5): [ka] (In formula (1-5), R Ais a hydrogen atom, a methyl group, or a trifluoromethyl group, and P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphonic group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group; b) a Wittig reaction step of forming an alkene from the carbonyl moiety of the iodine-containing aldehyde substrate or the iodine-containing ketone substrate by a Wittig reaction; Includes:

[0368] Examples of iodine-containing aldehyde substrates or iodine-containing ketone substrates having the general structure represented by formula (1-5) include 4-hydroxy-3-iodobenzaldehyde. The Wittig reaction step is a step of forming an alkene by the Wittig reaction, and is a step of forming an alkene from a carbonyl moiety having an aldehyde or ketone using a phosphorus ylide, although not limited thereto. As the phosphorus ylide, a triphenylalkylphosphine bromide such as triphenylmethylphosphine bromide, which can form a stable phosphorus ylide, can be used. Alternatively, a phosphorus ylide can be formed in the reaction system by reacting a phosphonium salt with a base, and the resulting phosphorus ylide can be used in the above-mentioned reaction. As the base, a conventionally known base can be used, and for example, an alkali metal salt of an alkoxide can be used as appropriate.

[0369] As another method for converting the aldehyde moiety into a vinyl group, a method of reacting malonic acid in the presence of a base (e.g., the methods described in Tetrahedron; Vol. 46; nb. 40; 2005; p. 6893, Tetrahedron; Vol. 63; nb. 4; 2007; p. 900, US2004 / 118673, etc.) can be appropriately used. In a third embodiment, a method for producing the compound (A) (iodine-containing vinyl monomer) represented by formula (1) includes the following steps: a) providing an iodine-containing aldehyde substrate or an iodine-containing ketone substrate having the general structure represented by formula (1-5); b) a malonic acid addition step of adding malonic acid to the iodine-containing aldehyde substrate or the iodine-containing ketone substrate; c) a hydrolysis step of hydrolyzing the malonic acid-added iodine-containing aldehyde substrate or the iodine-containing ketone substrate to produce an iodine-containing carboxylic acid substrate; d) a decarboxylation step of decarboxylating the hydrolyzed iodine-containing carboxylic acid substrate; Includes:

[0370] The malonate addition step in the third embodiment is a step of forming a malonate derivative, including but not limited to, the reaction of an aldehyde with malonic acid, a malonate ester, or malonic anhydride. The hydrolysis step in the third embodiment is a step of forming a carboxylic acid substrate by hydrolysis, and is, but is not limited to, a reaction of hydrolyzing an ester by the action of an acid or water. The decarboxylation step in the third embodiment is a step of obtaining a vinyl monomer by decarboxylating a carboxylic acid substrate, and although not limited thereto, is preferably carried out at a low temperature of 100°C or less, and more preferably uses a fluoride-based catalyst.

[0371] As a method for synthesizing the compound (A) of the third embodiment, for example, the method described in the above-mentioned reference material can be used appropriately, but is not limited thereto.

[0372] As for a compound represented by formula (1) in which P is an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, or a carbonate ester group, an example of a synthesis method is not particularly limited, and the compound can be obtained by reacting a compound represented by formula (1) in which P is a hydroxyl group with, for example, an activated carboxylic acid derivative compound such as an acid chloride, an acid anhydride, or a dicarbonate, an alkyl halide, a vinyl alkyl ether, a dihydropyran, or a halocarboxylic acid alkyl ester. For example, a compound represented by formula (1) in which P is a hydroxyl group is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran, or propylene glycol monomethyl ether acetate. Subsequently, a vinyl alkyl ether such as ethyl vinyl ether or dihydropyran is added, and the reaction is carried out at normal pressure at 20 to 60°C for 6 to 72 hours in the presence of an acid catalyst such as pyridinium p-toluenesulfonate. The reaction solution is neutralized with an alkaline compound and added to distilled water to precipitate a white solid. The separated white solid is then washed with distilled water and dried to obtain a compound represented by formula (1) in which P is an alkoxy group, ester group, acetal group, carboxyalkoxy group, or carbonate ester group. Alternatively, a compound represented by formula (1) in which P is a hydroxyl group is dissolved or suspended in an aprotic solvent such as acetone, THF, or propylene glycol monomethyl ether acetate. Subsequently, an alkyl halide such as ethyl chloromethyl ether or a halocarboxylic acid alkyl ester such as methyladamantyl bromoacetate is added, and the mixture is reacted at atmospheric pressure at 20 to 110°C for 6 to 72 hours in the presence of an alkali catalyst such as potassium carbonate. The reaction solution is neutralized with an acid such as hydrochloric acid, and added to distilled water to precipitate a white solid. The separated white solid is then washed with distilled water and dried to obtain a compound represented by formula (1) in which P is an alkoxy group, ester group, acetal group, carboxyalkoxy group, or carbonate ester group.

