Iodine-containing polymerizable compound and iodine-containing polymer

Abstract

The present invention addresses the problem of providing a compound that enables the efficient production of a resist material that exhibits additional improvements in sensitivity to exposure light sources. The solution provided by the present invention is a compound represented by formula (I). Ring A represents an aromatic ring or a non-aromatic ring; R1 represents a hydrogen atom, methyl group, or halogen atom; R2 and R3 each represent a hydrogen atom or a possibly substituted hydrocarbon group; R4, R5, and R6 each represent a possibly substituted hydrocarbon group; R7 represents a substituent; a and b each represent an integer equal to or greater than 1; c represents 0 or an integer equal to or greater than 1; n represents 0, 1, 2, or 3; and m represents 0 or 1.

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 hydroxyl groups and iodine have been proposed as resist materials (see, for example, Patent Documents 1 and 2).

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

[0007] However, in conventional polymerizable compounds containing hydroxyl groups, the decomposition of acid-unstable structures due to the acidity of the hydroxyl group is accelerated during heating in the polymerization reaction. Furthermore, the hydroxyl group can trigger chain transfer reactions, which can reduce the rate of introduction of corresponding structural units into the resulting polymer. It is also known that in conventional polymerizable compounds containing hydroxyl groups, the hydroxyl group traps radicals, making it difficult to obtain a stable polymer. Methods are also known in which the hydroxyl group is protected with acetal protecting groups such as THP (tetrahydro-2H-pyran-2-yl), EE (1-ethoxyethyl), EM (ethoxymethyl), and MOM (methoxymethyl) groups, or carbonate ester protecting groups such as Boc (tert-butoxycarbonyl) groups before polymerization. However, acetal protecting groups and carbonate ester protecting groups have poor introduction efficiency to hydroxyl groups due to the influence of electron-withdrawing groups such as iodine atoms (and other groups such as formyl, acyl, and cyano groups). Furthermore, for these protecting groups, which are primarily introduced under acidic conditions, the decomposition of acid-unstable structures during protection is accelerated, which also contributes to the decrease in introduction efficiency.

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

[0009] In order to achieve the objectives of the present invention, the inventors conducted diligent studies and found that the above problems could be solved by using a specific iodine-containing polymerizable compound, thus completing the present invention.

[0010] In other words, the present invention is as follows: [1] Formula (I):

[0011]

[0012] [In the formula, ring A represents an aromatic ring or a non-aromatic ring; R １ R represents a hydrogen atom, a methyl group, or a halogen atom; ２ and R ３each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent; R ４ R ５ and R ６ each independently represents a hydrocarbon group which may have a substituent; R ７ each independently represents a substituent; a and b each independently represent an integer of 1 or more; c represents 0 or an integer of 1 or more; n represents 0, 1, 2, or 3; m represents 0 or 1. ] A compound represented by. [2] The compound according to [1] above, wherein ring A is a 6- to 14-membered aromatic carbon ring or a 5- to 14-membered non-aromatic carbon ring. [3] (A) m is 0, or (B) n is 1 and m is 1, the compound according to [1] or [2] above. [4] Formula (1) or (2):

[0013]

[0014] [In the formula, ring A' represents a 6- to 14-membered aromatic carbon ring or a 5- to 14-membered non-aromatic carbon ring; R １１ represents a hydrogen atom or a methyl group; R ２１ and R ３１ each independently represent a hydrogen atom or an alkyl group; R ４ R ５ and R ６ each independently represent a hydrocarbon group which may have a substituent; R ７ each independently represents a substituent; a and b each independently represent an integer of 1 or more; c represents 0 or an integer of 1 or more. ] A compound represented by any one of [1] to [3] above. [5] 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; ２１ and R ３１ Each 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, and R ａ , R ｂ , R ｃ , R ｄ and R ｅ Of these, at least one displayed in each formula is -OSiR ４ R ５ R ６ And; R ４ , R ５ and R ６ Each independently represents a hydrocarbon group which may have substituents. A compound according to any of [1] to [4] above, represented by any of ]. [6] A compound having an iodine atom and a hydroxyl group is subjected to basic conditions, X-SiR ４ R ５ R ６ (In the formula, R ４ , R ５ and R ６ Each independently represents a hydrocarbon group which may have substituents; X represents a halogen atom. ) is reacted with a compound represented by to obtain an iodine atom and -OSiR ４ R ５ R ６A method for producing the compound according to any one of [1] to [5] above, comprising the step of converting it into a compound having a group represented by [1] to [5] above. [7] A composition for producing a lithography film-forming material, comprising the compound according to any one of [1] to [5] above. [8] A composition for producing a resist material, comprising the compound according to any one of [1] to [5] above. [9] A composition comprising the compound according to any one of [1] to [5] above and a radical polymerization initiator.

[10] (1) A composition comprising the compound according to any one of [1] to [5] above, and (2) at least one compound selected from adamantane skeleton-having (meth)acrylic acid ester compounds, lactone skeleton-having (meth)acrylic acid ester compounds, and hydroxystyrene skeleton-having compounds.

[11] A composition comprising the compound according to any one of [1] to [5] above and adamantane skeleton-having (meth)acrylic acid ester compound.

[12] A composition comprising the compound according to any one of [1] to [5] above and a lactone skeleton-having (meth)acrylic acid ester compound.

[13] Formula (UI):

[0022]

[0023] [In the formula, ring A represents an aromatic ring or a non-aromatic ring; R １ R represents a hydrogen atom, a methyl group, or a halogen atom; ２ and R ３ Each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent; R ４ , R ５ and R ６ Each independently represents a hydrocarbon group which may have substituents; R ７A polymer having repeating units represented by: a and b each independently represent substituents; a and b each independently represent integers of 1 or more; c represents 0 or an integer of 1 or more; n represents 0, 1, 2, or 3; m represents 0 or 1.

[14] The polymer according to

[13] , further having repeating units derived from 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.

[15] The polymer according to

[13] , further having repeating units derived from (meth)acrylic acid ester compounds having an adamantane skeleton.

[16] The polymer according to

[13] , further having repeating units derived from (meth)acrylic acid ester compounds having a lactone skeleton.

[17] The polymer according to any one of

[13] to

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

[18] A lithography composition comprising the polymer described in any of

[13] to

[17] above.

[19] A resist composition comprising the polymer described in any of

[13] to

[17] above.

[20] A composition comprising the polymer described in any of

[13] to

[17] above and an acid generator.

[21] A method for manufacturing a semiconductor integrated circuit, comprising the steps of: (aiii) forming a photoresist layer comprising the polymer described in any of

[13] to

[17] above on a substrate; (aiii) exposing the photoresist layer formed in step (aiii); and (aiv) developing the photoresist layer exposed in step (aiii).

[22] A method for manufacturing a semiconductor integrated circuit, comprising: (bi) a step of treating a polymer according to any one of

[13] to

[17] above with an acid to obtain a polymer containing a hydroxyl group; (biii) a step of forming a photoresist layer on a substrate containing the polymer containing a hydroxyl group obtained in step (bi); (biii) a step of exposing the photoresist layer formed in step (biii) to light; and (biv) a step of developing the photoresist layer exposed in step (biii).

[0024] 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.

[0025] 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.

[0026] <<Compound for Resist Material Manufacturing>> This embodiment uses formula (I):

[0027]

[0028] [In the formula, ring A represents an aromatic ring or a non-aromatic ring; R １ R represents a hydrogen atom, a methyl group, or a halogen atom; ２ and R ３ Each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent; R ４ , R ５ and R ６ Each independently represents a hydrocarbon group which may have substituents; R ７ The present invention provides a compound represented by [formula (I)], where each is independently a substituent; a and b are independently integers of 1 or more; c is 0 or an integer of 1 or more; n is 0, 1, 2, or 3; and m is 0 or 1. A compound having the structure of formula (I) can be efficiently manufactured to produce a resist material with improved sensitivity to exposure light sources. In one embodiment, there is also a tendency for suppression of changes in sensitivity over time, exposure stability (reduction of residue in the space between resist patterns), or the stability of etching defects over time to be further improved.

[0029] Ring A represents either an aromatic ring or a non-aromatic ring.

[0030] In this specification, an aromatic ring means a ring that obeys Hückel's rule, in which the number of electrons in the π-electron system on the ring is 4p + 2 (where p is a natural number). The aromatic ring may be an aromatic carbocyclic ring having only carbon atoms as ring constituent atoms, or an aromatic heterocyclic ring having one or more heteroatoms (e.g., 1, 2, or 3) such as oxygen, nitrogen, or 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 18 members, more preferably an aromatic ring with 5 to 14 members, and even more preferably an aromatic carbocyclic ring with 6 to 14 members.

[0031] Examples of aromatic rings include monocyclic aromatic carbocyclic rings or polycyclic fused aromatic carbocyclic rings such as benzene rings, naphthalene rings, anthracene rings, and phenanthrene rings; monocyclic aromatic heterocyclic rings such as furan rings, thiophene rings, pyrrole rings, pyrazole rings, oxazole rings, isoxazole rings, thiazole rings, imidazole rings, pyridine rings, pyridazine rings, pyrimidine rings, and pyrazine rings; and polycyclic fused aromatic heterocyclic rings such as benzofuran rings, isobenzofuran rings, indole rings, isoindole rings, benzothiophene rings, benzimidazole rings, indazole rings, benzoxazole rings, benzoisoxazole rings, benzothiazole rings, quinoline rings, isoquinoline rings, quinoxaline rings, acridine rings, quinazoline rings, sinnoline rings, and phthalazine rings.

[0032] In this specification, a non-aromatic ring means a ring other than an aromatic ring that has aromaticity throughout the entire ring. 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, 2, or 3) heteroatoms such as oxygen, nitrogen, or sulfur atoms in addition to carbon atoms as ring constituent atoms. A non-aromatic ring may be a monocyclic non-aromatic ring or a polycyclic non-aromatic ring, and may also include a fused ring that has partial aromaticity due to the condensation of an aromatic ring in part. 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 is preferably a 3- to 21-membered non-aromatic ring, more preferably a 4- to 18-membered non-aromatic ring, even more preferably a 5- to 14-membered non-aromatic ring, and particularly preferably a 5- to 14-membered non-aromatic carbocyclic ring.

[0033] Examples of non-aromatic rings include cyclobutane rings, cyclopentane rings, cyclohexane rings, cycloheptane rings, cyclooctane rings, cyclononane rings, cyclodecane rings, cycloundecane rings, cyclododecane rings, cyclopentene rings, cyclopentadiene rings, cyclohexene rings, 1,3-cyclohexadiene rings, 1,4-cyclohexadiene rings, bicyclo[2.2.1]heptane rings (norbornane rings), bicyclo[4.4.0]decane rings (decalin rings), bicyclo[5.3.0]decane rings, bicyclo[4.3.0]nonane rings (hydrindan rings), bicyclo[3.2.1]octane rings, bicyclo[5.4.0]undecane rings, bicyclo[3.3.0]octane rings, bicyclo[3.3.1]nonane rings, and tricyclo[5.2.1.0] ２，６ ] Decane ring (tetrahydrodicyclopentadiene ring), tricyclo[3.3.1.1 ３，７ ] Decane ring (adamantane ring), tricyclo[6.2.1.0 ２，７ Examples include non-aromatic carbocyclic rings such as undecane rings; and non-aromatic heterocyclic rings such as 1,3-dioxane rings, 1,4-dioxane rings, 1,3-dioxolane rings, tetrahydropyran rings, tetrahydrofuran rings, 2,3-dihydro-2H-pyran rings, 4,5-dihydro-2H-pyran rings, 2H-pyran rings, 4H-pyran rings, 2,3-dihydrofuran rings, and 2,5-dihydrofuran rings.

[0034] In one embodiment, ring A is preferably a 5-14 member aromatic ring or a 5-14 member non-aromatic ring; more preferably a 6-14 member aromatic carbocyclic ring or a 5-14 member non-aromatic carbocyclic ring; even more preferably a benzene ring, a naphthalene ring, or an adamantane ring; and particularly preferably a benzene ring.

[0035] R １ This represents a hydrogen atom, a methyl group, or a halogen atom.

[0036] In this specification, a halogen atom refers to a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0037] R １ In one embodiment, is preferably a hydrogen atom, a methyl group, or a chlorine atom; more preferably, a hydrogen atom or a methyl group.

[0038] R ２ and R ３ Each of these independently represents a hydrogen atom or a hydrocarbon group which may have substituents.

[0039] In this specification, a substituent means a monovalent group (or a divalent group if substitutable) consisting of one or more (e.g., 1 to 50 or 1 to 30) skeletal atoms selected from carbon, oxygen, nitrogen, sulfur, and silicon atoms, and, if there are bondable positions on the skeletal atoms, a non-skeletal atom selected from hydrogen and halogen atoms that can be bonded to those bondable positions, or a group consisting only of halogen atoms. Unless otherwise specified, the number of substituents on the substitution target is, for example, 1 to 10.

