Iodine-containing polymerizable compound and iodine-containing polymer

Abstract

The present invention addresses the problem of providing a compound that makes it possible to efficiently produce a resist material having improved sensitivity with respect to an exposure light source. Provided as a solution is a compound represented by formula (I). Ring A represents an aromatic ring. Ring B represents an aromatic ring, a non-aromatic ring, or a condensed ring of these. X1 and X2 each represent a single bond or a divalent organic group. R1, R2, and R3 each represent a hydrogen atom, a methyl group, or a halogen atom. R4 and R5 each represent a substituent. R6 and R7 each represent an alkyl group that may have a substituent. a, b, c, and e each represent an integer of 1 or more. d and f each represent 0 or an integer of 1 or more.

Description

Iodine-containing polymerizable compounds and iodine-containing polymers

[0001] This invention relates to iodine-containing polymerizable compounds and iodine-containing polymers.

[0002] In recent years, advances in lithography technology have led to rapid miniaturization of semiconductors (patterns) and pixels in the manufacturing of semiconductor devices and liquid crystal display elements. To achieve pixel miniaturization, the wavelength of the exposure light source is generally shortened. Specifically, while ultraviolet light, represented by g-line and i-line ultraviolet light, was conventionally used, methods using far-ultraviolet light such as KrF excimer lasers and ArF excimer lasers are now becoming the main method for mass production, and the introduction of extreme ultraviolet (EUV) lithography is also progressing. In addition, electron beams (EB) are used to form fine patterns.

[0003] Conventional resist materials are polymer-based resist materials capable of forming amorphous films. In the past, line patterns of approximately 10 to 100 nm were formed on resist thin films created by coating solutions of these resist compositions onto a substrate, and then irradiating these films with ultraviolet light, far-ultraviolet light, electron beams, extreme ultraviolet light, etc.

[0004] Furthermore, electron beam or extreme ultraviolet lithography has a different reaction mechanism than conventional photolithography. Moreover, electron beam or extreme ultraviolet lithography aims to form fine patterns ranging from a few nanometers to over ten nanometers in size. As the dimensions of the resist patterns become smaller, a resist composition with even higher sensitivity to the exposure light source is required. In particular, extreme ultraviolet lithography demands even higher sensitivity in terms of throughput.

[0005] To improve the aforementioned problems, polymers using polymerizable compounds containing iodine have been proposed as resist materials (see, for example, Patent Documents 1 to 3).

[0006] Japanese Patent Publication No. 2021-188041, International Publication No. 2020 / 137935, International Publication No. 2021 / 029395

[0007] However, conventional iodine-containing polymerizable compounds have not exhibited sufficient sensitivity to exposure light sources.

[0008] An object of the present invention is to provide a compound capable of efficiently producing a resist material with further improved sensitivity to an exposure light source, and a polymer that can be used as the resist material.

[0009] In order to achieve the object of the present invention, the present inventors conducted intensive studies, and as a result, found that the aforementioned problems can be solved by using a specific iodine-containing polymerizable compound, thereby completing the present invention.

[0010] That is, the present invention is as follows. [1] Formula (I):

[0011]

[0012] [wherein, Ring A represents an aromatic ring; each Ring B independently represents an aromatic ring, a non-aromatic ring, or a fused ring thereof; X １ and X ２ each independently represent a single bond or a divalent organic group; R １ , R ２ and R ３ each independently represent a hydrogen atom, a methyl group, or a halogen atom; R ４ and R ５ each independently represent a substituent; R ６ and R ７ each independently represent an optionally substituted alkyl group; a, b, c and e each independently represent an integer of 1 or more; d and f each independently represent 0 or an integer of 1 or more.] A compound represented by the formula. [2] The compound according to the above [1], wherein a is 1. [3] Formula (1) or (2):

[0013]

[0014] [wherein, Ring A' represents a 6 to 14-membered aromatic carbocycle; each Ring B' independently represents a 6 to 14-membered aromatic carbocycle, a 3 to 14-membered non-aromatic carbocycle, or a fused ring thereof; R １１R represents a hydrogen atom or a methyl group; ４ and R ５ Each of these independently represents a substituent; R ６ and R ７ Each independently represents an alkyl group which may have substituents; R ｘ , R ｙ and R ｚ Each of the following compounds is represented by [2] above: b, c, and e each independently represent an integer of 1 or more; d and f each independently represent 0 or an integer of 1 or more; g each independently represents 1, 2, 3, 4, or 5. [4] Formulas (1a) to (2r):

[0015]

[0016]

[0017]

[0018]

[0019]

[0020]

[0021] [In the formula, R １１ R represents a hydrogen atom or a methyl group; ｘ and R ｙ Each of these independently represents either a hydrogen atom or an alkyl group; R ａ , R ｂ , R ｃ , R ｄ and R ｅ Each of these independently represents a hydrogen atom or a substituent (excluding an iodine atom), and R ａ , R ｂ , R ｃ , R ｄ and R ｅ At least one of the terms displayed in each equation is equation (X):

[0022]

[0023] (In the formula, ring B'' represents a 6- to 14-membered aromatic carbon ring or a 3- to 14-membered non-aromatic carbon ring; R ５ Each of these independently represents a substituent; R ６ and R ７ Each independently represents an alkyl group which may have substituents; e represents an integer of 1 or more; f represents 0 or an integer of 1 or more; g represents 1, 2, 3, 4 or 5; * represents a bonding site.) The group is represented by any of the following, the compound described in [3] above. [5] A composition for manufacturing a resist material, comprising the compound described in any of [1] to [4] above. [6] (α) The compound described in any of [1] to [4] above, and (β) Formula (II):

[0024]

[0025] [In the formula, ring A ａ Each of these independently represents an aromatic ring; X ａ１ Each independently represents a single bond or a divalent organic group; R ａ１ and R ａ２ Each of these independently represents a hydrogen atom, a methyl group, or a halogen atom; R ａ４ Each of these independently represents a substituent; n ａ b indicates 1, 2, 3, 4, 5, 6, or 7; b ａ Each of these independently represents an integer greater than or equal to 1; d ａ represents 0 or an integer of 1 or more. A composition containing a compound represented by ]. [7] In formula (II), d ａ However, it is an integer greater than or equal to 1, R ａ４ However, each is independently a substituent and -(R ａ４ ) ｄ ａ Each d ａ Individual R ａ４ At least one of them is a hydroxyl group, or formula (XA''):

[0026]

[0027] [In the formula, ring B ａ X represents an aromatic ring, a non-aromatic ring, or a fused ring thereof;ａ２ R represents a single bond or a divalent organic group; ａ５ Each of these independently represents a substituent; R ａ６ and R ａ７ Each independently represents an alkyl group which may have substituents; e ａ f represents an integer greater than or equal to 1; ａ is an integer of 0 or 1 or more; * is a bonding site. The composition according to [6] above, wherein the group is represented by ]. [8] The composition according to [6] or [7] above, wherein the content of the compound represented by formula (II) is 0.0001% by mass to 10% by mass based on 100% by mass of the total of the compounds described in any of [1] to [4] above and the compound represented by formula (II). [9] (α) A compound described in any of [1] to [4] above, and (γ) Formula (III):

[0028]

[0029] [In the formula, ring B ｂ Each of these independently represents an aromatic ring; X ｂ Each of these independently exhibits an acid-dissociable linking group; R ｂ５ Each of these independently represents a substituent that does not have an intercarbon double bond; n ｂ e represents an integer greater than or equal to 1; ｂ Each of these independently represents an integer greater than or equal to 1; f ｂ A composition comprising a compound represented by [ ].

[10] In formula (III), X ｂ However, each is independent of equation (XB-1) or (XB-2):

[0030]

[0031] [In the formula, R ｂ６ and R ｂ７ Each independently represents an alkyl group which may have substituents; R ｂｚ Each independently represents either a hydrogen atom or an alkyl group; g ｂThe composition according to [9] above, wherein each independently represents 1, 2, 3, 4, or 5; * indicates a binding site.

[11] The composition according to [9] or

[10] above, wherein the content of the compound represented by formula (III) is 0.0001% by mass to 10% by mass, based on 100% by mass of the total of the compounds according to any one of [1] to [4] above and the compound represented by formula (III).

[12] A composition comprising (α) the compound according to any one of [1] to [4] above, and (δ) at least one compound selected from (meth)acrylic acid ester compounds having an adamantane skeleton, (meth)acrylic acid ester compounds having a lactone skeleton, and compounds having a hydroxystyrene skeleton.

[13] The composition according to any one of [6] to

[12] above, for use in a polymerization reaction to produce a polymer.

[14] Formula (UI):

[0032]

[0033] [In the formula, ring A represents an aromatic ring; ring B independently represents an aromatic ring, a non-aromatic ring, or a fused ring thereof; X １ and X ２ Each independently represents a single bond or an organic group; R １ , R ２ and R ３ Each of these independently represents a hydrogen atom, a methyl group, or a halogen atom; R ４ and R ５ Each of these independently represents a substituent; R ６ and R ７

[15] A polymer having repeating units represented by

[14] , wherein a is an alkyl group which may have substituents; a, b, c, and e are each an integer of 1 or more; and d and f are each an integer of 0 or 1 or more.

[16] A polymer according to

[14] or

[15] , further having repeating units derived from at least one compound selected from an adamantane skeleton (meth)acrylic acid ester compound, a lactone skeleton (meth)acrylic acid ester compound, and a compound having a hydroxystyrene skeleton.

[17] A polymer according to any one of

[14] to

[16] , having a weight-average molecular weight (Mw) of 5,000 to 30,000.

[18] A resist composition comprising the polymer according to any one of

[14] to

[17] .

[19] A composition comprising the polymer according to any one of

[14] to

[17] and an acid generator.

[20] A method for manufacturing a resist pattern, comprising the steps of: (i) forming a resist layer containing a polymer according to any one of

[14] to

[17] on a substrate; (ii) exposing the resist layer formed in step (i); and (iii) developing the resist layer exposed in step (ii).

[21] A method for manufacturing an electronic device, comprising the steps of: (i) forming a resist layer containing a polymer according to any one of

[14] to

[17] on a substrate; (ii) exposing the resist layer formed in step (i); and (iii) developing the resist layer exposed in step (ii).

[0034] According to the compound of the present invention, a resist material with improved sensitivity to an exposure light source can be efficiently manufactured. According to the polymer of the present invention, by using it as a resist material, the sensitivity of the photoresist layer to an exposure light source can be further improved.

[0035] The present invention will be described in detail below with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and can be modified and implemented as appropriate without departing from the scope of the claims and equivalents of the present invention.

[0036] <<Compound for Resist Material Manufacturing>> This embodiment uses formula (I):

[0037]

[0038] [In the formula, ring A represents an aromatic ring; ring B independently represents an aromatic ring, a non-aromatic ring, or a fused ring thereof; X １ and X ２ Each independently represents a single bond or a divalent organic group; R １ , R ２ and R ３ Each of these independently represents a hydrogen atom, a methyl group, or a halogen atom; R ４ and R ５ Each of these independently represents a substituent; R ６ and R ７ The present invention provides a compound represented by [formula (I)], where each independently represents an optionally substituted alkyl group; where each independently represents an integer of 1 or more; and where each independently represents 0 or an integer of 1 or more. A compound having the structure of formula (I) can efficiently produce a resist material with improved sensitivity to exposure light sources. In one embodiment, resolution can be further improved, roughness can be further reduced, and exposure defects can be further suppressed.

[0039] Ring A represents an aromatic ring.

[0040] In this specification, an aromatic ring means a ring that obeys Hückel's rule, where the number of electrons in the π-electron system on the ring is 4p + 2 (where p is a natural number) (a ring having aromaticity throughout). The aromatic ring may be an aromatic carbocyclic ring having only carbon atoms as ring constituent atoms, or an aromatic heterocyclic ring having 1 to 4 heteroatoms such as oxygen, nitrogen, and sulfur atoms in addition to carbon atoms as ring constituent atoms, but in one embodiment, it is preferably an aromatic carbocyclic ring. The aromatic ring may be a monocyclic aromatic ring or a polycyclic fused aromatic ring formed by the fusion of two or more monocyclic aromatic rings. The aromatic ring is preferably an aromatic ring with 5 to 22 members, more preferably an aromatic ring with 5 to 18 members, even more preferably an aromatic ring with 5 to 14 members, and particularly preferably an aromatic carbocyclic ring with 6 to 14 members. Examples of aromatic rings include, but are not limited to, the rings represented by formulas (A1) to (A11). In particular, it is preferable that the ring is a benzene ring (represented by formula (A1)) or a naphthalene ring (represented by formula (A2)), and especially preferable that it is a benzene ring (represented by formula (A1)).

[0041]

[0042] In one embodiment, ring A is preferably a 6- to 14-membered aromatic carbon ring; more preferably a benzene ring or a naphthalene ring; and particularly preferably a benzene ring.

[0043] Each ring B independently represents an aromatic ring, a non-aromatic ring, or a fused ring thereof.

[0044] In this specification, a non-aromatic ring means a ring that does not have aromaticity as a whole. A non-aromatic ring may be a non-aromatic carbocyclic ring having only carbon atoms as ring constituent atoms, or a non-aromatic heterocyclic ring having one or more (e.g., 1 to 4) heteroatoms such as oxygen, nitrogen, or sulfur atoms in addition to carbon atoms as ring constituent atoms, but a non-aromatic carbocyclic ring is preferred. A non-aromatic ring may be a monocyclic or polycyclic non-aromatic ring. A non-aromatic ring may be a saturated ring consisting only of single bonds, or an unsaturated ring having double bonds in addition to single bonds. A non-aromatic ring may be substituted with 1 to 3 oxo groups (=O). A non-aromatic ring is preferably a 3 to 22-membered non-aromatic ring, more preferably a 3 to 18-membered non-aromatic ring, and even more preferably a 3 to 14-membered non-aromatic ring. Examples of non-aromatic rings include, but are not limited to, the rings represented by formulas (B1) to (B77). Among these, the adamantane ring (the ring represented by formula (B12)) is preferred.

[0045]

[0046] Examples of fused rings of aromatic and non-aromatic rings include, but are not limited to, the rings represented by formulas (C1) to (C29).

[0047]

[0048] In one embodiment, ring B is preferably independently a 6-14 member aromatic carbon ring, a 3-14 member non-aromatic carbon ring, or a condensed ring thereof, more preferably a 6-14 member aromatic carbon ring or a 3-14 member non-aromatic carbon ring, even more preferably a benzene ring, a naphthalene ring, or an adamantane ring, and particularly preferably a benzene ring or an adamantane ring.

[0049] X １ This indicates a single bond or a divalent organic group.

[0050] In the present specification, the divalent organic group is not particularly limited, and means, for example, a divalent group composed of one or more (for example 1 to 100, preferably 1 to 50, particularly preferably 1 to 20) skeleton atoms selected from a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom (preferably a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom), non-skeleton atoms, if present, are composed of atoms selected from a hydrogen atom and a halogen atom, which may include a linear structure, a branched chain structure and / or a cyclic structure, and may be a group containing no aromatic ring or a group containing an aromatic ring.

[0051] X １ is, in one embodiment, preferably a single bond or a group represented by Formulas (L1) to (L44):

[0052]

[0053]

[0054] [In the formula, R Ｌ each independently represents a substituent; s represents 0, 1, 2, 3, or 4.] and more preferably a single bond or a group represented by Formulas (L6) to (L11).

[0055] In the present specification, the substituent is, for example, a monovalent group composed of one or more (for example 1 to 100, preferably 1 to 50, particularly preferably 1 to 20) skeleton atoms selected from a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom (preferably a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom), or a monovalent group consisting only of a halogen atom, non-skeleton atoms, if present, are composed of atoms selected from a hydrogen atom and a halogen atom, which may include a linear structure, a branched chain structure and / or a cyclic structure, and may be a group containing no aromatic ring or a group containing an aromatic ring. The number of substituents for the substitution target is, unless otherwise specified, for example 1 to 10. Examples of the substituent are not particularly limited, and include, for example, a halogen atom, -NO ２ , -CN, -CHO, -OH, -SH, -NH ２ , -COOH, -R Ａ , -COR Ａ , -ORＡ , -SR Ａ , -SOR Ａ , -SO ２ R Ａ , -NHR Ａ , -N(R Ａ ) ２ , -COOR Ａ , -OCOR Ａ , -OCOOR Ａ , -CONH ２ , -CONHR Ａ , -CON(R Ａ ) ２ , -NHCOR Ａ , -P(R Ａ ) ２ , -P(OR Ａ )R Ａ , -P(OR Ａ ) ２ , -PO(OR Ａ )R Ａ , -PO(OR Ａ ) ２ , -OP(R Ａ ) ２ , -OP(OR Ａ )R Ａ , -OP(OR Ａ ) ２ , -OPO(R Ａ ) ２ , -OPO(OR Ａ )R Ａ , -OPO(OR Ａ ) ２ and the like monovalent groups are exemplified (here, R Ａ is as defined below).

[0056] R ＡEach of these can independently be an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, or an optionally substituted heterocyclic group, more specifically, (1) an alkyl group which may be substituted with one or more (e.g., 1 to 5) groups selected from the following groups (a) to (x); (2) an alkenyl group which may be substituted with one or more (e.g., 1 to 5) groups selected from the following groups (a) to (x); (3) an aryl group which may be substituted with one or more (e.g., 1 to 5) groups selected from the following groups (a) to (aa); or (4) a heterocyclic group which may be substituted with one or more (e.g., 1 to 5) groups selected from the following groups (a) to (aa).

[0057] (a) halogen atom, (b) nitro group (-NO ２(c) cyano group (-CN), (d) hydroxyl group (-OH), (e) aryl group which may be substituted with a halogen atom, (f) alkyl-substituted aryl group which may be substituted with a halogen atom, (g) alkoxy group which may be substituted with a halogen atom, (h) alkenyloxy group which may be substituted with a halogen atom, (i) aryloxy group which may be substituted with a halogen atom, (j) aralkyloxy group which may be substituted with a halogen atom, (k) alkylcarbonyl group which may be substituted with a halogen atom, (l) alkenylcarbonyl group which may be substituted with a halogen atom, (m) arylcarbonyl group which may be substituted with a halogen atom, (n) aralkylcarbonyl group which may be substituted with a halogen atom, (o) alkylcarbonyloxy group which may be substituted with a halogen atom, (p) halogen atom (q) A arylcarbonyloxy group which may be substituted with a halogen atom, (r) Aalkylcarbonyloxy group which may be substituted with a halogen atom, (s) An alkoxycarbonyl group which may be substituted with a halogen atom, (t) An alkenyloxycarbonyl group which may be substituted with a halogen atom, (u) An aryloxycarbonyl group which may be substituted with a halogen atom, (v) An aralkyloxycarbonyl group which may be substituted with a halogen atom, (w) An alkylcarbonylamino group which may be substituted with a halogen atom, (x) An alkylcarbamoyl group which may be substituted with a halogen atom, (y) An alkyl group which may be substituted with a halogen atom, (z) An alkenyl group which may be substituted with a halogen atom, (aa) An aralkyl group which may be substituted with a halogen atom.

[0058] In this specification, halogen atoms refer to fluorine atoms, chlorine atoms, bromine atoms, or iodine atoms.

[0059] In this specification, alkyl groups mean linear, branched, and / or cyclic monovalent aliphatic saturated hydrocarbon groups. Unless otherwise specified, the number of carbon atoms in an alkyl group is preferably 1 to 18, more preferably 1 to 10, and even more preferably 1 to 6. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, neopentyl, tert-pentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, tert-octyl, cyclopentyl, cyclopentylmethyl, and 2-cyclopentylethyl. Examples include the group, cyclohexyl group, cyclohexylmethyl group, 2-cyclohexylethyl group, adamantan-1-yl group, adamantan-1-ylmethyl group, 2-(adamantan-1-yl)ethyl group, 2-methyladamantan-2-yl group, 2-ethyladamantan-2-yl group, 2-isopropyladamantan-2-yl group, norbornan-2-yl group, norbornan-2-ylmethyl group, and 2-(norbornan-2-yl)ethyl group.

[0060] In this specification, an alkenyl group means a linear, branched, and / or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. Unless otherwise specified, the number of carbon atoms in the alkenyl group is preferably 2 to 18, more preferably 2 to 10, and even more preferably 2 to 6. Examples of alkenyl groups include vinyl groups, propenyl groups (allyl group, 1-propenyl group, isopropenyl group), butenyl groups (1-butenyl group, clotyl group, methallyl group, isoclotyl group, etc.), pentenyl groups (1-pentenyl group, etc.), hexenyl groups (1-hexenyl group, etc.), heptenyl groups (1-heptenyl group, etc.), octenyl groups (1-octenyl group, etc.), cyclopentenyl groups (2-cyclopentenyl group, etc.), cyclohexenyl groups (3-cyclohexenyl group, etc.), and the like.

