Compound, (co)polymer, composition, method for forming resist pattern, and method for producing compound and (co)polymer

Abstract

An iodine-containing (meth)acrylate compound which is represented by formula (1). In formula (1), R1 represents a hydrogen atom, a methyl group, or a halogen; each one of R2 moieties independently represents a hydrogen atom, a linear organic group having from 1 to 20 carbon atoms, a branched organic group having from 3 to 20 carbon atoms, or a cyclic organic group having from 3 to 20 carbon atoms; A represents an organic group having from 1 to 30 carbon atoms, and A contains at least one acyl group; n1 represents 0 or 1; and n2 represents an integer from 1 to 20.

Description

[Technical Field]

[0001] The present invention relates to a compound, a (co)polymer, a composition, a method for forming a resist pattern, and a method for producing the compound and the (co)polymer. [Background technology]

[0002] In recent years, advances in lithography technology have led to rapid advances in miniaturization of semiconductors (patterns) and pixels in the manufacture of semiconductor elements and liquid crystal display elements. A common method for miniaturizing pixels is to shorten the wavelength of the exposure light source. Specifically, while ultraviolet light, typically g-line and i-line, was previously used, far-ultraviolet exposure using KrF excimer lasers (248 nm) and ArF excimer lasers (193 nm) is now becoming the norm for mass production, and extreme ultraviolet (EUV) lithography (13.5 nm) is also increasingly being introduced. Electron beams (EB) are also being used to form fine patterns.

[0003] Common resist materials include polymeric resist materials capable of forming amorphous films, such as polymethyl methacrylate, and polymeric resist materials such as 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 these resist materials onto a substrate, and then irradiating the thin resist film with ultraviolet light, far ultraviolet light, electron beams, extreme ultraviolet light, X-rays, etc. to form a line pattern of approximately 10 to 100 nm.

[0004] In addition, the reaction mechanism of electron beam or extreme ultraviolet lithography is different from that of conventional photolithography. Furthermore, electron beam or extreme ultraviolet lithography aims to form fine patterns of several nm to several tens of nm. As resist pattern dimensions become smaller, resist materials with higher sensitivity to the exposure light source are required. In particular, extreme ultraviolet lithography requires even higher sensitivity in terms of throughput. As a resist material that can solve the above-mentioned problems, inorganic resist materials containing metal elements such as titanium, tin, hafnium, and zirconium have been proposed (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-108781 [Non-patent literature]

[0006] [Non-Patent Document 1] Shinji Okazaki et al., "40 Years of Lithography Technology," S&T Publishing, December 9, 2016 Summary of the Invention [Problem to be solved by the invention]

[0007] However, the compounds and (co)polymers used in conventional resist materials have low stability, which leads to problems such as poor stability of the compounds and (co)polymers and poor productivity. Furthermore, conventionally developed resist materials have problems such as many film defects, insufficient sensitivity, insufficient etching resistance, or poor resist patterning. In particular, it is difficult to achieve both high resolution and high sensitivity because there is a trade-off between resolution and sensitivity. Furthermore, although (co)polymers having hydroxy groups are useful as resist materials, the productivity of these (co)polymers is poor due to the low stability of the raw material compounds and (co)polymers.

[0008] In view of the above circumstances, the present invention aims to provide a compound, a method for producing the compound, a (co)polymer and a composition that are suitable for use in resist materials, highly stable, highly sensitive, and capable of forming a film with high resolution, as well as a method for forming a resist pattern using the composition. Another object of the present invention is to provide a highly productive method for producing a (co)polymer having a hydroxy group that is useful for resist materials. [Means for solving the problem]

[0009] As a result of intensive research to solve the above-mentioned problems, the present inventors have found that compounds and (co)polymers having specific structures, as well as compositions containing these compounds and (co)polymers, are highly stable, highly sensitive, and capable of forming films with high resolution, and are therefore suitable for use as resist materials, thereby completing the present invention. Furthermore, the present inventors have found that because the compounds and (co)polymers having specific structures are highly stable, by using these (co)polymers, it is possible to efficiently produce (co)polymers having hydroxy groups that are useful for resist materials, and have thus completed the present invention. That is, the present invention is as follows.

[0010] [1] An iodine-containing (meth)acrylate compound represented by formula (1):

[0011] [ka]

[0012] (In formula (1), R 1 represents a hydrogen atom, a methyl group, or a halogen atom; R 2each independently represents a hydrogen atom, a linear organic group having 1 to 20 carbon atoms, a branched organic group having 3 to 20 carbon atoms, or a cyclic organic group having 3 to 20 carbon atoms; A represents an organic group having 1 to 30 carbon atoms; A contains at least one acyl group; n 1 represents 0 or 1, n 2 represents an integer between 1 and 20.

[0013] [1-1] n 1 The iodine-containing (meth)acrylate compound according to [1], wherein is 0 and A is an alicyclic ring having 5 to 30 carbon atoms which may have a substituent. [1-2] The iodine-containing (meth)acrylate compound according to [1-1], wherein the alicyclic ring having 5 to 30 carbon atoms which may have a substituent is an adamantane which may have a substituent.

[0014] [2] The iodine-containing (meth)acrylate compound according to [1], wherein the formula (1) is formula (2).

[0015] [ka]

[0016] (In formula (2), R 1 , A, and n 2 is the same as above.)

[0017] [3] The iodine-containing (meth)acrylate compound according to [2], wherein the formula (2) is formula (3).

[0018] [ka]

[0019] (In formula (3), B represents an organic group having 5 to 30 carbon atoms including an aromatic group, B includes at least one acyl group, and R 1 , and n 2 is the same as above.)

[0020] [3-1] The iodine-containing (meth)acrylate compound according to [3], wherein B is an aromatic group having 5 to 30 carbon atoms which may have a substituent. [3-2] The iodine-containing (meth)acrylate compound according to [3-1], wherein the aromatic group having 5 to 30 carbon atoms which may have a substituent is benzene which may have a substituent.

[0021] [4] The iodine-containing (meth)acrylate compound according to [2], wherein the formula (2) is formula (3').

[0022] [ka]

[0023] In formula (3'), B' represents an organic group having 5 to 30 carbon atoms and including an alicyclic ring, B' includes at least one acyl group, and R 1 , and n 2 is the same as above.)

[0024] [4-1] The iodine-containing (meth)acrylate compound according to [4], wherein B' is an alicyclic ring having 5 to 30 carbon atoms which may have a substituent. [4-2] The iodine-containing (meth)acrylate compound according to [4-1], wherein the alicyclic ring having 5 to 30 carbon atoms which may have a substituent is an adamantane which may have a substituent.

[0025] [5] n 2 The iodine-containing (meth)acrylate compound according to any one of [1] to [4-2], wherein represents an integer of 2 to 20.

[0026] [6] An iodine-containing (meth)acrylate (co)polymer having a structural unit represented by formula (4):

[0027] [ka]

[0028] (In formula (4), R 1 represents a hydrogen atom, a methyl group, or a halogen atom; R 2 each independently represents a hydrogen atom, a linear organic group having 1 to 20 carbon atoms, a branched organic group having 3 to 20 carbon atoms, or a cyclic organic group having 3 to 20 carbon atoms; A represents an organic group having 1 to 30 carbon atoms; A contains at least one acyl group; n 1 represents 0 or 1, n 2 represents an integer from 1 to 20, The symbol * indicates the point of attachment to the adjacent structural unit.

[0029] [6-1] n 1 The iodine-containing (meth)acrylate (co)polymer according to [6], wherein is 0 and A is an alicyclic ring having 5 to 30 carbon atoms which may have a substituent. [6-2] The iodine-containing (meth)acrylate (co)polymer according to [6-1], wherein the alicyclic ring having 5 to 30 carbon atoms which may have a substituent is an adamantane which may have a substituent.

[0030] [7] The iodine-containing (meth)acrylate (co)polymer according to [6], wherein the formula (4) is formula (5).

[0031] [ka]

[0032] (In formula (5), R 1 , n 2 , A, and the symbol * are as defined above.

[0033] [8] The iodine-containing (meth)acrylate (co)polymer according to [7], wherein the formula (5) is formula (6).

[0034] [ka]

[0035] In formula (6), B represents an organic group having 5 to 30 carbon atoms and including an aromatic group, B contains at least one acyl group, and R 1 , n 2 , and the symbol * are the same as above.

[0036] [8-1] The iodine-containing (meth)acrylate (co)polymer according to [8], wherein B is an aromatic group having 5 to 30 carbon atoms which may have a substituent. [8-2] The iodine-containing (meth)acrylate (co)polymer according to [8-1], wherein the aromatic group having 5 to 30 carbon atoms which may have a substituent is benzene which may have a substituent.

[0037] [9] The iodine-containing (meth)acrylate (co)polymer according to [7], wherein the formula (5) is formula (6').

[0038] [ka]

[0039] In formula (6'), B' represents an organic group having 5 to 30 carbon atoms and including an alicyclic ring, B' includes at least one acyl group, and R 1 , n 2 , and the symbol * are the same as above.

[0040] [9-1] The iodine-containing (meth)acrylate (co)polymer according to [9], wherein B' is an alicyclic ring having 5 to 30 carbon atoms which may have a substituent. [9-2] The iodine-containing (meth)acrylate (co)polymer according to [9-1], wherein the alicyclic ring having 5 to 30 carbon atoms which may have a substituent is an adamantane which may have a substituent.

[0041]

[10] n 2 The iodine-containing (meth)acrylate (co)polymer according to any one of [6] to [9-2], wherein represents an integer of 2 to 20.

[11] A composition comprising the iodine-containing (meth)acrylate compound according to any one of [1] to [5] and / or the iodine-containing (meth)acrylate (co)polymer according to any one of [6] to

[10] .

[12] The composition according to

[11] , further comprising a solvent.

[13] The composition according to

[11] or

[12] , further comprising an acid generator.

[14] The composition according to any one of

[11] to

[13] , further comprising an acid diffusion controller.

[15] forming a film using the composition according to any one of

[11] to

[14] ; a step of exposing the film formed in the step; and a step of removing the exposed portion of the film exposed in the step using a developer to form a pattern.

[0042]

[16] reacting an iodine-containing hydroxy compound represented by formula (a) with a (meth)acrylic acid compound represented by formula (b); The method for producing an iodine-containing (meth)acrylate compound according to any one of [1] to [5], comprising: a step of reacting the reaction product obtained in the above step with an acylating agent.

[0043] [ka]

[0044] (In formula (a), A' represents an organic group having 1 to 30 carbon atoms, A' has at least one hydroxy group, and R 2 , n 1 , and n 2 is the same as above.)

[0045] [ka]

[0046] (In formula (b), R 1 is the same as above, and R B is a hydroxy group, a halogen, a (meth)acryloyloxy group, or an alkoxy group.

[0047] [16-1] In formula (a), n 1 is 0, A' is an alicyclic ring having 5 to 30 carbon atoms which may have a substituent, and A' has at least one hydroxy group. [16-2] The method for producing an iodine-containing (meth)acrylate compound according to [16-1], wherein the alicyclic ring having 5 to 30 carbon atoms which may have a substituent is an adamantane which may have a substituent.

[0048]

[17] The method for producing an iodine-containing (meth)acrylate compound according to

[16] , wherein the formula (a) is formula (a1).

[0049] [ka]

[0050] (In formula (a1), A' and n 2 is the same as above.)

[0051]

[18] The method for producing an iodine-containing (meth)acrylate compound according to

[16] , wherein the formula (a) is formula (a2).

[0052] [ka]

[0053] (In formula (a2), B″ represents an organic group having 5 to 30 carbon atoms and including an aromatic group, B″ has at least one hydroxy group, and n 2 is the same as above.)

[0054] [18-1]

[18] The method for producing an iodine-containing (meth)acrylate compound according to

[18] , wherein in formula (a2), B'' is an aromatic group having 5 to 30 carbon atoms which may have a substituent, and B'' has at least one hydroxy group. [18-2] The method for producing an iodine-containing (meth)acrylate compound according to [18-1], wherein the aromatic compound having 5 to 30 carbon atoms which may have a substituent is benzene which may have a substituent.

[0055]

[19] The method for producing an iodine-containing (meth)acrylate compound according to

[16] , wherein the formula (a) is formula (a3).

[0056] [ka]

[0057] (In formula (a3), B''' represents an organic group having 5 to 30 carbon atoms and containing an alicyclic ring, B''' has at least one hydroxy group, and n 2 is the same as above.)

[0058] [19-1]

[19] The method for producing an iodine-containing (meth)acrylate compound according to

[19] , wherein in formula (a3), B''' is an alicyclic ring having 5 to 30 carbon atoms which may have a substituent, and B''' has at least one hydroxy group. [19-2] The method for producing an iodine-containing (meth)acrylate compound according to [19-1], wherein the alicyclic ring having 5 to 30 carbon atoms which may have a substituent is an adamantane which may have a substituent.

[20] n 2 represents an integer of 2 to 20, the method for producing an iodine-containing (meth)acrylate compound according to any one of

[16] to

[19] .

[0059] [twenty one] A method for producing a (co)polymer having a hydroxy group represented by formula (Y), comprising a step of hydrolyzing an acyl group in the iodine-containing (meth)acrylate (co)polymer according to any one of [6] to [9].

[0060] [ka]

[0061] (In formula (Y), R 1 represents a hydrogen atom, a methyl group, or a halogen atom; R 2 each independently represents a hydrogen atom, a linear organic group having 1 to 20 carbon atoms, a branched organic group having 3 to 20 carbon atoms, or a cyclic organic group having 3 to 20 carbon atoms; A' represents an organic group having 1 to 30 carbon atoms; A' has at least one hydroxy group; n 1 represents 0 or 1, n 2 represents an integer from 1 to 20, The symbol * indicates the point of attachment to the adjacent structural unit. [Effects of the Invention]

[0062] The present invention provides a compound, a method for producing the compound, a (co)polymer and composition, and a method for forming a resist pattern using the composition, which are suitable for use in resist materials, have high stability, high sensitivity, and are capable of forming a film with high resolution. Furthermore, by using the compound and (co)polymer, a method for efficiently producing a (co)polymer having a hydroxy group that is useful for resist materials can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0063] Hereinafter, an embodiment of the present invention will be described (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 the present embodiment.

[0064] In this specification, (meth)acrylate means acrylate and methacrylate. Other terms containing the term (meth) are also interpreted in the same manner as (meth)acrylate. In this specification, (co)polymer means a homopolymer and a copolymer.

[0065] [Iodine-containing (meth)acrylate compounds] The iodine-containing (meth)acrylate compound (also simply referred to as "compound") of this embodiment is represented by the following formula (1). Because the compound is highly stable, this compound can be produced efficiently. In addition, the compound can achieve high sensitivity in a lithography process, making it possible to form a film with high resolution. Furthermore, (co)polymers containing the compound as a constituent unit are also highly stable, allowing iodine-containing (meth)acrylate (co)polymers (also simply referred to as "(co)polymers") to be produced efficiently.

[0066] [ka]

[0067] In formula (1), R 1represents a hydrogen atom, a methyl group, or a halogen atom; R 2 each independently represents a hydrogen atom, a linear organic group having 1 to 20 carbon atoms, a branched organic group having 3 to 20 carbon atoms, or a cyclic organic group having 3 to 20 carbon atoms; A represents an organic group having 1 to 30 carbon atoms, A contains at least one acyl group; n 1 represents 0 or 1, and n 2 represents an integer from 1 to 20.

[0068] R 1 R can be a hydrogen atom, a methyl group, or a halogen. Known atoms can be used as the halogen, such as fluorine (F), chlorine (Cl), bromine (Br), and iodine (I). 1 is preferably a methyl group or a halogen from the viewpoint of exposure sensitivity and material stability when the compound of this embodiment is used as a structural unit of a resin for a resist, and is more preferably a methyl group from the viewpoint of superior stability. 1 is more preferably a halogen, and further preferably iodine (I).

[0069] R 2 may be a combination of two or more selected from the group consisting of linear organic groups having 1 to 20 carbon atoms, branched organic groups having 3 to 20 carbon atoms, and cyclic organic groups having 3 to 20 carbon atoms.

[0070] R 2 is preferably a hydrogen atom in order to suppress an increase in the Tg (glass transition temperature) of the resin and improve the effect of introducing the iodine element. On the other hand, it is also preferably an organic group having one or more carbon atoms in order to improve acid decomposition property in order to control solubility in a developer. Furthermore, it is more preferably a hydrogen atom in order to suppress acid decomposition property, ensure solubility in an alkaline developer in particular, and suppress residues.

[0071] R 2 R may have a substituent. 2Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms, which may have a substituent; an alkenyl group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 2 to 6 carbon atoms, which may have a substituent; an alkynyl group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 2 to 6 carbon atoms, which may have a substituent; a cycloalkyl group having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, and more preferably 3 to 6 carbon atoms, which may have a substituent; a cycloalkenyl group having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, and more preferably 3 to 6 carbon atoms, which may have a substituent; a cycloalkynyl group having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, and more preferably 3 to 6 carbon atoms, which may have a substituent; an aryl group having 5 to 20 carbon atoms, preferably 5 to 10 carbon atoms, and more preferably 5 to 6 carbon atoms, which may have a substituent; and combinations thereof.