[0040] R ２ and R ３ Examples of "substituted" in the "optionally substituted hydrocarbon group" shown are not particularly limited, but include, for example, halogen atoms, -NO ２ , -CN, -CHO, -OH, -SH, -NH ２ , -COOH, -COR Ｘ１ , -OR Ｘ１ , -SR Ｘ１ , -SOR Ｘ１ , -SO ２ RＸ１ , - NHR Ｘ１ , -N(R Ｘ１ ) ２ , -COOR Ｘ１ , -OCOR Ｘ１ , -CONH ２ , -CONHR Ｘ１ , -CON(R Ｘ１ ) ２ ,-NHCOR Ｘ１ Examples of monovalent groups include (where R Ｘ１ (The details are as follows.)

[0041] R Ｘ１ Each of these is an optionally substituted hydrocarbon group, more specifically, (1) an alkyl group which may be substituted with one or more (e.g., 1 to 5) groups selected from groups (a) to (x) of "Group α" below; (2) an alkenyl group which may be substituted with one or more (e.g., 1 to 5) groups selected from groups (a) to (x) of "Group α" below; or (3) an aryl group which may be substituted with one or more (e.g., 1 to 5) groups selected from groups (a) to (aa) of "Group α" below, but is not limited to these.

[0042] [Group α] (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.

[0043] 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.

[0044] 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.

[0045] In this specification, an aryl group means a monovalent aromatic hydrocarbon group formed by removing one hydrogen atom from an aromatic carbocyclic ring. The number of carbon atoms in the aryl group is preferably 6 to 18, particularly preferably 6 to 10, unless otherwise specified. Examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, etc.

[0046] In this specification, an aralkyl group means an alkyl group substituted with one or more (preferably one) aryl groups. The number of carbon atoms in the aralkyl group is preferably 7 to 19, particularly preferably 7 to 11, unless otherwise specified. Examples of the aralkyl group include a benzyl group, a phenethyl group, a hydrocinnamyl group, an α-methylbenzyl group, an α-cumyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, etc.

[0047] In this specification, an alkyl-substituted aryl group means an aryl group substituted with one or more alkyl groups. The number of carbon atoms in the alkyl-substituted aryl group is preferably 7 to 19, particularly preferably 7 to 11, unless otherwise specified. Examples of the alkyl-substituted aryl group include a 4-methylphenyl group, a 3-methylphenyl group, a 2-methylphenyl group, a 2,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a 2,4,6-trimethylphenyl group, a 4-ethylphenyl group, a 3-ethylphenyl group, a 2-ethylphenyl group, etc.

[0048] In this specification, an alkoxy group means a monovalent group formed by bonding an alkyl group to an oxygen atom (i.e., a group represented by -O-R Ｙ１ (where R Ｙ１ is an alkyl group)). 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, unless otherwise specified. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, etc.

[0049] In this specification, an alkenyloxy group means a monovalent group formed by bonding an alkenyl group to an oxygen atom (i.e., a group represented by -O-R Ｙ２ (where R Ｙ２means 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 the alkenyloxy group include a vinyloxy group, a propenyloxy group (allyloxy group, 1-propenyloxy group, isopropenyloxy group), and the like.

[0050] In the present specification, the aryloxy group means a monovalent group formed by bonding an aryl group to an oxygen atom (that is, -O-R Ｙ３ (where R Ｙ３ is an aryl 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 the aryloxy group include a phenoxy group, a 1-naphthoxy group, a 2-naphthoxy group, and the like.

[0051] In the present specification, the aralkyloxy group means a monovalent group formed by bonding an aralkyl group to an oxygen atom (that is, -O-R Ｙ４ (where R Ｙ４ is an aralkyl 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 the aralkyloxy group include a benzyloxy group, an α-methylbenzyloxy group, and the like.

[0052] In the present specification, the alkylcarbonyl group means a monovalent group formed by bonding an alkyl group to one side of the carbonyl group (that is, -C(=O)-R Ｙ１ (where R Ｙ１ is 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 the alkylcarbonyl group include an acetyl group, a propanoyl group, a butanoyl group, a pivaloyl group, a valeryl group, and the like.

[0053] In the present specification, the alkenylcarbonyl group means a monovalent group formed by bonding an alkenyl group to one side of the carbonyl group (that is, -C(=O)-R Ｙ２ (where R Ｙ２The 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, methacryloyl group), etc.

[0054] 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 Ｙ３ (R here) Ｙ３ 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.

[0055] 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. Ｙ４ (R here) Ｙ４ 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.

[0056] 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 Ｙ１ (R here) Ｙ１ 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.

[0057] 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 Ｙ２ (R here) Ｙ２ 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, methacryloyloxy group), etc.

[0058] 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 Ｙ３ (R here) Ｙ３ 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.

[0059] 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 Ｙ４ (R here) Ｙ４ 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.

[0060] 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 Ｙ１ (R here) Ｙ１The 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.

[0061] 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 Ｙ２ (R here) Ｙ２ 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.

[0062] 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 Ｙ３ (R here) Ｙ３ 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.

[0063] 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. Ｙ４ (R here) Ｙ４ 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.

[0064] In this specification, an alkylcarbonylamino group means an amino group monosubstituted with an alkylcarbonyl group (i.e., -NH-C(=O)-R Ｙ１ (R here) Ｙ１ 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.

[0065] In this specification, an alkylcarbamoyl group means a carbamoyl group mono- or disubstituted with an alkyl group (i.e., -C(=O)-NHR Ｙ１ or -C(=O)-N(R Ｙ１ ) ２ (This R Ｙ１ 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.

[0066] In this specification, a hydrocarbon group means a group whose constituent atoms consist only of carbon atoms and hydrogen atoms. Unless otherwise specified, the number of carbon atoms in the hydrocarbon group is preferably 1 to 20. Examples of hydrocarbon groups include alkyl groups, alkenyl groups, aryl groups, aralkyl groups, alkyl-substituted aryl groups, and the like.

[0067] R ２ and R ３ In one embodiment, is preferably an alkyl group which may be substituted with a hydrogen atom or a halogen atom; more preferably a hydrogen atom or an alkyl group; even more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; even more preferably a hydrogen atom, a methyl group or an ethyl group; particularly preferably R ２ However, it is a methyl group or an ethyl group, and R ３However, it is a hydrogen atom, a methyl group, or an ethyl group.

[0068] n represents 0, 1, 2, or 3, and m represents 0 or 1. Preferably, (A) m is 0, (B) n is 1 and m is 1, or (C) n is 0 and m is 1. More preferably, (A) m is 0, or (B) n is 1 and m is 1.

[0069] Equation (X) in Equation (I):

[0070]

[0071] [In the formula, each symbol is as described above.] The substructure represented by formula (Xa) to (Xc) in one embodiment is:

[0072]

[0073] [In the formula, R １１ R represents a hydrogen atom or a methyl group; ２１ and R ３１ Each independently represents either a hydrogen atom or an alkyl group. Preferably, the substructure is represented by one of the following: formula (Xa1) to (Xc2):

[0074]

[0075] It is more preferable that the substructure be represented by any of the following; it is even more preferable that the substructure be represented by formula (Xa1), formula (Xb2), formula (Xb4), formula (Xb6), formula (Xb8), or formula (Xb10), and it is particularly preferable that the substructure be represented by formula (Xa1), formula (Xb2), or formula (Xb8).

[0076] R １１ represents a hydrogen atom or a methyl group. If m is 0, R １１ In one embodiment, is preferably a hydrogen atom. When m is 1, R １１ In one embodiment, it is preferably a methyl group.

[0077] R２１ and R ３１ Each independently represents a hydrogen atom or an alkyl group; in one embodiment, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; more preferably a hydrogen atom, a methyl group, or an ethyl group; particularly preferably R ２１ However, it is a methyl group or an ethyl group, and R ３１ However, it is a hydrogen atom, a methyl group, or an ethyl group.

[0078] R ４ , R ５ and R ６ Each of these independently represents a hydrocarbon group which may have substituents.

[0079] R ４ , R ５ and R ６ Examples of "substituted" in the "optionally substituted hydrocarbon group" shown are not particularly limited, but include, for example, halogen atoms, -NO ２ , -CN, -CHO, -OH, -SH, -NH ２ , -COOH, -COR Ｘ２ , -OR Ｘ２ , -SR Ｘ２ , -SOR Ｘ２ , -SO ２ R Ｘ２ , - NHR Ｘ２ , -N(R Ｘ２ ) ２ , -COOR Ｘ２ , -OCOR Ｘ２ , -CONH ２ , -CONHR Ｘ２ , -CON(R Ｘ２ ) ２ ,-NHCOR Ｘ２ Examples of monovalent groups include (where R Ｘ２ (The details are as follows.)

[0080] R Ｘ２Each of these is independently a hydrocarbon group which may have substituents, and more specifically, it may be (1) an alkyl group which may be substituted with one or more (e.g., 1 to 5) groups selected from groups (a) to (x) of "Group α" above; (2) an alkenyl group which may be substituted with one or more (e.g., 1 to 5) groups selected from groups (a) to (x) of "Group α" above; or (3) an aryl group which may be substituted with one or more (e.g., 1 to 5) groups selected from groups (a) to (aa) of "Group α" above, but is not limited to these.

[0081] R ４ , R ５ and R ６ Each of these is independently, in one embodiment, preferably an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, or an optionally substituted alkyl-substituted aryl group; more preferably an alkyl group, an aryl group, an aralkyl group, or an alkyl-substituted aryl group; even more preferably an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 11 carbon atoms; particularly preferably an alkyl group having 1 to 6 carbon atoms, or a phenyl group.

[0082] Equation (Y) within Equation (I):

[0083]

[0084] [In the formulas, each symbol is as described above.] The substructures represented by each of the formulas (Y1) to (Y28) are independent of each other in one embodiment:

[0085]

[0086]

[0087] It is preferable that the substructure be represented by any of the following; it is particularly preferable that the substructure be represented by formula (Y6), formula (Y7), or formula (Y19).

[0088] R ７ Each of these independently represents a substituent.

[0089] R ７ Examples of "substituents" shown are not limited to halogen atoms, but include, for example, halogen atoms, -NO ２ , -CN, -CHO, -OH, -SH, -NH ２ , -COOH, -R Ｘ３ , -COR Ｘ３ , -OR Ｘ３ , -SR Ｘ３ , -SOR Ｘ３ , -SO ２ R Ｘ３ , - NHR Ｘ３ , -N(R Ｘ３ ) ２ , -COOR Ｘ３ , -OCOR Ｘ３ , -OCOOR Ｘ３ , -CONH ２ , -CONHR Ｘ３ , -CON(R Ｘ３ ) ２ ,-NHCOR Ｘ３ Examples of monovalent groups include (where R Ｘ３ (The details are as follows.)

[0090] R Ｘ３ Each of these is independently a hydrocarbon group which may have substituents, and more specifically, it may be (1) an alkyl group which may be substituted with one or more (e.g., 1 to 5) groups selected from groups (a) to (x) of "Group α" above; (2) an alkenyl group which may be substituted with one or more (e.g., 1 to 5) groups selected from groups (a) to (x) of "Group α" above; or (3) an aryl group which may be substituted with one or more (e.g., 1 to 5) groups selected from groups (a) to (aa) of "Group α" above, but is not limited to these.

[0091] R ７ These are, independently, in one embodiment, preferably -OH, -OR Ｘ３ , -OCOR Ｘ３ , or -OCOR Ｘ３The group is; more preferably a hydroxyl group (-OH), an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, or an arylcarbonyloxy group; even more preferably a hydroxyl group (-OH), an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an alkylcarbonyloxy group having 2 to 11 carbon atoms, or an arylcarbonyloxy group having 7 to 11 carbon atoms; particularly preferably an alkoxy group having 1 to 6 carbon atoms, or an alkylcarbonyloxy group having 2 to 7 carbon atoms.

[0092] a represents an integer of 1 or more; in one embodiment, it is preferably 1, 2, 3, or 4; more preferably 1, 2, or 3.

[0093] 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.

[0094] c 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.

[0095] Furthermore, the sum of a, b, and c does not exceed the number of substitutable positions of the aromatic or non-aromatic ring represented by ring A.

[0096] The compound represented by formula (I) is, in one embodiment, preferably formula (1), formula (2), or formula (3):

[0097]

[0098] [In the formula, ring A' represents a 6-14 member aromatic carbon ring or a 5-14 member non-aromatic carbon ring; R １１ R represents a hydrogen atom or a methyl group; ２１ and R ３１ Each independently represents either a hydrogen atom or an alkyl group; R ４ , R ５ and R ６ Each independently represents a hydrocarbon group which may have substituents; R ７a and b each independently represent substituents; a and b each independently represent integers of 1 or more; c represents 0 or an integer of 1 or more. The compound is represented by [ ]; more preferably, the compound is represented by formula (1) or formula (2).

