Iodine-containing (meth-) acrylic acid ester compound and method for producing iodine hydroxyl group-containing polymer

Abstract

The present invention addresses the problem of providing a compound which has excellent storage stability and is useful in the production of a photoresist layer-forming material with which it is possible to further improve EUV sensitivity and temporal stability. The problem is solved by a compound represented by formula (I) or formula (II). Ring A is an aromatic ring, ring B is a nonaromatic heterocyclic ring, R1 is hydrogen or methyl, R2 is a substituted or unsubstituted hydrocarbon group, R3 is hydrogen or a substituted or unsubstituted hydrocarbon group, R4 are substituents at least one of which being iodine, R5 is a substituent, R6 is a straight chain or branched chain alkyl group, X is O or S, a, b, and c, are each one or more, and d is 0 or 1.

Description

Iodine-containing (meth)acrylic acid ester compound and method for producing iodine- and hydroxyl-containing polymer

[0001] The present invention relates to an iodine-containing (meth)acrylic acid ester compound and a method for producing an iodine- and hydroxyl-containing polymer using the same.

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

[0003] Conventional resist materials are polymeric resist materials capable of forming amorphous films. Conventionally, a thin resist film is prepared by applying a solution of the resist composition onto a substrate, and then irradiating the thin resist film with ultraviolet light, far ultraviolet light, electron beams, extreme ultraviolet light, or the like to form a line pattern of approximately 10 to 100 nm.

[0004] Furthermore, the reaction mechanism of electron beam or extreme ultraviolet lithography differs from that of conventional photolithography. Furthermore, electron beam or extreme ultraviolet lithography aims to form fine patterns of several nanometers to several tens of nanometers. As the dimensions of resist patterns become smaller, resist compositions with even higher sensitivity to the exposure light source are required. In particular, extreme ultraviolet lithography requires even higher sensitivity in terms of throughput.

[0005] As a resist layer forming material that overcomes the above-mentioned problems, for example, a polymer using iodine and a (meth)acrylic acid ester compound containing a phenolic hydroxyl group has been proposed (see, for example, Patent Documents 1 and 2).

[0006] JP 2021-188041 A International Publication No. 2020 / 137935 A

[0007] However, in conventional (meth)acrylic acid ester compounds containing phenolic hydroxyl groups, the acidity of the phenolic hydroxyl groups accelerates decomposition of the acid-labile structure during heating during the polymerization reaction. Furthermore, the phenolic hydroxyl groups may cause chain transfer, resulting in a decrease in the introduction rate of the corresponding structural unit. It is also known that conventional (meth)acrylic acid ester compounds containing phenolic hydroxyl groups trap radicals, making it difficult to stably obtain a polymer. While a method of protecting the phenolic hydroxyl groups with a protecting group and polymerizing them is also conceivable, it is desirable to avoid deprotection under basic conditions because the iodine atom is unstable to bases. Furthermore, even when deprotection is performed under acidic conditions, the (meth)acrylic acid ester structure itself may decompose during deprotection, making it difficult to obtain the desired polymer containing iodine and hydroxyl groups (sometimes referred to herein as an "iodine-hydroxyl group-containing polymer"). A method is also known in which a resist layer is formed directly from a polymer with protected hydroxyl groups, and the structural units are decomposed simultaneously with deprotection during exposure, but this method fails to achieve sufficient EUV sensitivity or stability over time. Furthermore, there is also a problem with the storage stability of the (meth)acrylic acid ester compound itself.

[0008] An object of the present invention is to provide a compound that is useful for producing a photoresist layer-forming material that can further improve EUV sensitivity and stability over time and that has excellent storage stability; a method for producing a polymer that is useful as a photoresist layer-forming material using the compound; and a composition that can further improve the storage stability of the compound.

[0009] Means for Solving the Problems of the Invention The present inventors have conducted extensive research to achieve the objects of the present invention and have found that the above-mentioned problems can be solved by using a specific iodine-containing (meth)acrylic acid ester compound, thereby completing the present invention.

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

[0011]

[0012] wherein ring A represents a 6- to 14-membered aromatic ring; each ring B independently represents a 5- to 14-membered non-aromatic heterocycle; １ each independently represents a hydrogen atom or a methyl group; R ２ each independently represents a hydrocarbon group which may have a substituent; R ３ each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent; R ４ each independently represents a substituent, and c R ４ At least one of R represents an iodine atom; ５ each independently represents a substituent; R ６ each independently represent a linear or branched alkyl group; each X independently represent O or S; each a, b, and c independently represent an integer of 1 or more; and each d independently represent 0 or an integer of 1 or more.] A composition comprising two or more compounds selected from the group consisting of compounds represented by formula (1) and / or formula (2):

[0013]

[0014] [Wherein, ring A represents a 6- to 14-membered aromatic ring; R １ represents a hydrogen atom or a methyl group; R ２１ represents an alkyl group; R ４ each independently represents a substituent, and c R ４ at least one of the formula (1'): represents an iodine atom; and b and c each independently represent an integer of 1 or more.

[0015]

[0016] [Wherein, ring A represents a 6- to 14-membered aromatic ring; R １ represents a hydrogen atom or a methyl group; R ２１ represents an alkyl group; R ４ each independently represents a substituent, and c R４ at least one of represents an iodine atom; １ and c each independently represent an integer of 1 or more; ２ represents an integer of 0 or 1 or more.]. [3] The composition according to the above [1], comprising both a compound represented by formula (I) or formula (II):

[0017]

[0018] wherein ring A represents a 6- to 14-membered aromatic ring; each ring B independently represents a 5- to 14-membered non-aromatic heterocycle; １ each independently represents a hydrogen atom or a methyl group; R ２ each independently represents a hydrocarbon group which may have a substituent; R ３ each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent; R ４ each independently represents a substituent, and c R ４ At least one of R represents an iodine atom; ５ each independently represents a substituent; R ６ each independently represent a linear or branched alkyl group; each X independently represent O or S; each a, b, and c independently represent an integer of 1 or more; and each d independently represent 0 or an integer of 1 or more.] [4] A compound represented by formula (1):

[0019]

[0020] [Wherein, ring A represents a 6- to 14-membered aromatic ring; R １ represents a hydrogen atom or a methyl group; R ２１ represents an alkyl group; R ４ each independently represents a substituent, and c R ４ at least one of the following represents an iodine atom; and b and c each independently represent an integer of 1 or greater.] [5] The compound according to the above [3], represented by formula (1a) to formula (1i):

[0021]

[0022] [In the formula, R １ represents a hydrogen atom or a methyl group; R ２１ represents an alkyl group; R ４１ , R ４２ , R ４３ , R ４４ and R ４５ are each independently a hydrogen atom, -R ４ｘ , -OR ４ｘ , -COR ４ｘ , -OCOR ４ｘ , -COOR ４ｘ or an iodine atom, and R ４１ , R ４２ , R ４３ , R ４４ and R ４５ At least one of the groups represented in each formula represents an iodine atom; R ４ｘ represents an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-substituted aryl group, an alkyl-substituted aralkyl group, an alkenyl-substituted aryl group, or an alkenyl-substituted aralkyl group.] [6] The compound according to [5] above, represented by formula (1a) or formula (1c). [7] Formula (1'):

[0023]

[0024] [Wherein, ring A represents a 6- to 14-membered aromatic ring; R １ represents a hydrogen atom or a methyl group; R ２１ represents an alkyl group; R ４ each independently represents a substituent, and c R ４ at least one of represents an iodine atom; １ and c each independently represent an integer of 1 or more; ２ represents an integer of 0 or 1 or more.]. [8] The compound according to the above [3], represented by formula (1a') to formula (1ib'):

[0025]

[0026]

[0027] [In the formula, R １ represents a hydrogen atom or a methyl group; R ２１ represents an alkyl group; R ４１ , R ４２ , R ４３ , R ４４ and R ４５ are each independently a hydrogen atom, -R ４ｘ , -OR ４ｘ , -COR ４ｘ , -OCOR ４ｘ , -COOR ４ｘ or an iodine atom, and R ４１ , R ４２ , R ４３ , R ４４ and R ４５ At least one of the groups represented in each formula represents an iodine atom; R ４ｘ represents an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-substituted aryl group, an alkyl-substituted aralkyl group, an alkenyl-substituted aryl group, or an alkenyl-substituted aralkyl group.] [9] The compound according to [8] above, represented by formula (1a') or formula (1c').

[10] Formula (2):

[0028]

[0029] [Wherein, ring A represents a 6- to 14-membered aromatic ring; R １ represents a hydrogen atom or a methyl group; R ２１ represents an alkyl group; R ４ each independently represents a substituent, and c R ４ at least one of the following represents an iodine atom; and b and c each independently represent an integer of 1 or greater.]

[11] The compound according to the above [3], represented by formula (2a) to formula (2i):

[0030]

[0031] [In the formula, R １ represents a hydrogen atom or a methyl group; R ２１ represents an alkyl group; R ４１ , R ４２, R ４３ , R ４４ and R ４５ are each independently a hydrogen atom, -R ４ｘ , -OR ４ｘ , -COR ４ｘ , -OCOR ４ｘ , -COOR ４ｘ or an iodine atom, and R ４１ , R ４２ , R ４３ , R ４４ and R ４５ At least one of the groups represented in each formula represents an iodine atom; R ４ｘrepresents an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-substituted aryl group, an alkyl-substituted aralkyl group, an alkenyl-substituted aryl group, or an alkenyl-substituted aralkyl group.]

[12] The compound according to

[11] above, represented by formula (2a) or formula (2c).

[13] A composition for producing a photoresist layer-forming material, comprising the compound according to any of [3] to

[12] above.

[14] A composition comprising the compound according to any of [3] to

[12] above and a radical polymerization initiator.

[15] A composition comprising the compound according to any of [3] to

[12] above and a (meth)acrylic acid ester compound having an adamantane skeleton.

[16] A composition comprising the compound according to any of [3] to

[12] above and a (meth)acrylic acid ester compound having a lactone skeleton.

[17] A composition comprising the compound according to any one of [3] to

[12] above, a (meth)acrylic acid ester compound having an adamantane skeleton, and a (meth)acrylic acid ester compound having a lactone skeleton.

[18] A method for producing a polymer containing iodine and hydroxyl groups (iodine-hydroxyl group-containing polymer), comprising the steps of heating or irradiating a composition containing the compound according to any one of [3] to

[12] above, and further treating it with an acid to obtain a polymer containing iodine and hydroxyl groups (iodine-hydroxyl group-containing polymer).

[19] A method for producing an electronic device, comprising: (i) a step of heating or irradiating a composition containing the compound according to any one of the above [3] to

[12] with light, and further treating it with an acid to obtain a polymer containing iodine and a hydroxyl group (iodine-hydroxyl group-containing polymer), (ii) a step of forming a photoresist layer containing the polymer containing iodine and a hydroxyl group (iodine-hydroxyl group-containing polymer) obtained in the step (i) on a substrate, (iii) a step of exposing the photoresist layer formed in the step (ii), and (iv) a step of developing the photoresist layer exposed in the step (iii).

[20] A method for producing an electronic device, comprising: a compound represented by the formula (UI) and / or the formula (UII):

[0032]

[0033] wherein ring A represents a 6- to 14-membered aromatic ring; each ring B independently represents a 5- to 14-membered non-aromatic heterocycle;１ each independently represents a hydrogen atom or a methyl group; R ２ each independently represents a hydrocarbon group which may have a substituent; R ３ each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent; R ４ each independently represents a substituent, and c R ４ At least one of R represents an iodine atom; ５ each independently represents a substituent; R ６ each independently represent a straight-chain or branched-chain alkyl group; each X independently represent O or S; a, b, and c independently represent an integer of 1 or greater; and each d independently represent 0 or an integer of 1 or greater.] A polymer having a structural unit represented by the following formula (iodine-ether structure-containing polymer).

[21] The polymer according to

[20] above (iodine-ether structure-containing polymer), further having a repeating unit derived from a (meth)acrylic acid ester compound having an adamantane skeleton and / or a repeating unit derived from a (meth)acrylic acid ester compound having a lactone skeleton.

[22] A resist composition containing the polymer according to

[20] or

[21] above (iodine-ether structure-containing polymer).

[0034] The compound of the present invention has excellent storage stability, and the method for producing a polymer of the present invention using the compound of the present invention makes it possible to produce a photoresist layer-forming material that can further improve EUV sensitivity and stability over time. Furthermore, the composition of the present invention containing two or more compounds of the present invention can further improve the storage stability of the compound.

[0035] The present invention will be described in detail below with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and can be implemented with any modifications within the scope of the claims of the present invention and their equivalents.

[0036] <<Compound for producing a photoresist layer-forming material>> This embodiment provides a compound represented by formula (I) and formula (II):

[0037]

[0038] wherein ring A represents a 6- to 14-membered aromatic ring; each ring B independently represents a 5- to 14-membered non-aromatic heterocycle; R １ each independently represents a hydrogen atom or a methyl group; R ２ each independently represents a hydrocarbon group which may have a substituent; R ３ each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent; R ４ each independently represents a substituent, and c R ４ at least one of R represents an iodine atom; ５ each independently represents a substituent; R ６ each independently represent a linear or branched alkyl group; each X independently represent O or S; a, b, and c independently represent an integer of 1 or greater; and each d independently represent 0 or an integer of 1 or greater. Such a compound allows the production of a photoresist layer-forming material that can further improve EUV sensitivity and stability over time. More specifically, by producing a resist-forming material such as a resist composition (e.g., a photoresist layer-forming material, which will be described in detail later) using a compound represented by either Formula (I) or Formula (II) as a raw material, the EUV sensitivity and stability over time of the resist obtained using such a resist-forming material are further improved.

[0039] Ring A is a 6- to 14-membered aromatic ring.

[0040] In this specification, an aromatic ring refers to a ring that conforms to Huckel's rule, in which the number of electrons contained in the π electron system on the ring is 4p+2 (p is a natural number). The aromatic ring may be an aromatic carbocyclic ring containing only carbon atoms as ring-constituting atoms, or an aromatic heterocyclic ring containing, in addition to carbon atoms, one or more (e.g., 1 to 4) heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms as ring-constituting atoms, but an aromatic carbocyclic ring is preferred. The aromatic ring may be a monocyclic aromatic ring or a polycyclic aromatic ring. Examples of aromatic rings include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring.

[0041] In one embodiment, each ring A is independently preferably a 6- to 14-membered aromatic carbon ring, more preferably a benzene ring or a naphthalene ring, and particularly preferably a benzene ring.

[0042] Each ring B independently represents a 5- to 14-membered non-aromatic heterocycle.

[0043] In this specification, a non-aromatic heterocycle refers to a ring other than an aromatic ring that has aromaticity throughout the ring, and that has, in addition to carbon atoms, one or more (e.g., 1 to 4) heteroatoms such as oxygen atoms, nitrogen atoms, or sulfur atoms as ring-constituting atoms. The non-aromatic heterocycle may be a monocyclic non-aromatic heterocycle or a polycyclic non-aromatic heterocycle, or may be a fused ring in which an aromatic ring is fused to a portion thereof to thereby have partial aromaticity. The non-aromatic heterocycle may be a saturated ring consisting of only a single bond, or an unsaturated ring having a double bond in addition to a single bond. The non-aromatic heterocycle represented by Ring B is an oxygen-containing non-aromatic heterocycle or a sulfur-containing non-aromatic heterocycle. Examples of non-aromatic heterocycles include oxygen-containing non-aromatic heterocycles such as a tetrahydrofuran ring, a tetrahydropyran ring, a 1,4-dioxane ring, a 1,4-thioxane ring, and an oxepane ring, and sulfur-containing non-aromatic heterocycles such as a tetrahydrothiophene ring, a thiane ring, and a 1,4-dithiane ring.

[0044] In one embodiment, each ring B is independently preferably a 5- to 10-membered non-aromatic heterocycle, more preferably a 5- to 8-membered non-aromatic heterocycle, even more preferably a 5- or 6-membered non-aromatic heterocycle, and particularly preferably a tetrahydropyran ring. When ring B is any of these rings, the EUV sensitivity and stability over time of the resulting resist are further improved.

[0045] R １ each independently represents a hydrogen atom or a methyl group.

[0046] R ２ each independently represents a hydrocarbon group which may have a substituent.

[0047] In this specification, a hydrocarbon group refers to a group whose constituent atoms are only 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, alkyl-substituted aralkyl groups, alkenyl-substituted aryl groups, and alkenyl-substituted aralkyl groups.

[0048] In this specification, the term "alkyl group" refers to a linear, branched, and / or cyclic monovalent aliphatic saturated hydrocarbon group. Unless otherwise specified, the number of carbon atoms in the alkyl group is preferably 1 to 18, more preferably 1 to 10, and even more preferably 1 to 6. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a sec-pentyl group, a neopentyl group, a tert-pentyl group, a hexyl group, an isohexyl group, a heptyl group, an isoheptyl group, an octyl group, an isooctyl group, a tert-octyl group, a cyclopentyl group, a cyclohexyl group, and a cyclohexylmethyl group. Note that the linear or branched alkyl group does not include an alkyl group having a cyclic structure.

[0049] In this specification, the term "alkenyl group" refers to 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 the alkenyl group include a vinyl group, a propenyl group (allyl group, 1-propenyl group, isopropenyl group), a butenyl group (1-butenyl group, crotyl group, methallyl group, isocrotyl group, etc.), a pentenyl group (1-pentenyl group, etc.), a hexenyl group (1-hexenyl group, etc.), a heptenyl group (1-heptenyl group, etc.), an octenyl group (1-octenyl group, etc.), a cyclopentenyl group (2-cyclopentenyl group, etc.), and a cyclohexenyl group (3-cyclohexenyl group, etc.).

[0050] In this specification, an aryl group refers to a monovalent aromatic hydrocarbon group formed by removing one hydrogen atom from an aromatic carbon ring. Unless otherwise specified, the number of carbon atoms in the aryl group is preferably 6 to 18, and particularly preferably 6 to 10. Examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

[0051] In this specification, an aralkyl group refers to an alkyl group substituted with one or more (preferably one) aryl groups. Unless otherwise specified, the number of carbon atoms in the aralkyl group is preferably 7 to 19, and particularly preferably 7 to 11. Examples of 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, and a 2-naphthylmethyl group.

[0052] In this specification, an alkyl-substituted aryl group refers to an aryl group substituted with one or more alkyl groups. Unless otherwise specified, the number of carbon atoms in the alkyl-substituted aryl group is preferably 7 to 19, and particularly preferably 7 to 11. Examples of 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, and a 2-ethylphenyl group.

[0053] In this specification, an alkyl-substituted aralkyl group refers to an aralkyl group in which the aryl moiety is substituted with one or more alkyl groups. Unless otherwise specified, the number of carbon atoms in the alkyl-substituted aralkyl group is preferably 8 to 20, and particularly preferably 8 to 12. Examples of the alkyl-substituted aralkyl group include a 4-methylbenzyl group, a 3-methylbenzyl group, a 2-methylbenzyl group, a 2,4-dimethylbenzyl group, a 3,5-dimethylbenzyl group, a 2,4,6-trimethylbenzyl group, a 4-ethylbenzyl group, a 3-ethylbenzyl group, and a 2-ethylbenzyl group.

[0054] In this specification, an alkenyl-substituted aryl group refers to an aryl group substituted with one or more alkenyl groups. Unless otherwise specified, the number of carbon atoms in the alkenyl-substituted aryl group is preferably 8 to 20, and particularly preferably 8 to 12. Examples of the alkenyl-substituted aryl group include a 4-vinylphenyl group, a 3-vinylphenyl group, a 2-vinylphenyl group, a 2,4-divinylphenyl group, a 3,5-divinylphenyl group, a 4-isopropenylphenyl group, a 3-isopropenylphenyl group, a 2-isopropenylphenyl group, and a 4-allylphenyl group.

[0055] In this specification, an alkenyl-substituted aralkyl group refers to an aralkyl group in which the aryl moiety is substituted with one or more alkenyl groups. Unless otherwise specified, the number of carbon atoms in the alkenyl-substituted aralkyl group is preferably 9 to 20. Examples of the alkenyl-substituted aralkyl group include a 4-vinylbenzyl group, a 3-vinylbenzyl group, a 2-vinylbenzyl group, a 2,4-divinylbenzyl group, a 3,5-divinylbenzyl group, a 4-isopropenylbenzyl group, a 3-isopropenylbenzyl group, a 2-isopropenylbenzyl group, and a 4-allylbenzyl group.

[0056] R ２ Examples of the "substituent" of the "hydrocarbon group which may have a substituent" represented by the formula (I) include a monovalent group consisting of one or more (preferably 1 to 40, more preferably 1 to 20) skeletal atoms selected from carbon, oxygen, nitrogen, sulfur, and silicon atoms, and, when a bonding position exists on the skeletal atom, a non-skeletal atom selected from a hydrogen atom and a halogen atom bonded to the bonding position in addition to the skeletal atom, or a halogen atom, and more specifically, -OR ２ｘ , -COR ２ｘ , -OCOR ２ｘ , -COOR ２ｘ , -SR ２ｘ , -SOR ２ｘ , -SO ２ R ２ｘ , -NHR ２ｘ , -N(R ２ｘ ) ２ , -CONHR ２ｘ , -CON(R２ｘ ) ２ , -NHCOR ２ｘ , -NO ２ , -CN, -CHO, -OH, -SH, -NH ２ , —COOH, halogen atoms, etc. ２ｘ each independently represents a hydrocarbon group which may be substituted with a halogen atom.

[0057] In this specification, a halogen atom refers to a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0058] In this specification, examples of the hydrocarbon group which may be substituted with a halogen atom include an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-substituted aryl group, an alkyl-substituted aralkyl group, an alkenyl-substituted aryl group, an alkenyl-substituted aralkyl group, a halogen-substituted alkyl group, and a halogen-substituted aryl group.

[0059] In this specification, a halogen-substituted alkyl group refers to an alkyl group substituted with at least one halogen atom. Unless otherwise specified, the number of carbon atoms in the halogen-substituted alkyl group is preferably 1 to 18, more preferably 1 to 10, and even more preferably 1 to 6. Examples of the halogen-substituted alkyl group include a chloromethyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a heptafluoroisopropyl group.

[0060] In this specification, a halogen-substituted aryl group refers to an aryl group substituted with at least one halogen atom. Unless otherwise specified, the number of carbon atoms in the halogen-substituted aryl group is preferably 6 to 18, and particularly preferably 6 to 10. Examples of the halogen-substituted aryl group include a 4-fluorophenyl group, a 3-fluorophenyl group, a 2-fluorophenyl group, and a pentafluorophenyl group.

[0061] R ２In one embodiment, each independently represents preferably an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-substituted aryl group, an alkyl-substituted aralkyl group, an alkenyl-substituted aryl group, or an alkenyl-substituted aralkyl group, more preferably an alkyl group, even more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

[0062] R ３ R each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent. ３ Examples of the "substituent" of the "hydrocarbon group which may have a substituent" represented by the formula (I) include a monovalent group consisting of one or more (preferably 1 to 40, more preferably 1 to 20) skeletal atoms selected from carbon, oxygen, nitrogen, sulfur, and silicon atoms, and, when a bonding position exists on the skeletal atom, a non-skeletal atom selected from a hydrogen atom and a halogen atom bonded to the bonding position in addition to the skeletal atom, or a halogen atom, and more specifically, -OR ３ｘ , -COR ３ｘ , -OCOR ３ｘ , -COOR ３ｘ , -SR ３ｘ , -SOR ３ｘ , -SO ２ R ３ｘ , -NHR ３ｘ , -N(R ３ｘ ) ２ , -CONHR ３ｘ , -CON(R ３ｘ ) ２ , -NHCOR ３ｘ , -NO ２ , -CN, -CHO, -OH, -SH, -NH ２ , —COOH, halogen atoms, etc. ３ｘ each independently represents a hydrocarbon group which may be substituted with a halogen atom.

[0063] R ３In one embodiment, each independently represents preferably a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-substituted aryl group, an alkyl-substituted aralkyl group, an alkenyl-substituted aryl group, or an alkenyl-substituted aralkyl group, more preferably a hydrogen atom or an alkyl group, even more preferably a hydrogen atom, a methyl group, or an ethyl group, and particularly preferably a hydrogen atom.

[0064] Formula (I) and Formula (II) each contain a number of Formula (X):

[0065]

[0066] [wherein * represents a bonding site; other symbols are as defined above.] are each independently a group represented by formula (X1):

[0067]

[0068] [In the formula, R ２１ represents an alkyl group; and other symbols are as defined above.], and the groups represented by formulae (X21) to (X24):

[0069]

[0070] [wherein * is as defined above], and a group represented by formula (X21) or formula (X22) is particularly preferred.

[0071] R ２１ represents an alkyl group, and in one embodiment, is preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

[0072] R ４ each independently represents a substituent, and c R ４ At least one of R represents an iodine atom. ４Examples of the "substituent" represented by the formula (I) include one or more (preferably 1 to 40, more preferably 1 to 20) skeletal atoms selected from carbon, oxygen, nitrogen, sulfur, and silicon atoms, and, when a skeletal atom has a bonding position, a monovalent group consisting of a non-skeletal atom selected from a hydrogen atom and a halogen atom bonded to the bonding position in addition to the skeletal atom, or a halogen atom. More specifically, -R ４ｘ , -OR ４ｘ , -COR ４ｘ , -OCOR ４ｘ , -COOR ４ｘ , -SR ４ｘ , -SOR ４ｘ , -SO ２ R ４ｘ , -NHR ４ｘ , -N(R ４ｘ ) ２ , -CONHR ４ｘ , -CON(R ４ｘ ) ２ , -NHCOR ４ｘ , -NO ２ , -CN, -CHO, -OH, -SH, -NH ２ , —COOH, halogen atoms, etc. ４ｘ each independently represents a hydrocarbon group which may be substituted with a halogen atom.

[0073] R ４ In one embodiment, each independently is preferably —R ４ｘ , -OR ４ｘ , -COR ４ｘ , -OCOR ４ｘ , -COOR ４ｘ or an iodine atom, and more preferably, —R ４ｘ , -OR ４ｘ or an iodine atom, and more preferably, —OR ４ｘ or an iodine atom, particularly preferably a methoxy group or an iodine atom, and c R ４ At least one (preferably 1 to 3, particularly preferably 1 or 2) of the groups represents an iodine atom.