[0072] R 2 Specific examples of the alkyl group include optionally substituted methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, icosyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloicosyl, adamantyl, ethylene, propylene, butylene, phenyl, naphthyl, anthracene, phenanthrene, tetracene, chrysene, triphenylene, pyrene, benzopyrene, azulene, and fluorene groups. These groups may contain an ether bond, a ketone bond, or an ester bond.

[0073] In this embodiment, the exemplified groups include isomers, such as an n-propyl group and an isopropyl group for a propyl group, and an n-butyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group for a butyl group.

[0074] R 2The substituents on the aryl group are not particularly limited, but examples thereof include halogen, a hydroxy group, a cyano group, a nitro group, an amino group, a thiol group, a heterocyclic group, a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, an aryl group, an aralkyl group, an alkoxy group, an alkenyl group, an acyl group, an alkoxycarbonyl group, an alkyloyloxy group, an aryloyloxy group, and an alkylsilyl group, as well as various crosslinkable groups and acid-dissociable groups.

[0075] The term "crosslinkable group" refers to a group that crosslinks with the aid of an acid, an alkali, light, or heat, and that crosslinks in the presence or absence of a catalyst. The crosslinkable group is not particularly limited, and examples thereof include 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 urethane(meth)acryloyl group, a group having a hydroxy group, a group having a glycidyl group, a group having a vinylphenylmethyl group, a group having a styrene group, a group having an alkynyl group, a group having a carbon-carbon double bond, a group having a carbon-carbon triple bond, and groups containing these groups.

[0076] The term "acid-dissociable group" refers to a group that cleaves in the presence of an acid to generate an alkali-soluble group (e.g., a phenolic hydroxy group, a carboxyl group, a sulfonic acid group, or a hexafluoroisopropanol group). The acid-dissociable group is not particularly limited, and can be appropriately selected from those proposed for hydroxystyrene resins and (meth)acrylic resins used in chemically amplified resist compositions for KrF and ArF. Specific examples of the acid-dissociable group include those described in WO 2016 / 158168.

[0077] A may have a substituent. Examples of the compound that forms the skeleton of A include an alkane having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms, which may have a substituent; an alkene having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 2 to 6 carbon atoms, which may have a substituent; an alkyne ...3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and even more preferably 3 to 6 carbon atoms, which may have a substituent; Examples thereof include cycloalkanes preferably having 3 to 10 carbon atoms, more preferably having 3 to 6 carbon atoms; cycloalkenes which may have a substituent and have 3 to 30 carbon atoms, preferably having 3 to 20 carbon atoms, more preferably having 3 to 10 carbon atoms, and even more preferably having 3 to 6 carbon atoms; cycloalkynes which may have a substituent and have 3 to 30 carbon atoms, preferably having 3 to 20 carbon atoms, more preferably having 3 to 10 carbon atoms, and even more preferably having 3 to 6 carbon atoms; arenes which may have a substituent and have 5 to 30 carbon atoms, preferably having 5 to 20 carbon atoms, more preferably having 5 to 10 carbon atoms, and even more preferably having 5 to 6 carbon atoms; and combinations thereof.

[0078] Specific examples of the compound that serves as the skeleton of A include methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, icosane, triacontane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloicosane, cyclotriacontane, adamantane, ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, icosene, triacontene, benzene, phenol, naphthalene, anthracene, phenanthrene, tetracene, chrysene, triphenylene, pyrene, pentacene, benzopyrene, coronene, azulene, fluorene, and combinations thereof, which may have a substituent. These may contain an ether bond, a ketone bond, or an ester bond.

[0079] The substituents of the compound forming the skeleton of A are not particularly limited, but examples thereof include halogens (fluorine, chlorine, bromine), hydroxy groups, cyano groups, nitro groups, amino groups, thiol groups, heterocyclic groups, linear aliphatic hydrocarbon groups, branched aliphatic hydrocarbon groups, cyclic aliphatic hydrocarbon groups, aryl groups, aralkyl groups, alkoxy groups, alkenyl groups, acyl groups, alkoxycarbonyl groups, alkyloyloxy groups, aryloyloxy groups, and alkylsilyl groups, as well as various crosslinkable groups and acid-dissociable groups. From the viewpoint of improving the stability and productivity of the iodine-containing (meth)acrylate compound, it is preferable that the substituents of the compound forming the skeleton of A do not contain hydroxy groups.

[0080] The "crosslinkable group" and the "acid-dissociable group" are not particularly limited, but examples thereof include the above-mentioned R 2 The materials described in the description of the first embodiment can be used.

[0081] A can reduce film defects, stabilize the compound, and provide sensitivity and etching resistance. 1 is 0, and is preferably an alicyclic ring having 5 to 30 carbon atoms which may have a substituent, and n 1 is 0, and it is more preferable that the alkyl group is an alicyclic hydrocarbon having 5 to 30 carbon atoms which may have a substituent, and n 1 It is more preferable that the alicyclic ring is an adamantane which may have a substituent and is 0. Examples of the alicyclic ring include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloicosane, cyclotriacontane, and adamantane, which may contain an ether bond, a ketone bond, and an ester bond. Examples of alicyclic hydrocarbons include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloicosane, cyclotriacontane, and adamantane.

[0082] A contains at least one acyl group. The acyl group is preferably contained as a substituent in the compound that forms the skeleton of A. The substituent may contain an ether bond, a ketone bond, or an ester bond, but preferably contains an ether bond. Specific examples of the acyl group include a methanoyl group (formyl group), an ethanoyl group (acetyl group), a propanoyl group, a butanoyl group, a pentanoyl group, a hexanoyl group, an octanoyl group, a decanoyl group, and a benzoyl group. An ethanoyl group (acetyl group) and a benzoyl group are preferred, and an ethanoyl group (acetyl group) is more preferred.

[0083] It is preferable that A contains at least one acyl group from the viewpoint of enhancing the stability of the compound and (co)polymer. It is also preferable from the viewpoint of enhancing the productivity of the compound and (co)polymer. When an acyl group is contained as a substituent in the compound that forms the skeleton of A, the stability of the compound and (co)polymer is enhanced, and a resin incorporating the compound and (co)polymer is well dissolved in an organic solvent and has excellent storage stability. Therefore, the number of acyl groups in the compound that forms the skeleton of A is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and even more preferably 1.

[0084] n 1 represents 0 or 1, and is preferably 1.

[0085] Since A can reduce film defects, have sensitivity, and have etching resistance, it is 1 is 1, and is preferably an aromatic group having 5 to 30 carbon atoms which may have a substituent, and n 1 is 1, and is more preferably benzene which may have a substituent. Examples of aromatic groups include benzene, phenol, naphthalene, anthracene, phenanthrene, tetracene, chrysene, triphenylene, pyrene, pentacene, benzopyrene, and coronene. These may contain an ether bond, a ketone bond, and an ester bond.

[0086] A contains at least one acyl group. The acyl group is as defined above. 1 When is 1, among the acyl groups, an ethanoyl group (acetyl group) and a benzoyl group are preferred, and an ethanoyl group (acetyl group) is more preferred.

[0087] It is preferable that A contains at least one acyl group from the viewpoint of enhancing the stability of the compound and (co)polymer. It is also preferable from the viewpoint of enhancing the productivity of the compound and (co)polymer. When an acyl group is contained as an aromatic substituent, the stability of the compound and (co)polymer is enhanced, and a resin incorporating the compound and (co)polymer is easily dissolved in an organic solvent and has excellent storage stability. Therefore, the number of acyl groups contained as a substituent in the aromatic is preferably 1 to 8, more preferably 1 to 5, even more preferably 1 to 3, and even more preferably 1.

[0088] n 2 is an integer of 1 to 20, and is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and even more preferably an integer of 2 to 5, since both sensitivity and etching resistance can be achieved.

[0089] From the viewpoint of easy reactivity, the compound represented by the above formula (1) is preferably a compound represented by the following formula (2):

[0090] [ka]

[0091] In formula (2), R 1 , A, and n 2 is as defined in the above formula (1).

[0092] From the viewpoint of etching resistance, the compound represented by the above formula (1) is more preferably a compound represented by the following formula (3).

[0093] [ka]

[0094] In formula (3), B represents an organic group having 5 to 30 carbon atoms and containing an aromatic group, and B contains at least one acyl group. 1 , and n 2 is as defined in the above formula (1).

[0095] B may have a substituent. Examples of the compound that serves as the skeleton of B include arenes having 5 to 30 carbon atoms, preferably 5 to 20 carbon atoms, more preferably 5 to 10 carbon atoms, and even more preferably 5 to 6 carbon atoms, which may have a substituent.

[0096] Specific examples of the compound that serves as the skeleton of B include benzene, phenol, naphthalene, anthracene, phenanthrene, tetracene, chrysene, triphenylene, pyrene, pentacene, benzopyrene, coronene, azulene, fluorene, and combinations thereof, which may have a substituent, and which may contain an ether bond, a ketone bond, or an ester bond.

[0097] The substituents of the compound forming the skeleton of B are not particularly limited, but examples thereof include halogens (fluorine, chlorine, bromine), hydroxy groups, cyano groups, nitro groups, amino groups, thiol groups, heterocyclic groups, linear aliphatic hydrocarbon groups, branched aliphatic hydrocarbon groups, cyclic aliphatic hydrocarbon groups, aryl groups, aralkyl groups, alkoxy groups, alkenyl groups, acyl groups, alkoxycarbonyl groups, alkyloyloxy groups, aryloyloxy groups, and alkylsilyl groups, as well as various crosslinkable groups and acid-dissociable groups. From the viewpoint of improving the stability and productivity of the iodine-containing (meth)acrylate compound, it is preferable that the substituents of the compound forming the skeleton of B do not contain hydroxy groups.

[0098] The "crosslinkable group" and the "acid-dissociable group" are not particularly limited, but examples thereof include the above-mentioned R 2The acid-labile group bonded to the aromatic group of B is preferably a group that is cleaved in the presence of an acid to generate a hydroxy group.

[0099] B is preferably an aromatic group having 5 to 30 carbon atoms which may have a substituent, and more preferably benzene which may have a substituent, because it can reduce film defects, provide sensitivity, and provide etching resistance. Examples of aromatic groups include benzene, phenol, naphthalene, anthracene, phenanthrene, tetracene, chrysene, triphenylene, pyrene, pentacene, benzopyrene, and coronene.

[0100] B contains at least one acyl group. The acyl group is as described above. Among them, an ethanoyl group (acetyl group) and a benzoyl group are preferred, and an ethanoyl group (acetyl group) is more preferred.

[0101] It is preferable that B contains at least one acyl group from the viewpoint of enhancing the stability of the compound and (co)polymer. It is also preferable from the viewpoint of enhancing the productivity of the compound and (co)polymer. When an acyl group is contained as a substituent in the compound that forms the skeleton of B, the stability of the compound and (co)polymer is enhanced, and a resin incorporating the compound and (co)polymer is well dissolved in an organic solvent and has excellent storage stability. Therefore, the number of acyl groups in the compound that forms the skeleton of B is preferably 1 to 8, more preferably 1 to 5, even more preferably 1 to 3, and even more preferably 1.

[0102] From the viewpoint of etching resistance, the compound represented by the above formula (1) is more preferably a compound represented by the following formula (3').

[0103] [ka]

[0104] In formula (3'), B' represents an organic group having 5 to 30 carbon atoms and including an alicyclic ring, and B' contains at least one acyl group. 1 , and n 2 is as defined in the above formula (1).

[0105] B' may have a substituent. Examples of the compound that serves as the skeleton of B' include a cycloalkane having 5 to 30 carbon atoms, preferably 5 to 20 carbon atoms, more preferably 5 to 10 carbon atoms, and even more preferably 5 to 6 carbon atoms, which may have a substituent; a cycloalkene having 5 to 30 carbon atoms, preferably 5 to 20 carbon atoms, more preferably 5 to 10 carbon atoms, and even more preferably 5 to 6 carbon atoms, which may have a substituent; a cycloalkyne having 5 to 30 carbon atoms, preferably 5 to 20 carbon atoms, more preferably 5 to 10 carbon atoms, and even more preferably 5 to 6 carbon atoms, which may have a substituent; and combinations thereof.

[0106] Specific examples of the compound that serves as the skeleton of B' include optionally substituted cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloicosane, cyclotriacontane, adamantane, and combinations thereof, which may contain an ether bond, a ketone bond, or an ester bond.

[0107] The substituents of the compound forming the skeleton of B' are not particularly limited, but examples thereof include halogens (fluorine, chlorine, bromine), hydroxy groups, cyano groups, nitro groups, amino groups, thiol groups, heterocyclic groups, linear aliphatic hydrocarbon groups, branched aliphatic hydrocarbon groups, cyclic aliphatic hydrocarbon groups, aryl groups, aralkyl groups, alkoxy groups, alkenyl groups, acyl groups, alkoxycarbonyl groups, alkyloyloxy groups, aryloyloxy groups, alkylsilyl groups, various crosslinkable groups, and acid-dissociable groups. From the viewpoint of improving the stability and productivity of the iodine-containing (meth)acrylate compound, it is preferable that the substituents of the compound forming the skeleton of B' do not contain hydroxy groups.

[0108] The "crosslinkable group" and the "acid-dissociable group" are not particularly limited, but examples thereof include the above-mentioned R 2 The materials described in the description of the above can be used.

[0109] B' is preferably an alicyclic ring having 5 to 30 carbon atoms which may have a substituent, more preferably an alicyclic hydrocarbon having 5 to 30 carbon atoms which may have a substituent, and even more preferably an adamantane which may have a substituent, in order to achieve reduction in film defects, compound stability, sensitivity, and etching resistance. The alicyclic ring and alicyclic hydrocarbon are as described above.

[0110] B' contains at least one acyl group. The acyl group is as described above. Among them, an ethanoyl group (acetyl group) and a benzoyl group are preferred, and an ethanoyl group (acetyl group) is more preferred.

[0111] It is preferable that B' contains at least one acyl group from the viewpoint of enhancing the stability of the compound and (co)polymer. It is also preferable from the viewpoint of enhancing the productivity of the compound and (co)polymer. When an acyl group is contained as a substituent in the compound that forms the skeleton of B', the stability of the compound and (co)polymer is enhanced, and a resin incorporating the compound and (co)polymer is well dissolved in an organic solvent and has excellent storage stability. Therefore, the number of acyl groups in the compound that forms the skeleton of B' is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and even more preferably 1.

[0112] Specific examples of the iodine-containing (meth)acrylate compound of the present embodiment are listed below, but the present invention is not limited thereto. 1 represents a hydrogen atom, a methyl group, or a halogen. R' represents an acyl group, and an acetyl group is preferable. In the following examples, I represents an iodine atom, and I 1-9 means that 1 to 9 I's are bonded to the carbon atoms of the adamantane.

[0113] [ka]

[0114] [ka]

[0115] Regarding the structural formulae described herein, for example, as shown below, when the line showing the bond to C is in contact with ring A and ring B, it means that C may be bonded to either ring A or ring B.

[0116] [ka]

[0117] [Method for producing iodine-containing (meth)acrylate compound] The iodine-containing (meth)acrylate compound of the present embodiment can be produced by known method.This method is not particularly limited, but for example, the iodine-containing hydroxy compound represented by formula (a) and the (meth)acrylic acid compound represented by formula (b) are reacted to obtain the iodine-containing hydroxy (meth)acrylic acid compound, and then the hydroxy group derived from the iodine-containing hydroxy compound represented by formula (a) in this compound is reacted with an acylating agent to obtain; The hydroxy group in the iodine-containing hydroxy compound represented by formula (a) is reacted with an acylating agent to obtain a reactant, and then the reactant is reacted with the (meth)acrylic acid compound represented by formula (b) to obtain.

[0118] [ka]

[0119] In formula (a), A' represents an organic group having 1 to 30 carbon atoms, A' has at least one hydroxy group, and R 2 , n 1 , and n 2is as defined in the above formula (1). Furthermore, A' is the same as A in the above formula (1), except that A does not contain an acyl group but contains at least one hydroxy group. When a hydroxy group is contained as a substituent in the compound that forms the skeleton of A', the stability of the compound and (co)polymer is increased, and a resin into which the compound and (co)polymer have been introduced dissolves well in an organic solvent and has excellent storage stability. Therefore, the number of hydroxy groups in the compound that forms the skeleton of A' is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and even more preferably 1. The compound that forms the skeleton of A' is the same as the compound that forms the skeleton of A described above.

[0120] n 2 is an integer from 1 to 20. Since high sensitivity and high resolution can be achieved at the same time, n 2 is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and even more preferably an integer of 2 to 5.

[0121] [ka]

[0122] In formula (b), R 1 is as defined in the above formula (1). B is a hydroxy group, a halogen, a (meth)acryloyloxy group, or an alkoxy group. B Preferred are halogens and (meth)acryloyloxy groups. Chlorine is preferred as the halogen. Examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-hexanoxy, 2-methylpropoxy, methoxy, and phenoxy groups.

[0123] Formula (a) can reduce film defects, stabilize the compound, improve sensitivity, and improve etching resistance, and therefore, n 1is 0, A' is an alicyclic ring having 5 to 30 carbon atoms which may have a substituent, and A' has at least one hydroxy group, and n 1 is 0, A' is an alicyclic hydrocarbon having 5 to 30 carbon atoms which may have a substituent, and A' has at least one hydroxy group, and n 1 It is more preferable that A' is 0, A' is an adamantane which may have a substituent, and A' has at least one hydroxy group. The alicyclic and alicyclic hydrocarbons are as described above.

