Compounds, (co)polymers, compositions, pattern formation methods, and methods for producing compounds

Abstract

The present invention provides a composition capable of forming a film with high resolution and high sensitivity. [Solution] The above objective can be achieved by the following compound: an iodine-containing (meth)acrylate compound represented by general formula (1). JPEG2026108681000110.jpg69170 (In formula (1), R 1 represents a hydrogen atom, a methyl group, or a halogen, A represents an organic group with 1 to 30 carbon atoms, and n 1 represents 0 or 1, n 2 (This represents an integer between 1 and 20.)

Description

[Technical Field]

[0001] The present invention relates to compounds, (co)polymers, compositions, pattern forming methods, and methods for producing compounds. Regarding. [Background technology]

[0002] In recent years, advances in lithography technology have led to improvements in the manufacturing of semiconductor devices and liquid crystal display elements. The miniaturization of semiconductors (patterns) and pixels is progressing rapidly. Methods for pixel miniaturization include... Generally, the wavelength of the exposure light source is being shortened. Specifically, conventionally, the g-line and i-line were representative. While ultraviolet light was previously used, nowadays KrF excimer lasers (248nm) and A Far-ultraviolet lithography, such as rF excimer lasers (193nm), is becoming the main method for mass production. Furthermore, extreme ultraviolet (EUV) lithography The introduction of (13.5nm) is progressing. In addition, electron beams (E) are being used for the formation of fine patterns. B: Electron Beam is also used.

[0003] Conventional resist materials are polymer-based resist materials capable of forming amorphous films. These are materials. For example, polymethyl methacrylate and polyhydroxys having acid-dissociable groups. Examples include polymer-based resist materials such as ethylene or polyalkyl methacrylate (for example) , see Non-Patent Document 1). Conventionally, these resist materials were prepared by coating a solution of these resist materials onto a substrate. By irradiating a resist thin film with ultraviolet light, far ultraviolet light, electron beams, extreme ultraviolet light, etc., 10~ It forms a line pattern of approximately 100 nm.

[0004] Furthermore, electron beam or extreme ultraviolet lithography has a reaction mechanism that is different from that of normal photolithography. It is different from lithography. Furthermore, in electron beam or extreme ultraviolet lithography, the number The goal is to form fine patterns ranging from nanometers to over ten nanometers. As the size decreases, a resist material that is even more sensitive to the exposure light source is required. In lithography using extreme ultraviolet light, further improvements in sensitivity are being made in terms of throughput. This is what is required. Resist materials that improve the problems mentioned above include titanium, tin, hafnium, and zirconium. Inorganic resist materials containing metallic elements such as conium have been proposed (for example, Patent Document 1). reference). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication 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. [Overview of the project] [Problems that the invention aims to solve]

[0007] However, conventionally developed resist compositions have many film defects, insufficient sensitivity, and etch issues. There are issues such as insufficient resistance to aging or poor resist patterns. In particular, high resolution and high sensitivity are required. They are expected to be able to balance both.

[0008] In view of the above circumstances, the present invention provides a composition capable of forming a film having high resolution and high sensitivity, and The aim is to provide a method for forming a resist pattern and a method for forming an insulating film using this method. To target. [Means for solving the problem]

[0009] As a result of diligent research to solve the above-mentioned problems, the inventors have found a compound having a specific structure and The bipolymer has high solubility in safe solvents, and these compounds are photographically processed. When used in compositions for film formation applications such as for photoresists or photoresists, it provides high resolution and high sensitivity. We discovered that it is possible to form a film with a certain degree of density, and thus completed the present invention. In other words, the present invention is as follows:

[0010] [1] An iodine-containing (meth)acrylate compound represented by general formula (1). [ka] (In formula (1), R 1 This represents a hydrogen atom, a methyl group, or a halogen group. R 2 These are, independently, a hydrogen atom, a linear organic group with 1 to 20 carbon atoms, and a group with 3 to 20 carbon atoms. This represents a branched organic group with 20 carbon atoms, or a cyclic organic group with 3 to 20 carbon atoms. A represents an organic group with 1 to 30 carbon atoms. n 1 represents 0 or 1, n 2 (This represents an integer between 1 and 20.) [1-1] n 1 [1] The iodine-containing (meth)acrylate compounds described above. [1-2] The alicyclic ring having 5 to 30 carbon atoms which may have the substituent is an alicyclic ring having 5 to 30 carbon atoms which may have the substituent and is an alicyclic ring having 5 to 30 carbon atoms which may have the substituent and is an alicyclic ring having 5 to 30 carbon atoms which may have the substituent and is an alicyclic ring having 5 to 30 carbon atoms which may have the substituent and is an alicyclic ring having 5 to 30 carbon atoms which may have the substituent and is an alicyclic ring having 5 to 30 carbon atoms which may have the substituent and is an alicyclic ring having 5 to 30 carbon atoms which may have the substituent and is an alicyclic ring having 5 to 30 carbon atoms which may have the substituent and is an alicyclic ring having 5 to 30 carbon atoms which may have the substituent and is an alicyclic ring having 5 to 30 carbon atoms which may have the substituent and is an alicyclic ring having 5 to 30 carbon atoms which may have the substituent and is an alicyclic ring having 5 to 30 carbon atoms which may have the substituent and is an alicyclic ring having 5 to 30 carbon atoms which may have the substituent and is an alicyclic ring having 5 to 30 carbon atoms which may have the substituent and is an alicyclic ring having 5 to 30 carbon atoms which may have the substituent and is an alicyclic ring having 5 to 30 carbon atoms which may have the substituent and is an alicyclic ring having 5 to 30 carbon atoms which may have the substituent and is an alicyclic ring having 5 to 30 carbon atoms which may have the substituent and is an alicyclic ring having 5 to 30 carbon atoms which may have the substituent and is an alicyclic ring having 5 to 30 carbon atoms which may have the substituent and is an alicyclic ring having 5 to 30 carbon atoms which may have the substituent and is an alicyclic ring having 5 to 30 carbon atoms which may have the substituent and is an alicyclic ring having 5 to 30 carbon atoms which may 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the​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​1 , n 2 This is as defined in [1]. [4-1] B' is an alicyclic ring having 5 to 30 carbon atoms, which may have substituents, as described in [4]. Element-containing (meth)acrylate compounds. [4-2] The alicyclic ring with carbon atoms 5 to 30 which may have substituents may have substituents A damantane ring, an iodine-containing (meth)acrylate compound as described in [4-1]. [5] n 2 The iodine-containing (meta) product is described in any of [1] to [4], where is an integer between 2 and 20. Acrylate compounds. [6] Iodine-containing (meth)acrylate (co) having repeating units represented by general formula (4) ) Polymerization. [ka] (In formula (4), R 1 This represents a hydrogen atom, a methyl group, or a halogen. R 2 These are, independently, a hydrogen atom, a linear organic group with 1 to 20 carbon atoms, and a group with 3 to 20 carbon atoms. This represents a branched organic group with 20 carbon atoms, or a cyclic organic group with 3 to 20 carbon atoms. A represents an organic group with 1 to 30 carbon atoms. n 1 represents 0 or 1, n 2 This represents an integer between 1 and 20. The asterisk (*) indicates a connection point with an adjacent repeating unit. [6-1] n 1 [6] The iodine-containing (meth)acrylate (co)polymer described above. [6-2] The alicyclic ring with carbon atoms 5 to 30 which may have substituents may have substituents The iodine-containing (meth)acrylate (co) polymer described in [6-1] is a damantane ring. . [7] The iodine-containing (meth)acrylic described in [6], wherein the general formula (4) is general formula (5). Rate (co)polymer. [ka] (In formula (5), R 1 , n 2 , A, and the symbol * are defined as in [6]. [8] The iodine-containing (meth)acrylic described in [7], wherein the general formula (5) is general formula (6). Rate (co)polymer. [ka] (In formula (6), B represents an organic group with 5 to 30 carbon atoms that contains an aromatic ring. R 1 , n 2 The symbol * is defined as in [6]. [8-1] B is an aromatic ring having 5 to 30 carbon atoms, which may have substituents, as described in [8]. A chlorine-containing (meth)acrylate (co)polymer. [8-2] The aromatic ring having 5 to 30 carbon atoms, which may have the substituents, may have substituents. The iodine-containing (meth)acrylate (copolymer) described in [8-1] is a benzene ring. . [9] The iodine-containing (meth)actin described in [7] is the same as general formula (6') above. Relate (co)polymer. [ka] (In formula (6'), B' represents an organic group with 5 to 30 carbon atoms that includes an alicyclic ring. R 1 , n 2 The symbol * is defined as in [6]. [9-1] B' is an alicyclic ring having 5 to 30 carbon atoms, which may have substituents, as described in [9]. Element-containing (meth)acrylate (co)polymer. [9-2] The alicyclic ring with carbon atoms 5 to 30 which may have substituents may have substituents The iodine-containing (meth)acrylate (co)polymer described in [9-1] is a damantane ring. .

[10] n 2 The integer is 2 to 20, and the iodine-containing product is listed in any of [6] to [9-2]. Acrylate (co)polymer.

[11] The iodine-containing (meth)acrylate (co)polymer described in any of [6] to

[10] Includes, composition.

[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 control agent.

[15] A step of forming a film using any of the compositions described in

[11] to

[14] , A step of exposing the film, and A step of removing the exposed parts of the exposed film using a developing solution to form a pattern, A pattern formation method, including the following.

[16] Iodine-containing hydroxy compounds represented by general formula (a) are expressed by (me (t) The iodine-containing (meth) acrylic acid compound as described in [1], which includes reacting with an acrylic acid compound. Method for producing related compounds. [ka] (In formula (a), R 2 , A, n 1 , n 2 (This is as defined in [1]) [ka] (In formula (b), R 1 This is as defined in [1], R B It consists of a hydroxyl group, a halogen atom, and a (meth)acryloyloxy group. (Selected from the group.) [16-1] n 1 A method for producing an iodine-containing (meth)acrylate compound according to

[0016] , wherein is 0 and A is an alicyclic ring having 5 to 30 carbon atoms, which may have substituents. [16-2] The alicyclic ring with carbon atoms 5 to 30 which may have substituents may have substituents Preparation of iodine-containing (meth)acrylate compounds described in [16-1], which are damantane rings. Construction method.

[17] The general formula (a) is the general formula (a1) described in

[16] , which is the iodine-containing (meth)a A method for producing acrylate compounds. [ka] (In formula (a1), A, n 2 (This is as defined in [1])

[18] The iodine-containing (meth)a described in

[16] , wherein the general formula (a) is the same as the general formula (a2). A method for producing acrylate compounds. [ka] (In formula (a2), B represents an organic group with 5 to 30 carbon atoms that contains an aromatic ring. n 2 (This is as defined in [1]) [18-1] B is an aromatic ring having 5 to 30 carbon atoms, which may have substituents, as described in

[18] . A method for producing iodine-containing (meth)acrylate compounds. [18-2] The aromatic ring having 5 to 30 carbon atoms, which may have the substituents, may have substituents. The preparation of the iodine-containing (meth)acrylate compound described in [18-1], which is a benzene ring. Construction method.

[19] The iodine-containing (meth)a described in

[16] is the same as the general formula (a3). A method for producing acrylate compounds. [ka] (In formula (a3), B' represents an organic group with 5 to 30 carbon atoms that includes an alicyclic ring. n 2 (This is as defined in [1]) [19-1] B' is a carbon-5 to carbon-30 alicyclic ring which may have substituents, as described in

[19] . A method for producing a um-containing (meth)acrylate compound. [19-2] The alicyclic ring with carbon atoms 5 to 30 which may have substituents may have substituents Preparation of iodine-containing (meth)acrylate compounds described in [19-1], which are damantane rings. Construction method.

[20] n 2 The iodine-containing product is described in any of

[16] to [19-2], where is an integer between 2 and 20. A method for producing (meth)acrylate compounds. [twenty one] An iodine-containing hydroxy compound represented by general formula (a). [ka] (In formula (a), R 2 These are, independently, a hydrogen atom, a linear organic group with 1 to 20 carbon atoms, and a group with 3 to 20 carbon atoms. This represents a branched organic group with 20 carbon atoms, or a cyclic organic group with 3 to 20 carbon atoms. A represents an organic group with 1 to 30 carbon atoms. n 1 represents 0 or 1, n 2 (This represents an integer between 1 and 20.) [21-1] n 1 The iodine-containing hydroxy compound according to

[0021] , wherein is 0 and A is an alicyclic ring having 5 to 30 carbon atoms, which may have substituents. [21-2] The alicyclic ring with carbon atoms 5 to 30 which may have substituents may have substituents A damantane ring, an iodine-containing hydroxy compound as described in [21-2]. [twenty two] The iodine-containing hydroxyl group described in

[21] , wherein the general formula (a) is general formula (a1). compound. [ka] (In formula (a1), A is A, n 2 (This is as defined in claim 21.) [twenty three] The iodine-containing hydroxycin described in

[22] , wherein the general formula (a1) is the same as the general formula (a2). A compound. [ka] (In formula (a2), B represents an organic group with 5 to 30 carbon atoms that contains an aromatic ring. n 2This is as defined in

[21] . [23-1] B is an aromatic ring having 5 to 30 carbon atoms, which may or may not have substituents. The iodine-containing hydroxy compound described in

[23] . [23-2] The aromatic ring having 5 to 30 carbon atoms, which may have the substituents, may have substituents. A benzene ring, an iodine-containing hydroxy compound as described in [23-1]. [twenty four] The iodine-containing hydroxycin described in

[22] is the same as general formula (a1) (a3). A compound. [ka] (In formula (a3), B' represents an organic group with 5 to 30 carbon atoms that includes an alicyclic ring. n 2 This is as defined in

[21] . [24-1] B is an alicyclic ring having 5 to 30 carbon atoms, which may have substituents, as described in

[24] . A hydroxy compound containing an element. [24-2] The alicyclic ring with carbon atoms 5 to 30 which may have substituents may have substituents A damantane ring, an iodine-containing hydroxy compound as described in

[24] . [twenty five] n 2 The iodine-containing product is described in any of the following categories, where is an integer between 2 and 20:

[21] to [24-2] Hydroxyl compounds.

[26] Iodine introduction reaction for compounds represented by the following general formula (Sa1) or general formula (Sa2) The production of the iodine-containing (meth)acrylate compound described in

[16] further includes the step of performing the following method. [ka] (In formula (Sa1), R 2 , A, n 1 , n 2 This is defined as in [1], X is a hydroxyl group; a small number of groups selected from the group consisting of hydroxyl groups, aldehyde groups, and carboxyl groups. From: an aliphatic or aromatic group having 1 to 30 carbon atoms, having at least one of the following types; or a halogen group; (Selected from the following group) [ka] (In formula (Sa2), A, n 2 This is defined as in [1], X is defined as shown in equation (Sa1), E consists of hydroxyl groups, aldehyde groups, carboxyl groups, ether groups, thiol groups, and amino groups. (A hydrocarbon group having 1 to 30 carbon atoms, having at least one selected from the group consisting of the following.) [Effects of the Invention]

[0011] The present invention provides compounds, compositions, and other materials capable of forming films with high resolution and sensitivity. This provides a method for forming a resist pattern and an insulating film using [the specified method]. [Modes for carrying out the invention]

[0012] The embodiments of the present invention will be described below (hereinafter referred to as "this embodiment"). (This embodiment is an example for explaining the present invention, and the present invention is not limited to this embodiment.) It is not limited to just that.