[0074] R ５ R each independently represents a substituent. ５Examples of the "substituent" represented by the formula (I) include one or more (preferably 1 to 40, more preferably 1 to 20) skeletal atoms selected from carbon, oxygen, nitrogen, sulfur, and silicon atoms, and, when a skeletal atom has a bonding position, a monovalent group consisting of a non-skeletal atom selected from a hydrogen atom and a halogen atom bonded to the bonding position in addition to the skeletal atom, or a halogen atom. More specifically, -R ５ｘ , -OR ５ｘ , -COR ５ｘ , -OCOR ５ｘ , -COOR ５ｘ , -SR ５ｘ , -SOR ５ｘ , -SO ２ R ５ｘ , -NHR ５ｘ , -N(R ５ｘ ) ２ , -CONHR ５ｘ , -CON(R ５ｘ ) ２ , -NHCOR ５ｘ , -NO ２ , -CN, -CHO, -OH, -SH, -NH ２ , —COOH, a halogen atom, a heterocyclic group, ═O, etc. ５ｘ each independently represents a hydrocarbon group which may be substituted with a halogen atom.

[0075] In this specification, the term "heterocyclic group" refers to a monovalent group obtained by removing one hydrogen atom from a ring having, in addition to carbon atoms, one or more (e.g., 1 to 4) heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms as ring-constituting atoms. The heterocyclic group may be a monocyclic heterocyclic group or a polycyclic heterocyclic group. The heterocyclic group is preferably a 5- to 10-membered heterocyclic group, more preferably a 5- to 8-membered heterocyclic group, and even more preferably a 5- or 6-membered heterocyclic group.

[0076] The heterocyclic group may be an aromatic heterocyclic group or a non-aromatic heterocyclic group, but is preferably a non-aromatic heterocyclic group. The non-aromatic heterocyclic group may be a saturated ring consisting of only a single bond, or an unsaturated ring having a double bond in addition to a single bond, but is preferably a saturated ring. Examples of heterocyclic groups include a tetrahydropyranyl group (such as a tetrahydro-2H-pyran-2-yl group), a tetrahydrofuranyl group (such as a tetrahydrofuran-2-yl group), a 1,4-dioxanyl group (such as a 1,4-dioxan-2-yl group), a 1,4-thioxanyl group (such as a 1,4-thioxan-2-yl group), an oxepanyl group (such as an oxepan-2-yl group), a tetrahydrothienyl group (such as a tetrahydrothiophen-2-yl group), a thianil group (such as a thian-2-yl group), and a 1,4-dithianil group (such as a 1,4-dithian-2-yl group).

[0077] R ５ In one embodiment, each independently is preferably —R ５ｘ , -OR ５ｘ , -COR ５ｘ , -OCOR ５ｘ , -COOR ５ｘ or a heterocyclic group, more preferably -R ５ｘ , -OR ５ｘ or a heterocyclic group, more preferably a heterocyclic group, and particularly preferably a tetrahydropyranyl group. ５ When is one of these groups, the storage stability of the compound represented by formula (I) is further improved.

[0078] Each X independently represents O or S, and in one embodiment, O is preferred.

[0079] Each d independently represents an integer of 0 or 1 or more, and in one embodiment, is preferably 0 or 1.

[0080] b number of formula (Y) in formula (I):

[0081]

[0082] In one embodiment, the groups represented by the formula (Y11) or (Y12) are each independently represented by the formula (Y11) or (Y12):

[0083]

[0084] [In the formula, Y １ and Y ２ are each independently CH ２ , CHR ５２ or CR ５２ R ５３ Y ３ and Y ４ are each independently CH ２ , CHR ５２ , C.R. ５２ R ５３ , N.R. ５４ , O or S; R ５１ and R ５４ each independently represents a hydrogen atom or a hydrocarbon group which may be substituted with a halogen atom; R ５２ are each independently -R ５ｘ , -OR ５ｘ , -COR ５ｘ , -OCOR ５ｘ , -COOR ５ｘ or a heterocyclic group; R ５３ each independently represent a hydrocarbon group which may be substituted with a halogen atom; and other symbols are as defined above.], and the groups represented by formulae (Y21) to (Y25):

[0085]

[0086] [wherein * is as defined above], and particularly preferably a group represented by formula (Y22) or formula (Y25).

[0087] Y １ is CH ２ , CHR ５２ or CR ５２ R ５３ In one embodiment, particularly preferably CH ２ or CHR ５２ Y ２ is CH ２ , CHR ５２ or CR ５２ R ５３In one embodiment, preferably CH ２ or CHR ５２ and particularly preferably CH ２ Y ３ and Y ４ are each independently CH ２ , CHR ５２ , C.R. ５２ R ５３ , N.R. ５４ , O or S, and in one embodiment preferably CH ２ , CHR ５２ , O or S, particularly preferably CH ２ is.

[0088] R ５１ and R ５４ R each independently represents a hydrogen atom or a hydrocarbon group which may be substituted with a halogen atom, and in one embodiment, is preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom. ５２ are each independently -R ５ｘ , -OR ５ｘ , -COR ５ｘ , -OCOR ５ｘ , -COOR ５ｘ or a heterocyclic group, and in one embodiment, preferably -R ５ｘ , -OR ５ｘ or a heterocyclic group, more preferably a heterocyclic group, and particularly preferably a tetrahydropyranyl group. ５３ each independently represents a hydrocarbon group which may be substituted with a halogen atom, and in one embodiment, is preferably an alkyl group.

[0089] R ６ are each independently a straight-chain or branched-chain alkyl group, and in one embodiment, are preferably straight-chain or branched-chain alkyl groups having 2 or more carbon atoms, more preferably straight-chain or branched-chain alkyl groups having 2 to 6 carbon atoms, even more preferably an ethyl group, a propyl group, or an isopropyl group, and particularly preferably an ethyl group. ６is preferably the above group from the viewpoint of the EUV sensitivity and stability over time of the resulting resist.

[0090] a represents an integer of 1 or more, and in one embodiment, preferably 1 or 2, and particularly preferably 1. b represents an integer of 1 or more, and in one embodiment, preferably 1, 2, or 3, and more preferably 1 or 2, and particularly preferably 1. c represents an integer of 1 or more, and in one embodiment, preferably 1, 2, 3, or 4, and more preferably 1, 2, or 3, and particularly preferably 1 or 2.

[0091] In one embodiment, in formula (I), at least one of formula (Y):

[0092]

[0093] [wherein each symbol is as defined above.] Preferably, at least one of the carbon atoms adjacent to the carbon atom bonded to the group represented by the formula (I) is bonded to an iodine atom. This arrangement tends to further improve the EUV sensitivity and temporal stability of the resulting resist.

[0094] In one embodiment, in formula (II), at least one of formula (Z):

[0095]

[0096] [wherein each symbol is as defined above.] Preferably, at least one of the carbon atoms adjacent to the carbon atom bonded to the group represented by the formula (I) is bonded to an iodine atom. This arrangement tends to further improve the EUV sensitivity and temporal stability of the resulting resist.

[0097] In one embodiment, the compound of formula (I) is represented by formula (1):

[0098]

[0099] [wherein ring A represents a 6- to 14-membered aromatic ring; R １ represents a hydrogen atom or a methyl group; R ２１ represents an alkyl group; R ４ each independently represents a substituent, and c R４ at least one of b and c represents an iodine atom; and b and c each independently represent an integer of 1 or more.] or a compound represented by formula (1'):

[0100]

[0101] [wherein ring A represents a 6- to 14-membered aromatic ring; R １ represents a hydrogen atom or a methyl group; R ２１ represents an alkyl group; R ４ each independently represents a substituent, and c R ４ At least one of represents an iodine atom; b １ and c each independently represent an integer of 1 or more; ２ represents an integer of 0 or 1 or more.] When the compound represented by formula (I) is a compound represented by formula (1) and / or formula (1'), the EUV sensitivity and stability over time of the obtained resist are further improved. In addition, the EB sensitivity and exposure stability are also excellent.

[0102] The group represented by formula (X1) in formula (1) and formula (1′) is preferably a group represented by any one of formulas (X21) to (X24), and particularly preferably a group represented by formula (X21) or formula (X22).

[0103] b １ represents an integer of 1 or more, preferably 1, 2 or 3, more preferably 1 or 2, and particularly preferably 1. ２ represents an integer of 0 or 1 or more, preferably 0, 1 or 2, and particularly preferably 0 or 1.

[0104] In one embodiment, in formula (1) and formula (1′), at least one of formula (Y22):

[0105]

[0106] [wherein * is as defined above.] Preferably, at least one of the carbon atoms adjacent to the carbon atom bonded to the group represented by the formula (I) is bonded to an iodine atom. This arrangement tends to further improve the EUV sensitivity and temporal stability of the resulting resist.

[0107] In one embodiment, in formula (1′), at least one of formula (Y25):

[0108]

[0109] [wherein * is as defined above.] Preferably, at least one of the carbon atoms adjacent to the carbon atom bonded to the group represented by the formula (I) is bonded to an iodine atom. This arrangement tends to further improve the EUV sensitivity and temporal stability of the resulting resist.

[0110] In one embodiment, the compound represented by formula (1) is represented by formula (1a) to formula (1i):

[0111]

[0112] [In the formula, R １ represents a hydrogen atom or a methyl group; R ２１ represents an alkyl group; R ４１ , R ４２ , R ４３ , R ４４ and R ４５ are each independently a hydrogen atom, -R ４ｘ , -OR ４ｘ , -COR ４ｘ , -OCOR ４ｘ , -COOR ４ｘ or an iodine atom, and R ４１ , R ４２ , R ４３ , R ４４ and R ４５ At least one of the groups represented in each formula represents an iodine atom; R ４ｘrepresents an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-substituted aryl group, an alkyl-substituted aralkyl group, an alkenyl-substituted aryl group, or an alkenyl-substituted aralkyl group.] is preferred, a compound represented by formula (1a) or formula (1c) is more preferred, and a compound represented by formula (1a) is particularly preferred.

[0113] R ４１ , R ４２ , R ４３ , R ４４ and R ４５ are each independently a hydrogen atom, -R ４ｘ , -OR ４ｘ , -COR ４ｘ , -OCOR ４ｘ , -COOR ４ｘ or an iodine atom, and in one embodiment, preferably -R ４ｘ , -OR ４ｘ or an iodine atom, more preferably -OR ４ｘ or an iodine atom, particularly preferably a methoxy group or an iodine atom, and R ４１ , R ４２ , R ４３ , R ４４ and R ４５ At least one (preferably 1 to 3, particularly preferably 1 or 2) of the groups shown in each formula represents an iodine atom.

[0114] In one embodiment, the compound represented by formula (1a) comprises at least one of R ４２ and R ４４ Preferably, one or both of the groups are iodine atoms.

[0115] In one embodiment, the compound represented by formula (1b) is at least ４１ , R ４３ and R ４５ It is preferred that any one, two or all of the above be iodine atoms.

[0116] In one embodiment, the compound represented by formula (1c) comprises at least R ４２ and R ４４Preferably, one or both of R ４２ However, it is more preferably an iodine atom.

[0117] In one embodiment, the compound represented by formula (1d) comprises at least R ４２ and R ４４ Preferably, one or both of R ４２ However, it is more preferably an iodine atom.

[0118] In one embodiment, the compound represented by formula (1e) comprises at least one of R ４１ and R ４４ Preferably, one or both of R ４１ and R ４４ More preferably, both of the groups are iodine atoms.

[0119] In one embodiment, the compound represented by formula (1f) comprises at least R ４３ is preferably an iodine atom.

[0120] In one embodiment, the compound represented by formula (1g) comprises at least one of R ４１ , R ４３ and R ４５ Preferably, one or more of R ４３ is an iodine atom, or R ４１ and R ４５ More preferably, both of the groups are iodine atoms.

[0121] In one embodiment, the compound represented by formula (1h) comprises at least one of R ４１ , R ４３ and R ４４ is preferably an iodine atom, and at least one of R ４１ and R ４４ are both iodine atoms, or R ４３ and R ４４ More preferably, both of the groups are iodine atoms.

[0122] In one embodiment, the compound represented by formula (1i) comprises at least R４２ and R ４４ Preferably, one or both of R ４２ and R ４４ More preferably, both of the groups are iodine atoms.

[0123] Specific examples of the compound represented by formula (1) include, but are not limited to, compounds represented by formula (1a-1) to formula (1a-64):

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132] and the like.

[0133] In one embodiment, the compound represented by formula (1′) is represented by formula (1a′) to formula (1ib′):

[0134]

[0135]

[0136] [In the formula, R １ represents a hydrogen atom or a methyl group; R ２１ represents an alkyl group; R ４１ , R ４２ , R ４３ , R ４４ and R ４５ are each independently a hydrogen atom, -R ４ｘ , -OR ４ｘ , -COR ４ｘ , -OCOR ４ｘ , -COOR ４ｘ or an iodine atom, and R ４１ , R４２ , R ４３ , R ４４ and R ４５ At least one of the groups represented in each formula represents an iodine atom; R ４ｘ represents an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-substituted aryl group, an alkyl-substituted aralkyl group, an alkenyl-substituted aryl group, or an alkenyl-substituted aralkyl group.] is preferred, a compound represented by formula (1a') or formula (1c') is more preferred, and a compound represented by formula (1a') is particularly preferred.

[0137] In one embodiment, the compound represented by formula (1a′) comprises at least R ４２ and R ４４ Preferably, one or both of the groups are iodine atoms.

[0138] In one embodiment, the compound represented by formula (1b′) comprises at least R ４１ , R ４３ and R ４５ It is preferred that any one, two or all of the above be iodine atoms.

[0139] In one embodiment, the compound represented by formula (1c′) is a compound represented by formula (1c′) ４２ and R ４４ Preferably, one or both of R ４２ However, it is more preferably an iodine atom.

[0140] In one embodiment, the compounds represented by formula (1da′), formula (1db′), and formula (1dc′) each contain at least one of R ４２ and R ４４ Preferably, one or both of R ４２ However, it is more preferably an iodine atom.

[0141] In one embodiment, the compounds represented by formula (1ea′), formula (1eb′), and formula (1ec′) each contain at least one of R ４１ and R ４４Preferably, one or both of R ４１ and R ４４ More preferably, both of the groups are iodine atoms.

[0142] In one embodiment, the compounds represented by formula (1fa′), formula (1fb′), and formula (1fc′) each contain at least one of R ４３ is preferably an iodine atom.

[0143] In one embodiment, the compounds represented by formula (1ga′) and formula (1gb′) each contain at least one of R ４１ , R ４３ and R ４５ Preferably, one or more of R ４３ is an iodine atom, or R ４１ and R ４５ More preferably, both of the groups are iodine atoms.

[0144] In one embodiment, the compounds represented by formula (1ha'), formula (1hb') and formula (1hc') each contain at least one of R ４１ , R ４３ and R ４４ Preferably, one or more of R ４１ and R ４４ are both iodine atoms, or R ４３ and R ４４ More preferably, both of the groups are iodine atoms.

[0145] In one embodiment, the compounds represented by formula (1ia′) and formula (1ib′) each contain at least one of R ４２ and R ４４ Preferably, one or both of R ４２ and R ４４ More preferably, both of the groups are iodine atoms.

[0146] Specific examples of the compound represented by formula (1′) include, but are not limited to, formulas (1a′-1) to (1a′-64):

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160] Examples of the compound include compounds represented by the following formula:

[0161] In one embodiment, the compound represented by formula (II) is represented by formula (2):

[0162]

[0163] [wherein ring A represents a 6- to 14-membered aromatic ring; R １ represents a hydrogen atom or a methyl group; R ２１ represents an alkyl group; R ４ each independently represents a substituent, and c R ４ wherein at least one of b and c represents an iodine atom; and b and c each independently represent an integer of 1 or greater. When the compound represented by formula (II) is a compound represented by formula (2), the EUV sensitivity and stability over time of the resulting resist are further improved.

[0164] The group represented by formula (X1) in formula (2) is preferably a group represented by any one of formulas (X21) to (X24), and particularly preferably a group represented by formula (X21) or formula (X22).

[0165] In one embodiment, in formula (2), at least one of formula (Z1):

[0166]

[0167] [wherein * is as defined above.] Preferably, at least one of the carbon atoms adjacent to the carbon atom bonded to the group represented by the formula (I) is bonded to an iodine atom. This arrangement tends to further improve the EUV sensitivity and temporal stability of the resulting resist.

[0168] In one embodiment, the compound represented by formula (2) is represented by formula (2a) to formula (2i):

[0169]

[0170] [In the formula, R １ represents a hydrogen atom or a methyl group; R ２１ represents an alkyl group; R ４１ , R ４２ , R ４３ , R ４４ and R ４５ are each independently a hydrogen atom, -R ４ｘ , -OR ４ｘ , -COR ４ｘ , -OCOR ４ｘ , -COOR ４ｘ or an iodine atom, and R ４１ , R ４２ , R ４３ , R ４４ and R ４５ At least one of the groups represented in each formula represents an iodine atom; R ４ｘrepresents an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-substituted aryl group, an alkyl-substituted aralkyl group, an alkenyl-substituted aryl group, or an alkenyl-substituted aralkyl group.] is preferred, a compound represented by formula (2a) or formula (2c) is more preferred, and a compound represented by formula (2a) is particularly preferred.

[0171] In one embodiment, the compound represented by formula (2a) comprises at least R ４２ and R ４４ Preferably, one or both of the groups are iodine atoms.

[0172] In one embodiment, the compound represented by formula (2b) is at least ４１ , R ４３ and R ４５ It is preferred that any one, two or all of the above be iodine atoms.

[0173] In one embodiment, the compound represented by formula (2c) comprises at least R ４２ and R ４４ Preferably, one or both of R ４２ However, it is more preferably an iodine atom.

[0174] In one embodiment, the compound represented by formula (2d) comprises at least R ４２ and R ４４ Preferably, one or both of R ４２ However, it is more preferably an iodine atom.

[0175] In one embodiment, the compound represented by formula (2e) comprises at least R ４１ and R ４４ Preferably, one or both of R ４１ and R ４４ More preferably, both of the groups are iodine atoms.

[0176] In one embodiment, the compound represented by formula (2f) comprises at least R ４３ is preferably an iodine atom.

[0177] In one embodiment, the compound represented by formula (2g) is at least ４１ , R ４３ and R ４５ Preferably, one or more of R ４３ is an iodine atom, or R ４１ and R ４５ More preferably, both of the groups are iodine atoms.

[0178] In one embodiment, the compound represented by formula (2h) comprises at least R ４１ , R ４３ and R ４４ Preferably, one or more of R ４１ and R ４４ are both iodine atoms, or R ４３ and R ４４ More preferably, both of the groups are iodine atoms.

[0179] In one embodiment, the compound represented by formula (2i) comprises at least R ４２ and R ４４ Preferably, one or both of R ４２ and R ４４ More preferably, both of the groups are iodine atoms.

[0180] Specific examples of the compound represented by formula (2) include, but are not limited to, formulas (2a-1) to (2a-64):

[0181]

[0182]

[0183]

[0184]

[0185]

[0186]

[0187]

[0188]

[0189] and the like.

[0190] The compounds represented by formula (I) and formula (II) can be produced using known methods. For example, as shown in the following scheme, the compounds represented by formula (I) and formula (II) can be produced by etherifying carbonyl compound (a) to obtain carbonyl compound (bI) or (bII) (Step A1 or B1), converting this to alcohol compound (cI) or (cII) (Step A2 or B2), and then esterifying (Step A3 or B3). Alternatively, the compounds represented by formula (I) and formula (II) can be produced by obtaining alcohol compound (b) from carbonyl compound (a) (Step C1), esterifying this to obtain ester compound (c) (Step C2), and then etherifying this (Step CA or CB), as shown in the following scheme.

[0191]

[0192] [In the formula, each symbol is as defined above.]

[0193] In Steps A1, B1, CA, and CB, a general method for introducing an acetal-based protecting group into a hydroxy group can be used. Steps A1, B1, CA, and CB can be carried out by, for example, reacting the phenolic compound (a) or (c) in the above scheme with a compound represented by formula (Ia) or formula (IIa):

[0194]

[0195] [In the formula, LG is a leaving group such as a chlorine atom, a bromine atom, an iodine atom, a methylsulfonyloxy group, a p-toluenesulfonyloxy group, or the like, and other symbols are as defined above.] This reaction can be carried out by a Williamson ether synthesis reaction in which a leaving group-containing compound represented by the formula (I) is reacted in the presence of a base. The reaction temperature is, for example, −20 to 100° C., and the reaction time is, for example, 10 minutes to 100 hours. Examples of bases that can be used include carbonates such as potassium carbonate, cesium carbonate, and sodium carbonate; hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; and hydrides such as sodium hydride. The reaction can be carried out in an organic solvent such as an aliphatic ether solvent, an amide solvent, a sulfoxide solvent, a nitrile solvent, an aliphatic ester solvent, an aliphatic ketone solvent, an aliphatic hydrocarbon solvent, and an aromatic hydrocarbon solvent. In addition, in formula (I), a compound represented by the formula (Y):

[0196]

[0197] [wherein each symbol is as defined above] is a group represented by formula (Y11') or formula (Y12'):

[0198]

[0199] [wherein each symbol is as defined above], Steps A1 and CA can be carried out by reacting the phenolic compound (a) or (c) with a compound represented by the formula (Y11a) or (Y12a):

[0200]

[0201] [wherein each symbol is as defined above.] In the target formula (I), the group represented by formula (Y) is a group represented by formula (Y22):

[0202]

[0203] [wherein * is as defined above], 3,4-dihydro-2H-pyran (DHP) can be used as the olefin compound. When an excess amount of 3,4-dihydro-2H-pyran (DHP) is reacted with the phenolic compound (a) or (c), the group represented by formula (Y) in formula (I) of the target product is converted to a group represented by formula (Y25):

[0204]

[0205] [wherein * is as defined above].

[0206] Examples of the aliphatic ether solvent include tetrahydrofuran, 1,2-dimethoxyethane, diethyl ether, diisopropyl ether, methyl tert-butyl ether, and cyclopentyl methyl ether.

[0207] Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone.

[0208] Examples of sulfoxide solvents include dimethyl sulfoxide.

[0209] Examples of nitrile solvents include acetonitrile and propionitrile.

[0210] Examples of aliphatic ester solvents include fatty acid alkyl esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, ethyl propionate, and isopropyl propionate; hydroxy acid alkyl esters such as methyl lactate, ethyl lactate, and butyl lactate; keto acid alkyl esters such as methyl acetoacetate and ethyl acetoacetate; and lactones such as γ-butyrolactone.

[0211] Examples of halogen-based solvents include dichloromethane and chloroform.

[0212] Examples of the aliphatic ketone solvent include acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, diisopropyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, and isophorone.

[0213] Examples of the aliphatic hydrocarbon solvent include n-pentane, n-hexane, isohexane, n-heptane, n-octane, cyclopentane, cyclohexane, and methylcyclohexane.

[0214] Examples of aromatic hydrocarbon solvents include benzene, toluene, o-xylene, m-xylene, p-xylene, and ethylbenzene.

[0215] Steps A2, B2 and C1 can be carried out by, for example, reacting a carbonyl compound (bI), (bII) or (a) with R ２ MgX Ｈ (R ２ is as above, and X Ｈ The reaction can be carried out by a Grignard reaction in which a Grignard reagent represented by the formula (III) is reacted with a Grignard reagent represented by the formula (III) (wherein ⁻ is a chlorine atom, a bromine atom, or an iodine atom). General Grignard reaction conditions can be applied to this reaction as they are, and the reaction temperature is, for example, −20 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. Examples of the aliphatic ether solvent include those mentioned above.

[0216] Steps A3 and B3 can be carried out, for example, by reacting alcohol compound (cI) or (cII) with a methacrylic acid halide (i.e., methacrylic acid chloride, bromide, or iodide) or methacrylic acid anhydride, or an acrylic acid halide (i.e., acrylic acid chloride, bromide, or iodide) or acrylic acid anhydride in the presence of a base. The reaction temperature is, for example, −20 to 100° C., and the reaction time is, for example, 10 minutes to 100 hours. Examples of the base that can be used include organic bases such as diazabicycloundecene, 1,4-diazabicyclo[2.2.2]octane, triethylamine, pyridine, and N,N-dimethylaminopyridine. The reaction can be carried out in an organic solvent such as an aliphatic ester solvent, an aliphatic ether solvent, a halogenated solvent, an amide solvent, or an aliphatic ketone solvent. Examples of the various solvents include those described above.

[0217] Step C2 can be carried out, for example, by a Mitsunobu reaction in which alcohol compound (b) is reacted with methacrylic acid or acrylic acid in the presence of an azo reagent and a phosphine. General Mitsunobu reaction conditions can be applied to this reaction, with the reaction temperature being, for example, 0 to 25°C and the reaction time being, for example, 10 minutes to 100 hours. 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 azodicarboxylate, diisopropyl azodicarboxylate, dibenzyl azodicarboxylate, and di-tert-butyl azodicarboxylate; and azocarboxylic acid amides such as 1,1'-(azodicarbonyl)dipiperazine and N,N,N',N'-tetramethylazodicarboxamide. This reaction can be carried out in an organic solvent, for example, an aliphatic ether solvent or a halogenated solvent. Examples of various solvents include those described above.

[0218] The compounds represented by formulae (I) and (II) may be produced, if necessary, by combining, in addition to the steps shown in the above schemes, known reactions such as decarboxylation, condensation, hydrolysis, protecting group introduction, deprotection, oxidation, reduction, radical cyclization, nucleophilic substitution, nucleophilic addition, alkylation, amidation, esterification, and halogenation. Furthermore, in order to obtain a compound having a desired carbon skeleton, a Wittig reaction, Friedel-Crafts reaction, Grignard reaction, Knoevenagel condensation reaction, Horner-Wadsworth-Emmons reaction, Michael addition reaction, Vilsmeier-Haack reaction, Seyfarth-Gilbert reaction, and Corey-Fuchs reaction may also be used.