[0124] In addition, A' can reduce film defects, and has sensitivity and etching resistance. 1 is 1, A' is an aromatic group having 5 to 30 carbon atoms which may have a substituent, and A' preferably has at least one hydroxy group, and n 1 More preferably, A' is 1, is benzene which may have a substituent, and has at least one hydroxy group. The aromatic group is as described above.

[0125] The compound represented by the formula (a) is preferably a compound represented by the formula (a1) because it can reduce film defects, provide compound stability, sensitivity, and etching resistance.

[0126] [ka]

[0127] In formula (a1), A' and n 2 is as described above.

[0128] The compound represented by the formula (a) is preferably a compound represented by the formula (a2) because it can reduce film defects, and has good sensitivity and etching resistance.

[0129] [ka]

[0130] In formula (a2), B″ represents an organic group having 5 to 30 carbon atoms and including an aromatic group, B″ has at least one hydroxy group, and n 2 is as defined in the above formula (1). Furthermore, B" is the same as B in the above formula (3), except that B does not contain an acyl group but contains at least one hydroxy group. When a hydroxy group is contained as a substituent in the compound that forms the skeleton of B", the stability of the compound and (co)polymer is increased, and a resin into which the compound and (co)polymer have been introduced dissolves well in an organic solvent and has excellent storage stability. Therefore, the number of hydroxy groups in the compound that forms the skeleton of B" is preferably 1 to 8, more preferably 1 to 5, even more preferably 1 to 3, and even more preferably 1. The compound that forms the skeleton of B" is the same as the compound that forms the skeleton of B described above.

[0131] In formula (a2), B" is preferably an aromatic group having 5 to 30 carbon atoms which may have a substituent and B" has at least one hydroxy group, and more preferably B" is benzene which may have a substituent and B" has at least one hydroxy group, because this can reduce film defects, and provide sensitivity and etching resistance. The aromatic group is as described above.

[0132] The compound represented by the above formula (a) is preferably a compound represented by formula (a3) ​​because it can reduce film defects, provide compound stability, sensitivity, and etching resistance.

[0133] [ka]

[0134] In formula (a3), B''' represents an organic group having 5 to 30 carbon atoms and containing an alicyclic ring, B''' has at least one hydroxy group, and n 2is as defined in formula (1) above. Furthermore, B'" is the same as B' in formula (3') above, except that B' in formula (3') does not contain an acyl group but contains at least one hydroxy group. When a hydroxy group is contained as a substituent in the compound that forms the skeleton of B'", the stability of the compound and (co)polymer is increased, and a resin into which the compound and (co)polymer have been introduced is favorably dissolved in an organic solvent and has excellent storage stability. Therefore, the number of hydroxy groups in the compound that forms the skeleton of B'" is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and even more preferably 1. The compound that forms the skeleton of B'" is the same as the compound that forms the skeleton of B' above.

[0135] Formula (a3) ​​can simultaneously achieve reduced film defects, compound stability, sensitivity, and etching resistance, so that B'" is preferably an alicyclic ring having 5 to 30 carbon atoms which may have a substituent and B'" has at least one hydroxy group, more preferably B'" is an alicyclic hydrocarbon having 5 to 30 carbon atoms which may have a substituent and B'" has at least one hydroxy group, and even more preferably B'" is an adamantane which may have a substituent and B'" has at least one hydroxy group. The alicyclic ring and alicyclic hydrocarbon are as described above.

[0136] Specific examples of the (meth)acrylic acid compound represented by formula (b) of this embodiment are listed below, but are not limited thereto. 1 represents a hydrogen atom, a methyl group, or a halogen atom. 1 may be the same or different.

[0137] [ka]

[0138] <Method for producing an iodine-containing hydroxy compound represented by formula (a)> Next, a method for producing the iodine-containing hydroxy compound represented by formula (a) will be described. The production method of the iodine-containing hydroxy compound represented by formula (a) is not particularly limited, but it can be produced by carrying out an iodine introduction reaction to a compound of formula (Sa1) or (Sa2). When carrying out an iodine introduction reaction to a compound of formula (Sa2), the method further includes a step of converting the iodine-introduced product into a compound of formula (a). In this embodiment, an iodine-introduced product obtained by previously introducing iodine into a compound of formula (Sa2) may be used. Examples of such iodine-introduced products include 3,5-diiodosalicylaldehyde and 4-hydroxy-3,5-diiodobenzaldehyde. Examples of the step of converting into a compound of formula (a) include a reduction step.

[0139] [ka]

[0140] In formula (Sa1), R 2 , A', n 1 , and n 2 is as described above. X can be selected from a hydroxy group; an aliphatic or aromatic group having 1 to 30 carbon atoms and having at least one selected from the group consisting of a hydroxy group, an aldehyde group, and a carboxyl group; and a halogen (F, Cl, Br, etc.). Examples of compounds of formula (Sa1) include salicylic alcohol, 4-hydroxybenzyl alcohol, salicylic acid, 4-hydroxybenzoic acid, 1,3,5-adamantanetriol, 1,3-adamantanediol, 1-adamantanol, and 2-adamantanol.

[0141] [ka]

[0142] In formula (Sa2), A' and n 2are as defined above. X is as defined in formula (Sa1). E is a hydrocarbon group having 1 to 30 carbon atoms and having at least one group selected from the group consisting of a hydroxy group, an aldehyde group, a carboxyl group, an ether group, a thiol group, and an amino group. Examples of compounds of formula (Sa2) include salicylaldehyde and 4-hydroxybenzaldehyde.

[0143] Examples of iodine introduction reactions that can be used include the Sandmeyer method, the Halex method, an iodine introduction method using an iodizing agent or a compound that serves as an iodine source, an iodine introduction method using an iodizing agent or a compound that serves as an iodine source and an oxidizing agent, an iodine introduction method using an iodizing agent or a compound that serves as an iodine source and a radical generator, an iodine introduction method using an iodizing agent or a compound that serves as an iodine source and a system in which the catalytic activity is improved by using a zeolite or the like, and a method in which functional groups such as hydroxyl groups and halogen groups are iodized by a substitution reaction. As the iodinating agent, known compounds serving as iodine sources such as iodine, potassium iodide, hydrogen iodide (HI), iodine chloride, and N-iodosuccinimide can be appropriately used. These iodinating agents can be used alone or in combination of two or more. As the oxidizing agent, known oxidizing agents such as hydrogen peroxide, iodic acid, periodic acid, sulfuric acid, etc. These oxidizing agents may be used alone or in combination of two or more.

[0144] <Method for producing iodine-containing hydroxy(meth)acrylic acid compound> Next, a method for producing an iodine-containing hydroxy(meth)acrylic acid compound will be described. The iodine-containing hydroxy compound represented by formula (a) is used in an amount of, for example, 0.5 to 100 molar equivalents, preferably 1 to 20 molar equivalents, and more preferably 1.2 to 5 molar equivalents relative to the (meth)acrylic acid compound represented by formula (b). This range is preferred because the reaction proceeds sufficiently and the yield of the target iodine-containing hydroxy(meth)acrylic acid compound is high.

[0145] Commonly available solvents can be used as the solvent for this reaction. For example, alcohols, ethers, hydrocarbons, aromatic solvents, halogenated solvents, etc. can be used as appropriate as long as they do not inhibit the reaction. A mixture of multiple solvents can also be used as long as they do not inhibit the reaction. Since water inhibits the reaction, it is preferable to use a dehydrated solvent. Examples of the solvent include the solvents described in this specification.

[0146] For the purpose of improving the stability of materials and the efficiency of processes from reaction to obtaining the final compound, it is preferable to use a solvent with good solubility. The γP and γH in the Hansen Solubility Parameters (Hansen Solubility Parameters: A User's Handbook, CRC Press, Boca Raton, FL, 2007) can be used as indicators for suitable solvents, and γP and γH can be determined from the compound structure. The lower the γP and γH values, the better. A γP value of 6 or less is preferred, more preferably 4 or less, and even more preferably 2 or less. A γH value of 6 or less is preferred, more preferably 4 or less, and even more preferably 2 or less. As for such solvents, aromatic solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, and octane; and halogenated solvents such as dichloromethane, dichloroethane, and chloroform are preferred as the main solvents.

[0147] The reaction temperature and reaction time depend on the substrate concentration and the catalyst used, but generally the reaction temperature is -20°C to 100°C, the reaction time is 1 to 30 hours, and the pressure is normal, reduced, or increased. The reaction can be carried out by appropriately selecting a known method such as a batch system, a semi-batch system, or a continuous system.

[0148] A polymerization inhibitor may be added to the series of reactions, and a commercially available product may be used. Examples of such polymerization inhibitors include nitroso compounds such as 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl, N-nitrosophenylhydroxyamine ammonium salt, N-nitrosophenylhydroxyamine aluminum salt, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, N-nitrosodiphenylamine, N-nitroso-N-methylaniline, nitrosonaphthol, p-nitrosophenol, and N,N'-dimethyl-p-nitrosoaniline; sulfur-containing compounds such as phenothiazine, methylene blue, and 2-mercaptobenzimidazole; N,N'-diphenyl-p-phenylenediamine, N- Examples of the additive include amines such as phenyl-N'-isopropyl-p-phenylenediamine, 4-hydroxydiphenylamine, and aminophenol; quinones such as hydroxyquinoline, hydroquinone, methylhydroquinone, p-benzoquinone, and hydroquinone monomethyl ether; phenols such as 4-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, catechol, 3-s-butylcatechol, and 2,2-methylenebis-(6-t-butyl-4-methylphenol); imides such as N-hydroxyphthalimide; oximes such as cyclohexaneoxime and p-quinonedioxime; and dialkylthiodipropionates. The additive amount is, for example, 0.001 to 10 parts by mass, preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the (meth)acrylic acid compound represented by formula (b).

[0149] A catalyst may be added to the series of reactions, and a wide variety of catalysts that function under the reaction conditions of this embodiment can be used. As such a catalyst, for example, an acid catalyst or a base catalyst is preferred. Suitable acid catalysts include, for example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; organic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, 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 of two or more. Among these, organic acids and solid acids are preferred from the viewpoint of production, and p-toluenesulfonic acid, hydrochloric acid, and sulfuric acid are preferred from the viewpoint of production, such as ease of availability and handling. Suitable base catalysts include, for example, amine-containing catalysts such as pyridine and ethylenediamine; and non-amine basic catalysts such as metal salts, preferably potassium salts and acetate salts, including potassium acetate, potassium carbonate, potassium hydroxide, sodium acetate, sodium carbonate, sodium hydroxide, and magnesium oxide. Non-amine base catalysts are commercially available from, for example, EM Sciences and Aldrich. These catalysts may be used alone or in combination of two or more. 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.

[0150] The iodine-containing hydroxy(meth)acrylic acid compound obtained by the reaction can be isolated and purified by known purification methods such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, and separation and purification methods using activated carbon, etc., or a combination of these methods to obtain the iodine-containing hydroxy(meth)acrylic acid compound as a desired high-purity monomer. Furthermore, the obtained high-purity monomer can be further subjected to a purification method for removing metal impurities, such as metal ions and metal oxides, as described below. The resulting high-purity monomer typically has a content of various metals contained in the compound (e.g., sodium (Na), potassium (K), calcium (Ca), magnesium (Mg), iron (Fe), copper (Cu), nickel (Ni), tin (Sn), silver (Ag), molybdenum (Mo), manganese (Mn), zinc (Zn), cobalt (Co), aluminum (Al), lead (Pb), chromium (Cr), and titanium (Ti)) of 10 ppb or less, preferably 5 ppb or less, and more preferably 1 ppb or less. The iodine-containing hydroxy(meth)acrylic acid compound can also be acylated directly from the reaction mixture without isolation or purification.

[0151] The purification method for removing metal impurities is not particularly limited, but includes a step of dissolving an iodine-containing hydroxy(meth)acrylic acid compound in a solvent to obtain a solution (S), and a step (first extraction step) of contacting the solution (S) with an acidic aqueous solution to extract impurities in the iodine-containing hydroxy(meth)acrylic acid compound (hereinafter also referred to as "compound (A)"), wherein the solvent used in the step of obtaining the solution (S) includes an organic solvent that is arbitrarily immiscible with water. According to such a purification method, the contents of various metals contained as impurities in the compound (A) can be reduced. More specifically, compound (A) can be dissolved in an organic solvent that is immiscible with water to obtain solution (S), and then the solution (S) can be contacted with an acidic aqueous solution to carry out an extraction treatment. As a result, the extracted metals contained in solution (S) are transferred to the aqueous phase, and the organic and aqueous phases can be separated to obtain compound (A) with a reduced metal content.

[0152] The water-immiscible solvent used in the purification method is not particularly limited, but is preferably an organic solvent that can be safely applied to semiconductor manufacturing processes. Specifically, it is preferably an organic solvent whose solubility in water at room temperature (25°C) is less than 30%, more preferably less than 20%, and even more preferably less than 10%. The amount of the organic solvent used is preferably 1 to 100 times by mass relative to the total amount of compound (A) used.

[0153] Specific examples of solvents that are not miscible with water include 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 and ethyl acetate have a relatively high saturated solubility of compound (A) and a relatively low boiling point, making it possible to reduce the load in industrially distilling off the solvent and in the process of removing it by drying. These solvents may be used alone or in combination of two or more.

[0154] The acidic aqueous solution used in the purification method is appropriately selected from acidic aqueous solutions prepared by dissolving commonly known organic or inorganic compounds in water. Examples of such aqueous solutions include 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 polycarboxylic acids such as acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, and citric acid, and organic acids such as methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid in water. These acidic aqueous solutions may be used alone or in combination of two or more. Among these acidic aqueous solutions, aqueous solutions of sulfuric acid, nitric acid, and acetic acid, and aqueous solutions of polycarboxylic acids such as oxalic acid, tartaric acid, and citric acid are preferred, with aqueous solutions of sulfuric acid, oxalic acid, tartaric acid, and citric acid being more preferred, and aqueous solutions of oxalic acid being even more preferred. Polycarboxylic acids such as oxalic acid, tartaric acid, and citric acid coordinate with metal ions, producing a chelating effect, which is thought to tend to more effectively remove metals. In addition, in line with the purpose of the purification method of this embodiment, it is preferable to use water with a low metal content, such as ion-exchanged water.

[0155] The pH of the acidic aqueous solution used in the above purification method is not particularly limited, but it is preferable to adjust the acidity of the aqueous solution in consideration of the effect on compound (A). The pH range is usually about 0 to 5, and preferably about 0 to 3.

[0156] 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 viewpoints of reducing the number of extractions for metal removal and ensuring operability in consideration of the total liquid volume. From the above 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).

[0157] In the above purification method, the metal components can be extracted from the compound (A) in the solution (S) by bringing the acidic aqueous solution into contact with the solution (S).

[0158] In the above purification method, the solution (S) may further contain an organic solvent that is optionally miscible with water. When the solution contains an organic solvent that is optionally miscible with water, the amount of compound (A) charged can be increased, and separation properties are improved, tending to enable purification with high reactor efficiency. Examples of methods for adding the organic solvent that is optionally miscible with water include a method of adding it to a solution containing the organic solvent in advance, a method of adding it to water or an acidic aqueous solution in advance, and a method of adding it after contacting a solution containing the organic solvent with water or an acidic aqueous solution. Among these, the method of adding it to a solution containing the organic solvent in advance is preferred from the viewpoints of ease of operation and ease of control of the charged amount.

[0159] 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 the solvent phase and the aqueous phase are separated, 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 compound (A).

[0160] Examples of organic solvents that are miscible with water and used in the purification method include 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. These solvents may be used alone or in combination of two or more.

[0161] The temperature during the extraction treatment is not particularly limited, but is usually in the range of 20 to 90°C, preferably 30 to 80°C. The extraction operation is carried out, for example, by thoroughly mixing the components by stirring or the like to obtain a mixed solution, and then allowing the mixed solution to stand. This allows the metal components contained in 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 compound (A).

[0162] The mixed solution separates into a solvent phase containing compound (A) and a solvent and an aqueous phase upon standing, and the solvent 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 solvent phase 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. The extraction treatment may be performed only once, but it is also effective to repeat the operations of mixing, standing, and separation multiple times.

[0163] In the above purification method, it is preferable to further include a step (second extraction step) of contacting the solvent phase containing compound (A) with water after the first extraction step to extract impurities in compound (A). Specifically, for example, it is preferable to perform the above extraction treatment using an acidic aqueous solution, recover the aqueous solution, and then subject the remaining solvent phase containing compound (A) and the solvent to a further extraction treatment with water. The extraction treatment in the second extraction step is not particularly limited, but can be performed, for example, by thoroughly mixing the solvent 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 solvent phase containing compound (A) and the solvent, and an aqueous phase, and the solvent phase can be recovered by decantation or the like. In addition, in accordance with the object of this 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 operations of mixing, leaving to stand, and separating multiple times. In addition, the conditions for the extraction treatment, such as the ratio of the two components used, the temperature, and the time, are not particularly limited, but the above may be used as a reference.

[0164] Water that may be mixed into the solution containing compound (A) and a solvent obtained in this manner can be easily removed by performing an operation such as vacuum distillation, etc. Furthermore, if necessary, a solvent can be added to the above solution to adjust the concentration of compound (A) to any desired concentration.