[0061] In this specification, an aryl group means a monovalent aromatic hydrocarbon group consisting of an aromatic carbocyclic ring with one hydrogen atom removed. Unless otherwise specified, the number of carbon atoms in the aryl group is preferably 6 to 18, and particularly preferably 6 to 10. Examples of aryl groups include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and the like.

[0062] In this specification, an aralkyl group means an alkyl group substituted with one or more (preferably one) aryl groups. Unless otherwise specified, the number of carbon atoms in the aralkyl group is preferably 7 to 19, and particularly preferably 7 to 11. Examples of aralkyl groups include benzyl group, phenethyl group, hydrocinnamyl group, α-methylbenzyl group, α-cumyl group, 1-naphthylmethyl group, and 2-naphthylmethyl group.

[0063] In this specification, an alkyl-substituted aryl group means an aryl group substituted with one or more alkyl groups. Unless otherwise specified, the number of carbon atoms in the alkyl-substituted aryl group is preferably 7 to 19, and particularly preferably 7 to 11. Examples of alkyl-substituted aryl groups include 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 2,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4,6-trimethylphenyl, 4-ethylphenyl, 3-ethylphenyl, and 2-ethylphenyl.

[0064] In this specification, an alkoxy group means a monovalent group in which an alkyl group is bonded to an oxygen atom (i.e., -O-R Ｂ１ (R here) Ｂ１ The group is represented by an alkyl group. Unless otherwise specified, the number of carbon atoms in the alkoxy group is preferably 1 to 18, more preferably 1 to 10, and even more preferably 1 to 6. Examples of alkoxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, isobutyloxy, sec-butyloxy, and tert-butyloxy groups.

[0065] In this specification, an alkenyloxy group means a monovalent group (i.e., -O-R) in which an alkenyl group is bonded to an oxygen atom. Ｂ２ (R here) Ｂ２The term "alkenyloxy group" refers to a group represented by an alkenyl group. Unless otherwise specified, the number of carbon atoms in the alkenyloxy group is preferably 2 to 18, more preferably 2 to 10, and even more preferably 2 to 6. Examples of alkenyloxy groups include vinyloxy groups and propenyloxy groups (allyloxy group, 1-propenyloxy group, isopropenyloxy group).

[0066] In this specification, an aryloxy group means a monovalent group formed by the bonding of an aryl group to an oxygen atom (i.e., -O-R Ｂ３ (R here) Ｂ３ The group represented by aryloxy is a group. Unless otherwise specified, the number of carbon atoms in the aryloxy group is preferably 6 to 18, and particularly preferably 6 to 10. Examples of aryloxy groups include phenoxy, 1-naphthoxy, and 2-naphthoxy groups.

[0067] In this specification, an aralkyloxy group means a monovalent group (i.e., -O-R) formed by the bonding of an aralkyl group to an oxygen atom. Ｂ４ (R here) Ｂ４ The group represented by aralkyloxy is a group. Unless otherwise specified, the number of carbon atoms in the aralkyloxy group is preferably 7 to 19, and particularly preferably 7 to 11. Examples of aralkyloxy groups include the benzyloxy group and the α-methylbenzyloxy group.

[0068] In this specification, an alkylcarbonyl group means a monovalent group in which an alkyl group is bonded to one carbonyl group (i.e., -C(=O)-R Ｂ１ (R here) Ｂ１ The group is represented by an alkyl group. Unless otherwise specified, the number of carbon atoms in the alkylcarbonyl group is preferably 2 to 19, more preferably 2 to 11, and even more preferably 2 to 7. Examples of alkylcarbonyl groups include acetyl, propanoyl, butanoyl, pivaloyl, and valeryl groups.

[0069] In this specification, an alkenylcarbonyl group means a monovalent group (i.e., -C(=O)-R) in which an alkenyl group is bonded to one carbonyl group. Ｂ２ (R here) Ｂ２The group is represented by an alkenyl group. Unless otherwise specified, the number of carbon atoms in the alkenylcarbonyl group is preferably 3 to 19, more preferably 3 to 11, and even more preferably 3 to 7. Examples of alkenylcarbonyl groups include acryloyl group, propenylcarbonyl group (allylcarbonyl group, 1-propenylcarbonyl group, metacloyl group), etc.

[0070] In this specification, an arylcarbonyl group means a monovalent group in which an aryl group is bonded to one carbonyl group (i.e., -C(=O)-R Ｂ３ (R here) Ｂ３ The group represented by aryl carbonyl is a group. Unless otherwise specified, the number of carbon atoms in the arylcarbonyl group is preferably 7 to 19, and particularly preferably 7 to 11. Examples of arylcarbonyl groups include benzoyl, 1-naphthoyl, and 2-naphthoyl groups.

[0071] In this specification, an aralkylcarbonyl group means a monovalent group (i.e., -C(=O)-R) formed by the bonding of an aralkyl group to one carbonyl group. Ｂ４ (R here) Ｂ４ The group represented by aralkyl carbonyl is a group. Unless otherwise specified, the number of carbon atoms in the aralkyl carbonyl group is preferably 7 to 19, and particularly preferably 7 to 11. Examples of aralkyl carbonyl groups include the benzyl carbonyl group and the α-methylbenzyl carbonyl group.

[0072] In this specification, an alkylcarbonyloxy group means a monovalent group formed by the bonding of an alkylcarbonyl group to an oxygen atom (i.e., -O-C(=O)-R Ｂ１ (R here) Ｂ１ The group is represented by an alkyl group. Unless otherwise specified, the number of carbon atoms in the alkylcarbonyloxy group is preferably 2 to 19, more preferably 2 to 11, and even more preferably 2 to 7. Examples of alkylcarbonyloxy groups include acetoxy, propanoyloxy, butanoyloxy, pivaloyloxy, and valeryloxy groups.

[0073] In this specification, an alkenylcarbonyloxy group means a monovalent group formed by the bonding of an alkenylcarbonyl group to an oxygen atom (i.e., -O-C(=O)-R Ｂ２ (R here) Ｂ２ The group is represented by an alkenyl group. Unless otherwise specified, the number of carbon atoms in the alkenylcarbonyloxy group is preferably 3 to 19, more preferably 3 to 11, and even more preferably 3 to 7. Examples of alkenylcarbonyloxy groups include acryloyloxy group, propenylcarbonyloxy group (allylcarbonyloxy group, 1-propenylcarbonyloxy group, metacloyloxy group), etc.

[0074] In this specification, an arylcarbonyloxy group means a monovalent group formed by the bonding of an arylcarbonyl group to an oxygen atom (i.e., -O-C(=O)-R Ｂ３ (R here) Ｂ３ The group represented by aryl carbonyloxy is a group. Unless otherwise specified, the number of carbon atoms in the arylcarbonyloxy group is preferably 7 to 19, and particularly preferably 7 to 11. Examples of arylcarbonyloxy groups include benzoyloxy, 1-naphthoyloxy, and 2-naphthoyloxy groups.

[0075] In this specification, an aralkylcarbonyloxy group means a monovalent group formed by the bonding of an aralkylcarbonyl group to an oxygen atom (i.e., -O-C(=O)-R Ｂ４ (R here) Ｂ４ The group represented by aralkyl carbonyl is a group that is preferably 7 to 19 carbon atoms, and most preferably 7 to 11 carbon atoms, unless otherwise specified. Examples of aralkyl carbonyloxy groups include benzyl carbonyloxy group and α-methylbenzylcarbonyloxy group.

[0076] In this specification, an alkoxycarbonyl group means a monovalent group in which an alkoxy group is bonded to one carbonyl group (i.e., -C(=O)-O-R Ｂ１ (R here) Ｂ１The group is represented by an alkyl group. Unless otherwise specified, the number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 19, more preferably 2 to 11, and even more preferably 2 to 7. Examples of alkoxycarbonyl groups include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, and so on.

[0077] In this specification, an alkenyloxycarbonyl group means a monovalent group in which an alkenyloxy group is bonded to one carbonyl group (i.e., -C(=O)-O-R Ｂ２ (R here) Ｂ２ The group is represented by an alkenyl group. Unless otherwise specified, the number of carbon atoms in the alkenyloxycarbonyl group is preferably 3 to 19, more preferably 3 to 11, and even more preferably 3 to 7. Examples of alkenyloxycarbonyl groups include vinyloxycarbonyl group, propenyloxycarbonyl group (allyloxycarbonyl group, 1-propenyloxycarbonyl group, isopropenyloxycarbonyl group), etc.

[0078] In this specification, an aryloxycarbonyl group means a monovalent group in which an aryloxy group is bonded to one carbonyl group (i.e., -C(=O)-O-R Ｂ３ (R here) Ｂ３ The group is represented by an aryl group. Unless otherwise specified, the number of carbon atoms in the aryloxycarbonyl group is preferably 7 to 19, and particularly preferably 7 to 11. Examples of aryloxycarbonyl groups include phenoxycarbonyl group, 1-naphthoxycarbonyl group, and 2-naphthoxycarbonyl group.

[0079] In this specification, an aralkyloxycarbonyl group means a monovalent group (i.e., -C(=O)-O-R) formed by the bonding of an aralkyloxy group to one carbonyl group. Ｂ４ (R here) Ｂ４ The group represented by aralkyl carbonyl is a group that is aralkyl carbonyl. Unless otherwise specified, the number of carbon atoms in the aralkyl carbonyl group is preferably 7 to 19, and particularly preferably 7 to 11. Examples of aralkyl oxycarbonyl groups include the benzyl oxycarbonyl group and the α-methylbenzyl oxycarbonyl group.

[0080] In this specification, an alkylcarbonylamino group means an amino group monosubstituted with an alkylcarbonyl group (i.e., -NH-C(=O)-R Ｂ１ (R here) Ｂ１ The group is represented by an alkyl group. Unless otherwise specified, the number of carbon atoms in the alkylcarbonylamino group is preferably 2 to 19, more preferably 2 to 11, and even more preferably 2 to 7. Examples of alkylcarbonylamino groups include N-acetylamino group, N-propanoylamino group, and N-butanoylamino group.

[0081] In this specification, an alkylcarbamoyl group means a carbamoyl group mono- or disubstituted with an alkyl group (i.e., -C(=O)-NHR Ｂ１ or -C(=O)-N(R Ｂ１ ) ２ (This R Ｂ１ Each of these independently represents an alkyl group. Unless otherwise specified, the number of carbon atoms in the alkylcarbamoyl group is preferably 2 to 19, more preferably 2 to 11, and even more preferably 2 to 7. Examples of alkylcarbamoyl groups include N-methylcarbamoyl group, N-ethylcarbamoyl group, and N-propylcarbamoyl group.

[0082] In this specification, a heterocyclic group means a monovalent group obtained by removing one hydrogen atom from an aromatic heterocycle, i.e., an aromatic heterocyclic group, or a monovalent group obtained by removing one hydrogen atom from a non-aromatic heterocycle, i.e., a non-aromatic heterocyclic group. The heterocyclic group is preferably a 5-22 member aromatic heterocyclic group or a 3-22 member non-aromatic heterocyclic group, more preferably a 5-18 member aromatic heterocyclic group or a 3-18 member non-aromatic heterocyclic group, and even more preferably a 5-14 member aromatic heterocyclic group or a 3-14 member non-aromatic heterocyclic group. The non-aromatic heterocyclic group may be a saturated non-aromatic heterocyclic group consisting only of single bonds, or an unsaturated aromatic heterocyclic group having a double bond in addition to a single bond, but it is preferably a saturated non-aromatic heterocyclic group. Examples of heterocyclic groups include tetrahydrofuranyl groups.

[0083] R ＬEach independently represents a substituent; in one embodiment, preferably -OH, -OR Ａ , -OCOR Ａ , or -OCOR Ａ (R Ａ The group is as described above; more preferably, it is a hydroxyl group (-OH), an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, or an arylcarbonyloxy group; even more preferably, it is a hydroxyl group, an alkoxy group, or an alkylcarbonyloxy group; and particularly preferably, it is a methoxy group.

[0084] X １ In another embodiment, a single bond, or formula (L):

[0085]

[0086] [In the formula, R ｘ and R ｙ Each of these independently represents either a hydrogen atom or an alkyl group. Preferably, the group is represented by ].

[0087] R ｘ and R ｙ Each independently represents a hydrogen atom or an alkyl group; in one embodiment, it is preferably a hydrogen atom, a methyl group, or an ethyl group; more preferably a hydrogen atom or a methyl group; and particularly preferably a hydrogen atom.

[0088] X ２ Each independently represents a single bond or a divalent organic group; in one embodiment, -O-(CR ｚ ２ ) ｇ - is preferable; -O-(CH ２ ) ｇ - is more preferable; -O-CH ２ - is particularly preferable. Note that the left side is the side that bonds with ring A.

[0089] R ｚ Each of these independently represents either a hydrogen atom or an alkyl group; in one embodiment, a hydrogen atom is preferred.

[0090] g independently represents 1, 2, 3, 4, or 5; in one embodiment, it is preferably 1, 2, or 3; more preferably 1 or 2; and particularly preferably 1.

[0091] R １ , R ２ and R ３ Each independently represents a hydrogen atom, a methyl group, or a halogen atom; in one embodiment, from the viewpoint of further improving polymerizability, R １ However, it is a hydrogen atom, a methyl group, or a halogen atom, and R ２ and R ３ However, it is preferable that it be a hydrogen atom; R １ However, it is a hydrogen atom, a methyl group, or a chlorine atom, and R ２ and R ３ However, it is more preferable that it be a hydrogen atom; R １ However, it is a hydrogen atom or a methyl group, and R ２ and R ３ However, it is particularly preferable that it be a hydrogen atom.

[0092] R ４ and R ５ Each of these independently represents a substituent; in one embodiment, -OH, -COOH, -R Ａ , -OR Ａ , -OCOR Ａ , or -OCOR Ａ (R Ａ It is preferable that the group is as described above; more preferably that it is a hydroxyl group (-OH), a carboxyl group (-COOH), an alkyl group, an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, or an arylcarbonyloxy group; even more preferably that it is a hydroxyl group, a carboxyl group, an alkyl group, an alkoxy group, or an alkylcarbonyloxy group; particularly preferably that it is a carboxyl group, a methyl group, or a methoxy group.

[0093] R ６ and R ７Each independently represents an alkyl group which may have substituents; in one embodiment, it is preferably an alkyl group; more preferably a methyl group or an ethyl group; and particularly preferably a methyl group.

[0094] a represents an integer of 1 or more; in one embodiment, it is preferably 1 or 2; more preferably 1.

[0095] b represents an integer of 1 or more; in one embodiment, it is preferably 1, 2, 3, or 4; more preferably 1, 2, or 3.

[0096] c represents an integer of 1 or more; in one embodiment, it is preferably 1, 2, 3, or 4; more preferably 1, 2, or 3.

[0097] e represents an integer of 1 or more; in one embodiment, it is preferably 1, 2, 3, 4, or 5; more preferably 1, 2, or 3.

[0098] d represents 0 or an integer greater than or equal to 1; in one embodiment, it is preferably 0, 1, 2, or 3; more preferably 0, 1, or 2.

[0099] f represents 0 or an integer greater than or equal to 1; in one embodiment, it is preferably 0, 1, 2, or 3; more preferably 0, 1, or 2.

[0100] In this specification, the total number of groups attached to a ring in a chemical formula shall not exceed the number of substitutable positions on that ring.

[0101] In formula (I), formula (X''):

[0102]

[0103] [In the formula, * indicates a bonding site, and other symbols are as described above.] The group represented by formula (Xa) to (Xw) is preferably:

[0104]

[0105]

[0106]

[0107] [In the formula, R ６１ and R ７１ each independently represent an alkyl group; R ｆ , R ｇ , R ｈ , R ｉ and R ｊ each independently represent a hydrogen atom or a substituent (excluding iodine atom); * represents a bonding site. ] is a group represented by any of the above, and specific examples of the group are not particularly limited, and include groups represented by Formulas (X-1) to (X-375):

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117] [In the formula, * represents a bonding site. ] and the like can be mentioned as the group represented by the formula.

[0118] R ６１ and R ７１ each independently represent an alkyl group; in one embodiment, it is preferably a methyl group or an ethyl group; and particularly preferably a methyl group.

[0119] In one embodiment, the compound represented by Formula (I) is preferably Formula (1) or (2):

[0120]

[0121] [In the formula, ring A' represents a 6-14 member aromatic carbon ring; ring B' independently represents a 6-14 member aromatic carbon ring, a 3-14 member non-aromatic carbon ring, or a fused ring thereof; R １１ R represents a hydrogen atom or a methyl group; ４ and R ５ Each of these independently represents a substituent; R ６ and R ７ Each independently represents an alkyl group which may have substituents; R ｘ , R ｙ and R ｚ The compound is represented by [b, c, and e], where each independently represents a hydrogen atom or an alkyl group; b, c, and e, each independently represents an integer of 1 or more; d and f, each independently represents 0 or an integer of 1 or more; and g, each independently represents 1, 2, 3, 4, or 5.

[0122] Ring A' represents a 6- to 14-membered aromatic carbon ring; in one embodiment, it is preferably a benzene ring or a naphthalene ring; and it is particularly preferably a benzene ring.

[0123] Each ring B' independently represents a 6-14 member aromatic carbon ring, a 3-14 member non-aromatic carbon ring, or a fused ring thereof; in one embodiment, it is preferably a 6-14 member aromatic carbon ring or a 3-14 member non-aromatic carbon ring, more preferably a benzene ring, a naphthalene ring, or an adamantane ring, and particularly preferably a benzene ring or an adamantane ring.

[0124] R １１ represents a hydrogen atom or a methyl group; in formula (1), it is preferably a hydrogen atom, and in formula (2), it is preferably a methyl group.

[0125] In equations (1) and (2), equation (X'):

[0126]

[0127] [In the formula, * indicates a bonding site, and the other symbols are as described above.] The group represented by is preferably a group represented by any of the above formulas (Xa) to (Xw), and specific examples of such a group are not particularly limited, but include the groups represented by the above formulas (X-1) to (X-375).

[0128] The compound represented by formula (I) is, in one embodiment, more preferably, formulas (1a) to (2r):

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135] [In the formula, R １１ R represents a hydrogen atom or a methyl group; ｘ and R ｙ Each of these independently represents either a hydrogen atom or an alkyl group; R ａ , R ｂ , R ｃ , R ｄ and R ｅ Each of these independently represents a hydrogen atom or a substituent (excluding an iodine atom), and R ａ , R ｂ , R ｃ , R ｄ and R ｅ Of these, at least one (for example, one, two, three, or four, preferably one or two) shown in each formula is formula (X):

[0136]

[0137] (In the formula, ring B'' represents a 6- to 14-membered aromatic carbon ring or a 3- to 14-membered non-aromatic carbon ring; R ５ Each of these independently represents a substituent; R ６ and R ７each independently represents an alkyl group which may have a substituent; e represents an integer of 1 or more; f represents 0 or an integer of 1 or more; g represents 1, 2, 3, 4 or 5; * represents a bonding site. ) is a group represented by. ] It is a compound represented by any one of the above.

[0138] Ring B'' represents a 6 to 14-membered aromatic carbocyclic ring, or a 3 to 14-membered non-aromatic carbocyclic ring; in one embodiment, it is preferably a benzene ring, a naphthalene ring, or an adamantane ring, and particularly preferably a benzene ring or an adamantane ring.

[0139] R ａ , R ｂ , R ｃ , R ｄ and R ｅ each independently represent a hydrogen atom or a substituent (excluding iodine atom), and at least one (for example, 1, 2, 3, or 4) of R ａ , R ｂ , R ｃ , R ｄ and R ｅ shown in each formula is a group represented by formula (X); in one embodiment, 1 or 2 of R ａ , R ｂ , R ｃ , R ｄ and R ｅ shown in each formula is a group represented by formula (X).

[0140] In formulas (1a) to (2r), the group represented by formula (X) is preferably a group represented by any one of the aforementioned formulas (Xa) to (Xw), and specific examples of the group include, but are not particularly limited to, the groups represented by the aforementioned formulas (X-1) to (X-375).

[0141] Specific examples of the compound represented by formula (I) include formulas (1a-1) to (2n-4):

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155] [In the formula, -OR independently represents a group represented by any of the formulas (X-1) to (X-375).] Examples of compounds represented by these formulas include, but are not limited to, those.

[0156] <<Method for producing compounds for resist material production>> Compounds represented by formula (I) can be produced using known organic synthesis methods such as decarboxylation reactions, condensation reactions, hydrolysis reactions, protecting group introduction reactions, deprotection reactions, oxidation reactions, reduction reactions, radical cyclization reactions, nucleophilic substitution reactions, nucleophilic addition reactions, alkylation reactions, amidation reactions, esterification reactions, and halogenation reactions.

[0157] For example, among the compounds represented by formula (I), X ２ ga-O-(CR ｚ ２ ) ｇ The compound represented by formula (Ia) can be produced according to the method of the synthesis scheme described below.

[0158]

[0159] [In the formula, LG １ and LG ２ Each of the symbols indicates a leaving group such as a halogen atom; the other symbols are as described above.