[0219] The compounds obtained in each step shown in the above scheme can be used in the next step either as the reaction mixture or as a crude product. The compounds obtained in each step may be purified from the reaction mixture by a known purification method such as solvent extraction, concentration, crystallization, recrystallization, distillation, fractional distillation, chromatography, or a combination thereof.

[0220] <<Composition for Producing a Photoresist Layer-Forming Material>> This embodiment provides a composition containing a compound represented by Formula (I) and / or Formula (II) as a monomer component. Compositions containing the compounds represented by Formula (I) and / or Formula (II) are particularly useful as compositions for producing photoresist layer-forming materials (compositions for producing materials for forming photoresist layers), as described in detail below. Furthermore, compositions containing the compounds represented by Formula (I) and / or Formula (II) are useful as compositions for producing resist top layer film-forming materials, resist middle layer-forming materials, and resist underlayer film-forming materials. Furthermore, compositions containing the compounds represented by Formula (I) and / or Formula (II) are useful as compositions for producing resist materials for KrF excimer laser exposure, ArF excimer laser exposure, electron beam (EB) exposure, and EUV exposure.

[0221] In one embodiment, the composition containing the compound represented by formula (I) and / or formula (II) preferably contains two or more compounds selected from the group consisting of the compounds represented by formula (I) and formula (II). By containing two or more compounds in the composition, the storage stability of the compounds in the composition can be improved and a decrease in their purity can be prevented.

[0222] In one embodiment, a composition containing two or more compounds selected from the group consisting of compounds represented by formula (I) and formula (II) preferably contains both a compound represented by formula (1) and / or formula (2) and a compound represented by formula (1'); more preferably contains both a compound represented by formula (1) and a compound represented by formula (1'). By using such a combination, the storage stability of the compounds in the composition can be further improved, and a decrease in their purity can be further prevented.

[0223] In one embodiment, a composition containing both a compound represented by formula (1) and / or formula (2) (preferably a compound represented by formula (1)) and a compound represented by formula (1′) preferably contains 0.0001% by mass or more of the compound represented by formula (1′), when the total of the compound represented by formulas (1) and (2) (preferably a compound represented by formula (1)) and the compound represented by formula (1′) contained in the composition is taken as 100% by mass, more preferably 0.001% by mass or more, even more preferably 0.01% by mass or more, still more preferably 0.1% by mass or more, and particularly preferably 0.3% by mass or more of the compound represented by formula (1′). The upper limit of the content of the compound represented by formula (1') in the composition is not particularly limited, but may be, for example, 90% by mass or less, 70% by mass or less, 50% by mass or less, 30% by mass or less, 20% by mass or less, 10% by mass or less, 5% by mass or less, 2% by mass or less, 1% by mass or less, etc., when the total of the compounds represented by formulas (1) and (2) (preferably the compound represented by formula (1)) and the compound represented by formula (1') contained in the composition is taken as 100% by mass.

[0224] In one embodiment, the composition containing both the compound represented by formula (1) and the compound represented by formula (1′) preferably contains both a compound represented by any one of formulas (1a) to (1i) and a compound represented by any one of formulas (1a′) to (1ib′); a combination of a compound represented by formula (1a) and a compound represented by formula (1a′), a combination of a compound represented by formula (1b) and a compound represented by formula (1b′), a combination of a compound represented by formula (1c) and a compound represented by formula (1c′), a combination of a compound represented by formula (1d) and at least one compound selected from the compounds represented by formulas (1da′), (1db′) and (1dc′), a combination of a compound represented by formula (1e) and at least one compound selected from the compounds represented by formulas (1ea′), (1eb′) and (1ec′), a combination of a compound represented by formula (1f) and a compound represented by formula (1fa′), (1fb′), ) and a combination of at least one compound of the compounds represented by formula (1fc'), a compound represented by formula (1g) and a combination of at least one compound of the compounds represented by formula (1ga') and formula (1gb'), a compound represented by formula (1h) and a combination of at least one compound of the compounds represented by formula (1ha'), formula (1hb') and formula (1hc'), or a compound represented by formula (1i) and a combination of at least one compound of the compounds represented by formula (1ia') and formula (1ib'); a compound represented by formula (1a) and a combination of the compound represented by formula (1a'), or a compound represented by formula (1c) and a combination of the compound represented by formula (1c'), more preferably a compound represented by formula (1a) and a combination of the compound represented by formula (1a'), particularly preferably a compound represented by formula (1a').

[0225]

[0083] In one embodiment, the total content of the compounds represented by formula (I) and / or formula (II) in a composition containing the compounds is, when the total amount of all monomer components in the composition is taken as 100 mol%, preferably 5 mol% or more, more preferably 8 mol% or more, and even more preferably 10 mol% or more, and the upper limit is 100 mol% or less, preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 30 mol% or less.

[0226] The composition containing the compound represented by formula (I) and / or formula (II) may further contain, as a monomer component, a (meth)acrylic acid ester compound having an adamantane skeleton in addition to the compound represented by formula (I) and / or formula (II). The (meth)acrylic acid ester compound having an adamantane skeleton is not particularly limited, but examples thereof include compounds represented by formula (A1) and formula (A2):

[0227]

[0228] [In the formula, R ａ１ and R ａ５ represents a hydrogen atom or a methyl group; R 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 hydroxy group; L ａ１ and L ａ３ represents an alkylene group; ａ２ and L ａ４ represents a bond or an alkylene group; n ａ１ and n ａ２ represents 0, 1 or 2. The (meth)acrylic acid ester compound having an adamantane skeleton may be used alone or in any combination of two or more.

[0229] R ａ２ , R ａ３ , R ａ４ , R ａ６ , Rａ７ , R ａ８ , R ａ９ and R ａ１０ Examples of the "substituent" of the "hydrocarbon group which may have a substituent" represented by the formula (I) include a monovalent group consisting of one or more (preferably 1 to 40, more preferably 1 to 20) skeletal atoms selected from carbon, oxygen, nitrogen, sulfur, and silicon atoms, and, when a bonding position exists on the skeletal atom, a non-skeletal atom selected from a hydrogen atom and a halogen atom bonded to the bonding position in addition to the skeletal atom, or a halogen atom, and more specifically, -OR ａｘ , -COR ａｘ , -OCOR ａｘ , -COOR ａｘ , -SR ａｘ , -SOR ａｘ , -SO ２ R ａｘ , -NHR ａｘ , -N(R ａｘ ) ２ , -CONHR ａｘ , -CON(R ａｘ ) ２ , -NHCOR ａｘ , -NO ２ , -CN, -CHO, -OH, -SH, -NH ２ , —COOH, halogen atoms, etc. ａｘ each independently represents a hydrocarbon group which may be substituted with a halogen atom.

[0230] In this specification, the term "alkylene group" refers to 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 the alkylene group include -CH ２ -, -CH ２ CH ２ -, -CH ２ CH ２ CH ２ -, -CH ２ CH ２ CH ２ CH ２ -, -CH ２ CH ２ CH２ CH ２ CH ２ -, -CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ -, -CH ２ C(CH ３ ) H-, etc.

[0231] Specific examples of the (meth)acrylic acid ester compound having an adamantane skeleton include, but are not limited to, compounds represented by formula (A-1) to formula (A-32):

[0232]

[0233] and the like.

[0234] The content of the (meth)acrylic acid ester compound having an adamantane skeleton in the composition containing the compound represented by Formula (I) and / or Formula (II) is preferably 10 mol% or more, more preferably 40 mol% or more, and even more preferably 60 mol% or more, when the total amount of all monomer components in the composition is 100 mol%, and the upper limit is preferably 90 mol% or less, more preferably 85 mol% or less, and even more preferably 80 mol% or less.

[0235] The composition containing the compound represented by formula (I) and / or formula (II) may further contain, as a monomer component, a (meth)acrylic acid ester compound having a lactone skeleton in addition to the compound represented by formula (I) and / or formula (II). The (meth)acrylic acid ester compound having a lactone skeleton is not particularly limited, but examples thereof include compounds represented by formulas (B1) to (B5):

[0236]

[0237] [In the formula, R ｂ１ , R ｂ３ , R ｂ５ , R ｂ７ and R ｂ９ represents a hydrogen atom or a methyl group; R ｂ２ , R ｂ４ , R ｂ６ , R ｂ８and R ｂ１０ each independently represents a hydrocarbon group which may have a substituent, a halogen atom, or a hydroxy group; L ｂ１ , L ｂ３ , L ｂ５ , L ｂ７ and L ｂ９ represents an alkylene group; ｂ２ , L ｂ４ , L ｂ６ , L ｂ８ and L ｂ１０ represents a bond or an alkylene group; X ｂ is -CH ２ represents - or -O-; n ｂ１ , n ｂ２ , n ｂ４ , n ｂ６ , n ｂ８ and n ｂ１０ represents 0, 1 or 2; n ｂ３ , n ｂ５ , n ｂ７ , n ｂ９ and n ｂ１１ represents an integer of 0 to 5.] The (meth)acrylic acid ester compound having a lactone skeleton may be used alone or in any combination of two or more.

[0238] R ｂ２ , R ｂ４ , R ｂ６ , R ｂ８ and R ｂ１０ Examples of the "substituent" of the "hydrocarbon group which may have a substituent" represented by the formula (I) include a monovalent group consisting of one or more (preferably 1 to 40, more preferably 1 to 20) skeletal atoms selected from carbon, oxygen, nitrogen, sulfur, and silicon atoms, and, when a bonding position exists on the skeletal atom, a non-skeletal atom selected from a hydrogen atom and a halogen atom bonded to the bonding position in addition to the skeletal atom, or a halogen atom, and more specifically, -OR ｂｘ , -COR ｂｘ , -OCOR ｂｘ , -COOR ｂｘ , -SR ｂｘ , -SOR ｂｘ , -SO ２ Rｂｘ , -NHR ｂｘ , -N(R ｂｘ ) ２ , -CONHR ｂｘ , -CON(R ｂｘ ) ２ , -NHCOR ｂｘ , -NO ２ , -CN, -CHO, -OH, -SH, -NH ２ , —COOH, halogen atoms, etc. ｂｘ each independently represents a hydrocarbon group which may be substituted with a halogen atom.

[0239] Specific examples of the (meth)acrylic acid ester compound having a lactone skeleton include, but are not limited to, compounds represented by formula (B-1) to formula (B-36):

[0240]

[0241] and the like.

[0242] The content of the (meth)acrylic acid ester compound having a lactone skeleton in the composition containing the compound represented by Formula (I) and / or Formula (II) is preferably 1 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more, when the total amount of all monomer components in the composition is 100 mol%, and the upper limit is 100 mol% or less, preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less.

[0243] The composition containing the compound represented by formula (I) and / or formula (II) may contain, as monomer components, both a (meth)acrylic acid ester compound having an adamantane skeleton and a (meth)acrylic acid ester compound having a lactone skeleton, in addition to the compound represented by formula (I) and / or formula (II).

[0244] The composition containing the compound represented by formula (I) and / or formula (II) may further contain other (meth)acrylic acid ester compounds as monomer components. Examples of other (meth)acrylic acid ester compounds include (meth)acrylic acid alkyl 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.

[0245] The composition containing the compound represented by formula (I) and / or formula (II) may further contain a styrene-based compound as a monomer component. Examples of the styrene-based compound include 4-vinylphenol, 4-isopropenylphenol, 3-vinylphenol, 3-isopropenylphenol, 4-methoxymethoxystyrene, 4-methoxymethoxy-α-methylstyrene, 4-(1-ethoxyethoxy)styrene, and 4-(1-ethoxyethoxy)-α-methylstyrene.

[0246] <<Photoresist Layer-Forming Material (Iodine-Hydroxyl Group-Containing Polymer) and Production Method Thereof>> The composition containing the compound represented by formula (I) and / or formula (II) described above serves as a raw material for the photoresist layer-forming material (iodine-hydroxyl group-containing polymer). The iodine-hydroxyl group-containing polymer is produced by radically polymerizing a monomer component containing the compound represented by formula (I) and / or formula (II) in the composition described above to produce a polymer containing iodine and an ether structure (sometimes referred to herein as an “iodine-ether structure-containing polymer”), which is a radical polymer of the compound represented by formula (I) and / or formula (II), and then further producing a polymer of formula (Y) or formula (Z): derived from the compound represented by formula (I) and / or formula (II) in the iodine-ether structure-containing polymer:

[0247]

[0248] [wherein each symbol is as defined above.] can be produced by hydrolyzing a group represented by the formula (I) and / or formula (II) to a phenolic hydroxyl group. That is, the iodine-hydroxyl group-containing polymer can be obtained, for example, by heating or irradiating a composition containing a compound represented by formula (I) and / or formula (II) to radically polymerize the monomer components contained in the composition to produce an iodine-ether structure-containing polymer, and then further treating the polymer with an acid to hydrolyze the group represented by formula (Y) or formula (Z).

[0249] The reaction conditions for radical polymerization can be set arbitrarily based on the 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. The 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, halogenated solvents, alcohol solvents, and water. The aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, aliphatic ester solvents, ketone solvents, aliphatic ether solvents, and halogenated solvents listed above can be used.

[0250] Examples of alcohol solvents include methanol, ethanol, propanol, isopropanol, and tert-butanol.

[0251] The radical polymerization is preferably carried out by adding a radical polymerization initiator to the monomer component containing the compound represented by formula (I) and / or formula (II). That is, the composition containing the compound represented by formula (I) and / or formula (II) preferably contains a radical polymerization initiator when carrying out radical polymerization.

[0252] Examples of the radical polymerization initiator include peroxide-based radical polymerization initiators, azo-based radical polymerization initiators, etc. The radical polymerization initiators may be used alone or in any combination of two or more.

[0253] Examples of peroxide radical polymerization initiators include hydroperoxide compounds such as 1,1,3,3-tetramethylbutyl hydroperoxide; dialkyl peroxide 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. Compounds: peroxy ester compounds such as tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-butylperoxyisopropyl monocarbonate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyneodecanoate, tert-hexylperoxyisopropyl monocarbonate, tert-butyl peroxylaurate, (1,1-dimethylpropyl) 2-ethylperhexanoate, tert-butyl 2-ethylperhexanoate, tert-butyl 3,5,5-trimethylperhexanoate, tert-butylperoxy-2-ethylhexyl monocarbonate, and tert-butylperoxymaleic acid.

[0254] Examples of the azo radical polymerization initiator 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-carbonitrile), 1-[(1-cyano-1-methylethyl)azo]formamide, and 2-phenylazo-4-methoxy-2,4-dimethyl-valeronitrile; 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide], 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide], and 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide]. azoamide compounds such as 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 alkyl azo compounds such as 2,2'-azobis(2,4,4-trimethylpentane) and 2,2'-azobis(2-methylpropane).

[0255] The content of the radical polymerization initiator in the composition containing the compound represented by formula (I) and / or formula (II) is, for example, 0.0001 to 5% by mass, when the total amount of all monomer components is taken as 100% by mass.

[0256] The iodine-ether structure-containing polymer produced by radical polymerization includes an iodine-ether structure-containing polymer having a group represented by formula (Y) and / or formula (Z) derived from a compound represented by formula (I) and / or formula (II). That is, the iodine-ether structure-containing polymer is an iodine-ether structure-containing polymer having a group represented by formula (UI) and / or formula (UII): derived from a compound represented by formula (I) and / or formula (II):

[0257]

[0258] [wherein each symbol is as defined above].

[0259] In one embodiment, the structural unit represented by formula (UI) in the iodine-ether structure-containing polymer produced by radical polymerization is a structural unit represented by formula (U1) derived from the compound represented by formula (1):

[0260]

[0261] [wherein each symbol is as defined above] and / or a repeating unit represented by formula (U1') derived from a compound represented by formula (1'):

[0262]

[0263] It is preferable that the compound contains a repeating unit represented by the formula: wherein each symbol is as defined above.

[0264] In one embodiment, the repeating unit represented by formula (U1) in the iodine-ether structure-containing polymer produced by radical polymerization is a repeating unit represented by formula (U1a) to formula (U1i) derived from the compound represented by formula (1a) to formula (1i):

[0265]

[0266] [wherein each symbol is as defined above], more preferably contains a repeating unit represented by formula (U1a) or formula (U1c), and particularly preferably contains a repeating unit represented by formula (U1a).

[0267] In one embodiment, the repeating unit represented by formula (U1′) in the iodine-ether structure-containing polymer produced by radical polymerization is a repeating unit represented by formula (U1a′) to formula (U1ib′) derived from the compounds represented by formula (1a′) to formula (1ib′):

[0268]

[0269]

[0270] [wherein each symbol is as defined above], more preferably contains a repeating unit represented by formula (U1a') or formula (U1c'), and particularly preferably contains a repeating unit represented by formula (U1a').

[0271] In one embodiment, the structural unit represented by formula (UII) in the iodine-ether structure-containing polymer produced by radical polymerization is a structural unit represented by formula (U2) derived from a compound represented by formula (2):

[0272]

[0273] It is preferable that the compound contains a repeating unit represented by the formula: wherein each symbol is as defined above.

[0274] In one embodiment, the repeating unit represented by formula (2) in the iodine-ether structure-containing polymer produced by radical polymerization is a repeating unit represented by formula (U2a) to formula (U2i) derived from the compound represented by formula (U2a) to formula (U2i):

[0275]

[0276] [wherein each symbol is as defined above], more preferably contains a repeating unit represented by formula (U2a) or formula (U2c), and particularly preferably contains a repeating unit represented by formula (U2a).

[0277] In one embodiment, the iodine-ether structure-containing polymer produced by radical polymerization preferably contains two or more structural units selected from the group consisting of structural units represented by formula (UI) and formula (UII).

[0278] In one embodiment, the iodine-ether structure-containing polymer produced by radical polymerization preferably contains both a repeating unit represented by formula (U1) and / or formula (U2) and a repeating unit represented by formula (U1′); and more preferably contains both a repeating unit represented by formula (U1) and a repeating unit represented by formula (U1′).

[0279] In one embodiment, the iodine-ether structure-containing polymer produced by radical polymerization preferably contains 0.0001% by mass or more of the repeating unit represented by formula (U1) or (U2) (preferably the repeating unit represented by formula (U1)) and the repeating unit represented by formula (U1′) contained in the polymer, when the total of these repeating units is taken as 100% by mass, more preferably 0.001% by mass or more, even more preferably 0.01% by mass or more, even more preferably 0.1% by mass or more, and particularly preferably 0.3% by mass or more. The upper limit of the content of the repeating unit represented by formula (U1') in the polymer is not particularly limited, but may be, for example, 90% by mass or less, 70% by mass or less, 50% by mass or less, 30% by mass or less, 20% by mass or less, 10% by mass or less, 5% by mass or less, 2% by mass or less, 1% by mass or less, etc., when the total of the repeating units represented by formulas (U1) and (U2) (preferably the repeating unit represented by formula (U1)) and the repeating unit represented by formula (U1') contained in the polymer is taken as 100% by mass.

[0280] In one embodiment, the iodine-ether structure-containing polymer produced by radical polymerization preferably contains both a repeating unit represented by any one of formulas (U1a) to (U1i) and a repeating unit represented by any one of formulas (U1a') to (U1ib'); a combination of a repeating unit represented by formula (U1a) and a repeating unit represented by formula (U1a'), a combination of a repeating unit represented by formula (U1b) and a repeating unit represented by formula (U1b'), a combination of a repeating unit represented by formula (U1c) and a repeating unit represented by formula (U1c'), a combination of a repeating unit represented by formula (U1d) and at least one repeating unit selected from the group consisting of repeating units represented by formula (U1da'), (U1db') and (U1dc'); a combination of a repeating unit represented by formula (U1e) and at least one repeating unit selected from the group consisting of repeating units represented by formula (U1ea'), (U1eb') and (U1ec'); a combination of a repeating unit represented by formula (U1f) and at least one repeating unit selected from the group consisting of repeating units represented by formula (U1fa'), (U1fb') and (U1fc'); a combination of a repeating unit represented by formula (U1g) and at least one repeating unit of formula (U1ga') and formula (U1gb'); a combination of a repeating unit represented by formula (U1h) and at least one repeating unit of formula (U1ha'), formula (U1hb') and formula (U1hc'); or a combination of a repeating unit represented by formula (U1i) and at least one repeating unit of formula (U1i). It is more preferable to include a combination of at least one repeating unit selected from the repeating units represented by formula (U1ia') and formula (U1ib'); it is even more preferable to include a combination of a repeating unit represented by formula (U1a) with a repeating unit represented by formula (U1a'), or a combination of a repeating unit represented by formula (U1c) with a repeating unit represented by formula (U1c'); and it is particularly preferable to include a combination of a repeating unit represented by formula (U1a) with a repeating unit represented by formula (U1a').

[0281]

[0082] In one embodiment, the total content of the structural units represented by formula (UI) and / or formula (UII) in the iodine-ether structure-containing polymer produced by radical polymerization is, when all structural units derived from the monomer components in the polymer are taken as 100 mol%, preferably 5 mol% or more, more preferably 8 mol% or more, and even more preferably 10 mol% or more, and the upper limit is 100 mol% or less, preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 30 mol% or less.

[0282] The iodine-ether structure-containing polymer produced by radical polymerization may further contain, in addition to the structural units represented by formula (UI) and / or formula (UII), a repeating unit derived from a (meth)acrylic acid ester compound having an adamantane skeleton as described above. In one embodiment, the content of the repeating unit derived from a (meth)acrylic acid ester compound having an adamantane skeleton in the iodine-ether structure-containing polymer produced by radical polymerization is preferably 10 mol% or more, more preferably 40 mol% or more, and even more preferably 60 mol% or more, when all structural units derived from the monomer components in the polymer are taken as 100 mol%, and the upper limit is preferably 90 mol% or less, more preferably 85 mol% or less, and even more preferably 80 mol% or less.

[0283] The iodine-ether structure-containing polymer produced by radical polymerization may further contain, in addition to the structural units represented by formula (UI) and / or formula (UII), a repeating unit derived from a (meth)acrylic acid ester compound having a lactone skeleton as described above. In one embodiment, the content of the repeating unit derived from a (meth)acrylic acid ester compound having a lactone skeleton in the iodine-ether structure-containing polymer produced by radical polymerization is preferably 1 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more, when all structural units derived from the monomer components in the polymer are taken as 100 mol%, and the upper limit is 100 mol% or less, preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less.

[0284] The iodine-ether structure-containing polymer produced by radical polymerization may contain both 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. The iodine-ether structure-containing polymer produced by radical polymerization may further contain a repeating unit derived from another (meth)acrylic acid ester compound as described above. The iodine-ether structure-containing polymer produced by radical polymerization may further contain a repeating unit derived from a styrene-based compound as described above.

[0285] When the iodine-ether structure-containing polymer produced by radical polymerization contains two or more types of repeating units, it is preferred that these repeating units are arranged randomly.

[0286] The weight average molecular weight (Mw) of the iodine-ether structure-containing polymer produced by radical polymerization is preferably 5,000 to 32,000, more preferably 8,000 to 21,000, and particularly preferably 10,000 to 16,000.

[0287] The iodine-hydroxyl group-containing polymer is produced by radically polymerizing the compound represented by formula (I) and / or formula (II) and then treating the radical polymer, iodine-ether structure-containing polymer, with, for example, an acid, so that some or all of the groups represented by formula (Y) and formula (Z) derived from the compound represented by formula (I) and formula (II) in the iodine-ether structure-containing polymer are hydrolyzed to phenolic hydroxyl groups. The acid treatment may be carried out by adding the acid directly to the reaction solution after the radical polymerization.

[0288] The acid may be an organic acid, an inorganic acid, a Lewis acid, or a combination thereof, with organic acids being preferred. Examples of organic acids include methanesulfonic acid, ethanesulfonic acid, camphorsulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid, and pyridinium salts thereof. The amount of acid added may be, for example, 0.1 to 5 mass% with respect to the reaction liquid after radical polymerization. The temperature during 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 hour to 5 hours.

[0289] Of the groups represented by formula (Y) and formula (Z) derived from the compounds represented by formula (I) and formula (II) in the iodine-ether structure-containing polymer after radical polymerization and before treatment with acid, the proportion hydrolyzed to phenolic hydroxyl groups by acid treatment may be, when the total of the groups represented by formula (Y) and formula (Z) derived from the compounds represented by formula (I) and formula (II) in the iodine-ether structure-containing polymer is taken as 100 mol%, in one embodiment, 30 mol% or more, in one embodiment, 40 mol% or more, in one embodiment, 50 mol% or more, in one embodiment, 60 mol% or more, in one embodiment, 70 mol% or more, in one embodiment, 80 mol% or more, in one embodiment, 90 mol% or more, in one embodiment, 95 mol% or more, in one embodiment, 98 mol% or more, in one embodiment, 99 mol% or more, or in one embodiment, 100 mol%.

[0290] The iodine- and hydroxyl-containing polymer obtained after the acid treatment can be purified by a known purification method, such as ultrafiltration, crystallization, microfiltration, acid washing, water washing, extraction, or a combination thereof.

[0291] The iodine- and hydroxyl-containing polymer obtained after the acid treatment contains an iodine- and hydroxyl-containing polymer having a phenolic hydroxyl group derived from the compound represented by formula (I) and / or formula (II). That is, the iodine- and hydroxyl-containing polymer contains an iodine- and hydroxyl-containing polymer having a phenolic hydroxyl group derived from the compound represented by formula (I) and / or formula (II):

[0292]

[0293] [wherein each symbol is as defined above.] The presence of a phenolic hydroxyl group in the iodine- and hydroxyl-containing polymer further improves the solubility of the polymer in a solvent, thereby further improving the film-forming property, EUV sensitivity, and stability over time.

[0294] When the iodine-hydroxyl group-containing polymer obtained after the acid treatment is exposed to EUV light, the iodine atoms absorb the EUV light and are excited, and then react with the phenolic hydroxyl groups near the iodine atoms to form H ＋ Then, the generated H ＋ The decomposes the acid-dissociable unit (unit having a phenolic hydroxyl group) in the polymer, changing the solubility of the polymer in the developer, thereby enabling development.