[0165] Compound (A) can also be purified by dissolving compound (A) in a solvent and passing the solution through a filter. According to the purification method of this embodiment, the contents of various metals in compound (A) can be effectively and significantly reduced. In this embodiment, "passing through" 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 mode in which the solution is simply brought into contact with the surface of the filter, or a mode in which the solution is brought into contact with the surface of the filter and moves outside the ion exchange resin (i.e., a mode in which the solution simply comes into contact).

[0166] The purification method using a filter will be described in detail. As the filter, commercially available filters for liquid filtration can usually be used. The filtration accuracy of the filter is not particularly limited, but 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 usually 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 test, or a standard particle capture test. When a commercially available product is used, the value is listed in the manufacturer's catalog data. By setting the nominal pore size to 0.2 μm or less, the metal content of the solution after passing it through the filter once can be effectively reduced. To further reduce the content of each metal in the solution, the solution may be passed through the filter two or more times.

[0167] 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 the above, the filter is preferably one or more selected from the group consisting of a hollow fiber membrane filter, a membrane filter, and a pleated membrane filter. Furthermore, it is more preferable to use a hollow fiber membrane filter, particularly because of its high-precision filtration accuracy and a larger filtration area compared to other forms.

[0168] 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, and fluororesin. Furthermore, polyamide is more preferred because it can further reduce heavy metals such as chromium. It is preferable to use a filter made of a material other than sintered metal in order to avoid metal elution from the material.

[0169] Examples of polyamide filters include the Polyfix (registered trademark) nylon series manufactured by Kitz Microfilter Co., Ltd., Ultipleat (registered trademark) P-nylon 66 and Ultipore (registered trademark) N66 manufactured by Nippon Pall Co., Ltd., and the LifeAsure (registered trademark) PSN series and LifeAsure (registered trademark) EF series manufactured by 3M. Examples of polyolefin filters include Ultipleats (registered trademark) PE Clean and Ion Clean manufactured by Nippon Pall Co., Ltd., and Protego (registered trademark) series, Microguard (registered trademark) Plus HC10, and Optimizer D manufactured by Nippon Entegris LLC. Examples of polyester filters include Gelaflow DFE manufactured by Central Filter Kogyo Co., Ltd. and Breeze Type (registered trademark) PMC manufactured by Nippon Filter Co., Ltd. Examples of polyacrylonitrile filters include Ultrafilters AIP-0013D, ACP-0013D, and ACP-0053D manufactured by Advantec Toyo Co., Ltd. Examples of fluororesin filters include Enflon (registered trademark) HTPFR manufactured by Nippon Pall Co., Ltd., and LifeAsure FA series manufactured by 3M. These filters may be used singly or in combination of two or more.

[0170] 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 the Protego (registered trademark) series manufactured by Nippon Entegris LLC and Clangraft (registered trademark) manufactured by Kurashiki Seni Kako Co., Ltd. Furthermore, examples of filters containing a substance with a positive zeta potential, such as polyamide polyamine epichlorohydrin cationic resin, include Zeta Plus (registered trademark) 40QSH, Zeta Plus (registered trademark) 020GN, and Life Asure (registered trademark) EF series manufactured by 3M.

[0171] The method for isolating compound (A) from a solution containing compound (A) and a solvent is not particularly limited, and can be performed by known methods such as removal under reduced pressure, separation by reprecipitation, a combination thereof, etc. If necessary, known treatments such as concentration, filtration, centrifugation, and drying can be performed.

[0172] <Method for producing iodine-containing (meth)acrylate compound> Next, a method for producing the iodine-containing (meth)acrylate compound of this embodiment will be described. The iodine-containing (meth)acrylate compound can be obtained by reacting the hydroxy group of the iodine-containing hydroxy(meth)acrylic acid compound with an acylating agent. Suitable acylating agents include, but are not limited to, acetic anhydride, acetyl halide, and acetic acid. Among these, acetic anhydride is preferred.

[0173] This reaction may be carried out in an organic solvent. 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, a mixture of polar aprotic solvents, a mixture of protic polar solvents, a mixture of polar aprotic solvents and protic polar solvents, and a mixture of aprotic or protic solvents and nonpolar solvents can be used. Among these, polar aprotic solvents or mixtures thereof are preferred.

[0174] A solvent is effective but not essential. Suitable polar aprotic solvents include, for example, alcoholic solvents such as methanol and ethanol; etheric solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglyme, and triglyme; esteric 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. Among these, toluene and dimethyl sulfoxide are preferred. Suitable protic polar solvents include, for example, 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.

[0175] A catalyst may be used in this reaction. As the catalyst, a wide variety of acylation catalysts that function under the reaction conditions of this embodiment can be used, and an acid catalyst or a base catalyst is preferred. Suitable acid catalysts include, for example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; organic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, 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 of two or more. Among these, organic acids and solid acids are preferred from the viewpoint of production, and hydrochloric acid or sulfuric acid is more preferred from the viewpoint of production, such as ease of availability and handling. Suitable base catalysts include, for example, amine-containing catalysts such as pyridine and ethylenediamine; and non-amine basic catalysts such as metal salts. Preferred metal salts include potassium salts and acetate salts. Such catalysts include potassium acetate, potassium carbonate, potassium hydroxide, sodium acetate, sodium carbonate, sodium hydroxide, and magnesium oxide. Non-amine base catalysts are commercially available from, for example, EM Sciences and Aldrich. These catalysts may be used alone or in combination of two or more. 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.

[0176] A polymerization inhibitor may be used in this reaction. A wide variety of polymerization inhibitors that function under the reaction conditions of this embodiment may be used as the polymerization inhibitor. A polymerization inhibitor is effective but not essential. Suitable polymerization inhibitors include those described herein, as well as hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, phenothiazine, N-oxyl (nitroxide) inhibitors (e.g., Prostab® 5415 (bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, commercially available from Ciba Specialty Chemicals), 4-hydroxy-TEM. PO (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yloxy, available from Tokyo Chemical Industry Co., Ltd.), and Uvinul® 4040P (1,6-hexamethylene-bis(N-formyl-N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)amine, available from BASF). These polymerization inhibitors may be used alone or in combination of two or more. 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.

[0177] A polymerization inhibitor may be used in this reaction. A wide variety of polymerization inhibitors that function under the reaction conditions of this embodiment can be used as the polymerization inhibitor. The polymerization inhibitor is effective but not essential. Examples of polymerization inhibitors include hydroquinone, methoquinone, methoxyphenol, hydroxyanisole, di-t-butylhydroquinone, toluhydroquinone, butylhydroquinone, benzoquinone, methyl-p-benzoquinone, toluquinone, butyl-p-benzoquinone, and diphenyl-p-benzoquinone. These polymerization inhibitors can be used alone or in combination of two or more.

[0178] It is also effective to use a polymerization retarder in combination with a polymerization inhibitor. Polymerization retarders are well known in the art and are compounds that slow the polymerization reaction but cannot completely prevent it. Common polymerization 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). These polymerization retarders may be used alone or in combination. 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.

[0179] The reaction is carried out by adding an iodine-containing hydroxy(meth)acrylic acid compound, an acylating agent, and optionally an organic solvent, a catalyst, a polymerization inhibitor, a polymerization inhibitor, and a polymerization retarder to a reactor to form a reaction mixture. Any suitable reactor can be used for the reaction. The reaction can be carried out by any known method, such as a batch system, a semi-batch system, or a continuous system.

[0180] The reaction temperature is not particularly limited and varies depending on the concentration of the substrate, the stability of the formed product, the selection of the catalyst, and the desired yield. Generally, a temperature of 0 to 200°C is suitable, and from the viewpoint of yield, a temperature of 0 to 100°C is preferable.

[0181] The reaction pressure varies depending on the concentration of the substrate, the stability of the formed product, the catalyst selection, and the desired yield, and is not particularly limited. The pressure can be adjusted using an inert gas such as nitrogen or using an air pump. Conventional pressure reactors, including shaker vessels, rocker vessels, and stirred autoclaves, are used for reactions at high pressure.

[0182] The reaction time is not particularly limited and varies depending on the concentration of the substrate, the stability of the formed product, the catalyst selection, and the desired yield. Usually, most reactions are carried out in less than 12 hours, and the reaction time is generally 15 to 600 minutes.

[0183] 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 is poured onto ice water and extracted into an organic solvent such as ethyl acetate, butyl acetate, or diethyl ether. The product is then recovered by removing the solvent using evaporation under reduced pressure. The iodine-containing (meth)acrylate compound can be isolated and purified to obtain the desired high-purity monomer using separation and purification methods well known in the art, such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, and activated carbon, or a combination thereof. Furthermore, the obtained high-purity monomer can be further purified by a purification method aimed at removing metal impurities, such as contained metal ions and metal oxides. For details of the purification method, please refer to the methods described above and in the Examples, etc., herein. The resulting high-purity monomer typically has a content of various metals (e.g., Na, K, Ca, Mg, Fe, Cu, Ni, Sn, Ag, Mo, Mn, Zn, Co, Al, Pb, Cr, and Ti) contained in the compound of 10 ppb or less, preferably 5 ppb or less, and more preferably 1 ppb or less.

[0184] The compound of the present embodiment can be widely and effectively used in, for example, electrical insulating materials, resist resins, semiconductor sealing resins, adhesives for printed wiring boards, electrical laminates used in electrical equipment, electronic devices, industrial equipment, etc., matrix resins for prepregs used in electrical equipment, electronic devices, industrial equipment, etc., build-up laminate materials, resins for fiber-reinforced plastics, sealing resins for liquid crystal display panels, paints, various coating agents, adhesives, coating agents for semiconductors, resist resins for semiconductors, and resins for forming resist underlayer films.

[0185] [Iodine-containing (meth)acrylate (co)polymer] Since the compound of the present embodiment is highly stable, an iodine-containing (meth)acrylate (co)polymer containing this compound as a constituent unit also has high stability, and the (co)polymer can be produced efficiently. Furthermore, by forming a (co)polymer containing the compound of this embodiment as a structural unit, it is possible to form a polymer containing one or more halogen elements, one or more hydrophilic groups, or one or more decomposable groups. As a result, a resist composition containing a (co)polymer containing the compound of this embodiment as a structural unit as a resin component can achieve high sensitivity in the lithography process and high resolution due to an increase in the solubility contrast of the resin during development. The (co)polymer of this embodiment has a constitutional unit represented by the following formula (4).

[0186] [ka]

[0187] In formula (4), R 1 , R 2 , A, n 1 , and n 2 is as defined in the above formula (1), and the symbol * represents the bonding point to the adjacent structural unit. 2 is an integer of 1 to 20, and is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and even more preferably an integer of 2 to 5, since both sensitivity and etching resistance can be achieved.

[0188] A contains at least one acyl group. The acyl group is as described above. Among them, an ethanoyl group (acetyl group) and a benzoyl group are preferred, and an ethanoyl group (acetyl group) is more preferred.

[0189] It is preferable that A contains at least one acyl group from the viewpoint of enhancing the stability of the (co)polymer. It is also preferable from the viewpoint of enhancing the productivity of the (co)polymer. When an acyl group is contained as a substituent in the compound that forms the skeleton of A, the stability of the compound and the (co)polymer is enhanced, and a resin incorporating the compound and the (co)polymer dissolves well in an organic solvent and has excellent storage stability. Therefore, the number of acyl groups in the compound that forms the skeleton of A is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and even more preferably 1. The compound that forms the skeleton of A is as described above.

[0190] In practical embodiments, the (co)polymer can be used by hydrolyzing some or all of the acyl groups contained in A to form hydroxy groups. The presence of hydroxy groups makes it possible to obtain a (co)polymer that has excellent alkaline developability, reduced film defects, compound stability, and sensitivity. The (co)polymer may contain, in addition to the structural unit represented by formula (4), a structural unit having a hydroxy group obtained by hydrolyzing some or all of the acyl groups contained in A in formula (4).

[0191] The (co)polymer can be obtained as a polymer (homopolymer) made of the compound of this embodiment, as a copolymer obtained by polymerizing two or more compounds of this embodiment, or as a copolymer obtained by polymerizing one or more compounds of this embodiment with one or more other monomers. In this embodiment, these polymers are collectively referred to as "(co)polymer." The (co)polymer can be used as a film-forming material for lithography, a resist film-forming material, etc.

[0192] In formula (4), n 1 is preferably 0, A is an alicyclic ring having 5 to 30 carbon atoms which may have a substituent, and n 1 is 0, and A is an alicyclic hydrocarbon having 5 to 30 carbon atoms which may have a substituent, and n 1It is more preferable that A is 0 and A is an adamantane which may have a substituent. The alicyclic and alicyclic hydrocarbons are as described above.

[0193] In addition, in formula (4), since it is possible to simultaneously achieve reduction in film defects, sensitivity, and etching resistance, n 1 is preferably 1, A is an aromatic group having 5 to 30 carbon atoms which may have a substituent, and n 1 It is more preferable that the aromatic group is benzene, which may have a substituent and is 1. The aromatic group is as described above.

[0194] The (co)polymer contains a structural unit derived from the iodine-containing (meth)acrylate compound of this embodiment, and preferred aspects of the iodine-containing (meth)acrylate compound are as described above. The (co)polymer contains, for example, structural units derived from a compound represented by formula (1), a compound represented by formula (2), a compound represented by formula (3), and a compound represented by formula (3'). The structural unit derived from the compound represented by formula (1) corresponds to the structural unit represented by formula (4), and the same applies to the compound represented by formula (2), the compound represented by formula (3), and the compound represented by formula (3').

[0195] The other monomers are not particularly limited, but include, for example, compounds (monomers) described in WO 2016 / 125782, WO 2015 / 115613, JP 2015-117305, WO 2014 / 175275, and JP 2012-162498. The copolymer may also contain a structural unit represented by formula (C1) and a structural unit represented by formula (C2). These monomers and structural units may be used alone or in combination of two or more.

[0196] [ka]

[0197] In formula (C1), R C11 represents a hydrogen atom or a methyl group, and RC12 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R C13 is R C13 R represents a cycloalkyl or heterocycloalkyl group having 4 to 20 carbon atoms together with the carbon atom to which it is bonded, and the symbol * represents the bonding point to the adjacent structural unit. 13 may have a substituent (for example, an oxo group). Preferably, R C12 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R C13 is R C13 together with the carbon atom to which it is attached, form a cycloalkyl group or heterocycloalkyl group having 4 to 10 carbon atoms.

[0198] [ka]

[0199] In formula (C2), R C21 represents a hydrogen atom or a methyl group, and R C22 and R C23 each independently represents an alkyl group having 1 to 4 carbon atoms, and R C24 represents an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms, and R C22 ~R C24 Two or three of these may combine with the carbon atoms to which they are bonded to form an alicyclic structure having 3 to 20 carbon atoms, and the symbol * indicates the bonding point to the adjacent structural unit. The alicyclic structure may have a substituent (for example, a hydroxy group or an alkyl group). Preferably, R C22 represents an alkyl group having 1 to 3 carbon atoms, and R C24 is a cycloalkyl group having 5 to 10 carbon atoms. C22 ~R C24 The alicyclic structure formed by may contain multiple rings, such as an adamantyl group.

[0200] Examples of the monomer raw material for the structural unit represented by formula (C2) include 2-methyl-2-(meth)acryloyloxyadamantane (2-methyl-2-adamantyl(meth)acrylate), 2-ethyl-2-(meth)acryloyloxyadamantane, 2-isopropyl-2-(meth)acryloyloxyadamantane, 2-n-propyl-2-(meth)acryloyloxyadamantane, 2-n-butyl-2-(meth)acryloyloxyadamantane, 3-hydroxy-1-adamantyl(meth)acrylate, 1-methyl-1-(meth)acryloyloxycyclopentane, 1-ethyl-1-(meth)acryloyloxyadamantane, 1-iso ...isopropyl-2-(meth)acryloyloxyadamantane, 2-n-butyl-2-(meth)acryloyloxyadamantane, 3-hydroxy-1-adamantyl(meth)acrylate, 1-methyl-1-(meth)acryloyloxyadamantane, 1-ethyl-1-(meth)acryloyloxyadamantane, 1-isopropyl-2-(meth)acryloyloxyadamantane, 2-isopropyl-2-(meth)acryloyloxyadamantane, 2-isopropyl-2-(meth)acryloyloxyadamantane, 2-isopropyl-2-(meth)acryloyloxyadamantane, 2-isopropyl-2-(meth)acryloyloxy Examples of such monomers include acrylic oxycyclopentane, 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, and 2-ethyl-2-(meth)acryloyloxynorbornane. Commercially available products of these monomers can also be used.

[0201] Examples of structural units other than those represented by formulas (C1) and (C2) include structural units derived from monomers such as γ-butyrolactone (meth)acrylate, 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, 3,5-diiodo-4-hydroxystyrene, and maleic anhydride. Commercially available products of these monomers can also be used.

[0202] The iodine-containing (meth)acrylate (co)polymer represented by formula (5) obtained using the iodine-containing (meth)acrylate compound represented by formula (2) as a structural unit, the iodine-containing (meth)acrylate (co)polymer represented by formula (6) obtained using the iodine-containing (meth)acrylate compound represented by formula (3) as a structural unit, and the iodine-containing (meth)acrylate (co)polymer represented by formula (6') obtained using the iodine-containing (meth)acrylate compound represented by formula (3') as a structural unit can also be obtained by a similar method. The (co)polymer represented by formula (5), the (co)polymer represented by formula (6), and the (co)polymer represented by formula (6') are preferred for improving the performance of film-forming materials for lithography.