[0013] In this specification, (meth)acrylate means acrylate and methacrylate. The expression (meta) is used in other terms as well, and should be interpreted similarly to (meta)acrylate. ru. In this specification, (co)polymer means homopolymer and copolymer.

[0014] [Iodine-containing (meth)acrylate compounds] The iodine-containing (meth)acrylate compound of the present invention is a compound represented by the following formula (1). be. [ka]

[0015] In formula (1), R 1 This represents a hydrogen atom, a methyl group, or a halogen group. R 2 These are, independently, a hydrogen atom, a linear organic group with 1 to 20 carbon atoms, and a group with 3 to 20 carbon atoms. This represents a branched organic group with 20 carbon atoms, or a cyclic organic group with 3 to 20 carbon atoms. A represents an organic group with 1 to 30 carbon atoms. n 1 represents 0 or 1, n 2 This represents an integer between 1 and 20.

[0016] R 1 A hydrogen atom, a methyl group, or a halogen group can be used. Known atoms can be used, and F, Cl, Br, I, etc. can be used as appropriate. R 1 This refers to the exposure when the compound of the present invention is used as a constituent unit of a resin for resists. From the viewpoint of sensitivity and material stability, it is preferable that the group be a methyl group or a halogen group. Furthermore, from the viewpoint of exposure sensitivity in particular, it is more preferable to have a halogen group, and it is even more preferable to have I. preferable.

[0017] R 2 These include linear organic groups with 1 to 20 carbon atoms, branched organic groups with 3 to 20 carbon atoms, and carbon It is also acceptable to select two or more combinations from the group consisting of cyclic organic groups with prime numbers between 3 and 20. stomach.

[0018] R 2 The purpose is to suppress the increase in Tg of the resin and improve the effect of introducing iodine elements by adding hydrogen atoms. It is preferable that the acid decomposability is improved in order to control solubility by the developing solution. It is also preferable that the organic group has one or more carbon atoms, with the aim of suppressing acid decomposition. It is also preferable that the element be a hydrogen atom in order to ensure solubility in alkaline developing solution and suppress residue. .

[0019] R 2 R may have substituents. 2 For example, it may have substituents. Alkyl alkyl groups having 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 6 carbon atoms; even if they have substituents. A good alkenyl group having 2 to 20 carbon atoms, 2 to 10 carbon atoms, or 2 to 6 carbon atoms; having substituents Alkynyl groups having 2 to 20 carbon atoms, 2 to 10 carbon atoms, or 2 to 6 carbon atoms: substitution Cyclovalent compounds having 3 to 20, 3 to 10, or 3 to 6 carbon atoms, which may have a group. Kill group; may have substituents, C3-20, C3-10, or C3-6 A cycloalkenyl group; which may have substituents, having 3 to 20 carbon atoms, or 3 to 10 carbon atoms. This is a cycloalkynyl group having 3 to 6 carbon atoms; it may have substituents, having 5 to 20 carbon atoms, carbon Examples include aryl groups with 5 to 10 prime numbers or 5 to 6 carbon atoms; and combinations thereof.

[0020] R 2 Specific examples include, for example, methyl groups, ethyl groups, and p(s) which may have substituents. Ropyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, d Syl group, eicosyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopropyl group xyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cy Croicosyl group, adamantyl group, ethylene group, propylene group, butylene group, phenyl group Naphthyl group, anthracene group, phenanthrene group, tetracene group, chrysene group, truffle Examples include phenylene groups, pyrene groups, benzopyrene groups, azulene groups, and fluorene groups. These may contain ether bonds, ketone bonds, or ester bonds.

[0021] The groups illustrated here include isomers. For example, the propyl group has n-propyl and i It contains a sorbyl group, and the butyl group is an n-butyl group, a sec-butyl group, an isobutyl group, or a t Contains ert-butyl groups.

[0022] R 2 The substituents are not particularly limited, but for example, halogen atoms, hydroxyl groups, cyano Groups, nitro groups, amino groups, thiol groups, heterocyclic groups, linear aliphatic hydrocarbon groups, branched fats Alkyl hydrocarbon groups, cyclic aliphatic hydrocarbon groups, aryl groups, aralkyl groups, alkoxy groups, aryl groups Kenyl group, acyl group, alkoxycarbonyl group, alkylyloxy group, allyloyl Examples include xy groups, alkylsilyl groups, various crosslinking groups, and acid-dissociating groups.

[0023] A "crosslinkable group" is a group that crosslinks in the presence of an acid, alkali, light, or heat, and also in the presence of a catalyst. This refers to a group that crosslinks without a catalyst. The crosslinkable group is not particularly limited, but for example, Groups having an allyl group, groups having a (meth)acryloyl group, epoxy(meth)acryloyl Groups having a hydroxyl group, groups having a urethane (meth)acryloyl group, groups having a hydroxyl group, Groups having a cydyl group, groups having a vinylphenylmethyl group, groups having a styrene group, Groups having a rukinyl group, groups having a carbon-carbon double bond, carbon-carbon triple bond Groups having these groups, and groups containing these groups are examples.

[0024] An "acid-dissociable group" is a group that cleaves in the presence of an acid to become an alkali-soluble group (for example, phenol). (Produces hydroxyl groups, carboxyl groups, sulfonic acid groups, hexafluoroisopropanol groups, etc.) It is an acid-dissociating group. The acid-dissociating group is not particularly limited, but for example, KrF and ArF Hydroxystyrene resin and (meth)acrylic acid resin used in chemically amplified resist compositions Those proposed for use in fats and other materials can be appropriately selected and used. Acid-dissociating group For example, one can cite the work described in International Publication No. 2016 / 158168. It is possible.

[0025] A may have substituents. For example, a compound that forms the skeleton of A may have substituents. It may be, carbon number 1-30, carbon number 1-20, carbon number 1-10 or carbon number 1-6 Alkanes; may have substituents, 2-30 carbon atoms, 2-20 carbon atoms, 2-1 carbon atoms Alkenes with 0 or 2-6 carbon atoms; may have substituents, 2-30 carbon atoms, or 2 carbon atoms. ~20, C2-C10 or C2-C6 alkynes; may have substituents, carbon Cycloalkanes with 3 to 30 carbon atoms, 3 to 20 carbon atoms, 3 to 10 carbon atoms, or 3 to 6 carbon atoms; substitutions It may have a group, with 3 to 30 carbon atoms, 3 to 20 carbon atoms, 3 to 10 carbon atoms, or 3 carbon atoms. ~6 cycloalkenes; may have substituents, 3-30 carbon atoms, 3-20 carbon atoms, Cycloalkynes having 3 to 10 or 3 to 6 carbon atoms; may have substituents, carbon number Arenes with 5-30 carbon atoms, 5-20 carbon atoms, 5-10 carbon atoms, or 5-6 carbon atoms; combinations of these Examples include combinations and pairings.

[0026] A specific example of a compound that forms the backbone of A is, for example, methane, which may have substituents. ethane, propane, butane, pentane, hexane, heptane, octane, nonane, deca n, icosane, triacontane, cyclopropane, cyclobutane, cyclopentane, cy cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cyclo Cosane, cyclotriacontane, adamantane, ethylene, propylene, butene, pente n, hexene, heptene, octen, nonene, desen, icosen, triaconten, ben Zen, phenol, naphthalene, anthracene, phenanthrene, tetracene, chrycene Triphenylene, pyrene, pentacene, benzopyrene, coronene, azulene, fluorescein These include combinations of these, such as ether bonds, ketone bonds, and esters. It may include bonds.

[0027] The substituents of the compound that forms the backbone of A are not particularly limited, but for example, halogen atoms (Fluorine, chlorine, bromine), hydroxyl group, cyano group, nitro group, amino group, thiol group, heterocycle Group, linear aliphatic hydrocarbon group, branched aliphatic hydrocarbon group, cyclic aliphatic hydrocarbon group, Alley Alkyl group, Aralkyl group, Alkoxy group, Alkenyl group, Acyl group, Alkoxycarbonyl group , alkylyloxy groups, allyloxy groups, alkylsilyl groups, and various crosslinking groups Examples include acid-dissociating groups.

[0028] The "crosslinking group" and "acid dissociation group" are not particularly limited, but for example, the R2 Explanation You may use the items listed below.

[0029] n 1 This represents 0 or 1, and is preferably 1.

[0030] n 2 is an integer between 1 and 20, preferably an integer between 2 and 20, and more preferably 2 It is an integer between 10 and 10, and more preferably an integer between 2 and 5.

[0031] The compound represented by formula (1) above is, from the viewpoint of easy reactivity, the compound represented by formula (2) below A hybrid product is preferable. [ka]

[0032] In formula (2), R 1 , A, n 2 This is defined as in equation (1) above.

[0033] The compound represented by formula (1) above can be expressed by the following formula (3) from the viewpoint of etching resistance. It is more preferable that the compound is such that... [ka]

[0034] In formula (3), B represents an organic group having 5 to 30 carbon atoms that contains an aromatic ring, and R 1 , n 2 is the above formula ( As defined in 1).

[0035] B may have substituents. Examples of compounds that form the skeleton of B include those with substituents. It may be, carbon number 5-30, carbon number 5-20, carbon number 5-10 or carbon number 5-6 Alein is one example.

[0036] Specific examples of compounds that form the skeleton of B include, for example, benzene, which may have substituents. Phenol, naphthalene, anthracene, phenanthrene, tetracene, chrysene, Triphenylene, pyrene, pentacene, benzopyrene, coronene, azulene, fluorene These include combinations of these, such as ether bonds, ketone bonds, and ester bonds. It is acceptable to include combinations.

[0037] The substituents of the compound that forms the backbone of B are not particularly limited, but for example, halogen atoms (Fluorine, chlorine, bromine), hydroxyl group, cyano group, nitro group, amino group, thiol group, heterocycle Group, linear aliphatic hydrocarbon group, branched aliphatic hydrocarbon group, cyclic aliphatic hydrocarbon group, Alley Alkyl group, Aralkyl group, Alkoxy group, Alkenyl group, Acyl group, Alkoxycarbonyl group , alkylyloxy groups, allyloxy groups, alkylsilyl groups, and various crosslinking groups Examples include acid-dissociable groups, preferably hydroxyl groups or acid-dissociable groups.

[0038] The "crosslinking group" and "acid dissociation group" are not particularly limited, but for example, the R 2 Explanation The materials described above may be used. While not particularly limited, the materials must be bonded to the aromatic ring of B. The acid-dissociable group is preferably a group that cleaves in the presence of an acid to produce a hydroxyl group.

[0039] The compound represented by formula (1) above is expressed by the following formula (3') from the viewpoint of etching resistance. It is more preferable that the compound is such that it can be found. [ka]

[0040] In formula (3), B' represents an organic group with 5 to 30 carbon atoms that includes an alicyclic ring, and R 1 , n 2 The above formula (1 As defined in ).

[0041] B' may have substituents. Examples of compounds that form the skeleton of B' include substituents It may have 5 to 30 carbon atoms, 5 to 20 carbon atoms, 5 to 10 carbon atoms, or 5 to 6 cycloalkanes; which may have substituents, 5-30 carbon atoms, 5-20 carbon atoms, carbon Cycloalkenes with 5 to 10 prime numbers or 5 to 6 carbon atoms; may have substituents, C5 Cycloalkynes with up to 30 carbon atoms, 5 to 20 carbon atoms, 5 to 10 carbon atoms, or 5 to 6 carbon atoms; these Combinations and other similar combinations are examples.

[0042] Specific examples of compounds that form the B' skeleton include, for example, cyclamates which may have substituents. Lopentan, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclo Decane, cycloicosane, cyclotriacontane, adamantane, and combinations thereof, etc. These include ether bonds, ketone bonds, and ester bonds.

[0043] The substituents of the compound forming the B' skeleton are not particularly limited, but for example, halogen atoms (Fluorine, chlorine, bromine), hydroxyl group, cyano group, nitro group, amino group, thiol group, complex Ring group, linear aliphatic hydrocarbon group, branched aliphatic hydrocarbon group, cyclic aliphatic hydrocarbon group, ant alkyl group, aralkyl group, alkoxy group, alkenyl group, acyl group, alkoxycarbonyl Groups such as alkylyloxy groups, allyloxy groups, alkylsilyl groups, and various crosslinking properties Examples include acid-dissociable groups.

[0044] The "crosslinking group" and "acid dissociation group" are not particularly limited, but for example, the R 2 Explanation You may use the items listed below.

[0045] Specific examples of the iodine-containing (meth)acrylate compounds of the present invention are listed below, but these may be used in the present invention. It is not limited to this. Also, in the examples below, R 1 represents a hydrogen atom or a methyl group.

[0046] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0047] With respect to the structural formulas described herein, for example, as shown below, the line indicating the bond with C is ring A and If C is in contact with ring B, then C may be bonded to either ring A or ring B. It means. [ka]

[0048] The iodine-containing (meth)acrylate compound represented by formula (1) of the present invention is obtained by known methods. It can be synthesized more easily. For example, the iodine-containing hydroxy compound represented by general formula (a) One method involves reacting a substance with a (meth)acrylic acid compound represented by general formula (b). However, this is not the only example.

[0049] [ka] (In formula (a), R 2 , A, n 1 , n 2 (This is defined in equation (1)). [ka] (In formula (b), R 1 This is defined in equation (1). Also, R B is a hydroxyl group, ha Selected from the group consisting of a logen atom and a (meth)acryloyloxy group. B is good (For example, halogen atoms such as chlorine atoms.)

[0050] The compound represented by the general formula (a) is the compound represented by the general formula (a1). preferable. [ka] (In formula (a1), A, n 2 (This is as defined in formula (1) above.)

[0051] The compound represented by the general formula (a) is the compound represented by the general formula (a2). preferable. [ka] (In formula (a2), B represents an organic group with 5 to 30 carbon atoms that contains an aromatic ring. n 2 (This is as defined in formula (1) above.)

[0052] The compound represented by the general formula (a) is the compound represented by the general formula (a3). preferable. [ka] (In formula (a3), B' represents an organic group with 5 to 30 carbon atoms that includes an alicyclic ring. n 2 (This is as defined in formula (1) above.)

[0053] Examples of (meth)acrylic acid compounds represented by the general formula (b) of the present invention are shown below. [ka] Of these (meth)acrylic acid compounds, (meth)acrylic acid chloride showed the following reactivity From a certain point of view, it is preferable.

[0054] Next, we will explain the synthesis method of iodine-containing hydroxy compounds represented by general formula (a). Examples of the synthesis of iodine-containing hydroxy compounds represented by general formula (a) include general formula ( The compound is synthesized by introducing iodine into compound Sa1) or (Sa2). This is possible. When performing an iodine introduction reaction on a compound of general formula (Sa2), iodine introduction The process further includes converting a substance into a compound of general formula (a).