[0295] In addition, H generated near the iodine atom ＋ The more H propagates / diffuses in the polymer, the more acid-dissociable units are catalytically decomposed, and the higher the resolution during development. ＋ For the propagation of ＋ The iodine- and hydroxyl-containing polymer of the present embodiment contains a large number of phenolic hydroxyl groups, which are a typical example of highly polar protic functional groups, and therefore has a high affinity for H ＋ The transmission ability is high and excellent resolution can be achieved.

[0296] In one embodiment, the structural unit represented by formula (U) in the iodine- and hydroxyl-containing polymer obtained after the acid treatment is a structural unit represented by formula (U') derived from the compounds represented by formula (1), formula (1'), and formula (2):

[0297]

[0298] It is preferable that the compound contains a repeating unit represented by the formula: wherein each symbol is as defined above.

[0299] In one embodiment, the repeating unit represented by formula (U') in the iodine-hydroxyl group-containing polymer obtained after the acid treatment is a repeating unit represented by formula (Ua) to formula (Ui) derived from compounds represented by formulas (1a) to (1i), formulas (1a') to (1ib'), and formulas (2a) to (2i):

[0300]

[0301] [wherein each symbol is as defined above], more preferably contains a repeating unit represented by formula (Ua) or formula (Uc), and particularly preferably contains a repeating unit represented by formula (Ua).

[0302]

[0083] In one embodiment, the total content of the structural units represented by Formula (U) in the iodine- and hydroxyl-containing polymer obtained after the acid treatment is, when all structural units derived from the monomer components in the polymer are taken as 100 mol%, preferably 5 mol% or more, more preferably 8 mol% or more, and even more preferably 10 mol% or more, and the upper limit is 100 mol% or less, preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 30 mol% or less.

[0303] The iodine- and hydroxyl-containing polymer obtained after the acid treatment may contain structural units represented by formula (UI) and / or formula (UII) in addition to the structural unit represented by formula (U).

[0304] The iodine- and hydroxyl-containing polymer obtained after the acid treatment may further contain, in addition to the structural unit represented by formula (U), a repeating unit derived from the (meth)acrylic acid ester compound having an adamantane skeleton described above. The content of the repeating unit derived from the (meth)acrylic acid ester compound having an adamantane skeleton in the iodine- and hydroxyl-containing polymer obtained after the acid treatment is the same as that of the iodine- and ether-structure-containing polymer produced by radical polymerization described above.

[0305] The iodine- and hydroxyl-containing polymer obtained after the acid treatment may further contain, in addition to the structural unit represented by formula (U), a repeating unit derived from the (meth)acrylic acid ester compound having a lactone skeleton as described above. The content of the repeating unit derived from the (meth)acrylic acid ester compound having a lactone skeleton in the iodine- and hydroxyl-containing polymer obtained after the acid treatment is the same as that of the iodine- and ether-containing polymer produced by radical polymerization as described above.

[0306] The iodine- and hydroxyl-containing polymer obtained after the acid treatment may contain both 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. The iodine- and hydroxyl-containing polymer obtained after the acid treatment may further contain a repeating unit derived from another (meth)acrylic acid ester compound as described above. The iodine- and hydroxyl-containing polymer obtained after the acid treatment may further contain a repeating unit derived from a styrene-based compound as described above.

[0307] When the iodine- and hydroxyl-containing polymer obtained after the acid treatment contains two or more kinds of repeating units, it is preferred that these repeating units are arranged randomly.

[0308] The weight average molecular weight (Mw) of the iodine- and hydroxyl-containing polymer obtained after the acid treatment is preferably 5,000 to 30,000, more preferably 8,000 to 20,000, and particularly preferably 10,000 to 15,000. The dispersity (Mw / Mn) of the iodine- and hydroxyl-containing polymer obtained after the acid treatment is preferably 1.1 to 5.0, more preferably 1.4 to 3.0, and particularly preferably 1.6 to 2.5.

[0309] The above-mentioned iodine-ether structure-containing polymer produced by radical polymerization and the iodine-hydroxyl group-containing polymer obtained after acid treatment are useful as photoresist layer-forming materials. Furthermore, the iodine-ether structure-containing polymer and the iodine-hydroxyl group-containing polymer produced by radical polymerization are useful as resist top layer film-forming materials, resist middle layer-forming materials, and resist underlayer film-forming materials. Furthermore, the iodine-ether structure-containing polymer produced by radical polymerization and the iodine-hydroxyl group-containing polymer obtained after acid treatment are useful as resist materials for KrF excimer laser exposure, ArF excimer laser exposure, electron beam (EB) exposure, and EUV exposure. The iodine-ether structure-containing polymer produced by radical polymerization, particularly the iodine-hydroxyl group-containing polymer obtained after acid treatment, can form a film having high sensitivity and stability over time to the various exposure light sources described above, and can provide a good resist pattern shape. That is, the resist composition used as the material (the composition for forming the photoresist layer) contains an iodine-ether structure-containing polymer produced by radical polymerization and / or an iodine-hydroxyl group-containing polymer obtained after acid treatment, and preferably contains an iodine-hydroxyl group-containing polymer obtained after acid treatment. In particular, by using a resist composition containing the iodine-hydroxyl group-containing polymer of this embodiment, the EUV sensitivity and temporal stability of the resulting resist are further improved.

[0310] <<Method for manufacturing an electronic device using a resist composition containing a photoresist layer-forming material>> As described above, the iodine-ether structure-containing polymer produced by radical polymerization and the iodine-hydroxyl group-containing polymer obtained after acid treatment are useful for forming resist patterns, and are particularly suitable for the manufacture of semiconductor elements and liquid crystal display elements having finer wiring patterns, and are useful for the manufacture of electronic devices including semiconductor devices (e.g., semiconductor integrated circuits) having such wiring patterns.

[0311] When an electronic device is manufactured using the iodine- and hydroxyl-containing polymer obtained after the acid treatment, the electronic device can be manufactured by a method including, in addition to the above-described step (i) of heating or irradiating a composition containing a compound represented by formula (I) and / or formula (II) (preferably a composition further containing a radical polymerization initiator) and further treating it with acid to obtain an iodine- and hydroxyl-containing polymer, (ii) a step of forming a photoresist layer containing the iodine- and hydroxyl-containing polymer obtained in the step (i) on a substrate, (iii) a step of exposing the photoresist layer formed in the step (ii) to light, and (iv) a step of developing the photoresist layer exposed in the step (iii).

[0312] In step (ii), the formation of a photoresist layer on a substrate is carried out by coating the substrate with a resist composition obtained by mixing an iodine- and hydroxyl-containing polymer with an organic solvent and, if necessary, additives. The resist composition can be coated onto the substrate using a coating device such as a spin coater, a dip coater, or a roller coater. The substrate is not particularly limited, but examples thereof include a silicon wafer, a metal substrate, a plastic substrate, a glass substrate, and a ceramic substrate. Before coating the resist composition onto the substrate, the substrate may be cleaned, and an anti-reflective film or the like may be formed on the substrate.

[0313] In the production of an electronic device, when an iodine-ether structure-containing polymer produced by radical polymerization is used, the acid treatment is not performed in the above-mentioned step (i), and the electronic device can be produced by using the iodine-ether structure-containing polymer in place of the iodine-hydroxyl group-containing polymer obtained after the acid treatment in the steps from step (ii) onwards.

[0314] Examples of organic solvents used in the resist composition include glycol ether solvents, glycol ether ester solvents, aliphatic ether solvents, amide solvents, sulfoxide solvents, nitrile solvents, aliphatic ester solvents, halogenated solvents, aliphatic ketone solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, etc. As the aliphatic ether solvents, amide solvents, sulfoxide solvents, nitrile solvents, aliphatic ester solvents, halogenated solvents, aliphatic ketone solvents, aliphatic hydrocarbon solvents, and aromatic hydrocarbon solvents, the solvents exemplified above can be used.

[0315] Examples of glycol ether solvents include 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 (also known as methyl carbitol), and the like. carbitols such as diethylene glycol monopropyl ether (also known as propyl carbitol), 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.

[0316] 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.

[0317] Examples of additives used in the resist composition include acid generators, acid diffusion controllers, acid crosslinkers, dissolution promoters, dissolution controllers, sensitizers, surfactants, etc. These can be used alone or in combination of two or more.

[0318] 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), sulfones (e.g., disulfone, ketosulfone, sulfonyldiazomethane), etc. Examples of ionic acid generators include onium salts containing onium cations (e.g., diazonium salts, phosphonium salts, sulfonium salts, iodonium salts), etc. Examples of anions of onium salts include sulfonate anions, sulfonylimide anions, sulfonylmethide anions, etc.

[0319] Specific examples of the acid generator used in the resist composition include, but 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 nate, 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, diphenyl naphthylsulfonium trifluoromethanesulfonate, diphenyl-4-hydroxyphenylsulfonium-p-toluenesulfonate, triphenylsulfonium 10-camphorsulfonate, diphenyl-4-hydroxyphenylsulfonium 10-camphorsulfonate, and cyclo(1,3-perfluoropropanedisulfone imidate. The acid generators can be used alone or in combination with one another. The amount of acid generator blended into the resist composition is preferably 0.001 to 49 mass%, more preferably 1 to 40 mass%, even more preferably 3 to 30 mass%, and still more preferably 10 to 25 mass%, based on the total mass of the solid components of the resist composition.

[0320] Specific examples of the acid diffusion controller used in the resist composition include, but 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, 4-t-butylphenyl-4-hydroxyphenyliodonium salicylate, and the like. The amount of acid diffusion controller added to the resist composition is preferably 0.001 to 49 mass%, more preferably 0.01 to 10 mass%, even more preferably 0.01 to 5 mass%, and particularly preferably 0.01 to 3 mass%, based on the total mass of the solid components of the resist composition.

[0321] Examples of acid crosslinking agents used in the resist composition 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 glycoluril compounds, and methylol group-containing phenolic 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 glycoluril compounds, and alkoxyalkyl group-containing phenolic 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 glycoluril compounds, and carboxymethyl group-containing phenolic 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, resole resin-based epoxy compounds, and poly(hydroxystyrene)-based epoxy compounds. These acid crosslinking agents can be used alone or in combination. The amount of acid crosslinker blended into the resist composition is preferably 0 to 49 mass%, more preferably 0 to 40 mass%, even more preferably 0 to 30 mass%, and particularly preferably 0 to 20 mass%, based on the total mass of the solid components of the resist composition.

[0322] Examples of dissolution accelerators used in the resist composition include low-molecular-weight phenolic compounds, such as bisphenols and tris(hydroxyphenyl)methane. These dissolution accelerators can be used alone or in combination with other types. 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.

[0323] Examples of dissolution controllers used in the resist composition include aromatic hydrocarbons such as phenanthrene, anthracene, and acenaphthene; aromatic ketones such as acetophenone, benzophenone, and phenyl naphthyl ketone; and aromatic sulfones such as methyl phenyl sulfone, diphenyl sulfone, and dinaphthyl sulfone. These dissolution controllers can be used alone or in combination with other types of controllers. The amount of dissolution controller 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.

[0324] Examples of sensitizers used in the resist composition include, but are not limited to, benzophenones, biacetyls, pyrenes, phenothiazines, and fluorenes. These sensitizers can be used alone or in combination with one another. 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.

[0325] 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 alkyl phenyl ethers, and higher fatty acid diesters of polyethylene glycol. The surfactants may be used alone or in combination of two or more. The amount of surfactant blended in 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.

[0326] The resist composition may further contain known components that are generally used in resist compositions, such as dyes, pigments, adhesion aids, antihalation agents, storage stabilizers, antifoaming agents, and shape improvers.

[0327] After coating the resist composition on the substrate, the solvent is removed and the resist composition is dried to form a photoresist layer. Drying can be performed by, for example, heat drying using a hot plate or vacuum drying. In the case of heat 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 ５ The thickness of the photoresist layer formed is, for example, 50 nm to 1 μm.

[0328] In step (iii), the photoresist layer formed in step (ii) is exposed by irradiating it with radiation. For example, an exposure method using an exposure machine equipped with an exposure light source can be used. The exposure machine may be an immersion exposure machine. Examples of exposure light sources that can be used include light sources that emit ultraviolet laser light such as KrF excimer laser, ArF excimer laser, and F2 excimer laser; light sources that emit harmonic laser light in the far ultraviolet or vacuum ultraviolet range by wavelength conversion of laser light from a solid-state laser light source (e.g., YAG or semiconductor laser); and light sources that irradiate electron beams or extreme ultraviolet light (EUV). During exposure, exposure may be performed through a mask with a desired pattern, or by direct writing without using a mask. In order to stably form a highly accurate fine pattern, a heat treatment may be performed after exposure, for example, at a temperature of 50 to 200°C, preferably 70 to 150°C, for 30 seconds or more.

[0329] In step (iv), the photoresist layer exposed in step (iii) is developed with a developer to form a resist pattern. Examples of development methods include dipping, puddling, spraying, and dynamic dispensing. 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 either a positive resist pattern or a negative resist pattern.

[0330] When producing a positive resist pattern, an alkaline developer is used as the developer. Examples of alkaline developers include alkaline aqueous solutions in which alkaline compounds such as alkali metal hydroxides, aqueous ammonia, alkylamines, alkanolamines, heterocyclic amines, tetraalkylammonium hydroxides, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, and 1,5-diazabicyclo-[4.3.0]-5-nonene are dissolved to a concentration of typically 1 to 10% by mass, preferably 1 to 3% by mass. A water-soluble organic solvent or surfactant 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 water remaining on the substrate and the pattern.

[0331] When producing a negative resist pattern, an organic developer containing an organic solvent is used as the developer. Examples of the organic solvent contained 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 a trace amount of water, a surfactant, and the like. During development, the development may be stopped by replacing the organic developer with a different type of solvent.

[0332] The developed resist pattern is preferably washed with a rinse solution. The rinse solution is not particularly limited as long as it does not dissolve the resist pattern. After washing, it is preferable to remove the rinse solution remaining on the substrate and the pattern.

[0333] Examples of electronic devices obtained from compositions containing the compounds represented by formula (I) and / or formula (II) include personal computers, smartphones, smart watches, digital cameras, televisions, car navigation systems, printers, liquid crystal displays, electronic dictionaries, game consoles, automobiles, ships, trains, and aircraft.

[0334] The present invention will be described in more detail below with reference to examples. The present invention is not limited to these examples. In the following, room temperature is assumed to 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).

[0335] The LC (liquid chromatography) measurement conditions in each example are as follows. Apparatus name: Shimadzu Corporation (Nexera-i LC-2020C 3D) Column: Waters XBridge BEH C18 (2.5 μm 3.0 × 75 mm) Detector: PDA (photodiode array detector) Flow rate: 0.7 mL / min Column oven temperature: 40 ° C Autosampler temperature: 15 ° C Amount: 1.0 μL (2 mg / mL THF solution) Eluent (%): ultrapure water: MeCN: 1% phosphoric acid aqueous solution (0:98:2) to (93:5:2) Measured. LC purity was calculated as the ratio (area %) of the peak area of ​​the target compound to the total area of ​​all detected peaks in the chromatogram obtained by LC. The measurement wavelength was 220 nm. In the following, the unit of LC purity, "area %", may be abbreviated to simply "%".

[0336] Example A1: Synthesis of 1-(3-iodo-5-methoxy-4-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate

[0337] Step A: Synthesis of 4-(1-hydroxyethyl)-2-iodo-6-methoxyphenol

[0338]

[0339] Under a light-shielded condition, a 500 mL three-neck flask was prepared, and 108 mL of dehydrated tetrahydrofuran (THF) and 15.0 g (53.9 mmol) of 5-iodovanillin were added thereto. ２The mixture was stirred for 30 minutes under ice cooling under a flow rate to maintain the internal temperature at 10°C or below. 119 mL of methylmagnesium bromide (119 mmol, 1.0 M THF solution) was added to a 500 mL three-neck flask over 80 minutes, and stirring was continued for 15 minutes. 150 g of saturated aqueous ammonium chloride solution was added dropwise over 30 minutes so that the internal temperature remained at 15°C or below. 300 mL of ethyl acetate was added, stirred for 15 minutes, and allowed to stand, after which the aqueous layer was removed. 100 g of ion-exchanged water was added, stirred for 15 minutes, allowed to stand, and the aqueous layer was removed. This procedure was repeated twice. The recovered organic layer was concentrated by vacuum distillation until no solvent components were distilled out, yielding the target product, 4-(1-hydroxyethyl)-2-iodo-6-methoxyphenol (14.3 g, 48.7 mmol). The purity of the resulting 4-(1-hydroxyethyl)-2-iodo-6-methoxyphenol as measured by LC (liquid chromatography) at 220 nm was 98%.

[0340] Step B: Synthesis of 1-(4-hydroxy-3-iodo-5-methoxyphenyl)ethyl methacrylate

[0341]

[0342] Under a light-shielded condition, a 1000 mL three-neck flask was prepared, and 240 mL of dehydrated THF and 16 g (54.4 mmol) of 4-(1-hydroxyethyl)-2-iodo-6-methoxyphenol obtained in Step A of Example A1 were added thereto. ２Under flow, the mixture was stirred for 30 minutes while ice-cooling so that the internal temperature was 10 ° C. or less. 6.9 mL (81.6 mmol) of methacrylic acid and 34.4 mL (65.3 mmol) of diisopropyl azodicarboxylate (DIAD) were added to a 1000 mL three-necked flask, and a solution of 17.2 g (65.3 mmol) of triphenylphosphine dissolved in 40 mL of THF was added dropwise over 50 minutes while ice-cooling so that the internal temperature was 10 ° C. or less. Stirring was then continued for 30 minutes, and 100 g of saturated aqueous ammonium chloride solution was added so that the internal temperature was 10 ° C. or less. 400 mL of ethyl acetate was added, stirred for 15 minutes, and then allowed to stand, and the aqueous layer was drained. 100 g of ion-exchanged water was then added, stirred for 15 minutes, and then allowed to stand, and the aqueous layer was drained. This operation was repeated twice. Thereafter, 50 g of saturated saline was added, and the mixture was stirred for 15 minutes, then allowed to stand, and the aqueous layer was removed. 70 g of sodium sulfate was added to the recovered organic layer, and the mixture was stirred for 10 minutes and filtered. The resulting organic layer was concentrated until no more solvent components were distilled off, yielding 56.1 g of a crude product. The target product, 1-(4-hydroxy-3-iodo-5-methoxyphenyl)ethyl methacrylate, was partially decomposed under the purification conditions, so it was subjected to the next reaction without further purification.

[0343] Step C: Synthesis of 1-(3-iodo-5-methoxy-4-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate

[0344]

[0345] Under light-shielded conditions, a 500 mL three-neck flask was prepared and filled with N ２Under a flow condition, 56.1 g of the crude product of 1-(4-hydroxy-3-iodo-5-methoxyphenyl)ethyl methacrylate obtained in Step B of Example A1, 140 mL of dichloromethane, 49 mL (540 mmol) of 3,4-dihydro-2H-pyran (DHP), and 1.5 mL (19.6 mmol) of trifluoroacetic acid (TFA) were added, and the mixture was stirred at an internal temperature of 25°C for 24 hours. Thereafter, 4.79 mL (34.3 mmol) of triethylamine and 100 g of ion-exchanged water were added, and the mixture was stirred for 15 minutes and allowed to stand, after which the organic layer was recovered. The recovered organic layer was concentrated until no solvent components were distilled out, and a crude product was obtained. The resulting crude product was purified using NH silica gel, followed by column purification using silica gel, and then low-boiling components were removed by drying under reduced pressure at 20 hPa or less, 60°C, and heat at 60°C for 8 hours, thereby obtaining the target product, 1-(3-iodo-5-methoxy-4-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate (10.8 g, 24.2 mmol). The LC purity at 220 nm of the resulting 1-(3-iodo-5-methoxy-4-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate was 99.5%.

[0346] 1 H NMR (500 MHz, DMSO-d6) δ7.36(1H, Ph), 7.07(1H, Ph), 6.09(1H, =CH2), 5.79(1H, -CH-Ph), 5.72(1H, =CH2), 5.57(1H, O-CH-O), 4.09(1H, O-CH2-), 3.79(3H, -OCH3), 3.47(1H, O-CH2-), 1.97(1H, C-CH2-C), 1.89(4H, C-CH2-C, CH3-C=C), 1.76(1H, C-CH2-C), 1.60(3H, C-CH2-C), 1.49(3H, CH3-CH-Ph)

[0347] Example A2: Synthesis of 1-(3-iodo-5-methoxy-4-((octahydro-2H,2'H-[2,3'-bipyran]-2'-yl)oxy)phenyl)ethyl methacrylate

[0348]

[0349] Under light-shielded conditions, a 1000 mL three-neck flask was prepared and filled with N ２ Under a flow condition, 56.1 g of the 1-(4-hydroxy-3-iodo-5-methoxyphenyl)ethyl methacrylate crude product obtained in Step B of Example A1, 500 mL (5520 mmol) of 3,4-dihydro-2H-pyran (DHP), and 1.5 mL (19.6 mmol) of trifluoroacetic acid (TFA) were added, and the mixture was stirred at an internal temperature of 25°C for 24 hours. Thereafter, 4.79 mL (34.3 mmol) of triethylamine and 200 g of ion-exchanged water were added, and the mixture was stirred for 15 minutes and allowed to stand, after which the organic layer was recovered. The recovered organic layer was concentrated until no solvent components were distilled out, and a crude product was obtained. The resulting crude product was purified using NH silica gel, followed by column purification using silica gel, and then low-boiling components were removed by drying under reduced pressure at 20 hPa or less and 60°C for 8 hours with heating to obtain the target product, 1-(3-iodo-5-methoxy-4-((octahydro-2H,2'H-[2,3'-bipyran]-2'-yl)oxy)phenyl)ethyl methacrylate (11.8 g, 22.2 mmol). The LC purity at 220 nm of the resulting 1-(3-iodo-5-methoxy-4-((octahydro-2H,2'H-[2,3'-bipyran]-2'-yl)oxy)phenyl)ethyl methacrylate was 99.1%.

[0350] 1 H NMR (500 MHz, DMSO-d6) δ7.36(1H, Ph), 7.07(1H, Ph), 6.09(1H, =CH2), 5.79(1H, -CH-Ph), 5.72(1H, =CH2), 5.57(1H, O-CH-O), 4.09(1H, O-CH2-), 4.02(1H, O-CH2-), 3.79(3H, -OCH3), 3.50(1H, O-CH2-), 3.47(2H, O-CH2-, O-CH-CH), 1.97(2H, C-CH2-C), 1.89(4H, C-CH-C, CH3-C=C), 1.76(2H, C-CH2-C), 1.60(6H, C-CH2-C), 1.49(3H, CH3-CH-Ph) ​

[0351] Example A3: Synthesis of 1-(4-(ethoxymethoxy)-3-iodo-5-methoxyphenyl)ethyl methacrylate

[0352] Step A: Synthesis of 4-(ethoxymethoxy)-3-iodo-5-methoxybenzaldehyde

[0353]

[0354] Under light-shielded conditions, a 300 mL three-neck flask was prepared and filled with N ２ Under a flow condition, 27.8 g (99.9 mmol) of 5-iodovanillin and 150 g of DMF were added, and then 15.2 g (109.9 mmol) of potassium carbonate was added while ice-cooling to keep the internal temperature at 5°C or less, and stirring was continued for 30 minutes. Thereafter, 10.4 g (109.9 mmol) of chloromethyl ethyl ether was added while ice-cooling to keep the internal temperature at 5°C or less, and stirring was continued for 2 hours. Thereafter, 200 g of ion-exchanged water and 100 mL of ethyl acetate were added while ice-cooling to keep the internal temperature at 15°C or less, and the mixture was stirred at room temperature for 15 minutes, allowed to stand, and then the aqueous layer was drained. Further, 100 g of ion-exchanged water was added, stirred for 15 minutes, allowed to stand, and the aqueous layer was drained. This operation was repeated twice. The recovered organic layer was concentrated by vacuum distillation until no solvent components were distilled away, yielding the target product, 4-(ethoxymethoxy)-3-iodo-5-methoxybenzaldehyde (30.2 g, 89.8 mmol). The LC purity of the obtained 4-(ethoxymethoxy)-3-iodo-5-methoxybenzaldehyde at 254 nm was 99.3%.

[0355] Step B: Synthesis of 1-(4-(ethoxymethoxy)-3-iodo-5-methoxyphenyl)ethan-1-ol

[0356]

[0357] Under a light-shielded condition, a 2000 mL three-neck flask was prepared, and 420 mL of dehydrated THF and 30 g (89.2 mmol) of 4-(ethoxymethoxy)-3-iodo-5-methoxybenzaldehyde obtained in Step A of Example A3 were charged thereinto, and N ２The mixture was stirred for 30 minutes under ice cooling under a flow rate to maintain the internal temperature at 10°C or below. 135 mL of methylmagnesium bromide (135 mmol, 1.0 M THF solution) was added to a 2000 mL three-neck flask over 60 minutes, and stirring was continued for 45 minutes. 200 g of saturated aqueous ammonium chloride solution was added dropwise over 30 minutes so that the internal temperature remained at 15°C or below. 400 mL of toluene was added, and the mixture was stirred for 15 minutes and allowed to stand, after which the aqueous layer was removed. 200 g of ion-exchanged water was added, stirred for 15 minutes, allowed to stand, and the aqueous layer was removed. This procedure was repeated twice. The recovered organic layer was concentrated by vacuum distillation until no solvent components were distilled out, yielding a crude product. The crude product obtained was purified using a silica gel column to obtain the target product, 1-(4-(ethoxymethoxy)-3-iodo-5-methoxyphenyl)ethan-1-ol (20.8 g, 59.0 mmol). The LC purity of the resulting 1-(4-(ethoxymethoxy)-3-iodo-5-methoxyphenyl)ethan-1-ol at 220 nm was 96.5%.