[0203] [ka]

[0204] In formula (5), R 1 , n 2 , and A are as defined in the above formula (1), and the symbol * is as defined in the above formula (4).

[0205] [ka]

[0206] In formula (6), R 1 , n 2 , and B are as defined in the above formula (3), and the symbol * is as defined in the above formula (4).

[0207] B contains at least one acyl group. The acyl group is as described above. Among them, an ethanoyl group (acetyl group) and a benzoyl group are preferred, and an ethanoyl group (acetyl group) is more preferred.

[0208] It is preferable that B contains at least one acyl group from the viewpoint of enhancing the stability of the (co)polymer. It is also preferable from the viewpoint of enhancing the productivity of the (co)polymer. When an acyl group is contained as a substituent in the compound that forms the skeleton of B, the stability of the compound and the (co)polymer is enhanced, and a resin into which the compound and the (co)polymer have been introduced is favorably dissolved in an organic solvent, resulting in superior storage stability. Therefore, the number of acyl groups in the compound that forms the skeleton of B is preferably 1 to 8, more preferably 1 to 5, even more preferably 1 to 3, and even more preferably 1.

[0209] In practical embodiments, the (co)polymer can be used by hydrolyzing some or all of the acyl groups contained in B to form hydroxy groups. The presence of hydroxy groups makes it possible to obtain a (co)polymer that has excellent alkaline developability, reduced film defects, and good sensitivity. The (co)polymer may contain, in addition to the structural unit represented by formula (6), a structural unit having a hydroxy group obtained by hydrolyzing some or all of the acyl groups contained in B in formula (6).

[0210] In formula (6), B is preferably an aromatic group having 5 to 30 carbon atoms which may have a substituent, and more preferably benzene which may have a substituent, in order to achieve reduction in film defects, sensitivity, and etching resistance at the same time. The aromatic group is as described above.

[0211] [ka]

[0212] In formula (6'), R 1 , n 2 and B' are as defined in the above formula (3'), and the symbol * is as defined in the above formula (4).

[0213] B' contains at least one acyl group. The acyl group is as described above. Among them, an ethanoyl group (acetyl group) and a benzoyl group are preferred, and an ethanoyl group (acetyl group) is more preferred.

[0214] It is preferable that B' contains at least one acyl group from the viewpoint of enhancing the stability of the (co)polymer. It is also preferable from the viewpoint of enhancing the productivity of the (co)polymer. When an acyl group is contained as a substituent in the compound that forms the skeleton of B', the stability of the compound and the (co)polymer is enhanced, and a resin incorporating the compound and the (co)polymer is well dissolved in an organic solvent and has excellent storage stability. Therefore, the number of acyl groups in the compound that forms the skeleton of B' is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and even more preferably 1.

[0215] In practical embodiments, the (co)polymer can be used by hydrolyzing some or all of the acyl groups contained in B' to form hydroxy groups. The presence of hydroxy groups makes it possible to obtain a (co)polymer that has superior alkaline developability, reduced film defects, and high sensitivity. The (co)polymer may contain, in addition to the structural unit represented by formula (6'), a structural unit having a hydroxy group obtained by hydrolyzing some or all of the acyl groups contained in B' in formula (6').

[0216] In formula (6'), B' is preferably an alicyclic ring having 5 to 30 carbon atoms which may have a substituent, more preferably an alicyclic hydrocarbon having 5 to 30 carbon atoms which may have a substituent, and even more preferably an adamantane which may have a substituent, in order to achieve a reduction in film defects, compound stability, sensitivity, and etching resistance at the same time. Examples of the alicyclic ring and alicyclic hydrocarbon are as described above.

[0217] <Method for producing iodine-containing (meth)acrylate (co)polymer> Next, a method for producing the (co)polymer of this embodiment by polymerization reaction will be described. The polymerization reaction is carried out by dissolving the monomers that form the structural units in a solvent, adding a catalyst, and heating or cooling the resulting mixture. The reaction conditions can be set arbitrarily by adjusting the type of initiator, the initiation method (e.g., heat or light), the temperature, pressure, concentration, solvent, and additives. The (co)polymer can be produced by known methods, such as radical polymerization using a radical generator (e.g., azoisobutyronitrile and peroxide), or ionic polymerization using a catalyst (e.g., alkyllithium and Grignard reagent).

[0218] As the solvent used in the polymerization reaction, commercially available products that are generally available can be used. As such a solvent, various solvents such as alcohols, ethers, hydrocarbons, and halogenated solvents can be appropriately used as long as they do not inhibit the reaction. The solvent can be used alone or in combination with multiple solvents as long as they do not inhibit the reaction. Examples of the solvent include the solvents described in this specification.

[0219] The (co)polymer obtained by the polymerization reaction can be purified by a known method. Specifically, the purification can be performed by a combination of ultrafiltration, crystallization, microfiltration, acid washing, washing with water having an electrical conductivity of 10 mS / m or less, and extraction. By such a purification method, a (co)polymer of desired high purity can be obtained.

[0220] Furthermore, a purification method for removing metal impurities, such as metal ions and metal oxides, may be added to the obtained (co)polymer. For details of the purification method, please refer to the methods described above and in the Examples and other sections of this specification. The content of various metals (e.g., Na, K, Ca, Mg, Fe, Cu, Ni, Sn, Ag, Mo, Mn, Zn, Co, Al, Pb, Cr, and Ti) contained in the obtained (co)polymer is typically 10 ppb or less, preferably 5 ppb or less, and more preferably 1 ppb or less.

[0221] [Composition containing iodine-containing (meth)acrylate compound and / or iodine-containing (meth)acrylate (co)polymer] The composition of this embodiment (also simply referred to as "composition") contains the iodine-containing (meth)acrylate compound of this embodiment and / or the iodine-containing (meth)acrylate (co)polymer of this embodiment. The composition is suitable for lithography techniques. The composition can be used for forming a film for lithography, for example, for forming a resist film (i.e., a "resist composition"). The 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"), and an underlayer film (i.e., a "composition for forming an underlayer film"), etc. The composition of this embodiment can form a film with high sensitivity and can impart a good resist pattern shape with high resolution.

[0222] The composition can also be used as a composition for forming optical components using lithography technology. Optical components are used in film and sheet form. Examples of such optical components include 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 devices, 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 devices that require a high refractive index.

[0223] The composition may contain other components such as a base material, a solvent, an acid generator, an acid diffusion controller, and a base generator, as needed. These components may be used alone or in combination of two or more, as needed. Each component will be described below.

[0224] <Base material> The composition may include a substrate. In this embodiment, the term "substrate" refers to a compound (including a resin) other than the iodine-containing (meth)acrylate compound of this embodiment and the iodine-containing (meth)acrylate (co)polymer of this embodiment, which 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), and electron beam (EB) lithography (e.g., a substrate for lithography or a substrate for resist). These materials are not particularly limited as long as they are substrates, and can be used as substrates in this embodiment. Examples of substrates include phenol novolac resins, cresol novolac resins, hydroxystyrene resins, (meth)acrylic resins, hydroxystyrene-(meth)acrylic copolymers, cycloolefin-maleic anhydride copolymers, cycloolefins, vinyl ether-maleic anhydride copolymers; inorganic resist materials containing metal elements such as titanium, tin, hafnium, and zirconium; and derivatives thereof. Among these, phenol novolac resin, cresol novolac resin, hydroxystyrene resin, (meth)acrylic resin, hydroxystyrene-(meth)acrylic copolymer, inorganic resist material containing metal elements such as titanium, tin, hafnium, and zirconium, and derivatives thereof are preferred because they allow for finer resist patterns to be obtained. These substrates can be used singly or in combination of two or more.

[0225] Examples of the derivatives include those into which a dissociable group has been introduced and those into which a crosslinkable group has been introduced. The derivatives 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, or the like.

[0226] 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. Examples of the alkali-soluble group include a phenolic hydroxy group, a carboxyl group, a sulfonic acid group, and a hexafluoroisopropanol group. The phenolic hydroxy group and the carboxyl group are preferred, and the phenolic hydroxy group is more preferred.

[0227] The term "crosslinkable group" refers to a group that crosslinks in the presence or absence of a catalyst. Examples of the crosslinkable group 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 hydroxy group, a group having a urethane(meth)acryloyl group, a group having a glycidyl group, and a group having a vinylphenylmethyl group.

[0228] <Solvent> The composition may include a solvent. Any known solvent can be used as appropriate, as long as it can dissolve at least the iodine-containing (meth)acrylate compound of the present embodiment and / or the iodine-containing (meth)acrylate (co)polymer (B) of the present embodiment.Specific examples of the solvent 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; lactate esters such as methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, and n-amyl lactate; and methyl acetate. aliphatic carboxylic acid esters such as ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate, and ethyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl 3-methoxy-3-methylpropionate, butyl 3-methoxy-3-methylbutyrate, Examples of suitable esters include other esters such as 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), anisole, and cyclohexanone (CHN); amides such as N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpyrrolidone; lactones such as γ-lactone; and furans such as tetrahydrofuran.The solvent used in this embodiment is preferably a safe solvent, more preferably at least one selected from PGMEA, PGME, CHN, CPN, 2-heptanone, anisole, n-butyl acetate, and ethyl lactate, and even more preferably at least one selected from PGMEA, PGME, CHN, CPN, and ethyl lactate. These solvents may be used alone or in combination of two or more.

[0229] In this embodiment, the amounts of the solid component and the solvent are not particularly limited, but are preferably 1 to 80 mass% solid component and 20 to 99 mass% solvent relative to the total amount (100 mass%) of the solid component and the solvent, more preferably 1 to 50 mass% solid component and 50 to 99 mass% solvent, even more preferably 2 to 40 mass% solid component and 60 to 98 mass% solvent, and even more preferably 2 to 10 mass% solid component and 90 to 98 mass% solvent.

[0230] <Acid generator> The composition may also include an acid generator. The composition preferably contains one or more acid generators that generate acid directly or indirectly upon irradiation with any radiation selected from visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), X-ray, and ion beam. Examples of the acid generators that can be used include those described in International Publication No. 2013 / 024778. The acid generators may be used singly or in combination of two or more.

[0231] The amount of acid generator used 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 (100% by mass). Using the acid generator within the above range tends to result in a pattern profile with high sensitivity and low edge roughness. In this 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 rays such as g-rays and i-rays enables finer processing, and using an electron beam, extreme ultraviolet rays, X-rays, or ion beam as a high-energy beam enables even finer processing. Examples of the acid generator include compounds disclosed in International Publication No. 2017 / 033943. Acid generators having an aromatic ring are preferred, acid generators having a sulfonate ion with an aryl group are more preferred, and diphenyltrimethylphenylsulfonium p-toluenesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, and triphenylsulfonium nonafluoromethanesulfonate are even more preferred. The use of an acid generator can reduce line edge roughness.

[0232] <Base generator> The composition may include a base generator. The case where the base generator is a photobase generator will be described. In the present embodiment, the photobase generator refers to a substance that generates a base upon exposure to light, and 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.

[0233] Known photobase generators can be used, and examples thereof include carbamate derivatives, amide derivatives, imide derivatives, α-cobalt complexes, imidazole derivatives, cinnamic acid amide derivatives, and oxime derivatives.

[0234] The basic substance generated from the photobase generator is not particularly limited, but examples thereof include compounds having an amino group, such as monoamines, polyamines (e.g., diamines), and amidines. As the basic substance to be generated, a compound having an amino group with a higher basicity (a conjugate acid with a higher pKa value) is preferred from the viewpoints of sensitivity and resolution. 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, oxime structures as disclosed in JP 2007-249013 A and JP 2008-003581 A, base generators having a carbamoyloxime structure, and compounds described in JP 2010-243773 A. Other known base generator structures can also be used.

[0235] 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.

[0236] <Acid diffusion control agent> The composition may also include an acid diffusion inhibitor. In this embodiment, the composition may contain an acid diffusion controller, which has the effect of controlling the diffusion of the acid generated from the acid generator upon irradiation in the resist film and preventing undesired chemical reactions in unexposed areas. The use of an acid diffusion controller tends to improve the storage stability of the composition. Furthermore, the use of an acid diffusion controller can improve the resolution of a film formed using the composition of this embodiment, and can suppress changes in the line width of the resist pattern due to variations in the exposure time before and after radiation exposure, thereby tending to provide excellent process stability. Examples of acid diffusion controllers include nitrogen-containing basic compounds such as tributylamine, basic sulfonium compounds, and radiation-decomposable basic compounds such as basic iodonium compounds.

[0237] As the acid diffusion controller, for example, those described in WO 2013 / 024778 can be used. The acid diffusion controller can be used alone or in combination of two or more.

[0238] The amount of the acid diffusion controller 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 (100% by mass). When the amount of the acid diffusion controller is within the above range, deterioration of resolution, pattern shape, dimensional fidelity, and the like tends to be prevented. Furthermore, even if the exposure time between electron beam irradiation and post-exposure heating is long, deterioration of the shape of the upper layer of the pattern can be suppressed. Furthermore, when the amount is 10% by mass or less, deterioration of sensitivity, developability of unexposed areas, and the like tends to be prevented. The use of an acid diffusion controller improves the storage stability of the composition, improves resolution, and suppresses changes in the line width of the resist pattern due to variations in the exposure time before and after radiation exposure, thereby tending to provide excellent process stability.

[0239] <Other ingredients> To the composition of the present embodiment, one or more of various additives such as a crosslinking agent, a dissolution promoter, a dissolution controller, a sensitizer, a surfactant, and an organic carboxylic acid, a phosphorus oxoacid, or a derivative thereof may be added as other components, as needed.

[0240] (Crosslinking agent) The composition may contain one or more crosslinking agents. The crosslinking agent refers to a compound capable of crosslinking at least one of the substrate, the iodine-containing (meth)acrylate compound, and the iodine-containing (meth)acrylate (co)polymer. The crosslinking agent is preferably an acid crosslinking agent capable of intramolecularly or intermolecularly crosslinking the substrate in the presence of an acid generated from an acid generator. Examples of such acid crosslinking agents include compounds having one or more groups capable of crosslinking the substrate (hereinafter referred to as "crosslinkable groups").

[0241] Examples of the crosslinkable group include: (i) hydroxyalkyl groups such as hydroxy (alkyl groups having 1 to 6 carbon atoms), alkoxy (alkyl groups having 1 to 6 carbon atoms), and acetoxy (alkyl groups having 1 to 6 carbon atoms), or groups derived therefrom; (ii) carbonyl groups such as formyl and carboxy (alkyl groups having 1 to 6 carbon atoms), or groups derived therefrom; (iii) dimethylaminomethyl group, diethylaminomethyl group, dimethylolaminomethyl group, diethylolaminomethyl group, (iv) glycidyl group-containing groups such as a glycidyl ether group, a glycidyl ester group, and a glycidylamino group; (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 a benzyloxymethyl group and a benzoyloxymethyl group; and (vi) polymerizable multiple bond-containing groups such as a vinyl group and an isopropenyl group. Examples of the crosslinkable group of the crosslinking agent include hydroxyalkyl groups and alkoxyalkyl groups, and more preferably an alkoxymethyl group.

[0242] As the crosslinking agent having a crosslinkable group, for example, the acid crosslinking agents described in WO 2013 / 024778 can be used. The crosslinking agents can be used alone or in combination of two or more.

[0243] The amount of the crosslinking agent added 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 (100% by mass) of the solid components.

[0244] (solubility enhancer) The dissolution accelerator 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 accelerator is preferably a low-molecular-weight accelerator, and examples thereof include low-molecular-weight phenolic compounds. Examples of low-molecular-weight phenolic compounds include bisphenols and tris(hydroxyphenyl)methane. These dissolution accelerators may be used alone or in combination of two or more.

[0245] 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 even more preferably 0% by mass, relative to the total mass of the solid components (100% by mass).

[0246] (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.

[0247] Examples of the dissolution controller include aromatic hydrocarbons such as phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenyl naphthyl ketone; sulfones such as methyl phenyl sulfone, diphenyl sulfone, and dinaphthyl sulfone. These dissolution controllers may be used alone or in combination of two or more.

[0248] 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 even more preferably 0% by mass, relative to the total mass of the solid components (100% by mass).

[0249] (sensitizer) The sensitizer is a component that absorbs the energy of irradiated radiation and transfers that energy to the acid generator, thereby increasing the amount of acid produced and improving the apparent sensitivity of the resist. Examples of such sensitizers include benzophenones, biacetyls, pyrenes, phenothiazines, and fluorenes. These sensitizers can be used alone or in combination of two or more.

[0250] The amount of the sensitizer to be added is adjusted as appropriate 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 even more preferably 0% by mass, relative to the total mass of the solid components (100% by mass).

[0251] (surfactant) The surfactant is a component that has the effect of improving the coatability and striation of the composition, 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, and can further enhance the effects of the composition. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, and higher fatty acid diesters of polyethylene glycol. These surfactants may be commercially available products, and examples thereof include the following trade names: F-TOP (registered trademark) (manufactured by Gemco), Megafac (registered trademark) (manufactured by Dainippon Ink and Chemicals, Inc.), Fluorad (manufactured by Sumitomo ThreeM Limited), Asahi Guard (registered trademark), Surflon (registered trademark) (all manufactured by Asahi Glass Co., Ltd.), Pepol (registered trademark) (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.). These surfactants may be used alone or in combination of two or more.