[0373] From the viewpoint of yield and reducing the amount of waste, the synthesis method of the compound (A) of the third embodiment preferably includes the synthesis method shown below.

[0374] [Iodine-containing alcoholic substrate] The iodine-containing alcoholic substrate used in the third embodiment may be, for example, an iodine-containing alcoholic substrate having a general structure represented by the following formula (1-1):

[0375] [ka] (In formula (1-1), P represents a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphonic group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group; R 7 ~R 10 are each independently hydrogen, a hydroxyl group, a methoxy group, a halogen, or a cyano group, provided that R 7 ~R 10 One of the groups is a hydroxyl group or a methoxy group.)

[0376] Examples of suitable iodine-containing alcoholic substrates include, but are not limited to, 1-(4-hydroxy-3-iodophenyl)ethanol and 4-(1-hydroxyethyl)-3-iodophenol, which contain at least one iodine atom, and preferably two or more iodines.

[0377] These iodine-containing alcoholic substrates can be obtained by many methods, but the methods described below are preferred from the viewpoints of availability of raw materials and yield.

[0378] The method for producing the iodine-containing vinyl monomer represented by formula (1) is as follows: a) providing an iodine-containing alcoholic substrate having the general structure represented by formula (1-1); b) a dehydration step of subjecting the iodine-containing alcoholic substrate to a dehydration treatment; Includes.

[0379] Reaction conditions The iodine-containing alcoholic substrate having the formula (1-1), the catalyst, and the organic solvent are added to a reactor to form a reaction mixture. Any suitable reactor may be used. The reaction can be carried out by a known method appropriately selected from the batch method, semi-batch method, continuous method and the like.

[0380] The reaction temperature is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. Generally, a temperature of 0°C to 200°C is suitable, and from the viewpoint of yield, a temperature of 0°C to 100°C is preferred. For reactions using 1-(4-hydroxy-3-iodophenyl)ethanol as the iodine-containing alcoholic substrate, the preferred temperature range is 0°C to 100°C.

[0381] The reaction pressure is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. The pressure can be adjusted using an inert gas such as nitrogen, or by using an air pump, etc. For reactions at high pressure, conventional pressure reactors can be used, including, but not limited to, shaker vessels, rocker vessels, and stirred autoclaves. In the reaction using 1-(4-hydroxy-3-iodophenyl)ethanol as the iodine-containing alcoholic substrate, the reaction pressure is preferably reduced pressure to atmospheric pressure, with reduced pressure being preferred.

[0382] The reaction time is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. However, most reactions are carried out in less than 6 hours, and reaction times of 15 to 600 minutes are common. For reactions using 1-(4-hydroxy-3-iodophenyl)ethanol as the substrate, the preferred reaction time range is from 15°C to 600°C.

[0383] Isolation and purification can be carried out after the completion of the reaction using a suitable method known in the art. For example, the reaction mixture can be poured onto ice water and extracted into an organic solvent such as ethyl acetate or diethyl ether. The product can then be recovered by removing the solvent using evaporation under reduced pressure. The desired high-purity monomer can be isolated and purified using separation and purification methods well known in the art, such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, etc., or a combination thereof.

[0384] [Method for producing an iodine-containing alcoholic substrate represented by formula (1-1) (I)] The iodine-containing ketonic substrate used in the production of the iodine-containing alcoholic substrate represented by formula (1-1) is, for example, an iodine-containing ketonic substrate having a general structure represented by formula (1-2).

