Composition, resin composition, composition for film formation, composition for forming lithographic film, and composition for forming resist film

Abstract

Provided are a composition, a resin composition, a composition for film formation, a composition for forming a lithographic film, and a composition for forming a resist film, all which have excellent long-term storage stability. The composition comprises a compound A represented by formula (1) and a compound B represented by formula (B1) or formula (BP0-1). The substituents in formula (1), formula (B1), and formula (BP0-1) are as defined in the description.

Description

Composition, resin composition, film-forming composition, film-forming composition for lithography, resist film-forming composition

[0001] The present invention relates to a composition, a resin composition, a film-forming composition, a film-forming composition for lithography, and a resist film-forming composition.

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

[0003] Conventional resist materials are polymeric resist materials capable of forming amorphous films, such as polymethyl methacrylate, and polymeric resist materials such as polyhydroxystyrene or polyalkyl methacrylate having an acid-dissociable group (see, for example, Non-Patent Document 1).

[0004] Shinji Okazaki and 8 others, "40 Years of Lithography Technology," S&T Publishing, December 9, 2016

[0005] However, when a resist material that has been stored for a long period of time is resinified, there is a problem in that it is difficult to maintain the performance of the resist material.

[0006] In view of the above circumstances, an object of the present invention is to provide a composition, a resin composition, a film-forming composition, a film-forming composition for lithography, and a resist film-forming composition that are excellent in long-term storage stability.

[0007] As a result of intensive investigations to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using a composition containing compound A and compound B each having a specific structure, and have thus completed the present invention. That is, the present invention is as follows.

[0008] [1] A composition comprising a compound A represented by the following formula (1) and a compound B represented by the following formula (B1) or formula (BP0-1): (In the formula, R １ is a hydrogen atom, a methyl group or a halogen atom, R ２ , R ３ are each independently a hydrogen atom, a linear organic group having 1 to 20 carbon atoms, a branched organic group having 3 to 20 carbon atoms, or a cyclic organic group having 3 to 20 carbon atoms; A is an organic group having 1 to 30 carbon atoms which may have a protecting group; I is an iodine atom; and n １ is an integer of 0 or 1, ２ is an integer from 1 to 20. (Wherein, B is a group containing at least one cyclic structure which may have a protecting group, I is an iodine atom, and R ０ is a monovalent functional group having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, and R ０ When there are a plurality of Q's, they may be the same or different, Q is a single bond, a divalent group which may have a substituent, a group containing an alkylene group, a phenylene group, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group or a phosphate group, -O-CH ２ - or a group represented by the following formula (B1L), m' is an integer of 0 to 9, n' is an integer of 1 to 19, and n ２ and b is an integer from 1 to 4. (In the formula, R ２ , R ３ is the same as in formula (1), and X １is a divalent group containing an alkylene group, a phenylene group, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, which may have a substituent; and n1a is an integer of 0 or 1. (In the formula, B, I, R ０ , m', and n' are defined the same as in formula (B1). [2] The composition according to [1], wherein the compound B is a compound represented by the following formula (B2): (Wherein, Rx is a hydroxy group or a protecting group, B, I, R ０ , Q has the same meaning as in formula (B1), R ２ , R ３ is the same as in formula (1), and R ４ is a protecting group, and n １１ is an integer of 0 or 1, ２１ is an integer from 1 to 20, and n ３１ is an integer from 0 to 19, and n ４１ is an integer of 0 to 9.) [3] The composition according to [1] or [2], wherein the cyclic structure in B in formula (B1) is benzene, naphthalene, anthracene, pyrene, or a heteroaromatic ring, each of which may have a substituent. [4] The composition according to any one of [1] to [3], wherein the cyclic structure in B in formula (B1) is a polycyclic alicyclic ring, each of which may have a substituent. [5] The composition according to any one of [1] to [4], wherein compound A is a compound represented by the following formula (1'): (In the formula, A, I, R １ , R ２ , R ３ , n １ , n ２ is the same as in formula (1), and R ４ is a protecting group, and n ３ is 0 to 19. [6] The composition according to any one of [1] to [5], wherein the compound A is a compound represented by the following formula (1″): (In the formula, A, I, R １ , R ２ , R ３, n １ , n ２ is the same as in formula (1), and R ０ has the same meaning as formula (B1), and R ４ is a protecting group, and n ３ is 0 to 19, and n ４１ is 0 to 9.) [7] The composition according to any one of [1] to [6], wherein the organic group in A in formula (1) is benzene, naphthalene, anthracene, pyrene, or a heteroaromatic ring, each of which may have a substituent. [8] The composition according to any one of [1] to [7], wherein the organic group in A in formula (1) is a polycyclic alicyclic ring, each of which may have a substituent. [9] The composition according to any one of [1] to [8], wherein the content of compound B is 10 ppm to 50,000 ppm with respect to the total amount of compound A represented by formula (1).

[10] A resin composition made from the composition according to any one of [1] to [9], wherein the resin composition contains a polymer having a repeating unit represented by formula (C1): (In the formula, R １ is a hydrogen atom, a methyl group or a halogen atom, R ２ , R ３ are each independently a hydrogen atom, a linear organic group having 1 to 20 carbon atoms, a branched organic group having 3 to 20 carbon atoms, or a cyclic organic group having 3 to 20 carbon atoms; A is an organic group having 1 to 30 carbon atoms which may have a protecting group; I is an iodine atom; and n １ is an integer of 0 or 1, ２ is an integer of 1 to 20, and the symbol * represents a bonding site to an adjacent repeating unit.)

[11] A film-forming composition, comprising the composition according to any one of [1] to [9] or the resin composition according to

[10] .

[12] A film-forming composition for semiconductor lithography, comprising the film-forming composition according to

[11] .

[13] A resist film-forming composition for semiconductor lithography, comprising the film-forming composition according to

[11] or

[12] .

[0009] According to the present invention, it is possible to provide a composition, a resin composition, a film-forming composition, a film-forming composition for lithography, and a resist film-forming composition that are excellent in long-term storage stability.

[0010] Hereinafter, an embodiment of the present invention will be described (hereinafter, may be referred to as "the present embodiment"). Note that the present embodiment is an example for explaining the present invention, and the present invention is not limited to only the present embodiment.

[0011] In this specification, (meth)acrylate means acrylate and methacrylate. Other terms that contain the expression (meth) are also interpreted in the same manner as (meth)acrylate. In this specification, (co)polymer means a homopolymer and a copolymer. In this specification, "X to Y" includes the end values ​​X and Y.

[0012] [Compound A] Compound A in this embodiment is a compound represented by the following formula (1): Furthermore, hereinafter, "compound A" may be referred to as "iodine-containing (meth)acrylate compound."

[0013] In formula (1), R １ is a hydrogen atom, a methyl group or a halogen atom, R ２ , R ３ are each independently a hydrogen atom, a linear organic group having 1 to 20 carbon atoms, a branched organic group having 3 to 20 carbon atoms, or a cyclic organic group having 3 to 20 carbon atoms; A is an organic group having 1 to 30 carbon atoms which may have a protecting group; I is an iodine atom; and n １ is an integer of 0 or 1, ２ is an integer from 1 to 20.

[0014] R in formula (1) １ R is a hydrogen atom, a methyl group, or a halogen atom. As the halogen group, known atoms can be used, such as F, Cl, Br, and I. １is preferably a methyl group or a halogen group from the viewpoint of exposure sensitivity and material stability when compound A of this embodiment is used as a structural unit of a resin for a resist, and is more preferably a methyl group from the viewpoint of exposure sensitivity in particular.

[0015] R in formula (1) ２ and R ３ are each independently a hydrogen atom, a linear organic group having 1 to 20 carbon atoms, a branched organic group having 3 to 20 carbon atoms, or a cyclic organic group having 3 to 20 carbon atoms.

[0016] R in formula (1) ２ and R ３ is preferably a hydrogen atom for the purpose of suppressing an increase in the Tg of the resin and improving the effect of introducing the iodine element. Also, it is preferably an organic group having one or more carbon atoms for the purpose of improving acid decomposition property in order to control solubility in a developer. It is also preferably a hydrogen atom for the purpose of suppressing acid decomposition property and ensuring solubility in an alkaline developer, thereby suppressing residues.

[0017] R in formula (1) ２ and R ３ may have a substituent. ２ and R ３ Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 6 carbon atoms, which may have a substituent; an alkenyl group having 2 to 20 carbon atoms, 2 to 10 carbon atoms, or 2 to 6 carbon atoms, which may have a substituent; an alkynyl group having 2 to 20 carbon atoms, 2 to 10 carbon atoms, or 2 to 6 carbon atoms, which may have a substituent; a cycloalkyl group having 3 to 20 carbon atoms, 3 to 10 carbon atoms, or 3 to 6 carbon atoms, which may have a substituent; a cycloalkenyl group having 3 to 20 carbon atoms, 3 to 10 carbon atoms, or 3 to 6 carbon atoms, which may have a substituent; a cycloalkynyl group having 3 to 20 carbon atoms, 3 to 10 carbon atoms, or 3 to 6 carbon atoms, which may have a substituent; an aryl group having 5 to 20 carbon atoms, 5 to 10 carbon atoms, or 5 to 6 carbon atoms, which may have a substituent; and combinations thereof.

[0018] R in formula (1) ２ and R ３Specific examples of the organic group in the formula (I) include, for example, optionally substituted methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, icosyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloicosyl, adamantyl, ethylene, propylene, butylene, phenyl, naphthyl, anthracene, phenanthrene, tetracene, chrysene, triphenylene, pyrene, benzopyrene, azulene, and fluorene groups. These may contain an ether bond, a ketone bond, or an ester bond.

[0019] Here, the exemplified groups include isomers, for example, a propyl group includes an n-propyl group and an isopropyl group, and a butyl group includes an n-butyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group.

[0020] R in formula (1) ２ and R ３ The substituent is not particularly limited, but examples thereof include a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, a thiol group, a heterocyclic group, a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, an aryl group, an aralkyl group, an alkoxy group, an alkenyl group, an acyl group, an alkoxycarbonyl group, an alkyloyloxy group, an aryloyloxy group, an alkylsilyl group, various crosslinkable groups, and acid-dissociable groups.

[0021] The term "crosslinkable group" refers to a group that crosslinks with the aid of an acid, an alkali, light, or heat, and that crosslinks in the presence or absence of a catalyst. Examples of the crosslinkable group include, but are not limited to, a group having an allyl group, a group having a (meth)acryloyl group, a group having an epoxy(meth)acryloyl group, a group having a urethane(meth)acryloyl group, a group having a hydroxyl group, a group having a glycidyl group, a group having a vinyl-containing phenylmethyl group, a group having a styrene group, a group having an alkynyl group, a group having a carbon-carbon double bond, a group having a carbon-carbon triple bond, and groups containing these groups.

[0022] The term "acid-dissociable group" refers to a group that cleaves in the presence of an acid to generate an alkali-soluble group (e.g., a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, a hexafluoroisopropanol group), etc. The acid-dissociable group is not particularly limited, and can be appropriately selected from those proposed for, for example, hydroxystyrene resins and (meth)acrylic acid resins used in chemically amplified resist compositions for KrF and ArF. Specific examples of the acid-dissociable group include those described in WO 2016 / 158168.