[0055] [ka] (In formula (Sa1), R 2 , A, n 1 , n 2 This is defined as in equation (1). X is a hydroxyl group; a small number of groups selected from the group consisting of hydroxyl groups, aldehyde groups, and carboxyl groups. an aliphatic group or an aromatic group having at least one carbon atom and having 1 to 30 carbon atoms; or a halogen group (F, Cl, Br, etc.) can be selected) [Chemical formula] (In formula (Sa2), A, n 2 is as defined in formula (1). X is as defined in formula (Sa1). E is a hydrocarbon group having 1 to 30 carbon atoms having at least one selected from the group consisting of a hydroxyl group, an aldehyde group, a carboxyl group, an ether group, a thiol group, and an amino group)

[0056] As the iodine introduction reaction, the Sandmeyer method, the Halex method, the iodine introduction method using an iodinating agent or a compound serving as an iodine source, the iodine introduction method using an iodinating agent or a compound serving as an iodine source and an oxidizing agent, the iodine introduction method using an iodinating agent or a compound serving as an iodine source and a radical generator, the iodine introduction method using a system in which the catalytic activity is improved by an iodinating agent or a compound serving as an iodine source and zeolite, etc., and a method of iodinating by a substitution reaction with a functional group such as a hydroxyl group or a halogen group can be appropriately used. As the iodinating agent, a known iodine supply source compound such as iodine, potassium iodide, HI, iodine chloride, N-iodosuccinimide, etc. can be appropriately used. Further, as the oxidizing agent, a known oxidizing agent such as hydrogen peroxide, iodic acid, periodic acid, sulfuric acid, etc. can be used.

[0057]

[0058] Next, a method for producing an iodine-containing (meth) acrylate compound represented by the general formula (1) will be described. The iodine-containing hydroxy compound represented by the general formula (a) is represented by the general formula (b).

[0058]

[0059]

[0060]

[0061] <00009For the (meth)acrylic acid compound represented, for example, 0.5 to 100 molar equivalents, preferably is 1 to 20 molar equivalents, more preferably 1.2 to 5 molar equivalents are used. Within this range , the reaction proceeds sufficiently, and the yield of the iodine-containing (meth)acryl late compound represented by the general formula (1), which is the target product, is high, which is preferable.

[0058] As the solvent used in this reaction, generally available solvents can be used. For example, alcohols, ethers, hydrocarbons, aromatic solvents, halogenated solvents, etc. can be appropriately used within the range that does not inhibit the above reaction . Within the range that does not inhibit the above reaction , a plurality of solvents can also be mixed and used. Since water inhibits the reaction , the use of a dehydrated solvent is preferable.

[0059] Also, as the solvent used when producing the iodine-containing (meth)acrylate compound of the present invention , for the purpose of improving the efficiency in the process from the stability of the material and the reaction to the acquisition of the final compound, , it is preferable to use a solvent with good solubility. Preferred solvents include Hansen solubility parameters (Hansen Solubility Parameters: A User's Handbook, CRC Press, Boca Rat on FL, 2007.) can be used as indicators, and γP and γH can be obtained from the compound structure . It is better that γP and γH are each lower, and it is preferable that the γP value is 6 or less , more preferably 4 or less, and even more preferably 2 or less. Also, it is preferable that the γH value is 6 or less, more preferably 4 or less, and even more preferably 2 or less . Particularly preferred solvents include benzene, toluene, xylene, etc. Aromatic solvents, or aliphatic hydrocarbon solvents such as hexane, heptane, octane, dichloro It is preferable to use halogenated solvents such as romethane and dichloroethane as the main solvent.

[0060] The reaction temperature and reaction time depend on the substrate concentration and the catalyst used, but generally the reaction temperature is -2 The reaction should be carried out at a temperature of 0°C to 100°C, for a reaction time of 1 to 10 hours, under atmospheric pressure, reduced pressure, or increased pressure. This can be done. Furthermore, the reaction can be carried out using any known method, such as batch, semi-batch, or continuous reactions, as appropriate. It is possible.

[0061] Furthermore, polymerization inhibitors may be added to the series of reactions, and commercially available products that are generally available can be used. It is possible. For example, 2,2,6,6-tetramethyl-4-hydroxypiperidine-1 -Oxyl, N-nitrosophenylhydroxylamine ammonium salt, N-nitroso Phenylhydroxylamine aluminum salt, N-nitroso-N-(1-naphthyl)hydro xylamine ammonium salt, N-nitrosodiphenylamine, N-nitroso-N-methyl Luaniline, nitrosonaphthol, p-nitrosophenol, N,N'-dimethyl-p- Nitroso compounds such as nitrosoaniline, phenothiazine, methylene blue, 2-mercat. Sulfur-containing compounds such as putobenzoimidazole, N,N'-diphenyl-p-phenylenedi Amine, N-phenyl-N'-isopropyl-p-phenylenediamine, 4-hydroxy Amines such as diphenylamine and aminophenol, hydroxyquinoline, hydroquinone methylhydroquinone, p-benzoquinone, hydroquinone monomethyl ether, etc. Non-containing compounds, p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, catechin Phenols such as call, 3-s-butylcatechol, 2,2-methylenebis-(6-t-butyl-4-methyl phenol), imides such as N-hydroxyphthalimide, and oximes such as cyclohexanone oxime and p-quinonedioxime, and dialkylthiodiprop ionate and the like can be mentioned. As the addition amount, for 100 parts by mass of the (meth)acrylic acid compound represented by the general formula (b), for example, 0.001 to 10 parts by mass, preferably 0.01 to 1 part by mass.

[0062] The iodine-containing (meth)acrylate compound represented by the general formula (1) obtained by the reaction can be isolated and purified as a desired high-purity monomer by known purification methods such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography , separation and purification methods using activated carbon and the like, or methods by combinations thereof.

[0063] [Iodine-containing (meth)acrylate (co)polymer] By forming a polymer containing the compound of the present invention as a polymerization unit, a polymer containing one or more halogen elements, one or more hydrophilic groups or one or more decomposable groups can be formed. As a result, a resist composition having a polymer containing the compound of the present invention as a constituent unit as a resin component enables high sensitivity in the lithography process and high resolution by expanding the dissolution contrast of the resin in development. [[ID=3�]] The iodine-containing (meth)acrylate (co)polymer of the present invention has a repeating unit represented by the following formula (4). [Chemical formula] In formula (4), R 1 , R 2 , A, n 1 , n2 is as defined in the above formula (1), and the symbol * represents the bonding position with an adjacent repeating unit.

[0064] The iodine-containing (meth)acrylate (co)polymer represented by the above formula (4) is one or more of the present obtained by polymerizing the iodine-containing (meth)acrylate compound represented by the general formula (1) of the invention, or one or more iodine-containing (meth)acrylate compounds represented by the general formula (1) of the present invention can be obtained by polymerizing with other monomers. The iodine-containing (meth)acrylate (co)polymer can be used as a material for forming a film for lithography.

[0065] Regarding the iodine-containing (meth)acrylate copolymer represented by the above formula (4), the repeating units other than those in the above formula (4) are not particularly limited. For example, those described in International Publication WO2016 / 12578 No. 2, International Publication WO2015 / 115613, JP-A 2015 / 117305, International Publication WO2014 / 175275, JP-A 2012 / 162498, or compounds represented by the following formulas (C1) and (C2) can be used.

Chemical formula

[0066] Examples of the monomer raw material of the repeating unit represented by the general formula (C2) include, but are not limited to, 2-methyl-2-(meth)acryloyloxyadamantane, 2-ethyl-2-( (meth)acryloyloxyadamantane, 2-isopropyl-2-(meth)acryloylo (meth)acryloyloxyadamantane, 2-isopropyl-2-(meth)acryloylo ​​​​​Iloxyadamantane, 2-n-propyl-2-(meth)acryloyloxyadamantine Adamantane, 2-n-butyl-2-(meth)acryloyloxyadamantane, 1-methyl -1-(meth)acryloyloxycyclopentane, 1-ethyl-1-(meth)acryloyl hydroxycyclopentane Luroyloxycyclopentane, 1-methyl-1-(meth)acryloyloxycyclo Hexane, 1-ethyl-1-(meth)acryloyloxycyclohexane, 1-methyl -1-(meth)acryloyloxycycloheptane, 1-ethyl-1-(meth)acryloyl Luloyloxycycloheptane, 1-methyl-1-(meth)acryloyloxycyclo Octane, 1-ethyl-1-(meth)acryloyloxycyclooctane, 2-ethyl -2-(meth)acryloyloxydecahydro-1,4:5,8-dimethanonaphthalene Examples include 2-ethyl-2-(meth)acryloyloxynorbornane. Commercially available products can be used as monomers.

[0067] A general formula (2) obtained from an iodine-containing (meth)acrylate compound represented by general formula ( 5) Iodine-containing (meth)acrylate (co)polymer represented by general formula (3) Iodine-containing (meth)acrylate compounds obtained from iodine-containing (meth)acrylate compounds represented by general formula (6) (meth)acrylate(co)polymers, and iodine-containing (meth) polymers represented by general formula (3') Iodine-containing (meth)acrylates, represented by the general formula (6'), can be obtained from acrylate compounds. Copolymers can also be obtained by a similar method. General formula (5) and general formula (6) The iodine-containing (meth)acrylate (co) polymer represented by [formula] is used for lithography film formation. This is preferable for improving the performance of the material. [ka] (In formula (5), R 1 , n 2 A and the symbol * are defined as in formula (4) above. [ka] (In formula (6), B is defined as in equation (3) above, and R 1 , n 2 The symbol * is defined in formula (4) above. (As stated above.) [ka] (In formula (6'), B' is defined as in equation (3') above, and R 1 , n 2 The symbol * is in the above formula (4) As defined above.

[0068] Next, regarding the manufacturing method of iodine-containing (meth)acrylate (co)polymers by polymerization reaction... Let me explain. Polymerization reactions involve dissolving monomers, which form repeating units, in a solvent and adding a catalyst. The reaction is carried out while heating or cooling. The reaction conditions include the type of initiator, the method of initiation (heat, light, etc.), and temperature. The degree, pressure, concentration, solvent, additives, etc., can be arbitrarily set. Iodine of the present invention The production of the contained (meth)acrylate (co)polymer involves azoisobutyronitrile and peroxides. Which radical-generating agents are used in radical polymerization, and which alkyllithium or Grignard reagents are used? This can be carried out using known methods, such as ionic polymerization using any catalyst.

[0069] For the solvent used in the polymerization reaction, commercially available products that are generally available can be used. For example, various solvents such as alcohols, ethers, hydrocarbons, halogenated solvents, etc., can be used in the reaction. It can be used as appropriate within the limits that do not inhibit the above reaction. Multiple solvents can also be mixed and used.

[0070] The iodine-containing (meth)acrylate (co)polymer obtained by polymerization reaction can be processed by known methods. Purification can be carried out using ultrafiltration, crystallization, microfiltration, acid washing, and electrical conductivity. This can be done by combining water washing and extraction with a water flow rate of 10 mS / m or less.

[0071] [Iodine-containing (meth)acrylate compounds, and / or iodine-containing (meth)acrylate [Compositions containing (co)polymers] The composition of this embodiment is an iodine-containing (meth)acrylate compound and / or an iodine-containing A composition containing a (meth)acrylate (co)polymer, particularly suitable for lithography technology. Yes. While not particularly limited, the composition is used for lithography film formation applications, for example, For example, it can be used for resist film formation applications (i.e., “resist compositions”). Furthermore, The composition is used for upper layer formation (i.e., "upper layer formation composition"), and intermediate layer formation ( That is, "compositions for forming an intermediate layer," and for applications involving the formation of a base layer (i.e., "compositions for forming a base layer"), etc. It can be used for this purpose. According to the composition of this embodiment, a film having high sensitivity can be formed. Furthermore, it is possible to impart a good resist pattern shape.

[0072] The composition of this embodiment can also be used as an optical component forming composition applying lithography technology. It can be used. Optical components are used in film and sheet form, as well as plastic lenses ( Rhythmic lenses, lenticular lenses, microlenses, Fresnel lenses, field of view control lenses Lenses, contrast-enhancing lenses, etc., phase difference films, electromagnetic shielding films, prints Solder resists, plating resists, for smudges, optical fibers, and flexible printed circuit boards. Interlayer insulating films for multilayer printed circuit boards, photosensitive optical waveguides, liquid crystal displays, organic electro Luminescence (EL) displays, optical semiconductor (LED) elements, solid-state image sensors, organic thin films It is useful as a film solar cell, dye-sensitized solar cell, and organic thin-film transistor (TFT). The above composition is a component of a solid-state image sensor, particularly one that requires a high refractive index, and is photodynamic. Embedding film and planarization film on iod, planarization film before and after color filter, micro-layer It can be suitably used as a planarization film and conformal film on lenses, microlenses.

[0073] The composition of this embodiment is an iodine-containing (meth)acrylate compound and / or an iodine-containing It contains a methacrylate (co)polymer (B), and optionally a base material (A), a solvent ( It contains other components such as (S), an acid generator (C), an acid diffusion control agent (E), and a base generator (G). This is also acceptable. The following explains each component.

[0074] [Base material (A)] In this embodiment, "substrate (A)" refers to an iodine-containing (meth)acrylate compound, and and / or compounds other than iodine-containing (meth)acrylate (co)polymers (including resins) So, g-ray, i-ray, KrF excimer laser (248nm), ArF excimer laser ( (193nm), extreme ultraviolet (EUV) lithography (13.5nm), and electron beam (EB) Substrates to be used as resists (e.g., lithography substrates and resist substrates) This means that the substrates are not particularly limited to these, and the substrate in this embodiment (A It can be used as a substrate (A). For example, phenol novolac resin, creso Novolac resin, hydroxystyrene resin, (meth)acrylic resin, hydroxystyrene Len-(meth)acrylic copolymer, cycloolefin-maleic anhydride copolymer, cyclo Loolefin, vinyl ether-maleic anhydride copolymer, and titanium, tin, HAF Inorganic resist materials containing metallic elements such as nium and zirconium, and their derivatives. Among these, phenol novo is a good choice from the perspective of the shape of the resulting resist pattern. Lac resin, cresol novolac resin, hydroxystyrene resin, (meth)acrylic resin Lipids, hydroxystyrene-(meth)acrylic copolymers, and titanium, tin, hafnium Inorganic resist materials having metallic elements such as zirconium, and derivatives thereof are preferred. It's nice.

[0075] The aforementioned derivatives are not particularly limited, but for example, those into which a dissociable group is introduced. Examples include derivatives into which dissociable groups or crosslinking groups have been introduced. These materials can undergo dissociation or crosslinking reactions through the action of light, acid, or other substances.

[0076] A "dissociable group" is a functional group, such as an alkali-soluble group, that cleaves to change its solubility. This refers to characteristic groups. While not particularly limited, alkali-soluble groups include phenolic hydroxyl groups, Examples include carboxyl groups, sulfonic acid groups, hexafluoroisopropanol groups, etc. Nolic hydroxyl groups and carboxyl groups are preferred, and phenolic hydroxyl groups are particularly preferred.

[0077] A "crosslinkable group" refers to a group that crosslinks in the presence or absence of a catalyst. , but not limited to, for example, an alkoxy group having 1 to 20 carbon atoms, a group having an allyl group, Groups having (meth)acryloyl groups, groups having epoxy(meth)acryloyl groups, hydroxyl Groups having a group, groups having a urethane (meth)acryloyl group, groups having a glycidyl group, Examples include groups containing a vinylphenylmethyl group.