[0385] [ka] (In formula (1-2), P represents a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphonic group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group; R 7 ~R 10 are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7 ~R 10 One of the groups is a hydroxyl group or a methoxy group.)

[0386] Examples of suitable iodine-containing ketonic substrates include, but are not limited to, 4-hydroxy-3-iodophenylmethyl ketone.

[0387] These iodine-containing ketone substrates can be obtained by many methods, but the methods described below are preferred from the viewpoints of availability of raw materials and yield.

[0388] The method for producing an iodine-containing alcoholic substrate having the general structure represented by formula (1-1) includes the steps of: c) providing an iodine-containing ketonic substrate having the general structure represented by formula (1-2); d) a reduction step of subjecting the iodine-containing ketone substrate to a reduction treatment; Includes.

[0389] The method for producing an iodine-containing vinyl monomer having the general structure represented by formula (1) may include the method for producing an iodine-containing alcoholic substrate having the general structure represented by formula (1-1). That is, the method for producing an iodine-containing vinyl monomer having the general structure represented by formula (1) may include: c) providing an iodine-containing ketonic substrate having the general structure represented by formula (1-2); d) a reduction step of subjecting the iodine-containing ketone substrate to a reduction treatment.

[0390] Reaction conditions The iodine-containing ketonic substrate having formula (1-2), the catalyst, and the organic solvent are added to a reactor to form a reaction mixture. Any suitable reactor may be used. The reaction can be carried out by a known method appropriately selected from the batch method, semi-batch method, continuous method and the like.

[0391] The reaction temperature is not particularly limited. The preferred range varies depending on the concentration of the iodine-containing ketone substrate, the stability of the formed product, the catalyst selected, and the desired yield. Generally, a temperature of 0°C to 200°C is suitable, and from the viewpoint of yield, a temperature of 0°C to 100°C is preferred. For reactions using 4'-hydroxy-3'-iodoacetophenone as the iodine-containing ketonic substrate, the preferred temperature range is 0°C to 100°C.

[0392] The reaction pressure is not particularly limited. The preferred range varies depending on the concentration of the iodine-containing ketone substrate, the stability of the formed product, the choice of catalyst, and the desired yield. The pressure can be adjusted using an inert gas such as nitrogen or an air pump. For reactions at high pressure, conventional pressure reactors can be used, including, but not limited to, shaker vessels, rocker vessels, and stirred autoclaves. In the reaction using 4'-hydroxy-3'-iodoacetophenone as the iodine-containing ketone substrate, the reaction pressure is preferably reduced pressure to atmospheric pressure, with reduced pressure being preferred.

[0393] The reaction time is not particularly limited. The preferred range varies depending on the concentration of the iodine-containing ketone substrate, the stability of the formed product, the choice of catalyst, and the desired yield. However, most reactions are carried out in less than 6 hours, with reaction times of 15 to 600 minutes being typical. For reactions using 4'-hydroxy-3'-iodoacetophenone as the iodine-containing ketonic substrate, the preferred reaction time range is from 15°C to 600°C.

[0394] Isolation and purification can be carried out after the completion of the reaction using a suitable method known in the art. For example, the reaction mixture can be poured onto ice water and extracted into an organic solvent such as ethyl acetate or diethyl ether. The product can then be recovered by removing the solvent using evaporation under reduced pressure. The desired high-purity monomer can be isolated and purified using separation and purification methods well known in the art, such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, etc., or a combination thereof.

[0395] [Method for producing an iodine-containing alcoholic substrate represented by formula (1-1) (II)] The alcoholic substrate used in the production of the iodine-containing alcoholic substrate represented by formula (1-1) is, for example, an alcoholic substrate having a general structure represented by formula (1-3).

[0396] [ka] (In formula (1-3), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group; P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphonic group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group; R 7 ~R 10 are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7 ~R 10One of the groups is a hydroxyl group or a methoxy group.

[0397] Examples of suitable alcoholic substrates include, but are not limited to, 1-(4-hydroxyphenyl)ethanol, 4-(1-hydroxyethyl)phenol.

[0398] These alcoholic substrates can be obtained by many methods, but the methods described below are preferred from the viewpoints of availability of raw materials and yield.