[0358] Step C: Synthesis of 1-(4-(ethoxymethoxy)-3-iodo-5-methoxyphenyl)ethyl methacrylate

[0359]

[0360] Under light-shielded conditions, a 1000 mL three-neck flask was prepared and filled with N ２Under a flow condition, 20.8 g (59.0 mmol) of 1-(4-(ethoxymethoxy)-3-iodo-5-methoxyphenyl)ethan-1-ol obtained in Step B of Example A3 and 280 mL of THF were added, and then 8.96 g (88.5 mmol) of triethylamine and 1.0 g (8.1 mmol) of 4-dimethylaminopyridine (DMAP) were added while ice-cooling so that the internal temperature was 5°C or less, and stirring was continued for 30 minutes. Thereafter, 12.7 g (82.3 mmol) of methacrylic anhydride was added while ice-cooling so that the internal temperature was 5°C or less, and stirring was continued for 1 hour. Thereafter, 200 g of saturated aqueous ammonium chloride solution was added while ice-cooling so that the internal temperature was 15°C or less. An additional 200 mL of ethyl acetate was added, and the mixture was stirred for 15 minutes, allowed to stand, and then the aqueous layer was drained. Further, 100 g of ion-exchanged water was added, stirred for 15 minutes, allowed to stand, and the aqueous layer was drained. This operation was repeated twice. The recovered organic layer was concentrated by distillation under reduced pressure until no solvent components were distilled out, yielding a crude product. The crude product obtained was purified using a column with silica gel to obtain the target compound, 1-(4-(ethoxymethoxy)-3-iodo-5-methoxyphenyl)ethyl methacrylate (19.4 g, 46.1 mmol). The LC purity at 220 nm of the obtained 1-(4-(ethoxymethoxy)-3-iodo-5-methoxyphenyl)ethyl methacrylate was 99.0%.

[0361] 1 H NMR (500 MHz, DMSO-d6) δ7.36(1H, Ph), 7.07(1H, Ph), 6.09(1H, =CH2), 5.90(2H, O-CH2-O), 5.79(1H, -CH-Ph), 5.72(1H, =CH2), 3.83(3H, -OCH3), 3.47(2H, O-CH2-), 2.10(3H, CH3-C=C), 1.49(3H, CH3-CH-Ph), 1.15(3H, CH3-CH2)

[0362] Example A4: Synthesis of 1-(3,5-diiodo-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate

[0363] Step A: Synthesis of 2-(1-hydroxyethyl)-4,6-diiodophenol

[0364]

[0365] The procedure was repeated in the same manner as in Step A of Example A1, except that 20.2 g (53.9 mmol) of 2-hydroxy-3,5-diiodobenzaldehyde was used instead of 15.0 g (53.9 mmol) of 5-iodovanillin, to obtain 17.9 g (45.8 mmol) of 2-(1-hydroxyethyl)-4,6-diiodophenol. The LC purity at 220 nm of the obtained 2-(1-hydroxyethyl)-4,6-diiodophenol was 90%.

[0366] Step B: Synthesis of 1-(2-hydroxy-3,5-diiodophenyl)ethyl methacrylate

[0367]

[0368] In step B of Example A1, 50.3 g of 1-(2-hydroxy-3,5-diiodophenyl)ethyl methacrylate was obtained in the same manner as in step B of Example A1, except that 17.9 g (45.8 mmol) of 2-(1-hydroxyethyl)-4,6-diiodophenol obtained in step A of Example A4 was used instead of 4-(1-hydroxyethyl)-2-iodo-6-methoxyphenol. This was used in the next reaction without further purification.

[0369] Step C: Synthesis of 1-(3,5-diiodo-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate

[0370]

[0371] The procedure was repeated in the same manner as in Step C of Example A1, except that 50.3 g of the crude product of 1-(2-hydroxy-3,5-diiodophenyl)ethyl methacrylate obtained in Step B of Example A4 was used instead of 1-(4-hydroxy-3-iodo-5-methoxyphenyl)ethyl methacrylate in Step C of Example A1, to obtain 14.2 g (26.1 mmol) of 1-(3,5-diiodo-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate. The LC purity at 220 nm of the obtained 1-(3,5-diiodo-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate was 99.7%. 1 H NMR (500 MHz, DMSO-d6) δ8.15(1H, Ph), 7.67(1H, Ph), 6.06(1H, CH2=C), 5.79(1H, -CH-Ph), 5.72(1H, CH2=C), 5.42(1H, O-CH-O), 3.75(1H, O-CH2-C), 3.41(1H, O-CH2-C), 2.03(1H, C-CH2-C), 1.89(3H, CH3-C=C), 1.85(1H, C-CH2-C), 1.75(1H, C-CH2-C), 1.55(1H, C-CH2-C), 1.50(2H, C-CH2-C), 1.45 (3H, CH3-CH-Ph)

[0372] Example A5: Synthesis of 1-(3,5-diiodo-2-((octahydro-2H,2'H-[2,3'-bipyran]-2'-yl)oxy)phenyl)ethyl methacrylate

[0373]

[0374] The same procedure as in Example A2 was carried out, except that 50.3 g of the crude product of 1-(2-hydroxy-3,5-diiodophenyl)ethyl methacrylate obtained in Step B of Example A4 was used instead of 1-(4-hydroxy-3-iodo-5-methoxyphenyl)ethyl methacrylate in Example A2, to obtain 15.0 g (23.9 mmol) of 1-(3,5-diiodo-2-((octahydro-2H,2'H-[2,3'-bipyran]-2'-yl)oxy)phenyl)ethyl methacrylate. The LC purity at 220 nm of the obtained 1-(3,5-diiodo-2-((octahydro-2H,2'H-[2,3'-bipyran]-2'-yl)oxy)phenyl)ethyl methacrylate was 99.4%. 1 H NMR (500 MHz, DMSO-d6) δ8.15(1H, Ph), 7.67(1H, Ph), 6.06(1H, CH2=C), 5.79(1H, -CH-Ph), 5.72(1H, CH2=C), 5.42(1H, O-CH-O), 4.05 (1H, O-CH2-), 4.02 (1H, O-CH2-), 3.53(1H, O-CH2-), 3.47 (1H, O-CH-CH), 3.41 (1H, O-CH2-), 2.01 (2H, C-CH2-C), 1.95(1H, C-CH-C), 1.89(3H, CH3-C=C), 1.81 (2H, C-CH2-C), 1.72 (2H, C-CH2-C), 1.52 (4H, C-CH2-C), 1.47 (3H, CH3-CH-Ph)

[0375] Example A6: Synthesis of 1-(2-(ethoxymethoxy)-3,5-diiodophenyl)ethyl methacrylate

[0376] Step A: Synthesis of 2-(ethoxymethoxy)-3,5-diiodobenzaldehyde

[0377]

[0378] 21.2 g (49.0 mmol) of 2-(ethoxymethoxy)-3,5-diiodobenzaldehyde was obtained in the same manner as in Step A of Example A3, except that 18.7 g (50.0 mmol) of 2-hydroxy-3,5-diiodobenzaldehyde was used instead of 5-iodovanillin in Step A of Example A3. The LC purity of the obtained 2-(ethoxymethoxy)-3,5-diiodobenzaldehyde at 220 nm was 99.2%.

[0379] Step B: Synthesis of 1-(2-(ethoxymethoxy)-3,5-diiodophenyl)ethan-1-ol

[0380]

[0381] The procedure was repeated in the same manner as in Step B of Example A3, except that 21.2 g (49.0 mmol) of 2-(ethoxymethoxy)-3,5-diiodobenzaldehyde obtained in Step A of Example A6 was used instead of 4-(ethoxymethoxy)-3-iodo-5-methoxybenzaldehyde in Step B of Example A3, to obtain 15.8 g (35.3 mmol) of 1-(2-(ethoxymethoxy)-3,5-diiodophenyl)ethan-1-ol. The LC purity at 220 nm of the obtained 1-(2-(ethoxymethoxy)-3,5-diiodophenyl)ethan-1-ol was 99.6%.

[0382] Step C: Synthesis of 1-(2-(ethoxymethoxy)-3,5-diiodophenyl)ethyl methacrylate

[0383]

[0384] The procedure was repeated in the same manner as in Step C of Example A3, except that 15.8 g (35.3 mmol) of 1-(2-(ethoxymethoxy)-3,5-diiodophenyl)ethan-1-ol obtained in Step B of Example A6 was used instead of 1-(4-(ethoxymethoxy)-3-iodo-5-methoxyphenyl)ethan-1-ol in Step C of Example A3, to obtain 15.1 g (29.3 mmol) of 1-(2-(ethoxymethoxy)-3,5-diiodophenyl)ethyl methacrylate. The LC purity at 220 nm of the obtained 1-(2-(ethoxymethoxy)-3,5-diiodophenyl)ethyl methacrylate was 99.5%. 1 H NMR (500 MHz, DMSO-d6) δ8.15(1H, Ph), 7.67(1H, Ph), 6.06(1H, CH2=C), 5.89(2H, O-CH2-O), 5.79(1H, -CH-Ph), 5.72(1H, CH2=C), 3.43(2H, O-CH2-C), 1.89(3H, CH3-C=C), 1.39 (3H, CH3-CH-Ph). 1.13 (3H, CH3-CH2-)

[0385] Example A7: Synthesis of 1-(5-iodo-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate

[0386] Step A: Synthesis of 2-(1-hydroxyethyl)-4-iodophenol

[0387]

[0388] The procedure was repeated in the same manner as in Step A of Example A1, except that 13.4 g (53.9 mmol) of 2-hydroxy-5-iodobenzaldehyde was used instead of 15.0 g (53.9 mmol) of 5-iodovanillin, to obtain 12.7 g (48.2 mmol) of 2-(1-hydroxyethyl)-4-iodophenol. The LC purity at 220 nm of the obtained 2-(1-hydroxyethyl)-4-iodophenol was 92%.

[0389] Step B: Synthesis of 1-(2-hydroxy-5-iodophenyl)ethyl methacrylate

[0390]

[0391] In Step B of Example A1, 48.3 g of 2-(1-hydroxyethyl)-4-iodophenol was obtained in the same manner as in Step B of Example A1, except that 12.7 g (48.2 mmol) of 2-(1-hydroxyethyl)-4-iodophenol obtained in Step A of Example A7 was used instead of 4-(1-hydroxyethyl)-2-iodo-6-methoxyphenol. This gave 48.3 g of 2-(1-hydroxyethyl)-4-iodophenol, which was then subjected to the next reaction without further purification.

[0392] Step C: Synthesis of 1-(5-iodo-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate

[0393]

[0394] 9.0 g (21.7 mmol) of 1-(5-iodo-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate was obtained in the same manner as in Step C of Example A1, except that 48.3 g of the crude product of 1-(2-hydroxy-5-iodophenyl)ethyl methacrylate obtained in Step B of Example A7 was used instead of 1-(4-hydroxy-3-iodo-5-methoxyphenyl)ethyl methacrylate in Step C of Example A1. The LC purity at 220 nm of the obtained 1-(5-iodo-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate was 99.7%. 1 H NMR (500 MHz, DMSO-d6) δ7.71(1H, Ph), 7.54(1H, Ph), 6.76(1H, Ph), 6.11(1H, =CH2), 5.91(1H, O-CH-Ph), 5.70(1H, =CH2), 5.57(1H, O-CH-O), 4.12(1H, O-CH2-), 3.47(1H, O-CH2-),1.95(1H, C-CH2-C), 1.90(4H, C-CH2-C, CH3-C=C), 1.71(1H, C-CH2-C), 1.62(3H, C-CH2-C), 1.42 (3H, CH3-CH-Ph)

[0395] Example A8: Synthesis of 1-(5-iodo-2-((octahydro-2H,2'H-[2,3'-bipyran]-2'-yl)oxy)phenyl)ethyl methacrylate

[0396]

[0397] The procedure was repeated in the same manner as in Example A2, except that 48.3 g of the crude product of 1-(2-hydroxy-5-iodophenyl)ethyl methacrylate obtained in Step B of Example A7 was used instead of 1-(4-hydroxy-3-iodo-5-methoxyphenyl)ethyl methacrylate in Example A2, to obtain 10.1 g (20.1 mmol) of 1-(5-iodo-2-((octahydro-2H,2'H-[2,3'-bipyran]-2'-yl)oxy)phenyl)ethyl methacrylate. The LC purity at 220 nm of the obtained 1-(5-iodo-2-((octahydro-2H,2'H-[2,3'-bipyran]-2'-yl)oxy)phenyl)ethyl methacrylate was 99.2%. 1 H NMR (500 MHz, DMSO-d6) δ7.71(1H, Ph), 7.54(1H, Ph), 6.76(1H, Ph), 6.11(1H, =CH2), 5.91(1H, O-CH-Ph), 5.70(1H, =CH2), 5.49(1H, O-CH-O), 4.12 (1H, O-CH2-), 4.08 (1H, O-CH2-), 3.55(1H, O-CH2-), 3.47 (1H, O-CH-CH), 3.42 (1H, O-CH2-), 2.10 (2H, C-CH2-C), 1.92(1H, C-CH-C), 1.89(3H, CH3-C=C), 1.81 (2H, C-CH2-C), 1.75 (2H, C-CH2-C), 1.61 (4H, C-CH2-C), 1.47 (3H, CH3-CH-Ph)

[0398] Example A9: Synthesis of 1-(2-(ethoxymethoxy)-5-iodophenyl)ethyl methacrylate

[0399] Step A: Synthesis of 2-(ethoxymethoxy)-5-iodobenzaldehyde

[0400]

[0401] 14.4 g (47.0 mmol) of 2-(ethoxymethoxy)-5-iodobenzaldehyde was obtained in the same manner as in Step A of Example A3, except that 12.4 g (50.0 mmol) of 2-hydroxy-5-iodobenzaldehyde was used instead of 5-iodovanillin in Step A of Example A3. The LC purity of the obtained 2-(ethoxymethoxy)-5-iodobenzaldehyde at 220 nm was 99.1%.

[0402] Step B: Synthesis of 1-(2-(ethoxymethoxy)-5-iodophenyl)ethan-1-ol

[0403]

[0404] The procedure was repeated in the same manner as in Step B of Example A3, except that 14.4 g (47.0 mmol) of 2-(ethoxymethoxy)-5-iodobenzaldehyde obtained in Step A of Example A9 was used instead of 4-(ethoxymethoxy)-3-iodo-5-methoxybenzaldehyde in Step B of Example A3, to obtain 12.9 g (40.0 mmol) of 1-(2-(ethoxymethoxy)-5-iodophenyl)ethan-1-ol. The LC purity at 220 nm of the obtained 1-(2-(ethoxymethoxy)-5-iodophenyl)ethan-1-ol was 99.7%.

[0405] Step C: Synthesis of 1-(2-(ethoxymethoxy)-5-iodophenyl)ethyl methacrylate

[0406]

[0407] In Step C of Example A3, 11.9 g (30.4 mmol) of 1-(2-(ethoxymethoxy)-5-iodophenyl)ethyl methacrylate was obtained in the same manner as in Step C of Example A3, except that 12.9 g (40.0 mmol) of 1-(2-(ethoxymethoxy)-5-iodophenyl)ethan-1-ol obtained in Step B of Example A9 was used instead of 1-(4-(ethoxymethoxy)-3-iodo-5-methoxyphenyl)ethan-1-ol. The LC purity at 220 nm of the obtained 1-(2-(ethoxymethoxy)-5-iodophenyl)ethyl methacrylate was 99.5%. 1 H NMR (500 MHz, DMSO-d6) δ7.71(1H, Ph), 7.54(1H, Ph), 6.76(1H, Ph), 6.11(1H, =CH2), 5.91(1H, O-CH-Ph), 5.86 (2H, O-CH2-O), 5.70(1H, =CH2), 3.54 ((2H, O-CH2-C), 1.91(3H, CH3-C=C), 1.42 (3H, CH3-CH-Ph), 1.08 (3H, CH3-CH2-)

[0408] Example A10: Synthesis of 1-(5-iodo-3-methoxy-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate

[0409] Step A: Synthesis of 2-(1-hydroxyethyl)-4-iodo-6-methoxyphenol

[0410]

[0411] The procedure was repeated in the same manner as in Step A of Example A1, except that 15.0 g (53.9 mmol) of 2-hydroxy-5-iodo-3-methoxybenzaldehyde was used instead of 5-iodovanillin, to obtain 12.9 g (43.7 mmol) of 2-(1-hydroxyethyl)-4-iodo-6-methoxyphenol. The LC purity at 220 nm of the obtained 2-(1-hydroxyethyl)-4-iodo-6-methoxyphenol was 93%.

[0412] Step B: Synthesis of 1-(2-hydroxy-5-iodo-3-methoxyphenyl)ethyl methacrylate

[0413]

[0414] In Step B of Example A1, 42.9 g of 1-(2-hydroxy-5-iodo-3-methoxyphenyl)ethyl methacrylate was obtained in the same manner as in Step B of Example A1, except that 12.9 g (43.7 mmol) of 2-(1-hydroxyethyl)-4-iodo-6-methoxyphenol obtained in Step A of Example A10 was used instead of 4-(1-hydroxyethyl)-2-iodo-6-methoxyphenol. This was followed by the next reaction without further purification.

[0415] Step C: Synthesis of 1-(5-iodo-3-methoxy-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate

[0416]

[0417] The procedure was repeated in the same manner as in Step C of Example A1, except that 42.9 g of the crude product of 1-(2-hydroxy-5-iodo-3-methoxyphenyl)ethyl methacrylate obtained in Step B of Example A10 was used instead of 1-(4-hydroxy-3-iodo-5-methoxyphenyl)ethyl methacrylate in Step C of Example A1, to obtain 11.0 g (24.7 mmol) of 1-(5-iodo-3-methoxy-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate. The LC purity at 220 nm of the obtained 1-(5-iodo-3-methoxy-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate was 99.6%. 1H NMR (500 MHz, DMSO-d6) δ7.36(1H, Ph), 7.29(1H, Ph), 6.10(1H, =CH2), 5.90 (1H, O-CH-Ph), 5.77(1H, =CH2), 5.14(1H, O-CH-O), 3.87(1H, O-CH2-), 3.80(3H, -OCH3), 3.42(1H, O-CH2-), 1.87(3H, CH3-C=C), 1.80 (2H, C-CH2-C), 1.71(1H, C-CH2-C), 1.52(3H, C-CH2-C), 1.42 (3H, CH3-CH-Ph)

[0418] Example A11: Synthesis of 1-(5-iodo-3-methoxy-2-((octahydro-2H,2'H-[2,3'-bipyran]-2'-yl)oxy)phenyl)ethyl methacrylate

[0419]

[0420] The procedure of Example A2 was repeated, except that 42.9 g of the crude product of 1-(2-hydroxy-5-iodo-3-methoxyphenyl)ethyl methacrylate obtained in Step B of Example A10 was used instead of 1-(4-hydroxy-3-iodo-5-methoxyphenyl)ethyl methacrylate in Example A2, to obtain 12.6 g (23.8 mmol) of 1-(5-iodo-3-methoxy-2-((octahydro-2H,2'H-[2,3'-bipyran]-2'-yl)oxy)phenyl)ethyl methacrylate. The LC purity at 220 nm of the obtained 1-(5-iodo-3-methoxy-2-((octahydro-2H,2'H-[2,3'-bipyran]-2'-yl)oxy)phenyl)ethyl methacrylate was 99.1%. 1H NMR (500 MHz, DMSO-d6) δ7.36(1H, Ph), 7.29(1H, Ph), 6.10(1H, =CH2), 5.90 (1H, O-CH-Ph), 5.77(1H, =CH2), 5.45(1H, O-CH-O), 4.17 (1H, O-CH2-), 4.08 (1H, O-CH2-), 3.86(3H, -OCH3), 3.53(1H, O-CH2-), 3.42 (1H, O-CH-CH), 3.40 (1H, O-CH2-), 2.10 (2H, C-CH2-C), 1.96(1H, C-CH-C), 1.91 (3H, CH3-C=C), 1.81 (2H, C-CH2-C), 1.75 (2H, C-CH2-C), 1.61 (4H, C-CH2-C), 1.45 (3H, CH3-CH-Ph)

[0421] Example A12: Synthesis of 1-(2-(ethoxymethoxy)-5-iodo-3-methoxyphenyl)ethyl methacrylate

[0422] Step A: Synthesis of 2-(ethoxymethoxy)-5-iodo-3-methoxybenzaldehyde

[0423]

[0424] 16.5 g (48.5 mmol) of 2-(ethoxymethoxy)-5-iodo-3-methoxybenzaldehyde was obtained in the same manner as in Step A of Example A3, except that 13.9 g (50.0 mmol) of 2-hydroxy-5-iodo-3-methoxybenzaldehyde was used instead of 5-iodovanillin in Step A of Example A3. The LC purity of the obtained 2-(ethoxymethoxy)-5-iodo-3-methoxybenzaldehyde at 220 nm was 99.2%.

[0425] Step B: Synthesis of 1-(2-(ethoxymethoxy)-5-iodo-3-methoxyphenyl)ethan-1-ol

[0426]

[0427] The procedure was repeated in the same manner as in Step B of Example A3, except that 16.5 g (48.5 mmol) of 2-(ethoxymethoxy)-5-iodo-3-methoxybenzaldehyde obtained in Step A of Example A12 was used instead of 4-(ethoxymethoxy)-3-iodo-5-methoxybenzaldehyde in Step B of Example A3, to obtain 11.9 g (33.9 mmol) of 1-(2-(ethoxymethoxy)-5-iodo-3-methoxyphenyl)ethan-1-ol. The LC purity at 220 nm of the obtained 1-(2-(ethoxymethoxy)-5-iodo-3-methoxyphenyl)ethan-1-ol was 99.7%.

[0428] Step C: Synthesis of 1-(2-(ethoxymethoxy)-5-iodo-3-methoxyphenyl)ethyl methacrylate

[0429]

[0430] The procedure was repeated in the same manner as in Step C of Example A3, except that 11.9 g (33.9 mmol) of 1-(2-(ethoxymethoxy)-5-iodo-3-methoxyphenyl)ethan-1-ol obtained in Step B of Example A12 was used instead of 1-(4-(ethoxymethoxy)-3-iodo-5-methoxyphenyl)ethan-1-ol in Step C of Example A3, to obtain 10.8 g (25.7 mmol) of 1-(2-(ethoxymethoxy)-5-iodo-3-methoxyphenyl)ethyl methacrylate. The LC purity at 220 nm of the obtained 1-(2-(ethoxymethoxy)-5-iodo-3-methoxyphenyl)ethyl methacrylate was 99.5%. 1 H NMR (500 MHz, DMSO-d6) δ7.38(1H, Ph), 7.30(1H, Ph), 6.11(1H, =CH2), 5.90 (1H, O-CH-Ph), 5.82 (2H, O-CH2-O), 5.77(1H, =CH2), 3.80(3H, -OCH3), 3.56 (2H, O-CH2-C), 1.87(3H, CH3-C=C), 1.42 (3H, CH3-CH-Ph), 1.12 (3H, CH3-CH2-)

[0431] Comparative Example A1: Synthesis of 1-(4-(1-ethoxyethoxy)-3-iodo-5-methoxyphenyl)ethyl methacrylate

[0432]

[0433] The same procedure as in Step C of Example A1 was carried out, except that 38.9 g (540 mmol) of ethyl vinyl ether was used instead of 3,4-dihydro-2H-pyran (DHP) in Step C of Example A1, to obtain 12.1 g (27.8 mmol) of 1-(4-(1-ethoxyethoxy)-3-iodo-5-methoxyphenyl)ethyl methacrylate. The LC purity at 220 nm of the obtained 1-(4-(1-ethoxyethoxy)-3-iodo-5-methoxyphenyl)ethyl methacrylate was 99.3%. 1 H NMR (500 MHz, DMSO-d6) δ7.36(1H, Ph), 7.12(1H, Ph), 6.09(1H, =CH2), 5.79(1H, -CH-Ph), 5.72(1H, =CH2), 5.64 (1H, O-CH-O), 3.83(3H, -OCH3), 3.76 (1H, O-CH2-), 3.59 (1H, O-CH2-), 2.10(3H, CH3-C=C), 1.49(3H, CH3-CH-Ph), 1.34 (3H, CH3-CH), 1.07(3H, CH2-CH3)

[0434] Comparative Example A2: Synthesis of 1-(4-((cyclohexylmethoxy)methoxy)-3-iodo-5-methoxyphenyl)ethyl methacrylate

[0435] Step A: Synthesis of 4-((cyclohexylmethoxy)methoxy)-3-iodo-5-methoxybenzaldehyde

[0436]

[0437] Prepare a 200 mL three-neck flask and add N ２Under a flow of water, 3.3 g (110 mmol) of paraformaldehyde and 43.5 g (400 mmol) of trimethylsilyl chloride were added and cooled to an internal temperature of 0°C. After adding 11.4 g (100 mmol) of cyclohexylmethanol, the mixture was stirred at an internal temperature of 0°C for one hour, then warmed to room temperature and stirred at room temperature for another hour. The mixture was then concentrated until excess trimethylsilyl chloride was no longer distilled, yielding a crude product of ((chloromethoxy)methyl)cyclohexane. The entire amount of the obtained crude product of ((chloromethoxy)methyl)cyclohexane was used as is in the following reaction. A crude product of 4-((cyclohexylmethoxy)methoxy)-3-iodo-5-methoxybenzaldehyde was obtained in the same manner as in Step A of Example A3, except that in Step A of Example A3, 13.9 g (50.0 mmol) of 5-iodovanillin and the entire amount of the crude product of ((chloromethoxy)methyl)cyclohexane obtained above were used instead of chloromethyl ethyl ether. The resulting crude product was purified using a silica gel column to obtain 18.4 g (45.5 mmol) of the target compound, 4-((cyclohexylmethoxy)methoxy)-3-iodo-5-methoxybenzaldehyde. The LC purity at 220 nm of the resulting 4-((cyclohexylmethoxy)methoxy)-3-iodo-5-methoxybenzaldehyde was 99.6%.