[0099] Ring A' represents a 6- to 14-membered aromatic carbon ring or a 5- to 14-membered non-aromatic carbon ring; in one embodiment, it is preferably a benzene ring, a naphthalene ring, or an adamantane ring; particularly preferably a benzene ring.

[0100] In one embodiment, the substructure represented by formula (Xa) in formula (1) is particularly preferably the substructure represented by formula (Xa1).

[0101] In one embodiment, the substructure represented by formula (Xb) in formula (2) is preferably a substructure represented by any of formulas (Xb1) to (Xb12); more preferably a substructure represented by formula (Xb2), formula (Xb4), formula (Xb6), formula (Xb8), or formula (Xb10), and particularly preferably a substructure represented by formula (Xb2) or formula (Xb8).

[0102] In one embodiment, the substructure represented by formula (Xc) in formula (3) is particularly preferably the substructure represented by formula (Xc2).

[0103] The compound represented by formula (I) is, in one embodiment, more preferably, formulas (1a) to (2r):

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110] [In the formula, R １１R represents a hydrogen atom or a methyl group; ２１ and R ３１ Each 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, and R ａ , R ｂ , R ｃ , R ｄ and R ｅ Of these, at least one displayed in each formula is -OSiR ４ R ５ R ６ And; R ４ , R ５ and R ６ Each of these independently represents a hydrocarbon group which may have substituents. The compound is represented by either of the following:

[0111] R ａ , R ｂ , R ｃ , R ｄ and R ｅ Each of these independently represents a hydrogen atom or a substituent, and R ａ , R ｂ , R ｃ , R ｄ and R ｅ Of these, at least one displayed in each formula is -OSiR ４ R ５ R ６ That is the case.

[0112] R ａ , R ｂ , R ｃ , R ｄ and R ｅ Examples of "substituents" shown are not limited to halogen atoms, but include, for example, halogen atoms, -NO ２ , -CN, -CHO, -OH, -SH, -NH ２ , -COOH, -R Ｘ４ , -COR Ｘ４ , -OR Ｘ４ , -SR Ｘ４ , -SOR Ｘ４ , -SO ２ RＸ４ , - NHR Ｘ４ , -N(R Ｘ４ ) ２ , -COOR Ｘ４ , -OCOR Ｘ４ , -OCOOR Ｘ４ , -CONH ２ , -CONHR Ｘ４ , -CON(R Ｘ４ ) ２ ,-NHCOR Ｘ４ , -OSir ４ R ５ R ６ Examples of monovalent groups include (where R Ｘ４ (The details are as follows.)

[0113] R Ｘ４ Each of these is independently a hydrocarbon group which may have substituents, and more specifically, it may be (1) an alkyl group which may be substituted with one or more (e.g., 1 to 5) groups selected from groups (a) to (x) of "Group α" above; (2) an alkenyl group which may be substituted with one or more (e.g., 1 to 5) groups selected from groups (a) to (x) of "Group α" above; or (3) an aryl group which may be substituted with one or more (e.g., 1 to 5) groups selected from groups (a) to (aa) of "Group α" above, but is not limited to these.

[0114] R ａ , R ｂ , R ｃ , R ｄ and R ｅ These are, independently, in one embodiment, preferably -OH, -OR Ｘ４ , -OCOR Ｘ４ , -OCOOR Ｘ４ , or -OSiR ４ R ５ R ６ And R ａ , R ｂ , R ｃ , R ｄ and R ｅ Of these, at least one (i.e., 1, 2, 3, or 4) shown in each formula is -OSiR ４ R ５ R６ That is the case.

[0115] R ａ , R ｂ , R ｃ , R ｄ and R ｅ Each of these is independently, in one embodiment, more preferably, a hydroxyl group (-OH), an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, or -OSiR ４ R ５ R ６ And R ａ , R ｂ , R ｃ , R ｄ and R ｅ Of these, at least one (i.e., 1, 2, 3, or 4) shown in each formula is -OSiR ４ R ５ R ６ That is the case.

[0116] R ａ , R ｂ , R ｃ , R ｄ and R ｅ Each of these is independently, and more preferably in one embodiment, a hydroxyl group (-OH), a carbon 1-10 alkoxy group, a carbon 6-10 aryloxy group, a carbon 2-11 alkylcarbonyloxy group, a carbon 7-11 arylcarbonyloxy group, or -OSiR ４ R ５ R ６ And R ａ , R ｂ , R ｃ , R ｄ and R ｅ Of these, at least one (i.e., 1, 2, 3, or 4) shown in each formula is -OSiR ４ R ５ R ６ That is the case.

[0117] R ａ , R ｂ , R ｃ , R ｄ and R ｅEach of these is independently, in one embodiment, particularly preferably, an alkoxy group having 1 to 6 carbon atoms, an alkylcarbonyloxy group having 2 to 7 carbon atoms, or -OSiR ４ R ５ R ６ And R ａ , R ｂ , R ｃ , R ｄ and R ｅ Of these, at least one (i.e., 1, 2, 3, or 4) shown in each formula is -OSiR ４ R ５ R ６ That is the case.

[0118] In one embodiment, the substructure represented by formula (Xa) in formulas (1a) to (1r) is particularly preferably the substructure represented by formula (Xa1).

[0119] In one embodiment, the substructure represented by formula (Xb) in formulas (2a) to (2r) is preferably a substructure represented by any of formulas (Xb1) to (Xb12); more preferably a substructure represented by formula (Xb2), formula (Xb4), formula (Xb6), formula (Xb8), or formula (Xb10), and particularly preferably a substructure represented by formula (Xb2) or formula (Xb8).

[0120] Specific examples of compounds represented by formula (I) are shown below: formulas (1a-1) to (2r-12):

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160]

[0161]

[0162]

[0163]

[0164]

[0165]

[0166]

[0167]

[0168]

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182] [In the formula, TBS represents a tert-butyldimethylsilyl group (i.e., a group obtained by removing O from the substructure represented by formula (Y6)), TES represents a triethylsilyl group (i.e., a group obtained by removing O from the substructure represented by formula (Y7)), and DMPS represents a dimethylphenylsilyl group (i.e., a group obtained by removing O from the substructure represented by formula (Y19)).] Examples of compounds represented by these formulas include, but are not limited to, these.

[0183] <<Method for producing compounds for resist material manufacturing>> The compound represented by formula (I) can be produced using known methods.

[0184] The compound represented by formula (I) is, for example, a compound having an iodine atom and a hydroxyl group, which is subjected to X-SiR under basic conditions. ４ R ５ R ６ (X represents a halogen atom.) is reacted with a compound represented by to produce an iodine atom and -OSiR ４ R ５ R ６ It can be produced by a method that includes a step of converting to a compound having a group represented by (for example, step A2 of synthesis scheme 1, steps Ba3 and Bb1 of synthesis scheme 2, and steps Ca2 and Cb1 of synthesis scheme 3, etc., as described below).

[0185] Conventionally, in the above process, -SiR was applied to the hydroxyl group. ４ R ５ R ６Instead of the silyl protecting group represented by , acetal protecting groups such as the THP group (tetrahydro-2H-pyran-2-yl group), EE group (1-ethoxyethyl group), EM group (ethoxymethyl group), and MOM group (methoxymethyl group), which do not contain silicon atoms, and carbonate ester protecting groups such as the Boc group (tert-butoxycarbonyl group) were introduced. However, due to the influence of electron-withdrawing groups such as iodine atoms (and other groups such as formyl, acyl, and cyano groups), acetal and carbonate ester protecting groups had a lower introduction rate to hydroxyl groups and a higher retention rate of hydroxyl groups compared to silyl protecting groups. Furthermore, with these protecting groups, which are mainly introduced under acidic conditions, the decomposition of acid-unstable structures within the molecule is promoted during protection, which can reduce the yield of compounds for producing resist materials. In contrast, the method for producing the compound of this embodiment, represented by formula (I), differs from conventional methods in that a silyl protecting group is introduced to the hydroxyl group. This reduces the percentage of compounds with residual hydroxyl groups and suppresses the decomposition of acid-unstable structures within the molecule, resulting in superior production efficiency.

[0186] Among the compounds represented by formula (I), the compound represented by formula (Ia) where m is 0 can be produced, for example, by the method of synthesis scheme 1 below.

[0187]

[0188] [In the formula, each symbol is as defined above.]

[0189] The compound represented by formula (Ia) can be obtained, for example, from the compound represented by formula (IIa) by a Wittig reaction, as in step A1 of the synthesis scheme 1 described above. Specifically, the compound represented by formula (IIa) can be subjected to, for example, a Wittig reagent (methritriphenylphosphonium halide (Ph ３ P ＋ -CH ３ X －(In the formula, X represents a halogen atom.))) can be reacted in the presence of a strong base to obtain the compound represented by formula (Ia). Examples of strong bases that can be used include butyllithium, potassium hexamethyldisilazide, lithium diisopropylamide, sodium hydride, potassium hydride, potassium tert-butoxide, etc. 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.

[0190] The compound represented by formula (IIa) can be obtained, for example, by silylation of the hydroxyl group from the compound represented by formula (IIIa), as in step A2 of the synthesis scheme 1 described above. Specifically, the compound represented by formula (IIIa) can be subjected to, for example, X-SiR under basic conditions. ４ R ５ R ６ By reacting (wherein X represents a halogen atom) with the compound represented by formula (IIa), a compound represented by formula (IIa) can be obtained. As the base, for example, organic bases such as diazabicycloundecene, 1,4-diazabicyclo[2.2.2]octane, triethylamine, pyridine, and N,N-dimethylaminopyridine 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.

[0191] Among the compounds represented by formula (I), the compound represented by formula (Ib), where n is 1, 2, or 3 and m is 1, can be produced, for example, by the method of synthesis scheme 2 below.

[0192]

[0193] [In the formula, each symbol is as defined above.]

[0194] One method is to obtain the compound represented by formula (Ib) by esterifying the compound represented by formula (IIba), as in step Ba1 of the synthesis scheme 2 described above. Specifically, for the compound represented by formula (IIba), for example, (CH ２ =CR １ CO) ２ Compounds represented by O or CH ２ =CR １ COX Ｈ (X here) Ｈ A compound represented by formula (I) can be obtained by reacting a compound represented by (a chlorine atom, a bromine atom, or an iodine atom) in the presence of a base. As the base, organic bases such as diazabicycloundecene, 1,4-diazabicyclo[2.2.2]octane, triethylamine, pyridine, and N,N-dimethylaminopyridine 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.

[0195] The compound represented by formula (IIba) can be obtained by reducing the compound represented by formula (IIIba), as in step Ba2 of the synthesis scheme 2 described above. R bonded to the α-carbon atom (carbon atom to which the hydroxyl group is bonded) of formula (IIba) ３ When R is a "hydrogen atom", specifically, the compound represented by formula (IIIba) can be obtained by reacting the compound represented by formula (IIIba) with an aluminum hydride reagent such as lithium aluminum hydride, a boron hydride reagent such as sodium borohydride, etc. The reaction temperature for this reaction is, for example, -80 to 20°C, and the reaction time is, for example, 10 minutes to 100 hours. This reaction can be carried out in an organic solvent such as an alcohol-based solvent. R bonded to the carbon atom at the α position of formula (IIba) ３If is an "optional hydrocarbon group having substituents", then specifically, for the compound represented by formula (IIIba), R ３ MgX Ｈ (X here) Ｈ A compound represented by formula (IIba) can be obtained by reacting a Grignard reagent (which is represented by a chlorine atom, a bromine atom, or an iodine atom) with the above. The reaction temperature for this reaction is, for example, -80 to 70°C, and the reaction time is, for example, 10 minutes to 100 hours. This reaction can be carried out in an organic solvent, such as an aliphatic ether solvent.

[0196] The compound represented by formula (IIIba) can be obtained by silylation of the hydroxyl group from the compound represented by formula (IVb), as in step Ba3 of synthesis scheme 2 described above. Specifically, the same method as in step A2 of synthesis scheme 1 described above can be used.

[0197] Alternatively, the compound represented by formula (Ib) can be obtained by silylation of the hydroxyl group from the compound represented by formula (IIbb), as in step Bb1 of synthesis scheme 2 described above. Specifically, the same method as in step A2 of synthesis scheme 1 described above can be used.