[0399] The method for producing an iodine-containing alcoholic substrate having the general structure represented by formula (1-1) includes the steps of: e) providing an alcoholic substrate having the general structure represented by formula (1-3); f) an iodine introduction step of introducing an iodine atom into the alcoholic substrate; Includes. The iodine introduction step in the third embodiment is not particularly limited, and may be appropriately selected from, for example, a method of reacting an iodinating agent in a solvent (e.g., JP 2012-180326 A), or a method of adding iodine dropwise to an alkaline aqueous solution of phenol in the presence of β-cyclodextrin under alkaline conditions (JP 63-101342 A, JP 2003-64012 A). The iodinating agent is not particularly limited, and examples thereof include iodine chloride, iodine, and N-iodosuccinimide. Among these, iodine chloride is preferred. In the third embodiment, particularly when the purpose is to introduce multiple iodines, it is preferable to use an iodination reaction via iodine chloride in an organic solvent. As a method for synthesizing compound (A) in the third embodiment, for example, the method described in the above-mentioned reference material can be appropriately used, but is not limited thereto.

[0400] The method for producing an iodine-containing vinyl monomer having the general structure represented by formula (1) may include the method for producing an iodine-containing alcoholic substrate having the general structure represented by formula (1-1). That is, the method for producing an iodine-containing vinyl monomer having the general structure represented by formula (1) may include: e) providing an alcoholic substrate having the general structure represented by formula (1-3); f) Iodine introduction step; may include:

[0401] Reaction conditions The alcoholic substrate having formula (1-3), the catalyst, and the organic solvent are added to a reactor to form a reaction mixture. Any suitable reactor may be used. The reaction can be carried out by a known method appropriately selected from the batch method, semi-batch method, continuous method and the like.

[0402] The reaction temperature is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. Generally, a temperature of 0°C to 200°C is suitable, and from the viewpoint of yield, a temperature of 0°C to 100°C is preferred. For reactions using 1-(4-hydroxyphenyl)ethanol as substrate, the preferred temperature range is 0°C to 100°C.

[0403] The reaction pressure is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. The pressure can be adjusted using an inert gas such as nitrogen, or by using an air pump, etc. For reactions at high pressure, conventional pressure reactors can be used, including, but not limited to, shaker vessels, rocker vessels, and stirred autoclaves. In the reaction using 1-(4-hydroxyphenyl)ethanol as a substrate, the reaction pressure is preferably from reduced pressure to atmospheric pressure, with reduced pressure being preferred.

[0404] The reaction time is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. However, most reactions are carried out in less than 6 hours, and reaction times of 15 to 600 minutes are common. For reactions using 1-(4-hydroxyphenyl)ethanol as the substrate, the preferred reaction time range is from 15°C to 600°C.

[0405] Isolation and purification can be carried out after the completion of the reaction using a suitable method known in the art. For example, the reaction mixture can be poured onto ice water and extracted into an organic solvent such as ethyl acetate or diethyl ether. The product can then be recovered by removing the solvent using evaporation under reduced pressure. The desired high-purity monomer can be isolated and purified using separation and purification methods well known in the art, such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, etc., or a combination thereof.

[0406] [Method for producing an iodine-containing ketone substrate represented by formula (1-2)] The ketonic substrate used in the production of the iodine-containing ketonic substrate represented by formula (1-2) is, for example, a ketonic substrate having the general structure represented by formula (1-4).

[0407] [ka] In formula (1-4), P represents a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphonic group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group; R 7 ~R 10 are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a halogen atom, or a cyano group, provided that R 7 ~R 10 One of the groups is a hydroxyl group or a methoxy group.)

[0408] Examples of suitable ketonic substrates include, but are not limited to, 4-hydroxyphenylmethyl ketone.

[0409] These ketonic substrates can be obtained in a number of ways.