[0078] [Solvent (S)] The solvent in this embodiment is the iodine-containing (meth)acrylate compound described above, and / Or, an iodine-containing (meth)acrylate (co)polymer (B) that dissolves at least If so, known solvents can be used as appropriate. Specific examples of solvents are not particularly limited. However, for example, ethylene glycol monomethyl ether acetate, ethylene glycol mo Noethyl ether acetate, ethylene glycol mono-n-propyl ether acetate Ethylene glycol mono-n-butyl ether acetate and other ethylene glycol compounds Noalkyl ether acetates; ethylene glycol monomethyl ether, ethylene glycol Ethylene glycol monoalkyl ethers such as glycol monoethyl ether; propyl Propylene glycol monomethyl ether acetate (PGMEA), propylene glycol Noethyl ether acetate, propylene glycol mono-n-propyl ether acetate Propylene glycol mono-n-butyl ether acetate and other propylene glycols Polymethyl monoalkyl ether acetates; propylene glycol monomethyl ether (P GME), propylene glycol monoethyl ether and other propylene glycol monoethyl ethers Lactyl ethers; methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, lactic acid Lactic acid esters such as n-amyl; methyl acetate, ethyl acetate, n-propyl acetate, n-acetic acid Butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate Aliphatic carboxylic acid esters such as; methyl 3-methoxypropionate, 3-methoxypropionate Ethyl pionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, Methyl 3-methoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl Tyl-3-methoxybutyl acetate, butyl 3-methoxy-3-methylpropionate, 3-Methoxy-3-methylbutyrate butyl, acetoacetate methyl, pyruvate methyl, pyruvate Other esters such as ethyl acid; aromatic hydrocarbons such as toluene and xylene; acetone, 2 -Butanone, 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone (C Ketones such as PN, cyclohexanone (CHN); N,N-dimethylformamide, N - Methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. Examples include lactones such as γ-lactones, but this is not a limiting definition. The solvent used in the embodiment is preferably a safe solvent, and more preferably a PGM EA, PGME, CHN, CPN, 2-heptanone, anisole, butyl acetate and lactic acid At least one selected from CHIL, more preferably PGMEA, PGME, CH It is at least one selected from N, CPN, and ethyl lactate.

[0079] In this embodiment, the amount of solid component and the amount of solvent are not particularly limited, however, the amount of solid component The solid component is 1-80% by mass and the solvent is 20-99% by mass, relative to the total mass of the solid and solvent. Preferably, the solid component is 1 to 50% by mass and the solvent is 50 to 99% by mass. More preferably, the solid component is 2-40% by mass and the solvent is 60-98% by mass, and particularly preferably It consists of 2-10% solid components and 90-98% solvent by mass.

[0080] [Acid Generator (C)] In the composition of this embodiment, visible light, ultraviolet light, excimer laser, electron beam, extreme violet Directly by irradiation with one of the following types of radiation: external ultraviolet (EUV), X-rays, and ion beams. It is preferable to include one or more acid-generating agents (C) that generate acid directly or indirectly. C) is not particularly limited, but includes, for example, the information described in International Publication WO2013 / 024778. It is possible to use such materials. The acid generator (C) can be used alone or in combination of two or more types. Cut.

[0081] The amount of acid generator (C) used is preferably 0.001 to 49% by mass of the total mass of solid components, ~40% by mass is more preferable, 3 to 30% by mass is even more preferable, and 10 to 25% by mass is particularly preferable. This is preferable. By using the acid generator (C) within the above range, high sensitivity and low edge are achieved. A roughness pattern profile tends to be obtained. In this embodiment, acid is generated in the system. If produced, the method of acid generation is not particularly limited. Instead of ultraviolet rays such as g-rays and i-rays, exci Using a male laser allows for more precise processing, and also enables the use of electron beams as high-energy beams. Furthermore, even finer processing is possible by using extreme ultraviolet light, X-rays, and ion beams.

[0082] Base generator (G) This section explains the case where the base generator (G) is a photobase generator. A photobase generator is a device that generates a base upon exposure, under normal conditions at room temperature and pressure. It does not show activity, but when exposed to electromagnetic waves and heating as external stimuli, it becomes basic (basic It is not particularly limited as long as it generates (substance).

[0083] The photobase generator that can be used in the present invention is not particularly limited and any known one can be used. These can be used to create, for example, carbamate derivatives, amide derivatives, imide derivatives, and α-cobalt complexes. Examples include imidazole derivatives, cinnamic acid amide derivatives, and oxime derivatives.

[0084] The basic substance generated from the photobase generator is not particularly limited, but it has an amino group. Examples of such compounds include monoamines, polyamines such as diamines, and amidines. It can be done. The resulting basic substance contains an amino group with a higher degree of basicity (higher pKa value of the conjugate acid). The compound is preferred from the viewpoint of sensitivity and resolution. Examples of photobase generators include those described in Japanese Patent Publication No. 2009-80452 and International Publication No. 20 A base having a cinnamic acid amide structure as disclosed in the 09 / 123122 pamphlet Herbal medicines are disclosed in Japanese Patent Publication No. 2006-189591 and Japanese Patent Publication No. 2008-247747. A base generator having a carbamate structure as described above, Japanese Patent Publication No. 2007-249013 and oxime structures such as those disclosed in Japanese Patent Publication No. 2008-003581, carbamoyl Base generators having an oxime structure, compounds described in Japanese Patent Publication No. 2010-243773, etc. These are some examples, but are not limited to them; other known base-generating agent structures may also be used. It is possible.

[0085] The photobase generator can be used individually or in combination of two or more types. The preferred content of the photobase generator in the photosensitive or radiation-sensitive resin composition is as described above. The preferred content of the photoacid generator is the same as that in the photosensitive or radiation-sensitive resin composition. [Acid diffusion control agent (E)] In this embodiment, the acid generated from the acid generator by radiation irradiation is in the resist film. Acid diffusion controls diffusion and prevents undesirable chemical reactions in unexposed areas, among other effects. A diffusion control agent (E) may be added to the composition. By using an acid diffusion control agent (E) Furthermore, the storage stability of the composition of this embodiment tends to be improved. By using the control agent (E), the resolution of the film formed using the composition of this embodiment is improved. This can improve the waiting time before radiation irradiation and the waiting time after radiation irradiation. This suppresses changes in the line width of the resist pattern due to variations in setting time, resulting in process stability. It tends to be superior in this respect. The acid diffusion control agent (E) is not particularly limited, Basic compounds containing nitrogen atoms, basic sulfonium compounds, basic iodium compounds, etc. Examples include radioactive basic compounds.

[0086] The acid diffusion control agent (E) is not particularly limited, but for example, International Publication WO2013 / The product described in No. 024778 may be used. The acid diffusion control agent (E) may be used alone or You may use two or more types.

[0087] The amount of acid diffusion control agent (E) is preferably 0.001 to 49% by mass of the total mass of solid components. , 0.01 to 10% by mass is more preferred, 0.01 to 5% by mass is even more preferred, and 0.0 A concentration of 1 to 3% by mass is particularly preferred. When the amount of acid diffusion control agent (E) is within the above range, resolution This tends to prevent degradation of quality, pattern shape, and dimensional fidelity. Furthermore, even if the settling time from electron beam irradiation to post-radiation heating is extended, the upper layer of the pattern This can suppress deterioration of the shape of the part. Also, the amount added is 10% by mass or less. This tends to prevent a decrease in sensitivity, developability of unexposed areas, etc. By using dispersion control agents, the storage stability of the resist composition is improved, and the resolution is also improved. Furthermore, variations in the storage time before and after radiation irradiation can lead to... This suppresses line width changes in the resist pattern, resulting in excellent process stability. It is a tendency.

[0088] [Other ingredients (F)] The composition of this embodiment may optionally include a crosslinking agent and a dissolving agent as other components (F). Promoting agents, dissolution control agents, sensitizers, surfactants, and organic carboxylic acids or phosphorus oxoacids or One or more types of additives, such as derivatives of the compound, can be added.

[0089] (Crosslinking agent) In this embodiment, the composition may contain one or more crosslinking agents. Even if not present, the base material (A) or an iodine-containing (meth)acrylate compound and / or iodine-containing This refers to a compound that can crosslink any of the (meth)acrylate (co)polymers (B). The crosslinking agent is used to crosslink the substrate (A) intramolecularly or in the presence of acid generated from the acid generator (C). It is preferable that the acid crosslinking agent is capable of intermolecular crosslinking. Examples of such acid crosslinking agents include, for example... A compound having one or more groups (hereinafter referred to as "crosslinkable groups") that can crosslink a base material (A) It can be listed.

[0090] Examples of the crosslinkable group include (i) hydroxy (alkyl group having 1 to 6 carbon atoms), carbon Alkoxy (alkyl groups with 1 to 6 carbon atoms), acetoxy (alkyl groups with 1 to 6 carbon atoms) (ii) Hydroxyalkyl groups such as the chyl group or groups derived therefrom; (ii) Formyl group, Carbonyl groups such as carboxyls (alkyl groups with 1 to 6 carbon atoms) or groups derived therefrom. (iii) Dimethylaminomethyl group, diethylaminomethyl group, dimethylaminomethyl Nitrogen-containing groups such as tyl groups, diethylol-aminomethyl groups, and morpholinomethyl groups; (iv ) Glycidyl groups such as glycidyl ether groups, glycidyl ester groups, and glycidylamino groups Containing groups; (v) benzyloxymethyl group, benzoyloxymethyl group, etc., with 1 to 6 carbon atoms Allyloxy (alkyl group with 1-6 carbon atoms), aralkyloxy (carbon group with 1-6 carbon atoms) Groups derived from aromatic groups such as alkyl groups (numbers 1-6); (vi) vinyl group, isopropane Examples include polymerizable multiple bond-containing groups such as nyl groups. The crosslinking agent in this embodiment Preferred crosslinking groups include hydroxyalkyl groups and alkoxyalkyl groups, in particular An alkoxymethyl group is preferred.

[0091] The crosslinking agent having the crosslinkable group is not particularly limited, but for example, International Publication WO2 The acid crosslinking agent described in No. 013 / 024778 can be used. The crosslinking agent can be used alone or in combination with another agent. You can use more than one type.

[0092] In this embodiment, the amount of crosslinking agent is preferably 50% by mass or less of the total mass of the solid components. More preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 20% by mass or less. It is preferable.

[0093] (Dissolution accelerator) Dissolution accelerators enhance the solubility of solid components in the developer when their solubility is too low. It is a component that moderately increases the dissolution rate of the compound during development. As a decomposition accelerator, low molecular weight compounds are preferred, for example, low molecular weight phenolic compounds. Examples of low molecular weight phenolic compounds include bisphenol. Examples include rus compounds and tris(hydroxyphenyl)methane. Dissolution promotion of these compounds. The agents can be used individually or in combination of two or more.

[0094] The amount of dissolution accelerator added is adjusted as appropriate depending on the type of solid component used, but solid Preferably 0 to 49% by mass of the total mass of the component, more preferably 0 to 5% by mass, and 0 to 1% by mass More preferably, 0% by mass is particularly preferred.

[0095] (Soluble control agent) Dissolution control agents are used to control the solubility of solid components in the developer when their solubility is too high. This component has the effect of moderately reducing the dissolution rate during development. The agent must not undergo chemical changes during processes such as firing, irradiation, and development of the resist film. It is preferable to do so.

[0096] The dissolution control agent is not particularly limited, but examples include phenanthrene, anthracene, Aromatic hydrocarbons such as acenaphthenes; acetophenone, benzophenone, phenylnaphthate Ketones such as lucetones; methylphenylsulfone, diphenylsulfone, dinaphthylsulfone Examples include sulfones such as folliculars. These dissolution control agents can be used alone or in combination of two or more. The above can be used.

[0097] The amount of dissolution control agent is adjusted as appropriate depending on the type of compound used, but solid formation Preferably 0 to 49% of the total mass, more preferably 0 to 5% of the total mass, and 0 to 1% of the total mass. More preferably, 0% by mass is particularly preferred.

[0098] (Sensitizer) The sensitizer absorbs the energy of the irradiated radiation and converts that energy into an acid generator (C It transmits to the acid, thereby increasing the amount of acid produced and improving the apparent sensitivity of the resist. These are ingredients that enhance the effect. Examples of such sensitizers include benzophenones and biaceti. Examples include pyrenes, phenothiazines, fluorenes, etc., but are not particularly limited. These sensitizers can be used individually or in combination of two or more.

[0099] The amount of sensitizer is adjusted as appropriate depending on the type of compound used, but the total amount of solid components The amount is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, and even more preferably 0 to 1% by mass. Ideally, 0% by mass is particularly preferred.

[0100] (Surfactants) The surfactant affects the coatability and striation properties of the composition in this embodiment, the developability of the resist, etc. It is an ingredient that has the effect of improving [something]. Surfactants include anionic surfactants and cationic surfactants. It may be any surfactant, nonionic surfactant, or amphoteric surfactant. Preferred interface Nonionic surfactants are used as activators. The composition of this embodiment has good affinity with the solvent used in the manufacture of the composition, and the effect of the composition of this embodiment is further enhanced. It can be used. An example of a nonionic surfactant is polyoxyethylene higher alkyl Polyethylene ethers, polyoxyethylene higher alkylphenyl ethers, polyethylene glycerides Examples include, but are not limited to, higher fatty acid diesters of coal. Commercially available products of this agent include the following product names: F-Top (manufactured by Gemco), Megafuck (manufactured by Dainichi) (Manufactured by Hon Ink Chemical Industries Co., Ltd.), Florad (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflo N (manufactured by Asahi Glass Co., Ltd.), Pepol (manufactured by Toho Chemical Industry Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Examples include Polyflow (manufactured by Kyoeisha Oil & Fat Chemical Industry Co., Ltd.).

[0101] The amount of surfactant used is adjusted as appropriate depending on the type of solid component used, but solid Preferably 0 to 49% by mass of the total mass of the component, more preferably 0 to 5% by mass, and 0 to 1% by mass More preferably, 0% by mass is particularly preferred.

[0102] (Organic carboxylic acids or phosphorus oxoacids or their derivatives) For the purpose of preventing sensitivity degradation or improving resist pattern shape, storage stability, etc., further... The intended components include organic carboxylic acids, phosphorus oxoacids, or their derivatives. This can be done. Furthermore, organic carboxylic acids or phosphorus oxoacids or their derivatives can be subjected to acid diffusion. It can be used in combination with other agents or on its own. Examples of organic carboxylic acids include Malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, and the like are preferred. Phosphorus oxoacids or their derivatives include phosphoric acid, di-n-butyl phosphate, Phosphoric acid such as diphenyl phosphate or derivatives thereof such as esters thereof, phosphonic acid dimethyl phosphonate, di-n-butyl phosphonate, phenylphosphonate Phosphonic acids such as acids, diphenyl phosphonates, and dibenzyl phosphonates These include derivatives such as esters, phosphines such as phosphinic acid and phenylphosphinic acid. Examples include acids and their ester derivatives, with phosphonic acids being particularly preferred among them. It's nice.

[0103] Organic carboxylic acids or phosphorus oxoacids or their derivatives may be used individually or in combination of two or more. The amount of organic carboxylic acid or phosphorus oxoacid or its derivative can be: The amount is adjusted as appropriate depending on the type of compound used, but is between 0 and 49% by mass of the total mass of the solid components. Preferably, 0 to 5% by mass is more preferable, 0 to 1% by mass is even more preferable, and 0% by mass is Particularly preferable.

[0104] [Other additives] Furthermore, the composition of this embodiment may optionally contain one or more additives other than the components described above. Two or more types can be combined. Examples of such additives include dyes, pigments, and Examples include adhesive aids. For instance, incorporating dyes or pigments can make the latent image in the exposed area visible. This is preferable because it mitigates the effects of halation during exposure. Furthermore, the inclusion of an adhesive aid is desirable. This is preferable because it improves adhesion to the substrate. Furthermore, as other additives Specifically, 4-hydro Examples include xy-4'-methyl chalcone.