[0023] A in formula (1) is an organic group having 1 to 30 carbon atoms, which may have a protecting group. Examples of the organic group in A include a linear organic group having 1 to 20 carbon atoms, a branched organic group having 3 to 20 carbon atoms, and a cyclic organic group having 3 to 20 carbon atoms. Examples of such organic groups include an alkane having 1 to 30 carbon atoms, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 6 carbon atoms, which may have a substituent; an alkene having 2 to 30 carbon atoms, 2 to 20 carbon atoms, 2 to 10 carbon atoms, or 2 to 6 carbon atoms, which may have a substituent; an alkyne having 2 to 30 carbon atoms, 2 to 20 carbon atoms, 2 to 10 carbon atoms, or 2 to 6 carbon atoms, which may have a substituent; an alkyne having 3 to 30 carbon atoms, 3 to 20 carbon atoms, or 2 to 6 carbon atoms, which may have a substituent; Examples include cycloalkanes having 3 to 10 prime numbers or 3 to 6 carbon atoms; cycloalkenes having 3 to 30, 3 to 20, 3 to 10 or 3 to 6 carbon atoms which may have a substituent; cycloalkynes having 3 to 30, 3 to 20, 3 to 10 or 3 to 6 carbon atoms which may have a substituent; arenes having 5 to 30, 5 to 20, 5 to 10 or 5 to 6 carbon atoms which may have a substituent; and combinations thereof.

[0024] Specific examples of the organic group in A of formula (1) include, for example, methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, icosane, triacontane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloicosane, cyclotriacontane, adamantane, ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, icosene, triacontene, benzene, phenol, naphthalene, anthracene, phenanthrene, tetracene, chrysene, triphenylene, pyrene, pentacene, benzopyrene, coronene, azulene, fluorene, heteroaromatic rings, and combinations thereof, which may have a substituent. These may contain an ether bond, a ketone bond, or an ester bond.

[0025] The organic group in A of formula (1) is preferably, for example, an aromatic ring, a heteroaromatic ring, or a polycyclic alicyclic ring, which may have a substituent, more preferably benzene, naphthalene, anthracene, pyrene, or a heteroaromatic ring, which may have a substituent, and even more preferably benzene, naphthalene, anthracene, pyrene, or a heteroaromatic ring. Furthermore, the organic group in A is preferably, for example, a polycyclic alicyclic ring, which may have a substituent, and more preferably anthracene.

[0026] The substituent in A of formula (1) is not particularly limited, but examples thereof include a halogen atom (fluorine, chlorine, bromine), a hydroxyl group, a cyano group, a nitro group, an amino group, a thiol group, a heterocyclic group, a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkenyl group, an acyl group, an alkoxycarbonyl group, an alkyloyloxy group, an aryloyloxy group, an alkylsilyl group, various crosslinkable groups, and acid-dissociable groups, and a hydroxyl group or a linear aliphatic hydrocarbon group is preferred.

[0027] The "crosslinkable group" is not particularly limited, but examples thereof include the R ２ and R ３The materials described in the description of the above can be used.

[0028] n １ represents 0 or 1.

[0029] n ２ is an integer of 1 to 20, preferably an integer of 2 to 20, more preferably an integer of 2 to 10, and even more preferably an integer of 2 to 5.

[0030] When A in formula (1) has a protecting group, compound A may be a compound represented by the following formula (1′). In formula (1′), A, I, R １ , R ２ , R ３ , n １ , n ２ is the same as in formula (1), and R ４ is a protecting group, and n ３ is between 0 and 19.

[0031] When A in formula (1) has a protecting group, compound A may be a compound represented by the following formula (1″). In formula (1″), A, I, R １ , R ２ , R ３ , n １ , n ２ is the same as in formula (1), and R ０ has the same meaning as formula (B1), and R ４ is a protecting group, and n ３ is 0 to 19, and n ４１ is 0 to 9.

[0032] The protecting group of A in formula (1) is not particularly limited, but R ４ R in formula (1′) or formula (1″) may be a group represented by the formula: ４ Although not particularly limited, examples of the alkoxy group [* ３ -O-R ２ ], ester group [* ３ -O-(C=O)-R ２ or * ３ -(C=O)-OR ２ ], acetal group [* ３ -O-(C(R２１ ) ２ )-O-R ２ (R ２１ are each independently H or a hydrocarbon group having 1 to 10 carbon atoms.) ], a carboxyalkoxy group [* ３ -O-R ２２ -(C=O)-OR ２ (R ２２ is a divalent hydrocarbon group having 1 to 10 carbon atoms. )], and a carbonate group [* ３ -O-(C=O)-OR ２ In terms of increasing the exposure sensitivity of the resist composition, the ester group is preferably a tertiary ester group. ３ is the binding site for RG.

[0033] Among these, R in formula (1′) or formula (1″) ４ From the viewpoint of increasing the exposure sensitivity of the resist composition, R is preferably a tertiary ester group, an acetal group, a carbonate ester group, or a carboxyalkoxy group, more preferably an acetal group, a carbonate ester group, or a carboxyalkoxy group, and even more preferably an acetal group or a carboxyalkoxy group. ４ In terms of improving stability in acidic to weakly acidic steps in the production method of Compound A in this embodiment, and from the perspective of producing a polymer of stable quality by radical polymerization when Compound A is used as a resist material, an ester group, a carboxyalkoxy group, and a carbonate ester group are preferred, as they function as protecting groups and can form a hydroxyl group or a carboxyl group, which is preferred in terms of increasing the sensitivity of the resist composition, after deprotection. Furthermore, from the perspective of stability under basic conditions in the production method, an acetal group, a carbonate ester, and a tertiary ester are preferred.

[0034] R in formula (1′) or formula (1″) ４ are preferably each independently a group represented by the following formula (Y-1):

[0035] In formula (Y-1), L １is a group that is cleaved by the action of an acid or a base. The group that is dissociated by the action of an acid may have the same meaning as the above-mentioned "acid-dissociable group." Examples of the group that is cleaved by the action of an acid or a base include an ester group [* １ -O-(C=O)-* ２ or * １ -(C=O)-O-* ２ ], acetal group [* １ -O-(C(R ２１ ) ２ )-O-* ２ (R ２１ are each independently H or a hydrocarbon group having 1 to 10 carbon atoms.) ], a carboxyalkoxy group [* １ -O-R ２２ -(C=O)-O-* ２ (R ２２ is a divalent hydrocarbon group having 1 to 10 carbon atoms. )], and a carbonate group [* １ -O-(C=O)-O-* ２ In terms of increasing the exposure sensitivity of the resist composition, the ester group is preferably a tertiary ester group. １ indicates the binding site with RG, * ２ is R １ Among these, L １ From the viewpoint of increasing the exposure sensitivity of the resist composition, L is preferably a tertiary ester group, an acetal group, a carbonate ester group, or a carboxyalkoxy group, more preferably an acetal group, a carbonate ester group, or a carboxyalkoxy group, and even more preferably an acetal group or a carboxyalkoxy group. １ is preferably an ester group, a carboxyalkoxy group, or a carbonate ester group, from the viewpoint of improving stability in an acidic to weakly acidic step in the method for producing compound A in the present embodiment, and from the viewpoint of producing a polymer of stable quality by radical polymerization when compound A is used as a resist material.

[0036] Another effect is that when compound A in this embodiment is used as a polymerization unit of a copolymer, it is possible to control the polymerizability of the resin and set the degree of polymerization within a desired range by adding R４ is preferably a group represented by formula (Y-1). When compound A has a hydroxyl group, an aliphatic or aromatic group having 1 to 30 carbon atoms and having at least one selected from the group consisting of a hydroxyl group, an aldehyde group, and a carboxyl group, or a halogen group (F, Cl, Br, etc.), the effect on the active species during the polymer-forming reaction is significant, making it difficult to achieve the desired control. Therefore, by using a group represented by formula (Y-1) as the hydrophilic group in compound A, it is possible to suppress variations in copolymer formation and polymerization inhibition resulting from the hydrophilic group.

[0037] R in formula (Y-1) １ is a linear, branched or cyclic aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, a linear, branched or cyclic aliphatic group having 1 to 30 carbon atoms and containing a heteroatom, or a linear, branched or cyclic aromatic group having 1 to 30 carbon atoms and containing a heteroatom, and １ The aliphatic group, aromatic group, aliphatic group containing a hetero atom, and aromatic group containing a hetero atom may further have a substituent. The substituents used here are those described above, but linear, branched, or cyclic aliphatic groups having 1 to 20 carbon atoms and aromatic groups having 6 to 20 carbon atoms are preferred. R in formula (Y-1) １ Among these, R in formula (Y-1) is preferably an aliphatic group. １ The aliphatic group in the formula (I) is preferably a branched or cyclic aliphatic group. The number of carbon atoms in the aliphatic group is preferably 1 or more and 20 or less, more preferably 3 or more and 10 or less, and even more preferably 4 or more and 8 or less. The aliphatic group is not particularly limited, but examples thereof include a methyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a cyclohexyl group, a methylcyclohexyl group, and an adamantyl group. Among these, a tert-butyl group, a cyclohexyl group, or an adamantyl group is preferred.

[0038] L in formula (Y-1) １ but,* １ -(C=O)-O-* ２Alternatively, if the group is a carboxyalkoxy group, when cleaved by the action of an acid or a base, a carboxylic acid group is formed, and when used as a resist material, the difference in solubility and the difference in dissolution rate between the dissociated portion and the non-dissociated portion in the development process are increased, thereby improving resolution and suppressing residues at the bottom of the pattern, particularly in fine line patterns, which is preferable.

[0039] In formula (Y-1), L １ Although there is no particular limitation, for example, a group represented by the following formula is preferable.

[0040] In formula (Y-1), R １ Although there is no particular limitation, for example, a group represented by the following formula is preferable.

[0041] R in formula (1′) or formula (1″) ４ Although there is no particular limitation, for example, a group represented by the following formula is preferable.

[0042] R in formula (1′) or formula (1″) ４ Examples of the alkoxy group that can be used as the alkoxy group include alkoxy groups having one or more carbon atoms, and when compound A is used as a resist material, from the viewpoint of the solubility of the resin after being combined with other monomers to form a resin, alkoxy groups having two or more carbon atoms are preferred, and alkoxy groups having three or more carbon atoms or having a ring structure are more preferred. The alkoxy group is not particularly limited, but examples include the following:

[0043] R in formula (1′) or formula (1″) ４ The amino group and amide group that can be used as the amino group are preferably a primary amino group, a secondary amino group, a tertiary amino group, a group having a quaternary ammonium salt structure, an amide having a substituent, etc. The amino group or amide group is not particularly limited, but examples thereof include the following:

[0044]

[0045] n in formula (1') or formula (1'') ３is an integer of 0 to 19, preferably an integer of 0 to 9, more preferably an integer of 0 to 5, and even more preferably an integer of 0 to 2.

[0046] In the formula (1') or (1''), when the organic group in A is phenyl, n ２ +n ３ It is preferable that +1≦6 is satisfied, and when the organic group in A is naphthyl, n ２ +n ３ It is preferable that +1≦8 is satisfied, and when the organic group in A is anthracene, n ２ +n ３ It is preferable that n +1≦10 is satisfied, and when the organic group in A is adamantane, ２ +n ３ It is preferable to satisfy +1≦4.

[0047] From the viewpoint of easy reactivity, the compound represented by the formula (1) is preferably a compound represented by the following formula (2):

[0048] In formula (2), R １ , A, n ２ is as defined in the above formula (1).

[0049] From the viewpoint of etching resistance, the compound represented by the formula (1) is more preferably a compound represented by the following formula (3):

[0050] In formula (3), A1 represents an organic group having 5 to 30 carbon atoms and containing an aromatic ring, which may have a protecting group; R １ , n ２ is as defined in the above formula (1).