[0410] A method for producing an iodine-containing ketonic substrate having the general structure represented by formula (1-2) includes: g) providing a ketonic substrate having the general structure represented by formula (1-4); h) an iodine introduction step of introducing an iodine atom into the ketone substrate; may include:

[0411] The method for producing an iodine-containing vinyl monomer having the general structure represented by formula (1) may include the method for producing an iodine-containing ketonic substrate having the general structure represented by formula (1-2). That is, the method for producing an iodine-containing vinyl monomer having the general structure represented by formula (1) may include the method for producing an iodine-containing ketonic substrate having the general structure represented by formula (1-2): g) providing a ketonic substrate having the general structure represented by formula (1-4); h) an iodine introduction step of introducing an iodine atom into the ketone substrate; may include:

[0412] Reaction conditions The ketonic substrate having formula (1-4), the catalyst, and the organic solvent are added to a reactor to form a reaction mixture. Any suitable reactor may be used. The reaction can be carried out by a known method appropriately selected from the batch method, semi-batch method, continuous method and the like.

[0413] The reaction temperature is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. Generally, a temperature of 0°C to 200°C is suitable, and from the viewpoint of yield, a temperature of 0°C to 100°C is preferred. For reactions using 4'-hydroxy-3'-methoxyacetophenone as the substrate, the preferred temperature range is 0°C to 100°C.

[0414] The reaction pressure is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. The pressure can be adjusted using an inert gas such as nitrogen, or by using an air pump, etc. For reactions at high pressure, conventional pressure reactors can be used, including, but not limited to, shaker vessels, rocker vessels, and stirred autoclaves. In the reaction using 4'-hydroxyacetophenone as the substrate, the reaction pressure is preferably reduced pressure to atmospheric pressure, with reduced pressure being preferred.

[0415] The reaction time is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. However, most reactions are carried out in less than 6 hours, and reaction times of 15 to 600 minutes are common. For reactions using 4'-hydroxyacetophenone as the substrate, the preferred reaction time range is from 15°C to 600°C.

[0416] [Method for producing an alcoholic substrate represented by formula (1-3)] The ketone substrate used in the production of the alcoholic substrate having the general structure represented by formula (1-3) is, for example, a ketone substrate having the general structure represented by the above formula (1-4).

[0417] A method for producing an alcoholic substrate having the general structure represented by formula (1-3) is i) providing a ketonic substrate having the general structure represented by formula (1-4); j) a reduction step of subjecting the ketone substrate to a reduction treatment; may include:

[0418] The method for producing an iodine-containing vinyl monomer having the general structure represented by formula (1) may include the method for producing an alcoholic substrate having the general structure represented by formula (1-3), i.e., the method for producing an iodine-containing vinyl monomer having the general structure represented by formula (1) may include the method for producing an alcoholic substrate having the general structure represented by formula (1-3), i) providing a ketonic substrate having the general structure represented by formula (1-4); j) a reduction step of subjecting the ketone substrate to a reduction treatment; may include:

[0419] A wide variety of organic solvents can be used, including polar aprotic organic solvents and protic polar organic solvents. A single protic polar solvent or a single polar aprotic solvent can be used. Furthermore, mixtures of polar aprotic solvents, mixtures of protic polar solvents, mixtures of polar aprotic solvents and protic polar solvents, and mixtures of aprotic or protic solvents and nonpolar solvents can be used, with polar aprotic solvents or mixtures thereof being preferred. A solvent is useful but not essential. Suitable polar aprotic solvents include, but are not limited to, alcoholic solvents such as methanol and ethanol; ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglyme, and triglyme; ester solvents such as ethyl acetate and γ-butyrolactone; nitrile solvents such as acetonitrile; hydrocarbon solvents such as toluene and hexane; amide solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidinone, N,N-dimethylacetamide, hexamethylphosphoramide, and hexamethylphosphite triamide; and dimethyl sulfoxide. Dimethyl sulfoxide is preferred. Suitable protic polar solvents include, but are not limited to, di(propylene glycol) methyl ether, di(ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol, and n-butanol. The amount of solvent used can be appropriately set depending on the substrate, catalyst, and reaction conditions used, and is not particularly limited. Generally, however, an amount of 0 to 10,000 parts by mass per 100 parts by mass of reaction raw materials is suitable, and from the viewpoint of yield, an amount of 100 to 2,000 parts by mass is preferable.