[0105] In the composition of this embodiment, the total amount of optional component (F) is 0 to 99% of the total mass of the solid components. It can be in mass%, preferably 0 to 49 mass%, and more preferably 0 to 10 mass%, 0 to 5% by mass is more preferable, 0 to 1% by mass is even more preferable, and 0% by mass is particularly preferable. stomach.

[0106] To form a resist pattern from the composition of the present invention, the composition solution is applied to a spin coater, By appropriate coating means such as a dip coater or roller coater, for example, a silicon wafer - By applying it to substrates such as metal, plastic, glass, and ceramic, After forming a protective coating and, if necessary, pre-treating it at a temperature of approximately 50°C to 200°C, Exposure is performed through a predetermined mask pattern. The thickness of the coating film is, for example, 0.1 to 20 μm. The thickness is approximately 0.3 to 2 μm. Exposure requires light of various wavelengths, such as ultraviolet light and X-rays. Lines and other materials can be used, for example, as a light source, an F2 excimer laser (wavelength 157nm) ArF excimer laser (wavelength 193nm) and KrF excimer laser (wavelength 248nm) Far ultraviolet rays, extreme ultraviolet rays (wavelength 13n), X-rays, electron beams, etc., are selected and used as appropriate. Furthermore, exposure conditions such as exposure amount depend on the compound composition of the resin and / or compound mentioned above, and each additive. The appropriate type of agent is selected depending on the circumstances.

[0107] In this invention, in order to stably form high-precision fine patterns, after exposure, 50 It is preferable to heat-treat the temperature at ~200°C for 30 seconds or more. In this case, the temperature is 50°C. Below this level, there is a risk that the sensitivity variation depending on the type of substrate will widen. Subsequently, alkaline Depending on the imaging solution, the process is typically 10-200 seconds at 10-50°C, preferably 15-9 seconds at 20-25°C. By developing under conditions of 0 seconds, a predetermined resist pattern is formed.

[0108] Examples of the above alkaline developing solution include alkali metal hydroxide, aqueous ammonia, and alkyl Alkanolamines, heterocyclic amines, tetraalkylammonium amines Droxides, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1 Alkaline compounds such as ,5-diazabicyclo-[4.3.0]-5-nonene are typically used. An alkaline aqueous solution is prepared by dissolving the substance to a concentration of 1-10% by weight, preferably 1-3% by weight. It is used. In addition, the developer solution consisting of the above alkaline aqueous solution contains water-soluble organic solvents and surfactants. Aphrodisiacs can also be added as needed.

[0109] In this embodiment, in order to stably form high-precision fine patterns, exposure, PE After step B, the resist pattern is formed by developing with a developer mainly composed of organic solvents. It is also possible. Various organic solvents are widely used as organic solvents in developing solutions, for example, Ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and A solvent such as a hydrocarbon solvent can be used. Developers include, among others, ketone-based solvents, ester-based solvents, alcohol-based solvents, and ethers. It is preferable to contain at least one solvent selected from the solvent system.

[0110] Examples of ester solvents include methyl acetate, ethyl acetate, butyl acetate, and isopropyl 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 methoxyethyl acetate, ethyl ethoxyethyl acetate, propylene glycol monomethyl ether Acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane), ethylene glyceride Ethylene glycol monopropyl ether acetate Ethylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether acetate Nyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene Lenylene glycol monopropyl ether acetate, diethylene glycol monoethyl acetate Telacetate, diethylene glycol monophenyl ether acetate, diethylene glycol Recall monobutyl ether acetate, diethylene glycol monoethyl ether acetate Tate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate Butyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-meth Xybutyl acetate, propylene glycol monoethyl ether acetate, propylene Glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4- Toxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate Tate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-meth Lu-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate Tate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, ant Propyl lactate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, carbonate Butyl, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate Methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, pr Propyl propyl propionate, isopropyl propionate, butyl propionate, butyl propionate Sodium butyl, pentyl propionate, hexyl propionate, heptyl propionate, porcine Butyl nitrate, isobutyl butanoate, pentyl butanoate, hexyl butanoate, isobutanoic acid Isobutyl, propyl pentanoate, isopropyl pentanoate, butyl pentanoate, penta Pentyl hexanoate, ethyl hexanoate, propyl hexanoate, butyl hexanoate, hexanoic acid Isobutyl, methyl heptanoate, ethyl heptanoate, propyl heptanoate, cyclohexyl acetate Xyl, cycloheptyl acetate, 2-ethylhexyl acetate, cyclopentyl propionate, Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3- Methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxy Examples include propionates 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, or butyl butanoate are preferably used. Butyl acetate, isoamyl acetate, and methyl hydroxyisobutyrate are particularly preferred and used. ru.

[0111] Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, and 2 - Nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexa Non, diisobutylketone, cyclohexanone, methylcyclohexanone, phenylacetate Ton, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonyl Cetone, Ionone, Diacetonyl Alcohol, Acetyl Carbinol, Acetophenone, Methyl naphthyl ketone, isophorone, propylene carbonate, and γ-butyrolactone These are some examples, and among them, 2-heptanone is preferred.

[0112] Examples of alcohol-based solvents include methanol, ethanol, 1-propanol, and Sopropanol, 1-butanol, 2-butanol, 3-methyl-1-butanol, te rt-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 1 -Heptanol, 1-octanol, 1-decanol, 2-hexanol, 2-heptano 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4 -Octanol, 3-methyl-3-pentanol, cyclopentanol, 2,3-dimethicone 2-butanol, 3,3-dimethyl-2-butanol, 2-methyl-2-pentanol Lu, 2-methyl-3-pentanol, 3-methyl-2-pentanol, 3-methyl-3- Pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclo Hexanol, 5-methyl-2-hexanol, 4-methyl-2-hexanol, 4,5 -Dithyl-2-hexal, 6-methyl-2-heptanol, 7-methyl-2-octano 8-methyl-2-nonal, 9-methyl-2-decanol, and 3-methoxy-1 - Alcohols such as butanol (monohydric alcohols); ethylene glycol, diethylene glycol Recall, and glycol-based solvents such as triethylene glycol; ethylene glycol mono Methyl ether, propylene glycol monomethyl ether (PGME; also known as 1-methyl ether) C-2-propanol), diethylene glycol monomethyl ether, triethylene glycol Coal monoethyl ether, methoxymethylbutanol, ethylene glycol monoethyl Ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether Propylene glycol monoethyl ether, propylene glycol monopropyl Ethers, propylene glycol monobutyl ether, and propylene glycol monobutyl Examples include glycol ether solvents containing hydroxyl groups such as phenyl ethers; and so on. Among these, it is preferable to use a glycol ether-based solvent.

[0113] Examples of ether-based solvents include the glycol ether-based solvent containing the above-mentioned hydroxyl group. Others include propylene glycol dimethyl ether, propylene glycol diethyl ether, Diethylene glycol dimethyl ether, and diethylene glycol diethyl ether, etc. Glycol ether solvents that do not contain hydroxyl groups; aromatic compounds such as anisole and phenetol. Fragrance ether solvents; dioxane, tetrahydrofuran, tetrahydropyran, perfluorine Ro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, 1,4-dioxy Examples include ethanol and isopropyl ether. Among these, glycol ether-based solvents are particularly noteworthy. , and aromatic ether solvents such as anisole are preferred.

[0114] Examples of amide solvents include N-methyl-2-pyrrolidone and N,N-dimethylacetate. Triamide, N,N-dimethylformamide, hexamethylphosphoric triamide, and Examples include 1,3-dimethyl-2-imidazolidinone.

[0115] Examples of hydrocarbon solvents include pentane, hexane, octane, nonane, decane, Dodecane, Undecane, Hexadecane, 2,2,4-Trimethylpentane, 2,2,3- Aliphatic carbons such as trimethylhexane, perfluorohexane, and perfluoroheptane Hydrogen-based solvents: Toluene, xylene, ethylbenzene, propylbenzene, 1-methylpropylbenzene Pyrubenzel, 2-methylpropylbenzene, dimethylbenzene, diethylbenzene, erythrocyte Dimethylbenzene, trimethylbenzene, ethyldimethylbenzene, and dipropylbenzene Examples include aromatic hydrocarbon solvents such as lenzen. Furthermore, unsaturated hydrocarbon solvents can also be used as hydrocarbon solvents, for example, Unsaturated carbonized water containing octene, nonene, decene, undecene, dodecene, and hexadecene. Examples include elemental solvents. The number of double or triple bonds in unsaturated hydrocarbon solvents is not particularly limited. It is not fixed and may be located at any position in the hydrocarbon chain. Also, if the unsaturated hydrocarbon solvent is two If a double bond is present, the cis and trans isomers may be mixed together. Furthermore, in aliphatic hydrocarbon solvents, which are hydrocarbon solvents, different structures exist with the same number of carbon atoms. It may also be a mixture of compounds. For example, decane may be used as an aliphatic hydrocarbon solvent. In that case, 2-methylnonane and 2,2-dimethyl are compounds with the same number of carbon atoms but different structures. Octane, 4-ethyloctane, and isooctane are included in aliphatic hydrocarbon solvents. It's okay to be there. Furthermore, the above may include only one compound with the same number of carbon atoms but a different structure, or As noted, it may contain multiple species.

[0116] The developing solution consisting of the above organic solvent may further contain basic compounds, water-soluble organic solvents, and surfactants. It can also be added as needed. [Examples]

[0117] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is actually This is not limited in any way by the examples provided.

[0118] [Measurement method] (1) Structure of the compound The structure of the compound is as shown in the Bruker Advance600II spectromete Using r, under the following conditions, 1 This was confirmed by performing 1H-NMR measurements. Frequency: 400MHz Solvent: CDCl3 or d6-DMSO Internal standard: TMS Measurement temperature: 23℃

[0119] (Synthesis Example 1-1) Synthesis of MAC-4I Dissolve 23g (0.1mol) of 4-iodobenzaldehyde in 200ml of methanol, and add 49.5g (0.2) of NaBH. 5 mol was added at a temperature below 10°C. The mixture was then stirred and reacted for 3 hours, and methanol was removed by distillation under reduced pressure to concentrate the solution. It shrunk. Water and ethyl acetate were added to the concentrate and the organic phase was extracted. Sodium sulfate was added to this organic phase. The mixture was dried with added solvent, and the solvent was removed under reduced pressure to obtain the crude product of 4-iodobenzyl alcohol. The crude 4-iodobenzyl alcohol product obtained was purified by column chromatography. Then, 22 g of 4-iodobenzyl alcohol (yield 94%) was obtained as shown below. [ka]

[0120] Dissolve 11.5 g (50 mmol) of 4-iodobenzyl alcohol obtained above in chloroform. Under ice cooling, add 4.4 g (55 mmol) of pyridine, then dropwise add 5.7 g (55 mmol) of methacrylate chloride. , added. Then, the reaction was allowed to proceed with stirring under ice for 1 hour and at room temperature for 3 hours. After the reaction was complete, the reaction solution Add water, wash with saturated sodium bicarbonate solution, and add sodium sulfate to the organic phase. After drying and concentration, the following target product MAC was obtained by column chromatography. -4I 13g (88% yield) was obtained.

[0121] The obtained compound (MAC-4I) was subjected to NMR measurement under the above measurement conditions. The following peaks were found, and it was confirmed that it has the chemical structure shown in the following formula (MAC-4I). Ta. δ(ppm)(CDCl3):7.7(2H, Ph), 7.1(2H, Ph), 6.1 (1H, =CH2), 5.6(1H, =CH2), 5.1(2H), 2.0(3H, -CH 3) [ka]

[0122] (Synthesis Example 2-1) Synthesis of MAC-2H35I Dissolve 90g (0.24mol) of 3,5-diiodosalicyaldehyde in 900ml of methanol, and then add NaBH42 2.8g (0.60mol) was added at a temperature below 10°C. Subsequently, the mixture was stirred under ice for 3 hours, followed by stirring at 25°C for 16 hours. The mixture was mixed and reacted, and the methanol was removed by distillation under reduced pressure to concentrate the mixture. Water and ethyl acetate were added to the concentrate. The organic phase was extracted. Magnesium sulfate was added to this organic phase and dried, and the solvent was removed by distillation under reduced pressure. Crude product of 2-hydroxy-3,5-diiodobenzyl alcohol was obtained. The crude product of C-3,5-diiodobenzyl alcohol was purified by column chromatography. Then, 82.5 g of 2-hydroxy-3,5-diiodobenzyl alcohol (yield 91%) was obtained as shown below. [ka]

[0123] 10 g (27 mmol) of 2-hydroxy-3,5-diiodobenzyl alcohol obtained above Dissolve in 100 mL of dichloromethane, add 3.1 g (39 mmol) of pyridine under ice cooling, and methacrylic acid-free 4.1 g (27 mmol) of the aqueous solution was added dropwise. The mixture was then stirred for 4 hours under ice cooling and 18 hours at room temperature to allow the reaction to proceed. After the reaction was complete, water was added to the reaction solution and washed with an aqueous sodium bicarbonate solution to remove the organic phase. Magnesium sulfate is added and dried, then concentrated and purified by column chromatography. As a result, we obtained 9 g of the target product MAC-2H35I (yield 88%) as shown below.

[0124] The obtained compound (MAC-2H35I) was subjected to NMR measurement under the aforementioned measurement conditions. The following peaks were found, and the chemical structure is given by the following formula (MAC-2H35I). I confirmed that. 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) [ka]

[0125] (Synthesis Example 3-1) Synthesis of MAC-4H35I Dissolve 128g (0.78mol) of calcium chloride and 1.3g (2.4mol) of NaBH4 in 2.8L of ethanol, and Then, 410 g (1.1 mol) of 4-hydroxy-3,5-diiodobenzaldehyde was added under ice cooling at 25°C. After stirring and reacting for 18 hours, add 10 L of water and adjust the pH to 2.5 with hydrochloric acid, then filter out the precipitate. After washing with water, dry and prepare 401g of 4-hydroxy-3,5-diiodobenzyl alcohol as shown below (yield 97% was obtained. [ka]

[0126] 400 g (1.06 mol) of 4-hydroxy-3,5-diiodobenzyl alcohol obtained above Dissolve in 2.8L of toluene, add 916g (10.6mol) of methacrylic acid and p-toluenesulfonic acid monohydrate. Add 20 g (0.105 mol) of the substance and 13 mg (0.01 mmol) of 4-methoxyphenol, and reflux at 110°C for 2 hours. The mixture was stirred. After the reaction, 4 L of water was added, the organic layer was dried, and the mixture was recrystallized and purified twice using hexane. The target product MAC-4H35I, yielding 158g (33% yield), was obtained as shown below.

[0127] The obtained compound (MAC-4H35I) was subjected to NMR measurement under the aforementioned measurement conditions. The following peaks were found, and the chemical structure is given by the following formula (MAC-4H35I). I confirmed that. 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) [ka]

[0128] (Synthesis Example 3-2) Synthesis of MAC-4H35I 4-Hydroxybenzyl alcohol 45.0g (0.36mol), Iodine 92.4 Dissolve 0.36 mol of 1 g in 600 mL of methanol and dissolve in a 20°C water bath to remove hydrogen peroxide. After adding 0.2g (0.18mol) dropwise, the mixture was stirred and reacted at 80°C for 8 hours. After cooling, the mixture was chrysalis. After washing by liquid-liquid separation using sodium sulfuric acid solution and saline solution, the organic phase was extracted. Magnesium sulfate is added to this organic phase and dried, and the solvent is removed by distillation under reduced pressure to obtain 4-hydroxy-3 Crude product of ,5-diiodobenzyl alcohol was obtained. The crude product of 4-benzyl alcohol was purified by column chromatography. 95 g of roxy-3,5-diiodobenzyl alcohol (70% yield) was obtained.