[0051] The organic group of A1 having 5 to 30 carbon atoms and containing an aromatic ring may have a substituent. Examples of the organic group of A1 having 5 to 30 carbon atoms and containing an aromatic ring include arenes having 5 to 30 carbon atoms, 5 to 20 carbon atoms, 5 to 10 carbon atoms, or 5 to 6 carbon atoms, which may have a substituent.

[0052] In formula (3), specific examples of the organic group A1 having 5 to 30 carbon atoms and containing an aromatic ring include, for example, optionally substituted benzene, phenol, naphthalene, anthracene, phenanthrene, tetracene, chrysene, triphenylene, pyrene, pentacene, benzopyrene, coronene, azulene, fluorene, and combinations thereof, which may contain an ether bond, a ketone bond, or an ester bond.

[0053] In formula (3), the substituent of the organic group having 5 to 30 carbon atoms and containing an aromatic ring, A1, is not particularly limited, and examples thereof include a halogen atom (fluorine, chlorine, bromine), a hydroxyl group, a cyano group, a nitro group, an amino group, a thiol group, a heterocyclic group, a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkenyl group, an acyl group, an alkoxycarbonyl group, an alkyloyloxy group, an aryloyloxy group, an alkylsilyl group, various crosslinkable groups, and acid-dissociable groups, and preferably a hydroxyl group or a linear aliphatic hydrocarbon group.

[0054] The "crosslinkable group" and "acid-dissociable group" are not particularly limited, but examples thereof include the above-mentioned R ２ and R ３ Although not particularly limited, the acid-dissociable group bonded to the aromatic ring of B is preferably a group that is cleaved in the presence of an acid to generate a hydroxyl group.

[0055] In formula (3), A1 preferably has a protecting group, and the protecting group is R ４ is synonymous with.

[0056] From the viewpoint of etching resistance, the compound represented by the formula (1) is more preferably a compound represented by the following formula (3').

[0057] In formula (3), A1′ represents an organic group having 5 to 30 carbon atoms and containing an alicyclic ring which may have a protecting group; R １ , n ２ is as defined in the above formula (1).

[0058] In formula (3), the organic group having 5 to 30 carbon atoms and containing an alicyclic ring for A1' may have a substituent. Examples of the organic group having 5 to 30 carbon atoms and containing an alicyclic ring for A1' include optionally substituted cycloalkanes having 5 to 30 carbon atoms, 5 to 20 carbon atoms, 5 to 10 carbon atoms, or 5 to 6 carbon atoms; optionally substituted cycloalkenes having 5 to 30 carbon atoms, 5 to 20 carbon atoms, 5 to 10 carbon atoms, or 5 to 6 carbon atoms; optionally substituted cycloalkynes having 5 to 30 carbon atoms, 5 to 20 carbon atoms, 5 to 10 carbon atoms, or 5 to 6 carbon atoms; and combinations thereof.

[0059] Specific examples of the organic group having 5 to 30 carbon atoms and containing an alicyclic ring for A1' include, for example, optionally substituted cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloicosane, cyclotriacontane, adamantane, and combinations thereof, which may contain an ether bond, a ketone bond, or an ester bond.

[0060] The substituent of the organic group having 5 to 30 carbon atoms and containing an alicyclic ring for A1′ is not particularly limited, but examples thereof include a halogen atom (fluorine, chlorine, bromine), a hydroxyl group, a cyano group, a nitro group, an amino group, a thiol group, a heterocyclic group, a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkenyl group, an acyl group, an alkoxycarbonyl group, an alkyloyloxy group, an aryloyloxy group, an alkylsilyl group, various crosslinkable groups, and acid-dissociable groups, and preferably a hydroxyl group or a linear aliphatic hydrocarbon group.

[0061] The "crosslinkable group" and "acid-dissociable group" are not particularly limited, but examples thereof include the above-mentioned R ２ and R ３ The materials described in the description of the above can be used.

[0062] In formula (3), A1 preferably has a protecting group, and the protecting group is R ４ is synonymous with.

[0063] Specific examples of the iodine-containing (meth)acrylate compound (compound A) in this embodiment are listed below, but are not limited thereto. １ represents a hydrogen atom or a methyl group.

[0064]

[0065] With regard to the structural formulae described herein, for example, as shown below, when the line showing the bond to C is in contact with ring A and ring B, it means that C may be bonded to either ring A or ring B.

[0066] [Method for Producing Compound A] Compound A represented by formula (1) in this embodiment can be synthesized by a known method, for example, a method of reacting an iodine-containing hydroxy compound represented by general formula (a) with a (meth)acrylic acid compound represented by general formula (b), but is not limited thereto.

[0067] (In formula (a), R ２ and R ３ , A, n １ , n ２ is as defined in equation (1) (In formula (b), R １ is as defined in formula (1). Ｂ is selected from the group consisting of a hydroxyl group, a halogen atom, and a (meth)acryloyloxy group. Ｂ is preferably a halogen atom such as a chlorine atom.

[0068] The compound represented by the general formula (a) is preferably a compound represented by the general formula (a1). (In formula (a1), A, n ２ is as defined in the above formula (1).

[0069] The compound represented by the general formula (a) is preferably a compound represented by the general formula (a2). (In formula (a2), A' represents an organic group having 5 to 30 carbon atoms and containing an aromatic ring, and n ２ is as defined in the above formula (1).

[0070] The compound represented by the general formula (a) is preferably a compound represented by the general formula (a3). (In formula (a3), A″ represents an organic group having 5 to 30 carbon atoms and including an alicyclic ring, and n ２ is as defined in the above formula (1).

[0071] Examples of the (meth)acrylic acid compound represented by general formula (b) in this embodiment are shown below. Of these (meth)acrylic acid compounds, (meth)acrylic acid chloride is preferred from the viewpoint of reactivity.

[0072] Next, a method for synthesizing an iodine-containing hydroxy compound represented by general formula (a) will be described. An example of the synthesis of an iodine-containing hydroxy compound represented by general formula (a) is by subjecting a compound of general formula (Sa1) or (Sa2) to an iodine introduction reaction. When subjecting a compound of general formula (Sa2) to an iodine introduction reaction, the method further includes a step of converting the iodine-introduced product into a compound of general formula (a).

[0073] (In formula (Sa1), R ２ and R ３ , A, n １ , n ２ is as defined in formula (1). X can be selected from a hydroxyl group; an aliphatic or aromatic group having 1 to 30 carbon atoms and having at least one group selected from the group consisting of a hydroxyl group, an aldehyde group, and a carboxyl group; or a halogen group (F, Cl, Br, etc.) (In formula (Sa2), A, n ２is as defined in formula (1). X is as defined in formula (Sa1). E is a hydrocarbon group having 1 to 30 carbon atoms and having at least one group selected from the group consisting of a hydroxyl group, an aldehyde group, a carboxyl group, an ether group, a thiol group, and an amino group.

[0074] Examples of iodine introduction reactions that can be used include the Sandmeyer method, the Halex method, an iodine introduction method using an iodizing agent or a compound that serves as an iodine source, an iodine introduction method using an iodizing agent or a compound that serves as an iodine source and an oxidizing agent, an iodine introduction method using an iodizing agent or a compound that serves as an iodine source and a radical generator, an iodine introduction method using a system in which the catalytic activity of an iodizing agent or a compound that serves as an iodine source is improved by using a zeolite or the like, and a method in which iodination is performed by a substitution reaction of a functional group such as a hydroxyl group or a halogen group. Examples of iodine introduction agents that can be used include iodine, potassium iodide, HI, iodine chloride, and N-iodosuccinimide. Examples of oxidizing agents that can be used include known oxidizing agents such as hydrogen peroxide, iodic acid, periodic acid, and sulfuric acid.

[0075] Next, another method for producing compound A represented by general formula (1) will be described. The compound represented by formula (a) is used in an amount of, for example, 0.5 to 100 molar equivalents, preferably 1 to 20 molar equivalents, and more preferably 1.2 to 5 molar equivalents relative to the compound represented by formula (b). This range is preferred because the reaction proceeds sufficiently and the yield of the target compound A represented by formula (1) is high.

[0076] As the solvent used in this reaction, a commonly available solvent can be used. For example, alcohols, ethers, hydrocarbons, aromatic solvents, halogenated solvents, etc. can be used appropriately as long as they do not inhibit the reaction. A mixture of multiple solvents can also be used as long as they do not inhibit the reaction. Since water inhibits the reaction, it is preferable to use a dehydrated solvent.

[0077] Furthermore, as a solvent used in producing the iodine-containing (meth)acrylate compound (compound A) of this embodiment, a solvent with good solubility is preferably used for the purpose of improving the stability of the material and the efficiency of the processes from reaction to obtaining the final compound. As for preferred solvents, the γP and γH in the Hansen Solubility Parameters (Hansen Solubility Parameters: A User's Handbook, CRC Press, Boca Raton FL, 2007) can be used as indicators, and γP and γH can be determined from the compound structure. The lower the γP and γH, the better. A γP value of 6 or less is preferred, more preferably 4 or less, and even more preferably 2 or less. A γH value of 6 or less is preferred, more preferably 4 or less, and even more preferably 2 or less. Particularly preferred solvents include aromatic solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, and octane; and halogenated solvents such as dichloromethane and dichloroethane, which are preferably used as the main solvent.

[0078] The reaction temperature and reaction time depend on the substrate concentration and the catalyst used, but generally the reaction temperature is −20° C. to 100° C., the reaction time is 1 to 10 hours, and the pressure is normal, reduced, or increased. The reaction can be carried out by any known method appropriately selected from the batch, semi-batch, and continuous systems.

[0079] A polymerization inhibitor may be added to the series of reactions, and a commercially available product may be used. Examples of such a polymerization inhibitor include nitroso compounds such as 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl, N-nitrosophenylhydroxylamine ammonium salt, N-nitrosophenylhydroxylamine aluminum salt, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, N-nitrosodiphenylamine, N-nitroso-N-methylaniline, nitrosonaphthol, p-nitrosophenol, and N,N'-dimethyl-p-nitrosoaniline; sulfur-containing compounds such as phenothiazine, methylene blue, and 2-mercaptobenzimidazole; N,N'-diphenyl-p-phenylenediamine; and N-phenyl Examples of the compound include amines such as -N'-isopropyl-p-phenylenediamine, 4-hydroxydiphenylamine, and aminophenol, quinones such as hydroxyquinoline, hydroquinone, methylhydroquinone, p-benzoquinone, and hydroquinone monomethyl ether, phenols such as p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, catechol, 3-s-butylcatechol, and 2,2-methylenebis-(6-t-butyl-4-methylphenol), imides such as N-hydroxyphthalimide, oximes such as cyclohexaneoxime and p-quinonedioxime, and dialkylthiodipropionate. The amount added is, for example, 0.001 to 10 parts by mass, and preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the (meth)acrylic acid compound represented by general formula (b).

[0080] The compound A represented by general formula (1) obtained by the reaction can be isolated and purified as a desired high-purity monomer by a known purification method such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a separation and purification method using activated carbon, or a combination of these methods.

[0081] [Compound B] Compound B in this embodiment is a compound represented by the following formula (B1) or formula (BP0-1). In formula (B1), B is a group containing at least one cyclic structure which may have a protecting group, I is an iodine atom, and R０ is a monovalent functional group having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, and R ０ When there are a plurality of Q's, they may be the same or different, Q is a single bond, a divalent group which may have a substituent, a group containing an alkylene group, a phenylene group, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group or a phosphate group, -O-CH ２ - or a group represented by the following formula (B1L), m' is an integer of 0 to 9, n' is an integer of 1 to 19, and n ２ and b is an integer from 1 to 4.