[0198] The compound represented by formula (IIbb) can be obtained from the compound represented by formula (IIIbb) by the Mitsunobu reaction, as in step Bb2 of the synthesis scheme 2 described above. Specifically, the compound represented by formula (IIbb) can be obtained by reacting the compound represented by formula (IIIbb) with methacrylic acid or acrylic acid in the presence of an azo reagent and phosphines. Examples of phosphines that can be used include triphenylphosphine and tributylphosphine. Examples of azo reagents that can be used include azocarboxylic acid esters such as diethyl azodicarboxylic acid, diisopropyl azodicarboxylic acid, dibenzyl azodicarboxylic acid, and ditert-butyl azodicarboxylic acid; and azocarboxylic acid amides such as 1,1'-(azodicarbonyl)dipiperazine and N,N,N',N'-tetramethylazodicarboxamide. The reaction temperature for this reaction is, for example, 0 to 25°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 ethers and halogens.

[0199] The compound represented by formula (IIIbb) can be obtained by reducing the compound represented by formula (IVb), as in step Bb3 of the synthesis scheme 2 described above. Specifically, the same method as in step Ba2 of the synthesis scheme 2 described above can be used.

[0200] Among the compounds represented by formula (I), the compound represented by formula (Ic), where n is 0 and m is 1, can be produced, for example, by the method of synthesis scheme 3 below.

[0201]

[0202] [In the formula, each symbol is as defined above.]

[0203] One method is to obtain the compound represented by formula (Ic) by esterifying the compound represented by formula (IIca), as in step Ca1 of synthesis scheme 3 described above. Specifically, the same method as in step Ba1 of synthesis scheme 2 described above can be used.

[0204] The compound represented by formula (IIca) can be obtained by silylation of the hydroxyl group from the compound represented by formula (IIIc), as in step Ca2 of synthesis scheme 3 described above. Specifically, the same method as in step A2 of synthesis scheme 1 described above can be used.

[0205] Alternatively, the compound represented by formula (Ic) can be obtained by silylation of the hydroxyl group from the compound represented by formula (IIcb), as in step Cb1 of synthesis scheme 3 described above. Specifically, the same method as in step A2 of synthesis scheme 1 described above can be used.

[0206] The compound represented by formula (IIcb) can be obtained by esterifying the compound represented by formula (IIIc), as in step Cb2 of synthesis scheme 3 described above. Specifically, the same method as in step Ba1 of synthesis scheme 2 described above can be used.

[0207] The compound represented by formula (I) 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 synthesis scheme 1, synthesis scheme 2, or synthesis scheme 3 above. Furthermore, the compound represented by formula (I) may be produced by methods other than those shown in synthesis scheme 1, synthesis scheme 2, or synthesis scheme 3 above. 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.

[0208] The compounds obtained in each step shown in Synthesis Scheme 1, Synthesis Scheme 2, or Synthesis Scheme 3 above can be used in the next step either as is with the 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.

[0209] 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, and isophorone. Examples of aliphatic hydrocarbon solvents used herein include n-pentane, n-hexane, isohexane, n-heptane, n-octane, cyclopentane, cyclohexane, and methylcyclohexane. Examples of aromatic hydrocarbon solvents used herein include benzene, toluene, o-xylene, m-xylene, p-xylene, and ethylbenzene. Examples of alcoholic solvents used herein include methanol, ethanol, propanol, isopropanol, and tert-butanol.

[0210] <<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 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 composition for manufacturing resist materials (composition for manufacturing photoresist layer-forming materials), which will be described in detail later, and especially as a composition for manufacturing resist materials for the manufacture of semiconductor integrated circuits. In particular, the composition containing the compound represented by formula (I) is useful as a composition for manufacturing resist materials for processing by lithography. Furthermore, the composition containing the compound represented by formula (I) is also useful as a composition for manufacturing resist auxiliary film-forming materials (for example, a composition for manufacturing a resist upper layer film-forming material, a resist intermediate layer film-forming material, and a resist lower layer film-forming material), a composition for manufacturing a topcoat-forming material, a composition for manufacturing an anti-reflective film-forming material, and so on. 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.

[0211] 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, with an upper limit of 100 mol% or less, preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 30 mol% or less.

[0212] 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.

[0213] In one embodiment, a composition containing the compound represented by formula (I) more preferably contains, in addition to the compound represented by formula (I), a (meth)acrylic acid ester compound having an adamantane skeleton as a monomer component. In one embodiment, a composition containing the compound represented by formula (I) more preferably contains, in addition to the compound represented by formula (I), a (meth)acrylic acid ester compound having a lactone skeleton as a monomer component. In one embodiment, a composition containing the compound represented by formula (I) is even more preferably, in addition to the compound represented by formula (I), a (meth)acrylic acid ester compound having an adamantane skeleton and a (meth)acrylic acid ester compound having a lactone skeleton as monomer components.

[0214] The (meth)acrylic acid ester compounds having an adamantane skeleton are not particularly limited, but for example, formulas (A1) and (A2):

[0215]

[0216] [In the formula, R ａ１ and R ａ５ R represents a hydrogen atom or a methyl group; ａ２ , R ａ３ , R ａ４ , R ａ６ , R ａ７ , R ａ８ , R ａ９ and R ａ１０ Each independently represents a hydrogen atom, an optionally substituted hydrocarbon group, a halogen atom, or a hydroxyl group; L ａ１ and L ａ３ L indicates an alkylene group; ａ２ and L ａ４represents a bond or alkylene group; n ａ１ and n ａ２ 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.

[0217] R ａ２ , R ａ３ , R ａ４ , R ａ６ , R ａ７ , R ａ８ , R ａ９ and R ａ１０ Examples of "substituents" in the "optionally substituted hydrocarbon group" shown are not particularly limited, but include, for example, halogen atoms, -NO ２ , -CN, -CHO, -OH, -SH, -NH ２ , -COOH, -R Ｘａ , -COR Ｘａ , -OR Ｘａ , -SR Ｘａ , -SOR Ｘａ , -SO ２ R Ｘａ , - NHR Ｘａ , -N(R Ｘａ ) ２ , -COOR Ｘａ , -OCOR Ｘａ , -CONH ２ , -CONHR Ｘａ , -CON(R Ｘａ ) ２ ,-NHCOR Ｘａ Examples of monovalent groups include (where R Ｘａ (The details are as follows.)

[0218] R ＸａEach of these is independently a hydrocarbon group which may have substituents, and more specifically, it may be (1) an alkyl group which may be substituted with one or more (e.g., 1 to 5) groups selected from groups (a) to (x) of "Group α" above; (2) an alkenyl group which may be substituted with one or more (e.g., 1 to 5) groups selected from groups (a) to (x) of "Group α" above; or (3) an aryl group which may be substituted with one or more (e.g., 1 to 5) groups selected from groups (a) to (aa) of "Group α" above, but is not limited to these.

[0219] 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.

[0220] Specific examples of (meth)acrylic acid ester compounds having an adamantane skeleton include, but are not limited to, formulas (A-1) to (A-60):

[0221]

[0222] Examples of compounds represented by the following are included.

[0223] The content of the adamantane skeleton-containing (meth)acrylic acid ester compound in a composition containing the compound represented by formula (I) is not particularly limited, but is preferably 10 mol% or more, more preferably 40 mol% or more, even more preferably 60 mol% or more, with an upper limit of preferably 90 mol% or less, more preferably 85 mol% or less, and even more preferably 80 mol% or less.

[0224] The (meth)acrylic acid ester compounds having a lactone skeleton are not particularly limited, but for example, formulas (B1) to (B5):

[0225]

[0226] [In the formula, R ｂ１ , R ｂ３ , R ｂ５ , R ｂ７ and R ｂ９ R represents a hydrogen atom or a methyl group; ｂ２ , R ｂ４ , R ｂ６ , R ｂ８ and R ｂ１０ Each independently represents a hydrocarbon group which may have substituents, a halogen atom, or a hydroxyl group; L ｂ１ , L ｂ３ , L ｂ５ , L ｂ７ and L ｂ９ L indicates an alkylene group; ｂ２ , L ｂ４ , L ｂ６ , L ｂ８ and L ｂ１０ X represents a bond or alkylene group; ｂ is, -CH ２ - or -O- indicates; n ｂ１ , n ｂ２ , n ｂ４ , n ｂ６ , n ｂ８ and n ｂ１０ n represents 0, 1, or 2; ｂ３ , n ｂ５ , n ｂ７ , n ｂ９ and n ｂ１１represents 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.

[0227] R ｂ２ , R ｂ４ , R ｂ６ , R ｂ８ and R ｂ１０ Examples of "substituents" in the "optionally substituted hydrocarbon group" shown are not particularly limited, but include, for example, halogen atoms, -NO ２ , -CN, -CHO, -OH, -SH, -NH ２ , -COOH, -R Ｘｂ , -COR Ｘｂ , -OR Ｘｂ , -SR Ｘｂ , -SOR Ｘｂ , -SO ２ R Ｘｂ , - NHR Ｘｂ , -N(R Ｘｂ ) ２ , -COOR Ｘｂ , -OCOR Ｘｂ , -CONH ２ , -CONHR Ｘｂ , -CON(R Ｘｂ ) ２ ,-NHCOR Ｘｂ Examples of monovalent groups include (where R Ｘｂ (The details are as follows.)

[0228] R Ｘｂ Each of these is independently a hydrocarbon group which may have substituents, and more specifically, it may be (1) an alkyl group which may be substituted with one or more (e.g., 1 to 5) groups selected from groups (a) to (x) of "Group α" above; (2) an alkenyl group which may be substituted with one or more (e.g., 1 to 5) groups selected from groups (a) to (x) of "Group α" above; or (3) an aryl group which may be substituted with one or more (e.g., 1 to 5) groups selected from groups (a) to (aa) of "Group α" above, but is not limited to these.

[0229] Specific examples of (meth)acrylic acid ester compounds having a lactone skeleton include, but are not limited to, formulas (B-1) to (B-36):

[0230]

[0231] Examples of compounds represented by the following are included.

[0232] 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.

[0233] Compounds having a hydroxystyrene skeleton are not particularly limited, but for example, formula (C1):

[0234]

[0235] [In the formula, R ｃａ R represents a hydrogen atom or a methyl group; ｃ１ , R ｃ２ , R ｃ３ , R ｃ４ and R ｃ５ Each of these independently represents a hydrogen atom or a substituent, and R ｃ１ , R ｃ２ , R ｃ３ , R ｃ４ and R ｃ５ At least one of them is -OH, -OR Ｘｃ , -OCOR Ｘｃ , or -OCOR Ｘｃ R Ｘｃ The following are examples of compounds represented by [ ]. Compounds having a hydroxystyrene skeleton may be used individually or in any combination of two or more types.

[0236] R ｃ１ , R ｃ２ , R ｃ３ , R ｃ４ and Rｃ５ Examples of "substituents" shown are not limited to halogen atoms, but include, for example, halogen atoms, -NO ２ , -CN, -CHO, -OH, -SH, -NH ２ , -COOH, -R Ｘｃ , -COR Ｘｃ , -OR Ｘｃ , -SR Ｘｃ , -SOR Ｘｃ , -SO ２ R Ｘｃ , - NHR Ｘｃ , -N(R Ｘｃ ) ２ , -COOR Ｘｃ , -OCOR Ｘｃ , -OCOOR Ｘｃ , -CONH ２ , -CONHR Ｘｃ , -CON(R Ｘｃ ) ２ ,-NHCOR Ｘｃ Examples of monovalent groups include (where R Ｘｃ (The details are as follows.)

[0237] R Ｘｃ Each of these is independently a hydrocarbon group which may have substituents, and more specifically, it may be (1) an alkyl group which may be substituted with one or more (e.g., 1 to 5) groups selected from groups (a) to (x) of "Group α" above; (2) an alkenyl group which may be substituted with one or more (e.g., 1 to 5) groups selected from groups (a) to (x) of "Group α" above; or (3) an aryl group which may be substituted with one or more (e.g., 1 to 5) groups selected from groups (a) to (aa) of "Group α" above, but is not limited to these.

[0238] R ｃ１ , R ｃ２ , R ｃ３ , R ｃ４ and R ｃ５ Each of these independently represents a hydrogen atom or a substituent, and R ｃ１ , R ｃ２ , R ｃ３ , R ｃ４ and R ｃ５At least one of them (for example, 1, 2, or 3) is -OH, -OR Ｘｃ , -OCOR Ｘｃ , or -OCOR Ｘｃ It is preferable that this be the case.

[0239] Specific examples of compounds having a hydroxystyrene skeleton include, but are not limited to, formulas (C-1) to (C-36):

[0240]

[0241] Examples of compounds represented by the following are included.

[0242] 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 50 mol% or more. The upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 50 mol% or less, and may be 40 mol% or less.

[0243] 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.

[0244] <<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.

[0245] 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.

[0246] 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.

[0247] 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.

[0248] 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.

[0249] 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).

[0250] 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 monomer components are considered to be 100% by mass.

[0251] The polymer of this embodiment includes a polymer containing structural units derived from a 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):

[0252]

[0253] The polymer has repeating units represented by [In the formula, each symbol is as described above.]. The polymer of this embodiment includes a polymer containing structural units derived from the compound represented by formula (I), which allows for improved sensitivity to exposure light sources when used as a resist material. In one embodiment, there is also a tendency for improved suppression of changes in sensitivity over time, improved exposure stability (reduction of residue in the space between resist patterns), and improved stability of etching defects over time.