[0252] 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 even more preferably 0% by mass, relative to the total mass of the solid components (100% by mass).

[0253] (organic carboxylic acid or phosphorus oxoacid or its derivative) For the purpose of preventing sensitivity degradation or improving resist pattern shape and deposition stability, the composition may contain an organic carboxylic acid or a phosphorus oxo acid or a derivative thereof as an optional component. The organic carboxylic acid or phosphorus oxo acid or a derivative thereof may 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 or ester derivatives thereof, such as phosphoric acid, di-n-butyl phosphate, and diphenyl phosphate; phosphonic acid or ester derivatives thereof, such as phosphonic acid, dimethyl phosphonate, di-n-butyl phosphonate, phenylphosphonic acid, diphenyl phosphonate, and dibenzyl phosphonate; and phosphinic acid or ester derivatives thereof, such as phosphinic acid and phenylphosphinic acid. Among these, phosphonic acid is more preferred.

[0254] 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 even more preferably 0% by mass, based on the total mass of the solid components (100% by mass).

[0255] <Other additives> The composition of this embodiment may contain one or more additives other than the above 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. Further examples of other additives include antihalation agents, storage stabilizers, antifoaming agents, and shape modifiers. Specific examples include 4-hydroxy-4'-methylchalcone. These additives may be used alone or in combination of two or more.

[0256] In the composition of the present embodiment, the total amount of additives (optional components) can be 0 to 99 mass% relative to the total mass (100 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%.

[0257] [Method for forming resist pattern] The method for forming a resist pattern of this embodiment includes, in this order: a step of forming a film using the composition of this embodiment; a step of exposing the formed film to light; and a step of removing the exposed portion of the exposed film using a developer to form a pattern. To form a resist pattern from the composition of this embodiment, a solution of the composition is applied to a substrate, such as a silicon wafer, metal, plastic, glass, or ceramic, using a suitable coating method such as a spin coater, dip coater, or roller coater to form a resist film. This may be optionally pre-heated at a temperature of about 50°C to 200°C for a predetermined time (usually 15 to 600 seconds), and then exposed through a predetermined mask pattern. The thickness of the exposed coating is, for example, 0.01 to 20 μm, preferably about 0.05 to 10 μm, and more preferably about 0.07 to 2 μm. Light beams of various wavelengths, such as ultraviolet, far ultraviolet, electron beam, extreme ultraviolet, and X-ray, can be used for exposure. Light sources, such as far ultraviolet (e.g., F2 excimer laser (wavelength 157 nm), ArF excimer laser (wavelength 193 nm), and KrF excimer laser (wavelength 248 nm); extreme ultraviolet (wavelength 13 nm); X-ray; or electron beam, can be appropriately selected and used. The exposure conditions such as the exposure dose are appropriately selected depending on the compound, (co)polymer, and the formulation of the composition containing these, as well as the types of each additive.

[0258] In this 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 using 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.

[0259] Examples of alkaline developers include alkaline aqueous solutions prepared by dissolving alkaline compounds such as alkali metal hydroxides, aqueous ammonia, alkylamines, alkanolamines, heterocyclic amines, tetraalkylammonium hydroxides (e.g., tetramethylammonium hydroxide), choline, 1,8-diazabicyclo[5.4.0]-7-undecene, and 1,5-diazabicyclo[4.3.0]-5-nonene, usually in a concentration of 1 to 10% by weight, preferably 1 to 3% by weight. These alkaline developers may be used alone or in combination of two or more. A water-soluble organic solvent or surfactant may also be added to the alkaline aqueous developer.

[0260] In this embodiment, in order to stably form a highly accurate fine pattern, after exposure and PEB, a development process can be performed using a developer containing an organic solvent as a main component to form a resist pattern. Various organic solvents are widely used as the organic solvent for the developer. Examples of such solvents include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. These organic solvents may be used alone or in combination of two or more. The developer preferably contains a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, or an ether-based solvent.

[0261] Examples of ester solvents include methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, propyl acetate, isopropyl acetate, amyl acetate (pentyl acetate), isoamyl acetate (isopentyl acetate, 3-methylbutyl acetate), 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, isohexyl acetate, heptyl acetate, octyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane), ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and 2-methoxybutyl acetate. , 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methyl methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl hydroxyisobutyrate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate,Examples of the alkyl esters include butyl propionate, isobutyl propionate, pentyl propionate, hexyl propionate, heptyl propionate, butyl butanoate, isobutyl butanoate, pentyl butanoate, hexyl butanoate, isobutyl isobutanoate, propyl pentanoate, isopropyl pentanoate, butyl pentanoate, pentyl pentanoate, ethyl hexanoate, propyl hexanoate, butyl hexanoate, isobutyl hexanoate, methyl heptanoate, ethyl heptanoate, propyl heptanoate, cyclohexyl acetate, cycloheptyl acetate, 2-ethylhexyl acetate, cyclopentyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and propyl 3-methoxypropionate. Among these, butyl acetate, amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate, methyl hydroxyisobutyrate, and butyl butanoate are preferred, and butyl acetate, isoamyl acetate, and methyl hydroxyisobutyrate are more preferred.

[0262] Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, and γ-butyrolactone. Of these, 2-heptanone is preferred.

[0263] Examples of alcohol solvents include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-decanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and 3-methyl-1-butanol. methyl-3-pentanol, cyclopentanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-2-butanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclohexanol, 5-methyl-2-hexanol, 4-methyl-2-hexanol, 4,5-dimethyl-2-hexal, 6-methyl-2-heptanol Examples of suitable solvents include alcohols (monohydric alcohols) such as ethanol, 7-methyl-2-octanol, 8-methyl-2-nonal, 9-methyl-2-decanol, and 3-methoxy-1-butanol; glycol solvents such as ethylene glycol, diethylene glycol, and triethylene glycol; and glycol ether solvents containing a hydroxy group, such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether (PGME; also known as 1-methoxy-2-propanol), diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethylbutanol, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and propylene glycol monophenyl ether. Among these, glycol ether solvents are preferably used.

[0264] Examples of ether solvents include, in addition to the above-mentioned glycol ether solvents containing a hydroxy group, glycol ether solvents not containing a hydroxy group, such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether; aromatic ether solvents such as anisole and phenetole; dioxane, tetrahydrofuran, tetrahydropyran, perfluoro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, 1,4-dioxane, and isopropyl ether. Among these, glycol ether solvents not containing a hydroxy group and aromatic ether solvents such as anisole are preferred.

[0265] Examples of amide solvents include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoric triamide, and 1,3-dimethyl-2-imidazolidinone.

[0266] Examples of hydrocarbon solvents include aliphatic hydrocarbon solvents such as pentane, hexane, octane, nonane, decane, dodecane, undecane, hexadecane, 2,2,4-trimethylpentane, 2,2,3-trimethylhexane, perfluorohexane, and perfluoroheptane; and aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, propylbenzene, 1-methylpropylbenzene, 2-methylpropylbenzene, dimethylbenzene, diethylbenzene, ethylmethylbenzene, trimethylbenzene, ethyldimethylbenzene, and dipropylbenzene. In addition, unsaturated hydrocarbon solvents can also be used as the hydrocarbon solvent. Examples of such solvents include unsaturated hydrocarbon solvents such as octene, nonene, decene, undecene, dodecene, and hexadecene. The number of double bonds or triple bonds in the unsaturated hydrocarbon solvent is not particularly limited, and they may be located at any position in the hydrocarbon chain. In addition, when the unsaturated hydrocarbon solvent has a double bond, cis and trans isomers may be present together. The aliphatic hydrocarbon solvent may be a mixture of compounds having the same carbon number but different structures. For example, when decane is used as the aliphatic hydrocarbon solvent, the aliphatic hydrocarbon solvent may contain compounds having the same carbon number but different structures, such as 2-methylnonane, 2,2-dimethyloctane, 4-ethyloctane, and isooctane. Furthermore, the compound having the same carbon number but different structure may contain only one type, or may contain multiple types as described above.

[0267] A known basic compound, a known water-soluble organic solvent, and a known surfactant may also be added to the developer comprising the organic solvent.

[0268] [Method for producing a (co)polymer having a hydroxy group represented by formula (Y)]

[0269] In a practical embodiment, the (co)polymer of this embodiment can be converted into a (co)polymer having hydroxy groups represented by formula (Y) by hydrolyzing some or all of the acyl groups. Such a (co)polymer can be obtained by hydrolyzing the acyl groups in the iodine-containing (meth)acrylate (co)polymer of this embodiment. Because the compound is highly stable, (co)polymers containing the compound as a structural unit are also highly stable. By using such a (co)polymer, it is possible to efficiently and stably produce (co)polymers having hydroxy groups that are useful for resist materials.

[0270] [ka]

[0271] In formula (Y), R 1 , R 2 , A', n 1 , and n 2 is as described above, and the symbol * represents the bonding point to the adjacent structural unit.

[0272] The hydrolysis can be carried out by a known method, for example, hydrolysis with an acid, hydrolysis with a base, and the like. Suitable acid catalysts include, for example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; organic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, 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. Suitable base catalysts include, for example, amine-containing catalysts such as pyridine and ethylenediamine, and non-amine basic catalysts such as metal salts. Preferred metal salts include potassium salts and acetate salts. Such catalysts include potassium acetate, potassium carbonate, potassium hydroxide, sodium acetate, sodium carbonate, sodium hydroxide, and magnesium oxide. Non-amine base catalysts are commercially available from, for example, EM Sciences and Aldrich. These catalysts may be used alone or in combination of two or more. 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.

[0273] This reaction may be carried out in an organic solvent. A wide variety of organic solvents can be used, including polar aprotic organic solvents and protic polar organic solvents. A single protic polar solvent and 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, for example, 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 hexamethylphosphorous triamide; and dimethyl sulfoxide. Among these, tetrahydrofuran and dimethyl sulfoxide are preferred. Suitable protic polar solvents include, for example, 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.

[0274] The reaction is carried out by adding the iodine-containing (meth)acrylate (co)polymer, a catalyst, and optionally an organic solvent to a reactor to form a reaction mixture. Any suitable reactor can be used for the reaction. The reaction can be carried out by a known method such as a batch method, a semi-batch method, or a continuous method.

[0275] The reaction temperature is not particularly limited and varies depending on the concentration of the substrate, the stability of the formed product, the selection of the catalyst, and the desired yield. Generally, a temperature of 0 to 200°C is suitable, and from the viewpoint of yield, a temperature of 0 to 100°C is preferable.

[0276] The reaction pressure varies depending on the concentration of the substrate, the stability of the formed product, the catalyst selection, and the desired yield, and is not particularly limited. The pressure can be adjusted using an inert gas such as nitrogen or using an air pump. Conventional pressure reactors, including shaker vessels, rocker vessels, and stirred autoclaves, are used for reactions at high pressure.

[0277] The reaction time is not particularly limited and varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. Usually, most reactions are carried out in less than 12 hours, and the reaction time is generally 15 to 600 minutes.

[0278] Isolation and purification can be carried out after the completion of the reaction using appropriate conventional methods. For example, the reaction mixture is poured onto ice water and extracted into an organic solvent such as ethyl acetate, butyl acetate, or diethyl ether. The product is then 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, and activated carbon, as well as combinations thereof. Furthermore, the obtained high-purity monomer can be subjected to additional purification methods for removing metal impurities, such as metal ions and metal oxides. For details of the purification method, please refer to the methods described above and in the Examples herein. The obtained high-purity monomer typically has a content of various metals (e.g., Na, K, Ca, Mg, Fe, Cu, Ni, Sn, Ag, Mo, Mn, Zn, Co, Al, Pb, Cr, and Ti) contained in the compound of 10 ppb or less, preferably 5 ppb or less, and more preferably 1 ppb or less. [Example]

[0279] Hereinafter, the present embodiment will be described in more detail with reference to examples and comparative examples, but the present embodiment is not limited to these examples in any way.

[0280] [Measurement method] (1) Compound structure The structure of the compound was determined using a Bruker Advance 600 II spectrometer under the following conditions: 1 This was confirmed by H-NMR measurement. Frequency: 400MHz Solvent: CDCl3 or d6-DMSO Internal standard: TMS Measurement temperature: 23℃

[0281] (2) Measurement of the content of various metals (impurities) contained in the precipitate The contents of various metals (Na, K, Ca, Mg, Fe, Cu, Ni, Sn, Ag, Mo, Mn, Zn, Co, Al, Pb, Cr, and Ti) contained in the precipitates were measured using ICP-MS under the following measurement conditions. Apparatus: Triple quadrupole ICP-MS (inductively coupled plasma mass spectrometer) (Agilent Technologies, Inc., 8900 ICP-QQQ (trade name))

[0282] (Synthesis Example 1-1) Synthesis of MAC-2H35I and Ac-MAC-2H35I 90 g (0.24 mol) of 3,5-diiodosalicylaldehyde was dissolved in 900 ml of methanol, and 22.8 g (0.60 mol) of NaBH4 was added at temperatures below 10°C. The mixture was then stirred for 3 hours under ice cooling, followed by 16 hours of stirring at 25°C. The reaction was then carried out, and the methanol was removed by distillation under reduced pressure. Water and ethyl acetate were added to the concentrate, and the organic phase was extracted. This organic phase was dried over magnesium sulfate, and the solvent was removed by distillation under reduced pressure to obtain a crude product of 2-hydroxy-3,5-diiodobenzyl alcohol. The resulting crude product of 2-hydroxy-3,5-diiodobenzyl alcohol was purified by column chromatography to obtain 82.5 g (91% yield) of the 2-hydroxy-3,5-diiodobenzyl alcohol shown below.

[0283] [ka]

[0284] 10 g (27 mmol) of the 2-hydroxy-3,5-diiodobenzyl alcohol obtained above was dissolved in 100 mL of dichloromethane, and 3.1 g (39 mmol) of pyridine was added under ice cooling, followed by dropwise addition of 4.1 g (27 mmol) of methacrylic anhydride. The mixture was then stirred for 4 hours under ice cooling and then for 18 hours at room temperature. After completion of the reaction, water was added to the reaction solution, which was then washed with aqueous sodium bicarbonate. The organic phase was dried over magnesium sulfate, concentrated, and purified by column chromatography to obtain 9 g (88% yield) of the target product MAC-2H35I shown below.

[0285] When the obtained compound (MAC-2H35I) was subjected to NMR measurement under the above measurement conditions, the following peaks were detected, and it was confirmed that the compound had the chemical structure of the following formula (MAC-2H35I). δ(ppm)(CDCl3):7.2~8.0(2H, Ph), 7.6(1H, -OH), 6.2(1H, =CH2), 5.7(1H, =CH2), 5.1(2H, -CH2-), 2.0(3H, -CH3)

[0286] [ka]

[0287] 9 g (20 mmol) of MAC-2H35I obtained above was dissolved in 100 mL of dimethyl sulfoxide, and 2 eq. of acetic anhydride and 1 eq. of sulfuric acid were added. The mixture was then heated to 80°C and stirred for 3 hours to react. After the reaction was completed, water was added to the reaction solution, which was then washed with an aqueous sodium bicarbonate solution. Magnesium sulfate was added to the organic phase, which was then dried, concentrated, and purified by column chromatography to obtain 6 g (yield 60%) of the target product Ac-MAC-2H35I shown below.

[0288] When the obtained compound (Ac-MAC-2H35I) was subjected to NMR measurement under the above measurement conditions, the following peaks were detected, confirming that it had the chemical structure of the following formula (Ac-MAC-2H35I). δ(ppm)(CDCl3):7.2~8.0(2H, Ph), 6.2(1H, =CH2), 5.7(1H, =CH2), 5.1(2H, -CH2-), 2.2(3H, -CH3), 2.0(3H, -CH3)

[0289] [ka]

[0290] (Synthesis Example 2-1) Synthesis of MAC-4H35I and Ac-MAC-4H35I 128 g (0.78 mol) of calcium chloride and 491.3 g (2.4 mol) of NaBH4 were dissolved in 2.8 L of ethanol, and 410 g (1.1 mol) of 4-hydroxy-3,5-diiodobenzaldehyde was added to the solution under ice cooling. After stirring at 25°C for 18 hours, 10 L of water was added and the pH was adjusted to 2.5 with hydrochloric acid. The precipitate was filtered, washed with water, and dried to obtain 401 g (97% yield) of 4-hydroxy-3,5-diiodobenzyl alcohol shown below.

[0291] [ka]

[0292] 400 g (1.06 mol) of 4-hydroxy-3,5-diiodobenzyl alcohol obtained above was dissolved in 2.8 L of toluene, and 916 g (10.6 mol) of methacrylic anhydride, 20 g (0.105 mol) of paratoluenesulfonic acid monohydrate, and 13 mg (0.01 mmol) of 4-methoxyphenol were added, followed by stirring for 2 hours under reflux at 110° C. After the reaction, 4 L of water was added, the organic layer was dried, and the mixture was recrystallized twice with hexane to obtain 158 g (33% yield) of the target product MAC-4H35I shown below.