[0082] In formula (B1L), R ２ , R ３ is the same as in formula (1), and X １ is a divalent group which contains a single bond or an alkylene group, a phenylene group, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, each of which may have a substituent; and n1a is an integer of 0 or 1.

[0083] In formula (BP0-1), B, I, R ０ , m', and n' are defined the same as in formula (B1).

[0084] In formula (B1), B is a group containing at least one cyclic structure which may have a protecting group. The valence of B is determined by the groups I and R described below. ０ , R ０The number of substituents other than the above is appropriately adjusted. The cyclic structure in B may contain an aromatic ring, a polycyclic alicyclic ring, or a heterocyclic ring, but is preferably a group having 6 to 60 carbon atoms, which may have a substituent, and is preferably a group derived from an aromatic ring such as benzene, naphthalene, biphenyl, anthracene, phenanthrene, pyrene, or fluorene, or a polycyclic alicyclic ring such as cyclohexane, cyclododecane, dicyclopentane, tricyclodecane, or adamantane, or a heteroaromatic ring, which may have a substituent. Furthermore, B does not need to contain a ring assembly in which single rings are bonded by a single bond (e.g., biphenyl, binaphthyl, bicyclopropyl, etc.). In this case, B is preferably a group having at least one cyclic structure selected from a monocyclic aromatic ring structure, a fused-ring aromatic structure, and a polycyclic alicyclic structure.

[0085] Among these, from the viewpoint of availability etc., the cyclic structure in B of formula (B1) is preferably an aromatic ring or heteroaromatic ring which may have a substituent, more preferably benzene, naphthalene, anthracene, pyrene or a heteroaromatic ring which may have a substituent, and even more preferably benzene, naphthalene, anthracene, pyrene or a heteroaromatic ring. Furthermore, from the viewpoint of availability etc., the cyclic structure in B of formula (B1) is preferably a polycyclic alicyclic ring which may have a substituent, more preferably phenanthrene, fluorene or adamantane.

[0086] In formula (B1), I is an iodine atom. n' represents the number of I and is an integer of 1 to 9. ２ n is an integer below 1. From the viewpoints of the sensitizing effect, solubility in solvents, and chemical stability, n is preferably an integer of 1 to 3, and more preferably 1 or 2. When n is greater than 1, the sensitizing effect can be obtained, and when n is 5 or less, the solubility of the compound in solvent components commonly used for semiconductors and the stability of the compound itself can be ensured.

[0087] In formula (B1), R ０ is a monovalent functional group having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, and R ０When there are a plurality of R, they may be the same or different functional groups. ０ By converting R to another group or bonding R to another group, a derivative of the compound of formula (1) can be produced. The polymerizable unsaturated bond is an ethylenic double bond or triple bond. ０ When the above is true, the stability and solubility are excellent.

[0088] In formula (B1), R ０ is a functional group and is not an alkyl group. ０ is, for example, an alkoxy group having 1 to 30 carbon atoms, a carboxyl group having 1 to 30 carbon atoms, a carboxylic acid ester group having 2 to 10 carbon atoms, an alkoxyalkyl group or a hydroxyalkyl group having 2 to 30 carbon atoms, an aldehyde group, a halogen atom other than iodine, a formyl group, a nitro group, an amino group, a thiol group, or a hydroxyl group. ０ is preferably a hydroxyl group, a carboxyl group, an ester group, an alkoxy group, or a hydroxyalkyl group from the viewpoint of sensitizing effect, etc. Among these groups, groups that can have a substituent may have a substituent. In formula (B1), the substituent is not particularly limited, but examples include a halogen atom, a hydroxyl group, a cyano group, a nitro group, a thiol group, a heterocyclic group, a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 20 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an amino group having 0 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an acyl group having 1 to 30 carbon atoms (preferably an alkyloyloxy group having 1 to 20 carbon atoms or an aryloyloxy group having 7 to 30 carbon atoms), an alkoxycarbonyl group having 2 to 20 carbon atoms, and an alkylsilyl group having 1 to 20 carbon atoms. These groups may be groups within or bearing substituents, or other R ０ Suitable examples of the group that may form a ring structure include a glycidyl group, a cyclic acetal group, and a group in which two adjacent hydroxyl groups have an acetal protecting group structure.

[0089] Among them, in formula (B1), R ０ is preferably —OR ２wherein R is selected from a group represented by the formula (I), an alkoxy group having 1 to 30 carbon atoms, a hydroxyl group, a carboxyl group having 1 to 30 carbon atoms, a carboxylic acid ester group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, or an aldehyde group. ０ R in ２ is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 1 to 30 carbon atoms, or a cyclic alkyl ether group having 1 to 5 carbon atoms. The carboxyl group or carboxylic acid ester group is more preferably —COOR ３ where R ０ R in ３ is a hydrogen atom, an alkyl group having 1 to 29 carbon atoms, or an aryl group having 1 to 29 carbon atoms. The alkoxyalkyl group or hydroxyalkyl group is more preferably —CH ２ -OR ４ where R ０ R in ４ is a hydrogen atom, an alkyl group having 1 to 29 carbon atoms, or an aryl group having 1 to 29 carbon atoms. The alkyl group or aryl group may have a substituent. Examples of the substituent include an alkoxy group. Therefore, the -OR ２ R ２ In one embodiment, is —CH ２ -OC ２ H ５ It is possible.

[0090] R ０ The R in ２ ~R ４ The alkyl group in the formula (I) is preferably a methyl group, an ethyl group, or a propyl group (including isomers, the same applies hereinafter). The aryl group is preferably a phenyl group or a naphthyl group.

[0091] In formula (B1), R ０may have a protecting group. The protecting group may be the same as the protecting group of A in formula (1), and the protecting group is preferably an acid-dissociable group that dissociates in the presence of an acid. Preferred examples of the protecting group include a 1-substituted ethyl group, a 1-substituted n-propyl group, a 1-branched alkyl group, a silyl group, an acyl group, a 1-substituted alkoxymethyl group, a cyclic ether group, an alkoxycarbonyl group, or an alkoxycarbonylalkyl group. In one embodiment, R ０ may be a hydroxyl group or a carboxyl group protected by a protecting group. For example, R ０ Ha -O-CH ２ -O-R'. R' is, for example, an alkyl group having 1 to 5 carbon atoms. In this embodiment, R ０ Ga-OR ２ (However, R ２ is CH ３ ) and R ２ has an alkoxy group (—O—R′) as a substituent.

[0092] In formula (B1), m′ is R ０ and is an integer of 1 to 9. From the viewpoint of solubility in a solvent, m' is preferably 4, 3, 2, or 1. When m' is 2 or 3, a plurality of R ０ may be different or may be the same. m' is more preferably 2 or 3, and even more preferably 2. The total number of m' and n' is appropriately adjusted depending on the valence of B.

[0093] In formula (B1), B may optionally include R ０ The compound B may have an organic group other than R. The organic group may be an alkyl group having 1 to 30 carbon atoms. A plurality of such groups may be present. However, the compound B may have an organic group other than R. ０ It is preferable that the iodine-containing organic compound does not contain any organic groups other than iodine.

[0094] In formula (B1), B is a group containing a benzene ring, and R ０ If there are multiple R ０does not include a combination of an alkoxy group and an aldehyde group, an alkoxy group and a hydroxyl group, or an aldehyde group and a hydroxyl group. The alkoxy group here does not include those having a protecting group. The alkoxy group is, for example, a methoxy group or an ethoxy group. When B is a group containing a naphthalene ring and R ０ If there are multiple R ０ does not include a combination of a hydroxyl group and a carboxyl group.

[0095] In formula (B1), R ０ is an ether group having a hydroxyl group and a protecting group. ｆ R' is a hydroxyl group or an ether group having a protecting group that is cleaved by an acid, an alkali, or heat. B may be a hydrocarbon group having 0 to 30 carbon atoms that may contain a substituent. In particular, when B is a benzene or naphthalene structure, R ０ is one or more R selected from the group consisting of a hydroxyl group and an ether group having a protecting group; ０ and hydrocarbon groups having 0 to 30 carbon atoms which may contain zero or more substituents.

[0096] In formula (B1), Q is a single bond, a divalent group which may have a substituent, a group containing an alkylene group, a phenylene group, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, -O-CH ２- or a group represented by the above formula (B1L), and the substituent is not particularly limited, but examples thereof include a halogen atom, a hydroxyl group, a cyano group, a nitro group, a thiol group, a heterocyclic group, a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 20 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an amino group having 0 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an acyl group having 1 to 30 carbon atoms (preferably an alkyloyloxy group having 1 to 20 carbon atoms, an aryloyloxy group having 7 to 30 carbon atoms), an alkoxycarbonyl group having 2 to 20 carbon atoms, and an alkylsilyl group having 1 to 20 carbon atoms. Q is an alkylene group, a phenylene group, a single bond, an ether group, an amino group, -O-CH ２ -, an ester group is preferred, and an alkylene group, a single bond, an ether group, an amino group, -O-CH ２ - and an ester group are more preferred, and a single bond, an ether group, an amino group, or -O-CH ２ In one embodiment, Q may be a single bond, a divalent group which is an optionally substituted group containing an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, or a group represented by the following formula (B1L):

[0097] In formula (B1L), R ２ , R ３ is preferably a hydrogen atom, a linear organic group having 1 to 20 carbon atoms, a branched organic group having 3 to 20 carbon atoms, or a cyclic organic group having 3 to 20 carbon atoms, more preferably a hydrogen atom, a linear organic group having 1 to 10 carbon atoms, a branched organic group having 3 to 10 carbon atoms, or a cyclic organic group having 3 to 15 carbon atoms, and particularly preferably a hydrogen atom, a linear organic group having 1 to 5 carbon atoms, a branched organic group having 3 to 8 carbon atoms, or a cyclic organic group having 3 to 10 carbon atoms.

[0098] In formula (B1L), X １is a divalent group containing a single bond or an alkylene group, a phenylene group, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, which may have a substituent. The substituent is not particularly limited, but examples thereof include a halogen atom, a hydroxyl group, a cyano group, a nitro group, a thiol group, a heterocyclic group, a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group having 3 to 4 carbon atoms, a hydroxyl group having 4 to 5 carbon atoms, a hydroxyl group having 5 to 6 carbon atoms, a hydroxyl group having 6 to 8 carbon atoms, a hydroxyl group having 1 to 20 carbon atoms, a hydroxyl group having 3 to 4 ... Examples of the alkyl group include a branched aliphatic hydrocarbon group having from 1 to 20 carbon atoms, a cyclic aliphatic hydrocarbon group having from 3 to 20 carbon atoms, an aryl group having from 6 to 20 carbon atoms, an alkoxyl group having from 1 to 20 carbon atoms, an amino group having from 0 to 20 carbon atoms, an alkenyl group having from 2 to 20 carbon atoms, an alkynyl group having from 2 to 20 carbon atoms, an acyl group having from 1 to 30 carbon atoms (preferably an alkyloyloxy group having from 1 to 20 carbon atoms, or an aryloyloxy group having from 7 to 30 carbon atoms), an alkoxycarbonyl group having from 2 to 20 carbon atoms, and an alkylsilyl group having from 1 to 20 carbon atoms. １ is preferably a single bond, an alkylene group, a phenylene group, or an ether group, more preferably a single bond, an alkylene group, or an ether group, and particularly preferably a single bond or an alkylene group. １ is a divalent group which may have a substituent and may be a group containing an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group.