[0254] Expression (UX) within Expression (UI):

[0255]

[0256] [In the formula, each symbol is as described above.] The substructure represented by formula (UXa) to (UXc) in one embodiment is:

[0257]

[0258] [In the formulas, each symbol is as described above.] It is preferable that the substructure be represented by one of the following: Formulas (UXa1) to (UXc2):

[0259]

[0260] It is more preferable that the substructure be represented by any of the following; it is even more preferable that the substructure be represented by formula (UXa1), formula (UXb2), formula (UXb4), formula (UXb6), formula (UXb8), or formula (UXb10), and it is particularly preferable that the substructure be represented by formula (UXa1), formula (UXb2), or formula (UXb8).

[0261] In one embodiment, the repeating units in the polymer represented by formula (UI) are preferably formulas (U1), (U2), or (U3) derived from compounds represented by formula (1), formula (2), or formula (3):

[0262]

[0263] [In the formula, each symbol is as described above.] Includes a repeating unit represented by ], and more preferably includes a repeating unit represented by formula (U1) or formula (U2).

[0264] In one embodiment, the substructure represented by formula (UXa) in formula (U1) is particularly preferably the substructure represented by formula (UXa1).

[0265] In one embodiment, the substructure represented by formula (UXb) in formula (U2) is preferably a substructure represented by any of formulas (UXb1) to (UXb12); more preferably a substructure represented by formula (UXb2), formula (UXb4), formula (UXb6), formula (UXb8), or formula (UXb10), and particularly preferably a substructure represented by formula (UXb2) or formula (UXb8).

[0266] In one embodiment, the substructure represented by formula (UXc) in formula (U3) is particularly preferably the substructure represented by formula (UXc2).

[0267] In this embodiment, the repeating unit represented by formula (UI) in the polymer is, more preferably in one embodiment, derived from compounds represented by formulas (1a) to (2r):

[0268]

[0269]

[0270]

[0271]

[0272]

[0273]

[0274] [In the formula, each symbol is as described above.] Includes a repeating unit represented by one of the following:

[0275] In one embodiment, the substructure represented by formula (UXa) in formulas (U1a) to (U1r) is particularly preferably the substructure represented by formula (UXa1).

[0276] In one embodiment, the substructure represented by formula (UXb) in formulas (U2a) to (U2r) is preferably a substructure represented by any of formulas (UXb1) to (UXb12); more preferably a substructure represented by formula (UXb2), formula (UXb4), formula (UXb6), formula (UXb8), or formula (UXb10), and particularly preferably a substructure represented by formula (UXb2) or formula (UXb8).

[0277] 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, with an upper limit of 100 mol% or less, preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 30 mol% or less.

[0278] 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.

[0279] In one embodiment, the polymer of this embodiment preferably has, as structural units derived from the monomer component, a repeating unit represented by formula (UI), in addition to a repeating unit derived from a (meth)acrylic acid ester compound having an adamantane skeleton. In one embodiment, the polymer of this embodiment preferably has, as structural units derived from the monomer component, a repeating unit represented by formula (UI), in addition to a repeating unit derived from a (meth)acrylic acid ester compound having a lactone skeleton. In one embodiment, the polymer of this embodiment preferably has, as structural units derived from the monomer component, a repeating unit represented by formula (UI), in addition to a repeating unit derived from a (meth)acrylic acid ester compound having an adamantane skeleton and a repeating unit derived from a (meth)acrylic acid ester compound having a lactone skeleton.

[0280] 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 10 mol% or more, more preferably 40 mol% or more, even more preferably 60 mol% or more, with an upper limit of preferably 90 mol% or less, more preferably 85 mol% or less, and even more preferably 80 mol% or less.

[0281] 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 100 mol% or less, preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less.

[0282] 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 may be 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 50 mol% or more, and the upper limit may be preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 50 mol% or less, and may be 40 mol% or less.

[0283] 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.

[0284] When the polymer of this embodiment contains two or more repeating units, it is preferable that these repeating units are arranged randomly.

[0285] 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, and particularly preferably 1.6 to 2.5. 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.

[0286] 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.

[0287] <<Method for Manufacturing Semiconductor Integrated Circuits Using Resist Materials>> The polymer of this embodiment can be used as a resist material in the manufacture of semiconductor integrated circuits. A resist composition (a composition for forming a photoresist layer) containing the polymer of this embodiment can be used in the manufacture of semiconductor integrated circuits. The polymer of this embodiment contains -OSiR derived from the compound represented by formula (I). ４ R ５ R ６ The polymer of this embodiment contains a group represented by -OSiR ４ R ５ R ６ The group represented by may remain and be used as a resist material, or the polymer of this embodiment may be treated with an acid, for example, to remove the -OSiR contained in the polymer of this embodiment. ４ R ５ R ６Some or all of the groups represented by -OSiR may be hydrolyzed to -OH (hydroxyl group) before being used as a resist material. ４ R ５ R ６ Even when a photoresist layer is formed while leaving the group represented by -OSiR in the exposure and development steps, ４ R ５ R ６ The group represented by is hydrolyzed to -OH (hydroxyl group).

[0288] In the first embodiment, the polymer of this embodiment can be used as a resist material in a method for manufacturing a semiconductor integrated circuit, which includes the steps of: (aiii) forming a photoresist layer containing the polymer of this embodiment on a substrate; (aiii) exposing the photoresist layer formed in step (aiii); and (aiv) developing the photoresist layer exposed in step (aiii).

[0289] In a second embodiment, the polymer of this embodiment can be used as a resist material in a method for manufacturing a semiconductor integrated circuit, which includes the steps of: (bi) treating the polymer of this embodiment with acid to obtain a polymer containing hydroxyl groups; (biii) forming a photoresist layer on a substrate containing the polymer containing hydroxyl groups obtained in step (bi); (biii) exposing the photoresist layer formed in step (biii) to light; and (biv) developing the photoresist layer exposed in step (biii).

[0290] The acid treatment in step (bi) may be carried out by directly adding the acid to the reaction solution after radical polymerization of the compound represented by formula (I). The acid that can be used in the acid treatment in step (bi) may be an organic acid, an inorganic acid, a Lewis acid, or a combination thereof, but an organic acid is preferred. Examples of organic acids include methanesulfonic acid, ethanesulfonic acid, 10-camphorsulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid, and their pyridium salts. The amount of acid added may be, for example, 0.1 to 5% by mass relative to the reaction solution after radical polymerization. The temperature during the acid treatment is, for example, -10 to 100°C, preferably 10 to 30°C. The acid treatment time is, for example, 10 minutes to 100 hours, preferably 1 to 5 hours.

[0291] The polymer obtained after the acid treatment in step (bi) can be purified by known purification methods. Purification methods include ultrafiltration, crystallization, microfiltration, acid washing, water washing, extraction, or a combination thereof.

[0292] The formation of the photoresist layer on the substrate in steps (aii) and (bii) is carried out by applying a resist composition, obtained by mixing the polymer of this embodiment with an organic solvent and, if necessary, additives, onto the substrate. The resist composition can be applied to the substrate using a coating apparatus 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.

[0293] 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.

[0294] 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.

[0295] 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.

[0296] 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.

[0297] 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.

[0298] 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.

[0299] Specific examples of acid diffusion control agents used in resist compositions are not limited to 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.

[0300] 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.

[0301] 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.

[0302] 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.

[0303] 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.

[0304] 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.

[0305] 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.

[0306] After coating the substrate with the resist composition, the solvent is removed and the resist composition is dried to form a photoresist 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 The setting should be Pa. The thickness of the formed photoresist layer is, for example, 50 nm to 1 μm.

[0307] In steps (aiii) and (biii), the photoresist layers formed in steps (aiii) and (biii) are exposed by irradiating them 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 high-precision fine patterns, 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.

[0308] In steps (aiv) and (biv), the photoresist layer exposed in steps (aiii) and (biii) 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 resist pattern formed may be a positive-type resist pattern or a negative-type resist pattern.

[0309] 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.

[0310] 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.

[0311] 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.

[0312] Semiconductor integrated circuits obtained from a resist composition containing the compound represented by formula (I) can be used in the manufacture of semiconductor devices. Examples of semiconductor devices include personal computers, smartphones, smartwatches, digital cameras, televisions, car navigation systems, printers, liquid crystal displays, electronic dictionaries, game consoles, automobiles, ships, trains, and aircraft.

[0313] The present invention will be described in detail below with reference to examples. The present invention is not limited to these examples. In the following, the room temperature will be 25°C ± 5°C. 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).

[0314] [Example A1: Synthesis of 1-(4-((tert-butyldimethylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate]

[0315] Step 1: Synthesis of 4-((tert-butyldimethylsilyl)oxy)-3-iodo-5-methoxybenzaldehyde

[0316]

[0317] Under light-shielding conditions, prepare a 200 mL three-necked flask, add 48 mL of tetrahydrofuran (THF) and 2.0 g (7.2 mmol) of 4-hydroxy-3-iodo-5-methoxybenzaldehyde, and N ２ Under flow conditions, while cooling with ice to maintain an internal temperature of 10°C, 2.0 mL (14.4 mmol) of triethylamine (TEA), 89.4 mg (0.72 mmol) of DMAP (4-dimethylaminopyridine), and 1.6 g (10.8 mmol) of t-butyldimethylsilyl chloride (TBSCl) were added, and the mixture was stirred for 30 minutes. While cooling with ice to maintain an internal temperature below 10°C, 30 g of saturated ammonium chloride aqueous solution was added dropwise over 10 minutes. 53 g of ethyl acetate and 20 g of deionized water were added, and the mixture was stirred for 15 minutes. After standing, the aqueous layer was drained. The recovered organic layer was concentrated by vacuum distillation until no more solvent components were distilled off to obtain the crude product. The obtained residue was purified by silica gel column chromatography to obtain the target product, 4-((tert-butyldimethylsilyl)oxy)-3-iodo-5-methoxybenzaldehyde (2.82 g, 7.2 mmol). The LC purity of the obtained 4-((tert-butyldimethylsilyl)oxy)-3-iodo-5-methoxybenzaldehyde at 220 nm was 98.1%.

[0318] In this example, all LC (liquid chromatography) measurements were performed according to the following: Instrument name: Shimadzu Corporation (Nexera-i LC-2020C 3D) Column: WaterR Ｙ XBridge BEH C18 (2.5 μm 3.0 × 75 mm) Detector: PDA; Flow rate: 0.7 mL / min, Column oven temperature: 40°C, Autosampler temperature: 15°C, Input volume: 1.0 μL (2 mg / mL THF solution) Eluent (%), Ultrapure water: MeCN: Measured in the range of 1 mass% phosphoric acid aqueous solution (0:98:2) to (93:5:2)

[0319] Step 2: Synthesis of 1-(4-((tert-butyldimethylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-ol

[0320]

[0321] Under light-shielding conditions, prepare a 200 mL three-necked flask, add 48 mL of tetrahydrofuran (THF) and 3.1 g (7.9 mmol) of 4-((tert-butyldimethylsilyl)oxy)-3-iodo-5-methoxybenzaldehyde obtained in step 1 of Example A1, and N ２ Under flow conditions, while cooling with ice to maintain an internal temperature of 10°C, 9.5 mL (9.5 mmol) of a 1.0 M tetrahydrofuran solution of methylmagnesium bromide (MeMgBr) was added dropwise over 10 minutes, and the mixture was stirred for 30 minutes. While cooling with ice to maintain an internal temperature below 10°C, 12 g of saturated ammonium chloride aqueous solution was added dropwise over 10 minutes. 52 g of ethyl acetate and 31 g of deionized water were added, and the mixture was stirred for 15 minutes and allowed to stand before the aqueous layer was removed. The recovered organic layer was concentrated by vacuum distillation until no more solvent components were distilled off to obtain the target product, 1-(4-((tert-butyldimethylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-ol (2.87 g, 7.0 mmol). The LC purity of the obtained 1-(4-((tert-butyldimethylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-ol at 220 nm was 89.0%.