[0420] Reaction conditions The ketonic substrate having formula (1-4), the catalyst, and the organic solvent are added to a reactor to form a reaction mixture. Any suitable reactor may be used. The reaction can be carried out by a known method appropriately selected from the batch method, semi-batch method, continuous method and the like.

[0421] The reaction temperature is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. Generally, a temperature of 0°C to 200°C is suitable, and from the viewpoint of yield, a temperature of 0°C to 100°C is preferred. For reactions using 4'-hydroxyacetophenone as the substrate, the preferred temperature range is 0°C to 100°C.

[0422] The reaction pressure is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. The pressure can be adjusted using an inert gas such as nitrogen, or by using an air pump, etc. For reactions at high pressure, conventional pressure reactors can be used, including, but not limited to, shaker vessels, rocker vessels, and stirred autoclaves. In the reaction using 4'-hydroxyacetophenone as the substrate, the reaction pressure is preferably reduced pressure to atmospheric pressure, with reduced pressure being preferred.

[0423] The reaction time is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. However, most reactions are carried out in less than 6 hours, and reaction times of 15 to 600 minutes are common. For reactions using 4'-hydroxyacetophenone as the substrate, the preferred reaction time range is from 15°C to 600°C.

[0424] Isolation and purification can be carried out after the completion of the reaction using a suitable method known in the art. For example, the reaction mixture can be poured onto ice water and extracted into an organic solvent such as ethyl acetate or diethyl ether. The product can then be recovered by removing the solvent using evaporation under reduced pressure. The desired high-purity monomer can be isolated and purified using separation and purification methods well known in the art, such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, etc., or a combination thereof.

[0425] [Method for producing an iodine-containing vinyl monomer represented by formula (2)] The method for producing an iodine-containing vinyl monomer according to the third embodiment may be a method for producing an iodine-containing vinyl monomer represented by formula (2), and specifically, may be a method for producing an iodine-containing alkoxystyrene.

[0426] [ka] (In formula (2), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R C is a substituted or unsubstituted acyl group having 1 to 30 carbon atoms.

[0427] Examples of acetoxystyrenes produced by the method of the third embodiment include, but are not limited to, 4-acetoxy-3-iodostyrene.

[0428] [Iodine-containing vinyl monomers] The iodine-containing vinyl monomer used in the third embodiment is, for example, an iodine-containing vinyl monomer having the general structure represented by the above formula (1).

[0429] Iodine-containing vinyl monomers having the general structure represented by formula (2) are k) providing an iodine-containing vinyl monomer having the general structure represented by formula (1); l) an acylation step of subjecting the iodine-containing vinyl monomer to an acylation treatment; may include:

[0430] A wide variety of organic solvents can be used, including polar aprotic organic solvents and protic polar organic solvents. A single protic polar solvent or a single polar aprotic solvent can be used. Furthermore, mixtures of polar aprotic solvents, mixtures of protic polar solvents, mixtures of polar aprotic solvents and protic polar solvents, and mixtures of aprotic or protic solvents and nonpolar solvents can be used, with polar aprotic solvents or mixtures thereof being preferred. A solvent is useful but not essential. Suitable polar aprotic solvents include, but are not limited to, alcoholic solvents such as methanol and ethanol; ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglyme, and triglyme; ester solvents such as ethyl acetate and γ-butyrolactone; nitrile solvents such as acetonitrile; hydrocarbon solvents such as toluene and hexane; amide solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidinone, N,N-dimethylacetamide, hexamethylphosphoramide, and hexamethylphosphite triamide; and dimethyl sulfoxide. Dimethyl sulfoxide is preferred. Suitable protic polar solvents include, but are not limited to, di(propylene glycol) methyl ether, di(ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol, and n-butanol. The amount of solvent used can be appropriately set depending on the substrate, catalyst, and reaction conditions used, and is not particularly limited. Generally, however, an amount of 0 to 10,000 parts by mass per 100 parts by mass of reaction raw materials is suitable, and from the viewpoint of yield, an amount of 100 to 2,000 parts by mass is preferable.

[0431] Reaction conditions The iodine-containing vinyl monomer having formula (1), the catalyst, and the organic solvent are added to a reactor to form a reaction mixture. Any suitable reactor may be used. The reaction can be carried out by a known method appropriately selected from the batch method, semi-batch method, continuous method and the like.