[0099] In formula (B1L), n1a is preferably 0.

[0100] The compound B is preferably a compound represented by the following formula (B2): In formula (B2), Rx is a hydroxy group or a protecting group, and B, I, R ０ , Q has the same meaning as in formula (B1), R ２ , R ３ is the same as in formula (1), and R ４ is a protecting group, and n １１ is an integer of 0 or 1, ２１ is an integer from 1 to 20, and n３１ is an integer from 0 to 19, and n ４１ is an integer from 0 to 9.

[0101] In formula (B2), n ２１ , n ４１ is preferably 0 to 7, more preferably 0 to 5, and particularly preferably 0 to 3. ３１ is preferably 0 to 10, more preferably 0 to 5, and particularly preferably 0 to 3. In a preferred embodiment, the compound of formula (B2) is represented by the following formula (B3).

[0102]

[0103] In formula (B3), Rx, B, I, R ０ , R ２ , R ３ has the same meaning as formula (B1), and R ４ａ represents a single bond or a divalent group containing an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, which may have a substituent; n ２ ~n ３ is an integer from 1 to 20. ３ -1 is n ３ means a value one less than n ３ -1 is an integer from 0 to 19.

[0104] [Bz Series] In a preferred embodiment, the compound of formula (B1) is represented by formula (DM1a).

[0105]

[0106] In formula (DM1a), R is a non-functional organic group, ０ , R ４ , Q has the same meaning as in formula (B1), Z is H, I, R ０or a linking group for forming a dimer, r1 to r4 are integers of 0 to 5, and the sum of r1 to r4 in one benzene is equal to or less than the valence of the benzene. r4-1 means a value smaller by 1 than r4, and r4-1 is an integer of 0 to 4. In formula (DM1a), Z is preferably H or R ０ is.

[0107] An example of a dimer compound is shown below: ０ , R ４ , Q is defined the same as in formula (DM1a).

[0108]

[0109] Specific dimer compounds are shown below.

[0110]

[0111] [N Series] In another preferred embodiment, the compound of formula (B1) is represented by formula (Dn1).

[0112]

[0113] In another preferred embodiment, the compound of formula (B1) is represented by formula (Dn1-1).

[0114] In formula (Dn1-1), I, R ０ , R ４ is defined the same as in formula (DM1a), R″ is a hydrogen atom or R ０ an organic group other than I, R ０ , R ４ , R" is bonded to a bondable position, Q is defined the same as in formula (B1), s1 is an integer of 1 to 7, and s2 to s4 are integers of 0 to 7. However, s1 to s4 are selected so that the total of s1 to s4 satisfies the valence of the naphthalene ring, and either s2 or s3 is 1 or more. nd is an integer of 1 to 4.

[0115] In formula (Dn1), R ０ , R ４and Q has the same meaning as in formula (B1). x is an integer of 0 to 3, y is an integer of 0 to 1, and bn is an integer of 1 to 4. In formula (Dn1), it is preferable that Q is a single bond and bn is 1. Non-limiting specific examples of formula (Dn1) are shown below.

[0116]

[0117] [Ad Series] In yet another preferred embodiment, the compound of formula (B1) is represented by formula (Da1) or formula (Da2).

[0118]

[0119] In formula (Da1) and formula (Da2), R ０ , Q has the same meaning as in formula (B1), ba is an integer of 0 to 4, R″ is a hydrogen atom or R ０ and is preferably a phenoxy group which may have a hydrogen atom or a substituent (e.g., an alkyl group) other than the above. Furthermore, in formula (Da1), it is preferable that Q is O and ba is 0 or 1. Non-limiting specific examples of formulas (Da1) and (Da2) are shown below.

[0120]

[0121] In formula (BP0-1), B, I, R ０ , m', and n' are defined as in formula (1), and n'-1 means a number that is 1 less than n'.

[0122] The compound represented by formula (BP0-1) is preferably represented by the following formula (BP1a), (Bn1), or (Ba1): １, R", A, r1 to r4, s2 to s3, and t2 to t3 are defined as above. a1 and r4a are integers of 0 to 4, and a1 and r4a are numbers satisfying a1+r4a≦r4. r4 is defined as above, but preferably has the same meaning as r4 in formula (Bz). s1b is an integer of 0 to 6 and is an integer that satisfies s1b≦(s1−1). s1 is defined as above, but preferably has the same meaning as s1 in formula (N). t1b is an integer of 0 to 9 and is an integer that satisfies t1b≦(t1−1). t1 is defined as above, but preferably has the same meaning as t1 in formula (Ad).

[0123]

[0124] [B] In formula (BP0-1), B is a group containing at least one cyclic structure. The valence of B is determined by the groups I and R described below. ０ , R ０ The number of substituents other than the above is appropriately adjusted. The group containing a cyclic structure may contain an aromatic ring, an alicyclic ring, or a heterocyclic ring, but is preferably a group having 6 to 60 carbon atoms, and is more preferably a group derived from an aromatic ring, a heteroaromatic ring, such as benzene, naphthalene, biphenyl, anthracene, phenanthrene, pyrene, or fluorene, or an alicyclic ring, such as cyclohexane, cyclododecane, dicyclopentane, tricyclodecane, or adamantane, which may have a substituent. Furthermore, B does not need to contain a ring assembly in which single rings are bonded by a single bond (e.g., biphenyl, binaphthyl, bicyclopropyl, etc.). In this case, B is preferably a group having at least one cyclic structure selected from a monocyclic aromatic ring structure, a fused-ring aromatic structure, and a polycyclic alicyclic structure.

[0125] Among these, from the viewpoint of availability and the like, B is preferably a group derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, fluorene, or adamantane, which may have a substituent, and more preferably a group derived from benzene, naphthalene, or adamantane, which may have a substituent.

[0126] [I] In formula (BP0-1), I is an iodine atom. n' represents the number of I and is an integer of 1 to 5. From the viewpoints of the sensitizing effect, solubility in solvents, and chemical stability, n' is preferably an integer of 1 to 3, and more preferably 1 or 2. When n' is greater than 1, the sensitizing effect can be obtained, and when n' is 5 or less, the solubility of the compound in solvent components commonly used for semiconductors and the stability of the compound itself can be ensured.

[0127] [R ０ ] In formula (BP0-1), R ０ R may be the same or different and are monovalent functional groups having 0 to 30 carbon atoms and containing no polymerizable unsaturated bonds. ０ By converting R to another group or bonding it to another group, a derivative of the compound of formula (B1) can be produced. The polymerizable unsaturated bond is an ethylenic double bond or triple bond. ０ When the above is true, the stability and solubility are excellent.

[0128] In formula (BP0-1), R ０ is a functional group and is not an alkyl group. ０ is, for example, an alkoxy group having 1 to 30 carbon atoms, a carboxyl group having 1 to 30 carbon atoms, a carboxylic acid ester group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, a hydroxyalkyl group having 1 to 30 carbon atoms, an aldehyde group, a halogen atom other than an iodine atom, a nitro group, an amino group, a thiol group, a cyano group, or a hydroxyl group. ０From the viewpoint of sensitizing effect, etc., is preferably a hydroxyl group, a carboxyl group, an ester group, a hydroxyalkyl group, a halogen atom other than an iodine atom, a nitro group, an amino group, or a cyano group. Among these groups, those that can have a substituent may have a substituent. Unless otherwise defined, "substituted" means that one or more hydrogen atoms in the functional group are substituted with a substituent. The "substituent" is not particularly limited, but examples thereof include a halogen atom, a hydroxyl group, a cyano group, a nitro group, a thiol group, a heterocyclic group, a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 20 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an amino group having 0 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an acyl group having 1 to 30 carbon atoms (preferably an alkyloyloxy group having 1 to 20 carbon atoms, an aryloyloxy group having 7 to 30 carbon atoms), an alkoxycarbonyl group having 2 to 20 carbon atoms, or an alkylsilyl group having 1 to 20 carbon atoms. These groups may be groups within a substituent, a group having a substituent, or other R ０ Suitable examples of the group that may form a ring structure include a glycidyl group, a cyclic acetal group, and a group in which two adjacent hydroxyl groups are protected by an acetal protecting group structure.

[0129] Among them, in formula (BP0-1), R ０ is preferably —OR ２ wherein R is selected from a group represented by the formula (I), an alkoxy group having 1 to 30 carbon atoms, a hydroxyl group, a carboxyl group having 1 to 30 carbon atoms, a carboxylic acid ester group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, or an aldehyde group. ２ is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 1 to 30 carbon atoms, or a cyclic alkyl ether group having 1 to 5 carbon atoms. The carboxyl group or carboxylic acid ester group is more preferably —COOR ３ where R ３is a hydrogen atom, an alkyl group having 1 to 29 carbon atoms, or an aryl group having 1 to 29 carbon atoms. The alkoxyalkyl group or hydroxyalkyl group is more preferably —CH ２ -OR ４ where R ４ is a hydrogen atom, an alkyl group having 1 to 29 carbon atoms, or an aryl group having 1 to 29 carbon atoms. The alkyl group or aryl group may have a substituent. Examples of the substituent include an alkoxy group. Therefore, the -OR ２ R ２ In one embodiment, is —CH ２ -OC ２ H ５ It is possible.

[0130] The R ２ ~R ４ The alkyl group in the formula (I) is preferably a methyl group, an ethyl group, or a propyl group (including isomers, the same applies hereinafter). The aryl group is preferably a phenyl group or a naphthyl group.

[0131] R ０ may have a protecting group. A protecting group is a group that dissociates under specific conditions and is also called a dissociable group. The protecting group is preferably an acid-dissociable group that dissociates in the presence of an acid. Preferred examples of such groups include a 1-substituted ethyl group, a 1-substituted-n-propyl group, a 1-branched alkyl group, a silyl group, an acyl group, a 1-substituted alkoxymethyl group, a cyclic ether group, an alkoxycarbonyl group, or an alkoxycarbonylalkyl group. In one embodiment, R ０ may be a hydroxyl group or a carboxyl group protected by a protecting group. For example, R ０ Ha -O-CH ２ -O-R'. R' is, for example, an alkyl group having 1 to 5 carbon atoms. In this embodiment, R ０ Ga-OR ２ (However, R ２ is CH ３ ) and R ２ has an alkoxy group (—O—R′) as a substituent. １ is a group having a protecting group, as described below, R ０is sometimes written as A or A'.

[0132] [Method for producing compound B] 1-4. Production method Compound B can be produced by any method as long as its effects are not impaired. However, if an iodine atom or R ０ For example, the step of introducing an iodine atom into a compound having an aromatic ring may be carried out by reacting the compound having an aromatic ring with iodine I. ２ This can be carried out by reacting the compounds under acidic or alkaline conditions. This reaction can produce compounds and dimers with different numbers of iodine atoms. The production ratios of these compounds can be adjusted by the reaction conditions. In particular, lowering the reaction temperature or shortening the reaction time tends to increase the number of compounds with fewer iodine atoms and decrease the number of dimers. Increasing the reaction temperature or lengthening the reaction time tends to decrease the number of compounds with fewer iodine atoms and increase the number of dimers. In addition, the step of introducing iodine atoms into a compound having an alicyclic ring can be carried out by reacting the compound having an alicyclic ring with HI (hydrogen iodide). A preferred method for producing the compound comprises reacting B in formula (B1), a functional group capable of replacing the iodine atom by a substitution reaction, and, if necessary, R ０ Another method for producing the compound may include an iodination step of introducing iodine atoms into a raw material containing RG and, if necessary, R ０ The method may include an iodination step of introducing iodine into a raw material containing the above in the form of a radical or as a cation or anion.