[0160] The compound represented by formula (Ia) can be produced by a Williamson ether synthesis reaction, as in step 1 of the synthesis scheme described above, in which the compound represented by formula (Ib) and the compound represented by formula (a) are reacted in the presence of a base. As the base, alkali metal carbonates such as potassium carbonate, sodium carbonate, sodium bicarbonate, and cesium carbonate, and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide can be used. The reaction temperature for this reaction is, for example, -20 to 100°C, and the reaction time is, for example, 10 minutes to 100 hours. This reaction can be carried out in organic solvents such as aliphatic ether solvents, amide solvents, sulfoxide solvents, nitrile solvents, aliphatic ester solvents, halogen solvents, aliphatic ketone solvents, aliphatic hydrocarbon solvents, and aromatic hydrocarbon solvents.

[0161] The compound represented by formula (Ib) can be produced by mixing and reacting, for example, the compound represented by formula (Ic) and the compound represented by formula (b), as in step 2 of the synthesis scheme described above. The reaction temperature for this reaction is, for example, -20 to 100°C, and the reaction time is, for example, 10 minutes to 100 hours. This reaction can be carried out in organic solvents such as aliphatic ether solvents, amide solvents, sulfoxide solvents, nitrile solvents, aliphatic ester solvents, halogen solvents, aliphatic ketone solvents, aliphatic hydrocarbon solvents, and aromatic hydrocarbon solvents.

[0162] The compound represented by formula (Ia) may be produced by combining, as necessary, known decarboxylation reactions, condensation reactions, hydrolysis reactions, protecting group introduction reactions, deprotection reactions, oxidation reactions, reduction reactions, radical cyclization reactions, nucleophilic substitution reactions, nucleophilic addition reactions, alkylation reactions, amidation reactions, esterification reactions, halogenation reactions, etc., in addition to the steps shown in the above synthesis scheme. Furthermore, the compound represented by formula (Ia) may be produced by methods other than those in the above synthesis scheme. In addition, to obtain a compound with a desired carbon skeleton, the Wittig reaction, Friedel-Crafts reaction, Grignard reaction, Kneefenagel condensation reaction, Horner-Wadsworth-Emmons reaction, Michael addition reaction, Wilsmeyer-Hack reaction, Seyfers-Gilbert reaction, Corey-Fuchs reaction, etc. may be used.

[0163] The compounds obtained in each step of the synthesis scheme described above can be used in the next step either as a reaction mixture or as a crude product. Furthermore, the compounds obtained in each step may be purified from the reaction mixture by known purification methods such as solvent extraction, concentration, crystallization, recrystallization, distillation, fractional distillation, chromatography, or a combination thereof.

[0164] Examples of aliphatic ether solvents used herein include tetrahydrofuran, 1,2-dimethoxyethane, diethyl ether, diisopropyl ether, methyl tert-butyl ether, and cyclopentyl methyl ether. Examples of amide solvents used herein include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone. Examples of sulfoxide solvents used herein include dimethyl sulfoxide. Examples of nitrile solvents used herein include acetonitrile and propionitrile. Examples of aliphatic ester solvents used herein include fatty acid alkyl esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, ethyl propionate, and isopropyl propionate; alkyl hydroxyates such as methyl lactate, ethyl lactate, and butyl lactate; alkyl ketoates such as methyl acetoacetate and ethyl acetoacetate; and lactones such as γ-butyrolactone. Examples of halogenated solvents used herein include dichloromethane and chloroform. Examples of aliphatic ketone solvents used herein include acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, diisopropyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, isophorone, and the like. Examples of aliphatic hydrocarbon solvents used herein include n-pentane, n-hexane, isohexane, n-heptane, n-octane, cyclopentane, cyclohexane, methylcyclohexane, and the like. Examples of aromatic hydrocarbon solvents used herein include benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, and the like.

[0165] <<Composition for Manufacturing Resist Materials>> This embodiment provides a composition containing a compound represented by formula (I) as a monomer component of a resist material (polymer), which will be described in detail later. The composition containing the compound represented by formula (I) is useful as a composition for use in polymerization reactions for manufacturing resist materials (polymers). The composition containing the compound represented by formula (I) is useful as a composition for manufacturing lithography film-forming materials (composition for manufacturing materials for forming films obtained by lithography). In particular, the composition containing the compound represented by formula (I) is useful as a resist material manufacturing composition (photoresist layer-forming material manufacturing composition), which will be described in detail later, and especially as a resist material manufacturing composition for the manufacture of semiconductor integrated circuits. In particular, the composition containing the compound represented by formula (I) is useful as a resist material manufacturing composition for processing by lithography. Furthermore, the composition containing the compound represented by formula (I) is also useful as a resist auxiliary film-forming material manufacturing composition (for example, a resist upper layer film-forming material manufacturing composition, a resist intermediate layer film-forming material manufacturing composition, and a resist lower layer film-forming material manufacturing composition), a topcoat-forming material manufacturing composition, an anti-reflective film-forming material manufacturing composition, and the like. Furthermore, compositions containing the compound represented by formula (I) are useful as compositions for manufacturing resist materials for KrF excimer laser exposure, ArF excimer laser exposure, electron beam (EB) exposure, EUV exposure, and the like.

[0166] The total content of the compound represented by formula (I) in a composition is not particularly limited, but when the total amount of all monomer components in the composition (specifically, all monomer components constituting the resist material (polymer) described in detail later) is taken as 100 mol%, in one embodiment it is preferably 5 mol% or more, more preferably 8 mol% or more, even more preferably 10 mol% or more, and may also be 20 mol% or more, 30 mol% or more, and the upper limit is 100 mol% or less, preferably 80 mol% or less, more preferably 70 mol% or less, even more preferably 60 mol% or less, and may also be 50 mol% or less, 40 mol% or less.

[0167] In one embodiment, a composition containing the compound represented by formula (I) preferably contains, as a monomer component, the compound represented by formula (I), in addition to the compound represented by formula (I), at least one compound selected from a different compound, which is an adamantane skeleton (meth)acrylic acid ester compound, a lactone skeleton (meth)acrylic acid ester compound, and a hydroxystyrene skeleton.

[0168] The (meth)acrylic acid ester compounds having an adamantane skeleton are not particularly limited, but for example, formulas (Aa) and (Ab):

[0169]

[0170] [In the formula, R ａｂ and R ａｆ R represents a hydrogen atom or a methyl group; ａｃ , R ａｄ , R ａｅ , R ａｇ , R ａｈ , R ａｉ , R ａｊ and R ａｋ Each of these independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxy group, an optionally substituted aryloxy group, a halogen atom, or a hydroxyl group; L ａａ and L ａｃ L indicates an alkylene group; ａｂ and L ａｄ This indicates a single bond or an alkylene group; n ａａ and n ａｂ A is 0, 1, or 2. Examples of compounds represented by ] are shown. (meth)acrylic acid ester compounds having an adamantane skeleton may be used individually or in any combination of two or more types.

[0171] In this specification, an alkylene group means a linear, branched, and / or cyclic divalent aliphatic saturated hydrocarbon group. Unless otherwise specified, the number of carbon atoms in the alkylene group is preferably 1 to 18, more preferably 1 to 10, and even more preferably 1 to 6. Examples of alkylene groups include -CH ２-ien-CH ２ CH ２ -ien-CH ２ CH ２ CH ２ -ien-CH ２ CH ２ CH ２ CH ２ -ien-CH ２ CH ２ CH ２ CH ２ CH ２ -ien-CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ -ien-CH ２ C (CH ３ Examples include H-, etc.

[0172] Specific examples of (meth)acrylic acid ester compounds having an adamantane skeleton include, but are not limited to, formulas (A-1) to (A-60):

[0173]

[0174] Examples of compounds represented by the following are included.

[0175] The content of the (meth)acrylic acid ester compound having an adamantane skeleton in a composition containing the compound represented by formula (I) is not particularly limited, but when the total amount of all monomer components in the composition is taken as 100 mol%, it is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, and may also be 30 mol% or more. The upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and may also be 50 mol% or less, or 40 mol% or less.

[0176] The (meth)acrylic acid ester compounds having a lactone skeleton are not particularly limited, but for example, formulas (Ba) to (Be):

[0177]

[0178] [In the formula, R ｂａ , R ｂｃ, R ｂｅ , R ｂｇ and R ｂｉ R represents a hydrogen atom or a methyl group; ｂｂ , R ｂｄ , R ｂｆ , R ｂｈ and R ｂｊ Each independently represents a hydrocarbon group which may have substituents, a halogen atom, or a hydroxyl group; L ｂａ , L ｂｃ , L ｂｅ , L ｂｇ and L ｂｉ L indicates an alkylene group; ｂｂ , L ｂｄ , L ｂｆ , L ｂｈ and L ｂｊ X represents a single bond or an alkylene group; ｂ is, -CH ２ - or -O- indicates; n ｂａ , n ｂｂ , n ｂｄ , n ｂｆ , n ｂｈ and n ｂｊ n represents 0, 1, or 2; ｂｃ , n ｂｅ , n ｂｇ , n ｂｉ and n ｂｋ represents an integer from 0 to 5. Examples of compounds represented by any of the following are given. (meth)acrylic acid ester compounds having a lactone skeleton may be used individually or in any combination of two or more types.

[0179] Specific examples of (meth)acrylic acid ester compounds having a lactone skeleton include, but are not limited to, formulas (B-1) to (B-36):

[0180]

[0181] Examples of compounds represented by the following are included.

[0182] The content of the lactone skeleton-containing (meth)acrylic acid ester compound in a composition containing the compound represented by formula (I) is not particularly limited, but is preferably 1 mol% or more, more preferably 3 mol% or more, even more preferably 5 mol% or more, with an upper limit of preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less.

[0183] Compounds having a hydroxystyrene skeleton are not particularly limited, but for example, formula (Ca):

[0184]

[0185] [In the formula, R ｃａ represents a hydrogen atom or a methyl group; n ｃ indicates 1, 2, 3, 4, or 5; R ｃｂ Each of these independently represents a substituent, and n ｃ Individual R ｃｂ At least one of them (for example, one, two, three, or four, preferably one or two) is -OH, -OR Ａ , -OCOR Ａ , or -OCOR Ａ And; R Ａ The above applies. Compounds represented by [ ] are examples. Compounds having a hydroxystyrene skeleton may be used individually or in any combination of two or more types.

[0186] Specific examples of compounds having a hydroxystyrene skeleton include, but are not limited to, formulas (C-1) to (C-36):

[0187]

[0188] Examples of compounds represented by the following are included.

[0189] The content of the compound having a hydroxystyrene skeleton in a composition containing the compound represented by formula (I) is not particularly limited, but when the total amount of all monomer components in the composition is taken as 100 mol%, it is, for example, 0 mol% or more, preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, and may be 30 mol% or more. The upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and may be 50 mol% or less or 40 mol% or less.

[0190] A composition containing the compound represented by formula (I) may further contain other (meth)acrylic acid ester compounds as monomer components. Examples of other (meth)acrylic acid ester compounds include alkyl (meth)acrylic acid ester compounds such as tert-butyl (meth)acrylate, 1,1-diethylpropyl (meth)acrylate, 1-cyclopentyl-1-methylethyl (meth)acrylate, and 1-cyclohexyl-1-methylethyl (meth)acrylate; (meth)acrylic acid ester compounds having a phenolic hydroxyl group such as 4-hydroxyphenyl (meth)acrylate, 3-hydroxyphenyl (meth)acrylate, 3,4-dihydroxyphenyl (meth)acrylate, 4-hydroxy-3-methylphenyl (meth)acrylate, and 4-hydroxy-3-methoxyphenyl (meth)acrylate; and (meth)acrylic acid ester compounds having a fluorine atom such as trifluoromethyl (meth)acrylate, pentafluoroethyl (meth)acrylate, and heptafluoropropyl (meth)acrylate.

[0191] A composition containing the compound represented by formula (I) may, from the viewpoint of further suppressing exposure defects, include the additive of formula (II):

[0192]

[0193] [In the formula, ring A ａ Each of these independently represents an aromatic ring; X ａ１ Each independently represents a single bond or a divalent organic group; R ａ１ and R ａ２Each of these independently represents a hydrogen atom, a methyl group, or a halogen atom; R ａ４ Each of these independently represents a substituent; n ａ b indicates 1, 2, 3, 4, 5, 6, or 7; b ａ Each of these independently represents an integer greater than or equal to 1; d ａ It is preferable to include a compound represented by ], where is 0 or an integer of 1 or more.

[0194] Ring A ａ , X ａ１ , R ａ１ , R ａ２ , R ａ４ , b ａ , and d ａ The definitions and preferred groups are, respectively, rings A and X as described above. １ , R １ , R ２ , R ４ This is the same as b and d.

[0195] n ａ represents 1, 2, 3, 4, 5, 6, or 7; in one embodiment, it is preferably 1, 2, 3, 4, or 5; more preferably 1, 2, or 3; even more preferably 1 or 2; and particularly preferably 1.

[0196] In a preferred embodiment, the compound represented by formula (II) is d ａ However, it is an integer greater than or equal to 1, R ａ４ However, each is independently a substituent and -(R ａ４ ) ｄ ａ Each d ａ Individual R ａ４ At least one of these (for example, one, two, three, or four, preferably one or two) is a hydroxyl group, or formula (XA''):

[0197]

[0198] [In the formula, ring B ａ X represents an aromatic ring, a non-aromatic ring, or a fused ring thereof; ａ２ R represents a single bond or a divalent organic group; ａ５Each of these independently represents a substituent; R ａ６ and R ａ７ Each independently represents an alkyl group which may have substituents; e ａ f represents an integer greater than or equal to 1; ａ represents 0 or an integer greater than or equal to 1; * represents a bonding site. The base is represented by ].

[0199] Ring B ａ , R ａ５ , R ａ６ , R ａ７ , e ａ , and f ａ The definitions and preferred groups are, respectively, rings B and R as described above. ５ , R ６ , R ７ It is the same as e and f.

[0200] X ａ２ represents a single bond or a divalent organic group; in one embodiment, -O-(CR ａｚ ２ ) ｇ ａ - is preferable; -O-(CH ２ ) ｇ ａ - is more preferable; -O-CH ２ - is particularly preferable. Note that the left side is ring A. ａ It is the side that connects to it.

[0201] R ａｚ Each of these independently represents either a hydrogen atom or an alkyl group; in one embodiment, a hydrogen atom is preferred.

[0202] g ａ Each independently represents 1, 2, 3, 4, or 5; in one embodiment, it is preferably 1, 2, or 3; more preferably 1 or 2; and particularly preferably 1.

[0203] In one embodiment, the group represented by formula (XA'') is preferably a group represented by any of the above-described formulas (Xa) to (Xw). Specific examples of this group are not limited to, but include groups represented by any of the above-described formulas (X-1) to (X-375).

[0204] In one embodiment, the compound represented by formula (II) is preferably formula (II-1) or (II-2):

[0205]

[0206] [In the formula, ring A ａ Each of these independently represents an aromatic ring; R ａ１１ R represents a hydrogen atom or a methyl group; ａ４ However, each is independently a substituent and -(R ａ４ ) ｄ ａ Each d ａ Individual R ａ４ At least one of them (for example, one, two, three, or four, preferably one or two) is a hydroxyl group, or formula (XA'):

[0207]

[0208] (In the formula, ring B ａ ' indicates an aromatic ring, a non-aromatic ring, or a fused ring thereof; R ａ５ Each of these independently represents a substituent; R ａ６ and R ａ７ Each independently represents an alkyl group which may have substituents; R ｚａ Each independently represents either a hydrogen atom or an alkyl group; e ａ f represents an integer greater than or equal to 1; ａ g represents an integer of 0 or 1 or greater; g ａ Each of these independently represents 1, 2, 3, 4, or 5; * indicates a binding site.) The group is represented by R ｘａ and R ｙａ Each of these independently represents either a hydrogen atom or an alkyl group; b ａ Each of these independently represents an integer greater than or equal to 1; d ａrepresents an integer greater than or equal to 1. It is a compound represented by ].

[0209] Ring A ａ ', R ａ１１ , ring B ａ ', R ｘａ , and R ｙａ The definitions and preferred groups are as described above for rings A' and R, respectively. １１ , ring B', R ｘ , and R ｙ It is similar to that.

[0210] In one embodiment, the group represented by formula (XA') is preferably a group represented by any of the above-described formulas (Xa) to (Xw). Specific examples of this group are not limited to, but include groups represented by any of the above-described formulas (X-1) to (X-375).

[0211] The compound represented by formula (II) is, in one embodiment, more preferably, formulas (II-1a) to (II-2r):

[0212]

[0213]

[0214]

[0215]

[0216]

[0217]

[0218]

[0219] [In the formula, R ａ１１ R represents a hydrogen atom or a methyl group; ｘａ and R ｙａ Each of these independently represents either a hydrogen atom or an alkyl group; R ａａ , R ｂａ , R ｃａ , R ｄａ and R ｅａ Each of these independently represents a hydrogen atom or a substituent (excluding an iodine atom), and R ａａ , R ｂａ , Rｃａ , R ｄａ and R ｅａ Of these, at least one (for example, one, two, three, or four, preferably one or two) shown in each formula is a hydroxyl group, or formula (XA):

[0220]

[0221] (In the formula, ring B ａ '' represents an aromatic carbon ring with 6 to 14 members; R ａ５ Each of these independently represents a substituent; R ａ６ and R ａ７ Each independently represents an alkyl group which may have substituents; e ａ f represents an integer greater than or equal to 1; ａ g represents an integer of 0 or 1 or greater; g ａ represents 1, 2, 3, 4, or 5; * represents the binding site. ) It is a group represented by ). It is a compound represented by any of ].

[0222] Ring B ａ The definition and preferred groups of '' are the same as those of ring B'' described above.

[0223] In one embodiment, the group represented by formula (XA) is preferably a group represented by any of the above-described formulas (Xa) to (Xw). Specific examples of this group are not limited to, but include groups represented by any of the above-described formulas (X-1) to (X-375).

[0224] Specific examples of compounds represented by formula (II) are not limited to formulas (II1) to (II32):

[0225]

[0226]

[0227] Examples include compounds represented by [the formula shown].

[0228] The content of the compound represented by formula (II) in a composition containing the compound represented by formula (I) is not particularly limited, but it is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, even more preferably 0.01% by mass or more, and particularly preferably 0.05% by mass or more, when the total amount of the compound represented by formula (I) and the compound represented by formula (II) in the composition is taken as 100% by mass. The upper limit of the content of the compound represented by formula (II) is not particularly limited, but when the total amount of the compound represented by formula (I) and the compound represented by formula (II) in the composition is taken as 100% by mass, for example, it may be 50% by mass or less, 30% by mass or less, 20% by mass or less, 10% by mass or less, 5% by mass or less, 2% by mass or less, 1% by mass or less, etc.

[0229] A composition containing the compound represented by formula (I) may, from the viewpoint of further suppressing exposure defects, include the additive of formula (III):

[0230]

[0231] [In the formula, ring B ｂ Each of these independently represents an aromatic ring; X ｂ Each of these independently exhibits an acid-dissociable linking group; R ｂ５ Each of these independently represents a substituent that does not have an intercarbon double bond; n ｂ e represents an integer greater than or equal to 1; ｂ Each of these independently represents an integer greater than or equal to 1; f ｂ It is preferable to include a compound represented by ], where is 0 or an integer of 1 or more.

[0232] n ｂ n represents an integer of 1 or more, and in one embodiment, it is preferably 1, 2, 3, 4, or 5; more preferably 1, 2, or 3; even more preferably 1 or 2; and particularly preferably 1.

[0233] Ring B ｂ , e ｂ , and f ｂ The definition and preferred groups are the same as those for rings B, e, and f described above, respectively.

[0234] R ｂ５ Each of these independently represents a substituent that does not have an intercarbon double bond; in one embodiment, -OH, -COOH, -R Ｃ , -OR Ｃ , -OCOR Ｃ , or -OCOR Ｃ (R Ａ It is preferable that the group is as follows: more preferably a hydroxyl group (-OH), a carboxyl group (-COOH), an alkyl group, an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, or an arylcarbonyloxy group; even more preferably a hydroxyl group, a carboxyl group, an alkyl group, an alkoxy group, or an alkylcarbonyloxy group; particularly preferably a carboxyl group, a methyl group, or a methoxy group.

[0235] In this specification, a carbon-carbon double bond means a covalent bond formed between two carbon atoms by four electrons from two electron pairs, and does not include aromatic carbon-carbon bonds that constitute aromatic rings. Examples of substituents that do not have a carbon-carbon double bond are not limited to, but include, for example, halogen atoms and -NO ２ , -CN, -CHO, -OH, -SH, -NH ２ -COOH, -R Ｃ , -COR Ｃ , -OR Ｃ ,-SR Ｃ , -SOR Ｃ , -SO ２ R Ｃ , - NHR Ｃ , -N(R Ｃ ) ２ , -COOR Ｃ , -OCOR Ｃ , -OCOOR Ｃ , -CONH ２ , -CONHR Ｃ , -CON(R Ｃ ) ２ ,-NHCOR Ｃ , -P(R Ｃ ) ２ , -P(OR Ｃ ) R Ｃ , -P(OR Ｃ ) ２, -PO(OR Ｃ ) R Ｃ , -PO(OR Ｃ ) ２ , -OP(R Ｃ ) ２ , -OP(OR Ｃ ) R Ｃ , -OP(OR Ｃ ) ２ , -OPO(R Ｃ ) ２ , -OPO(OR Ｃ ) R Ｃ , -OPO(OR Ｃ ) ２ Examples of monovalent groups include (where R Ｃ (The details are as follows.)