[0438] Step B: Synthesis of 1-(4-((cyclohexylmethoxy)methoxy)-3-iodo-5-methoxyphenyl)ethan-1-ol

[0439]

[0440] 13.6 g (32.3 mmol) of 1-(4-((cyclohexylmethoxy)methoxy)-3-iodo-5-methoxyphenyl)ethan-1-ol was obtained in the same manner as in Step B of Example A3, except that 18.4 g (45.5 mmol) of 4-((cyclohexylmethoxy)methoxy)-3-iodo-5-methoxybenzaldehyde obtained in Step A of Comparative Example A2 was used instead of 4-(ethoxymethoxy)-3-iodo-5-methoxybenzaldehyde in Step B of Example A3. The LC purity at 220 nm of the obtained 1-(4-((cyclohexylmethoxy)methoxy)-3-iodo-5-methoxyphenyl)ethan-1-ol was 99.1%.

[0441] Step C: Synthesis of 1-(4-((cyclohexylmethoxy)methoxy)-3-iodo-5-methoxyphenyl)ethyl methacrylate

[0442]

[0443] The synthesis in Step C of Example A3 was carried out in the same manner as in Step C of Example A3, except that 13.6 g (32.3 mmol) of 1-(4-((cyclohexylmethoxy)methoxy)-3-iodo-5-methoxyphenyl)ethan-1-ol obtained in Step B of Comparative Example A2 was used instead of 1-(4-(ethoxymethoxy)-3-iodo-5-methoxyphenyl)ethan-1-ol, to obtain 13.9 g (28.4 mmol) of 1-(4-((cyclohexylmethoxy)methoxy)-3-iodo-5-methoxyphenyl)ethyl methacrylate. The LC purity at 220 nm of the obtained 1-(4-((cyclohexylmethoxy)methoxy)-3-iodo-5-methoxyphenyl)ethyl methacrylate was 99.4%. 1H NMR (500 MHz, DMSO-d6) δ7.31(1H, Ph), 7.07(1H, Ph), 6.12(1H, =CH2), 5.93(2H, O-CH2-O), 5.79(1H, -CH-Ph), 5.74(1H, =CH2), 3.89(3H, -OCH3), 3.34(2H, O-CH2-), 2.10(3H, CH3-C=C), 1.83-1.68 (6H, C-CH2-C), 1.49(3H, CH3-CH-Ph), 1.31-1.12 (3H, C-CH-C, C-CH2-C), 1.01-0.89 (2H, C-CH2-C)

[0444] Comparative Example A3: Synthesis of 1-(4-(1-ethoxyethoxy)-3-iodophenyl)ethyl methacrylate

[0445] Step A: Synthesis of 4-(1-hydroxyethyl)-2-iodophenol

[0446]

[0447] The procedure was repeated in the same manner as in Step A of Example A1, except that 13.4 g (53.9 mmol) of 4-hydroxy-3-iodobenzaldehyde was used instead of 5-iodovanillin, to obtain 12.6 g (47.9 mmol) of 4-(1-hydroxyethyl)-2-iodophenol. The LC purity at 220 nm of the obtained 4-(1-hydroxyethyl)-2-iodophenol was 97%.

[0448] Step B: Synthesis of 1-(4-hydroxy-3-iodophenyl)ethyl methacrylate

[0449]

[0450] In step B of Example A1, 50.2 g of crude 1-(4-hydroxy-3-iodophenyl)ethyl methacrylate was obtained in the same manner as in step B of Example A1, except that 12.6 g (47.9 mmol) of 4-(1-hydroxyethyl)-2-iodophenol obtained in step A of Comparative Example A3 was used instead of 4-(1-hydroxyethyl)-2-iodo-6-methoxyphenol. This was used to obtain the next reaction without further purification.

[0451] Step C: Synthesis of 1-(4-(1-ethoxyethoxy)-3-iodophenyl)ethyl methacrylate

[0452]

[0453] The synthesis in Step C of Example A1 was carried out in the same manner as in Step C of Example A1, except that 50.2 g of 1-(4-hydroxy-3-iodophenyl)ethyl methacrylate obtained in Step B of Comparative Example A3 was used instead of 1-(4-hydroxy-3-iodo-5-methoxyphenyl)ethyl methacrylate, and 34.6 g (480 mmol) of ethyl vinyl ether was used instead of 3,4-dihydro-2H-pyran (DHP). 11.6 g (28.7 mmol) of 1-(4-(1-ethoxyethoxy)-3-iodophenyl)ethyl methacrylate was obtained. The LC purity at 220 nm of the obtained 1-(4-(1-ethoxyethoxy)-3-iodophenyl)ethyl methacrylate was 99.6%. 1 H NMR (500 MHz, DMSO-d6) δ7.82(1H, Ph), 7.25(1H, Ph), 6.79(1H, Ph), 6.13(1H, =CH2), 5.78(1H, O-CH-Ph), 5.69(1H, =CH2), 5.61(1H, O-CH-O), 3.65(1H, O-CH2-),3.53(1H, O-CH2-), 1.93(3H, CH3-C=C), 1.43(3H, CH3-CH-Ph), 1.32 (3H, CH3-CH), 1.11(3H, CH2-CH3)

[0454] Comparative Example A4: Synthesis of 1-(4-(1-ethoxyethoxy)-5-iodo-2-methoxyphenyl)ethyl methacrylate

[0455] Step A: Synthesis of 4-(1-hydroxyethyl)-2-iodo-5-methoxyphenol

[0456]

[0457] 4.7 g (16.0 mmol) of 4-(1-hydroxyethyl)-2-iodo-5-methoxyphenol was obtained in the same manner as in Step A of Example A1, except that 5 g (18.0 mmol) of 4-hydroxy-5-iodo-2-methoxybenzaldehyde was used instead of 5-iodovanillin. The LC purity of the obtained 4-(1-hydroxyethyl)-2-iodo-5-methoxyphenol at 220 nm was 98%.

[0458] Step B: Synthesis of 1-(4-hydroxy-5-iodo-2-methoxyphenyl)ethyl methacrylate

[0459]

[0460] In the same manner as in Step B of Example A1, except that 4.7 g (16.0 mmol) of 4-(1-hydroxyethyl)-2-iodo-5-methoxyphenol obtained in Step A of Comparative Example A4 was used instead of 4-(1-hydroxyethyl)-2-iodo-6-methoxyphenol, 17.9 g of crude 1-(4-hydroxy-5-iodo-2-methoxyphenyl)ethyl methacrylate was obtained, and the next reaction was carried out without further purification.

[0461] Step C: Synthesis of 1-(4-(1-ethoxyethoxy)-5-iodo-2-methoxyphenyl)ethyl methacrylate

[0462]

[0463] The procedure was repeated in the same manner as in Step C of Example A1, except that 17.9 g of the crude product of 1-(4-hydroxy-5-iodo-2-methoxyphenyl)ethyl methacrylate obtained in Step B of Comparative Example A4 was used instead of 1-(4-hydroxy-3-iodo-5-methoxyphenyl)ethyl methacrylate, and 11.5 g (160 mmol) of ethyl vinyl ether was used instead of 3,4-dihydro-2H-pyran (DHP). 4.52 g (10.4 mmol) of 1-(4-(1-ethoxyethoxy)-5-iodo-2-methoxyphenyl)ethyl methacrylate was obtained. The LC purity at 220 nm of the obtained 1-(4-(1-ethoxyethoxy)-5-iodo-2-methoxyphenyl)ethyl methacrylate was 99.4%. 1 H NMR (500 MHz, DMSO-d6) δ7.83(1H, Ph), 6.43(1H, Ph), 6.12(1H, =CH2), 5.89 (1H, O-CH-Ph), 5.70(1H, =CH2), 5.57(1H, O-CH-O), 3.87(3H, -OCH3), 3.71 (1H, O-CH2-), 3.56(1H, O-CH2-), 1.92(3H, CH3-C=C), 1.47 (3H, CH3-CH-Ph), 1.35(3H, CH3-CH-), 1.13(3H, CH2-CH3)

[0464] Comparative Example A5: Synthesis of 1-(4-((tert-butoxycarbonyl)oxy)-3-iodo-5-methoxyphenyl)ethyl methacrylate

[0465] Step A: Synthesis of tert-butyl (4-formyl-2-iodo-6-methoxyphenyl) carbonate

[0466]

[0467] Under light-shielded conditions, a 1000 mL three-neck flask was prepared and filled with N ２ Under a flow rate, 27.8 g (100 mmol) of 5-iodovanillin and 200 mL (0.5 M) of dichloromethane were added at room temperature, followed by addition of 1.2 g (10 mmol) of DMAP and di-tert-butyl dicarbonate ((Boc) ２21.8 g (100 mmol) of 4-iodo-6-methoxyphenyl (4-formyl-2-iodo-6-methoxyphenyl) carbonate was added and stirred for 60 minutes. Subsequently, 200 g of pure water was added while ice-cooling to maintain the internal temperature at 15°C or below. After 15 minutes of stirring and standing, the organic layer was drained. This procedure of adding 200 mL of dichloromethane, stirring for 15 minutes, standing, and draining the organic layer was repeated twice. The recovered organic layer was concentrated by vacuum distillation until no solvent components were distilled out, yielding a crude product. The resulting crude product was purified using a silica gel column to yield the target product, tert-butyl(4-formyl-2-iodo-6-methoxyphenyl) carbonate (36.3 g, 96 mmol). The LC purity of the resulting tert-butyl(4-formyl-2-iodo-6-methoxyphenyl) carbonate at 220 nm was 99.4%.

[0468] Step B: Synthesis of tert-butyl (4-(1-hydroxyethyl)-2-iodo-6-methoxyphenyl) carbonate

[0469]

[0470] 28.7 g (72.9 mmol) of tert-butyl(4-(1-hydroxyethyl)-2-iodo-6-methoxyphenyl)carbonate was obtained in the same manner as in Step B of Example A3, except that 36.3 g (96 mmol) of tert-butyl(4-formyl-2-iodo-6-methoxyphenyl)carbonate obtained in Step A of Comparative Example A5 was used instead of 4-(ethoxymethoxy)-3-iodo-5-methoxybenzaldehyde in Step B of Example A3. The LC purity at 220 nm of the obtained tert-butyl(4-(1-hydroxyethyl)-2-iodo-6-methoxyphenyl)carbonate was 99.5%.

[0471] Step C: Synthesis of 1-(4-((tert-butoxycarbonyl)oxy)-3-iodo-5-methoxyphenyl)ethyl methacrylate

[0472]

[0473] 28.0 g (60.5 mmol) of 1-(4-((tert-butoxycarbonyl)oxy)-3-iodo-5-methoxyphenyl)ethyl methacrylate was obtained in the same manner as in Step C of Example A3, except that 28.7 g (72.9 mmol) of tert-butyl(4-(1-hydroxyethyl)-2-iodo-6-methoxyphenyl)carbonate obtained in Step B of Comparative Example A5 was used instead of 1-(4-(ethoxymethoxy)-3-iodo-5-methoxyphenyl)ethan-1-ol in Step C of Example A3. The LC purity at 220 nm of the obtained 1-(4-((tert-butoxycarbonyl)oxy)-3-iodo-5-methoxyphenyl)ethyl methacrylate was 99.6%. 1 H NMR (500 MHz, DMSO-d6) δ7.38(1H, Ph), 7.21(1H, Ph), 6.02(1H, =CH2), 5.82(1H, O-CH-Ph), 5.73(1H, =CH2), 3.90(3H, -OCH3), 1.92(3H, CH3-C=C), 1.56 (9H, C-CH3), 1.49(3H, CH3-CH-Ph)

[0474] Comparative Example A6: Synthesis of 1-(4-((tert-butoxycarbonyl)oxy)-5-iodo-2-methoxyphenyl)ethyl methacrylate

[0475] Step A: Synthesis of tert-butyl (4-formyl-2-iodo-5-methoxyphenyl) carbonate

[0476]

[0477] 6.54 g (17.3 mmol) of tert-butyl(4-formyl-2-iodo-5-methoxyphenyl)carbonate was obtained in the same manner as in Step A of Comparative Example A5, except that 5 g (18 mmol) of 4-hydroxy-5-iodo-2-methoxybenzaldehyde was used instead of 5-iodovanillin in Step A of Comparative Example A5. The LC purity at 220 nm of the obtained tert-butyl(4-formyl-2-iodo-5-methoxyphenyl)carbonate was 99.4%.

[0478] Step B: Synthesis of tert-butyl (4-(1-hydroxyethyl)-2-iodo-5-methoxyphenyl) carbonate

[0479]

[0480] 5.32 g (13.5 mmol) of tert-butyl(4-(1-hydroxyethyl)-2-iodo-5-methoxyphenyl)carbonate was obtained in the same manner as in Step B of Example A3, except that 6.54 g (17.3 mmol) of tert-butyl(4-formyl-2-iodo-5-methoxyphenyl)carbonate obtained in Step A of Comparative Example A6 was used instead of 4-(ethoxymethoxy)-3-iodo-5-methoxybenzaldehyde in Step B of Example A3. The LC purity at 220 nm of the obtained tert-butyl(4-(1-hydroxyethyl)-2-iodo-5-methoxyphenyl)carbonate was 99.5%.

[0481] Step C: Synthesis of 1-(4-((tert-butoxycarbonyl)oxy)-5-iodo-2-methoxyphenyl)ethyl methacrylate

[0482]

[0483] 5.36 g (11.6 mmol) of 1-(4-((tert-butoxycarbonyl)oxy)-5-iodo-2-methoxyphenyl)ethyl methacrylate was obtained in the same manner as in Step C of Example A3, except that 5.32 g (13.5 mmol) of tert-butyl(4-(1-hydroxyethyl)-2-iodo-5-methoxyphenyl)carbonate obtained in Step B of Comparative Example A6 was used instead of 1-(4-(ethoxymethoxy)-3-iodo-5-methoxyphenyl)ethan-1-ol in Step C of Example A3. The LC purity at 220 nm of the obtained 1-(4-((tert-butoxycarbonyl)oxy)-5-iodo-2-methoxyphenyl)ethyl methacrylate was 99.6%. 1H NMR (500 MHz, DMSO-d6) δ7.82(1H, Ph), 6.51(1H, Ph), 6.09(1H, =CH2), 5.89 (1H, O-CH-Ph), 5.71(1H, =CH2), 3.92(3H, -OCH3), 1.98(3H, CH3-C=C), 1.56 (9H, C-CH3), 1.45 (3H, CH3-CH-Ph)

[0484] Test Example 1-1: Storage stability test of the compound of Example A1 1-(3-iodo-5-methoxy-4-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate (220 nm LC purity 99.5%) obtained in Example A1 was stored at 0°C under light-shielded conditions for 60 days, and the LC purity of 1-(3-iodo-5-methoxy-4-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate at 220 nm measured after 60 days had decreased to 97%.

[0485] On the other hand, a sample was prepared by mixing 0.5 mass% of 1-(3-iodo-5-methoxy-4-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate obtained in Example A2 with 1-(3-iodo-5-methoxy-4-((octahydro-2H,2'H-[2,3'-bipyran]-2'-yl)oxy)phenyl)ethyl methacrylate obtained in Example A1 (220 nm LC purity 99.5%), and similarly stored at 0°C under light-blocking conditions for 60 days. The LC purity of 1-(3-iodo-5-methoxy-4-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate at 220 nm measured after 60 days was 99.0%.

[0486] Test Example 1-2: Storage stability test for the compound of Example A3 The 1-(4-(ethoxymethoxy)-3-iodo-5-methoxyphenyl)ethyl methacrylate (220 nm LC purity 99.0%) obtained in Example A3 was stored at 0°C under light-shielded conditions for 60 days, and the LC purity of 1-(4-(ethoxymethoxy)-3-iodo-5-methoxyphenyl)ethyl methacrylate at 220 nm measured after 60 days was 99.0%.

[0487] Test Example 1-3: Storage stability test for the compound of Example A4 1-(3,5-diiodo-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate (220 nm LC purity 99.7%) obtained in Example A4 was stored at 0°C under light-shielded conditions for 60 days, and the LC purity of 1-(3,5-diiodo-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate at 220 nm measured after 60 days had decreased to 97%.

[0488] On the other hand, a sample was prepared by mixing 0.5 mass% of 1-(3,5-diiodo-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate obtained in Example A5 with 1-(3,5-diiodo-2-((octahydro-2H,2'H-[2,3'-bipyran]-2'-yl)oxy)phenyl)ethyl methacrylate obtained in Example A4 (220 nm LC purity 99.7%), and similarly stored at 0°C under light-blocking conditions for 60 days. The LC purity of 1-(3,5-diiodo-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate at 220 nm measured after 60 days was 99.2%.

[0489] Test Example 1-4: Storage stability test for the compound of Example A6 The 1-(2-(ethoxymethoxy)-3,5-diiodophenyl)ethyl methacrylate (220 nm LC purity: 99.5%) obtained in Example A6 was stored at 0°C under light-shielded conditions for 60 days, and the LC purity of 1-(2-(ethoxymethoxy)-3,5-diiodophenyl)ethyl methacrylate at 220 nm measured after 60 days was 99.5%.

[0490] Test Example 1-5: Storage stability test for the compound of Example A7 1-(5-iodo-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate (220 nm LC purity 99.7%) obtained in Example A7 was stored at 0°C under light-shielded conditions for 60 days, and the LC purity of 1-(5-iodo-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate at 220 nm measured after 60 days had decreased to 96%.

[0491] On the other hand, a sample was prepared by mixing 0.5 mass% of 1-(5-iodo-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate obtained in Example A8 with 1-(5-iodo-2-((octahydro-2H,2'H-[2,3'-bipyran]-2'-yl)oxy)phenyl)ethyl methacrylate obtained in Example A7 (220 nm LC purity 99.7%), and similarly stored at 0°C under light-blocking conditions for 60 days. After 60 days, the LC purity of 1-(5-iodo-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate at 220 nm was measured and found to be 99.2%.

[0492] Test Example 1-6: Storage stability test of the compound of Example A9 The 1-(2-(ethoxymethoxy)-5-iodophenyl)ethyl methacrylate (220 nm LC purity: 99.5%) obtained in Example A9 was stored at 0°C under light-shielded conditions for 60 days, and the LC purity of 1-(2-(ethoxymethoxy)-5-iodophenyl)ethyl methacrylate at 220 nm measured after 60 days was 99.5%.

[0493] Test Example 1-7: Storage stability test for the compound of Example A10 1-(5-iodo-3-methoxy-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate (220 nm LC purity 99.6%) obtained in Example A10 was stored at 0°C for 60 days under light-shielded conditions, and the LC purity of 1-(5-iodo-3-methoxy-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate at 220 nm measured after 60 days had decreased to 97%.

[0494] On the other hand, a sample was prepared by mixing 0.5 mass% of 1-(5-iodo-3-methoxy-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate obtained in Example A11 with 1-(5-iodo-3-methoxy-2-((octahydro-2H,2'H-[2,3'-bipyran]-2'-yl)oxy)phenyl)ethyl methacrylate obtained in Example A10 (220 nm LC purity 99.6%), and similarly stored at 0°C under light-blocking conditions for 60 days. The LC purity of 1-(5-iodo-3-methoxy-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate at 220 nm measured after 60 days was 99.1%.

[0495] Test Example 1-8: Storage stability test for the compound of Example A12 The 1-(2-(ethoxymethoxy)-5-iodo-3-methoxyphenyl)ethyl methacrylate (220 nm LC purity: 99.5%) obtained in Example A12 was stored at 0°C for 60 days under light-shielded conditions, and the LC purity of 1-(2-(ethoxymethoxy)-5-iodo-3-methoxyphenyl)ethyl methacrylate at 220 nm measured after 60 days was 99.5%.

[0496] Test Example 1-9: Storage stability test for the compound of Comparative Example A1 The 1-(4-(1-ethoxyethoxy)-3-iodo-5-methoxyphenyl)ethyl methacrylate (220 nm LC purity: 99.3%) obtained in Comparative Example A1 was stored at 0°C under light-shielded conditions for 60 days. After 60 days, the LC purity of 1-(4-(1-ethoxyethoxy)-3-iodo-5-methoxyphenyl)ethyl methacrylate at 220 nm measured was reduced to 82%.

[0497] Test Example 1-10: Storage stability test for the compound of Comparative Example A3 The 1-(4-(1-ethoxyethoxy)-3-iodophenyl)ethyl methacrylate (220 nm LC purity: 99.6%) obtained in Comparative Example A3 was stored at 0°C under light-shielded conditions for 60 days. After 60 days, the LC purity of 1-(4-(1-ethoxyethoxy)-3-iodophenyl)ethyl methacrylate at 220 nm measured was reduced to 89%.

[0498] Test Example 1-11: Storage stability test for the compound of Comparative Example A4 The 1-(4-(1-ethoxyethoxy)-5-iodo-2-methoxyphenyl)ethyl methacrylate (220 nm LC purity: 99.4%) obtained in Comparative Example A4 was stored at 0°C for 60 days under light-shielded conditions. After 60 days, the LC purity of 1-(4-(1-ethoxyethoxy)-5-iodo-2-methoxyphenyl)ethyl methacrylate at 220 nm measured was reduced to 88%.

[0499] From the results of Test Examples 1-1 to 1-11, the storage stability of the monomer alone was evaluated as "G" when the LC purity was 93% or more, and "N" when it was less than 93%.

[0500] Test Example 2-1: Hydrolysis test of the compound of Example A1 Under light-shielded conditions, a 5 mL vial was prepared, and 50 mg of 1-(3-iodo-5-methoxy-4-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate obtained in Example A1, 0.5 mL of methyl isobutyl ketone, and 0.5 mL of a 5% aqueous solution of p-toluenesulfonic acid were added thereto, followed by stirring at room temperature for 1 hour. 20 μL of triethylamine was added thereto, and the mixture was stirred for 10 minutes. 50 μL of the resulting organic layer was taken and dissolved in 2 mL of THF, followed by LC measurement. As a result, analysis at 220 nm showed that no undecomposed 1-(3-iodo-5-methoxy-4-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate was detected, and 100% hydrolyzed 1-(4-hydroxy-3-iodo-5-methoxyphenyl)ethyl methacrylate was detected.

[0501] Test Example 2-2: Hydrolysis test of the compound of Example A3 Under light-shielding conditions, a 5 mL vial was prepared, and 50 mg of 1-(4-(ethoxymethoxy)-3-iodo-5-methoxyphenyl)ethyl methacrylate obtained in Example A3, 0.5 mL of methyl isobutyl ketone, and 0.5 mL of a 5% aqueous solution of p-toluenesulfonic acid were added thereto, followed by stirring at room temperature for 1 hour. 20 μL of triethylamine was added thereto, and the mixture was stirred for 10 minutes. 50 μL of the obtained organic layer was taken and dissolved in 2 mL of THF, followed by LC measurement. As a result, analysis at 220 nm detected 44% of undecomposed 1-(4-(ethoxymethoxy)-3-iodo-5-methoxyphenyl)ethyl methacrylate and 56% of hydrolyzed 1-(4-hydroxy-3-iodo-5-methoxyphenyl)ethyl methacrylate.

[0502] Test Example 2-3: Hydrolysis test of the compound of Example A4 Under light-shielding conditions, a 5 mL vial was prepared, and 50 mg of 1-(3,5-diiodo-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate obtained in Example A4, 0.5 mL of methyl isobutyl ketone, and 0.5 mL of a 5% aqueous solution of p-toluenesulfonic acid were added thereto, followed by stirring at room temperature for 1 hour. 20 μL of triethylamine was added thereto, and the mixture was stirred for 10 minutes. 50 μL of the obtained organic layer was taken and dissolved in 2 mL of THF, followed by LC measurement. As a result, analysis at 220 nm showed that no undecomposed 1-(3,5-diiodo-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate was detected, and 100% hydrolyzed 1-(2-hydroxy-3,5-diiodophenyl)ethyl methacrylate was detected.

[0503] Test Example 2-4: Hydrolysis test of the compound of Example A6 Under light-shielded conditions, a 5 mL vial was prepared, and 50 mg of 1-(2-(ethoxymethoxy)-3,5-diiodophenyl)ethyl methacrylate obtained in Example A6, 0.5 mL of methyl isobutyl ketone, and 0.5 mL of a 5% aqueous solution of p-toluenesulfonic acid were added thereto, followed by stirring at room temperature for 1 hour. 20 μL of triethylamine was added thereto, and the mixture was stirred for 10 minutes. 50 μL of the obtained organic layer was taken and dissolved in 2 mL of THF, followed by LC measurement. As a result, analysis at 220 nm detected 44% of undecomposed 1-(2-(ethoxymethoxy)-3,5-diiodophenyl)ethyl methacrylate, and 56% of hydrolyzed 1-(2-hydroxy-3,5-diiodophenyl)ethyl methacrylate.

[0504] Test Example 2-5: Hydrolysis test of the compound of Example A7 Under light-shielding conditions, a 5 mL vial was prepared, and 50 mg of 1-(5-iodo-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate obtained in Example A7, 0.5 mL of methyl isobutyl ketone, and 0.5 mL of a 5% aqueous solution of p-toluenesulfonic acid were added thereto, followed by stirring at room temperature for 1 hour. 20 μL of triethylamine was added thereto, and the mixture was stirred for 10 minutes. 50 μL of the obtained organic layer was taken and dissolved in 2 mL of THF, followed by LC measurement. As a result, analysis at 220 nm showed that no undecomposed 1-(5-iodo-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate was detected, and 100% hydrolyzed 1-(2-hydroxy-5-iodophenyl)ethyl methacrylate was detected.

[0505] Test Example 2-6: Hydrolysis test of the compound of Example A9 Under light-shielding conditions, a 5 mL vial was prepared, and 50 mg of 1-(2-(ethoxymethoxy)-5-iodophenyl)ethyl methacrylate obtained in Example A9, 0.5 mL of methyl isobutyl ketone, and 0.5 mL of a 5% aqueous solution of p-toluenesulfonic acid were added thereto, followed by stirring at room temperature for 1 hour. 20 μL of triethylamine was added thereto, and the mixture was stirred for 10 minutes. 50 μL of the obtained organic layer was taken and dissolved in 2 mL of THF, followed by LC measurement. As a result, analysis at 220 nm detected 48% of undecomposed 1-(2-(ethoxymethoxy)-5-iodophenyl)ethyl methacrylate, and 52% of hydrolyzed 1-(2-hydroxy-5-iodophenyl)ethyl methacrylate.