[0432] The reaction temperature is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. Generally, a temperature of 0°C to 200°C is suitable, and from the viewpoint of yield, a temperature of 0°C to 100°C is preferred. For reactions using 4-hydroxy-3-iodostyrene as the substrate, the preferred temperature range is 0°C to 100°C.

[0433] The reaction pressure is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. The pressure can be adjusted using an inert gas such as nitrogen, or by using an air pump, etc. For reactions at high pressure, conventional pressure reactors can be used, including, but not limited to, shaker vessels, rocker vessels, and stirred autoclaves. In the reaction using 4-hydroxy-3-iodostyrene as the substrate, the reaction pressure is preferably reduced pressure to atmospheric pressure, with reduced pressure being preferred.

[0434] The reaction time is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. However, most reactions are carried out in less than 6 hours, and reaction times of 15 to 600 minutes are common. For reactions using 4-hydroxy-3-iodostyrene as the substrate, the preferred reaction time range is from 15°C to 600°C.

[0435] Isolation and purification can be carried out after the completion of the reaction using a suitable method known in the art. For example, the reaction mixture can be poured onto ice water and extracted into an organic solvent such as ethyl acetate or diethyl ether. The product can then be recovered by removing the solvent using evaporation under reduced pressure. The desired high-purity monomer can be isolated and purified using separation and purification methods well known in the art, such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, etc., or a combination thereof.

[0436] It is preferable that the compound in the third embodiment is obtained as a crude product by the above-described reaction, and then further purified to remove remaining metal impurities. That is, from the viewpoint of preventing deterioration of the resin over time and storage stability, and further from the viewpoint of process suitability and production yield due to defects when the resin is applied to a semiconductor manufacturing process, it is preferable to avoid the remaining metal impurities resulting from the contamination of metal components used as reaction aids in the compound manufacturing process or contaminating from the reaction vessel used in the manufacturing or other manufacturing equipment.

[0437] The residual amounts of the above-mentioned metal impurities are preferably less than 1 ppm, more preferably less than 100 ppb, even more preferably less than 50 ppb, even more preferably less than 10 ppb, and most preferably less than 1 ppb, relative to the resin. In particular, for transition metals such as Fe, Ni, Sb, W, and Al, if the residual metal amount is 1 ppm or more, there is a concern that interaction with the compound of the third embodiment may cause denaturation or deterioration of the material over time. Furthermore, if the residual metal amount is 1 ppm or more, the residual metal amount cannot be sufficiently reduced when the compound is used to produce a resin for semiconductor processing, which may result in defects or performance degradation due to the residual metal in the semiconductor manufacturing process, resulting in a decrease in yield.

[0438] The purification method is not particularly limited, but includes a step of dissolving the compound of the third embodiment in a solvent to obtain a solution (S), and a step (first extraction step) of contacting the obtained solution (S) with an acidic aqueous solution to extract impurities in the compound of the third embodiment, wherein the solvent used in the step of obtaining the solution (S) includes an organic solve...

Claims

1. A compound represented by the following formula (1), The compound represented by the following formula (1A) and / or the compound represented by the following formula (1B) is contained in an amount of 1 ppm by mass or more and 10% by mass or less relative to the total amount of the compound: composition. 【Chemistry 1】 (In formula (1), R A is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R X is OR B or a hydrogen atom, and R B is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group. 【Chemistry 2】 (In formula (1A), formula (1A1), and formula (1A2), R A , R X , R B and P are the same as defined in formula (1), and R sub represents formula (1A1) or formula (1A2), and * represents the bonding site to the adjacent structural unit. 【Transformation 3】 (In formula (1B), formula (1B1), or formula (1B2), R A , R X , R B and P are the same as defined in formula (1), and n 2 is an integer of 0 to 4, and R sub2 represents formula (1B1) or formula (1B2), and * represents the bonding site to the adjacent structural unit.

2. R of the compound represented by formula (1) A The composition of claim 1 , wherein is a hydrogen atom or a methyl group.