[0236] R Ｃ Each of these can be, independently, an alkyl group which may have substituents that do not contain an intercarbon double bond, an aryl group which may have substituents that do not contain an intercarbon double bond, an aromatic heterocyclic group which may have substituents that do not contain an intercarbon double bond, or a saturated non-aromatic heterocyclic group which may have substituents that do not contain an intercarbon double bond, more specifically, (1') an alkyl group which may be substituted with one or more (e.g., 1 to 5) groups selected from the following groups (a') to (s'); (2') an aryl group which may be substituted with one or more (e.g., 1 to 5) groups selected from the following groups (a') to (u'); (3') an aromatic heterocyclic group which may be substituted with one or more (e.g., 1 to 5) groups selected from the following groups (a') to (u'); or (4') a saturated non-aromatic heterocyclic group which may be substituted with one or more (e.g., 1 to 5) groups selected from the following groups (a') to (u'), but is not limited to these.

[0237] (a') halogen atom, (b') nitro group (-NO ２(c') cyano group (-CN), (d') hydroxyl group (-OH), (e') aryl group which may be substituted with a halogen atom, (f') alkyl-substituted aryl group which may be substituted with a halogen atom, (g') alkoxy group which may be substituted with a halogen atom, (n') aryloxy group which may be substituted with a halogen atom, (i') aralkyloxy group which may be substituted with a halogen atom, (k') alkylcarbonyl group which may be substituted with a halogen atom, (j') arylcarbonyl group which may be substituted with a halogen atom, (k') aralkylcarbonyl group which may be substituted with a halogen atom, (l') alkylcarbonyl group which may be substituted with a halogen atom A vonyloxy group, an arylcarbonyloxy group which may be substituted with a halogen atom (m'), an aralkylcarbonyloxy group which may be substituted with a halogen atom (n'), an alkoxycarbonyl group which may be substituted with a halogen atom (o'), an aryloxycarbonyl group which may be substituted with a halogen atom (p'), an aralkyloxycarbonyl group which may be substituted with a halogen atom (q'), an alkylcarbonylamino group which may be substituted with a halogen atom (r'), an alkylcarbamoyl group which may be substituted with a halogen atom (s'), an alkyl group which may be substituted with a halogen atom (t'), and an aralkyl group which may be substituted with a halogen atom (u').

[0238] X ｂ Each of these independently exhibits an acid-dissociable linking group.

[0239] In this specification, a linking group means a divalent group composed of one or more skeletal atoms (e.g., 1 to 100, preferably 1 to 50, particularly preferably 1 to 20) selected from carbon, oxygen, nitrogen, sulfur, phosphorus, and silicon atoms (preferably carbon, oxygen, nitrogen, and sulfur atoms). If non-skeletal atoms are present, they consist of atoms selected from hydrogen and halogen atoms, and may include linear, branched, and / or cyclic structures, and may be a group that does not include an aromatic ring or a group that does. An acid-dissociable linking group means a linking group that dissociates by treatment with an acid (e.g., organic acids such as methanesulfonic acid, ethanesulfonic acid, 10-camphorsulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid, etc., or inorganic acids such as hydrochloric acid). ｂ For example, formula (G1) or (G2):

[0240]

[0241] [In the formula, R ｓ Y represents a hydrogen atom or an alkyl group which may have substituents; ｓ R indicates -O- or -S-; ｔ and R ｕ Each independently represents an alkyl group which may have substituents, or R ｔ and R ｕ However, they bond together to form a non-aromatic ring which may have substituents; * indicates the bonding site. Examples of linking groups include structures represented by ], preferably formula (XB-1) or (XB-2):

[0242]

[0243] [In the formula, R ｂ６ and R ｂ７ Each independently represents an alkyl group which may have substituents; R ｂｚ Each independently represents either a hydrogen atom or an alkyl group; g ｂ Each of these independently represents 1, 2, 3, 4, or 5; * indicates a binding site. These are groups represented by ].

[0244] R ｂ６ , R ｂ７ , R ｂｚ , and g ｂ The definitions and preferred groups are as described above for R ６ , R ７ , R ｚ , and are the same as g.

[0245] In one embodiment, the compound represented by formula (III) is preferably formula (III-1):

[0246]

[0247] [In the formula, ring B ｂ Each of the '' independently represents a 6- to 14-membered aromatic carbon ring; R ｂ５ Each of these independently represents a substituent that does not have an intercarbon double bond; R ｂ６ and R ｂ７ Each independently represents an alkyl group which may have substituents; e ｂ Each of these independently represents an integer greater than or equal to 1; f ｂ g represents an integer of 0 or 1 or greater; g ｂ Each of these independently represents 1, 2, 3, 4, or 5. It is preferable to include a compound represented by ].

[0248] Ring B ｂ The definition and preferred groups of '' are the same as those of ring B'' described above.

[0249] The compound represented by formula (III) is, in one embodiment, more preferably, formulas (III-a) to (III-y):

[0250]

[0251]

[0252]

[0253]

[0254] [In the formula, R ｂ６１ and R ｂ７１ Each of these independently represents an alkyl group; R ｆｂ , Rｇｂ , R ｈｂ , R ｉｂ and R ｊｂ Each of these independently represents either a hydrogen atom or a substituent (excluding iodine) that does not have an intercarbon double bond. The compound is represented by either of the following:

[0255] R ｂ６１ and R ｂ７１ The definition and preferred group of R are as described above. ６１ and R ７１ It is similar to that.

[0256] Specific examples of compounds represented by formula (III) are not limited to formulas (III1) to (III84):

[0257]

[0258]

[0259]

[0260]

[0261] Examples include compounds represented by [the formula shown].

[0262] The content of the compound represented by formula (III) in a composition containing the compound represented by formula (I) is not particularly limited, but it is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, even more preferably 0.01% by mass or more, and particularly preferably 0.05% by mass or more, when the total amount of the compound represented by formula (I) and the compound represented by formula (III) in the composition is taken as 100% by mass. The upper limit of the content of the compound represented by formula (III) is not particularly limited, but when the total amount of the compound represented by formula (I) and the compound represented by formula (III) in the composition is taken as 100% by mass, for example, it may be 10% by mass or less, 5% by mass or less, 2% by mass or less, 1% by mass or less, 0.5% by mass or less, 0.5% by mass or less, etc.

[0263] A composition containing the compound represented by formula (I) may also contain both the compound represented by formula (II) and the compound represented by formula (III).

[0264] <<Resist Material (Polymer)>> The above-mentioned composition containing the compound represented by formula (I) serves as a raw material for a resist material (polymer of this embodiment). The polymer of this embodiment can be produced by radical polymerization of the monomer component containing the compound represented by formula (I) in the above-mentioned composition. That is, the polymer of this embodiment can be obtained, for example, by heating or irradiating a composition containing the compound represented by formula (I) with light to radically polymerize the monomer component contained in the composition.

[0265] The reaction conditions for radical polymerization can be arbitrarily set based on general conditions used in known radical polymerization reactions of (meth)acrylic acid ester compounds or styrene compounds. The reaction temperature for radical polymerization is, for example, 50 to 120°C. The reaction time for radical polymerization is, for example, 1 to 100 hours. Radical polymerization may be carried out in a solvent. Examples of solvents that can be used include aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, aliphatic ester solvents, ketone solvents, aliphatic ether solvents, halogen solvents, alcohol solvents, and water. Examples of alcohol solvents used herein include methanol, ethanol, propanol, isopropanol, and tert-butanol.

[0266] Radical polymerization is preferably carried out by adding a radical polymerization initiator to a monomer component containing the compound represented by formula (I). That is, a composition containing the compound represented by formula (I) preferably contains a radical polymerization initiator when radical polymerization is carried out.

[0267] Examples of radical polymerization initiators include peroxide-based radical polymerization initiators and azo-based radical polymerization initiators. A single radical polymerization initiator may be used alone, or two or more may be used in any combination.

[0268] Examples of peroxide-based radical polymerization initiators include hydroperoxide compounds such as 1,1,3,3-tetramethylbutyl hydroperoxide; dialkylperoxide compounds such as tert-butylcumyl peroxide, di-tert-butyl peroxide, di-tert-hexyl peroxide, dicumyl peroxide, 1,4-bis(1-tert-butylperoxy-1-methylethyl)benzene, and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane; and diacyl peroxides such as dilauroyl peroxide, didecanoyl peroxide, dicyclohexyl peroxydicarbonate, and bis(4-tert-butylcyclohexyl) peroxydicarbonate. Examples of compounds include peroxyester compounds such as tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyneodecanoate, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxylaurate, (1,1-dimethylpropyl)2-ethyl perhexanoate, tert-butyl 2-ethyl perhexanoate, tert-butyl 3,5,5-trimethyl perhexanoate, tert-butyl peroxy-2-ethylhexyl monocarbonate, and tert-butyl peroxymaleic acid.

[0269] Examples of azo radical polymerization initiators include azonitrile compounds such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitride), 1-[(1-cyano-1-methylethyl)azo]formamide, and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile; 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide], and 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)] Examples include azoamide compounds such as methyl(ethyl)propionamide, 2,2'-azobis[2-methyl-N-[2-(1-hydroxybutyl)]-propionamide], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], 2,2'-azobis(2-methylpropionamide) dihydrate, 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis(N-butyl-2-methylpropionamide), and 2,2'-azobis(N-cyclohexyl-2-methylpropionamide); and alkylazo compounds such as 2,2'-azobis(2,4,4-trimethylpentane) and 2,2'-azobis(2-methylpropane).

[0270] The content of the radical polymerization initiator in a composition containing the compound represented by formula (I) is, for example, 0.0001 to 5% by mass, when the total amount of all monomer components in the composition is taken as 100% by mass.

[0271] The polymer of this embodiment includes structural units derived from the compound represented by formula (I). That is, the polymer of this embodiment includes structural units derived from the monomer component, specifically formula (UI) derived from the compound represented by formula (I):

[0272]

[0273] The polymer of this embodiment has repeating units represented by [In the formula, each symbol is as described above.]. When used as a resist material, the sensitivity of the photoresist layer to the exposure light source can be further improved. In one embodiment, resolution can be further improved, roughness can be further reduced, and exposure defects can be further suppressed.

[0274] In one embodiment, the repeating unit represented by formula (UI) in the polymer is preferably formula (U1) or (U2) derived from a compound represented by formula (1) or (2):

[0275]

[0276] [In the formula, each symbol is as described above.] Includes a repeating unit represented by .

[0277] In this embodiment, the repeating unit represented by formula (UI) in the polymer is, more preferably, derived from the compounds represented by formulas (1a) to (2r) described above:

[0278]

[0279]

[0280]

[0281]

[0282]

[0283]

[0284] [In the formula, each symbol is as described above.] Includes a repeating unit represented by one of the following:

[0285] The total content of repeating units represented by formula (UI) in the polymer of this embodiment is not particularly limited, but when the total structural units derived from monomer components in the polymer are taken as 100 mol%, in one embodiment it is preferably 5 mol% or more, more preferably 8 mol% or more, even more preferably 10 mol% or more, and may also be 20 mol% or more, 30 mol% or more, and the upper limit is 100 mol% or less, preferably 80 mol% or less, more preferably 70 mol% or less, even more preferably 60 mol% or less, and may also be 50 mol% or less, 40 mol% or less.

[0286] In one embodiment, the polymer of this embodiment preferably has, as a structural unit derived from monomer components, a repeating unit represented by formula (UI), in addition to a repeating unit derived from at least one compound selected from a (meth)acrylic acid ester compound having an adamantane skeleton, a (meth)acrylic acid ester compound having a lactone skeleton, and a compound having a hydroxystyrene skeleton.

[0287] The content of repeating units derived from (meth)acrylic acid ester compounds having an adamantane skeleton in the polymer of this embodiment is not particularly limited, but when the total structural units derived from monomer components in the polymer are taken as 100 mol%, in one embodiment it is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, and may also be 30 mol% or more. The upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and may also be 50 mol% or less, or 40 mol% or less.

[0288] The content of repeating units derived from (meth)acrylic acid ester compounds having a lactone skeleton in the polymer of this embodiment is not particularly limited, but when the total structural units derived from monomer components in the polymer are taken as 100 mol%, in one embodiment it is preferably 1 mol% or more, more preferably 3 mol% or more, even more preferably 5 mol% or more, with an upper limit of preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less.

[0289] The content of repeating units derived from compounds having a hydroxystyrene skeleton in the polymer of this embodiment is not particularly limited, but when the total structural units derived from monomer components in the polymer are taken as 100 mol%, in one embodiment, for example, it is 0 mol% or more, preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, and may be 30 mol% or more. The upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and may be 50 mol% or less, or 40 mol% or less.

[0290] In one embodiment, the polymer of this embodiment may further have repeating units derived from other (meth)acrylic acid ester compounds as structural units derived from monomer components.

[0291] When the polymer of this embodiment contains two or more repeating units, it is preferable that these repeating units are arranged randomly.

[0292] The weight-average molecular weight (Mw) of the polymer in this embodiment is preferably 5,000 to 30,000, more preferably 8,000 to 20,000, and particularly preferably 10,000 to 15,000. The degree of dispersion (Mw / Mn) of the polymer in this embodiment is preferably 1.1 to 5.0, more preferably 1.4 to 3.0, even more preferably 1.6 to 2.5, and particularly preferably 1.7 to 2.0. The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polymer are the weight-average molecular weight or number-average molecular weight in terms of polystyrene, measured by gel permeation chromatography.

[0293] The polymer of this embodiment is useful as a lithography material (lithography film-forming material). In particular, the polymer of this embodiment is useful as a resist material (photoresist layer-forming material), especially as a resist material for the manufacture of semiconductor integrated circuits. In particular, the polymer of this embodiment is useful as a resist material for processing by lithography. Furthermore, the polymer of this embodiment is also useful as a resist auxiliary film-forming material (e.g., a resist upper layer film-forming material, a resist intermediate layer film-forming material, and a resist lower layer film-forming material), a topcoat-forming material, an anti-reflective film-forming material, etc. Furthermore, the polymer of this embodiment is useful as a resist material for KrF excimer laser exposure, a resist material for ArF excimer laser exposure, a resist material for electron beam (EB) exposure, a resist material for EUV exposure, etc. According to the polymer of this embodiment, it is possible to form a film that has high sensitivity and temporal stability to the above-mentioned various exposure light sources, and it is possible to impart a good resist pattern shape. Specific examples of the lithography material and resist material of this embodiment include a lithography composition (a composition for forming a lithography film) and a resist composition (a composition for forming a photoresist layer) containing the polymer of this embodiment.

[0294] <<Method for manufacturing resist patterns and electronic devices using resist materials>> This embodiment provides a method for manufacturing resist patterns using the polymer of this embodiment as a resist material.

[0295] In a preferred embodiment, the method for manufacturing a resist pattern of this embodiment includes: (i) forming a resist layer containing the polymer of this embodiment on a substrate; (ii) exposing the resist layer formed in step (i); and (iii) developing the resist layer exposed in step (ii).

[0296] Such a method for manufacturing resist patterns is suitable for manufacturing semiconductor elements and liquid crystal display elements having finer wiring patterns, and is useful for manufacturing electronic devices equipped with semiconductor devices (e.g., semiconductor integrated circuits) having such wiring patterns. This embodiment provides a method for forming an electronic device equipped with a semiconductor device having a resist pattern. In a preferred embodiment, the method for manufacturing an electronic device of this embodiment includes: (i) forming a resist layer containing the polymer of this embodiment on a substrate; (ii) exposing the resist layer formed in step (i) to light; and (iii) developing the resist layer exposed in step (ii).

[0297] Such electronic devices can be installed in electronic equipment such as personal computers, smartphones, smartwatches, digital cameras, televisions, car navigation systems, printers, LCD displays, electronic dictionaries, game consoles, automobiles, ships, trains, and aircraft.

[0298] The formation of a resist layer (hereinafter sometimes referred to as the "photoresist layer") on the substrate in step (i) is carried out by applying a resist composition (a composition containing the polymer of this embodiment) obtained by mixing the polymer of this embodiment with an organic solvent and, if necessary, an additive, onto the substrate. The resist composition can be applied to the substrate using a coating device such as a spin coater, dip coater, or roller coater. The substrate is not particularly limited, but examples include silicon wafers, metal substrates, plastic substrates, glass substrates, and ceramic substrates. Before applying the resist composition to the substrate, the substrate may be cleaned, and an anti-reflective film or the like may be formed on the substrate.

[0299] Examples of organic solvents used in resist compositions include glycol ether solvents, glycol ether ester solvents, aliphatic ether solvents, amide solvents, sulfoxide solvents, nitrile solvents, aliphatic ester solvents, halogen solvents, aliphatic ketone solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, and the like.

[0300] In this specification, glycol ether solvents include, for example, cellosolves such as ethylene glycol monomethyl ether (also known as methyl cellosolve), ethylene glycol monoethyl ether (also known as cellosolve), ethylene glycol monopropyl ether (also known as propyl cellosolve), ethylene glycol monobutyl ether (also known as butyl cellosolve), ethylene glycol monoisobutyl ether (also known as isobutyl cellosolve), ethylene glycol mono-tert-butyl ether (also known as tert-butyl cellosolve), and ethylene glycol monohexyl ether; diethylene glycol monomethyl ether (also known as methyl carbitol), diethylene glycol monoethyl ether Examples include carbitols such as carbitol (also known as propyl carbitol), diethylene glycol monopropyl ether (also known as propyl carbitol), and diethylene glycol monobutyl ether (DB) (also known as butyl carbitol); propylene glycol ethers such as propylene glycol monomethyl ether (PGM), propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; and dipropylene glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether.

[0301] In this specification, examples of glycol ether ester solvents include cellosolve esters such as ethylene glycol monomethyl ether acetate (also known as methyl cellosolve acetate), ethylene glycol monoethyl ether acetate (also known as cellosolve acetate), and ethylene glycol monobutyl ether acetate (also known as butyl cellosolve acetate); carbitol esters such as diethylene glycol monoethyl ether acetate (also known as carbitol acetate) and diethylene glycol monobutyl ether acetate (also known as butyl carbitol acetate); propylene glycol ether esters such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate; and dipropylene glycol ether esters such as dipropylene glycol monomethyl ether acetate.

[0302] Examples of additives used in resist compositions include acid generators, acid diffusion controllers, acid crosslinking agents, dissolution accelerators, dissolution controllers, sensitizers, and surfactants. These can be used individually or in combination of two or more.

[0303] In this embodiment, the resist composition preferably includes an acid generator in addition to the polymer of this embodiment. The acid generator used in the resist composition may be either nonionic or ionic. Examples of nonionic acid generators include sulfonate esters (e.g., 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate) and sulfones (e.g., disulfone, ketosulfone, sulfonyldiazomethane). Examples of ionic acid generators include onium salts containing onium cations (e.g., diazonium salt, phosphonium salt, sulfonium salt, iodonium salt). Examples of onium salt anions include sulfonic acid anions, sulfonylimide anions, and sulfonylmethide anions.

[0304] Specific examples of acid generators used in resist compositions are not limited to triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, diphenyltolylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, di-2,4,6-trimethylphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenylsulfonium nonafluoro-n-butanesulfonate, diphenyl-4-hydroxyphenylsulfonium trifluoromethanesulfonate, bis(4-fluorophenyl)-4-hydroxyphenylsulfonium trifluoromethanesulfonate, diphenyl-4-hydroxyphenylsulfonium nonafluoro-n-butanesulfonate, bis(4-hydroxyphenyl)-phenylsulfonium trifluoromethanesulfonate Sodium, tri(4-methoxyphenyl)sulfonium trifluoromethanesulfonate, tri(4-fluorophenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium benzenesulfonate, diphenyl-2,4,6-trimethylphenyl-p-toluenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-2-trifluoromethylbenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-4-trifluoromethylbenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-2,4-difluorobenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium hexafluorobenzenesulfonate, diphenylnaphthylsulfonium trifluoromethanesulfonate, diphenyl-4-hydroxyphenylsulfonium-p-toluenesulfonate, triphenylsulfonium 10-camphorsulfonate, diphenyl-4-hydroxyphenylsulfonium 10-camphorsulfonate and cyclo(1,Examples include 3-perfluoropropanedisulfone (imidate). The acid generator can be used alone or in combination of two or more. The amount of acid generator added to the resist composition is preferably 0.001 to 49% by mass, more preferably 1 to 40% by mass, even more preferably 3 to 30% by mass, and even more preferably 10 to 25% by mass, relative to the total mass of the solid components of the resist composition.