[0133] [Iodination Step] In this embodiment, the iodination step is a step of introducing a halogen or a halogen-containing group into a target compound. Examples of the iodination step include, but are not limited to, a method of introducing a halogen from an amino group by the Sandmeyer reaction or the like, a method of reacting iodine chloride in an organic solvent (e.g., JP 2012-180326 A), and a method of adding iodine dropwise to an alkaline aqueous solution of phenol under alkaline conditions in the presence of β-cyclodextrin (JP 63-101342 A, JP 2003-64012 A). The halogen or halogen-containing group to be introduced is not particularly limited, but from the viewpoint of the performance, particularly the effect of improving sensitivity to EUV, when compound A obtained by the production method of this embodiment is applied to a resist resin, it is preferably F, I, or a group containing F or I, and more preferably I or a group containing I.

[0134] The halogenating agent is not particularly limited, but examples thereof include iodinating agents such as iodine chloride, iodine, and N-iodosuccinimide, fluorinating agents such as potassium fluoride and tetramethylammonium fluoride, chlorinating agents such as thionyl chloride and dichloromethyl methyl ether, and brominating agents such as bromine molecules, carbon tetrabromide, and N-bromosuccinimide. Among these, iodinating agents are preferred, and iodine chloride is more preferred.

[0135] In the iodination step, the ratio of the halogenating agent to the substrate is preferably 1.2 molar times or more, more preferably 1.5 molar times or more, and even more preferably 2.0 molar times or more.

[0136] In the iodination step, when I or a group containing I is introduced into a target compound, the iodine introduction reaction can proceed by reacting at least an iodinating agent with a substrate. More specifically, although not particularly limited, a compound into which I or a group containing I has been introduced can be obtained under known iodine introduction reaction conditions using methods described in non-patent documents such as Adv. Synth. Catal. 2007, 349, 1159-1172 and Organic Letters; Vol. 6; (2004); pp. 2785-2788, and patent documents such as US Pat. No. 5,300,506, US Pat. No. 5,434,154, US 2009 / 281114, EP 1,439,164, and WO 2006 / 101318.

[0137] The iodinating agent that can be used is not particularly limited, but includes iodine chloride, iodine, N-iodosuccinimide, iodine compounds, monochloride iodide, N-iodosuccinimide, benzyltrimethylammonium dichloroiodate, tetraethylammonium iodide, tetra-n-butylammonium iodide, lithium iodide, sodium iodide, potassium iodide, 1-chloro-2-iodoethane, and silver iodine fluoride. , tert-butyl hypoiodide, 1,3-diiodo-5,5-dimethylhydantoin, iodine-morpholine complex, trifluoroacetyl hypoiodide, iodine-iodic acid, iodine-periodic acid, iodine-hydrogen peroxide, 1-iodoheptafluoropropane, triphenylphosphate-methyl iodide, iodine-thallium(I) acetate, 1-chloro-2-iodoethane, iodine-copper(II) acetate, and the like.

[0138] When I or a group containing I is introduced in the iodination step, one or more additives may be added to the iodine introduction reaction for the purpose of promoting the reaction or suppressing by-products. Examples of additives include, but are not limited to, acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, p-toluenesulfonic acid, ferric chloride, aluminum chloride, copper chloride, antimony pentachloride, silver sulfate, silver nitrate, and silver trifluoroacetate; bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate, and potassium bicarbonate; oxidizing agents such as cerium (IV) ammonium nitrate and sodium peroxodisulfate; inorganic compounds such as sodium chloride, potassium chloride, mercury (II) oxide, and cerium oxide; organic compounds such as acetic anhydride; and zeolites.

[0139] In the iodination step, from the viewpoint of improving reaction efficiency and purity, it is preferable to introduce iodine using at least an iodine source and an oxidizing agent. The iodination source is not particularly limited, but examples thereof include the above-mentioned iodinating agents. The oxidizing agent is not particularly limited, but examples thereof include iodic acid, hydrogen peroxide, and predetermined additives (hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, etc.).

[0140] In the iodination step, the reaction of introducing a halogen or a halogen-containing group may be carried out in the absence of a solvent or in the presence of a solvent. The solvent is not particularly limited, but examples thereof include halogen-based solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride, alkyl-based solvents such as hexane, cyclohexane, heptane, pentane, and octane, aromatic hydrocarbon-based solvents such as benzene and toluene, alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol, ether-based solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran, cyclopentyl methyl ether, 1,4-dioxane, and diglyme, acetic acid, dimethylformamide, dimethyl sulfoxide, and water.

[0141] In the iodination step, when I or a group containing I is introduced, the iodine introduction reaction can be carried out by reacting at least an iodinating agent with a substrate (a target compound). For example, the target compound can be obtained under known iodine introduction reaction conditions by a Sandmeyer reaction or the like using the methods described in Chemistry - A European Journal, 24(55), 14622-14626; 2018, Synthesis (2007)(1), 81-84, or the like.

[0142] In the iodination step, the reaction temperature for introducing a halogen or a halogen-containing group is not particularly limited and may be any temperature from the freezing point to the boiling point of the solvent used in the reaction, but is preferably 0°C or higher and 150°C or lower.

[0143] The iodination step can be appropriately selected from a method of introducing a halogen from an amino group by the Sandmeyer reaction or the like, a method of reacting with iodine chloride in an organic solvent (e.g., JP 2012-180326 A, JP 2000-256231 A, JP 2010-159233 A, J. Chem. Soc. 636, 1943), a method of adding iodine dropwise to an alkaline aqueous solution of phenol in the presence of β-cyclodextrin under alkaline conditions (JP 63-101342 A, JP 2003-64012 A), and the like.

[0144] The iodinating agent is not particularly limited, and examples thereof include iodine chloride, iodine, N-iodosuccinimide, iodic acid, etc. In the iodination step, the ratio of the iodinating agent to the substrate is preferably 1.2 molar times or more, more preferably 1.5 molar times or more, and even more preferably 2.0 molar times or more.

[0145] The iodination introduction reaction can be carried out by reacting at least an iodinating agent with a substrate. For example, the target compound can be obtained under known iodination reaction conditions using methods described in non-patent documents such as Adv. Synth. Catal. 2007, 349, 1159-1172, Organic Letters; Vol. 6; (2004); pp. 2785-2788, "Organic Synthesis Reagents and Synthesis Methods of Bromine and Iodine Compounds" (edited by Suzuki Hitomi, published by Manac Corporation Research Institute, Maruzen Publishing), and patent documents such as US Pat. No. 5,300,506, US Pat. No. 5,434,154, US Pat. No. 2009 / 281114, EP1,439,164, and WO2006 / 101318. Examples of iodinating agents that can be used include, but are not limited to, iodine compounds, iodide monochloride, N-iodosuccinimide, benzyltrimethylammonium dichloroiodate, tetraethylammonium iodide, tetra-normal-butylammonium iodide, lithium iodide, sodium iodide, potassium iodide, 1-chloro-2-iodoethane, silver iodine fluoride, tert-butylhypoiodide, 1,3-diiodo-5,5-dimethylhydantoin, iodine-morpholine complex, trifluoroacetylhypoiodide, iodine-iodic acid, iodine-periodic acid, iodine-hydrogen peroxide, 1-iodoheptafluoropropane, triphenylphosphate-methyl iodide, iodine-thallium(I) acetate, 1-chloro-2-iodoethane, iodine-copper(II) acetate, and the like.

[0146] One or more additives can be added to the iodination reaction for the purpose of promoting the reaction or suppressing by-products. Examples of additives include acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, p-toluenesulfonic acid, ferric chloride, aluminum chloride, copper chloride, antimony pentachloride, silver sulfate, silver nitrate, and silver trifluoroacetate; bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate, and potassium bicarbonate; oxidizing agents such as cerium (IV) ammonium nitrate and sodium peroxodisulfate; inorganic compounds such as sodium chloride, potassium chloride, mercury (II) oxide, and cerium oxide; organic compounds such as acetic anhydride; and porous substances such as zeolites. In the iodination step, the ratio of the additive to the iodinating agent is preferably 1.0 molar amount, more preferably 1.2 molar amounts or more, even more preferably 1.5 molar amounts or more, and even more preferably 2.0 molar amounts or more.

[0147] In the iodination step, iodine is preferably introduced into the mother nucleus using at least an iodine source and an oxidizing agent. Using an iodine source and an oxidizing agent is preferred from the viewpoints of reaction efficiency and improved purity. Examples of the iodination source include the iodinating agents described above. Examples of the oxidizing agent include iodic acid, periodic acid, hydrogen peroxide, and other additives (hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, silver trifluoroacetate, cerium (IV) ammonium nitrate (CAN), etc.). Furthermore, for phenols having a carboxylic acid group or a nitro group, the iodination reaction can also be carried out using an iodine cation species formed by combining an iodine source such as iodine with a silver salt or fuming sulfuric acid. Furthermore, for other relatively inert aromatic compounds, the iodination reaction can be carried out by combining an iodine source with an inorganic salt to form hypoiodous acid and an iodine cation species. An example of an inorganic salt that can be used as appropriate is potassium peroxodisulfate. A method of introducing iodine into an aliphatic alcohol group by a substitution reaction can also be used as appropriate. Examples of iodinating agents that can be used include hydrogen halides, phosphorus halides, sulfonyl halides (a combination of NaI / acetone), thionyl halides, trimethylsilane halides, Vilsmeier reagents, and the Abbel reaction (a combination of triphenylphosphine and an iodine source).

[0148] The reaction in the iodination step can be carried out neat without a solvent, but examples of usable reaction solvents include halogen-based solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; alkyl-based solvents such as hexane, cyclohexane, heptane, pentane, and octane; aromatic hydrocarbon-based solvents such as benzene and toluene; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol; ether-based solvents such as diethyl ether, diisopropyl ether, and tetrahydrofuran; acetic acid, dimethylformamide, dimethyl sulfoxide, and water.

[0149] The reaction temperature for the iodination step is not particularly limited and may be any temperature between the freezing point and the boiling point of the solvent used in the reaction, with a temperature of 0°C to 150°C being particularly preferred. The reaction system may be refluxed to allow the iodination to proceed more efficiently. Furthermore, the concentration of the iodinating agent in the reaction system may be controlled by using a reflux tube equipped with a Dean-Stark or the like.

[0150] The iodine substitution reaction in the iodination step can proceed by reacting at least an iodinating agent with a substrate. For example, the target compound can be obtained under known iodine substitution reaction conditions such as a Sandmeyer reaction using the method described in Chemistry - A European Journal, 24(55), 14622-14626; 2018, Synthesis (2007)(1), 81-84, etc.

[0151] [Protective group introduction step] R in the preferred production method of the compound ４ The introduction of a protecting group represented by the following formula can be introduced into B in formula (B1) by a known method. For example, the method can be appropriately selected from the methods described in Green's Protective Groups in Organic Synthesis (Peter GM Wuts, Wiley), pp. 17 to 553.

[0152] [Reduction Step] In the formula (B1), R ０ When R is a hydroxyalkyl group, a hydroxy group, or an aldehyde group, for example, R ０ The compound can be obtained by introducing a carboxyl group, an ester group, or an aldehyde group into the compound and then reducing the resulting compound.