[0322] Step 3: Synthesis of 1-(4-((tert-butyldimethylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate

[0323]

[0324] Under light-shielding conditions, prepare a 200 mL three-necked flask, add 35 mL of tetrahydrofuran (THF), and add 2.87 g (7.0 mmol) of 1-(4-((tert-butyldimethylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-ol obtained in step 2 of Example A1, and N ２ Under flow conditions, while cooling with ice to maintain an internal temperature of 10°C, 1.2 mL (8.4 mmol) of triethylamine, 88.9 mg (0.70 mmol) of DMAP, and 1.6 mL (10.6 mmol) of methacrylic anhydride were added, and the mixture was stirred for 40 minutes. While cooling with ice to maintain an internal temperature below 10°C, 3.1 g of saturated ammonium chloride aqueous solution was added. 30 g of ethyl acetate and 32 g of deionized water were added, and the mixture was stirred for 15 minutes and allowed to stand, after which the aqueous layer was drained. The recovered organic layer was concentrated by vacuum distillation until no more solvent components were distilled off to obtain the crude product. The obtained residue was purified by silica gel column chromatography to obtain the target product, 1-(4-((tert-butyldimethylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate (2.24 g, 4.69 mmol). The LC purity of the obtained 1-(4-((tert-butyldimethylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate at 220 nm was 92.3%.

[0325] 1 H-NMR(500 MHz, DMSO-d6)δ7.31(1H, Ph), 7.03(1H, Ph), 6.08(1H, C=CH2), 5.77(1H, Ph-CH(Me)-O-), 5.71(1H, C=CH2), 3.78(3H, PHOCH3), 1.89(3H, CH3-C=C), 1.48(3H, Ph-CH(CH3)-O-), 1.01(9H, -O-Si(Me2)-C(CH3)3), 0.20(9H, -O-Si-(CH3)2)

[0326] [Example A2: Synthesis of tert-butyl(2-iodo-6-methoxy-4-vinylphenoxy)dimethylsilane]

[0327]

[0328] Under light-shielding conditions, prepare a 200 mL three-necked flask and add 10 mL of tetrahydrofuran (THF) and methyltriphenylphosphonium bromide (MePPh). ３ Add 2.03 g (5.7 mmol) of Br) and N ２ Under flow cooling, while keeping the internal temperature at 10°C with ice, 848 mg (7.6 mmol) of tert-butoxy potassium (t-BuOK) was added and stirred for 30 minutes. With the internal temperature kept below 10°C with ice cooling, 1.48 g (3.78 mmol) of 4-((tert-butyldimethylsilyl)oxy)-3-iodo-5-methoxybenzaldehyde obtained in step 1 of Example A1 was added and stirred for 1 hour. With the internal temperature kept below 10°C with ice cooling, 10 g of saturated ammonium chloride aqueous solution was added. 30 g of toluene and 32 g of deionized water were added, and after stirring for 15 minutes and allowing to stand, the aqueous layer was drained. The recovered organic layer was concentrated by vacuum distillation until no more solvent components distilled off to obtain the crude product. The obtained residue was purified by silica gel column chromatography to obtain the target product, tert-butyl(2-iodo-6-methoxy-4-vinylphenoxy)dimethylsilane. The LC purity of the obtained tert-butyl(2-iodo-6-methoxy-4-vinylphenoxy)dimethylsilane at 220 nm was 94.8%.

[0329] 1 H-NMR(500 MHz, DMSO-d6)δ7.19(1H, Ph), 7.05(1H, Ph), 6.72(1H, Ph-CH=CH2), 5.76(1H, CH=CH2), 5.25(1H, CH=CH2), 3.83(3H, PHOCH3), 0.98(9H, -O-Si(Me2)-C(CH3)3), 0.21(9H, -O-Si-(CH3)2)

[0330] [Example A3: Synthesis of 1-(4-((dimethylphenylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate]

[0331] Step 1: Synthesis of 4-((dimethylphenylsilyl)oxy)-3-iodo-5-methoxybenzaldehyde

[0332]

[0333] Under light-shielding conditions, prepare a 200 mL three-necked flask, add 48 mL of tetrahydrofuran (THF) and 2.0 g (7.2 mmol) of 4-hydroxy-3-iodo-5-methoxybenzaldehyde, and N ２ Under flow conditions, while cooling with ice to maintain an internal temperature of 10°C, 2.0 mL (14.4 mmol) of triethylamine (TEA), 89.8 mg (0.72 mmol) of 4-dimethylaminopyridine (DMAP), and 1.80 mL (10.8 mmol) of dimethylphenylsilyl chloride were added, and the mixture was stirred for 2 hours. While cooling with ice to maintain an internal temperature below 10°C, 50 g of deionized water was added dropwise over 10 minutes. 63 g of ethyl acetate and 20 g of deionized water were added, and the mixture was stirred for 15 minutes and allowed to stand before the aqueous layer was drained. The recovered organic layer was concentrated by vacuum distillation until no more solvent components were distilled off to obtain the crude product. The obtained residue was purified by silica gel column chromatography to obtain the target product, 4-((phenyldimethylsilyl)oxy)-3-iodo-5-methoxybenzaldehyde (2.6 g, 6.2 mmol). The LC purity of the obtained 4-((dimethylphenylsilyl)oxy)-3-iodo-5-methoxybenzaldehyde at 220 nm was 99.2%.

[0334] Step 2: Synthesis of 1-(4-((dimethylphenylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-ol

[0335]

[0336] Under light-shielding conditions, prepare a 200 mL three-necked flask, add 48 mL of tetrahydrofuran (THF) and 2.0 g (4.9 mmol) of 4-((dimethylphenylsilyl)oxy)-3-iodo-5-methoxybenzaldehyde obtained in step 1 of Example A3, and N ２ Under flow conditions, while cooling with ice to maintain an internal temperature of 10°C, 5.8 mL (5.8 mmol) of 1.0 M tetrahydrofuran solution of methylmagnesium bromide was added dropwise over 10 minutes, and the mixture was stirred for 1 hour. While cooling with ice to maintain an internal temperature below 10°C, 10 g of saturated ammonium chloride aqueous solution was added dropwise over 10 minutes. 48 g of ethyl acetate and 28 g of deionized water were added, and the mixture was stirred for 15 minutes and allowed to stand before the aqueous layer was removed. The recovered organic layer was concentrated by vacuum distillation until no more solvent components were distilled off, yielding the target product, 1-(4-((dimethylphenylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-ol (1.9 g, 4.4 mmol). The LC purity of the obtained 1-(4-((dimethylphenylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-ol at 220 nm was 90.4%.

[0337] Step 3: Synthesis of 1-(4-((dimethylphenylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate

[0338]

[0339] Under light-shielding conditions, prepare a 200 mL three-necked flask, add 24 mL of tetrahydrofuran (THF) and 2.0 g (4.7 mmol) of 1-(4-((dimethylphenylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-ol obtained in step 2 of Example A3, and N ２Under flow conditions, while cooling with ice to maintain an internal temperature of 10°C, 0.78 mL (5.6 mmol) of triethylamine, 57.4 mg (0.70 mmol) of 4-dimethylaminopyridine (DMAP), and 1.1 mL (7.1 mmol) of methacrylic anhydride were added, and the mixture was stirred for 1 hour. While cooling with ice to maintain an internal temperature below 10°C, 7.3 g of saturated ammonium chloride aqueous solution was added. 24 g of ethyl acetate and 13 g of deionized water were added, and the mixture was stirred for 15 minutes. After standing, the aqueous layer was drained. The recovered organic layer was concentrated by vacuum distillation until no more solvent components were distilled off to obtain the crude product. The obtained residue was purified by silica gel column chromatography to obtain the target product, 1-(4-((dimethylphenylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate (2.16 g, 4.4 mmol). The LC purity of the obtained 1-(4-((dimethylphenylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate at 220 nm was 99.5%. 1 H-NMR (500 MHz, DMSO-d6) δ 7.32(1H, Ph), 7.27(3H, Ph), 7.18(2H, Ph), 6.84(1H, Ph), 6.22(1H, C=CH2), 6.14(1H, Ph-CH(Me)-O-), 6.05(1H, C=CH2), 3.83(3H, PHOCH3), 1.92(3H, CH3-C=C), 1.49(3H, Ph-CH(CH3)-O-), 0.38(6H, -O-Si-(CH3)2)

[0340] [Example A4: Synthesis of 1-(4-((triethylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate]

[0341]

[0342] Under light-shielding conditions, prepare a 200 mL three-necked flask, add 48 mL of tetrahydrofuran (THF) and 2.0 g (7.2 mmol) of 4-hydroxy-3-iodo-5-methoxybenzaldehyde, and N ２Under flow conditions, while cooling with ice to maintain an internal temperature of 10°C, 2.0 mL (14.4 mmol) of triethylamine (TEA), 88.1 mg (0.72 mmol) of 4-dimethylaminopyridine (DMAP), and 1.8 mL (10.8 mmol) of triethylsilyl chloride (TESCl) were added, and the mixture was stirred for 30 minutes. While cooling with ice to maintain an internal temperature of 10°C, 22 mL (22 mmol) of 1.0 M tetrahydrofuran solution of methylmagnesium bromide was added dropwise over 20 minutes, and the mixture was stirred for 30 minutes. While cooling with ice to maintain an internal temperature of 10°C, 57.4 mg (0.70 mmol) of 4-dimethylaminopyridine (DMAP) and 1.1 mL (7.1 mmol) of methacrylic anhydride were added, and the mixture was stirred for 1 hour. While cooling with ice to maintain an internal temperature below 10°C, 20 g of saturated ammonium chloride aqueous solution was added dropwise over 10 minutes. 60 g of ethyl acetate and 54 g of deionized water were added, and the mixture was stirred for 15 minutes and allowed to stand. The aqueous layer was then drained. The recovered organic layer was concentrated by vacuum distillation until no more solvent components were distilled off to obtain the crude product. The resulting residue was purified by silica gel column chromatography to obtain the target product, 1-(4-((triethyll-silyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate (1.73 g, 3.6 mmol). The LC purity of the obtained 1-(4-((triethylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate at 220 nm was 98.8%. 1 H NMR (500 MHz, CDCl3) δ 7.32(1H, Ph), 6.80(1H, Ph), 6.14(1H, C=CH2), 5.83(1H, Ph-CH(Me)-O-), 5.57(1H, C=CH2), 3.79(3H, PHOCH3), 1.95(3H, CH3-C=C), 1.53(3H, Ph-CH(CH3)-O-), 0.98(6H, -O-Si-(CH2CH3), 0.78(6H, -O-Si-(CH2CH3)

[0343] [Comparative Example A1: Synthesis of 3-iodo-5-methoxy-4-((tetrahydro-2H-pyran-2-yl)oxy)methoxybenzaldehyde]

[0344]

[0345] Under light-shielding conditions, prepare a 200 mL three-necked flask, add 48 mL of dichloromethane and 2.0 g (7.2 mmol) of 4-hydroxy-3-iodo-5-methoxybenzaldehyde, and N ２ Under flow conditions, 55.0 μL (0.72 mmol) of trifluoroacetic acid and 2.6 g (28.8 mmol) of 3,4-dihydro-2H-pyran were added, and the mixture was stirred for 4 hours. While the mixture was cooled with ice to a temperature of 10°C or lower, 30 g of saturated sodium bicarbonate aqueous solution was added dropwise over 10 minutes. 20 g of deionized water was added, the mixture was stirred for 15 minutes, and then allowed to stand before the aqueous layer was removed. The recovered organic layer was concentrated by vacuum distillation until no more solvent components were distilled off to obtain the crude product. However, the intended 3-iodo-5-methoxy-4-((tetrahydro-2H-pyran-2-yl)oxy)methoxybenzaldehyde was not obtained at all.

[0346] [Test Example 1-1: Hydrolysis test of the compound obtained in Example A1 (1-(4-((tert-butyldimethylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate)] Under light-shielding conditions, a 5 mL vial was prepared, and 50 mg of 1-(4-((tert-butyldimethylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate obtained in Example A1, 0.5 mL of methyl isobutyl ketone, and 0.5 mL of 5% by mass p-toluenesulfonic acid aqueous solution were added and stirred at room temperature for 1 hour. 20 μL of triethylamine was added and stirred for 10 minutes. 50 μL of the resulting organic layer was taken and dissolved in 2.0 mL of tetrahydrofuran, and the LC was measured. As a result, no undegraded 1-(4-((tert-butyldimethylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate was detected at 220 nm, while 100% of hydrolyzed 1-(4-hydroxy-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate was detected.

[0347] [Test Example 1-2: Hydrolysis test of the compound obtained in Example A3 (1-(4-((dimethylphenylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate)] Under light-shielding conditions, a 5 mL vial was prepared, and 50 mg of 1-(4-((dimethylphenylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate obtained in Example A3, 0.5 mL of methyl isobutyl ketone, and 0.5 mL of 5% by mass p-toluenesulfonic acid aqueous solution were added and stirred at 40°C for 1 hour. 20 μL of triethylamine was added and stirred for 10 minutes. 50 μL of the resulting organic layer was taken and dissolved in 2.0 mL of tetrahydrofuran and the LC was measured. As a result, LC analysis at 220 nm did not detect any undegraded 1-(4-((dimethylphenylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate, while 100% of hydrolyzed 1-(4-hydroxy-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate was detected.