[0293] When the obtained compound (MAC-4H35I) was subjected to NMR measurement under the above measurement conditions, the following peaks were detected, and it was confirmed that the compound had the chemical structure of the following formula (MAC-4H35I). δ(ppm)(CDCl3): 9.7(1H, -OH), 7.8(2H, Ph), 6.7(1H, =CH2), 5.0(1H, =CH2), 5.0(2H, -CH2-), 1.9(3H, -CH3)

[0294] [ka]

[0295] 50.0 g of the obtained compound (MAC-4H35I) was dissolved in 100 mL of toluene. Then, a separation treatment using 100 mL of 0.1 N aqueous sulfuric acid was performed twice, followed by a separation treatment using 100 mL of 0.1 mmol / L aqueous oxalic acid. This was followed by multiple washing treatments using 100 mL of ultrapure water until the pH of the aqueous layer recovered after the separation treatment reached 4 or higher. The resulting toluene solution was concentrated to obtain a toluene solution with a solids concentration of 50%. 1 L of hexane was added to the solution, yielding 41.1 g of precipitate (MAC-4H35Ip). The obtained precipitate was subjected to NMR measurement under the above measurement conditions, and it was confirmed that the precipitate was identical to the compound (MAC-4H35I). Furthermore, when the metal (impurity) content of the obtained precipitate was measured under the above measurement conditions, it was confirmed that the content of each of the metals Na, K, Ca, Mg, Fe, Cu, Ni, Sn, Ag, Mo, Mn, Zn, Co, Al, Pb, Cr, and Ti was 1 ppb or less.

[0296] 9 g (20 mmol) of MAC-4H35I obtained above was dissolved in 100 mL of dimethyl sulfoxide, and 2 eq. of acetic anhydride and 1 eq. of sulfuric acid were added. The mixture was then heated to 80°C and stirred for 3 hours to react. After the reaction was completed, water was added to the reaction solution, which was then washed with an aqueous sodium bicarbonate solution. The organic phase was dried over magnesium sulfate, concentrated, and purified by column chromatography to obtain 6 g (yield 60%) of the target product Ac-MAC-4H35I shown below.

[0297] When the obtained compound (Ac-MAC-4H35I) was subjected to NMR measurement under the above measurement conditions, the following peaks were detected, confirming that it had the chemical structure of the following formula (Ac-MAC-4H35I). 7.8(2H, Ph), 6.7(1H, =CH2), 5.0(1H, =CH2), 5.0(2H, -CH2-), 2.0(3H, -CH3), 1.9(3H, -CH3)

[0298] [ka]

[0299] 50.0 g of the obtained compound (Ac-MAC-4H35I) was dissolved in 100 mL of toluene. Then, a separation treatment using 100 mL of 0.1 N aqueous sulfuric acid was performed twice, followed by a separation treatment using 100 mL of 0.1 mmol / L aqueous oxalic acid. This was followed by multiple washing treatments using 100 mL of ultrapure water until the pH of the aqueous layer recovered after the separation treatment reached 4 or higher. The resulting toluene solution was concentrated to obtain a toluene solution with a solids concentration of 50%. 1 L of hexane was added to the solution, yielding 38.4 g of precipitate (Ac-MAC-4H35Ip). The obtained precipitate was subjected to NMR measurement under the above measurement conditions, and it was confirmed that the precipitate was identical to the compound (Ac-MAC-4H35I). Furthermore, when the metal (impurity) content of the obtained precipitate was measured under the above measurement conditions, it was confirmed that the content of each of the metals Na, K, Ca, Mg, Fe, Cu, Ni, Sn, Ag, Mo, Mn, Zn, Co, Al, Pb, Cr, and Ti was 1 ppb or less.

[0300] (Synthesis Example 3-1) Synthesis of ACLAC-2H35I and Ac-ACLAC-2H35I

[0301] In a 300 mL recovery flask equipped with a Dean-Stark tube and reflux condenser, 10.2 g (27 mmol) of 2-hydroxy-3,5-diiodobenzyl alcohol obtained in Synthesis Example 1-1 was dissolved in 100 mL of toluene. 0.05 g (0.3 mmol) of p-toluenesulfonic acid was added under ice cooling, and 2.9 g (27 mmol) of acrylic acid chloride was added dropwise. The mixture was then stirred under reflux for 1 hour to allow the reaction to proceed. After completion of the reaction, water was added to the reaction solution, which was then washed with aqueous sodium bicarbonate. The organic phase was dried over magnesium sulfate, concentrated, and purified by column chromatography to obtain 9.3 g (73% yield) of the target product, ACLAC-2H35I, shown below.

[0302] When the obtained compound (ACLAC-2H35I) was subjected to NMR measurement under the above measurement conditions, the following peaks were detected, and it was confirmed that the compound had the chemical structure of the following formula (ACLAC-2H35I). δ(ppm)(CDCl3):7.2~8.0(2H, Ph), 9.6(1H, -OH), 6.0(1H, =CH2), 6.6(1H, =CH2), 5.1(2H, -CH2-)

[0303] [ka]

[0304] 9.3 g (20 mmol) of the ACLAC-2H35I obtained above was dissolved in 100 mL of dimethyl sulfoxide, and 2 eq. of acetic anhydride and 1 eq. of sulfuric acid were added. The temperature was then raised to 80°C, and the mixture was stirred for 3 hours to react. After the reaction was completed, water was added to the reaction solution, which was then washed with an aqueous sodium bicarbonate solution. Magnesium sulfate was added to the organic phase, which was then dried, concentrated, and purified by column chromatography to obtain 5.1 g (yield 50%) of the target product Ac-ACLAC-2H35I shown below.

[0305] When the obtained compound (Ac-ACLAC-2H35I) was subjected to NMR measurement under the above measurement conditions, the following peaks were detected, and it was confirmed that the compound had the chemical structure of the following formula (Ac-ACLAC-2H35I). δ(ppm)(CDCl3):7.2~8.0(2H, Ph), 6.0(1H, =CH2), 6.6(1H, =CH2), 5.1(2H, -CH2-), 2.0(3H, -CH3)

[0306] [ka]

[0307] (Synthesis Example 4-1) Synthesis of MAC-ADIOH and Ac-MAC-ADIOH 2.3 g (12.5 mmol) of 1,3,5-adamantanetriol (manufactured by Mitsubishi Gas Chemical Company) was dissolved in 100 mL of toluene, and 28.1 g (125 mmol) of 57% aqueous hydrogen iodide solution was added, followed by stirring and reaction for 13 hours at 80° C. After the reaction, water was added and the mixture was washed with sodium bicarbonate. The organic layer was concentrated and then separated and purified by column chromatography to obtain 0.9 g of 3-iodo-1,5-dihydroxyadamantane represented by the following formula.

[0308] [ka]

[0309] 4.04 g (10 mmol) of 5-iodo-1,3-dihydroxyadamantane was dissolved in chloroform, and 0.96 g (12 mmol) of pyridine was added under ice cooling, followed by dropwise addition of 1.25 g (12 mmol) of methacrylic acid chloride. The mixture was then stirred for 1 hour under ice cooling and then for 3 hours at room temperature to allow the reaction to proceed. After completion of the reaction, water was added to the reaction solution, which was then washed with a saturated aqueous solution of sodium bicarbonate. The organic phase was then dried over sodium sulfate, concentrated, and purified by column chromatography to obtain 3.5 g of the target product, MAC-ADIOH, shown below.

[0310] When the obtained compound (MAC-ADIOH) was subjected to NMR measurement under the above measurement conditions, the following peaks were detected, and it was confirmed that the compound had the chemical structure of the following formula (MAC-ADIOH). δ(ppm)(d-DMSO): 6.4~6.5(2H, =CH2), 1.5~3.9(14H, Ad-H, -C(CH3)=C), 4.5(1H, -OH)

[0311] [ka]

[0312] 50.0 g of the obtained compound (MAC-ADIOH) was dissolved in 100 mL of methyl ethyl ketone. Then, a separation treatment using 100 mL of 0.1 N aqueous sulfuric acid was performed twice, followed by a separation treatment using 100 mL of 0.1 mmol / L aqueous oxalic acid. This was followed by multiple washing treatments using 100 mL of ultrapure water until the pH of the aqueous layer recovered after the separation treatment reached 4 or higher. The resulting methyl ethyl ketone solution was concentrated to obtain a methyl ethyl ketone solution with a solids concentration of 50%. 1 L of hexane was added to the solution, yielding 41.1 g of precipitate (MAC-ADIOHp). The obtained precipitate was subjected to NMR measurement under the above measurement conditions, and it was confirmed that the precipitate was identical to the compound (MAC-ADIOH). Furthermore, when the metal (impurity) content of the obtained precipitate was measured under the above measurement conditions, it was confirmed that the content of each of the metals Na, K, Ca, Mg, Fe, Cu, Ni, Sn, Ag, Mo, Mn, Zn, Co, Al, Pb, Cr, and Ti was 1 ppb or less.

[0313] 3.5 g (10 mmol) of the MAC-ADIOH obtained above was dissolved in 100 mL of dimethyl sulfoxide, and 2 eq. of acetic anhydride and 1 eq. of sulfuric acid were added. The mixture was then heated to 80°C and stirred for 3 hours to react. After the reaction was completed, water was added to the reaction solution, which was then washed with an aqueous sodium bicarbonate solution. The organic phase was dried over magnesium sulfate, concentrated, and purified by column chromatography to obtain 2.4 g (yield 60%) of the target product Ac-MAC-ADIOH shown below.

[0314] When the obtained compound (Ac-MAC-ADIOH) was subjected to NMR measurement under the above measurement conditions, the following peaks were detected, and it was confirmed that the compound had the chemical structure of the following formula (Ac-MAC-ADIOH). δ(ppm)(CDCl3):6.4~6.5(2H,=CH2), 1.5~3.9(14H, Ad-H, -C(CH3)=C), 2.0(3H, -CH3)

[0315] [ka]

[0316] 50.0 g of the obtained compound (Ac-MAC-ADIOH) was dissolved in 100 mL of methyl ethyl ketone. Then, a separation treatment using 100 mL of 0.1 N aqueous sulfuric acid was performed twice, followed by a separation treatment using 100 mL of 0.1 mmol / L aqueous oxalic acid. This was followed by multiple washing treatments using 100 mL of ultrapure water until the pH of the aqueous layer recovered after separation reached 4 or higher. The resulting methyl ethyl ketone solution was concentrated to obtain a methyl ethyl ketone solution with a solids concentration of 50%. 1 L of hexane was added to the solution, yielding 41.1 g of precipitate (Ac-MAC-ADIOHp). The obtained precipitate was subjected to NMR measurement under the above measurement conditions, and it was confirmed that the precipitate was identical to the compound (Ac-MAC-ADIOH). Furthermore, when the metal (impurity) content of the obtained precipitate was measured under the above measurement conditions, it was confirmed that the content of each of the metals Na, K, Ca, Mg, Fe, Cu, Ni, Sn, Ag, Mo, Mn, Zn, Co, Al, Pb, Cr, and Ti was 1 ppb or less.

[0317] (Synthesis Example 5-1) Synthesis of MAC-ADI4H4M 2.3 g (12.5 mmol) of 4-methyl-adamantane-1,4-diol was dissolved in 100 mL of toluene, and 11.2 g (50 mmol) of 57% aqueous hydrogen iodide solution was added, followed by stirring and reaction for 8 hours at 80° C. After the reaction, water was added and the mixture was washed with sodium bicarbonate. The organic layer was concentrated and then separated and purified by column chromatography to obtain 1.1 g of 1-iodo-4-methyl-4-hydroxyadamantane represented by the following formula.

[0318] [ka]

[0319] 2.92 g (10 mmol) of 1-iodo-4-methyl-4-hydroxyadamantane was dissolved in chloroform, and 0.96 g (12 mmol) of pyridine was added under ice cooling, followed by dropwise addition of 1.25 g (12 mmol) of methacrylic acid chloride. The mixture was then stirred for 1 hour under ice cooling and then for 3 hours at room temperature to allow the reaction to proceed. After completion of the reaction, water was added to the reaction solution, which was then washed with a saturated aqueous solution of sodium bicarbonate. The organic phase was then dried over sodium sulfate, concentrated, and purified by column chromatography to obtain 3.1 g of the target compound MAC-ADI4H4M shown below.

[0320] When the obtained compound (MAC-ADI4H4M) was subjected to NMR measurement under the above measurement conditions, the following peaks were detected, and it was confirmed that the compound had the chemical structure of the following formula (MAC-ADI4H4M). δ(ppm)(d-DMSO): 6.4~6.5(2H,=CH2), 1.2~2.4(19H, Ad-H, Ad-CH3, -C(CH3)=C)

[0321] [ka]

[0322] (Synthesis Example 1) Synthesis of P-Ac-MAC-2H35I resin 2.4 g of Ac-MAC-2H35I obtained in Synthesis Example 1-1, 3.0 g of 2-methyl-2-adamantyl methacrylate, 2.0 g of γ-butyrolactone methacrylate, and 1.5 g of 3-hydroxy-1-adamantyl methacrylate were dissolved in 45 mL of tetrahydrofuran, and 0.20 g of azobisisobutyronitrile was added. After refluxing for 12 hours, the reaction solution was added dropwise to 2 L of n-heptane. The precipitated resin was filtered and dried under reduced pressure to obtain a white powdery resin represented by the following chemical formula (P-Ac-MAC-2H35I). The molecular weight (Mw) of this resin was 15,400, and the polydispersity (Mw / Mn) was 2.2. 13 C-NMR analysis revealed that the molar composition ratio of a:b:c:d in the following chemical formula (P-Ac-MAC-ADIOH) was 40:30:15:15. Note that although the following chemical formula (P-Ac-MAC-2H35I) is written simply to indicate the ratio of each structural unit, P-Ac-MAC-2H35I is not a block copolymer in which each structural unit forms an independent block.

[0323] [ka]

[0324] (Synthesis Example 2) Synthesis of P-Ac-MAC-4H35I resin A resin represented by the following chemical formula (P-Ac-MAC-4H35I) was obtained in the same manner as in Synthesis Example 1, except that Ac-MAC-4H35I (2.4 g) obtained in Synthesis Example 2-1 was used instead of Ac-MAC-2H35I (2.4 g) in Synthesis Example 1. The molecular weight (Mw) of this resin was 15,000, and the polydispersity (Mw / Mn) was 2.1. 13 C-NMR analysis revealed that the molar composition ratio of a:b:c:d in the following chemical formula (P-Ac-MAC-4H35I) was 40:30:15:15. Note that although the following chemical formula (P-Ac-MAC-4H35I) is written simply to indicate the ratio of each structural unit, P-Ac-MAC-4H35I is not a block copolymer in which each structural unit forms an independent block.

[0325] [ka]

[0326] (Synthesis Example 3) Synthesis of P-Ac-MAC-ADIOH1 resin A resin represented by the following chemical formula (P-Ac-MAC-ADIOH1) was obtained in the same manner as in Synthesis Example 1, except that Ac-MAC-ADIOH (2.0 g) obtained in Synthesis Example 4-1 was used instead of Ac-MAC-2H35I (2.4 g) in Synthesis Example 1. The molecular weight (Mw) of this resin was 15,800, and the polydispersity (Mw / Mn) was 1.8. 13 C-NMR analysis revealed that the molar composition ratio of a:b:c:d in the following chemical formula (P-Ac-MAC-ADIOH1) was 40:30:15:15. Note that although the following chemical formula (P-Ac-MAC-ADIOH1) is written simply to indicate the ratio of each structural unit, P-Ac-MAC-ADIOH1 is not a block copolymer in which each structural unit forms an independent block.

[0327] [ka]

[0328] (Synthesis Example 4) Synthesis of P-Ac-MAC-ADIOH2 resin A resin represented by the following chemical formula (P-Ac-MAC-ADIOH2) was obtained in the same manner as in Synthesis Example 1, except that 4.7 g of MAC-ADI4H4M obtained in Synthesis Example 5-1, 2.0 g of γ-butyrolactone methacrylate, and 4.0 g of Ac-MAC-ADIOH obtained in Synthesis Example 4-1 were used as the monomer (raw material). The molecular weight (Mw) of this resin was 15,800, and the polydispersity (Mw / Mn) was 2.3. 13 C-NMR analysis revealed that the composition ratio (molar ratio) of the compound in the following chemical formula (P-Ac-MAC-ADIOH2) was a:b:c = 40:30:30. Note that the following chemical formula (P-Ac-MAC-ADIOH2) is written simply to indicate the ratio of each structural unit, but P-Ac-MAC-ADIOH2 is not a block copolymer in which each structural unit forms an independent block.

[0329] [ka]

[0330] (Synthesis Example 5) Synthesis of P-Ac-MAC-ADIOH3 resin A resin represented by the following chemical formula (P-Ac-MAC-ADIOH3) was obtained in the same manner as in Synthesis Example 1, except that 4.7 g of MAC-ADI4H4M obtained in Synthesis Example 5-1, 2.0 g of γ-butyrolactone methacrylate, 0.6 g of 4-hydroxystyrene, and 2.0 g of Ac-MAC-ADIOH obtained in Synthesis Example 4-1 were used as monomers (raw materials). The molecular weight (Mw) of this resin was 15,500, and the polydispersity (Mw / Mn) was 2.1. 13 C-NMR analysis revealed that the molar composition ratio of a:b:c:d in the following chemical formula (P-Ac-MAC-ADIOH3) was 40:30:15:15. Note that although the following chemical formula (P-Ac-MAC-ADIOH3) is written simply to indicate the ratio of each structural unit, P-Ac-MAC-ADIOH3 is not a block copolymer in which each structural unit forms an independent block.