[0506] Test Example 2-7: Hydrolysis test of the compound of Example A10 Under light-shielding conditions, a 5 mL vial was prepared, and 50 mg of 1-(5-iodo-3-methoxy-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate obtained in Example A10, 0.5 mL of methyl isobutyl ketone, and 0.5 mL of a 5% aqueous solution of p-toluenesulfonic acid were added thereto, followed by stirring at room temperature for 1 hour. 20 μL of triethylamine was added thereto, and the mixture was stirred for 10 minutes. 50 μL of the obtained organic layer was taken and dissolved in 2 mL of THF, followed by LC measurement. As a result, analysis at 220 nm showed that no undecomposed 1-(5-iodo-3-methoxy-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate was detected, and 100% hydrolyzed 1-(2-hydroxy-5-iodo-3-methoxyphenyl)ethyl methacrylate was detected.

[0507] Test Example 2-8: Hydrolysis Test of the Compound of Example A12 Under light-shielded conditions, a 5 mL vial was prepared, and 50 mg of 1-(2-(ethoxymethoxy)-5-iodo-3-methoxyphenyl)ethyl methacrylate obtained in Example A12, 0.5 mL of methyl isobutyl ketone, and 0.5 mL of a 5% aqueous solution of p-toluenesulfonic acid were added thereto, followed by stirring at room temperature for 1 hour. 20 μL of triethylamine was added thereto, and the mixture was stirred for 10 minutes. 50 μL of the obtained organic layer was taken and dissolved in 2 mL of THF, followed by LC measurement. As a result, analysis at 220 nm detected 46% of undecomposed 1-(2-(ethoxymethoxy)-5-iodo-3-methoxyphenyl)ethyl methacrylate, and 54% of hydrolyzed 1-(2-hydroxy-5-iodo-3-methoxyphenyl)ethyl methacrylate.

[0508] Test Example 2-9: Hydrolysis Test of the Compound of Comparative Example A1 Under light-shielded conditions, a 5 mL vial was prepared, and 50 mg of 1-(4-(1-ethoxyethoxy)-3-iodo-5-methoxyphenyl)ethyl methacrylate obtained in Comparative Example A1, 0.5 mL of methyl isobutyl ketone, and 0.5 mL of a 5% aqueous solution of p-toluenesulfonic acid were added thereto, followed by stirring at room temperature for 1 hour. 20 μL of triethylamine was added thereto, and the mixture was stirred for 10 minutes. 50 μL of the obtained organic layer was taken and dissolved in 2 mL of THF, followed by LC measurement. As a result, analysis at 220 nm showed that no undecomposed 1-(4-(1-ethoxyethoxy)-3-iodo-5-methoxyphenyl)ethyl methacrylate was detected, and 100% hydrolyzed 1-(4-hydroxy-3-iodo-5-methoxyphenyl)ethyl methacrylate was detected.

[0509] Test Example 2-10: Hydrolysis Test of the Compound of Comparative Example A2 Under light-shielding conditions, a 5 mL vial was prepared, and 50 mg of 1-(4-((cyclohexylmethoxy)methoxy)-3-iodo-5-methoxyphenyl)ethyl methacrylate obtained in Comparative Example A2, 0.5 mL of methyl isobutyl ketone, and 0.5 mL of a 5% aqueous solution of p-toluenesulfonic acid were added thereto, followed by stirring at room temperature for 1 hour. 20 μL of triethylamine was added thereto, and the mixture was stirred for 10 minutes. 50 μL of the obtained organic layer was taken and dissolved in 2 mL of THF, followed by LC measurement. As a result, analysis at 220 nm detected 87% of undecomposed 1-(4-((cyclohexylmethoxy)methoxy)-3-iodo-5-methoxyphenyl)ethyl methacrylate, and 13% of hydrolyzed 1-(4-hydroxy-3-iodo-5-methoxyphenyl)ethyl methacrylate.

[0510] Test Example 2-11: Hydrolysis Test of the Compound of Comparative Example A3 Under light-shielding conditions, a 5 mL vial was prepared, and 50 mg of 1-(4-(1-ethoxyethoxy)-3-iodophenyl)ethyl methacrylate obtained in Comparative Example A3, 0.5 mL of methyl isobutyl ketone, and 0.5 mL of a 5% aqueous solution of p-toluenesulfonic acid were added thereto, followed by stirring at room temperature for 1 hour. 20 μL of triethylamine was added thereto, and the mixture was stirred for 10 minutes. 50 μL of the obtained organic layer was taken and dissolved in 2 mL of THF, followed by LC measurement. As a result, analysis at 220 nm showed that no undecomposed 1-(4-(1-ethoxyethoxy)-3-iodophenyl)ethyl methacrylate was detected, and 100% hydrolyzed 1-(4-hydroxy-3-iodophenyl)ethyl methacrylate was detected.

[0511] Test Example 2-12: Hydrolysis Test of the Compound of Comparative Example A4 Under light-shielding conditions, a 5 mL vial was prepared, and 50 mg of 1-(4-(1-ethoxyethoxy)-5-iodo-2-methoxyphenyl)ethyl methacrylate obtained in Comparative Example A4, 0.5 mL of methyl isobutyl ketone, and 0.5 mL of a 5% aqueous solution of p-toluenesulfonic acid were added thereto, followed by stirring at room temperature for 1 hour. 20 μL of triethylamine was added thereto, and the mixture was stirred for 10 minutes. 50 μL of the obtained organic layer was taken and dissolved in 2 mL of THF, followed by LC measurement. As a result, analysis at 220 nm showed that no undecomposed 1-(4-(1-ethoxyethoxy)-5-iodo-2-methoxyphenyl)ethyl methacrylate was detected, and 100% hydrolyzed 1-(4-hydroxy-5-iodo-2-methoxyphenyl)ethyl methacrylate was detected.

[0512] Test Example 2-13: Hydrolysis test of the compound of Comparative Example A5 Under light-shielding conditions, a 5 mL vial was prepared, and 50 mg of 1-(4-((tert-butoxycarbonyl)oxy)-3-iodo-5-methoxyphenyl)ethyl methacrylate obtained in Comparative Example A5, 0.5 mL of methyl isobutyl ketone, and 0.5 mL of a 5% aqueous solution of p-toluenesulfonic acid were added thereto, followed by stirring at room temperature for 1 hour. 20 μL of triethylamine was added thereto, and the mixture was stirred for 10 minutes. 50 μL of the obtained organic layer was taken and dissolved in 2 mL of THF, followed by LC measurement. As a result, analysis at 220 nm detected 100% undecomposed 1-(4-((tert-butoxycarbonyl)oxy)-3-iodo-5-methoxyphenyl)ethyl methacrylate, and absolutely no hydrolyzed 1-(4-hydroxy-3-iodo-5-methoxyphenyl)ethyl methacrylate was detected.

[0513] Test Example 2-14: Hydrolysis Test of the Compound of Comparative Example A6 Under light-shielding conditions, a 5 mL vial was prepared, and 50 mg of 1-(4-((tert-butoxycarbonyl)oxy)-5-iodo-2-methoxyphenyl)ethyl methacrylate obtained in Comparative Example A6, 0.5 mL of methyl isobutyl ketone, and 0.5 mL of a 5% aqueous solution of p-toluenesulfonic acid were added thereto, followed by stirring at room temperature for 1 hour. 20 μL of triethylamine was added thereto, and the mixture was stirred for 10 minutes. 50 μL of the resulting organic layer was taken and dissolved in 2 mL of THF, followed by LC measurement. As a result, analysis at 220 nm detected 100% undecomposed 1-(4-((tert-butoxycarbonyl)oxy)-5-iodo-2-methoxyphenyl)ethyl methacrylate, and no hydrolyzed 1-(4-hydroxy-5-iodo-2-methoxyphenyl)ethyl methacrylate was detected at all.

[0514] Test Example 2-15: Hydrolysis test of comparative compounds

[0515]

[0516] Under light-shielded conditions, a 5 mL vial was prepared, and 50 mg of the comparative compound 1-(4-iodo-3-methoxyphenyl)ethyl methacrylate, 0.5 mL of methyl isobutyl ketone, and 0.5 mL of a 5% aqueous solution of p-toluenesulfonic acid were added, followed by stirring at room temperature for 1 hour. 20 μL of triethylamine was added, and the mixture was stirred for 10 minutes. 30 μL of the resulting organic layer was taken and dissolved in 2 mL of acetonitrile, followed by LC analysis. As a result, 100% undecomposed 1-(4-iodo-3-methoxyphenyl)ethyl methacrylate was detected in analysis at 220 nm, and no hydrolyzed compound was detected at all.

[0517] From the results of Test Examples 2-1 to 2-15, the hydrolyzability was evaluated as "G" when the LC purity of the hydrolysate (deprotected product) was 30% or more, and "N" when it was less than 30%.

[0518] Test Example 3-1: Acid Dissociation Test of Deprotected Compounds of Examples A1 to A3 and Comparative Examples A1, A2, and A5 Under light-shielded conditions, a 10 mL vial was prepared, and 0.4 g of 1-(4-hydroxy-3-iodo-5-methoxyphenyl)ethyl methacrylate obtained in Step B of Example A1, 1.8 g of cyclopentyl methyl ether, 1.8 g of toluene, and 0.4 g of a 1% cyclopentyl methyl ether solution of trifluoromethanesulfonic acid were added thereto, followed by stirring at 60°C for 30 minutes. After allowing to cool to room temperature, 50 μL of the organic layer was taken and dissolved in 2 mL of tetrahydrofuran (THF), followed by LC analysis. As a result, analysis at 220 nm detected no deprotected 1-(4-hydroxy-3-iodo-5-methoxyphenyl)ethyl methacrylate, but 31.1% methacrylic acid and 68.3% of the eliminated compound (2-methoxy-6-iodo-4-vinylphenol) were detected.

[0519] Test Example 3-2: Acid Dissociation Test of the Deprotected Compounds of Examples A4 to A6 Under light-shielded conditions, a 10 mL vial was prepared, and 0.4 g of 1-(2-hydroxy-3,5-diiodophenyl)ethyl methacrylate obtained in Step B of Example A4, 1.8 g of cyclopentyl methyl ether, 1.8 g of toluene, and 0.4 g of a 1% cyclopentyl methyl ether solution of trifluoromethanesulfonic acid were added thereto, followed by stirring at 60°C for 30 minutes. After allowing to cool to room temperature, 50 μL of the organic layer was taken and dissolved in 2 mL of tetrahydrofuran (THF), followed by LC analysis. As a result, analysis at 220 nm detected no deprotected 1-(2-hydroxy-3,5-diiodophenyl)ethyl methacrylate, but 30.2% methacrylic acid and 69.4% of the eliminated compound (2,4-diiodo-6-vinylphenol) were detected.

[0520] Test Example 3-3: Acid Dissociation Test of the Deprotected Compounds of Examples A7 to A9 Under light-shielded conditions, a 10 mL vial was prepared, and 0.4 g of 1-(2-hydroxy-5-iodophenyl)ethyl methacrylate obtained in Step B of Example A7, 1.8 g of cyclopentyl methyl ether, 1.8 g of toluene, and 0.4 g of a 1% cyclopentyl methyl ether solution of trifluoromethanesulfonic acid were added, followed by stirring at 60°C for 30 minutes. After cooling to room temperature, 50 μL of the organic layer was taken and dissolved in 2 mL of tetrahydrofuran (THF), followed by LC analysis. As a result, analysis at 220 nm detected no deprotected 1-(2-hydroxy-5-iodophenyl)ethyl methacrylate, but 32.5% methacrylic acid and 67.1% of the eliminated compound (4-iodo-2-vinylphenol) were detected.

[0521] Test Example 3-4: Acid Dissociation Test of the Deprotected Compounds of Examples A10 to A12 Under light-shielded conditions, a 10 mL vial was prepared, and 0.4 g of 1-(2-hydroxy-5-iodo-3-methoxyphenyl)ethyl methacrylate obtained in Step B of Example A10, 1.8 g of cyclopentyl methyl ether, 1.8 g of toluene, and 0.4 g of a 1% cyclopentyl methyl ether solution of trifluoromethanesulfonic acid were added thereto, followed by stirring at 60°C for 30 minutes. After allowing to cool to room temperature, 50 μL of the organic layer was taken and dissolved in 2 mL of tetrahydrofuran (THF), followed by LC analysis. As a result, analysis at 220 nm detected no deprotected 1-(2-hydroxy-5-iodo-3-methoxyphenyl)ethyl methacrylate, but 31.1% methacrylic acid and 68.1% of the eliminated compound (4-iodo-2-methoxy-6-vinylphenol) were detected.

[0522] Test Example 3-4: Acid Dissociation Test of the Deprotected Product of the Compound of Comparative Example A3 Under light-shielded conditions, a 10 mL vial was prepared, and 0.4 g of 1-(4-hydroxy-3-iodophenyl)ethyl methacrylate obtained in Step B of Comparative Example A3, 1.8 g of cyclopentyl methyl ether, 1.8 g of toluene, and 0.4 g of a 1% cyclopentyl methyl ether solution of trifluoromethanesulfonic acid were added, followed by stirring at 60°C for 30 minutes. After cooling to room temperature, 50 μL of the organic layer was taken and dissolved in 2 mL of tetrahydrofuran (THF), followed by LC analysis. As a result, analysis at 220 nm detected no deprotected 1-(4-hydroxy-3-iodophenyl)ethyl methacrylate, but 30.9% methacrylic acid and 68.5% of the eliminated product (2-iodo-4-vinylphenol) were detected.

[0523] Test Example 3-4: Acid Dissociation Test of the Deprotected Compounds of Comparative Examples A4 and A6 Under light-shielded conditions, a 10 mL vial was prepared, and 0.4 g of 1-(4-hydroxy-5-iodo-2-methoxyphenyl)ethyl methacrylate obtained in Step B of Comparative Example A4, 1.8 g of cyclopentyl methyl ether, 1.8 g of toluene, and 0.4 g of a 1% cyclopentyl methyl ether solution of trifluoromethanesulfonic acid were added, followed by stirring at 60°C for 30 minutes. After cooling to room temperature, 50 μL of the organic layer was removed and dissolved in 2 mL of tetrahydrofuran (THF), followed by LC analysis. As a result, analysis at 220 nm detected no deprotected 1-(4-hydroxy-5-iodo-2-methoxyphenyl)ethyl methacrylate, but 31.2% methacrylic acid and 67.9% of the eliminated compound (2-iodo-5-methoxy-4-vinylphenol) were detected.

[0524] Test Example 3-5: Acid dissociation test of comparative compound Under light-shielding conditions, a 10 mL vial was prepared, and 0.4 g of the comparative compound 1-(4-iodo-3-methoxyphenyl)ethyl methacrylate, 1.8 g of cyclopentyl methyl ether, 1.8 g of toluene, and 0.4 g of a 1% cyclopentyl methyl ether solution of trifluoromethanesulfonic acid were added, followed by stirring at 60°C for 30 minutes. After cooling to room temperature, 50 μL of the organic layer was taken and dissolved in 2 mL of THF, followed by LC measurement. As a result, analysis at 220 nm detected 1-(4-iodo-3-methoxyphenyl)ethyl methacrylate as 100%, and no acid dissociation at the benzyl position was observed.

[0525] Example B1: Synthesis of Polymer B1 using the Compound of Example A1

[0526]

[0527] 1.5 g of 1-(3-iodo-5-methoxy-4-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate obtained in Example A1, 4.0 g of 2-methyl-2-adamantyl methacrylate, 0.9 g of γ-butyrolactone methacrylic acid ester, and 1.5 g of hydroxyadamantyl methacrylic acid ester 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 allowing to cool to room temperature, 15 mL of a 5% aqueous solution of p-toluenesulfonic acid was added, and the mixture was stirred for 3 hours. Thereafter, 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 (B1a), (B1b), (B1c), and (B1d). The weight average molecular weight (Mw) of polymer B1 was 12,000, and the dispersity (Mw / Mn) was 1.90. １３As a result of C-NMR measurement, the composition ratio (molar ratio) of repeating units in polymer B1 was (B1a):(B1b):(B1c):(B1d) = 60:10:15:15. The repeating unit (B1d) was determined based on the carbon at the base of the benzene ring, and the repeating units (B1a), (B1b), and (B1c) were determined based on the carbonyl carbon of the ester bond, and the molar ratio was calculated based on the integral ratio of each. Note that no repeating units having a tetrahydro-2H-pyran-2-yl group were detected. Furthermore, the arrangement order of each repeating unit in polymer B1 was random, and it was not a block copolymer of each repeating unit.

[0528] Example B3: Synthesis of Polymer B3 using the Compound of Example A3

[0529]

[0530] 1.5 g of 1-(4-(ethoxymethoxy)-3-iodo-5-methoxyphenyl)ethyl methacrylate obtained in Example A3, 4.0 g of 2-methyl-2-adamantyl methacrylate, 0.9 g of γ-butyrolactone methacrylic acid ester, and 1.5 g of hydroxyadamantyl methacrylic acid ester 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 allowing to cool to room temperature, 15 mL of a 5% aqueous solution of p-toluenesulfonic acid was added, and the mixture was stirred for 3 hours. Thereafter, 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 B3 having repeating units (B3a), (B3b), (B3c), (B3d), and (B3e). The weight average molecular weight (Mw) of polymer B3 was 12,000, and the dispersity (Mw / Mn) was 1.90. １３As a result of C-NMR measurement, the composition ratio (molar ratio) of the repeating units in polymer B3 was (B3a):(B3b):(B3c):(B3d):(B3e) = 60:10:15:7.5:7.5. The repeating units (B3d) and (B3e) were determined based on the carbon at the base of the benzene ring and the carbon at the acetal moiety of the EM group, and the repeating units (B3a), (B3b), and (B3c) were determined based on the carbonyl carbon of the ester bond, and the molar ratio was calculated based on the integral ratio of each. Note that the arrangement order of the repeating units in polymer B3 was random, and it was not a block copolymer of the repeating units.

[0531] Example B4: Synthesis of Polymer B4 using the Compound of Example A4

[0532] 1.5 g of 1-(3,5-diiodo-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate obtained in Example A4, 4.0 g of 2-methyl-2-adamantyl methacrylate, 0.9 g of γ-butyrolactone methacrylic acid ester, and 1.5 g of hydroxyadamantyl methacrylic acid ester 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 allowing to cool to room temperature, 15 mL of a 5% aqueous solution of p-toluenesulfonic acid was added, and the mixture was stirred for 3 hours. Thereafter, 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 B4 having repeating units (B4a), (B4b), (B4c), and (B4d). The weight average molecular weight (Mw) of polymer B4 was 12,000, and the dispersity (Mw / Mn) was 1.90. １３As a result of C-NMR measurement, the composition ratio (molar ratio) of repeating units in polymer B4 was (B4a):(B4b):(B4c):(B4d) = 60:10:15:15. The repeating unit (B4d) was determined based on the carbon at the base of the benzene ring, and the repeating units (B4a), (B4b), and (B4c) were determined based on the carbonyl carbon of the ester bond, and the molar ratio was calculated based on the integral ratio of each. Note that no repeating units having a tetrahydro-2H-pyran-2-yl group were detected. Furthermore, the arrangement order of each repeating unit in polymer B4 was random, and it was not a block copolymer of each repeating unit.

[0533] Example B6: Synthesis of Polymer B6 using the Compound of Example A6

[0534]

[0535] 1.5 g of 1-(2-(ethoxymethoxy)-3,5-diiodophenyl)ethyl methacrylate obtained in Example A6, 4.0 g of 2-methyl-2-adamantyl methacrylate, 0.9 g of γ-butyrolactone methacrylic acid ester, and 1.5 g of hydroxyadamantyl methacrylic acid ester 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 allowing to cool to room temperature, 15 mL of a 5% aqueous solution of p-toluenesulfonic acid was added, and the mixture was stirred for 3 hours. Thereafter, 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 B6 having repeating units (B6a), (B6b), (B6c), (B6d), and (B6e). The weight average molecular weight (Mw) of polymer B6 was 12,000, and the dispersity (Mw / Mn) was 1.90. １３As a result of C-NMR measurement, the composition ratio (molar ratio) of the repeating units in polymer B6 was (B6a):(B6b):(B6c):(B6d):(B6e) = 60:10:15:7.5:7.5. The repeating units (B6d) and (B6e) were determined based on the carbon at the base of the benzene ring and the carbon at the acetal moiety of the EM group, and the repeating units (B6a), (B6b) and (B6c) were determined based on the carbonyl carbon of the ester bond, and the molar ratio was calculated based on the integral ratio of each. Note that the arrangement order of the repeating units in polymer B6 is random, and it is not a block copolymer of the repeating units.

[0536] Example B7: Synthesis of Polymer B7 using the Compound of Example A7

[0537]

[0538] 1.5 g of 1-(5-iodo-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate obtained in Example A7, 4.0 g of 2-methyl-2-adamantyl methacrylate, 0.9 g of γ-butyrolactone methacrylic acid ester, and 1.5 g of hydroxyadamantyl methacrylic acid ester 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 allowing to cool to room temperature, 15 mL of a 5% aqueous solution of p-toluenesulfonic acid was added, and the mixture was stirred for 3 hours. Thereafter, 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 B7 having repeating units (B7a), (B7b), (B7c), and (B7d). The weight average molecular weight (Mw) of polymer B7 was 12,000, and the dispersity (Mw / Mn) was 1.90. １３As a result of C-NMR measurement, the composition ratio (molar ratio) of repeating units in polymer B7 was (B7a):(B7b):(B7c):(B7d) = 60:10:15:15. The repeating unit (B7d) was determined based on the carbon at the base of the benzene ring, and the repeating units (B7a), (B7b), and (B7c) were determined based on the carbonyl carbon of the ester bond, and the molar ratio was calculated based on the integral ratio of each. Note that no repeating units having a tetrahydro-2H-pyran-2-yl group were detected. Furthermore, the arrangement order of each repeating unit in polymer B7 was random, and it was not a block copolymer of each repeating unit.

[0539] Example B9: Synthesis of Polymer B9 using the Compound of Example A9

[0540]

[0541] 1.5 g of 1-(2-(ethoxymethoxy)-5-iodophenyl)ethyl methacrylate obtained in Example A9, 4.0 g of 2-methyl-2-adamantyl methacrylate, 0.9 g of γ-butyrolactone methacrylic acid ester, and 1.5 g of hydroxyadamantyl methacrylic acid ester 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 allowing to cool to room temperature, 15 mL of a 5% aqueous solution of p-toluenesulfonic acid was added, and the mixture was stirred for 3 hours. Thereafter, 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 B9 having repeating units (B9a), (B9b), (B9c), (B9d), and (B9e). The weight average molecular weight (Mw) of polymer B9 was 12,000, and the dispersity (Mw / Mn) was 1.90. １３As a result of C-NMR measurement, the composition ratio (molar ratio) of the repeating units in polymer B9 was (B9a):(B9b):(B9c):(B9d):(B9e) = 60:10:15:7.5:7.5. The repeating units (B9d) and (B9e) were determined based on the carbon at the base of the benzene ring and the carbon at the acetal moiety of the EM group, and the repeating units (B9a), (B9b) and (B9c) were determined based on the carbonyl carbon of the ester bond, and the molar ratio was calculated based on the integral ratio of each. Note that the arrangement order of the repeating units in polymer B9 was random, and it was not a block copolymer of the repeating units.

[0542] Example B10: Synthesis of Polymer B10 Using the Compound of Example A10

[0543]

[0544] 1.5 g of 1-(5-iodo-3-methoxy-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)ethyl methacrylate obtained in Example A10, 4.0 g of 2-methyl-2-adamantyl methacrylate, 0.9 g of γ-butyrolactone methacrylic acid ester, and 1.5 g of hydroxyadamantyl methacrylic acid ester 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 allowing to cool to room temperature, 15 mL of a 5% aqueous solution of p-toluenesulfonic acid was added, and the mixture was stirred for 3 hours. Thereafter, 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 B10 having repeating units (B10a), (B10b), (B10c), and (B10d). The weight average molecular weight (Mw) of polymer B10 was 12,000, and the dispersity (Mw / Mn) was 1.90. １３As a result of C-NMR measurement, the compositional ratio (molar ratio) of the repeating units in polymer B10 was (B10a):(B10b):(B10c):(B10d) = 60:10:15:15. The repeating unit (B10d) was determined based on the carbon at the base of the benzene ring, and the repeating units (B10a), (B10b), and (B10c) were determined based on the carbonyl carbon of the ester bond, and the molar ratio was calculated based on the integral ratio of each. Note that no repeating units having a tetrahydro-2H-pyran-2-yl group were detected. Furthermore, the arrangement order of the repeating units in polymer B10 was random, and it was not a block copolymer of the repeating units.

[0545] Example B12: Synthesis of Polymer B12 using the Compound of Example A12

[0546]

[0547] 1.5 g of 1-(2-(ethoxymethoxy)-5-iodo-3-methoxyphenyl)ethyl methacrylate obtained in Example A12, 4.0 g of 2-methyl-2-adamantyl methacrylate, 0.9 g of γ-butyrolactone methacrylic acid ester, and 1.5 g of hydroxyadamantyl methacrylic acid ester 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 allowing to cool to room temperature, 15 mL of a 5% aqueous solution of p-toluenesulfonic acid was added, and the mixture was stirred for 3 hours. Thereafter, 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 B12 having repeating units (B12a), (B12b), (B12c), (B12d), and (B12e). The weight average molecular weight (Mw) of polymer B12 was 12,000, and the dispersity (Mw / Mn) was 1.90. １３As a result of C-NMR measurement, the composition ratio (molar ratio) of the repeating units in polymer B12 was (B12a):(B12b):(B12c):(B12d):(B12e) = 60:10:15:7.5:7.5. The repeating units (B12d) and (B12e) were determined based on the carbon at the base of the benzene ring and the carbon at the acetal moiety of the EM group, and the repeating units (B12a), (B12b), and (B12c) were determined based on the carbonyl carbon of the ester bond, and the molar ratio was calculated based on the integral ratio of each. Note that the arrangement order of the repeating units in polymer B12 was random, and it was not a block copolymer of the repeating units.