[0348] [Test Example 1-3: Hydrolysis test of the compound obtained in Example A4 (1-(4-((triethylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate)] Under light-shielding conditions, a 5 mL vial was prepared, and 50 mg of 1-(4-((triethylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate obtained in Example A4, 0.5 mL of methyl isobutyl ketone, and 0.5 mL of 5% by mass p-toluenesulfonic acid aqueous solution were added and stirred at room temperature for 1 hour. 20 μL of triethylamine was added and stirred for 10 minutes. 50 μL of the resulting organic layer was taken and dissolved in 2.0 mL of tetrahydrofuran, and the LC was measured. As a result, LC analysis at 220 nm did not detect any undegraded 1-(4-((triethylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate, while 100% of hydrolyzed 1-(4-hydroxy-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate was detected.

[0349] [Test Example 2: Acid dissociation test of the compound (1-(4-((tert-butyldimethylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate) obtained in Example A1] Under light-shielding conditions, a 50 mL flask was prepared, and 200 mg (0.42 mmol) of 1-(4-((tert-butyldimethylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate obtained in Example A1 and 4.2 mL of methanol were added. Then, at room temperature, TsOH·H ２ 8.0 mg (0.042 mmol) of oxygen was added, and stirring was continued for 20 minutes. 20 g of deionized water was added. 30 mL of ethyl acetate was added, and the mixture was stirred for 15 minutes and allowed to stand, after which the aqueous layer was removed. 20 g of saturated saline solution was then added, and the mixture was stirred for 15 minutes, after which it was allowed to stand, and the aqueous layer was removed. The recovered organic layer was concentrated by reduced-pressure distillation until no more solvent components were distilled off to obtain the crude product. The obtained residue was purified by silica gel column chromatography to obtain the target product, 1-(4-hydroxy-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate (137 mg, 0.38 mmol). The LC purity of the obtained 1-(4-hydroxy-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate at 220 nm was 99.2%.

[0350] Under light-shielding conditions, a 10 mL vial was prepared, and 0.4 g of the obtained hydrolysate, 1-(4-hydroxy-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate, 1.8 g of cyclopentyl methyl ether, 1.8 g of toluene, and 0.4 g of a 1% by mass cyclopentyl methyl ether solution of trifluoromethanesulfonic acid were added. The mixture was stirred at 60°C for 30 minutes. After cooling to room temperature, 50 μL of the organic layer was taken and dissolved in 2.0 mL of tetrahydrofuran, and LC was measured. As a result, at 220 nm, the deprotected product 1-(4-hydroxy-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate was not detected at all, while methacrylic acid was detected at 31.4% and the desorbed product (2-iodo-6-methoxy-4-vinylphenol) at 76.2%.

[0351] [Example B1: Synthesis of polymer B1 using the compound obtained in Example A1 (1-(4-((tert-butyldimethylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate)]

[0352]

[0353] 1.5 g of 1-(4-((tert-butyldimethylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate obtained in Example A1, 4.0 g of 2-methyl-2-adamantyl methacrylate, 0.9 g of γ-butyrolactone methacrylate, and 1.5 g of hydroxyadamantyl methacrylate were dissolved in 45 mL of tetrahydrofuran, and 0.20 g of 2,2'-azobisisobutyronitrile was added. The mixture was refluxed for 12 hours. After cooling to room temperature, 15 mL of 5% by mass p-toluenesulfonic acid aqueous solution was added, and the mixture was stirred for 3 hours. The reaction solution was then added dropwise to 2 L of n-heptane. The precipitated polymer was filtered off and dried under reduced pressure to obtain a white powdery polymer B1 having repeating units (B1a), (B1b), (B1c), and (B1d). The weight-average molecular weight (Mw) of polymer B1 was 12,000, and its dispersion degree (Mw / Mn) was 1.90. Furthermore, １３ ¹³C-NMR measurements revealed that the composition ratio (molar ratio) of repeating units in polymer B1 was (B1a):(B1b):(B1c):(B1d) = 60:10:15:15. The molar ratio of repeating unit (B1d) was determined based on the carbon at the base of the benzene ring, while the molar ratios of repeating units (B1a), (B1b), and (B1c) were determined based on the integral ratio of the carbonyl carbons of the ester bonds. Furthermore, in polymer B1, the arrangement order of each repeating unit is random, and it is not a block copolymer of each repeating unit.

[0354] [Example B2: Synthesis of polymer B2 using the compound obtained in Example A2 (tert-butyl(2-iodo-6-methoxy-4-vinylphenoxy)dimethylsilane)]

[0355]

[0356] 1.5 g of tert-butyl(2-iodo-6-methoxy-4-vinylphenoxy)dimethylsilane obtained in Example A2, 4.0 g of 2-methyl-2-adamantyl methacrylate, 0.9 g of γ-butyrolactone methacrylate, and 1.5 g of hydroxyadamantyl methacrylate were dissolved in 45 mL of tetrahydrofuran, and 0.20 g of 2,2'-azobisisobutyronitrile was added. The mixture was refluxed for 12 hours. After cooling to room temperature, 15 mL of 5% by mass p-toluenesulfonic acid aqueous solution was added, and the mixture was stirred for 3 hours. The reaction solution was then added dropwise to 2 L of n-heptane. The precipitated polymer was filtered off and dried under reduced pressure to obtain a white powdery polymer B2 having repeating units (B2a), (B2b), (B2c), and (B2d). The weight-average molecular weight (Mw) of polymer B2 was 13,000, and its dispersion degree (Mw / Mn) was 1.70. Furthermore, １３ ¹³C-NMR measurements revealed that the composition ratio (molar ratio) of repeating units in polymer B1 was (B2a):(B2b):(B2c):(B2d) = 60:10:15:15. The molar ratio of repeating unit (B2d) was determined based on the carbon at the base of the benzene ring, while the molar ratios of repeating units (B2a), (B2b), and (B2c) were determined based on the integral ratio of the carbonyl carbons of the ester bonds. Furthermore, in polymer B2, the arrangement order of each repeating unit is random, and it is not a block copolymer of each repeating unit.

[0357] [Example B3: Synthesis of polymer B3 using the compound obtained in Example A3 (1-(4-((dimethylphenylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate)]

[0358]

[0359] 1.8 g of 1-(4-((dimethylphenylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate obtained in Example A3, 4.0 g of 2-methyl-2-adamantyl methacrylate, 0.9 g of γ-butyrolactone methacrylate, and 1.5 g of hydroxyadamantyl methacrylate were dissolved in 45 mL of tetrahydrofuran, and 0.20 g of 2,2'-azobisisobutyronitrile was added. The mixture was refluxed for 12 hours. After cooling to room temperature, the reaction solution was added dropwise to 2 L of n-heptane. The precipitated polymer was filtered off and dried under reduced pressure to obtain a white powdery polymer B3 having repeating units (B3a), (B3b), (B3c), and (B3d). The weight-average molecular weight (Mw) of polymer B3 was 13,000, and its dispersion degree (Mw / Mn) was 1.88. Furthermore, １３ ¹³C-NMR measurements revealed that the composition ratio (molar ratio) of repeating units in polymer B3 was (B3a):(B3b):(B3c):(B3d) = 60:10:15:15. The molar ratio of repeating unit (B3d) was determined based on the carbon at the base of the benzene ring, while the molar ratios of repeating units (B3a), (B3b), and (B3c) were determined based on the integral ratio of the carbonyl carbons of the ester bonds. Furthermore, in polymer B3, the arrangement order of each repeating unit is random, and it is not a block copolymer of each repeating unit.

[0360] [Example B4: Synthesis of polymer B4 using the compound (1-(4-((triethylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate) obtained in Example A4]

[0361]

[0362] 1.5 g of 1-(4-((triethylsilyl)oxy)-3-iodo-5-methoxyphenyl)ethane-1-yl methacrylate obtained in Example A4, 4.0 g of 2-methyl-2-adamantyl methacrylate, 0.9 g of γ-butyrolactone methacrylate, and 1.5 g of hydroxyadamantyl methacrylate were dissolved in 45 mL of tetrahydrofuran, and 0.20 g of 2,2'-azobisisobutyronitrile was added. The mixture was refluxed for 12 hours. After cooling to room temperature, the reaction solution was added dropwise to 2 L of n-heptane. The precipitated polymer was filtered off and dried under reduced pressure to obtain polymer B4, a white powder having repeating units (B4a), (B4b), (B4c), and (B4d). The weight-average molecular weight (Mw) of polymer B4 was 12,500, and its dispersion degree (Mw / Mn) was 1.86. Furthermore, １３ ¹³C-NMR measurements revealed that the composition ratio (molar ratio) of repeating units in polymer B4 was (B4a):(B4b):(B4c):(B4d) = 60:10:15:15. The molar ratio of repeating unit (B4d) was determined based on the integral ratio of the carbon at the base of the benzene ring, while the molar ratios of repeating units (B4a), (B4b), and (B4c) were determined based on the integral ratio of the carbonyl carbon of the ester bond. Furthermore, in polymer B4, the arrangement order of each repeating unit is random, and it is not a block copolymer of each repeating unit.

[0363] [Comparative Example B1: Synthesis of polymer B1' using comparative compound (1-(3-iodophenyl)ethyl methacrylate)]

[0364]

[0365] 1.5 g of comparative compound 1-(3-iodophenyl)ethyl methacrylate, 4.0 g of 2-methyl-2-adamantyl methacrylate, 0.9 g of γ-butyrolactone methacrylate, and 1.5 g of hydroxyadamantyl methacrylate were dissolved in 45 mL of tetrahydrofuran, and 0.20 g of 2,2'-azobisisobutyronitrile was added. The mixture was refluxed for 12 hours. After cooling to room temperature, the reaction solution was added dropwise to 2 L of n-heptane. The precipitated polymer was filtered and dried under reduced pressure to obtain a white powdery polymer B1' having repeating units (B1'a), (B1'b), (B1'c), and (B1'd). The weight-average molecular weight (Mw) of polymer B1' was 12,000, and the dispersion degree (Mw / Mn) was 1.90. １３ ¹³C-NMR measurements revealed that the composition ratio (molar ratio) of repeating units in polymer B1' was (B1'a):(B1'b):(B1'c):(B1'd) = 60:10:15:15. The molar ratio was determined based on the integral ratio of each repeating unit (B1'd), which is the carbon at the base of the benzene ring, and the carbonyl carbons of the ester bonds (B1'a), (B1'b), and (B1'c). In polymer B1', the arrangement order of each repeating unit is random, and it is not a block copolymer of each repeating unit.

[0366] [Comparative Example B2: Synthesis of polymer B2' using comparative compound (1-(4-iodo-3-methoxyphenyl)ethyl methacrylate)]

[0367]

[0368] 1.5 g of comparative compound 1-(4-iodo-3-methoxyphenyl)ethyl methacrylate, 4.0 g of 2-methyl-2-adamantyl methacrylate, 0.9 g of γ-butyrolactone methacrylate, and 1.5 g of hydroxyadamantyl methacrylate were dissolved in 45 mL of tetrahydrofuran, and 0.20 g of 2,2'-azobisisobutyronitrile was added. The mixture was refluxed for 12 hours. After cooling to room temperature, the reaction solution was added dropwise to 2 L of n-heptane. The precipitated polymer was filtered off and dried under reduced pressure to obtain a white powdery polymer B2' having repeating units (B2'a), (B2'b), (B2'c), and (B2'd). The weight-average molecular weight (Mw) of polymer B2' was 12,000, and the dispersion degree (Mw / Mn) was 1.90. １３ 1C-NMR measurements revealed that the composition ratio (molar ratio) of repeating units in polymer B2' was (B2'a):(B2'b):(B2'c):(B2'd) = 60:10:15:15. The molar ratio was determined based on the integral ratio of each repeating unit (B2'd), which is the carbon at the base of the benzene ring, and the repeating units (B2'a), (B2'b), and (B2'c), which are based on the carbonyl carbon of the ester bond. In polymer B2', the arrangement order of each repeating unit is random, and it is not a block copolymer of each repeating unit.

[0369] [Comparative Example B3: Synthesis of polymer B3' using comparative compound (1-iodo-3-vinylbenzene)]

[0370]

[0371] 1.5 g of the comparative compound 1-iodo-3-vinylbenzene, 4.0 g of 2-methyl-2-adamantyl methacrylate, 0.9 g of γ-butyrolactone methacrylate, and 1.5 g of hydroxyadamantyl methacrylate were dissolved in 45 mL of tetrahydrofuran, and 0.20 g of 2,2'-azobisisobutyronitrile was added. The mixture was refluxed for 12 hours. After cooling to room temperature, the reaction solution was added dropwise to 2 L of n-heptane. The precipitated polymer was filtered off and dried under reduced pressure to obtain a white powdery polymer B3' having repeating units (B3'a), (B3'b), (B3'c), and (B3'd). The weight-average molecular weight (Mw) of polymer B3' was 12,000, and the dispersion degree (Mw / Mn) was 1.90. １３ 1C-NMR measurements revealed that the composition ratio (molar ratio) of repeating units in polymer B2 was (B3'a):(B3'b):(B3'c):(B3'd) = 60:10:15:15. The molar ratio was determined based on the integral ratio of each repeating unit (B3'd), which is the carbon at the base of the benzene ring, and the repeating units (B3'a), (B3'b), and (B3'c), which are based on the carbonyl carbon of the ester bond. In polymer B3', the arrangement order of each repeating unit is random, and it is not a block copolymer of each repeating unit.