[0305] Examples of acid diffusion control agents used in resist compositions are not limited to tributylamine, triphenylsulfonium hydroxide, triphenylsulfonium acetate, triphenylsulfonium salicylate, diphenyl-4-hydroxyphenylsulfonium hydroxide, diphenyl-4-hydroxyphenylsulfonium acetate, diphenyl-4-hydroxyphenylsulfonium salicylate, bis(4-t-butylphenyl)iodonium hydroxide, bis(4-t-butylphenyl)iodonium acetate, bis(4-t-butylphenyl)iodonium hydroxide, bis(4-t-butylphenyl)iodonium acetate, bis(4-t-butylphenyl)iodonium salicylate, 4-t-butylphenyl-4-hydroxyphenyliodonium hydroxide, 4-t-butylphenyl-4-hydroxyphenyliodonium acetate, and 4-t-butylphenyl-4-hydroxyphenyliodonium salicylate. The acid diffusion control agent can be used alone or in combination of two or more types. The amount of acid diffusion control agent added to the resist composition is preferably 0.001 to 49% by mass, more preferably 0.01 to 10% by mass, even more preferably 0.01 to 5% by mass, and particularly preferably 0.01 to 3% by mass, based on the total mass of the solid components of the resist composition.

[0306] Examples of acid crosslinking agents used in resist compositions include methylol group-containing compounds such as methylol group-containing melamine compounds, methylol group-containing benzoguanamine compounds, methylol group-containing urea compounds, methylol group-containing glycoluryl compounds, and methylol group-containing phenol compounds; alkoxyalkyl group-containing compounds such as alkoxyalkyl group-containing melamine compounds, alkoxyalkyl group-containing benzoguanamine compounds, alkoxyalkyl group-containing urea compounds, alkoxyalkyl group-containing glycoluryl compounds, and alkoxyalkyl group-containing phenol compounds; carboxymethyl group-containing compounds such as carboxymethyl group-containing melamine compounds, carboxymethyl group-containing benzoguanamine compounds, carboxymethyl group-containing urea compounds, carboxymethyl group-containing glycoluryl compounds, and carboxymethyl group-containing phenol compounds; and epoxy compounds such as bisphenol A-based epoxy compounds, bisphenol F-based epoxy compounds, bisphenol S-based epoxy compounds, novolac resin-based epoxy compounds, resol resin-based epoxy compounds, and poly(hydroxystyrene)-based epoxy compounds. Acid crosslinking agents can be used individually or in combination of two or more types. The amount of acid crosslinking agent added to the resist composition is preferably 0 to 49% by mass, more preferably 0 to 40% by mass, even more preferably 0 to 30% by mass, and particularly preferably 0 to 20% by mass, based on the total mass of the solid components of the resist composition.

[0307] Examples of dissolution accelerators used in resist compositions include low molecular weight phenolic compounds, such as bisphenols and tris(hydroxyphenyl)methane. Dissolution accelerators can be used individually or in combination of two or more. The amount of dissolution accelerator added to the resist composition is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, and even more preferably 0 to 1% by mass, based on the total mass of the solid components of the resist composition.

[0308] Examples of dissolution control agents used in resist compositions include aromatic hydrocarbons such as phenanthrene, anthracene, and acenaphthene; aromatic ketones such as acetophenone, benzophenone, and phenylnaphthyl ketone; and aromatic sulfones such as methylphenyl sulfone, diphenyl sulfone, and dinaphthyl sulfone. Dissolution control agents can be used individually or in combination of two or more. The amount of dissolution control agent added to the resist composition is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, and even more preferably 0 to 1% by mass, relative to the total mass of the solid components of the resist composition.

[0309] Examples of sensitizers used in the resist composition include benzophenones, biacetyls, pyrenes, phenothiazines, fluorenes, etc., but are not particularly limited. One sensitizer or two or more sensitizers can be used. The amount of sensitizer added to the resist composition is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, and even more preferably 0 to 1% by mass, based on the total mass of the solid components of the resist composition.

[0310] The surfactant used in the resist composition may be anionic, cationic, nonionic, or amphoteric, but nonionic surfactants are preferred. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, and higher fatty acid diesters of polyethylene glycol. One surfactant or two or more surfactants can be used. The amount of surfactant added to the resist composition is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, and even more preferably 0 to 1% by mass, based on the total mass of the solid components of the resist composition.

[0311] The resist composition may further contain known components commonly used in resist compositions, such as dyes, pigments, adhesion aids, anti-halation agents, preservatives, defoamers, and shape modifiers.

[0312] The resist composition preferably contains a compound represented by formula (II).

[0313] The content of the compound represented by formula (II) in the resist composition is not particularly limited, but when the total amount of the polymer of this embodiment and the compound represented by formula (II) contained in the composition is taken as 100% by mass, it is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, even more preferably 0.01% by mass or more, and particularly preferably 0.05% by mass or more. The upper limit of the content of the compound represented by formula (II) is not particularly limited, but when the total amount of the polymer of this embodiment and the compound represented by formula (II) contained in the composition is taken as 100% by mass, for example, it may be 50% by mass or less, 30% by mass or less, 20% by mass or less, 10% by mass or less, 5% by mass or less, 2% by mass or less, 1% by mass or less, etc.

[0314] The resist composition preferably contains a compound represented by formula (III).

[0315] The content of the compound represented by formula (III) in the resist composition is not particularly limited, but when the total amount of the polymer of this embodiment and the compound represented by formula (III) contained in the composition is taken as 100% by mass, it is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, even more preferably 0.01% by mass or more, and particularly preferably 0.05% by mass or more. The upper limit of the content of the compound represented by formula (III) is not particularly limited, but when the total amount of the polymer of this embodiment and the compound represented by formula (III) contained in the composition is taken as 100% by mass, for example, it may be 50% by mass or less, 30% by mass or less, 20% by mass or less, 10% by mass or less, 5% by mass or less, 2% by mass or less, 1% by mass or less, etc.

[0316] The resist composition may contain both the compound represented by formula (II) and the compound represented by formula (III).

[0317] After coating the substrate with the resist composition, the solvent is removed and the resist composition is dried to form a resist layer. Drying can be performed, for example, by heating using a hot plate or by vacuum drying. In the case of heating drying, the heating temperature is, for example, 50 to 200°C, and the heating time is, for example, 10 to 180 seconds. In the case of vacuum drying, the pressure during vacuum drying is, for example, 1 Pa to 1.0 × 10⁻⁶. ５ It should be set to Pa. The thickness of the resist layer that is formed is, for example, 50 nm to 1 μm.

[0318] In step (ii), the resist layer formed in step (i) is exposed by irradiating it with radiation. As an exposure method, for example, a method using an exposure machine equipped with an exposure light source can be used. The exposure machine may be an immersion exposure machine. As an exposure light source, a light source that emits ultraviolet laser light such as a KrF excimer laser, ArF excimer laser, or F2 excimer laser, a light source that emits far-ultraviolet or vacuum-ultraviolet harmonic laser light by wavelength conversion of laser light from a solid-state laser light source (such as a YAG or semiconductor laser), an electron beam, or a light source that irradiates with ultra-ultraviolet (EUV) light can be used. During exposure, exposure may be performed through a mask of the desired pattern, or exposure may be performed by direct drawing without using a mask. In order to stably form a high-precision fine pattern, after exposure, a heat treatment may be performed at a temperature of, for example, 50 to 200°C, preferably 70 to 150°C for 30 seconds or more.

[0319] In step (iii), the resist layer exposed in step (ii) is developed with a developer to form a resist pattern. Development methods include the dip method, paddle method, spray method, and dynamic dispensing method. Development can be carried out, for example, at 10 to 50°C for 10 to 200 seconds, preferably at 20 to 25°C for 15 to 90 seconds. The formed resist pattern may be a positive-type resist pattern or a negative-type resist pattern.

[0320] When manufacturing positive resist patterns, an alkaline developer is used as the developer. As the alkaline developer, for example, an alkaline aqueous solution is typically used, prepared by dissolving an alkaline compound such as alkali metal hydroxide, aqueous ammonia, alkylamines, alkanolamines, heterocyclic amines, tetraalkylammonium hydroxides, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, or 1,5-diazabicyclo-[4.3.0]-5-nonene at a concentration of 1 to 10% by mass, preferably 1 to 3% by mass. Water-soluble organic solvents and surfactants may also be added to the alkaline developer as appropriate. After development, it is preferable to wash the resist pattern with ultrapure water, and then remove any remaining water from the substrate and pattern.

[0321] When manufacturing negative resist patterns, an organic developer containing an organic solvent is used as the developer. Examples of organic solvents in the organic developer include aliphatic ketone solvents, glycol ether ester solvents, ester solvents, glycol ether solvents, and amide solvents. The content of the organic solvent in the organic developer is, for example, 90% by mass or more and 100% by mass or less. The organic developer may contain trace amounts of water, surfactants, etc. During development, development may be stopped by substituting the organic developer with a different type of solvent.

[0322] After development, the resist pattern is preferably washed with a rinsing solution. The rinsing solution is not particularly limited as long as it does not dissolve the resist pattern. After washing, it is preferable to remove any remaining rinsing solution from the substrate and the pattern.

[0323] The present invention will be described in detail below with reference to examples. The present invention is not limited to these examples. In these examples, unless otherwise specified, the temperature condition is room temperature (25°C ± 5°C), and unless otherwise specified, the pressure condition is atmospheric pressure (1 atm).

[0324] (1) Measurement of NMR In this embodiment, １¹H-NMR measurements were performed under the following conditions: Measurement device: Bruker Avance 500 III spectrum meter Frequency: 500 MHz Solvent: CDCl ３ or d ６ - DMSO Internal standard: TMS Measurement temperature: 23°C In this embodiment, １３ C-NMR measurements were performed under the following conditions: Measurement device: Bruker Avance 500 III spectrum meter Frequency: 125 MHz Solvent: d ６ -DMSO Internal standard: TMS Measurement temperature: 23℃

[0325] (2) Liquid Chromatography-Mass Spectrometry (LC-MS) Measurement In this embodiment, LC-MS measurement was performed under the following conditions: Measurement equipment: Shimadzu Nexera X3 (LC unit), Shimadzu LCMS-2020 (MS unit) Column: ACQUITY BEH C18 1.7 μm (2.1 x 100 mm) Column temperature: 40 °C Flow rate: 0.4 mL / min. Ionization: ESI ±

[0326] (3) Measurement of weight-average molecular weight (Mw) and number-average molecular weight (Mn) of polymers In this embodiment, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of polymers were measured by gel permeation chromatography (GPC) under the following conditions. Measuring apparatus: Showa Denko Co., Ltd. Shodex® GPC-101 (product name) Flow rate: 1 mL / min Column: Shodex® GPC KF-80M (product name) x 3 Column temperature: 40°C Detector: RI (Refractory Index) detector Standard material: Polystyrene

[0327] [Example A1: Monomer compound A1]

[0328]

[0329] Step 1: Synthesis of 2-(4-iodophenyl)propan-2-ol Prepare a 200 mL three-necked flask, add 38 mL of anhydrous tetrahydrofuran (THF) and 5.0 g (19.1 mmol) of methyl 4-iodobenzoate, and N ２ The mixture was stirred for 30 minutes under flowing current while being cooled with ice to maintain an internal temperature of 10°C or lower. 57 mL of methylmagnesium bromide (57 mmol, 1.0 M THF solution) was added to a 200 mL three-necked flask over 5 minutes, then the internal temperature was allowed to rise to 25°C over 15 minutes, followed by a rise to 50°C over 20 minutes, and stirring was continued for 40 minutes. After the reaction, the mixture was cooled to 0°C, and then quenched under ice by adding 20 mL of saturated ammonium chloride aqueous solution and 20 mL of deionized water, followed by extraction with ethyl acetate. The organic layer was concentrated and then separated and purified by column chromatography to obtain 2-(4-iodophenyl)propan-2-ol (4.05 g, 15.5 mmol).

[0330] 1 H-NMR(500 MHz, CDCl3):δ(ppm) 7.66(2H, Ph), 7.24(2H, Ph), 1.55(6H, -CH3)

[0331] Step 2: Synthesis of 2-(4-iodophenyl)propan-2-yl chloroacetate Prepare a 200 mL three-necked flask, add 40 mL of N-methyl-2-pyrrolidone (NMP) and 2-(4-iodophenyl)propan-2-ol (4.0 g, 15.3 mmol) obtained in Step 1, and N ２ The mixture was stirred under flow conditions at room temperature (23°C) for 30 minutes. Then, chloroacetyl chloride (1.40 ml, 17.6 mmol) was added over 5 minutes, the internal temperature was increased to 60°C over 20 minutes, and stirring was continued for 120 minutes. After the reaction, the mixture was cooled to 0°C, and then quenched with 30 mL of deionized water under ice cooling. The mixture was then extracted with ethyl acetate. The organic layer was washed twice by adding an additional 30 mL of deionized water. After concentrating the organic layer, it was separated and purified by column chromatography to obtain 2-(4-iodophenyl)propan-2-yl chloroacetate (3.21 g, 9.5 mmol).

[0332] 1H-NMR(500 MHz, CDCl3):δ(ppm) 7.65(2H, Ph), 7.12(2H, Ph), 3.99(2H, -CH2-), 1.77(6H, -CH3)

[0333] Step 3: Synthesis of monomer compound A1 Prepare a 200 mL three-necked flask and add 30 mL of N,N-dimethylformamide (DMF), 2-(4-iodophenyl)propan-2-yl chloroacetate (3.0 g, 9.0 mmol) obtained in Step 2, and potassium carbonate (1.86 g, 13.5 mmol), N ２ The mixture was stirred under flow at 0°C for 30 minutes. Then, 2-iodo-6-methoxy-4-vinylphenol (2.61 g, 9.45 mmol) was added, and the internal temperature was increased to 40°C over 20 minutes, followed by continued stirring for 120 minutes. After the reaction, the mixture was cooled to room temperature (23°C), 30 mL of deionized water was added to quench the mixture, and it was extracted with ethyl acetate. The organic layer was then washed twice by adding an additional 30 mL of deionized water. After concentrating the organic layer, it was separated and purified by column chromatography to obtain the target monomer compound A1 (3.80 g, 6.57 mmol).

[0334] 1 H-NMR(500 MHz, CDCl3):δ(ppm): 7.65(2H, Ph), 7.40(1H, Ph), 7.13(2H, Ph), 6.91(1H, Ph), 6.58(1H, -CH=), 5.67(1H, =CH2), 5.25(1H, =CH2), 4.58(2H, -CH2-), 3.82(3H, -OCH3), 1.80(6H, -CH3)

[0335] [Example A2: Monomer compound A2]

[0336]

[0337] Prepare a 200 mL three-necked flask, add 30 mL of N,N-dimethylformamide (DMF), 2-(4-iodophenyl)propan-2-yl chloroacetate (3.0 g, 9.0 mmol) obtained in step 2 of Example A1, and potassium carbonate (1.86 g, 13.5 mmol), and N ２The mixture was stirred under flow at 0°C for 30 minutes. Then, 2,6-diiodo-4-vinylphenol (3.51 g, 9.44 mmol) was added, and the internal temperature was increased to 40°C over 20 minutes, followed by continued stirring for 120 minutes. After the reaction, the mixture was cooled to room temperature (23°C), 30 mL of deionized water was added to quench the mixture, and it was extracted with ethyl acetate. The organic layer was then washed twice by adding an additional 30 mL of deionized water. After concentrating the organic layer, it was separated and purified by column chromatography to obtain the target monomer compound A2 (4.11 g, 6.11 mmol).

[0338] 1 H-NMR(500 MHz, d6-DMSO)δ(ppm): 7.67(2H, Ph), 7.60(2H, Ph), 7.05(2H, Ph), 6.72(1H, -CH=), 5.76(1H, =CH2), 5.25(1H, =CH2), 4.99(2H, -CH2-), 1.80(6H, -CH3)

[0339] [Example A3: Monomer compound A3]

[0340]

[0341] Prepare a 200 mL three-necked flask, add 30 mL of N,N-dimethylformamide (DMF), 2-(4-iodophenyl)propan-2-yl chloroacetate (3.0 g, 9.0 mmol) obtained in step 2 of Example A1, and potassium carbonate (1.86 g, 13.5 mmol), and N ２ The mixture was stirred under flow at 0°C for 30 minutes. Then, 2-hydroxy-3,5-diiodobenzyl methacrylate (9.20 g, 9.46 mmol) was added, and the internal temperature was increased to 40°C over 20 minutes, followed by continued stirring for 120 minutes. After the reaction, the mixture was cooled to room temperature (23°C), 30 mL of deionized water was added to quench the mixture, and it was extracted with ethyl acetate. The organic layer was then washed twice by adding an additional 30 mL of deionized water. After concentrating the organic layer, it was separated and purified by column chromatography to obtain the target monomer compound A3 (4.49 g, 6.02 mmol).

[0342] 1H-NMR(500 MHz, d6-DMSO)δ(ppm): 7.99(1H, Ph), 7.80(1H, Ph), 7.60(2H, Ph), 7.05(2H, Ph), 6.48(1H, =CH2), 6.40(1H, =CH2), 5.12(2H, -CH2-), 4.99(2H, -CH2-), 2.01(3H, -CH3), 1.80(6H, -CH3)

[0343] [Example A4: Monomer compound A4]

[0344]

[0345] monomer compound A4 of the target product was obtained in the same manner as in Example A1, except that methyl 3-methyl-4-iodobenzoate was used instead of methyl 4-iodobenzoate.

[0346] 1 H-NMR(500 MHz, CDCl3)δ(ppm): 7.75(1H, Ph), 7.36(1H, Ph), 7.22(1H, Ph), 6.96(1H, Ph), 6.95(1H, Ph), 6.72(1H, -CH=), 5.76(1H, =CH2), 5.25(1H, =CH2), 4.98(2H, -CH2-), 3.83(3H, -OCH3), 2.33(3H, -CH3), 1.80(6H, -CH3)

[0347] [Example A5: Monomer compound A5]

[0348]

[0349] monomer compound A5 of the target product was obtained in the same manner as in steps 1 and 2 of Example A1 and Example A2, except that methyl 3-methyl-4-iodobenzoate was used instead of methyl 4-iodobenzoate.

[0350] 1H-NMR(500 MHz, d6-DMSO)δ(ppm): 7.75(1H, Ph), 7.67(2H, Ph), 6.96(1H, Ph), 6.95(1H, Ph), 6.74(1H, -CH=), 5.81(1H, =CH2), 5.27(1H, =CH2), 4.99(2H, -CH2-), 2.33(3H, -CH3), 1.80(6H, -CH3)

[0351] [Example A6: Monomer compound A6]

[0352]

[0353] The monomer compound A6 of the target product was obtained in the same manner as in steps 1 and 2 of Example A1 and Example A3, except that methyl 3-methyl-4-iodobenzoate was used instead of methyl 4-iodobenzoate.

[0354] 1 H-NMR(500 MHz, d6-DMSO)δ(ppm): 7.99(1H, Ph), 7.80(1H, Ph), 7.75(1H, Ph), 6.96(1H, Ph), 6.95(1H, Ph), 6.48(1H, =CH2), 6.40(1H, =CH2), 5.12(2H, -CH2-), 4.99(2H, -CH2-), 2.33(3H, -CH3), 2.01(3H, -CH3), 1.80(6H, -CH3)

[0355] [Example AA1: Monomer compound AA1]

[0356]

[0357] Prepare a 200 mL three-necked flask, add 30 mL of DMF (N,N-dimethylformamide), 2-(4-iodophenyl)propan-2-yl chloroacetate (3.0 g, 9.0 mmol), and potassium carbonate (1.86 g, 13.5 mmol), and N ２The mixture was stirred under flow at 0°C for 30 minutes. Then, 2-hydroxy-3-iodo-5-vinylbenzoic acid (2.73 g, 9.45 mmol) was added, and the internal temperature was increased to 40°C over 20 minutes, followed by continued stirring for 120 minutes. After the reaction, the mixture was cooled to room temperature (23°C), 30 mL of deionized water was added to quench the mixture, and it was extracted with ethyl acetate. The organic layer was then washed twice by adding an additional 30 mL of deionized water. After concentrating the organic layer, it was separated and purified by column chromatography to obtain the target monomer compound AA1 (1.84 g, 3.12 mmol).

[0358] 1 H-NMR (500MHz, CDCl3)δ(ppm): 12.04(1H, COOH), 8.02(1H, Ph), 7.60(2H, Ph), 7.49(1H, Ph), 7.05(2H, Ph), 6.72(1H, -CH=), 5.76(1H, =CH2), 5.25(1H, =CH2), 4.99(2H, -CH2-), 1.80(6H, -CH ３ )

[0359] [Example AA2: Monomer compound AA2]

[0360]

[0361] The monomer compound AA2 of the target product was obtained in the same manner as in steps 1 and 2 of Example A1 and Example A3, except that methyl 3-methyl-4-iodobenzoate was used instead of methyl 4-iodobenzoate.