[0129] Using the 4-hydroxy-3,5-diiodobenzyl alcohol obtained above, synthesis MAC-4H35I was obtained using the same method as in Example 3-1.

[0130] (Synthesis Example 4-1) Synthesis of MAC-2H35I-BOC In a container with an internal volume of 200 mL equipped with a stirrer, a condenser, and a burette, the above synthesis example 5.5 g (12.4 mmol) of the compound (MAC-2H35I) obtained in 2-1 and di-t -Butyl dicarbonate (Aldrich) 2.7g (12.4 mmol) and acetone Prepare 100mL of liquid and add 1.71g of potassium carbonate (Aldrich brand) (12.4mmo l) was added, and the contents were stirred at 20°C for 6 hours to carry out the reaction and obtain the reaction solution. Next, the reaction solution The solution is concentrated, 100g of pure water is added to the concentrate to precipitate the reaction product, and after cooling to room temperature, The solid matter was separated by filtration. The obtained solid is filtered and dried, and then separated and purified by column chromatography. The target compound (MAC-2H35I-BOC) is represented by the following formula (MAC-2H35I-BOC). I obtained 1.5g of BOC. The obtained compound (MAC-2H35I-BOC) was subjected to NMR measurement under the above measurement conditions. Upon analysis, the following peaks were found, and the following equation (MAC-2H35I-BOC) It was confirmed that it possesses a chemical structure. δ(ppm)(CDCl3):7.2~8.0(2H, Ph), 6.2(1H, =CH2 ), 5.7(1H, =CH2), 5.1(2H, -CH2-), 2.0(3H, -CH3) , 1.4(9H, -CH3)3)

[0131] [ka]

[0132] (Synthesis Example 5-1) Synthesis of MAC-2H35I-MeBOC In a container with an internal volume of 200 mL equipped with a stirrer, a condenser, and a burette, the above synthesis example 5.5 g (12.4 mmol) of the compound (MAC-2H35I) obtained in 2-1 and bromo 2.42g (12.4 mmol) of t-butyl acetate (Aldrich) and acetone 10 Prepare 0 mL and add 1.71 g (12.4 mmol) of potassium carbonate (Aldrich) and Add 0.4g of 18-crown-6 and stir the contents under reflux for 3 hours to carry out the reaction. The reaction solution was then obtained. Next, the reaction solution was concentrated, and 100g of pure water was added to the concentrate to precipitate the reaction product. After allowing it to cool to room temperature, the solid matter was separated by filtration. The obtained solid is filtered and dried, and then separated and purified by column chromatography. The target compound (MAC-2H35I-MeBOC) is represented by the following formula (MAC-2H35I-MeBOC). 1.4 g of I-MeBOC was obtained. The obtained compound (MAC-2H35I-MeBOC) was subjected to the above measurement conditions, NM When R measurements were performed, the following peak was found, and the following equation was used: (MAC-2H35I-MeB It was confirmed that it has the chemical structure of OC. δ(ppm)(CDCl3):7.8(2H, Ph), 6.7(1H, =CH2), 5. 7(1H, =CH2), 5.0(4H, O-CH2-Ph, O-CH2-O), 1.9(3 H, -CH3), 1.4(9H,-(CH3)3)

[0133] [ka]

[0134] (Synthesis Example 6-1) Synthesis of MAC-4H35I-BOC Except for using compound (MAC-4H35I) instead of compound (MAC-2H35I), the formula is otherwise the same. The target compound represented by the following formula (MAC-4H35I-BOC) is synthesized in the same manner as in Example 4-1. 1.5 g of (MAC-4H35I-BOC) was obtained. The obtained compound (MAC-4H35I-BOC) was subjected to NMR measurement under the above measurement conditions. Upon analysis, the following peaks were found, and the following equation (MAC-4H35I-BOC) It was confirmed that it possesses a chemical structure. δ(ppm)(CDCl3):7.8(2H, Ph), 6.2(1H, =CH2), 5. 7(1H, =CH2), 5.1(2H, -CH2-), 2.0(3H, -CH3), 1.4 (9H, -CH3)3)

[0135] [ka]

[0136] (Synthesis Example 7-1) Synthesis of MAC-4H35I-MeBOC Except for using compound (MAC-4H35I) instead of compound (MAC-2H35I), the formula is otherwise the same. In the same manner as in Example 5-1, the objective is expressed by the following formula (MAC-4H35I-MeBOC). I obtained 1.5g of the compound (MAC-4H35I-MeBOC). The obtained compound (MAC-4H35I-MeBOC) was subjected to the above measurement conditions, NM When R measurements were performed, the following peak was found, and the following equation was used: (MAC-4H35I-MeB It was confirmed that it has the chemical structure of OC. δ(ppm)(CDCl3):7.8(2H, Ph), 6.8(2H, O-CH2-O) , 6.7(1H, =CH2), 5.7(1H, =CH2), 5.1(2H, O-CH2-P h), 2.0(2H, -CH3), 1.4(9H,-(CH3)3))

[0137] [ka]

[0138] (Synthesis Example 8-1) Synthesis of ACLAC-2H35I

[0139] In a 300 mL round-bottom flask equipped with a Dean-Stark filter and reflux condenser, (Synthesis Example 2-1) 10.2 g (27 mmol) of 2-hydroxy-3,5-diiodobenzyl alcohol Dissolve in 100 mL of toluene, and under ice cooling, add 0.05 g (0.3 mm) of p-toluenesulfonic acid. Add (ol), then add 2.9 g (27 mmol) of α-chloroacrylate dropwise. The mixture was stirred and reacted under reflux conditions for 1 hour. After the reaction was complete, water was added to the reaction solution, and sodium bicarbonate was added. Washed with an aqueous solution of um, magnesium sulfate was added to the organic phase and dried, then concentrated and processed in a column chromatography. Purified by matrixing, the target product ACLAC-2H35I 9.3g (as shown below) A success rate of 73% was achieved.

[0140] The obtained compound (ACLAC-2H35I) was subjected to NMR measurement under the above measurement conditions. Upon investigation, the following peaks were found, and the chemical structure is given by the following formula (ACLAC-2H35I). It was confirmed that it possesses [the characteristic]. 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-) [ka]

[0141] (Synthesis Example 9-1) Synthesis of MAC-ADI 1,3-Adamantanediol (manufactured by Mitsubishi Gas Chemical Co., Ltd.) 16.8g (0.1mol) Dissolve in 200 mL of ene, add 89.8 g (0.4 mol) of 57% hydrogen iodide aqueous solution, The reaction was carried out by stirring at 80°C for 8 hours. After the reaction, water was added and washed with sodium bicarbonate. After concentrating the cell layer, separation and purification are performed by column chromatography to obtain 3-yo, represented by the following formula. 12 g of do-1-hydroxyadamantane was obtained. [ka] 2.78 g (10 mmol) of 3-iodo-1-hydroxyadamantane obtained above Dissolve in chloroform, add 0.96 g (12 mmol) of pyridine under ice cooling, and metak 1.25 g (12 mmol) of lylic acid chloride was added dropwise. Then, it was cooled on ice for 1 hour. The mixture was stirred and allowed to react at room temperature for 3 hours. After the reaction was complete, water was added to the reaction solution, and saturated sodium bicarbonate was added. Washed with an aqueous solution of um, sodium sulfate was added to the organic phase and dried, then concentrated and processed by column chromatography. Purification by tography yielded 2.7 g of the target substance (MAC-ADI) shown below.

[0142] The obtained compound (MAC-ADI) was subjected to NMR measurement under the above measurement conditions. Furthermore, the following peaks were found, confirming that it has the chemical structure shown in the following formula (MAC-ADI). I acknowledged it. δ(ppm)(d-DMSO):6.4~6.5(2H,=CH2), 1.3~3.2 (17H, Ad-H, -C(CH3)=C) [ka]

[0143] (Synthesis Example 10-1) Synthesis of MAC-ADI2 1,3,5-Adamantanetriol (manufactured by Mitsubishi Gas Chemical Co., Ltd.) 2.3g (12.5 mmol) Dissolve ) in 100 mL of toluene to make 28.1 g (125 mmol) of 57% hydrogen iodide aqueous solution. ) was added and the mixture was stirred at 80°C for 13 hours to allow the reaction to proceed. After the reaction, water was added and sodium bicarbonate was added. After washing and concentrating the organic layer, separation and purification are performed by column chromatography, resulting in the following expression: 0.9 g of 3,5-diiodo-1-hydroxyadamantane was obtained. [ka] Replace 2.78g of 3-iodo-1-hydroxyadamantane with the 3,5 obtained above. The rest is synthetic, except for the use of 4.04 g (10 mmol) of diiodo-1-hydroxyadamantane. Similarly to Example 9-1, the target compound (MAC-ADI2) represented by the following formula (MAC-A DI2) 3.5g was obtained.

[0144] The obtained compound (MAC-ADI2) was subjected to NMR measurement under the above measurement conditions. At that time, the following peaks were found, and it was determined that it has the chemical structure shown in the following formula (MAC-ADI2). I confirmed it. δ(ppm)(d-DMSO):6.4~6.5(2H,=CH2), 1.5~3.9 (16H, Ad-H, -C(CH3)=C) [ka]

[0145] (Synthesis Example 11-1) Synthesis of MAC-ADIOH 1,3,5-Adamantanetriol (manufactured by Mitsubishi Gas Chemical Co., Ltd.) 2.3g (12.5 mmol) Dissolve ) in 100 mL of toluene to make 28.1 g (125 mmol) of 57% hydrogen iodide aqueous solution. ) was added and the mixture was stirred at 80°C for 13 hours to allow the reaction to proceed. After the reaction, water was added and sodium bicarbonate was added. After washing and concentrating the organic layer, separation and purification are performed by column chromatography, resulting in the following expression: 0.9 g of 5-iodo-1,5-dihydroxyadamantane was obtained. [ka] Replace 2.78g of 3-iodo-1-hydroxyadamantane with the 5-iodo-obtained above. The rest is synthetic, except for the use of 4.04 g (10 mmol) of 1,3-dihydroxyadamantane. Similarly to Example 9-1, the target compound represented by the following formula (MAC-ADIOH) (MAC- ADI2) 3.5g was obtained.

[0146] The obtained compound (MAC-ADIOH) was subjected to NMR measurement under the above measurement conditions. However, the following peak was found, and it has the chemical structure shown in the following formula (MAC-ADIOH). I confirmed that. δ(ppm)(d-DMSO):6.4~6.5(2H,=CH2), 1.5~3.9 (14H, Ad-H, -C(CH3)=C), 4.5(1H, -OH) [ka]

[0147] (Synthesis Example 12-1) Synthesis of MAC-ADI4H4M 4-methyl-adamantane-1,4-diol 2.3g (12.5 mmol) Dissolve in 100 mL, add 11.2 g (50 mmol) of 57% hydrogen iodide aqueous solution, and 8 The reaction was carried out by stirring at 0°C for 8 hours. After the reaction, water was added and washed with sodium bicarbonate, and the organic solution was removed. After concentrating the layer, separation and purification are performed by column chromatography to obtain 1-iodine represented by the following formula. 1.1 g of -4-methyl-4-hydroxyadamantane was obtained. [ka] Replace 2.78g of 3-iodo-1-hydroxyadamantane with the 1-iodo obtained above. In addition to using 2.92g (10 mmol) of methyl-4-hydroxyadamantane, The target compound represented by the following formula (MAC-ADI4H4M) was synthesized in the same manner as in Synthesis Example 9-1. (MAC-ADI4H4M) 3.1g was obtained.

[0148] The obtained compound (MAC-ADI4H4M) was subjected to NMR measurement under the above measurement conditions. Upon investigation, the following peaks were found, and the chemical structure is given by the following formula (MAC-ADI4H4M). It was confirmed that it possesses [the characteristic]. δ(ppm)(d-DMSO):6.4~6.5(2H,=CH2), 1.2~2.4 (19H, Ad-H, Ad-CH3, -C(CH3)=C) [ka]

[0149] (Synthesis Example 13-1) Synthesis of ACLAC-ADI2

[0150] 3,5-diiod-1- Dissolve 10.9 g (27 mmol) of hydroxyadamantane in 100 mL of toluene. Under ice cooling, add 0.05 g (0.3 mmol) of p-toluenesulfonic acid and α-chloroacrylate. 2.9 g (27 mmol) of phosphate was added dropwise. Then, the mixture was stirred under reflux conditions for 1 hour. The reaction was carried out. After the reaction was complete, water was added to the reaction solution and washed with sodium bicarbonate solution. Magnesium sulfate was added to the phase and dried, then concentrated and purified by column chromatography. Thus, the target product ACLAC-ADI2, 8.9 g (yield 65%), was obtained as shown below.

[0151] The obtained compound (ACLAC-ADI2) was subjected to NMR measurement under the above measurement conditions. Upon investigation, the following peaks were found, and the chemical structure was given by the following formula (ACLAC-ADI2). I confirmed that it would be done. δ(ppm)(CDCl3):6.0~6.6(2H,=CH2), 1.5~4.4( 13H, Ad-H) [ka]

[0152] (Synthesis Example 1) Synthesis of MAC-4I resin 1.5g MAC-4I and 3.0g 2-methyl-2-adamantyl methacrylate, 2.0 g of γ-butyrolactone methacrylate and hydroxyadamantyl methacrylate Dissolve 1.5 g of azobisisobutyrate ester in 45 mL of tetrahydrofuran, and 0.20 g of nitrile 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 powder with the following chemical formula (P-MAC). A resin represented by -4I) was obtained. The molecular weight (Mw) of this resin is 12000, and the degree of dispersion (Mw) is 12000. / Mn) was 1.90. Also, 13 The following chemical formula (PM) was obtained by measuring C-NMR. The composition ratio (molar ratio) in AC-4I was a:b:c:d = 40:30:15:15. The following chemical formula (P-MAC-4I) is a simplified representation to show the proportions of each constituent unit. As described, P-MAC-4I is a system where each component unit forms an independent block. It is not a block copolymer.

[0153] [ka]

[0154] (Synthesis Example 2) Synthesis of MAC-2H35I resin In Synthesis Example 1, replace MAC-4I (1.5g) with MAC-2H35I (2.2g). Aside from the use of the chemical, the following chemical formula (P-MAC-2H35I) is obtained by the same method as in Synthesis Example 1. A resin was obtained. The molecular weight (Mw) of this resin is 14000, and the degree of dispersion (Mw / Mn) is 2.0 That was the case. Also, 13 The following chemical formula (P-MAC-2H35I) was obtained from 1C-NMR measurements. The composition ratio (molar ratio) of the contents was a:b:c:d = 40:30:15:15. See below for further details. The chemical formula (P-MAC-2H35I) is a simplified representation to show the proportion of each constituent unit. However, in the P-MAC-2H35I, each component unit forms an independent block. It is not a block copolymer.