[0548] Comparative Example B2: Synthesis of Polymer B2′ Using the Compound of Comparative Example A2

[0549]

[0550] 1.5 g of 1-(4-((cyclohexylmethoxy)methoxy)-3-iodo-5-methoxyphenyl)ethyl methacrylate obtained in Comparative Example A2, 4.0 g of 2-methyl-2-adamantyl methacrylate, 0.9 g of γ-butyrolactone methacrylic acid ester, and 1.5 g of hydroxyadamantyl methacrylic acid ester 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 allowing to cool to room temperature, 15 mL of a 5% aqueous solution of p-toluenesulfonic acid was added, and the mixture was stirred for 3 hours. Thereafter, 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 B2' having repeating units (B2'a), repeating units (B2'b), repeating units (B2'c), repeating units (B2'd), and repeating units (B2'e). The weight average molecular weight (Mw) of polymer B2' was 12,000, and the dispersity (Mw / Mn) was 1.90. １３As a result of C-NMR measurement, the composition ratio (molar ratio) of repeating units in polymer B2' was (B2'a):(B2'b):(B2'c):(B2'd):(B2'e) = 60:10:15:1.5:13.5. For repeating units (B2'd) and (B2'e), the carbon at the base of the benzene ring and the carbon at the acetal moiety of the EM group were used, and for repeating units (B2'a), (B2'b), and (B2'c), the molar ratio was determined based on the integral ratio of each based on the carbonyl carbon of the ester bond. Note that the arrangement order of each repeating unit in polymer B2' is random, and it is not a block copolymer of each repeating unit.

[0551] Comparative Example B3: Synthesis of Polymer B3′ Using the Compound of Comparative Example A3

[0552]

[0553] 1.5 g of 1-(4-(1-ethoxyethoxy)-3-iodophenyl)ethyl methacrylate obtained in Comparative Example A3, 4.0 g of 2-methyl-2-adamantyl methacrylate, 0.9 g of γ-butyrolactone methacrylic acid ester, and 1.5 g of hydroxyadamantyl methacrylic acid ester 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 allowing to cool to room temperature, 15 mL of a 5% aqueous solution of p-toluenesulfonic acid was added, and the mixture was stirred for 3 hours. Thereafter, 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 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 dispersity (Mw / Mn) was 1.90. １３As a result of C-NMR measurement, the composition ratio (molar ratio) of the repeating units in polymer B3' was (B3'a):(B3'b):(B3'c):(B3'd) = 60:10:15:15. The repeating unit (B3'd) was determined based on the carbon at the base of the benzene ring, and the repeating units (B3'a), (B3'b), and (B3'c) were determined based on the carbonyl carbon of the ester bond, and the molar ratio was calculated based on the respective integral ratios. Note that no repeating units having an ethoxyethyl group were detected. Furthermore, the arrangement order of each repeating unit in polymer B3' was random, and it was not a block copolymer of each repeating unit.

[0554] Comparative Example B4: Synthesis of Polymer B4′ Using the Compound of Comparative Example A4

[0555]

[0556] 1.5 g of 1-(4-(1-ethoxyethoxy)-5-iodo-2-methoxyphenyl)ethyl methacrylate obtained in Comparative 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 allowing to cool to room temperature, 15 mL of a 5% aqueous solution of p-toluenesulfonic acid was added, and the mixture was stirred for 3 hours. Thereafter, 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 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 dispersity (Mw / Mn) was 1.90. １３As a result of C-NMR measurement, the composition ratio (molar ratio) of the repeating units in polymer B4' was (B4'a):(B4'b):(B4'c):(B4'd) = 60:10:15:15. The repeating unit (B4'd) was determined based on the carbon at the base of the benzene ring, and the repeating units (B4'a), (B4'b), and (B4'c) were determined based on the carbonyl carbon of the ester bond, and the molar ratio was calculated based on the integral ratio of each. Note that no repeating units having an ethoxyethyl group were detected. Furthermore, the arrangement order of each repeating unit in polymer B4' was random, and it was not a block copolymer of each repeating unit.

[0557] Comparative Example B5: Synthesis of Polymer B5′ Using the Compound of Comparative Example A5

[0558]

[0559] 1.5 g of 1-(4-((tert-butoxycarbonyl)oxy)-3-iodo-5-methoxyphenyl)ethyl methacrylate obtained in Comparative Example A5, 4.0 g of 2-methyl-2-adamantyl methacrylate, 0.9 g of γ-butyrolactone methacrylic acid ester, and 1.5 g of hydroxyadamantyl methacrylic acid ester 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 allowing to cool to room temperature, 15 mL of a 5% aqueous solution of p-toluenesulfonic acid was added, and the mixture was stirred for 3 hours. Thereafter, 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 B5′ having repeating units (B5′a), repeating units (B5′b), repeating units (B5′c), and repeating units (B5′d). The weight average molecular weight (Mw) of polymer B5' was 12,000, and the dispersity (Mw / Mn) was 1.90. １３As a result of C-NMR measurement, the composition ratio (molar ratio) of repeating units in polymer B5' was (B5'a):(B5'b):(B5'c):(B5'd) = 60:10:15:15. The repeating unit (B5'd) was determined based on the carbon at the base of the benzene ring, and the repeating units (B5'a), (B5'b), and (B5'c) were determined based on the carbonyl carbon of the ester bond, and the molar ratio was calculated based on the integral ratio of each. Note that the arrangement order of each repeating unit in polymer B5' is random, and it is not a block copolymer of each repeating unit.

[0560] Comparative Example B6: Synthesis of Polymer B6′ Using the Compound of Comparative Example A6

[0561]

[0562] 1.5 g of 1-(4-((tert-butoxycarbonyl)oxy)-5-iodo-2-methoxyphenyl)ethyl methacrylate obtained in Comparative Example A6, 4.0 g of 2-methyl-2-adamantyl methacrylate, 0.9 g of γ-butyrolactone methacrylic acid ester, and 1.5 g of hydroxyadamantyl methacrylic acid ester 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 allowing to cool to room temperature, 15 mL of a 5% aqueous solution of p-toluenesulfonic acid was added, and the mixture was stirred for 3 hours. Thereafter, 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 B6′ having repeating units (B6′a), (B6′b), (B6′c), and (B6′d). The weight average molecular weight (Mw) of polymer B6' was 12,000, and the dispersity (Mw / Mn) was 1.90. １３As a result of C-NMR measurement, the composition ratio (molar ratio) of repeating units in polymer B6' was (B6'a):(B6'b):(B6'c):(B6'd) = 60:10:15:15. The repeating unit (B6'd) was determined based on the carbon at the base of the benzene ring, and the repeating units (B6'a), (B6'b), and (B6'c) were determined based on the carbonyl carbon of the ester bond, and the molar ratio was calculated based on the integral ratio of each. Note that the arrangement order of each repeating unit in polymer B6' is random, and it is not a block copolymer of each repeating unit.

[0563] Comparative Example BA: Synthesis of Polymer BA Using Comparative Compound

[0564]

[0565] 1.5 g of the 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, 15 mL of a 5% aqueous solution of p-toluenesulfonic acid was added and stirred for 3 hours. The reaction solution was then added dropwise to 2 L of n-heptane. The precipitated polymer was filtered and dried under reduced pressure to obtain a white powdery polymer BA having repeating units (BAa), (BAb), (BAc), and (BAd). The weight average molecular weight (Mw) of the polymer BA was 12,000, and the dispersity (Mw / Mn) was 1.90. １３ As a result of measuring C-NMR, the composition ratio (molar ratio) of the repeating units in polymer BA was (BAa):(BAb):(BAc):(BAd) = 60:10:15:15. The repeating unit (BAd) is based on the carbon at the base of the benzene ring, and the repeating units (BAa), (BAb), and (BAc) are based on the carbonyl carbon of the ester bond, and the molar ratio was calculated based on the integral ratio of each. Note that in polymer BA, the arrangement order of each repeating unit is random, and it is not a block copolymer of each repeating unit.

[0566] Test Example 4-1: Evaluation of EUV sensitivity by TMAH aqueous solution development 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) were blended to prepare a solution (resist composition). The solution was applied to a silicon wafer and baked at 110°C for 60 seconds to form a photoresist layer (resist film) with a film thickness of 100 nm. Next, the resist was exposed to 1 mJ / cm using an extreme ultraviolet (EUV) exposure device "EUVES-7000" (product name, manufactured by LithoTech Japan Co., Ltd.). ２ to 1 mJ / cm ２ 80 mJ / cm ２ After maskless shot exposure with the exposure dose increased to 1000 ppm, the wafer was baked (PEB) at 110°C for 90 seconds and developed with a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, yielding a wafer with 80 shots of exposure on the wafer. For each of the resulting shot exposure areas, the film thickness was measured using an optical interference film thickness meter "VM3200" (product name, manufactured by SCREEN Semiconductor Solutions Co., Ltd.), profile data of the film thickness versus exposure dose was obtained, and the exposure dose at which the slope of the film thickness variation versus exposure dose was greatest was determined as the sensitivity value (mJ / cm). ２ ) and used as an index of the EUV sensitivity of the resist. The sensitivity value was 21 mJ / cm ２ If it is less than 21 mJ / cm, it is marked as "G" ２ If it was greater than 100%, it was evaluated as "N".

[0567] [Test Example 4-2: Evaluation of Sensitivity Over Time by Development in TMAH Aqueous Solution] For each of the Examples and Comparative Examples, the solutions prepared in the EUV sensitivity evaluation of Test Example 4-1 were subjected to forced aging treatment under light-shielded conditions at 40°C for 240 hours, and the EUV sensitivity evaluation of Test Example 4-1 was similarly performed on the solutions after aging treatment, and an evaluation was performed according to the amount of change in sensitivity. Specifically, in the EUV sensitivity evaluation of Test Example 4-1, the sensitivity value at which the slope of the film thickness-sensitivity curve after development, with the horizontal axis representing sensitivity and the vertical axis representing film thickness, was measured as the standard sensitivity. The standard sensitivity of the solutions before and after the forced aging treatment was determined, and the sensitivity deviation due to the aging treatment was evaluated using the numerical value obtained from the following calculation formula. The evaluation criteria were as follows:

[0568] [Sensitivity deviation] = 1 - ([Standard sensitivity of solution after aging] ÷ [Standard sensitivity of solution before aging])

[0569] (Evaluation criteria) A: [Sensitivity deviation]≦0.005 B: 0.005< [Sensitivity deviation]≦0.02 C: 0.02< [Sensitivity deviation]≦0.05 D: 0.05< [Sensitivity deviation]

[0570] Test Example 4-3: Evaluation of EB Pattern by Development with TMAH Aqueous Solution A solution (resist composition) was prepared by blending 5 parts by weight of the polymer obtained in each of the Examples and Comparative Examples, 1 part by weight of triphenylsulfonium nonafluorobutanesulfonate, 0.1 parts by weight of tributylamine, and 92 parts by weight of PGMEA. The solution was applied to a silicon wafer and baked at 110 to 130°C for 60 seconds to form a photoresist layer (resist film) with a thickness of 100 nm. The resist was then 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 for 60 seconds with a 2.38% by weight aqueous tetramethylammonium hydroxide (TMAH) solution to obtain a positive pattern. The exposure dose was adjusted to obtain a line-and-space pattern with a half pitch of 50 nm. Eighty pattern images of the obtained resist pattern were taken at a magnification of 100,000 times using a scanning electron microscope "S-4800" (product name, manufactured by Hitachi, Ltd.), and the number of residues in the spaces between the resist patterns was counted and evaluated based on the total amount of residues. The evaluation criteria were as follows:

[0571] (Evaluation criteria) A: Number of residues≦10 B: 10<Number of residues≦80 C: 80<Number of residues≦400 D: 400<Number of residues

[0572] Test Example 4-4: Evaluation of etching defects by development with TMAH aqueous solution A solution (resist composition) was prepared by blending 5 parts by mass of the polymer obtained in each of the Examples and Comparative Examples, 1 part by mass of triphenylsulfonium nonafluorobutanesulfonate, 0.2 parts by mass of tributylamine, 80 parts by mass of PGMEA, and 12 parts by mass of PGME. The solution was applied to an 8-inch silicon wafer having a 100 nm-thick oxide film formed on its outermost surface, and baked at 110°C for 60 seconds to form a 100 nm-thick photoresist layer (resist film). Next, using an extreme ultraviolet (EUV) exposure device "EUVES-7000" (product name, manufactured by Litho Tech Japan Co., Ltd.), shot exposure was performed on the entire surface of the wafer at an exposure amount 10% less than the EUV sensitivity value obtained in the EUV sensitivity evaluation of Test Example 4-1, and the wafer was then baked (PEB) at 110°C for 90 seconds and developed with a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, thereby obtaining a wafer that had been shot-exposed for 80 shots on the entire surface of the wafer. The exposed wafer thus produced was then subjected to CF ４ The oxide film was etched by 50 nm using Ar / Ar gas. The wafers produced by etching were subjected to defect evaluation using a defect inspection system "Surfscan SP5" (product name, manufactured by KLA Corporation), and the number of cone defects of 19 nm or more was calculated as an index of etching defects.

[0573] (Evaluation criteria) A: Number of cone defects ≦ 10 B: 10 < Number of cone defects ≦ 80 C: 80 < Number of cone defects ≦ 400 D: 400 < Number of cone defects

[0574] [Test Example 4-5: Evaluation of changes over time in etching defects due to development in TMAH aqueous solution] For each of the examples and comparative examples, the solutions prepared in the etching defect evaluation of Test Example 4-4 were left to stand at room temperature under light-shielded conditions for 7 days, and the etching defect evaluation of Test Example 4-4 was similarly carried out on the solutions after standing, and an evaluation was carried out according to the amount of change in the number of defects. Specifically, the evaluation was carried out by assigning a "G" when the change in EUV sensitivity before and after standing was less than 6%, and an "N" when it was 6% or more.

[0575] Test Example 5-1: Evaluation of EUV sensitivity by organic solvent development Using the same method as in Test Example 4-1, a solution (resist composition) containing the polymer obtained in the Example or Comparative Example was prepared, applied to a silicon wafer, and baked at 110°C for 60 seconds to form a photoresist layer (resist film) with a film thickness of 100 nm. Then, the resist film was irradiated with 1 mJ / cm using an extreme ultraviolet (EUV) exposure device "EUVES-7000" (product name, manufactured by LithoTech Japan Co., Ltd.). ２ to 1 mJ / cm ２ 80 mJ / cm ２ After maskless shot exposure with the exposure dose increased to 1000, the wafer was baked at 110°C for 90 seconds (PEB) and developed with butyl acetate for 30 seconds, yielding a wafer with 80 shots of exposure on the wafer. For each of the resulting shot exposure areas, the film thickness was measured using an optical interference film thickness meter "VM3200" (product name, manufactured by SCREEN Semiconductor Solutions Co., Ltd.), profile data of the film thickness versus the exposure dose was obtained, and the exposure dose at which the slope of the film thickness variation versus the exposure dose was greatest was determined as the sensitivity value (mJ / cm). ２ ) and used as an index of the EUV sensitivity of the resist. ２ If it is less than 23 mJ / cm, it is marked "G"; ２ If it was greater than 100%, it was evaluated as "N".

[0576] Test Example 5-2: Evaluation of sensitivity over time by organic solvent development For each of the Examples and Comparative Examples, the sensitivity over time was evaluated in the same manner as in Test Example 4-2, using the solution prepared in the EUV sensitivity evaluation of Test Example 5-1. Development was performed using butyl acetate for 30 seconds.

[0577] Test Example 5-3: Evaluation of EB Patterns by Organic Solvent Development Using the same method as in Test Example 4-3, a solution (resist composition) containing the polymer obtained in the Examples or Comparative Examples was prepared, coated on a silicon wafer, and baked at 110 to 130°C for 60 seconds to form a 100 nm-thick photoresist layer (resist film). The resist was then 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 butyl acetate for 30 seconds to obtain a negative pattern. The exposure dose was adjusted to obtain a 50 nm half-pitch line-and-space pattern. Eighty pattern images of the obtained resist pattern were obtained at 100,000x magnification 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 evaluation was performed based on the total amount of residue. The evaluation criteria are as follows:

[0578] (Evaluation criteria) A: Number of residues≦10 B: 10<Number of residues≦80 C: 80<Number of residues≦400 D: 400<Number of residues

[0579] Test Example 5-4: Evaluation of etching defects by organic solvent development Etching defects were evaluated in the same manner as in Test Example 4-4, except that development was performed with butyl acetate for 30 seconds instead of with a 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds.

[0580] Test Example 5-5: Evaluation of change over time in etching defects due to organic solvent development Using the solution prepared in the etching defect evaluation of Test Example 5-4, evaluation of change over time in etching defects was carried out in the same manner as in Test Example 4-5. Development was carried out using butyl acetate for 30 seconds.

[0581] For Examples A1 to A12, Comparative Examples A1 to A6, and the comparative compounds, as well as the corresponding Examples B1 to B12 and Comparative Examples B1 to BA, the results of Test Examples 1-1 to 1-11, Test Examples 2-1 to 2-15, Test Examples 4-1 to 4-5, and Test Examples 5-1 to 5-5 are summarized in Table 1 for each Example and Comparative Example.

[0582]

[0583] As can be seen from Table 1 above, the compounds represented by formula (I) and (II) in which the hydroxyl groups are protected with a THP (tetrahydro-2H-pyran-2-yl) group or an EM (ethoxymethyl) group (Examples A1 to A12) have excellent hydrolysis properties and storage stability as monomers, and it was confirmed that the use of iodine- and hydroxyl-containing polymers (Examples B1 to B12) obtained using such compounds further improved EUV sensitivity and stability over time of etching defects. In particular, it was confirmed that the use of iodine- and hydroxyl-containing polymers (Examples B1, B4, B7, and B10) obtained using the compounds represented by formula (I) in which the hydroxyl groups are protected with a THP group (Examples A1, A4, A7, and A10) improved sensitivity to the exposure light source and suppressed change in sensitivity over time, thereby reducing residue (exposure stability) and improving stability over time of etching defects.

[0584] On the other hand, it was confirmed that compounds in which the hydroxyl group was protected with an EE (1-ethoxyethyl) group (Comparative Examples A1, A3, and A4) had poor storage stability and therefore presented problems in industrial productivity. Furthermore, compounds in which the hydroxyl group was protected with a CHMM (cyclohexylmethoxymethyl) group or a Boc (tert-butoxycarbonyl) group (Comparative Examples A2, A5, and A6), or compounds without a protected hydroxyl group (Comparative Compound), presented problems with hydrolysis, and it was confirmed that polymers obtained by polymerizing compositions containing these compounds and subjecting them to hydrolysis treatment (Comparative Examples B2, B5, B6, and BA) were unable to achieve excellent EUV sensitivity and stability over time against etching defects.

[0585] This application claims priority to a Japanese patent application (Patent Application No. 2024-155160) filed on September 9, 2024, the entire contents of which are deemed to be part of the disclosure of this application and are incorporated herein by reference.

Claims

1. Formula (I) and Formula (II): wherein ring A represents a 6- to 14-membered aromatic ring; each ring B independently represents a 5- to 14-membered non-aromatic heterocycle; １ each independently represents a hydrogen atom or a methyl group; R ２ each independently represents a hydrocarbon group which may have a substituent; R ３ each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent; R ４ each independently represents a substituent, and c R ４ At least one of R represents an iodine atom; ５ each independently represents a substituent; R ６ each independently represent a linear or branched alkyl group; each X independently represent O or S; each a, b, and c independently represent an integer of 1 or greater; and each d independently represent 0 or an integer of 1 or greater.

2. Formula (1) and / or Formula (2): [Wherein, ring A represents a 6- to 14-membered aromatic ring; R １ represents a hydrogen atom or a methyl group; R ２１ represents an alkyl group; R ４ each independently represents a substituent, and c R ４ at least one of the formula (1'): represents an iodine atom; and b and c each independently represent an integer of 1 or more. [Wherein, ring A represents a 6- to 14-membered aromatic ring; R １ represents a hydrogen atom or a methyl group; R ２１ represents an alkyl group; R ４ each independently represents a substituent, and c R ４ at least one of represents an iodine atom; １ and c each independently represent an integer of 1 or more; ２ represents an integer of 0 or 1 or more.] The composition according to claim 1, comprising both a compound represented by the formula:

3. Formula (I) or Formula (II): wherein ring A represents a 6- to 14-membered aromatic ring; each ring B independently represents a 5- to 14-membered non-aromatic heterocycle; １ each independently represents a hydrogen atom or a methyl group; R ２ each independently represents a hydrocarbon group which may have a substituent; R ３ each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent; R ４ each independently represents a substituent, and c R ４ At least one of R represents an iodine atom; ５ each independently represents a substituent; R ６ each independently represent a linear or branched alkyl group; each X independently represent O or S; each a, b, and c independently represent an integer of 1 or more; and each d independently represent 0 or an integer of 1 or more.

4. Formula (1): [Wherein, ring A represents a 6- to 14-membered aromatic ring; R １ represents a hydrogen atom or a methyl group; R ２１ represents an alkyl group; R ４ each independently represents a substituent, and c R ４ and b and c each independently represent an integer of 1 or greater.

5. Formulas (1a) to (1i): [In the formula, R １ represents a hydrogen atom or a methyl group; R ２１ represents an alkyl group; R ４１ , R ４２ , R ４３ , R ４４ and R ４５ are each independently a hydrogen atom, -R ４ｘ , -OR ４ｘ , -COR ４ｘ , -OCOR ４ｘ , -COOR ４ｘ or an iodine atom, and R ４１ , R ４２ , R ４３ , R ４４ and R ４５ At least one of the groups represented in each formula represents an iodine atom; R ４ｘ represents an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-substituted aryl group, an alkyl-substituted aralkyl group, an alkenyl-substituted aryl group, or an alkenyl-substituted aralkyl group.

6. The compound according to claim 5, which is represented by formula (1a) or formula (1c).

7. Formula (1'): [Wherein, ring A represents a 6- to 14-membered aromatic ring; R １ represents a hydrogen atom or a methyl group; R ２１ represents an alkyl group; R ４ each independently represents a substituent, and c R ４ at least one of represents an iodine atom; １ and c each independently represent an integer of 1 or more; ２ represents an integer of 0 or 1 or more.

8. Formula (1a') ~ Formula (1ib'): [In the formula, R １ represents a hydrogen atom or a methyl group; R ２１ represents an alkyl group; R ４１ , R ４２ , R ４３ , R ４４ and R ４５ are each independently a hydrogen atom, -R ４ｘ , -OR ４ｘ , -COR ４ｘ , -OCOR ４ｘ , -COOR ４ｘ or an iodine atom, and R ４１ , R ４２ , R ４３ , R ４４ and R ４５ At least one of the groups represented in each formula represents an iodine atom; R ４ｘ represents an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-substituted aryl group, an alkyl-substituted aralkyl group, an alkenyl-substituted aryl group, or an alkenyl-substituted aralkyl group.

9. The compound according to claim 8, which is represented by formula (1a') or formula (1c').

10. Formula (2): [Wherein, ring A represents a 6- to 14-membered aromatic ring; R １ represents a hydrogen atom or a methyl group; R ２１ represents an alkyl group; R ４ each independently represents a substituent, and c R ４ and b and c each independently represent an integer of 1 or greater.

11. Equations (2a) to (2i): [In the formula, R １ represents a hydrogen atom or a methyl group; R ２１ represents an alkyl group; R ４１ , R ４２ , R ４３ , R ４４ and R ４５ are each independently a hydrogen atom, -R ４ｘ , -OR ４ｘ , -COR ４ｘ , -OCOR ４ｘ , -COOR ４ｘ or an iodine atom, and R ４１ , R ４２ , R ４３ , R ４４ and R ４５ At least one of the groups represented in each formula represents an iodine atom; R ４ｘ represents an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-substituted aryl group, an alkyl-substituted aralkyl group, an alkenyl-substituted aryl group, or an alkenyl-substituted aralkyl group.

12. The compound according to claim 11, which is represented by formula (2a) or formula (2c).

13. A composition for producing a photoresist layer-forming material, comprising the compound according to any one of claims 3 to 12.

14. A composition comprising the compound according to any one of claims 3 to 12 and a radical polymerization initiator.

15. A composition comprising the compound according to any one of claims 3 to 12 and a (meth)acrylic acid ester compound having an adamantane skeleton.

16. A composition comprising the compound according to any one of claims 3 to 12 and a (meth)acrylic acid ester compound having a lactone skeleton.

17. A composition comprising the compound according to any one of claims 3 to 12, a (meth)acrylic acid ester compound having an adamantane skeleton, and a (meth)acrylic acid ester compound having a lactone skeleton.

18. A method for producing a polymer containing iodine and hydroxyl groups, comprising the steps of heating or irradiating a composition containing the compound according to any one of claims 3 to 12, and then treating it with an acid to obtain a polymer containing iodine and hydroxyl groups.

19. A method for manufacturing an electronic device, comprising: (i) heating or irradiating a composition containing the compound according to any one of claims 3 to 12 with light, and further treating it with an acid to obtain a polymer containing iodine and hydroxyl groups; (ii) forming a photoresist layer on a substrate, the photoresist layer containing the polymer containing iodine and hydroxyl groups obtained in step (i); (iii) exposing the photoresist layer formed in step (ii); and (iv) developing the photoresist layer exposed in step (iii).

20. Formula (UI) and / or Formula (UII): wherein ring A represents a 6- to 14-membered aromatic ring; each ring B independently represents a 5- to 14-membered non-aromatic heterocycle; １ each independently represents a hydrogen atom or a methyl group; R ２ each independently represents a hydrocarbon group which may have a substituent; R ３ each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent; R ４ each independently represents a substituent, and c R ４ At least one of R represents an iodine atom; ５ each independently represents a substituent; R ６ each independently represent a linear or branched alkyl group; each X independently represent O or S; each a, b, and c independently represent an integer of 1 or more; and each d independently represent 0 or an integer of 1 or more.

21. The polymer according to claim 20, further comprising a repeating unit derived from a (meth)acrylic acid ester compound having an adamantane skeleton and / or a repeating unit derived from a (meth)acrylic acid ester compound having a lactone skeleton.

22. A resist composition containing the polymer according to claim 20 or 21.

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