[0362] 1 H-NMR (500MHz, CDCl3)δ(ppm): 12.04(1H, COOH), 8.02(1H, Ph), 7.75(1H, Ph), 7.49(1H, Ph), 6.96(1H, Ph), 6.95(1H, Ph), 6.73(1H, -CH=), 5.76(1H, =CH2), 5.25(1H, =CH2), 4.98(2H, -CH2-), 2.33(3H, -CH3), 1.80(6H, -CH3)

[0363] [Example AA3: Monomer compound AA3]

[0364]

[0365] Prepare a 200 mL three-necked flask, add 30 mL of DMF (N,N-dimethylformamide), 2-(4-iodophenyl)propan-2-yl chloroacetate (3.0 g, 9.0 mmol), and potassium carbonate (1.86 g, 13.5 mmol), and N ２ The mixture was stirred under flow at 0°C for 30 minutes. Then, 2-hydroxy-3-methoxy-5-iodobenzyl methacrylate (3.28 g, 9.46 mmol) was added, and the internal temperature was increased to 40°C over 20 minutes, followed by continued stirring for 120 minutes. After the reaction, the mixture was cooled to room temperature (23°C), 30 mL of deionized water was added to quench the mixture, and it was extracted with ethyl acetate. The organic layer was then washed twice by adding an additional 30 mL of deionized water. After concentrating the organic layer, it was separated and purified by column chromatography to obtain the target monomer compound AA3 (3.62 g, 6.11 mmol).

[0366] 1 H-NMR (500MHz, CDCl3)δ(ppm): 7.60(2H, Ph), 7.49(1H, Ph), 7.32(1H, Ph), 7.05(2H, Ph), 6.48(1H, =CH2), 6.40(1H, =CH2), 5.12(2H, -CH2-), 4.98(2H, -CH2-), 3.83(3H, -OCH3), 2.01(3H, -CH3), 1.80(6H, -CH3)

[0367] [Example AA4: Monomer compound AA4]

[0368]

[0369] The monomer compound AA4 of the target product was obtained in the same manner as in the above example, except that methyl 3-methyl-4-iodobenzoate was used instead of methyl 4-iodobenzoate. 1H-NMR (500MHz, CDCl3)δ(ppm): 7.75(1H, Ph), 7.49(1H, Ph), 7.32(1H, Ph), 6.96(1H, Ph), 6.95(1H, Ph), 6.48(1H, =CH2), 6.40(1H, =CH2), 5.12(2H, -CH2-), 4.98(2H, -CH2-), 3.83(3H, -OCH3), 2.33(3H, -CH3), 2.01(3H, -CH3), 1.80(6H, -CH3)

[0370] [Example AA5: Monomer compound AA5]

[0371]

[0372] Prepare a 200 mL three-necked flask, add 30 mL of DMF (N,N-dimethylformamide), 2-(4-iodophenyl)propan-2-yl chloroacetate (3.0 g, 9.0 mmol), and potassium carbonate (1.86 g, 13.5 mmol), and N ２ The mixture was stirred under flow at 0°C for 30 minutes. Then, 2-hydroxy-4-methoxy-3,5-diiodobenzyl methacrylate (4.47 g, 9.46 mmol) was added, and the internal temperature was increased to 40°C over 20 minutes, followed by continued stirring for 120 minutes. After the reaction, the mixture was cooled to room temperature (23°C), 30 mL of deionized water was added to quench the mixture, and it was extracted with ethyl acetate. The organic layer was then washed twice by adding an additional 30 mL of deionized water. After concentrating the organic layer, it was separated and purified by column chromatography to obtain the target monomer compound AA5 (4.75 g, 6.13 mmol).

[0373] 1 H-NMR (500MHz, CDCl3)δ(ppm): 7.80(1H, Ph), 7.60(2H, Ph), 7.05(2H, Ph), 6.48(1H, =CH2), 6.40(1H, =CH2), 5.12(2H, -CH2-), 4.98(2H, -CH2-), 3.83(3H, -OCH3), 2.01(3H, -CH3), 1.80(6H, -CH3)

[0374] [Example AA6: Monomer compound AA6]

[0375]

[0376] The monomer compound AA6 of the target product was obtained in the same manner as in the above example, except that methyl 3-methyl-4-iodobenzoate was used instead of methyl 4-iodobenzoate.

[0377] 1 H-NMR (500MHz, CDCl3)δ(ppm): 7.80(1H, Ph), 7.75(1H, Ph), 6.96(1H, Ph), 6.95(1H, Ph), 6.48(1H, =CH2), 6.40(1H, =CH2), 5.12(2H, -CH2-), 4.98(2H, -CH2-), 3.83(3H, -OCH3), 2.33(3H, -CH3), 2.01(3H, -CH3), 1.80(6H, -CH3)

[0378] [Example AA7: Monomer compound AA7]

[0379]

[0380] Step 1: Synthesis of 3-iodo-1-adamantanecarboxylic acid Prepare a 500 mL three-necked flask, add 140 mL of toluene and 15.6 g (80 mmol) of 3-hydroxy-1-adamantanecarboxylic acid, N ２ Under flow conditions, 178 ml of 57% hydroiodic acid was added over 5 minutes, then the temperature was raised to 85°C and stirred for 2 hours. After the reaction, the mixture was cooled to room temperature, 100 ml of saturated sodium bisulfite aqueous solution was added to quench the mixture, and it was extracted with ethyl acetate. The organic layer was concentrated, crystallized with hexane, and 3-iodo-1-adamantanecarboxylic acid (21.6 g, 70.4 mmol) was obtained by vacuum filtration.

[0381] Step 2: Synthesis of methyl 3-iodo-1-adamantanecarboxylate 20.0 g (66 mmol) of 3-iodo-1-adamantanecarboxylic acid was dissolved in 200 ml of dichloromethane, and 9.50 g (80 mmol) of thionyl chloride was added at a temperature below 10°C. The reaction was carried out for 2 hours while maintaining a temperature below 10°C. Subsequently, 100 ml of methanol was added at a temperature below 10°C. The temperature was then raised to 60°C, and the reaction was carried out with stirring for 3 hours. After the reaction was complete, water was added to the reaction mixture, and extraction was performed with ethyl acetate. The organic layer was washed twice with deionized water, and the organic layer was removed by distillation under reduced pressure to concentrate the mixture. The concentrate was purified by column chromatography to obtain 18.8 g of methyl 3-iodo-1-adamantanecarboxylate (yield 89%).

[0382] Step 3: Synthesis of 2-((1r,3s,5R,7S)-3-iodoadamantan-1-yl)propan-2-ol Prepare a 500 mL three-necked flask, add 180 mL of anhydrous THF and 18.0 g (56 mmol) of methyl 3-iodo-1-adamantanecarboxylate obtained above, and N ２ The mixture was stirred for 30 minutes under flowing water while being cooled with ice to maintain an internal temperature of 10°C or lower. 126 mL (126 mmol, 1.0 M THF solution) of methylmagnesium bromide (nucleophile: Grignard reagent) was added to a 500 mL three-necked flask over 10 minutes. The internal temperature was then allowed to return to 25°C over 15 minutes, then to 50°C over 20 minutes, and stirring was continued for 40 minutes. After the reaction, the mixture was cooled to 0°C, and then quenched under ice cooling by adding 135 mL of saturated ammonium chloride aqueous solution and 50 mL of deionized water, followed by extraction with ethyl acetate. The organic layer was concentrated and then separated and purified by column chromatography to obtain 2-((1r,3s,5R,7S)-3-iodoadamantan-1-yl)propan-2-ol (13.8 g, 43.1 mmol).

[0383] Step 4: Synthesis of 2-((1r,3s,5R,7S)-3-iodoadamantan-1-yl)propan-2-yl chloroacetic acid A 300 mL three-necked flask was prepared, and 80 mL of N-methyl-2-pyrrolidone (NMP) and the obtained 2-((1r,3s,5R,7S)-3-iodoadamantan-1-yl)propan-2-ol (9.8 g, 30.6 mmol) were added. The mixture was stirred under N2 flow at room temperature (23°C) for 30 minutes. Then, chloroacetyl chloride (2.80 mL, 35.2 mmol) was added over 5 minutes, and the internal temperature was increased to 60°C over 20 minutes, with stirring continued for 120 minutes. After the reaction, the mixture was cooled to 0°C, and then quenched with 60 mL of deionized water under ice cooling. The mixture was then extracted with ethyl acetate. The organic layer was washed twice by adding an additional 60 mL of deionized water. After concentrating the organic layer, separation and purification were performed by column chromatography to obtain 2-((1r,3s,5R,7S)-3-iodoadamantan-1-yl)propan-2-yl chloroacetic acid (7.8 g, 19.7 mmol), represented by the following formula.

[0384] Step 5: Synthesis of monomer compound AA7 Prepare a 200 mL three-necked flask and add 30 mL of DMF (N,N-dimethylformamide), 2-((1r,3s,5R,7S)-3-iodoadamantan-1-yl)propan-2-yl chloroacetate (3.5 g, 9.0 mmol), and potassium carbonate (1.86 g, 13.5 mmol), N ２ The mixture was stirred under flow at 0°C for 30 minutes. Then, 2-iodo-6-methoxy-4-vinylphenol (2.61 g, 9.45 mmol) was added, and the internal temperature was increased to 40°C over 20 minutes, followed by continued stirring for 120 minutes. After the reaction, the mixture was cooled to room temperature (23°C), 30 mL of deionized water was added to quench the mixture, and it was extracted with ethyl acetate. The organic layer was then washed twice by adding an additional 30 mL of deionized water. After concentrating the organic layer, it was separated and purified by column chromatography to obtain the target monomer compound AA7 (3.67 g, 5.77 mmol).

[0385] 1H-NMR (500MHz, CDCl3)δ(ppm): 7.36(1H, Ph), 7.22(1H, Ph), 6.72(1H, -CH=), 5.76(1H, =CH2), 5.25(1H, =CH2), 4.90(2H, -CH2-), 3.82(3H, -OCH3), 2.80-2.10(8H), 1.40(6H, -CH3), 1.40-1.10(6H)

[0386] [Example AA8: Monomer compound AA8]

[0387]

[0388] The monomer compound AA8 of the target product was obtained in the same manner as in Example AA7, except that 3,5-diiodo-4-vinylphenol was used instead of 2-iodo-6-methoxy-4-vinylphenol.

[0389] 1 H-NMR (500MHz, CDCl3)δ(ppm): 7.67(2H, Ph), 6.72(1H, -CH=), 5.76(1H, =CH2), 5.25(1H, =CH2), 4.90(2H, -CH2-), 2.80-2.10(8H), 1.40(6H, -CH3), 1.40-1.10(6H)

[0390] [Example AA9: Monomer compound AA9]

[0391]

[0392] The monomer compound AA9 of the target product was obtained in the same manner as in Example AA7, except that 2-hydroxy-3,5-diiodobenzyl methacrylate was used instead of 2-iodo-6-methoxy-4-vinylphenol.

[0393] 1 H-NMR(500MHz, CDCl3)δ(ppm): 7.99(1H, Ph), 7.80(1H, Ph), 6.48(1H, =CH2), , 6.40(1H, =CH2), 5.12(2H, -CH2-), 4.90(2H, -CH2-), 2.80-2.10(8H), 2.01(3H, -CH3), 1.40(6H, -CH3), 1.40-1.10(6H)

[0394] [Example AA10: Monomer compound AA10]

[0395]

[0396] The monomer compound AA10 of the target product was obtained in the same manner as in Example AA7, except that 2-hydroxy-3-iodo-5-vinylbenzoic acid was used instead of 2-iodo-6-methoxy-4-vinylphenol.

[0397] 1 H-NMR(500MHz, CDCl3)δ(ppm): 12.04(1H, COOH), 8.02(1H, Ph), 7.49(1H, Ph), 6.72(1H, -CH=), 5.76(1H, =CH2), 5.25(1H, =CH2), 4.90(2H, -CH2-), 2.80-2.10(8H), 1.40(6H, -CH3), 1.40-1.10(6H)

[0398] [Example AA11: Monomer compound AA11]

[0399]

[0400] The monomer compound AA11 of the target product was obtained in the same manner as in Example AA7, except that 2-hydroxy-3-methoxy-5-iodobenzyl methacrylate was used instead of 2-iodo-6-methoxy-4-vinylphenol.

[0401] 1 H-NMR (500MHz, CDCl3)δ(ppm): 7.49(1H, Ph), 7.31(1H, Ph), 6.48(1H, =CH2), 6.40(1H, =CH2), 5.12(2H, -CH2-), 4.90(2H, -CH2-), 3.82(3H, -OCH3), 2.80-2.10(8H), 2.01(3H, -CH3), 1.40(6H, -CH3), 1.40-1.10(6H)

[0402] [Example AA12: Monomer compound AA12]

[0403]

[0404] The target monomer compound AA12 was obtained in the same manner as the synthesis example of monomer compound X7, except that 2-hydroxy-4-methoxy-3,5-diiodobenzyl methacrylate was used instead of 2-iodo-6-methoxy-4-vinylphenol.

[0405] 1 H-NMR (500MHz, CDCl3)δ(ppm): 7.80(1H, Ph), 6.48(1H, =CH2), 6.40(1H, =CH2), 5.12(2H, -CH2-), 4.90(2H, -CH2-), 3.82(3H, -OCH3), 2.80-2.10(8H), 2.01(3H, -CH3)1.40(6H, -CH3), 1.40-1.10(6H)

[0406] [Synthesis Example B1: Additive Compound B1]

[0407]

[0408] 15.6 g of 1-(4-hydroxy-3,5-diiodophenyl)ethanol, 0.15 g of methanesulfonic acid, 0.04 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, and 60 mL of dimethyl sulfoxide (DMSO) were charged into the reactor, and stirring was started. Next, the reduced pressure conditions for reflux at 120°C were adjusted using a Dean-Stark filter and a condenser, and air was blown into the reaction mixture at a flow rate of 1 mL / min. Water recovered in the Dean-Stark filter was removed from the system as needed. The reactor was then immersed in a 90°C water bath and stirring was continued for 30 hours. The reactor was then immersed in a 25°C water bath to cool the reaction mixture. Next, the reaction mixture was gradually added to 500 g of a 0.1% by mass sodium bisulfite aqueous solution while vigorously stirring and mixing. The precipitate was then filtered using a suction filter, pressed, and washed with 200 mL of a 33.3% by volume methanol aqueous solution. After isolating the main component from the precipitate obtained by column chromatography, the solvent was removed by evaporation, and the resulting solid was vacuum-dried at 40°C to obtain additive compound B1 (8.1 g, yield 26%). Analysis by liquid chromatography-mass spectrometry (LC-MS) revealed a molecular weight of 743.9, confirming that additive compound B1 had been obtained.

[0409] 1 H-NMR(500 MHz, d6-DMSO)δ(ppm): 9.6(2H, OH), 7.5(2H, Ph), 7.8(2H, Ph), 3.6(1H, -CH-), 1.3(3H, -CH3), 6.4-6.7(2H, -CH=CH-)

[0410] [Synthesis Example B2: Additive Compound B2]

[0411]

[0412] Additive compound B2 was synthesized in the same manner as in synthesis example B1, except that 11.8 g of 1-(4-hydroxy-3-)methoxy-5-iodophenyl)ethanol was used instead of 15.6 g of 1-(4-hydroxy-3,5-diiodophenyl)ethanol.

[0413] [Synthesis Example B3: Additive Compound B3]

[0414]

[0415] Additive compound B3 was synthesized in the same manner as in Example A2, except that additive compound B1 obtained in Synthesis Example B1 was used instead of 2,6-diiodo-4-vinylphenol. Analysis by liquid chromatography-mass spectrometry (LC-MS) revealed a molecular weight of 1348, confirming that additive compound B3 had been obtained.

[0416] [Synthesis Example B4: Additive Compound B4]

[0417]

[0418] Additive compound B4 was synthesized in the same manner as in Example A5, except that additive compound B1 obtained in Synthesis Example B1 was used instead of 2,6-diiodo-4-vinylphenol. Analysis by liquid chromatography-mass spectrometry (LC-MS) revealed a molecular weight of 1376, confirming that additive compound B4 had been obtained.

[0419] [Synthesis Example B5: Additive Compound B5]

[0420]

[0421] Additive compound B5 was synthesized in the same manner as in Example A1, except that additive compound B2 obtained in Synthesis Example B2 was used instead of 2-iodo-6-methoxy-4-vinylphenol. Analysis by liquid chromatography-mass spectrometry (LC-MS) revealed a molecular weight of 1156, confirming that additive compound B5 had been obtained.

[0422] [Synthesis Example B6: Additive Compound B6]

[0423]

[0424] Additive compound B6 was synthesized in the same manner as in Example A4, except that additive compound B2 obtained in Synthesis Example B2 was used instead of 2-iodo-6-methoxy-4-vinylphenol. Analysis by liquid chromatography-mass spectrometry (LC-MS) revealed a molecular weight of 1184, confirming that additive compound B6 had been obtained.

[0425] [Synthesis Example BA1: Additive Compound BA1]

[0426]

[0427] The additive compound BA1 of the target product was obtained in the same manner as in Synthesis Example B1, except that 2-hydroxy-5-(1-hydroxyethyl)-3-iodobenzoic acid was used instead of 1-(4-hydroxy-3,5-diiodophenyl)ethanol. 1 H-NMR(500MHz, CDCl3)δ(ppm): 21.08(2H, OH), 12.04(2H, COOH), 8.14(1H, Ph), 8.09(1H, Ph), 7.85(1H, Ph), 7.32(1H, Ph), 6.66(1H, -CH=CH-), 6.37(1H, -CH=CH-), 3.56(1H,-CH-), 1.25(3H, -CH3)

[0428] [Synthesis example BA2: Additive compound BA2]

[0429]

[0430] Additive compound B3 was synthesized in the same manner as in Example A2, except that additive compound BA1 obtained in Synthesis Example BA1 was used instead of 2,6-diiodo-4-vinylphenol. Analysis by liquid chromatography-mass spectrometry (LC-MS) revealed a molecular weight of 1183, confirming that additive compound BA2 was obtained.

[0431] [Synthesis Example BA3: Additive Compound BA3]

[0432]

[0433] Additive compound BA3 was synthesized in the same manner as in Example A4, except that additive compound BA1 obtained in Synthesis Example BA1 was used instead of 2-iodo-6-methoxy-4-vinylphenol. Analysis by liquid chromatography-mass spectrometry (LC-MS) revealed a molecular weight of 1211, confirming that additive compound BA3 had been obtained.

[0434] [Synthesis Example BA4: Additive Compound BA4]

[0435]

[0436] Additive compound BA4 was synthesized in the same manner as in Example AA7, except that additive compound B2 obtained in Synthesis Example B2 was used instead of 2-iodo-6-methoxy-4-vinylphenol. Analysis by liquid chromatography-mass spectrometry (LC-MS) revealed a molecular weight of 1272, confirming that additive compound BA4 had been obtained.

[0437] [Synthesis Example BA5: Additive Compound BA5]

[0438]

[0439] Additive compound BA5 was synthesized in the same manner as in Example AA7, except that additive compound B2 obtained in Synthesis Example B2 was used instead of 2-iodo-6-methoxy-4-vinylphenol. Analysis by liquid chromatography-mass spectrometry (LC-MS) revealed a molecular weight of 1272, confirming that additive compound BA5 had been obtained.

[0440] [Synthesis example BA6: Additive compound BA6]

[0441]

[0442] Additive compound BA6 was synthesized in the same manner as in Example A2, except that additive compound BA1 obtained in Synthesis Example BA1 was used instead of 2,6-diiodo-4-vinylphenol. Analysis by liquid chromatography-mass spectrometry (LC-MS) revealed a molecular weight of 1300, confirming that additive compound BA6 had been obtained.

[0443] [Synthesis Example C1: Additive Compound C1]

[0444]

[0445] A 200 mL three-necked flask was prepared, and 30 mL of N,N-dimethylformamide (DMF), 2-(4-iodophenyl)propan-2-ol (2.02 g, 7.7 mmol) obtained in step 1 of Example A1, and triethylamine (1.16 g, 11.5 mmol) were added. The mixture was stirred under N2 flow at 0°C for 30 minutes. Then, 2-(4-iodophenyl)propan-2-yl chloroacetate (2.60 g, 7.7 mmol) was added, and the internal temperature was increased to 40°C over 20 minutes, with stirring continuing for 120 minutes. After the reaction, the mixture was cooled to room temperature (23°C), 30 mL of deionized water was added to quench the mixture, and it was extracted with ethyl acetate. The organic layer was washed twice by adding an additional 30 mL of deionized water. After concentrating the organic layer, it was separated and purified by column chromatography to obtain the target additive compound C1 (3.44 g, 6.1 mmol). Analysis by liquid chromatography-mass spectrometry (LC-MS) revealed a molecular weight of 564, confirming that additive compound C1 was obtained.