[0155] [ka]

[0156] (Synthesis Example 3) Synthesis of MAC-4H35I resin Replace MAC-4H35I (2.2g) with MAC-4I (1.5g) in Synthesis Example 1. Aside from the use of the chemical, the following chemical formula (P-MAC-4H35I) is obtained by the same method as in Synthesis Example 1. A resin was obtained. The molecular weight (Mw) of this resin is 14000, and the degree of dispersion (Mw / Mn) is 2.0 That was the case. Also, 13 The following chemical formula (P-MAC-4H35I) was obtained from 1C-NMR measurements. The composition ratio (molar ratio) of the contents was a:b:c:d = 40:30:15:15. See below for further details. The chemical formula (P-MAC-4H35I) is a simplified representation to show the proportions of each constituent unit. However, in the P-MAC-4H35I, each component unit forms an independent block. It is not a block copolymer.

[0157] [ka]

[0158] (Synthesis Example 4) Synthesis of MAC-2H35I-BOC resin In Synthesis Example 1, MAC-4I (1.5g) was replaced with MAC-2H35I-BOC(2. Except for using 7g, the method is the same as in Synthesis Example 1, and the chemical formula (P-MAC-2H35I-) is shown below. A resin indicated by BOC was obtained. The molecular weight (Mw) of this resin is 14200, and the degree of dispersion (Mw) is 14200. / Mn) was 2.0. Also, 13 The results of the 1C-NMR measurement revealed the following chemical formula (P-MA The composition ratio (molar ratio) in C-2H35I-BOC is a:b:c:d = 40:30:15: The result was 15. Note that the following chemical formula (P-MAC-2H35I-BOC) represents the individual components of each building block. Although simplified to show the ratio, P-MAC-2H35I-BOC is each component It is not a block copolymer in which each component unit forms an independent block.

[0159] [ka]

[0160] (Synthesis Example 5) Synthesis of MAC-2H35I-MeBOC resin In Synthesis Example 1, MAC-2H35I-MeBOC( ) was used instead of MAC-4I (1.5g) Except for using 2.8g, the method is the same as in Synthesis Example 1, and the chemical formula (P-MAC-2H35) is as follows. A resin represented by I-MeBOC was obtained. The molecular weight (Mw) of this resin is 14300, and the dispersion The degree (Mw / Mn) was 2.0. Also, 13 The following chemical formula was obtained by measuring C-NMR ( The composition ratio (molar ratio) in P-MAC-2H35I-MeBOC) is a:b:c:d=40: The time was 30:15:15. The chemical formula is as follows: (P-MAC-2H35I-MeBOC) This is a simplified description to show the ratio of each constituent unit, but P-MAC-2H35I -MeBOC is a block copolymer in which each constituent unit forms an independent block. It's not the body.

[0161] [ka]

[0162] (Synthesis Example 6) Synthesis of MAC-4H35I-BOC resin In Synthesis Example 1, MAC-4H35I-BOC(2.5g) was used instead of MAC-4I(1.5g). Except for using 7g, the method is the same as in Synthesis Example 1, and the chemical formula (P-MAC-4H35I-) is shown below. A resin indicated by BOC was obtained. The molecular weight (Mw) of this resin is 14300, and the degree of dispersion (Mw) is 14300. / Mn) was 2.0. Also,13 The results of the 1C-NMR measurement revealed the following chemical formula (P-MA The composition ratio (molar ratio) in C-4H35I-BOC is a:b:c:d = 40:30:15: The result was 15. Note that the following chemical formula (P-MAC-4H35I-BOC) represents the individual components of each building block. Although simplified to show the ratio, P-MAC-4H35I-BOC is each component It is not a block copolymer in which each component unit forms an independent block.

[0163] [ka]

[0164] (Synthesis Example 7) Synthesis of MAC-4H35I-MeBOC resin In Synthesis Example 1, MAC-4H35I-MeBOC( ) was used instead of MAC-4I (1.5g) Except for using 2.8g, the method is the same as in Synthesis Example 1, and the chemical formula (P-MAC-4H35) is as follows. A resin represented by I-MeBOC was obtained. The molecular weight (Mw) of this resin is 14400, and the dispersion The degree (Mw / Mn) was 2.0. Also, 13 The following chemical formula was obtained by measuring C-NMR ( The composition ratio (molar ratio) in P-MAC-4H35I-MeBOC) is a:b:c:d=40: The time was 30:15:15. The chemical formula is as follows: (P-MAC-4H35I-MeBOC) This is a simplified description to show the ratio of each constituent unit, but P-MAC-4H35I -MeBOC is a block copolymer in which each constituent unit forms an independent block. It's not the body.

[0165] [ka]

[0166] (Synthesis Example 8) Synthesis of MAC-ADI resin In Synthesis Example 1, MAC-ADI (1.8g) was used instead of MAC-4I (1.5g). Otherwise, the resin represented by the following chemical formula (P-MAC-ADI) is synthesized using the same method as in Synthesis Example 1. The molecular weight (Mw) of this resin was 14400, and its dispersion degree (Mw / Mn) was 1.8. .Also, 13 The results of the 1C-NMR measurement showed that the composition ratio in the following chemical formula (P-MAC-ADI) is The molar ratio was a:b:c:d = 40:30:15:15. The chemical formula (P- MAC-ADI is a simplified representation of the proportion of each constituent unit, but PM AC-ADI is a block copolymer in which each constituent unit forms an independent block. It's not the body. [ka]

[0167] (Synthesis Example 9) Synthesis of MAC-ADI2 resin MAC-ADI2 (2.4g) was used instead of MAC-4I (1.5g) in Synthesis Example 1. Otherwise, the tree represented by the following chemical formula (P-MAC-ADI2) is synthesized in the same manner as in Synthesis Example 1. A lipid was obtained. The molecular weight (Mw) of this resin is 14400, and the degree of dispersion (Mw / Mn) is 1.8. And, 13 The results of the 1C-NMR measurement showed the composition ratio in the following chemical formula (MAC-ADI2) The molar ratio was a:b:c:d = 40:30:15:15. Note that the following chemical formula (P -MAC-ADI2) is a simplified representation to show the ratio of each constituent unit, but P -MAC-ADI2 is a block in which each constituent unit forms an independent block. It is not a copolymer.

[0168] [ka]

[0169] (Synthesis Example 10) Synthesis of MAC-ADIOH resin In Synthesis Example 1, replace MAC-4I (1.5g) with MAC-ADIOH (1.8g). Aside from the use of the compound, the following chemical formula (P-MAC-ADIOH) is obtained by the same method as in Synthesis Example 1. A resin was obtained. The molecular weight (Mw) of this resin is 14400, and the degree of dispersion (Mw / Mn) is 1.7 That was the case. Also, 13 The following chemical formula (P-MAC-ADIOH) was obtained from the 1C-NMR measurement: The composition ratio (molar ratio) of the contents was a:b:c:d = 40:30:15:15. See below for further details. The chemical formula (P-MAC-ADIOH) is written in a simplified form to show the ratio of each constituent unit. However, P-MAC-ADIOH is formed by each constituent unit forming an independent block. It is not a block copolymer.

[0170] [ka]

[0171] (Synthesis Example 11) Synthesis of MAC-MADI resin 4.7g of MAC-MADI and γ-butyrolactone methacrylate were used as monomer raw materials. Using 2.0 g of acid ester and 3.0 g of hydroxyadamantyl methacrylate, A resin represented by the following chemical formula (P-MAC-MADI) was obtained by the same method as in Synthesis Example 1. The molecular weight (Mw) of this resin was 14400, and the degree of dispersion (Mw / Mn) was 1.9. Ta, 13 The results of the 1C-NMR measurement showed that the composition ratio (M) in the following chemical formula (P-MAC-MADI) is The ratio was a:b:c = 40:30:30. The chemical formula is shown below (P-MAC-MA). DI) is a simplified representation to show the ratio of each constituent unit, but P-MAC-MA DI is not a block copolymer in which each constituent unit forms an independent block. stomach.

[0172] [ka]

[0173] (Synthesis Example 12) Synthesis of MAC-MADI-ADIOH resin 2.5g of MAC-ADIOH and 1.8g of MAC-MA are used as monomer monomer raw materials. DI 4.7g, γ-butyrolactone methacrylate 2.0g, and hydroxya Using 1.5 g of mantyl methacrylate, the following chemical formula was synthesized in the same manner as in Synthesis Example 1 ( A resin represented by P-MAC-MADI-ADIOH was obtained. The molecular weight (Mw) of this resin is The value was 14400, and the variance (Mw / Mn) was 2.0. Also, 13 1C-NMR was measured. As a result, the composition ratio (molar ratio) in the following chemical formula (P-MAC-MADI-ADIOH) is a:b The values ​​were :c:d=40:30:15:15. The chemical formula is shown below (P-MAC-MADI). -ADIOH) is a simplified representation to show the ratio of each constituent unit, but P-MA C-MADI-ADIOH is a block in which each constituent unit forms an independent block. It is not a rock copolymer.

[0174] [ka]

[0175] (Synthesis Example 13) Synthesis of MAC-MADI-ADIOH2 resin 4.7g of MAC-MADI and γ-butyrolactone methacrylate were used as monomer raw materials. 2.0 g of ruic acid ester and 3.6 g of MAC-ADIOH were used, with the rest being the same as in Synthesis Example 1. A resin represented by the following chemical formula (P-MAC-MADI-ADIOH2) was obtained using the method described below. The molecular weight (Mw) of this resin was 14400, and the degree of dispersion (Mw / Mn) was 2.0. , 13 The results of the 1C NMR measurement showed that in the following chemical formula (P-MAC-MADI-ADIOH2) The composition ratio (molar ratio) was a:b:c = 40:30:30. The chemical formula (P- MAC-MADI-ADIOH2) is a simplified representation of the proportions of each constituent unit. However, P-MAC-MADI-ADIOH2 is a block in which each constituent unit is independent. It is not a block copolymer that forms a block.

[0176] [ka]

[0177] (Synthesis Example 14) Synthesis of MAC-MADI-35IST resin 4.7g of MAC-MADI and γ-butyrolactone methacrylate were used as monomer raw materials. Using 2.0 g of diiodo-4-hydroxystyrene and 3.7 g of 3,5-diiodo-4-hydroxystyrene, It was synthesized in the same manner as in Synthesis Example 1, with the chemical formula (P-MAC-MADI-35IST) shown below. A resin was obtained. The molecular weight (Mw) of this resin is 14400, and the degree of dispersion (Mw / Mn) is 2. It was 0. Also, 13 The results of the 1C NMR measurement revealed the following chemical formula (P-MAC-MADI- The composition ratio (molar ratio) in 35IST) was a:b:c = 40:30:30. The chemical formula (P-MAC-MADI-35IST) is simplified to show the proportion of each constituent unit. Although it is described as such, P-MAC-MADI-35IST is a unique product where each component unit is independent. It is not a block copolymer that forms upright blocks.

[0178] [ka]

[0179] (Synthesis Example 15) Synthesis of MAC-MADI-35IST-ADIOH resin 4.7g of MAC-MADI and γ-butyrolactone methacrylate were used as monomer raw materials. 2.0g of acid ester, 1.9g of 3,5-diiodo-4-hydroxystyrene, MAC-A Using 1.8 g of DIOH, and otherwise following the same method as in Synthesis Example 1, the following chemical formula (P-MAC-) was synthesized. A resin represented by MADI-35IST-ADIOH was obtained. The molecular weight (Mw) of this resin is The value was 14400, and the variance (Mw / Mn) was 2.0. Also, 13 1C-NMR was measured. As a result, the composition ratio (moles) in the following chemical formula (P-MAC-MADI-35IST-ADIOH) The ratio was a:b:c:d = 40:30:15:15. The chemical formula (P-MA) is shown below. C-MADI-35IST-ADIOH) is a simplified notation used to show the ratio of each constituent unit. Although it is listed, P-MAC-MADI-35IST-ADIOH is a compound where each component unit is It is not a block copolymer in which each component forms an independent block.

[0180] [ka]

[0181] (Synthesis Example 16) Synthesis of MAC-ADIOH-CLMAA resin 8.1g of MAC-ADIOH and 2-methyl chloroacrylate were used as monomer raw materials. Using 1.9 g of ruester, the following chemical formula (P-MAC-) was prepared by the same method as in Synthesis Example 1. A resin represented by ADIOH-CLMAA was obtained. The molecular weight (Mw) of this resin is 1440. The variance (Mw / Mn) was 0, and the variance was 2.0. Also, 13 The following results were obtained from measuring C-NMR: The composition ratio (molar ratio) in the chemical formula (P-MAC-ADIOH-CLMAA) is a:b = 50: The result was 50. Note that the following chemical formula (P-MAC-ADIOH-CLMAA) represents each of the constituent elements. It is written simply to show the ratio of the positions, but P-MAC-MADIOH-CLMA A is not a block copolymer in which each constituent unit forms an independent block. .

[0182] [ka] [ka]

[0183] (Synthesis Example 17) Synthesis of MAC-4H35I-CLMAA resin 7.4g of MAC-4H35I and methyl 2-chloroacrylate were used as monomer raw materials. Using 1.9 g of ruester, the following chemical formula (P-MAC-) was prepared by the same method as in Synthesis Example 1. A resin represented by 4H35I-CLMAA was obtained. The molecular weight (Mw) of this resin is 1440. The variance (Mw / Mn) was 0, and the variance was 2.0. Also, 13 The following results were obtained from measuring C-NMR: The composition ratio (molar ratio) in the chemical formula (P-MAC-4H35I-CLMAA) is a:b = 50: The result was 50. Note that the following chemical formula (P-MAC-4H35I-CLMAA) represents each of the constituent elements. It is written simply to show the ratio of positions, but P-MAC-4H35I-CLMAA It is not a block copolymer in which each constituent unit forms an independent block.

[0184] [ka]

[0185] (Synthesis Example 18) Synthesis of MAC-ADI2-4H35I resin The monomer monomer raw materials are MAC-ADI2 3.9g and MAC-4H35I 3. 7g of methyl 2-chloroacrylate and 1.9g of methyl 2-chloroacrylate were used, and the rest was the same as in Synthesis Example 1. A resin represented by the following chemical formula (P-MAC-ADI2-4H35I) was obtained using this method. The molecular weight (Mw) of the lipid was 14400, and the degree of dispersion (Mw / Mn) was 2.0. Also, 13 C -NMR measurements revealed the composition ratio in the following chemical formula (P-MAC-ADI2-4H35I) The molar ratio was a:b:c = 25:25:50. The chemical formula (P-MAC-) is shown below. ADI2-4H35I) is a simplified description to show the ratio of each constituent unit, The P-MAC-ADI2-4H35I consists of components that each form an independent block. It is not a block copolymer.

[0186] [ka]

[0187] (Synthesis Example 19) Synthesis of ACLAC-2H35I-AMST resin 7.4g of ACLAC-2H35I and α-methylstyrene 1 as monomer monomer raw materials. Using 0.9g, the rest of the synthesis was carried out in the same manner as in Synthesis Example 1, resulting in the following chemical formula (P-ACLAC-2H35 A resin represented by I-AMST was obtained. The molecular weight (Mw) of this resin was 14400, and the degree of dispersion was (Mw / Mn) was 2.0. Also, 13 The results of the 1C-NMR measurement revealed the following chemical formula (P The composition ratio (molar ratio) in ACLAC-2H35I-AMST is a:b = 50:50. The chemical formula below (P-ACLAC-2H35I-AMST) represents the ratio of each constituent unit. Although it is described simply to show the rate, P-ACLAC-2H35I-AMST is, It is not a block copolymer in which each constituent unit forms an independent block.