[0153] Known methods can be used for the reduction, including, for example, methods using metal hydride complex compounds such as sodium borohydride, lithium aluminum hydride, sodium bis(2-methoxyethoxy)aluminum hydride (SBMEA), and diisobutylaluminum hydride (DIBAL); methods using metal hydrides such as aluminum hydride; and methods using these reducing agents together with reduction promoters such as aluminum chloride and ethanedithiol. The reducing ability of the reducing agent may be adjusted by modifying a portion of its structure with an alkoxy group or a hydrocarbon group, or by using it in combination with a Lewis acid. Known solvents such as methanol, ethanol, 2-propanol, DMF, and DMSO can be used as the solvent for the reduction reaction. The reaction can be performed at room temperature or under heated conditions, but it can also be performed under cooled conditions to adjust the reactivity.

[0154] In this embodiment, it is preferable to remove residual metal impurities from Compound B obtained as a crude product by the above reaction by further purifying it. That is, it is preferable to avoid residual metal impurities from the viewpoints of preventing deterioration of the resin over time and storage stability, as well as from the viewpoints of process suitability and production yield due to defects when the resin is applied to a semiconductor manufacturing process. Metal impurities may originate from reaction aids in the manufacturing process of Compound B, or from the reaction vessel or other manufacturing equipment used in the manufacturing process.

[0155] The residual amount of the above-mentioned metal impurities is preferably less than 1 ppm, more preferably less than 100 ppb, even more preferably less than 50 ppb, even more preferably less than 10 ppb, and most preferably less than 1 ppb, relative to compound B. In particular, for metal species classified as transition metals, such as Fe, Ni, Sn, Zn, Cu, Sb, W, and Al, if the residual metal amount is 1 ppm or more, there is a concern that interaction with other compounds may cause denaturation or deterioration of the material over time. Furthermore, for alkali metals and alkalinity metals such as Na, K, Ca, and Mg contained in the resin, if the residual metal amount is 1 ppm or more, the residual metal amount cannot be sufficiently reduced when using the compound to produce a resin for semiconductor processing, which may cause defects or performance degradation due to residual metals in the semiconductor manufacturing process, resulting in a decrease in yield, and there is a concern that the doping effect of metal elements on the substrate may cause a decrease in characteristics.

[0156] The purification method is not particularly limited, but the method described in International Publication No. 2015 / 080240 or International Publication No. 2018 / 159707 can be used. Specifically, this purification method includes dissolving the compound in an organic solvent that is immiscible with water to obtain an organic phase, contacting the organic phase with an acidic aqueous solution to perform an extraction process, thereby transferring metal components contained in the organic phase containing the compound and the organic solvent to the aqueous phase, and then separating the organic phase from the aqueous phase. The organic solvent that is immiscible with water is typically an organic solvent classified as a non-aqueous solvent. The organic solvent is not particularly limited, but is preferably an organic solvent that can be safely used in semiconductor manufacturing processes. The amount of organic solvent used is typically about 10% by mass relative to the compound used.

[0157] Specific examples of the organic solvent to be used include those described in International Publication No. 2015 / 080240. Among these, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate (PGMEA), ethyl acetate, etc. are preferred, with cyclohexanone and propylene glycol monomethyl ether acetate being particularly preferred.

[0158] The acidic aqueous solution can be appropriately selected from aqueous solutions prepared by dissolving commonly known organic or inorganic compounds in water. Examples include those described in International Publication No. 2015 / 080240. These acidic aqueous solutions can be used alone or in combination of two or more. Examples of the acidic aqueous solution include mineral acid aqueous solutions and organic acid aqueous solutions. Examples of the mineral acid aqueous solution include an aqueous solution containing one or more acids selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. Examples of the organic acid aqueous solution include an aqueous solution containing one or more acids selected from the group consisting of acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid. The pH range of the acidic aqueous solution is approximately 0 to 5, and more preferably approximately 0 to 3.

[0159] Other production methods that can be used appropriately include a method using a filter as described below, a method using an adsorptive ion exchange resin, passing a liquid through a column, a method of dispersing and suspending an ion exchange resin in a container, and a method using distillation.

[0160] In the method for producing compound B, the order and number of the iodination step, the protecting group introduction step, and the reduction step are not particularly limited, and can be appropriately selected depending on the structure of the target compound.

[0161] [Composition] The composition of the present embodiment contains the compound A and the compound B. The composition is particularly useful as a composition for lithography, and therefore, hereinafter, a composition containing the compounds will be described using a composition for lithography as an example.

[0162] The composition of the present embodiment has excellent long-term storage stability due to the inclusion of Compound A and Compound B. The reason for this is not limited, but one of the reasons is thought to be that by using Compound B which has a similar structure to Compound A, affinity with Compound A can be ensured and Compound B can function with higher affinity as a deterioration sacrificial agent or deterioration inhibitor during storage.

[0163] The compounds A and B exhibit a sensitizing effect on the lithography composition containing them upon irradiation with radiation. While the reason for this is not limited, it is believed that the compounds promote radiation absorption. This effect is particularly pronounced with extreme ultraviolet (EUV) radiation. The sensitizing effect can take several forms. When a photosensitive layer formed using a lithography composition is used as a lithography resist film, the sensitizing effect can be confirmed, for example, as follows: 1) Using a patternless surface exposure method, after exposure, a PEB process (a process of performing a post-exposure heat treatment) is optionally performed, and a development process (a process of dissolving and removing exposed or unexposed areas with a developer) is optionally performed, and the film thickness is measured. 2) The exposure dose is varied, and the film thickness is measured. The exposure dose at which the film thickness changes drastically is defined as the sensitivity in the surface exposure method. 3) If sensitivity is confirmed on the low exposure dose side, the sensitizing effect can be confirmed. Furthermore, in a method of forming a pattern by exposure, 1) a pattern is formed by varying the exposure dose, and the exposure dose at which a specified line width is obtained after exposure is defined as the sensitivity. If sensitivity is confirmed on the lower exposure side than 2), it can be determined that a sensitization effect has been achieved. Furthermore, particularly in pattern evaluation using extreme ultraviolet (EUV) light, this can also be confirmed by a reduction in defects such as pitting and bridging. These defects are caused by fluctuations in optical exposure or by exposure conditions where the exposure is low and the exposure is essentially similar to defects. However, if the resist film has a sensitization effect, the fluctuations and defects are avoided by promoting absorption, and the defects are reduced. When compound A and compound B are used in a lithography composition, compound A and compound B can be used directly as components of the composition. Alternatively, compound A can be processed into a resin (substrate (A)) containing compound A as a partial structure, additives (acid generator (C), crosslinking agent (G), acid diffusion inhibitor (E), other components (F), etc., and used as a lithography composition containing these resins and additives as components.

[0164] The composition for lithography according to this embodiment contains a compound represented by formula (B1) or formula (BP0-1) (hereinafter also referred to as "compound (B)"), and may contain other components, such as a base material (A), a solvent (S), an acid generator (C), a crosslinking agent (G), and an acid diffusion controller (E), as necessary. Each component will be described below.

[0165] [Compound (B)] The composition in this embodiment contains one or more compounds (B). Although not limited thereto, it is preferable that the composition contains two or more compounds (B). When two or more compounds (B) are contained, etching defects verified by the solid film exposure defect evaluation shown in the examples described later tend to be reduced. The reason for the reduction in etching defects is unclear, but it is thought that, for example, the compatibility of compound (B) in the composition is improved, which may reduce fine defects when the film is formed.

[0166] The amount of compound (B) is not limited. However, when a compound (B) is present in a smaller amount than compound (A) (this compound is referred to as compound (B')), the amount of compound (B') is preferably 1 ppm or more, and more preferably 10 ppm or more, of the total amount of compounds (B), from the viewpoint of improving etching defects. Furthermore, when a compound (B) is present in the largest amount (this compound is referred to as compound (B")), the content of compound (B'"), which has a lower iodine atom content in its molecule than compound (B"), is preferably 40% by mass or less, more preferably 10% by mass or less, and most preferably 5% by mass or less, of the total amount of compounds (B), from the viewpoint of improving sensitivity.

[0167] In one embodiment, when the monomer compound having a large number of iodines is H, the monomer compound having a small number of iodines is L, and the dimer compound is D in the compound (B), the following combinations can be exemplified: H / L (mass ratio, the same applies hereinafter) = (99 to 99.9): (1 to 0.1) H / D = (99 to 99.9): (1 to 0.1) H / L / D = (98 to 99.9): (1 to 0.05): (1 to 0.05)

[0168] In the present embodiment, the content of the compound B relative to the total amount of the compound A is preferably 1 ppm to 50,000 ppm, more preferably 10 ppm to 30,000 ppm, even more preferably 20 ppm to 10,000 ppm, still more preferably 20 ppm to 5,000 ppm, and particularly preferably 20 ppm to 2,000 ppm.

[0169] The method for mixing two or more types of compound (B) is not limited, and two or more types of compound (B) may be mixed, or may be simultaneously synthesized as a mixture in the process of synthesizing compound (B).

[0170] More preferred embodiments of compound B include the following: 1) A combination of a reference compound of formula (1) and a compound represented by formula (1) but having fewer iodine atoms than the reference compound (preferably a compound of formula (BP0-1)). 2) A combination of a reference compound of formula (1) and a multimer of a compound represented by formula (1) (preferably formula (B1)). 3) A combination of a reference compound of formula (1), the compound having fewer iodine atoms, and the multimer.

[0171] An example of a compound having a small number of iodine atoms is a compound represented by formula (BP0-1).

[0172] By including a compound of formula (B1) or formula (BP0-1), the composition is expected to be highly effective in ensuring stability over time, particularly due to inorganic substances and inorganic components, and the high trapping effect of the causative components is expected to lead to improved stability over time. In another preferred embodiment, by including a compound of formula (BP0-1), the mechanism resulting from the difference in redox potential with the compound of formula (1) is expected to be effective in ensuring stability over time, leading to improved stability over time due to natural oxidation and deterioration of coexisting substances over time.

[0173] [Substrate (A)] In this embodiment, "substrate (A)" refers to a compound (including a resin) other than Compound A and Compound B, and is used as a resist for g-line, i-line, KrF excimer laser (248 nm), ArF excimer laser (193 nm), extreme ultraviolet (EUV) lithography (13.5 nm), or electron beam (EB) (e.g., a substrate for lithography or a substrate for resist). Any of these substrates can be used as the substrate (A) in this embodiment without any particular limitation. Examples of the substrate (A) include phenol novolac resin, cresol novolac resin, hydroxystyrene resin, (meth)acrylic resin, hydroxystyrene-(meth)acrylic copolymer, cycloolefin-maleic anhydride copolymer, cycloolefin, vinyl ether-maleic anhydride copolymer, and inorganic resist materials containing metal elements such as titanium, tin, hafnium, and zirconium, as well as derivatives thereof. Among these, from the viewpoint of the shape of the resulting resist pattern, preferred are phenol novolac resins, cresol novolac resins, hydroxystyrene resins, (meth)acrylic resins, hydroxystyrene-(meth)acrylic copolymers, and inorganic resist materials containing metal elements such as titanium, tin, hafnium, and zirconium, as well as derivatives of these.

[0174] The derivative is not particularly limited, but examples thereof include those into which a dissociable group has been introduced, those into which a crosslinkable group has been introduced, etc. Derivatives into which a dissociable group or a crosslinkable group has been introduced can undergo a dissociation reaction or a crosslinking reaction by the action of light, acid, etc.

[0175] The term "dissociable group" refers to a characteristic group that cleaves to generate a functional group such as an alkali-soluble group that changes solubility. The alkali-soluble group is not particularly limited, but examples thereof include a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, and a hexafluoroisopropanol group. The phenolic hydroxyl group and the carboxyl group are preferred, and the phenolic hydroxyl group is particularly preferred.