[0446] [Synthesis example CA1: Additive compound CA1]

[0447]

[0448] Additive compound CA1 was obtained in the same manner as in steps 1 and 2 of Example A1 and the synthesis example of additive compound C1, except that methyl 3-methyl-4-iodobenzoate was used instead of methyl 4-iodobenzoate.

[0449] [Synthesis example CA2: Additive compound CA2]

[0450]

[0451] Prepare a 200 mL three-necked flask, add 30 mL of N,N-dimethylformamide (DMF), 2-((1r,3s,5R,7S)-3-iodoadamantan-1-yl)propan-2-ol (2.30 g, 7.2 mmol) obtained in step 3 of Example AA7, and triethylamine (1.16 g, 11.5 mmol), and N ２ The mixture was stirred under flow at 0°C for 30 minutes. Then, 2-((1r,3s,5R,7S)-3-iodoadamantan-1-yl)propan-2-yl chloroacetic acid (2.85 g, 7.2 mmol) was added, and the internal temperature was increased to 40°C over 20 minutes, followed by continued stirring for 120 minutes. After the reaction, the mixture was cooled to room temperature (23°C), 30 mL of deionized water was added to quench the mixture, and it was extracted with ethyl acetate. The organic layer was then washed twice by adding an additional 30 mL of deionized water. After concentrating the organic layer, it was separated and purified by column chromatography to obtain the target additive compound CA2 (3.80 g, 5.6 mmol).

[0452] [Example X1: Composition X1 containing a polymer]

[0453]

[0454] 3.7 g of monomer compound A1 obtained in Example A1, 1.8 g of 2-ethyl-2-adamantyl methacrylate (EAMA), 0.4 g of γ-butyrolactone methacrylate (GMA), and 1.2 g of 4-vinylphenyl acetate (PHS-Ac) were dissolved in 45 mL of cyclohexanone, and 0.20 g of azobisisobutyronitrile was added. After stirring at an internal temperature of 80°C for 12 hours, the reaction solution was added dropwise to 2 L of n-heptane. Composition X1 containing the precipitated polymer was filtered off, rinsed with 20 mL of methanol, and then dried under reduced pressure to obtain 6.8 g of a white powder.

[0455] The obtained white powder was dissolved in 50 mL of tetrahydrofuran. While stirring at 120 rpm using a stirring blade, 40 mL of 1 M sodium hydroxide aqueous solution was gradually added, and the internal temperature was raised to 40°C and stirred for 8 hours. The internal temperature was cooled to 10°C and stirring was continued, and 40 mL of 1 M ammonium chloride aqueous solution was gradually added and stirred for 30 minutes. After that, extraction was performed twice using 60 mL of ethyl acetate, and the obtained organic phase was concentrated by vacuum distillation. To the obtained concentrate, 20 mL of ethyl acetate was added, followed by the addition of 100 mL of hexane to crystallize, and the product was recovered by filtration. After rinsing with hexane, 6.2 g of a white solid was obtained by vacuum drying, yielding composition X1 containing the polymer.

[0456] The weight-average molecular weight (Mw) of the polymer contained in composition X1 was 10962, and the degree of dispersion (Mw / Mn) was 1.85. Furthermore, １３ Analysis of the 13C-NMR measurement results revealed that, when the structural units derived from monomer compound A1 in the polymer are denoted as a, the structural units derived from EAMA as b, the structural units derived from GMA as c, and the structural units derived from PHS-Ac (units obtained by decomposing the -OAc portion into -OH after addition polymerization) as d, the molar ratio of each unit was a:b:c:d = 30:30:10:30.

[0457] [Example X2: Composition X2 containing a polymer]

[0458]

[0459] A composition X2 containing the polymer was obtained in the same manner as in Example X1, except that an equimolar amount of monomer compound A2 obtained in Example A2 was used instead of monomer compound A1 obtained in Example A1. The weight-average molecular weight (Mw) of the polymer contained in composition X2 was 11956, and the degree of dispersion (Mw / Mn) was 1.84. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X1.

[0460] [Example X3: Composition X3 containing polymer]

[0461]

[0462] A composition X3 containing the polymer was obtained in the same manner as in Example X1, except that an equimolar amount of monomer compound A3 obtained in Example A3 was used instead of monomer compound A1 obtained in Example A1. The weight-average molecular weight (Mw) of the polymer contained in composition X3 was 10155, and the degree of dispersion (Mw / Mn) was 1.77. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X1.

[0463] [Example X4: Composition X4 containing a polymer]

[0464]

[0465] A composition X4 containing the polymer was obtained in the same manner as in Example X1, except that an equimolar amount of monomer compound A4 obtained in Example A4 was used instead of monomer compound A1 obtained in Example A1. The weight-average molecular weight (Mw) of the polymer contained in composition X4 was 11749, and the degree of dispersion (Mw / Mn) was 1.78. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X1.

[0466] [Example X5: Composition X5 containing a polymer]

[0467]

[0468] A composition X5 containing the polymer was obtained in the same manner as in Example X1, except that an equimolar amount of monomer compound A5 obtained in Example A5 was used instead of monomer compound A1 obtained in Example A1. The weight-average molecular weight (Mw) of the polymer contained in composition X5 was 11768, and the degree of dispersion (Mw / Mn) was 1.80. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X1.

[0469] [Example X6: Composition X6 containing a polymer]

[0470]

[0471] A composition X6 containing the polymer was obtained in the same manner as in Example X1, except that an equimolar amount of monomer compound A6 obtained in Example A6 was used instead of monomer compound A1 obtained in Example A1. The weight-average molecular weight (Mw) of the polymer contained in composition X6 was 10613, and the degree of dispersion (Mw / Mn) was 1.78. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X1.

[0472] [Example X7: Composition X7 containing polymer] 50 g of monomer compound A1 obtained in Example A1 was dissolved in 500 g of ethyl acetate. Then, 0.05 g (1000 ppm) of additive compound B2 obtained in Synthesis Example B2 was added, and the mixture was stirred for 30 minutes. After that, the solvent component (ethyl acetate) was removed by vacuum concentration and vacuum drying to prepare the raw material composition.

[0473] A composition X7 containing the polymer was obtained in the same manner as in Example X1, except that instead of using monomer compound A1 obtained in Example A1 as is, the above raw material composition containing equimolar amounts of monomer compound A1 and further containing additive compound B2 was used. The weight-average molecular weight (Mw) of the polymer contained in composition X7 was 11914, and the degree of dispersion (Mw / Mn) was 1.90. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X1.

[0474] [Example X8: Composition X8 containing polymer] Composition X8 containing polymer was obtained in the same manner as in Example X7, except that an equal mass of additive compound B5 obtained in Synthesis Example B5 was used instead of additive compound B2 obtained in Synthesis Example B2. The weight-average molecular weight (Mw) of the polymer contained in composition X8 was 11350, and the degree of dispersion (Mw / Mn) was 1.91. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0475] [Example X9: Composition X9 containing polymer] Composition X9 containing polymer was obtained in the same manner as in Example X7, except that an equal mass of additive compound C1 obtained in Synthesis Example C1 was used instead of additive compound B2 obtained in Synthesis Example B2. The weight-average molecular weight (Mw) of the polymer contained in composition X9 was 10297, and the degree of dispersion (Mw / Mn) was 1.89. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0476] [Example X10: Composition X10 containing polymer] Composition X10 containing polymer was obtained in the same manner as in Example X7, except that instead of monomer compound A1 obtained in Example A1, an equimolar amount of monomer compound A2 obtained in Example A2 was used, and instead of additive compound B2 obtained in Synthesis Example B2, an equimass of additive compound B1 obtained in Synthesis Example B1 was used. The weight-average molecular weight (Mw) of the polymer contained in composition X10 was 11145, and the degree of dispersion (Mw / Mn) was 1.83. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0477] [Example X11: Composition X11 containing polymer] Composition X11 containing polymer was obtained in the same manner as in Example X7, except that an equimolar amount of monomer compound A2 obtained in Example A2 was used instead of monomer compound A1 obtained in Example A1, and an equimass of additive compound B3 obtained in Synthesis Example B3 was used instead of additive compound B2 obtained in Synthesis Example B2. The weight-average molecular weight (Mw) of the polymer contained in composition X11 was 11848, and the degree of dispersion (Mw / Mn) was 1.88. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0478] [Example X12: Composition X12 containing polymer] Composition X12 containing polymer was obtained in the same manner as in Example X7, except that an equimolar amount of monomer compound A2 obtained in Example A2 was used instead of monomer compound A1 obtained in Example A1, and an equimass of additive compound C1 obtained in Synthesis Example C1 was used instead of additive compound B2 obtained in Synthesis Example B2. The weight-average molecular weight (Mw) of the polymer contained in composition X12 was 11292, and the degree of dispersion (Mw / Mn) was 1.79. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0479] [Example X13: Composition X13 containing polymer] Composition X13 containing polymer was obtained in the same manner as in Example X7, except that an equimolar amount of monomer compound A3 obtained in Example A3 was used instead of monomer compound A1 obtained in Example A1, and an equimass of additive compound C1 obtained in Synthesis Example C1 was used instead of additive compound B2 obtained in Synthesis Example B2. The weight-average molecular weight (Mw) of the polymer contained in composition X13 was 11225, and the degree of dispersion (Mw / Mn) was 1.77. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0480] [Example X14: Composition X14 containing polymer] Composition X14 containing polymer was obtained in the same manner as in Example X7, except that an equimolar amount of monomer compound A4 obtained in Example A4 was used instead of monomer compound A1 obtained in Example A1. The weight-average molecular weight (Mw) of the polymer contained in composition X14 was 10968, and the degree of dispersion (Mw / Mn) was 1.92. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0481] [Example X15: Composition X15 containing polymer] Composition X15 containing polymer was obtained in the same manner as in Example X7, except that instead of monomer compound A1 obtained in Example A1, an equimolar amount of monomer compound A4 obtained in Example A4 was used, and instead of additive compound B2 obtained in Synthesis Example B2, an equimass amount of additive compound B6 obtained in Synthesis Example B6 was used. The weight-average molecular weight (Mw) of the polymer contained in composition X15 was 10151, and the degree of dispersion (Mw / Mn) was 1.95. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0482] [Example X16: Composition X16 containing polymer] Composition X16 containing polymer was obtained in the same manner as in Example X7, except that instead of monomer compound A1 obtained in Example A1, an equimolar amount of monomer compound A5 obtained in Example A5 was used, and instead of additive compound B2 obtained in Synthesis Example B2, an equimass of additive compound B1 obtained in Synthesis Example B1 was used. The weight-average molecular weight (Mw) of the polymer contained in composition X16 was 11000, and the degree of dispersion (Mw / Mn) was 1.77. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0483] [Example X17: Composition X17 containing polymer] Composition X17 containing polymer was obtained in the same manner as in Example X7, except that instead of monomer compound A1 obtained in Example A1, an equimolar amount of monomer compound A5 obtained in Example A5 was used, and instead of additive compound B2 obtained in Synthesis Example B2, an equimass amount of additive compound B4 obtained in Synthesis Example B4 was used. The weight-average molecular weight (Mw) of the polymer contained in composition X17 was 10898, and the degree of dispersion (Mw / Mn) was 1.94. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0484] [Example X18: Composition X18 containing polymer] Composition X18 containing polymer was obtained in the same manner as in Example X7, except that instead of monomer compound A1 obtained in Example A1, an equimolar amount of monomer compound A6 obtained in Example A6 was used, and instead of additive compound B2 obtained in Synthesis Example B2, an equimass amount of additive compound C1 obtained in Synthesis Example C1 was used. The weight-average molecular weight (Mw) of the polymer contained in composition X18 was 10671, and the degree of dispersion (Mw / Mn) was 1.89. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0485] [Example XA1: Composition XA1 containing polymer]

[0486]

[0487] Composition XA1 containing the polymer was obtained in the same manner as in Example X1, except that an equimolar amount of monomer compound AA1 obtained in Example AA1 was used instead of monomer compound A1 obtained in Example A1. The weight-average molecular weight (Mw) of the polymer contained in composition XA1 was 10255, and the degree of dispersion (Mw / Mn) was 1.90. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X1.

[0488] [Example XA2: Composition XA2 containing polymer]

[0489]

[0490] Composition XA2 containing the polymer was obtained in the same manner as in Example X1, except that an equimolar amount of monomer compound AA2 obtained in Example AA2 was used instead of monomer compound A1 obtained in Example A1. The weight-average molecular weight (Mw) of the polymer contained in composition XA2 was 10691, and the degree of dispersion (Mw / Mn) was 1.87. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X1.

[0491] [Example XA3: Composition XA3 containing polymer]

[0492]

[0493] Composition XA3 containing the polymer was obtained in the same manner as in Example X1, except that an equimolar amount of monomer compound AA3 obtained in Example AA3 was used instead of monomer compound A1 obtained in Example A1. The weight-average molecular weight (Mw) of the polymer contained in composition XA3 was 10474, and the degree of dispersion (Mw / Mn) was 1.89. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X1.

[0494] [Example XA4: Composition XA4 containing polymer]

[0495]

[0496] Composition XA4 containing the polymer was obtained in the same manner as in Example X1, except that an equimolar amount of monomer compound AA4 obtained in Example AA4 was used instead of monomer compound A1 obtained in Example A1. The weight-average molecular weight (Mw) of the polymer contained in composition XA4 was 10210, and the degree of dispersion (Mw / Mn) was 1.93. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X1.

[0497] [Example XA5: Composition XA5 containing polymer]

[0498]

[0499] Composition XA5 containing the polymer was obtained in the same manner as in Example X1, except that an equimolar amount of monomer compound AA5 obtained in Example AA5 was used instead of monomer compound A1 obtained in Example A1. The weight-average molecular weight (Mw) of the polymer contained in composition XA5 was 10820, and the degree of dispersion (Mw / Mn) was 1.85. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X1.

[0500] [Example XA6: Composition XA6 containing the polymer]

[0501]

[0502] Composition XA6 containing the polymer was obtained in the same manner as in Example X1, except that an equimolar amount of monomer compound AA6 obtained in Example AA6 was used instead of monomer compound A1 obtained in Example A1. The weight-average molecular weight (Mw) of the polymer contained in composition XA6 was 10737, and the degree of dispersion (Mw / Mn) was 1.88. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X1.

[0503] [Example XA7: Composition XA7 containing the polymer]

[0504]

[0505] Composition XA7 containing the polymer was obtained in the same manner as in Example X1, except that an equimolar amount of monomer compound AA7 obtained in Example AA7 was used instead of monomer compound A1 obtained in Example A1. The weight-average molecular weight (Mw) of the polymer contained in composition XA7 was 10903, and the degree of dispersion (Mw / Mn) was 1.87. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X1.

[0506] [Example XA8: Composition XA8 containing polymer]

[0507]

[0508] Composition XA8 containing the polymer was obtained in the same manner as in Example X1, except that an equimolar amount of monomer compound AA8 obtained in Example AA8 was used instead of monomer compound A1 obtained in Example A1. The weight-average molecular weight (Mw) of the polymer contained in composition XA8 was 10348, and the degree of dispersion (Mw / Mn) was 1.82. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X1.

[0509] [Example XA9: Composition XA9 containing polymer]

[0510]

[0511] Composition XA9 containing the polymer was obtained in the same manner as in Example X1, except that an equimolar amount of monomer compound AA9 obtained in Example AA9 was used instead of monomer compound A1 obtained in Example A1. The weight-average molecular weight (Mw) of the polymer contained in composition XA9 was 11048, and the degree of dispersion (Mw / Mn) was 1.89. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X1.

[0512] [Example XA10: Composition XA10 containing polymer]

[0513]

[0514] Composition XA10 containing the polymer was obtained in the same manner as in Example X1, except that an equimolar amount of monomer compound AA10 obtained in Example AA10 was used instead of monomer compound A1 obtained in Example A1. The weight-average molecular weight (Mw) of the polymer contained in composition XA10 was 10932, and the degree of dispersion (Mw / Mn) was 1.81. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X1.

[0515] [Example XA11: Composition XA11 containing polymer]

[0516]

[0517] Composition XA11 containing the polymer was obtained in the same manner as in Example X1, except that an equimolar amount of monomer compound AA11 obtained in Example AA11 was used instead of monomer compound A1 obtained in Example A1. The weight-average molecular weight (Mw) of the polymer contained in composition XA11 was 11339, and the degree of dispersion (Mw / Mn) was 1.88. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X1.

[0518] [Example XA12: Composition XA12 containing polymer]

[0519]

[0520] Composition XA12 containing the polymer was obtained in the same manner as in Example X1, except that an equimolar amount of monomer compound AA12 obtained in Example AA12 was used instead of monomer compound A1 obtained in Example A1. The weight-average molecular weight (Mw) of the polymer contained in composition XA12 was 10519, and the degree of dispersion (Mw / Mn) was 1.92. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X1.