[0331] [ka]

[0332] (Synthesis Example 6) Synthesis of P-Ac-MAC-ADIOH4 resin A resin represented by the following chemical formula (P-Ac-MAC-ADIOH4) was obtained in the same manner as in Synthesis Example 1, except that 4.7 g of MAC-ADI4H4M obtained in Synthesis Example 5-1, 2.0 g of γ-butyrolactone methacrylate, 1.9 g of 3,5-diiodo-4-hydroxystyrene, and 2.0 g of Ac-MAC-ADIOH obtained in Synthesis Example 4-1 were used as monomers (raw materials). The molecular weight (Mw) of this resin was 15,600, and the polydispersity (Mw / Mn) was 2.3. 13 C-NMR analysis revealed that the molar composition ratio of a:b:c:d in the following chemical formula (P-Ac-MAC-ADIOH4) was 40:30:15:15. Note that although the following chemical formula (P-Ac-MAC-ADIOH4) is written simply to indicate the ratio of each structural unit, P-Ac-MAC-ADIOH4 is not a block copolymer in which each structural unit forms an independent block.

[0333] [ka]

[0334] (Comparative Synthesis Example 1) Synthesis of P-AC-1 Resin A resin represented by the following chemical formula (P-AC-1) was obtained in the same manner as in Synthesis Example 1, except that Ac-MAC-2H35I was not used. The molecular weight (Mw) of this resin was 13,500, and the polydispersity (Mw / Mn) was 2.3.

[0335] [ka]

[0336] In the above formula (P-AC-1), "40", "40", and "20" represent the molar ratios of the respective structural units. Formula (P-AC-1) is written simply to show the ratio of the respective structural units, but P-AC-1 is not a block copolymer in which the respective structural units form independent blocks.

[0337] Example 1 The P-Ac-MAC-2H35I resin solution obtained in Synthesis Example 1 was applied to a silicon wafer and baked at 110 to 130°C for 60 seconds to form a photoresist layer with a thickness of 100 nm. The resin solution was prepared by blending 5 parts by mass of P-Ac-MAC-2H35I resin, 1 part by mass of triphenylsulfonium nonafluoromethanesulfonate, 0.1 parts by mass of tributylamine, and 92 parts by mass of PGMEA (propylene glycol monomethyl ether acetate). The photoresist layer was then exposed to light using an electron beam lithography system (ELS-7500 (trade name), manufactured by Elionix Corporation, 50 keV), baked at 115°C for 90 seconds (PEB, post-exposure bake), and developed using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) at 23°C for 60 seconds to obtain a positive pattern. The resolution (50 nm L / S) of the obtained pattern was evaluated using a scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation).

[0338] The resin solution thus obtained was filled into a light-shielding bottle and stored for 30 days at 40° C. After storage, the resin solution was evaluated for changes over time by the following method. That is, the resin solutions before and after storage were each applied to separate silicon wafers using a spin coater, and then heated on a hot plate at 110° C. for 1 minute to form a resist layer with a thickness of 80 nm. Next, each of the obtained resist layers was exposed to 1 mJ / cm using an extreme ultraviolet (EUV) exposure device "EUVES-7000" (trade name, manufactured by LithoTech Japan Co., Ltd.). 2 to 1 mJ / cm 2 80mJ / cm 2Maskless shot exposure was performed at different exposure doses up to 1 mJ / cm 2 Wafers were obtained in which the resist layer was exposed to different exposure doses. The entire wafer was then baked (PEB) at 110°C for 90 seconds, and developed using isoamyl acetate at 23°C for 60 seconds. The film thickness of each of the 80 developed locations was measured using an optical interference film thickness meter "VM3200" (trade name, manufactured by SCREEN Semiconductor Solutions Co., Ltd.), and film thickness profile data for each exposure dose was obtained. The exposure dose at which the slope of the film thickness variation with exposure dose was greatest was determined as the sensitivity value (mJ / cm 2 ) and used as an index of the EUV sensitivity of the resist layer. Then, using the sensitivity values ​​before and after storage, the rate of change was calculated according to the following index. "Fluctuation rate (%)" = [("Sensitivity value of resin solution before storage" - "Sensitivity value of resin solution after storage") / "Sensitivity value of resin solution before storage"] x 100 The obtained fluctuation rate was used to evaluate the change over time of the resin solution as follows: A fluctuation rate of less than 2% means that the resist composition has good storage stability, prevents defects in microfabrication, and is excellent in productivity. A: Fluctuation rate is less than 2% B: Fluctuation rate is 2% or more

[0339] The results for resolution, sensitivity, and time course are shown in Table 1.

[0340] Examples 2 to 6 Resin solutions were prepared in the same manner as in Example 1, except that the resins obtained in Synthesis Examples 2 to 6 were used instead of P-Ac-MAC-2H35I resin, and photoresist layers were formed using the resin solutions. Then, using each photoresist layer, resolution and sensitivity were evaluated in the same manner as in Example 1. Furthermore, each resin solution was used to evaluate changes over time in the same manner as in Example 1. The results are shown in Table 1.

[0341] (Comparative Example 1) A resin solution was prepared in the same manner as in Example 1, except that the P-AC-1 resin obtained in Synthesis Comparative Example 1 was used instead of the P-Ac-MAC-2H35I resin, and a photoresist layer was formed using the resin solution. The photoresist layer was then evaluated for resolution and sensitivity in the same manner as in Example 1. The resin solution was also used to evaluate changes over time in the same manner as in Example 1. The results are shown in Table 1.

[0342] [Table 1]

[0343] As described above, the iodine-containing (meth)acrylate compound and the iodine-containing (meth)acrylate (co)polymer of the present embodiment have excellent stability and high sensitivity, and can provide a composition capable of forming a resist film with high resolution.

[0344] (Synthesis Example 7) Synthesis of P-MAC-2H35I resin 5.0 g of the P-Ac-MAC-2H35I resin obtained in Synthesis Example 1 was dissolved in 45 mL of tetrahydrofuran, and 0.5 g of 37% by mass hydrochloric acid was added to the solution. After stirring at 50°C for 5 hours, 45 mL of butyl acetate and 45 mL of water were added to the reaction solution for liquid separation and purification. The organic layer was then concentrated under reduced pressure, redissolved in propylene glycol monomethyl ether, and then poured into a large amount of water. The precipitated resin was filtered and dried under reduced pressure to obtain a white powdery resin represented by the following chemical formula (P-MAC-2H35I). The conversion of the acetyl groups to hydroxy groups was confirmed by 1 The molecular weight (Mw) of this resin was 14,400 and the polydispersity (Mw / Mn) was 2.2. 13 C-NMR analysis revealed that the molar composition of the compound represented by the following formula (P-MAC-2H35I) was a:b:c:d = 40:30:15:15. Note that the formula (P-MAC-2H35I) is simplified to indicate the ratio of each structural unit, but P-MAC-2H35I is not a block copolymer in which each structural unit forms an independent block.

[0345] [ka]

[0346] (Synthesis Example 8) Synthesis of P-MAC-4H35I resin P-MAC-4H35I resin, represented by the following structural formula, was synthesized in the same manner as in Synthesis Example 7, except that P-Ac-MAC-4H35I resin obtained in Synthesis Example 2 was used instead of P-Ac-MAC-2H35I resin. The conversion of the acetyl group to a hydroxy group was confirmed by the following: 1 This was confirmed by H-NMR. 13 C-NMR analysis revealed that the molar composition of the compound represented by the following formula (P-MAC-4H35I) was a:b:c:d = 40:30:15:15. The formula (P-MAC-4H35I) is simplified to show the ratio of each structural unit, but P-MAC-4H35I is not a block copolymer in which each structural unit forms an independent block.

[0347] [ka]

[0348] (Synthesis Example 9) Synthesis of P-MAC-ADIOH1 resin P-MAC-ADIOH1 resin, represented by the following structural formula, was synthesized in the same manner as in Synthesis Example 7, except that P-Ac-MAC-ADIOH1 resin obtained in Synthesis Example 3 was used instead of P-Ac-MAC-2H35I resin. The conversion of the acetyl group to a hydroxy group was confirmed by the following: 1 This was confirmed by H-NMR. 13 C-NMR analysis revealed that the molar composition of the compound represented by the following chemical formula (P-MAC-ADIOH1) was a:b:c:d = 40:30:15:15. The following chemical formula (P-MAC-ADIOH1) is simplified to indicate the ratio of each structural unit, but P-MAC-ADIOH1 is not a block copolymer in which each structural unit forms an independent block.

[0349] [ka]

[0350] (Synthesis Example 10) Synthesis of P-MAC-ADIOH2 resin P-MAC-ADIOH2 resin, represented by the following structural formula, was synthesized in the same manner as in Synthesis Example 7, except that P-Ac-MAC-ADIOH2 resin obtained in Synthesis Example 4 was used instead of P-Ac-MAC-2H35I resin. The conversion of the acetyl group to a hydroxy group was confirmed by the following: 1 This was confirmed by H-NMR. 13 C-NMR analysis revealed that the molar composition ratio of a:b:c in the following chemical formula (P-MAC-ADIOH2) was 40:30:30. The following chemical formula (P-MAC-ADIOH2) is written simply to indicate the ratio of each structural unit, but P-MAC-ADIOH2 is not a block copolymer in which each structural unit forms an independent block.

[0351] [ka]

[0352] (Synthesis Example 11) Synthesis of P-MAC-ADIOH3 resin P-MAC-ADIOH3 resin, represented by the following structural formula, was synthesized in the same manner as in Synthesis Example 7, except that P-Ac-MAC-ADIOH3 resin obtained in Synthesis Example 5 was used instead of P-Ac-MAC-2H35I resin. The conversion of the acetyl group to a hydroxy group was confirmed by the following: 1 This was confirmed by H-NMR. 13 C-NMR analysis revealed that the molar composition ratio of a:b:c:d in the following chemical formula (P-MAC-ADIOH3) was 40:30:15:15. The following chemical formula (P-MAC-ADIOH3) is simplified to show the ratio of each structural unit, but P-MAC-ADIOH3 is not a block copolymer in which each structural unit forms an independent block.

[0353] [ka]

[0354] (Synthesis Example 12) Synthesis of P-MAC-ADIOH4 resin P-MAC-ADIOH4 resin, represented by the following structural formula, was synthesized in the same manner as in Synthesis Example 7, except that P-Ac-MAC-ADIOH4 resin obtained in Synthesis Example 6 was used instead of P-Ac-MAC-2H35I resin. The conversion of the acetyl group to a hydroxy group was confirmed by the following: 1 This was confirmed by H-NMR. 13 C-NMR analysis revealed that the molar composition ratio of a:b:c:d in the following chemical formula (P-MAC-ADIOH4) was 40:30:15:15. The following chemical formula (P-MAC-ADIOH4) is written simply to indicate the ratio of each structural unit, but P-MAC-ADIOH4 is not a block copolymer in which each structural unit forms an independent block.

[0355] [ka]

[0356] This application is based on a Japanese patent application (Patent Application No. 2020-085904) filed on May 15, 2020, the contents of which are incorporated herein by reference. [Industrial Applicability]

[0357] According to the present embodiment, there are provided a compound, a method for producing the compound, a (co)polymer and a composition, and a method for forming a resist pattern using the composition, which are suitable for use in resist materials, have high stability, high sensitivity, and are capable of forming a film with high resolution. Furthermore, by using the compound and (co)polymer, there is provided a method for efficiently producing a (co)polymer having a hydroxy group, which is useful for resist materials. The compound, (co)polymer, and composition of the present embodiment can be widely and effectively used in, for example, electrical insulating materials, resist resins, semiconductor sealing resins, adhesives for printed wiring boards, electrical laminates used in electrical equipment, electronic devices, industrial equipment, etc., matrix resins for prepregs used in electrical equipment, electronic devices, industrial equipment, etc., build-up laminate materials, resins for fiber-reinforced plastics, sealing resins for liquid crystal display panels, paints, various coating agents, adhesives, coating agents for semiconductors, resist resins for semiconductors, and resins for forming resist underlayer films.

Claims

1. An iodine-containing (meth)acrylate compound represented by formula (1): 【Chemistry 1】 (In formula (1), R 1 represents a hydrogen atom, a methyl group, or a halogen atom; R 2 represents a hydrogen atom, A is an adamantane or benzene containing at least one acetoxy group; n 1 represents 0 or 1, n 2 represents an integer from 1 to 20.

2. The iodine-containing (meth)acrylate compound according to claim 1 , wherein the formula (1) is formula (2): 【Chemistry 2】 (In formula (2), R 1 , A, and n 2 is the same as above.

3. The iodine-containing (meth)acrylate compound according to claim 2, wherein the formula (2) is formula (3). 【Transformation 3】 (In formula (3), B is benzene containing at least one acetoxy group, and R 1 , and n 2 is the same as above.

4. The iodine-containing (meth)acrylate compound according to claim 1, wherein the formula (1) is formula (3'). 【Chemistry 4】 (In formula (3'), B' is an adamantane containing at least one acetoxy group, and R 1 , and n 2 is the same as above.

5. n 2 The iodine-containing (meth)acrylate compound according to any one of claims 1 to 4, wherein represents an integer of 2 to 20.

6. An iodine-containing (meth)acrylate (co)polymer having a structural unit represented by formula (4): 【Transformation 5】 (In formula (4), R 1 represents a hydrogen atom, a methyl group, or a halogen atom; R 2 represents a hydrogen atom, A is an adamantane or benzene containing at least one acetoxy group; n 1 represents 0 or 1, n 2 represents an integer from 1 to 20, The symbol * represents the bonding point to the adjacent structural unit.

7. The iodine-containing (meth)acrylate (co)polymer according to claim 6, wherein the formula (4) is formula (5). 【Transformation 6】 (In formula (5), R 1 , n 2 , A, and the symbol * are the same as above.

8. The iodine-containing (meth)acrylate (co)polymer according to claim 7, wherein the formula (5) is formula (6). 【Transformation 7】 (In formula (6), B is benzene containing at least one acetoxy group, and R 1 , n 2 , and the symbol * are the same as above.

9. The iodine-containing (meth)acrylate (co)polymer according to claim 6, wherein the formula (4) is formula (6'): 【Transformation 8】 (In formula (6'), B' is an adamantane containing at least one acetoxy group, and R 1 , n 2 , and the symbol * are the same as above.

10. n 2 The iodine-containing (meth)acrylate (co)polymer according to any one of claims 6 to 9, wherein represents an integer of 2 to 20.

11. A composition comprising the iodine-containing (meth)acrylate compound according to any one of claims 1 to 5, and / or the iodine-containing (meth)acrylate (co)polymer according to any one of claims 6 to 10.

12. The composition of claim 11 further comprising a solvent.

13. The composition according to claim 11 or 12, further comprising an acid generator.

14. The composition according to any one of claims 11 to 13, further comprising an acid diffusion control agent.

15. forming a film using the composition according to any one of claims 11 to 14; a step of exposing the film formed in the step; and a step of removing the exposed portion of the film exposed in the step using a developer to form a pattern.

16. reacting an iodine-containing hydroxy compound represented by formula (a) with a (meth)acrylic acid compound represented by formula (b); The method for producing an iodine-containing (meth)acrylate compound according to any one of claims 1 to 5, comprising: a step of reacting the reaction product obtained in the step with an acylating agent. 【Chemistry 9】 (In formula (a), A' is an adamantane or benzene having at least one hydroxy group, and R 2 , n 1 , and n 2 is the same as above.) 【Chemistry 10】 (In formula (b), R 1 is the same as above, and R B is a hydroxy group, a halogen, a (meth)acryloyloxy group, or an alkoxy group.

17. The method for producing an iodine-containing (meth)acrylate compound according to claim 16, wherein the formula (a) is formula (a1). 【Chemistry 11】 (In formula (a1), A′ and n 2 is the same as above.

18. The method for producing an iodine-containing (meth)acrylate compound according to claim 16, wherein the formula (a) is formula (a2). 【Chemistry 12】 (In formula (a2), B″ is a benzene having at least one hydroxy group, n 2 is the same as above.

19. The method for producing an iodine-containing (meth)acrylate compound according to claim 16, wherein the formula (a) is formula (a3). 【Chemistry 13】 (In formula (a3), B''' is an adamantane having at least one hydroxy group, and n 2 is the same as above)

20. n 2 The method for producing an iodine-containing (meth)acrylate compound according to any one of claims 16 to 19, wherein represents an integer of 2 to 20.

21. A method for producing a (co)polymer having a hydroxy group represented by formula (Y), comprising a step of hydrolyzing an acetoxy group in the iodine-containing (meth)acrylate (co)polymer according to any one of claims 6 to 9. 【Chemistry 14】 (In formula (Y), R 1 represents a hydrogen atom, a methyl group, or a halogen atom; R 2 represents a hydrogen atom, A' is an adamantane or benzene having at least one hydroxy group; n 1 represents 0 or 1, n 2 represents an integer from 1 to 20, The symbol * represents the bonding point to the adjacent structural unit.

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