3. R of the compound represented by formula (1) B The composition according to claim 1 or claim 2, wherein is an alkyl group having 1 to 4 carbon atoms.

4. The composition according to any one of claims 1 to 3, wherein P in the compound represented by formula (1) is a hydroxyl group, an ester group, an acetal group, a carbonate ester group, or a carboxyalkoxy group.

5. The composition according to any one of claims 1 to 4, wherein P in the compound represented by formula (1) is an ester group, an acetal group, or a carbonate ester group.

6. The compound represented by the following formula (1C) is contained in an amount of 1 ppm by mass or more and 10% by mass or less relative to the total compound represented by formula (1) according to any one of claims 1 to 5: The composition according to any one of claims 1 to 5. 【Chemistry 4】 (In formula (1C), R A , R X , R B and P are defined as in formula (1). B and P do not contain I.

7. The content of impurities including K is 1 mass ppm or less in terms of elements relative to the total amount of the compound represented by formula (1). The composition according to any one of claims 1 to 6.

8. The composition according to claim 7, wherein the content of the peroxide is 10 ppm by mass or less based on the total amount of the compound represented by formula (1).

9. 9. The composition according to claim 7 or 8, wherein the content 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, in terms of element, based on the total amount of the compound represented by formula (1).

10. The composition according to any one of claims 7 to 9, wherein the content of the phosphorus-containing compound is 10 ppm by mass or less based on the total amount of the compound represented by formula (1).

11. The composition according to any one of claims 7 to 10, wherein the content of maleic acid is 10 ppm by mass or less based on the total amount of the compound represented by formula (1).

12. The polymer further includes a structural unit represented by the following formula (1-A): The polymer contains a structural unit derived from a compound represented by formula (1) according to any one of claims 1 to 5. The composition according to any one of claims 1 to 11. 【Transformation 5】 (In formula (1-A), R A , R X , R B and P are defined as in formula (1), and * represents a bonding site to an adjacent structural unit.

13. The composition according to claim 12, wherein the polymer further contains a constitutional unit represented by the following formula (C0), the following formula (C1), or the following formula (C2): 【Transformation 6】 (In formula (C0), X's each independently represent I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 to 5 substituents selected from the group consisting of I, F, Cl, and Br; L 1 are each independently a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and 1 The ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, or phosphate group may have a substituent, Y's each independently represent a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphonic group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphonic group, urethane group, urea group, amide group, imide group, and phosphate group of Y may have a substituent, R A is the same as defined in formula (1), A is an organic group having 1 to 30 carbon atoms, Z's each independently represent an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, or a carbonate ester group, and the alkoxy group, ester group, acetal group, carboxyalkoxy group, or carbonate ester group of Z may have a substituent; m is an integer of 0 or greater, n is an integer of 1 or greater, and r is an integer of 0 or greater. 【Transformation 7】 (In formula (C1), R C11 is a hydrogen atom, a methyl group, or a trifluoromethyl group, R C12 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R C13 is R C13 and the carbon atom to which they are bonded are taken together to form a cycloalkyl or heterocycloalkyl group having 4 to 20 carbon atoms, * indicates the bonding site with the adjacent structural unit. In addition, in formula (C2), R C21 is a hydrogen atom, a methyl group, or a trifluoromethyl group, R C22 and R C23 are each independently an alkyl group having 1 to 4 carbon atoms, R C24 is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms, R C22 , R C23 , and R C24 Two or three of the R C22 , R C23 , and R C24 may form an alicyclic structure having 3 to 20 carbon atoms, formed together with carbon atoms bonding to two or three of * indicates the bonding site with the adjacent structural unit.)

14. A film-forming composition, The composition according to any one of claims 1 to 13.

15. The film-forming composition according to claim 14, further comprising an acid generator, a base generator, or a basic compound.

16. forming a resist film on a substrate using the film-forming composition of claim 14 or 15; exposing the resist film to a pattern; a step of developing the resist film after exposure; A method for forming a resist pattern, comprising:

17. forming a resist film on a substrate using the film-forming composition of claim 14 or 15; exposing the resist film to a pattern; and developing the resist film after exposure.

18. The composition according to any one of claims 1 to 15, which is applied in extreme UV applications.

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