[0521] [Example XA13: Composition XA13 containing polymer] Composition XA13 containing polymer was obtained in the same manner as in Example X7, except that instead of monomer compound A1 obtained in Example A1, an equimolar amount of monomer compound AA1 obtained in Example AA1 was used, and instead of additive compound B2 obtained in Synthesis Example B2, an equimass amount of additive compound BA1 obtained in Synthesis Example BA1 was used. The weight-average molecular weight (Mw) of the polymer contained in composition XA13 was 10280, and the degree of dispersion (Mw / Mn) was 1.80. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0522] [Example XA13-2: Composition XA13-2 containing polymer] Composition XA13-2 containing polymer was obtained in the same manner as in Example X7, except that instead of monomer compound A1 obtained in Example A1, an equimolar amount of monomer compound AA1 obtained in Example AA1 was used, and instead of additive compound B2 obtained in Synthesis Example B2, an equimass amount of additive compound BA2 obtained in Synthesis Example BA2 was used. The weight-average molecular weight (Mw) of the polymer contained in composition XA13-2 was 11542, and the degree of dispersion (Mw / Mn) was 1.79. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0523] [Example XA13-3: Composition XA13-3 containing polymer] Composition XA13-3 containing polymer was obtained in the same manner as in Example X7, except that instead of monomer compound A1 obtained in Example A1, an equimolar amount of monomer compound AA1 obtained in Example AA1 was used, and instead of additive compound B2 obtained in Synthesis Example B2, an equimass amount of additive compound C1 obtained in Synthesis Example C1 was used. The weight-average molecular weight (Mw) of the polymer contained in composition XA13-3 was 10057, and the degree of dispersion (Mw / Mn) was 1.83. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0524] [Example XA14: Composition XA14 containing polymer] Composition XA14 containing polymer was obtained in the same manner as in Example X7, except that instead of monomer compound A1 obtained in Example A1, an equimolar amount of monomer compound AA2 obtained in Example AA2 was used, and instead of additive compound B2 obtained in Synthesis Example B2, an equimass amount of additive compound BA1 obtained in Synthesis Example BA1 was used. The weight-average molecular weight (Mw) of the polymer contained in composition XA14 was 11300, and the degree of dispersion (Mw / Mn) was 1.75. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0525] [Example XA14-2: Composition XA14-2 containing polymer] Composition XA14-2 containing polymer was obtained in the same manner as in Example X7, except that instead of monomer compound A1 obtained in Example A1, an equimolar amount of monomer compound AA2 obtained in Example AA2 was used, and instead of additive compound B2 obtained in Synthesis Example B2, an equimass amount of additive compound BA3 obtained in Synthesis Example BA3 was used. The weight-average molecular weight (Mw) of the polymer contained in composition XA14-2 was 10525, and the degree of dispersion (Mw / Mn) was 1.87. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0526] [Example XA14-3: Composition XA14-3 containing polymer] Composition XA14-3 containing polymer was obtained in the same manner as in Example X7, except that instead of monomer compound A1 obtained in Example A1, an equimolar amount of monomer compound AA2 obtained in Example AA2 was used, and instead of additive compound B2 obtained in Synthesis Example B2, an equimass of additive compound CA1 obtained in Synthesis Example CA1 was used. The weight-average molecular weight (Mw) of the polymer contained in composition XA14-3 was 10802, and the degree of dispersion (Mw / Mn) was 1.91. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0527] [Example XA15: Composition XA15 containing polymer] Composition XA15 containing polymer was obtained in the same manner as in Example X7, except that instead of monomer compound A1 obtained in Example A1, an equimolar amount of monomer compound AA3 obtained in Example AA3 was used, and instead of additive compound B2 obtained in Synthesis Example B2, an equimass amount of additive compound C1 obtained in Synthesis Example C1 was used. The weight-average molecular weight (Mw) of the polymer contained in composition XA15 was 10581, and the degree of dispersion (Mw / Mn) was 1.93. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0528] [Example XA16: Composition XA16 containing polymer] Composition XA16 containing polymer was obtained in the same manner as in Example X7, except that instead of monomer compound A1 obtained in Example A1, an equimolar amount of monomer compound AA4 obtained in Example AA4 was used, and instead of additive compound B2 obtained in Synthesis Example B2, an equimass amount of additive compound CA1 obtained in Synthesis Example CA1 was used. The weight-average molecular weight (Mw) of the polymer contained in composition XA16 was 11072, and the degree of dispersion (Mw / Mn) was 1.85. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0529] [Example XA17: Composition XA17 containing polymer] Composition XA17 containing polymer was obtained in the same manner as in Example X7, except that instead of monomer compound A1 obtained in Example A1, an equimolar amount of monomer compound AA5 obtained in Example AA5 was used, and instead of additive compound B2 obtained in Synthesis Example B2, an equimass amount of additive compound C1 obtained in Synthesis Example C1 was used. The weight-average molecular weight (Mw) of the polymer contained in composition XA17 was 10101, and the degree of dispersion (Mw / Mn) was 1.94. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0530] [Example XA18: Composition XA18 containing polymer] Composition XA18 containing polymer was obtained in the same manner as in Example X7, except that instead of monomer compound A1 obtained in Example A1, an equimolar amount of monomer compound AA6 obtained in Example AA6 was used, and instead of additive compound B2 obtained in Synthesis Example B2, an equimass of additive compound CA1 obtained in Synthesis Example CA1 was used. The weight-average molecular weight (Mw) of the polymer contained in composition XA18 was 10034, and the degree of dispersion (Mw / Mn) was 1.94. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0531] [Example XA19: Composition XA19 containing polymer] Composition XA19 containing polymer was obtained in the same manner as in Example X7, except that an equimolar amount of monomer compound AA7 obtained in Example AA7 was used instead of monomer compound A1 obtained in Example A1. The weight-average molecular weight (Mw) of the polymer contained in composition XA19 was 11039, and the degree of dispersion (Mw / Mn) was 1.78. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0532] [Example XA19-2: Composition XA19-2 containing polymer] Composition XA19-2 containing polymer was obtained in the same manner as in Example X7, except that instead of monomer compound A1 obtained in Example A1, an equimolar amount of monomer compound AA7 obtained in Example AA7 was used, and instead of additive compound B2 obtained in Synthesis Example B2, an equimass amount of additive compound BA4 obtained in Synthesis Example BA4 was used. The weight-average molecular weight (Mw) of the polymer contained in composition XA19-2 was 11259, and the degree of dispersion (Mw / Mn) was 1.82. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0533] [Example XA19-3: Composition XA19-3 containing polymer] Composition XA19-3 containing polymer was obtained in the same manner as in Example X7, except that instead of monomer compound A1 obtained in Example A1, an equimolar amount of monomer compound AA7 obtained in Example AA7 was used, and instead of additive compound B2 obtained in Synthesis Example B2, an equimass amount of additive compound CA2 obtained in Synthesis Example CA2 was used. The weight-average molecular weight (Mw) of the polymer contained in composition XA19-3 was 11922, and the degree of dispersion (Mw / Mn) was 1.81. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0534] [Example XA20: Composition XA20 containing polymer] Composition XA20 containing polymer was obtained in the same manner as in Example X7, except that instead of monomer compound A1 obtained in Example A1, an equimolar amount of monomer compound AA8 obtained in Example AA8 was used, and instead of additive compound B2 obtained in Synthesis Example B2, an equimass amount of additive compound B1 obtained in Synthesis Example B1 was used. The weight-average molecular weight (Mw) of the polymer contained in composition XA20 was 11004, and the degree of dispersion (Mw / Mn) was 1.80. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0535] [Example XA20-2: Composition XA20-2 containing polymer] Composition XA20-2 containing polymer was obtained in the same manner as in Example X7, except that instead of monomer compound A1 obtained in Example A1, an equimolar amount of monomer compound AA8 obtained in Example AA8 was used, and instead of additive compound B2 obtained in Synthesis Example B2, an equimass amount of additive compound BA5 obtained in Synthesis Example BA5 was used. The weight-average molecular weight (Mw) of the polymer contained in composition XA20-2 was 11962, and the degree of dispersion (Mw / Mn) was 1.86. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0536] [Example XA20-3: Composition XA20-3 containing polymer] Composition XA20-3 containing polymer was obtained in the same manner as in Example X7, except that instead of monomer compound A1 obtained in Example A1, an equimolar amount of monomer compound AA8 obtained in Example AA8 was used, and instead of additive compound B2 obtained in Synthesis Example B2, an equimass amount of additive compound CA2 obtained in Synthesis Example CA2 was used. The weight-average molecular weight (Mw) of the polymer contained in composition XA20-3 was 11625, and the degree of dispersion (Mw / Mn) was 1.78. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0537] [Example XA21: Composition XA21 containing polymer] Composition XA21 containing polymer was obtained in the same manner as in Example X7, except that instead of monomer compound A1 obtained in Example A1, an equimolar amount of monomer compound AA9 obtained in Example AA9 was used, and instead of additive compound B2 obtained in Synthesis Example B2, an equimass amount of additive compound CA2 obtained in Synthesis Example CA2 was used. The weight-average molecular weight (Mw) of the polymer contained in composition XA21 was 10523, and the degree of dispersion (Mw / Mn) was 1.82. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0538] [Example XA22: Composition XA22 containing polymer] Composition XA22 containing polymer was obtained in the same manner as in Example X7, except that instead of monomer compound A1 obtained in Example A1, an equimolar amount of monomer compound AA10 obtained in Example AA10 was used, and instead of additive compound B2 obtained in Synthesis Example B2, an equimass of additive compound BA1 obtained in Synthesis Example BA1 was used. The weight-average molecular weight (Mw) of the polymer contained in composition XA22 was 10012, and the degree of dispersion (Mw / Mn) was 1.77. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0539] [Example XA22-2: Composition XA22-2 containing polymer] Composition XA22-2 containing polymer was obtained in the same manner as in Example X7, except that instead of monomer compound A1 obtained in Example A1, an equimolar amount of monomer compound AA10 obtained in Example AA10 was used, and instead of additive compound B2 obtained in Synthesis Example B2, an equimass amount of additive compound BA6 obtained in Synthesis Example BA6 was used. The weight-average molecular weight (Mw) of the polymer contained in composition XA22-2 was 10316, and the degree of dispersion (Mw / Mn) was 1.91. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0540] [Example XA22-3: Composition XA22-3 containing polymer] Composition XA22-3 containing polymer was obtained in the same manner as in Example X7, except that instead of monomer compound A1 obtained in Example A1, an equimolar amount of monomer compound AA10 obtained in Example AA10 was used, and instead of additive compound B2 obtained in Synthesis Example B2, an equimass amount of additive compound CA2 obtained in Synthesis Example CA2 was used. The weight-average molecular weight (Mw) of the polymer contained in composition XA22-3 was 10052, and the degree of dispersion (Mw / Mn) was 1.88. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0541] [Example XA23: Composition XA23 containing polymer] Composition XA23 containing polymer was obtained in the same manner as in Example X7, except that instead of monomer compound A1 obtained in Example A1, an equimolar amount of monomer compound AA11 obtained in Example AA11 was used, and instead of additive compound B2 obtained in Synthesis Example B2, an equimass amount of additive compound CA2 obtained in Synthesis Example CA2 was used. The weight-average molecular weight (Mw) of the polymer contained in composition XA23 was 10226, and the degree of dispersion (Mw / Mn) was 1.79. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0542] [Example XA24: Composition XA24 containing polymer] Composition XA24 containing polymer was obtained in the same manner as in Example X7, except that instead of monomer compound A1 obtained in Example A1, an equimolar amount of monomer compound AA12 obtained in Example AA12 was used, and instead of additive compound B2 obtained in Synthesis Example B2, an equimass amount of additive compound CA2 obtained in Synthesis Example CA2 was used. The weight-average molecular weight (Mw) of the polymer contained in composition XA24 was 11137, and the degree of dispersion (Mw / Mn) was 1.86. １３ Analysis of the C-NMR measurement results showed that the molar ratios of each unit were the same as in Example X7.

[0543] [Comparative Example X1: Composition X1' containing a polymer]

[0544]

[0545] A composition X1' containing the polymer was obtained in the same manner as in Example X1, except that equimolar amounts of EAMA were used instead of monomer compound A1 obtained in Example A1. The weight-average molecular weight (Mw) of the polymer contained in composition X1' was 12300, and the degree of dispersion (Mw / Mn) was 2.10. １３ Analysis of the 1C-NMR measurement results revealed that when the structural units derived from EAMA are denoted as b, the structural units derived from GMA as c, and the structural units derived from PHS-Ac (units in which the -OAc portion decomposes into -OH after addition polymerization) as d, the molar ratio of each unit was b:c:d = 60:10:30.

[0546] [Test Example 1: Evaluation of EB drawing (EB sensitivity, resolution, and roughness)] A resist layer forming composition was prepared by combining 5 parts by mass of the composition obtained in the Examples and Comparative Examples, 1 part by mass of triphenylsulfonium nonafluoromethanesulfonate (acid generator), 0.1 parts by mass of tributylamine, and 94 parts by mass of propylene glycol monomethyl ether acetate (PGMEA). Furthermore, the prepared resist layer forming composition was filtered in a cleanroom using a filter line connected to a PTFE filter with a pore size of 15 nm (manufactured by Integris Co., Ltd.) to obtain a filtered resist layer forming composition.

[0547] The obtained resist layer-forming composition was coated onto a silicon wafer and baked at 110-130°C for 60 seconds to form a photoresist layer with a thickness of 100 nm. Next, it was exposed using an electron beam lithography system (ELS-7500, 100 keV, manufactured by Elionix Corporation), baked at 105°C for 60 seconds (PEB), and paddle developed for 60 seconds using a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution. After that, it was rinsed with pure water and rotated at 1500 rpm for 30 seconds to obtain a positive pattern. The obtained pattern was observed using a scanning electron microscope (S4800, manufactured by Hitachi, Ltd.) and its sensitivity, resolution, and roughness were evaluated. The results are shown in the table below.

[0548] Here, the "sensitivity" evaluation refers to the lower limit of exposure (mJ / cm²) required to form a pattern with a line width of 40 nm and a half-pitch of 40 nm. ２ The following was determined as the EB sensitivity:

[0549] Furthermore, for the "resolution" evaluation, a pattern layout condition PL was used in which patterns with an L (line) / S (space) ratio of 1 / 1 were reduced in increments of 1 nm from a half-pitch of 60 nm, and the exposure dose was 60 mL / cm². ２ From 1 mJ / cm ２ Using exposure conditions D, which were progressively reduced, the pattern formation properties were evaluated using a matrix of conditions PL and D, and the line width that provided the minimum resolution was determined.

[0550] Furthermore, for the "roughness" evaluation, the roughness value was calculated by taking 30 line width values ​​at 1 nm intervals per line for any 10 line patterns obtained, and multiplying the standard deviation of these line width values ​​by 3.

[0551] [Test Example 2: Evaluation of EUV Sensitivity] The sensitivity to EUV light sources for each resist layer formation composition prepared as described above was evaluated by the following method. First, each prepared resist layer formation composition was coated onto a separate silicon wafer using a spin coater, and then heated on a hot plate at 105°C for 60 seconds to form a photoresist layer with a thickness of 100 nm.

[0552] Next, using the extreme ultraviolet (EUV) exposure system "EUVES-7000" (product name, manufactured by Lithotech Japan Co., Ltd.), the exposure was measured at 1 mJ / cm². ２ From 1 mJ / cm ２ 80 mJ / cm ２ After performing maskless shot exposure across the entire wafer, increasing the exposure amount up to a certain point, the wafer was baked (PEB) at 105°C for 60 seconds, and then paddle developed with a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds to obtain a wafer with 80 shot exposures. For each shot exposure area obtained, the film thickness was measured using an optical interferometer "VM3200" (product name, manufactured by SCREEN Semiconductor Solutions Co., Ltd.), and profile data of film thickness against exposure amount was obtained. The exposure amount at which the slope of film thickness variation with respect to exposure amount was largest was set to the sensitivity value (mJ / cm²). ２ The result was calculated as follows and used as an indicator of the EUV sensitivity of the resist. The results are shown in the table below.

[0553] [Test Example 3: Evaluation of Solid Film Exposure Defects] The composition used in the EUV exposure sensitivity measurement was applied to a 12-inch silicon wafer with a 100 nm thick oxide film formed on the outermost layer, and baked at 105°C for 60 seconds to form a 100 nm thick photoresist layer. Then, using an extreme ultraviolet (EUV) exposure apparatus "EUVES-7000" (product name, manufactured by Lithotech Japan Co., Ltd.), the entire wafer was shot exposed with the same exposure dose as the EUV sensitivity value obtained in the EUV sensitivity evaluation described above, and then baked at 105°C for 90 seconds (PEB), followed by paddle development with a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds to obtain an exposed wafer with 80 shots of exposure across the entire wafer.

[0554] The fabricated exposed wafer is then subjected to CH etching using the "Telius SCCM" etching system (product name, manufactured by Tokyo Electron Limited). ４ / CF ４ Etching was performed using Ar gas until the oxide film thickness reached 40 nm. The wafers fabricated by etching were evaluated for defects using the "Surfscan SP3" defect inspection system (manufactured by KLA), and the number of cone defects larger than 25 nm was determined as an indicator of etching defects according to the evaluation criteria below. The results are shown in the table below.

[0555] (Evaluation Criteria) S: Number of cone defects ≤ 5 A: 5 < Number of cone defects ≤ 20 B: 20 ​​< Number of cone defects ≤ 60 C: 60 < Number of cone defects ≤ 400 D: 400 < Number of cone defects

[0556] The raw materials used in the examples and comparative examples, the physical properties of the polymers contained in the obtained compositions, and the evaluation results of the test examples are summarized in the table below. In the table below, "〇" indicates that the raw material was used.

[0557]

[0558]

[0559]

[0560]

[0561] As shown in the table above, it can be confirmed that using the compound represented by formula (I) can further improve sensitivity to the exposure light source. Furthermore, it can be confirmed that it can further improve resolution, reduce roughness, and suppress exposure defects. Moreover, it can be confirmed that using the compound represented by formula (II) or formula (III) can further suppress exposure defects.

[0562] This application claims priority to Japanese Patent Application No. 2025-066276, filed on 14 April 2025, the entire contents of said application being deemed to be part of the disclosure of this application and incorporated herein by reference.

Claims

1. Formula (I): [In the formula, Ring A represents an aromatic ring; each Ring B independently represents an aromatic ring, a non-aromatic ring, or a fused ring thereof; X １ and X ２ each independently represent a single bond or a divalent organic group; R １ , R ２ and R ３ each independently represent a hydrogen atom, a methyl group, or a halogen atom; R ４ and R ５ each independently represent a substituent; R ６ and R ７ each independently represent an optionally substituted alkyl group; a, b, c and e each independently represent an integer of 1 or more; d and f each independently represent 0 or an integer of 1 or more. A compound represented by the formula.] 2. The compound according to claim 1, wherein a is 1.

3. Equation (1) or (2): [In the formula, ring A' represents a 6-14 member aromatic carbon ring; ring B' independently represents a 6-14 member aromatic carbon ring, a 3-14 member non-aromatic carbon ring, or a fused ring thereof; R １１ R represents a hydrogen atom or a methyl group; ４ and R ５ Each of these independently represents a substituent; R ６ and R ７ Each independently represents an alkyl group which may have substituents; R ｘ , R ｙ and R ｚ The compound according to claim 2, represented by: b, c, and e each independently represent a hydrogen atom or an alkyl group; d and f each independently represent 0 or an integer of 1 or more; g each independently represent 1, 2, 3, 4, or 5.

4. Formulas (1a) to (2r): [In the formula, R １１ R represents a hydrogen atom or a methyl group; ｘ and R ｙ Each of these independently represents either a hydrogen atom or an alkyl group; R ａ , R ｂ , R ｃ , R ｄ and R ｅ Each of these independently represents a hydrogen atom or a substituent (excluding an iodine atom), and R ａ , R ｂ , R ｃ , R ｄ and R ｅ At least one of the terms displayed in each equation is equation (X): (In the formula, ring B'' represents a 6- to 14-membered aromatic carbon ring or a 3- to 14-membered non-aromatic carbon ring; R ５ Each of these independently represents a substituent; R ６ and R ７ The compound according to claim 3, which is represented by any of the following: each independently represents an alkyl group which may have substituents; e represents an integer of 1 or more; f represents 0 or an integer of 1 or more; g represents 1, 2, 3, 4 or 5; * represents a bonding site.

5. A composition for manufacturing a resist material, comprising the compound described in any one of claims 1 to 4.

6. (α) A compound according to any one of claims 1 to 4, and (β) Formula (II): [In the formula, Ring A ａ Each of these independently represents an aromatic ring; X ａ１ Each independently represents a single bond or a divalent organic group; R ａ１ and R ａ２ Each of these independently represents a hydrogen atom, a methyl group, or a halogen atom; R ａ４ Each of these independently represents a substituent; n ａ b indicates 1, 2, 3, 4, 5, 6, or 7; b ａ Each of these independently represents an integer greater than or equal to 1; d ａ A composition containing a compound represented by ], where represents 0 or an integer of 1 or more.

7. In formula (II), d ａ However, it is an integer greater than or equal to 1, R ａ４ However, each is independently a substituent and -(R ａ４ ) ｄ ａ Each d ａ Individual R ａ４ At least one of them is a hydroxyl group, or formula (XA''): [In the formula, ring B ａ X represents an aromatic ring, a non-aromatic ring, or a fused ring thereof; ａ２ R represents a single bond or a divalent organic group; ａ５ Each of these independently represents a substituent; R ａ６ and R ａ７ Each independently represents an alkyl group which may have substituents; e ａ f represents an integer greater than or equal to 1; ａ The composition according to claim 6, wherein represents 0 or an integer of 1 or more; * represents a bonding site.

8. The composition according to claim 6, wherein the content of the compound represented by formula (II) is 0.0001% by mass to 10% by mass, relative to 100% by mass of the total of the compounds described in any one of claims 1 to 4 and the compound represented by formula (II).

9. (α) A compound according to any one of claims 1 to 4, and (γ) Formula (III): [In the formula, ring B ｂ Each of these independently represents an aromatic ring; X ｂ Each of these independently exhibits an acid-dissociable linking group; R ｂ５ Each of these independently represents a substituent that does not have an intercarbon double bond; n ｂ e represents an integer greater than or equal to 1; ｂ Each of these independently represents an integer greater than or equal to 1; f ｂ A composition containing a compound represented by ], where represents 0 or an integer of 1 or more.

10. In formula (III), X ｂ However, each is independent of equation (XB-1) or (XB-2): [In the formula, R ｂ６ and R ｂ７ Each independently represents an alkyl group which may have substituents; R ｂｚ Each independently represents either a hydrogen atom or an alkyl group; g ｂ The composition according to claim 9, wherein each of the following independently represents 1, 2, 3, 4, or 5; * indicates a binding site.

11. The composition according to claim 9, wherein the content of the compound represented by formula (III) is 0.0001% by mass to 10% by mass, relative to 100% by mass of the total of the compounds described in any one of claims 1 to 4 and the compound represented by formula (III).

12. (α) A compound according to any one of claims 1 to 4, and (δ) A composition comprising at least one compound selected from (meth)acrylic acid ester compounds having an adamantane skeleton, (meth)acrylic acid ester compounds having a lactone skeleton, and compounds having a hydroxystyrene skeleton.

13. A composition according to any one of claims 6 to 12, for use in a polymerization reaction for producing a polymer.

14. Formula (UI): [In the formula, ring A represents an aromatic ring; ring B independently represents an aromatic ring, a non-aromatic ring, or a fused ring thereof; X １ and X ２ Each independently represents a single bond or an organic group; R １ , R ２ and R ３ Each of these independently represents a hydrogen atom, a methyl group, or a halogen atom; R ４ and R ５ Each of these independently represents a substituent; R ６ and R ７ A polymer having repeating units represented by ], where each independently represents an alkyl group which may have substituents; a, b, c, and e each independently represent an integer of 1 or more; and d and f each independently represent 0 or an integer of 1 or more.

15. The polymer according to claim 14, wherein a is 1.

16. The polymer according to claim 14, further comprising repeating units derived from at least one compound selected from a (meth)acrylic acid ester compound having an adamantane skeleton, a (meth)acrylic acid ester compound having a lactone skeleton, and a compound having a hydroxystyrene skeleton.

17. The polymer according to claim 14, wherein the weight-average molecular weight (Mw) is 5,000 to 30,000.

18. A resist composition comprising the polymer according to any one of claims 14 to 17.

19. A composition comprising the polymer according to any one of claims 14 to 17 and an acid generator.

20. A method for manufacturing a resist pattern, comprising: (i) forming a resist layer containing a polymer according to any one of claims 14 to 17 on a substrate; (ii) exposing the resist layer formed in step (i) to light; and (iii) developing the resist layer exposed in step (iii).

21. A method for manufacturing an electronic device, comprising: (i) forming a resist layer on a substrate containing a polymer according to any one of claims 14 to 17; (ii) exposing the resist layer formed in step (i) to light; and (iii) developing the resist layer exposed in step (iii).

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