[0188] [ka]

[0189] (Synthesis Example 20) Synthesis of MAC-4H35I-ACLAC-2H35I resin 7.4g of MAC-4H35I and ACLAC-2H35I were used as monomer raw materials. Using 7.4g, the rest was synthesized in the same manner as in Synthesis Example 1, resulting in the following chemical formula (P-MAC-4H35I A resin represented by (ACLAC-2H35I) was obtained. The molecular weight (Mw) of this resin is 144. The variance (Mw / Mn) was 2.0. Also, 13 The results of measuring C-NMR were as follows: The composition ratio (molar ratio) in the chemical formula (P-MAC-4H35I-ACLAC-2H35I) is a:b=50:50. The chemical formula is shown below (P-MAC-4H35I-ACLAC). -2H35I) is a simplified representation to show the ratio of each constituent unit, but P-MA C-4H35I-ACLAC-2H35I is a system where each component unit is an independent block. It is not a block copolymer that has been formed.

[0190] [ka]

[0191] (Synthesis Example 21) Synthesis of ACLAC-ADI2-AMST resin The monomer monomer raw materials are ACLAC-ADI2 7.9g and α-methylstyrene 1. Using 9g, the rest of the process was carried out in the same manner as in Synthesis Example 1, resulting in the following chemical formula (P-ACLAC-ADI2- A resin indicated by AMST was obtained. The molecular weight (Mw) of this resin is 14400, and the degree of dispersion (M w / Mn was 2.0. Also, 13 The following chemical formula (PA) was obtained by measuring C-NMR. The composition ratio (molar ratio) in CLAC-ADI2-AMST was a:b = 50:50. The following chemical formula (P-ACLAC-ADI2-AMST) indicates the ratio of each constituent unit. Although described in a simplified manner for the sake of brevity, P-ACLAC-ADI2-AMST is a component unit of each component. It is not a block copolymer in which each component forms an independent block.

[0192] [ka]

[0193] (Synthesis Comparison Example 1) The synthesis was carried out in the same manner as in Synthesis Example 1, except that MAC-4I was not used, and the following chemical formula (P-AC A resin represented by -1) was obtained. The molecular weight (Mw) of this resin is 13500, and the degree of dispersion is ( The ratio of Mw / Mn was 2.30.

[0194] [ka]

[0195] In the above formula (P-AC-1), "40", "40", and "20" represent the molar ratio of each constituent unit. As shown, equation (P-AC-1) is written in a simplified form to show the ratio of each constituent unit. P-AC-1 is a block-based system where each constituent unit forms an independent block. It's not a fusion.

[0196] (Example 1) MAC-4I resin (P-MAC-4I) solution is applied to a silicon wafer, and 110~ A photoresist layer with a thickness of 100 nm was formed by baking at 130°C for 60 seconds. The resin solution consists of 5 parts by mass of the resin with the above chemical formula (P-MAC-4I) and triphenylsulfonyl Munonafluoromethanesulfonate: 1 part by mass, Tributylamine: 0.1 parts by mass, PG Prepared by incorporating 92 parts by mass of MEA. Next, exposure was performed using an electron beam lithography system (ELS-7500, 50keV, manufactured by Elionix Corporation). Then, bake at 115°C for 90 seconds (PEB) to 2.38% by mass of tetramethylammonium. Developed with an aqueous solution of hydrogen peroxide (TMAH) for 60 seconds to obtain a positive-type pattern. Resolution and The sensitivity results are shown in Table 1.

[0197] (Example 2) MAC-2H35I resin (PM) can be used instead of MAC-4I resin (P-MAC-4I) solution. A photoresist layer was formed in the same manner as in Example 1, except that the AC-2H35I solution was used. The resolution and sensitivity results are shown in Table 1.

[0198] (Example 3) MAC-4H35I resin (PM) can be used instead of MAC-4I resin (P-MAC-4I) solution. A photoresist layer is formed in the same manner as in Example 1, except that an AC-4H35I solution is used. The resolution and sensitivity results are shown in Table 1.

[0199] (Comparative Example 1) In a resin solution, the resin with chemical formula (P-MAC-4I) is replaced with the resin with chemical formula (P-AC-1). Except for the substitution of one component, the resin solution was prepared in the same manner as in Example 1, and a photoresist layer was formed. The pattern was developed in the same manner as in Example 1 to obtain a positive type pattern. The resolution and sensitivity results are shown in Table 1. show.

[0200] (Time elapsed) The resin solution used to form the prepared resist layer was stored in a light-shielding bottle at 40°C for 3 minutes. A 0-day time-lapse test was conducted, and defects after the time lapse were evaluated using the following method. In other words, the resin solutions used for forming the resist layer before and after the time-lapse test were made from different silicon The wafer is coated with a spin coater, and then heated on a hot plate at 110°C for 1 minute. A resist layer with a thickness of 80 nm was formed by performing a procedure. Next, the extreme ultraviolet (EUV) exposure system "EUVES-7000" (product name, lithotech) (Manufactured by K Japan Co., Ltd.) 1 mJ / cm² 2 From 1 mJ / cm 2 80 mJ / cm² each 2 Until the dew After performing maskless shot exposure with increased light intensity across the entire wafer, it was heated at 110°C for 9 Bake for 0 seconds (PEB), develop with isoamyl acetate for 60 seconds, and apply 80 shots to the wafer. A wafer was obtained after exposure of several shots. For each of the obtained shot exposure areas, light drying was performed. Film thickness gauge "VM3200" (product name, manufactured by SCREEN Semiconductor Solutions Co., Ltd.) The film thickness is measured using a device (manufactured by YONS), and profile data of the film thickness in relation to the exposure amount is obtained. The exposure value (mJ / cm²) at which the slope of film thickness variation with respect to light intensity is greatest is the sensitivity value. 2 ) This was calculated and used as an indicator of the EUV sensitivity of the resist. Furthermore, the resin solution used to form the created resist layer underwent a 30-day time-lapse test at 40°C. The above sensitivity evaluation was performed on the resin solution before and after the treatment, and the rate of change in sensitivity over time was determined by the following indicators. This was determined by [method / method]. "Rate of change" = [("Sensitivity of resin solution before time passage" - "Sensitivity of resin solution after time passage") / "Time passage" Sensitivity of the previous resin solution] × 100 A. Fluctuation rate is less than 2% B. Fluctuation rate is 2% or more but less than 5% C. Fluctuation rate is 5% or more but less than 10% D. Fluctuation rate of 10% or more

[0201] [Table 1]

[0202] (Example 16) (Resolution evaluation) P-MAC-ADIOH-CLMMA resin (P-MAC-AD) described in Synthesis Example 16 The IOH-CLMMA solution is applied to a silicon wafer and baked at 110°C for 60 seconds. A photoresist layer with a thickness of 100 nm was formed. Here, the resin solution was the above chemical formula (P- The mixture contains 7 parts by mass of MAC-ADIOH-CLMMA resin and 93.9 parts by mass of PGMEA. Combined and prepared. Next, exposure was performed using an electron beam lithography system (ELS-7500, 50keV, manufactured by Elionix Corporation). Then, bake at 115°C for 90 seconds (PEB), and use isoamyl acetate as the developer for 60 seconds. The film was developed for several seconds to obtain a positive-type pattern. The resolution and sensitivity results are shown in Table 2.

[0203] (Time elapsed) P-MAC-ADIOH-CLMMA resin (P-MAC-AD) described in Synthesis Example 16 Using an IOH-CLMMA solution, the treatment before and after 30 days of incubation at 40°C in a light-shielded environment was performed. After preparing identical resin solutions except for the presence or absence of a particle, and depositing each onto a wafer using a spin coater... Developing was performed using isoamyl acetate as the developer, and the sensitivity before and after time was determined as follows: The performance over time was evaluated by deriving the rate of change using the indicator. "Rate of change" = [("Sensitivity of resin solution before time passage" - "Sensitivity of resin solution after time passage") / "Time passage" Sensitivity of the previous resin solution] × 100 A. Fluctuation is less than 2% B. Fluctuation rate is 2% or more but less than 5% C. Fluctuation rate is 5% or more but less than 10% D. Fluctuation rate of 10% or more

[0204] Similar evaluations were performed on materials from Synthesis Example 17 onward. The results are shown in the table. [Table 2]

[0205] As described above, the iodine-containing (meth)acrylate compound of this embodiment, and / or iodine By using a polymer-containing (meth)acrylate (co)polymer, high-resolution and high-sensitivity lithography is achieved. A composition capable of forming a film can be obtained.

[0206] The present invention provides compounds, compositions, and other materials capable of forming films with high resolution and sensitivity. This provides a method for forming a resist pattern and an insulating film using this method.

Claims

1. An iodine-containing (meth)acrylate compound represented by general formula (1). 【Chemistry 1】 (In formula (1), R 1 This represents a hydrogen atom, a methyl group, or a halogen group. R 2 These are, independently, a hydrogen atom, a linear organic group with 1 to 20 carbon atoms, and a group with 3 to 20 carbon atoms. This represents 20 branched organic groups, or cyclic organic groups with 3 to 20 carbon atoms. A represents an organic group with 1 to 30 carbon atoms. n 1 represents 0 or 1, n 2 (This represents an integer between 1 and 20.)

2. The iodine-containing (meth)actin according to claim 1, wherein the general formula (1) is general formula (2). Relate compounds. 【Chemistry 2】 (In formula (2), R 1 , A, n 2 (This is as defined in claim 1.)

3. The iodine-containing (meth)actin according to claim 2, wherein the general formula (2) is general formula (3). Relate compounds. 【Transformation 3】 (In formula (3), B represents an organic group with 5 to 30 carbon atoms that contains an aromatic ring. R 1 , n 2 (This is as defined in claim 1.)

4. The iodine-containing (meth)a according to claim 2, wherein the general formula (2) is general formula (3'). Crilate compounds. 【Chemistry 4】 (In formula (3'), B' represents an organic group with 5 to 30 carbon atoms that includes an alicyclic ring. R 1 、n 2 is as defined in claim 1.)

5. n 2 The iodine-containing (meth) axle represents an integer from 2 to 20, according to any one of claims 1 to 4. Crilate compounds.

6. Iodine-containing (meth)acrylate (co) having repeating units represented by general formula (4) ) Polymer. 【Transformation 5】 (In formula (4), R 1 This represents a hydrogen atom, a methyl group, or a halogen. R 2 These are, independently, a hydrogen atom, a linear organic group with 1 to 20 carbon atoms, and a group with 3 to 20 carbon atoms. This represents 20 branched organic groups, or cyclic organic groups with 3 to 20 carbon atoms. A represents an organic group with 1 to 30 carbon atoms. n 1 represents 0 or 1, n 2 This represents an integer from 1 to 20. The asterisk (*) indicates a connection point with an adjacent repeating unit.

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

8. The iodine-containing (meth)actin according to claim 7, wherein the general formula (5) is general formula (6). Relate (co)polymer. 【Transformation 7】 (In formula (6), B represents an organic group with 5 to 30 carbon atoms that contains an aromatic ring. R 1 , n 2 (The symbol * is as defined in claim 6.)

9. The iodine-containing (meth)a according to claim 7, wherein the general formula (5) is general formula (6'). acrylate (co)polymer. 【Transformation 8】 (In formula (6'), B' represents an organic group with 5 to 30 carbon atoms that includes an alicyclic ring. R 1 , n 2 (The symbol * is as defined in claim 6.)

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

11. The iodine-containing (meth)acrylate (co)polymer according to any one of claims 6 to 10 is included. Hmm, composition.

12. The composition according to 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. A step of forming a film using the composition according to any one of claims 11 to 14, The step of exposing the film, and A step of removing the exposed parts of the exposed film using a developing solution to form a pattern, A pattern formation method, including the following.

16. Iodine-containing hydroxy compounds represented by general formula (a) are expressed by (me (t) The iodine-containing (meth) acrylic acid compound according to claim 1, comprising reacting with an acrylic acid compound. A method for producing acrylate compounds. 【Chemistry 9】 (In formula (a), R 2 , A, n 1 , n 2 (This is as defined in claim 1.) 【Chemistry 10】 (In formula (b), R 1 This is as defined in claim 1, R B It consists of a hydroxyl group, a halogen atom, and a (meth)acryloyloxy group. (Selected from the group.)

17. The iodine-containing (meth) according to claim 16, wherein the general formula (a) is general formula (a1) A method for producing acrylate compounds. 【Chemistry 11】 (In formula (a1), A, n 2 (This is as defined in claim 1.)

18. The iodine-containing (meth) product according to claim 16, wherein the general formula (a) is general formula (a2). A method for producing acrylate compounds. 【Chemistry 12】 (In formula (a2), B represents an organic group with 5 to 30 carbon atoms that contains an aromatic ring. n 2 (This is as defined in claim 1.)

19. The iodine-containing (meth) product according to claim 16, wherein the general formula (a) is general formula (a3) A method for producing acrylate compounds. 【Chemistry 13】 (In formula (a3), B' represents an organic group with 5 to 30 carbon atoms that includes an alicyclic ring. n 2 (This is as defined in claim 1.)

20. n 2 The iodine-containing (meta) according to any one of claims 16 to 19, wherein is an integer from 2 to 20. ) A method for producing acrylate compounds.

21. An iodine-containing hydroxy compound represented by general formula (a). 【Chemistry 14】 (In formula (a), R 2 These are, independently, a hydrogen atom, a linear organic group with 1 to 20 carbon atoms, and a group with 3 to 20 carbon atoms. This represents 20 branched organic groups, or cyclic organic groups with 3 to 20 carbon atoms. A represents an organic group with 1 to 30 carbon atoms. n 1 represents 0 or 1, n 2 (This represents an integer between 1 and 20.)

22. The general formula (a) is the general formula (a1) as described in claim 21, the iodine-containing hydro A compound. 【Chemistry 15】 (In formula (a1), A, n 2 (This is as defined in claim 21.)

23. The iodine-containing hydro according to claim 22, wherein the general formula (a1) is general formula (a2). Xy compounds. 【Chemistry 16】 (In formula (a2), B represents an organic group with 5 to 30 carbon atoms that contains an aromatic ring. n 2 (This is as defined in claim 21.)

24. The iodine-containing hydro according to claim 22, wherein the general formula (a1) is general formula (a3). Xy compounds. 【Chemistry 17】 (In formula (a3), B' represents an organic group with 5 to 30 carbon atoms that includes an alicyclic ring. n 2 (This is as defined in claim 21.)

25. n 2 The iodine-containing hydro according to any one of claims 21 to 24, wherein is an integer from 2 to 20 Xy compounds.

26. Iodine introduction reaction for compounds represented by the following general formula (Sa1) or general formula (Sa2) The preparation of the iodine-containing (meth)acrylate compound according to claim 16, further comprising the step of performing the following steps. Construction method. [Chemistry 18] (In formula (Sa1), R 2 , A, n 1 , n 2 This is as defined in claim 1, X is a hydroxyl group; a small number of groups selected from the group consisting of hydroxyl groups, aldehyde groups, and carboxyl groups. Aliphatic or aromatic group having 1 to 30 carbon atoms, having at least one of these; or a halogen group; (Selected from the following group) 【Chemistry 19】 (In formula (Sa2), A, n 2 This is as defined in claim 1, X is defined as in equation (Sa1), E is a hydroxyl group, aldehyde group, carboxyl group, ether group, thiol group and amino group (A hydrocarbon group having 1 to 30 carbon atoms, having at least one selected from the group consisting of the following.)

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