[0372] [Comparative Example B4: Synthesis of Polymer B4' using Comparative Compound (1-iodo-2-methoxy-4-vinylbenzene)]

[0373]

[0374] 1.5 g of the comparative compound 1-iodo-2-methoxy-4-vinylbenzene, 4.0 g of 2-methyl-2-adamantyl methacrylate, 0.9 g of γ-butyrolactone methacrylate, and 1.5 g of hydroxyadamantyl methacrylate were dissolved in 45 mL of tetrahydrofuran, and 0.20 g of 2,2'-azobisisobutyronitrile was added. The mixture was refluxed for 12 hours. After cooling to room temperature, the reaction solution was added dropwise to 2 L of n-heptane. The precipitated polymer was filtered off and dried under reduced pressure to obtain a white powdery polymer B4' having repeating units (B4'a), (B4'b), (B4'c), and (B4'd). The weight-average molecular weight (Mw) of polymer B4' was 12,000, and the dispersion degree (Mw / Mn) was 1.90. １３ ¹³C-NMR measurements revealed that the composition ratio (molar ratio) of repeating units in polymer B4' was (B4'a):(B4'b):(B4'c):(B4'd) = 60:10:15:15. The molar ratio was determined based on the integral ratio of each repeating unit (B4'd), which is the carbon at the base of the benzene ring, and the repeating units (B4'a), (B4'b), and (B4'c), which are based on the carbonyl carbon of the ester bond. In polymer B4', the arrangement order of each repeating unit is random, and it is not a block copolymer of each repeating unit.

[0375] [Test Example 3-1: EUV Sensitivity Evaluation by TMAH Aqueous Solution Development] A solution (resist composition) was prepared by blending 5 parts by mass of the polymer obtained in the Examples and Comparative Examples, 1 part by mass of triphenylsulfonium nonafluorobutanesulfonate, 0.2 parts by mass of tributylamine, 80 parts by mass of propylene glycol monomethyl ether acetate (PGMEA), and 12 parts by mass of propylene glycol monomethyl ether (PGME). The solution was applied to a silicon wafer and baked at 110°C for 60 seconds to form a photoresist layer with a thickness of 100 nm. Then, it was exposed to extreme ultraviolet (EUV) light at 1 mJ / cm using the "EUVES-7000" (product name, manufactured by Lithotech Japan Co., Ltd.) lithography apparatus. ２ From 1 mJ / cm ２ 80 mJ / cm ２After performing maskless shot exposure with increasing exposure, the wafer was baked (PEB) at 110°C for 90 seconds and 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 was obtained. The exposure value at which the slope of film thickness variation with respect to exposure was largest was set to the sensitivity value (mJ / cm²). ２ The following criteria were used to calculate the EUV sensitivity of the resist and to evaluate its sensitivity.

[0376] (Evaluation Criteria) A: Sensitivity value ≤ 15 mJ / cm ２ B: 15 mJ / cm ２ < Sensitivity value ≤ 20 mJ / cm ２ C: 20 mJ / cm ２ < Sensitivity value ≤ 25 mJ / cm ２ D: 25 mJ / cm ２ < Sensitivity value

[0377] [Test Example 3-2: EB Pattern Evaluation by TMAH Aqueous Solution Development] A solution (resist composition) was prepared by blending 5 parts by mass of the polymer obtained in the Examples and Comparative Examples, 1 part by mass of triphenylsulfonium nonafluorobutanesulfonate, 0.1 parts by mass of tributylamine, and 92 parts by mass of PGMEA. The solution was applied to 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" (product name, manufactured by Elionix Co., Ltd., 50 keV), baked at 115°C for 90 seconds (PEB), and developed with a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds to obtain a positive pattern. The exposure amount was adjusted to achieve a half-pitch of 50 nm line and space. For the obtained resist patterns, 80 pattern images were acquired at a magnification of 100,000x using a scanning electron microscope "S-4800" (product name, manufactured by Hitachi, Ltd.). The number of residues in the spaces between the resist patterns was counted, and the total amount of residue was used for evaluation. The evaluation criteria are as follows:

[0378] (Evaluation Criteria) A: Number of residues ≤ 10 B: 10 < Number of residues ≤ 80 C: 80 < Number of residues ≤ 400 D: 400 < Number of residues

[0379] [Test Example 4-1: EUV Sensitivity Evaluation by Organic Solvent Development] Using the same method as in Test Example 3-1, a solution (resist composition) containing the polymer obtained in the example or comparative example was prepared, coated onto a silicon wafer, and baked at 110°C for 60 seconds to form a photoresist layer with a thickness of 100 nm. Then, an extreme ultraviolet (EUV) exposure system "EUVES-7000" (product name, manufactured by Lithotech Japan Co., Ltd.) was used to expose the wafer at 1 mJ / cm². ２ From 1 mJ / cm ２ 80 mJ / cm ２After performing maskless shot exposure with increasing exposure, the wafer was baked (PEB) at 110°C for 90 seconds, developed with butyl acetate for 30 seconds, and obtained 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 was obtained. The exposure value at which the slope of film thickness variation with respect to exposure was largest was set as the sensitivity value (mJ / cm²). ２ The following criteria were used to calculate the EUV sensitivity of the resist and to evaluate its sensitivity.

[0380] (Evaluation Criteria) A: Sensitivity value ≤ 15 mJ / cm ２ B: 15 mJ / cm ２ < Sensitivity value ≤ 20 mJ / cm ２ C: 20 mJ / cm ２ < Sensitivity value ≤ 25 mJ / cm ２ D: 25 mJ / cm ２ < Sensitivity value

[0381] [Test Example 4-2: EB Pattern Evaluation by Organic Solvent Development] Using the same method as in Test Example 3-2, a solution (resist composition) containing the polymer obtained in the example or comparative example was prepared, 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 with an electron beam lithography system "ELS-7500" (product name, manufactured by Elionix Co., Ltd., 50 keV), baked at 115°C for 90 seconds (PEB), and developed with butyl acetate for 60 seconds to obtain a negative-type pattern. The exposure amount was adjusted so that the half-pitch was 50 nm line and space. Eighty pattern images were acquired of the obtained resist pattern at a magnification of 100,000x using a scanning electron microscope "S-4800" (product name, manufactured by Hitachi, Ltd.), and the number of residues in the space between the resist patterns was counted, and the evaluation was performed from the total amount of residue. The evaluation criteria are as follows.

[0382] (Evaluation Criteria) A: Number of residues ≤ 10 B: 10 < Number of residues ≤ 80 C: 80 < Number of residues ≤ 400 D: 400 < Number of residues

[0383] Table 1 summarizes the results of Test Examples 3-1 and 3-2, and Test Examples 4-1 and 4-2, for Examples A1 to A12, comparative compounds, and their corresponding Examples B1 to B4 and Comparative Examples B1 to B4, separately for Examples and Comparative Examples. In Table 1, TBS means tert-butyldimethylsilyl group, TES means triethylsilyl group, and DMPS means dimethylphenylsilyl group.

[0384]

[0385] As shown in Table 1, silyl protecting groups (SiR ４ R ５ R ６ It was confirmed that by using the polymer of this embodiment obtained using the compound of this embodiment represented by formula (I) having a hydroxyl group protected by a silyl protecting group, EUV sensitivity can be further improved and residue in the space between resist patterns can be further reduced (exposure stability) compared to using a compound that does not have a hydroxyl group protected by a silyl protecting group.

[0386] This application claims priority to a Japanese patent application (Japanese Patent Application No. 2024-193759) filed on 5 November 2024, the entire contents of said application being deemed to be part of the disclosure of this application and incorporated herein by reference.

Claims

1. Equation (I): [In the formula, ring A represents an aromatic ring or a non-aromatic ring; R １ R represents a hydrogen atom, a methyl group, or a halogen atom; ２ and R ３ Each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent; R ４ , R ５ and R ６ Each independently represents a hydrocarbon group which may have substituents; R ７ A compound represented by [where a and b each independently represent a substituent; a and b each independently represent an integer of 1 or more; c represents 0 or an integer of 1 or more; n represents 0, 1, 2, or 3; and m represents 0 or 1].

2. The compound according to claim 1, wherein ring A is a 6- to 14-membered aromatic carbon ring or a 5- to 14-membered non-aromatic carbon ring.

3. The compound according to claim 1, wherein (A) m is 0, or (B) n is 1 and m is 1.

4. Formula (1) or (2): [In the formula, ring A' represents an aromatic carbon ring having 6 to 14 members or a non-aromatic carbon ring having 5 to 14 members; R １１ represents a hydrogen atom or a methyl group; R ２１ and R ３１ each independently represent a hydrogen atom or an alkyl group; R ４ , R ５ and R ６ each independently represent a hydrocarbon group which may have a substituent; R ７ each independently represents a substituent; a and b each independently represent an integer of 1 or more; c represents 0 or an integer of 1 or more.], the compound according to claim 1.

5. Formulas (1a) to (2r): [In the formula, R １１ R represents a hydrogen atom or a methyl group; ２１ and R ３１ Each 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, and R ａ , R ｂ , R ｃ , R ｄ and R ｅ Of these, at least one displayed in each formula is -OSiR ４ R ５ R ６ And; R ４ , R ５ and R ６ Each of these independently represents a hydrocarbon group which may have substituents. The compound according to claim 1, represented by any of the following:

6. A compound having an iodine atom and a hydroxyl group is subjected to X-SiR under basic conditions. ４ R ５ R ６ (In the formula, R ４ , R ５ and R ６ Each independently represents a hydrocarbon group which may have substituents; X represents a halogen atom. ) is reacted with a compound represented by to obtain an iodine atom and -OSiR ４ R ５ R ６ A method for producing a compound according to any one of claims 1 to 5, comprising the step of converting into a compound having a group represented by .

7. A composition for producing a lithography film-forming material, comprising the compound described in any one of claims 1 to 5.

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

9. A composition comprising a compound according to any one of claims 1 to 5, and a radical polymerization initiator.

10. (1) A compound according to any one of claims 1 to 5, and (2) 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.

11. A composition comprising a compound according to any one of claims 1 to 5, and a (meth)acrylic acid ester compound having an adamantane skeleton.

12. A composition comprising a compound according to any one of claims 1 to 5, and a (meth)acrylic acid ester compound having a lactone skeleton.

13. Formula (UI): [In the formula, ring A represents an aromatic ring or a non-aromatic ring; R １ R represents a hydrogen atom, a methyl group, or a halogen atom; ２ and R ３ Each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent; R ４ , R ５ and R ６ Each independently represents a hydrocarbon group which may have substituents; R ７ A polymer having repeating units represented by ], where each independently represents a substituent; a and b each independently represent an integer of 1 or more; c represents 0 or an integer of 1 or more; n represents 0, 1, 2, or 3; and m represents 0 or 1.

14. The polymer according to claim 13, 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.

15. The polymer according to claim 13, further comprising repeating units derived from an adamantane skeleton (meth)acrylic acid ester compound.

16. The polymer according to claim 13, further comprising repeating units derived from a (meth)acrylic acid ester compound having a lactone skeleton.

17. The polymer according to claim 13, wherein the weight-average molecular weight (Mw) is 5,000 to 30,000.

18. A lithography composition comprising the polymer according to any one of claims 13 to 17.

19. A resist composition comprising the polymer according to any one of claims 13 to 17.

20. A composition comprising the polymer according to any one of claims 13 to 17 and an acid generator.

21. A method for manufacturing a semiconductor integrated circuit, comprising: (aiii) forming a photoresist layer containing a polymer according to any one of claims 13 to 17 on a substrate; (aiii) exposing the photoresist layer formed in step (aiii) to light; and (aiv) developing the photoresist layer exposed in step (aiii).

22. A method for manufacturing a semiconductor integrated circuit, comprising: (bi) a step of treating a polymer according to any one of claims 13 to 17 with an acid to obtain a polymer containing a hydroxyl group; (biii) a step of forming a photoresist layer on a substrate containing the polymer containing a hydroxyl group obtained in step (bi); (biii) a step of exposing the photoresist layer formed in step (bii); and (biv) a step of developing the photoresist layer exposed in step (biii).

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