[0176] The term "crosslinkable group" refers to a group that crosslinks in the presence or absence of a catalyst. The crosslinkable group is not particularly limited, but examples thereof include an alkoxy group having 1 to 20 carbon atoms, a group having an allyl group, a group having a (meth)acryloyl group, a group having an epoxy(meth)acryloyl group, a group having a hydroxyl group, a group having a urethane(meth)acryloyl group, a group having a glycidyl group, and a group having a vinyl-containing phenylmethyl group.

[0177] [Solvent (S)] In the present embodiment, any known solvent can be used as appropriate, as long as it can dissolve at least the iodine-containing (meth)acrylate compound and / or the iodine-containing (meth)acrylate (co)polymer (B) described above.Specific examples of the solvent include, but are not limited to, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol mono-n-butyl ether acetate; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, and propylene glycol mono-n-butyl ether acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether; ester lactates such as methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, and n-amyl lactate. esters; aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate, and ethyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl 3-methoxy-3-methylpropionate, 3-meth Examples of the ester include, but are not particularly limited to, other esters such as butyl oxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate, and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; ketones such as acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone (CPN), and cyclohexanone (CHN); amides such as N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpyrrolidone; and lactones such as γ-lactone.The solvent used in the present embodiment is preferably a safe solvent, more preferably at least one selected from PGMEA, PGME, CHN, CPN, 2-heptanone, anisole, butyl acetate, and ethyl lactate, and even more preferably at least one selected from PGMEA, PGME, CHN, CPN, and ethyl lactate.

[0178] In this embodiment, the amounts of the solid component and the solvent are not particularly limited, but are preferably 1 to 80% by mass of the solid component and 20 to 99% by mass of the solvent, more preferably 1 to 50% by mass of the solid component and 50 to 99% by mass of the solvent, even more preferably 2 to 40% by mass of the solid component and 60 to 98% by mass of the solvent, and particularly preferably 2 to 10% by mass of the solid component and 90 to 98% by mass of the solvent. In this specification, the term "solid component" refers to components other than the solvent contained in the composition of this embodiment.

[0179] [Acid Generator (C)] The composition of this embodiment preferably contains one or more acid generators (C) that generate an acid directly or indirectly upon irradiation with any radiation selected from visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-rays, and ion beams. The acid generator (C) is not particularly limited, but for example, those described in International Publication WO 2013 / 024778 can be used. The acid generators (C) can be used alone or in combination of two or more.

[0180] The content of the acid generator (C) is preferably 0.001 to 49% by mass, more preferably 1 to 40% by mass, even more preferably 3 to 30% by mass, and particularly preferably 10 to 25% by mass, of the total mass of the solid components. By using the acid generator (C) within the above range, a pattern profile with high sensitivity and low edge roughness tends to be obtained. In this embodiment, the method for generating the acid is not particularly limited as long as an acid is generated in the system. Using an excimer laser instead of ultraviolet light such as g-line or i-line enables finer processing, and using an electron beam, extreme ultraviolet light, X-ray, or ion beam as a high-energy beam enables even finer processing.

[0181] [Base Generator (G)] The case where the base generator (G) is a photobase generator will be described. The photobase generator is a compound that generates a base upon exposure to light, and is not particularly limited as long as it is inactive under normal conditions of room temperature and normal pressure, but generates a base (basic substance) upon irradiation with electromagnetic waves and heating as external stimuli.

[0182] The photobase generator that can be used in the present embodiment is not particularly limited, and known photobase generators can be used, such as carbamate derivatives, amide derivatives, imide derivatives, α-cobalt complexes, imidazole derivatives, cinnamic acid amide derivatives, and oxime derivatives.

[0183] The basic substance generated from the photobase generator is not particularly limited, and examples thereof include compounds having an amino group, particularly polyamines such as monoamines and diamines, and amidines. From the viewpoints of sensitivity and resolution, the generated basic substance is preferably a compound having an amino group with a higher basicity (a higher pKa value of the conjugate acid). Examples of the photobase generator include base generators having a cinnamic acid amide structure as disclosed in JP 2009-80452 A and WO 2009 / 123122 A, base generators having a carbamate structure as disclosed in JP 2006-189591 A and JP 2008-247747 A, base generators having an oxime structure or a carbamoyloxime structure as disclosed in JP 2007-249013 A and JP 2008-003581 A, and compounds described in JP 2010-243773 A, but are not limited to these, and other known base generator structures can also be used.

[0184] The photobase generators may be used alone or in combination of two or more. The preferred content of the photobase generator is the same as the preferred content of the acid generator (C) described above.

[0185] [Acid Diffusion Controller (E)] In this embodiment, an acid diffusion controller (E) may be incorporated into the composition. The acid diffusion controller (E) has the effect of controlling the diffusion of the acid generated from the acid generator upon irradiation in the resist film, thereby preventing undesirable chemical reactions in unexposed regions. The use of the acid diffusion controller (E) tends to improve the storage stability of the composition of this embodiment. Furthermore, the use of the acid diffusion controller (E) tends to improve the resolution of the film formed using the composition of this embodiment, and also tends to suppress changes in the line width of the resist pattern due to variations in the waiting time before and after radiation exposure, thereby resulting in excellent process stability. The acid diffusion controller (E) is not particularly limited, and examples thereof include radiation-decomposable basic compounds such as nitrogen-containing basic compounds, basic sulfonium compounds, and basic iodonium compounds.

[0186] The acid diffusion controller (E) is not particularly limited, but for example, those described in International Publication WO 2013 / 024778 can be used. The acid diffusion controller (E) can be used alone or in combination of two or more.

[0187] The content of the acid diffusion controller (E) is preferably 0.001 to 49% by mass, more preferably 0.01 to 10% by mass, even more preferably 0.01 to 5% by mass, and particularly preferably 0.01 to 3% by mass, based on the total mass of the solid components. When the amount of the acid diffusion controller (E) is within the above range, degradation of resolution, pattern shape, dimensional fidelity, and the like tends to be prevented. Furthermore, even if the exposure time between electron beam irradiation and post-exposure heating is long, degradation of the shape of the upper layer of the pattern can be suppressed. Furthermore, when the amount is 10% by mass or less, degradation of sensitivity, developability of unexposed areas, and the like tends to be prevented. Furthermore, the use of such an acid diffusion controller improves the storage stability and resolution of the resist composition, and also suppresses changes in the line width of the resist pattern due to variations in exposure time before and after radiation exposure, tending to result in excellent process stability.

[0188] [Other Components (F)] If necessary, one or more of various additives such as a crosslinking agent, a dissolution promoter, a dissolution controller, a sensitizer, a surfactant, and an organic carboxylic acid, a phosphorus oxoacid, or a derivative thereof may be added to the composition of the present embodiment as other components (F).

[0189] (Crosslinking Agent) In this embodiment, the composition may contain one or more crosslinking agents. The crosslinking agent refers to a compound capable of crosslinking at least the substrate (A) or the iodine-containing (meth)acrylate compound and / or the iodine-containing (meth)acrylate (co)polymer (B). The crosslinking agent is preferably an acid crosslinking agent capable of intramolecularly or intermolecularly crosslinking the substrate (A) in the presence of an acid generated from the acid generator (C). Examples of such acid crosslinking agents include compounds having one or more groups (hereinafter referred to as "crosslinkable groups") capable of crosslinking the substrate (A).

[0190] Examples of the crosslinkable group include (i) hydroxyalkyl groups such as hydroxy (alkyl group having 1 to 6 carbon atoms), alkoxy (alkyl group having 1 to 6 carbon atoms), and acetoxy (alkyl group having 1 to 6 carbon atoms), or groups derived therefrom; (ii) carbonyl groups such as formyl group and carboxy (alkyl group having 1 to 6 carbon atoms), or groups derived therefrom; (iii) dimethylaminomethyl group, diethylaminomethyl group, dimethylolaminomethyl group, diethylolaminomethyl group, and the like. (iv) glycidyl group-containing groups such as a glycidyl ether group, a glycidyl ester group, and a glycidylamino group; (v) groups derived from aromatic groups such as allyloxy (alkyl groups having 1 to 6 carbon atoms) and aralkyloxy (alkyl groups having 1 to 6 carbon atoms) having 1 to 6 carbon atoms, such as a benzyloxymethyl group and a benzoyloxymethyl group; and (vi) polymerizable multiple bond-containing groups such as a vinyl group and an isopropenyl group. Examples of the crosslinkable group of the crosslinking agent in this embodiment include hydroxyalkyl groups and alkoxyalkyl groups, and particularly alkoxymethyl groups.

[0191] The crosslinking agent having a crosslinkable group is not particularly limited, and for example, the acid crosslinking agents described in International Publication WO 2013 / 024778 can be used. The crosslinking agents can be used alone or in combination of two or more.

[0192] In the present embodiment, the blending amount of the crosslinking agent is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 20% by mass or less, of the total mass of the solid components.

[0193] (Dissolution accelerator) When the solubility of a solid component in a developer is too low, the dissolution accelerator is a component that has the effect of increasing the solubility and appropriately increasing the dissolution rate of the compound during development. As the dissolution accelerator, a low molecular weight one is preferred, and for example, a low molecular weight phenolic compound can be mentioned. As the low molecular weight phenolic compound, for example, bisphenols, tris(hydroxyphenyl)methane, etc. can be mentioned. These dissolution accelerators can be used alone or in combination of two or more kinds.

[0194] The amount of the dissolution promoter to be added is adjusted appropriately depending on the type of solid component used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass, of the total mass of the solid components.

[0195] (Dissolution Controller) A dissolution controller is a component that has the effect of controlling the solubility of a solid component in a developer when the solubility of the solid component is too high, thereby appropriately reducing the dissolution rate during development. Such a dissolution controller is preferably one that does not undergo chemical changes during processes such as baking, irradiation, and development of the resist film.

[0196] The dissolution controller is not particularly limited, but examples thereof include aromatic hydrocarbons such as phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenyl naphthyl ketone; and sulfones such as methyl phenyl sulfone, diphenyl sulfone, and dinaphthyl sulfone. These dissolution controllers can be used alone or in combination of two or more.

[0197] The amount of the dissolution controller is adjusted appropriately depending on the type of the compound used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass, of the total mass of the solid components.

[0198] (Sensitizer) The sensitizer is a component that absorbs the energy of the irradiated radiation and transfers that energy to the acid generator (C), thereby increasing the amount of acid generated, thereby improving the apparent sensitivity of the resist. Examples of such sensitizers include, but are not limited to, benzophenones, biacetyls, pyrenes, phenothiazines, and fluorenes. These sensitizers can be used alone or in combination of two or more.

[0199] The amount of the sensitizer to be added is adjusted as appropriate depending on the type of the compound to be used, but is preferably 0 to 49 mass % of the total mass of the solid components, more preferably 0 to 5 mass %, even more preferably 0 to 1 mass %, and particularly preferably 0 mass %.

[0200] (Surfactant) The surfactant is a component that has the effect of improving the coatability and striation of the composition of this embodiment, the developability of the resist, etc. The surfactant may be any of anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. Preferred surfactants include nonionic surfactants. Nonionic surfactants have good affinity with the solvent used in producing the composition of this embodiment, and can further enhance the effects of the composition of this embodiment. Examples of nonionic surfactants include, but are not limited to, polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, and higher fatty acid diesters of polyethylene glycol. Examples of commercially available surfactants include, by trade name, F-TOP (manufactured by GEMCO), MEGAFAC (manufactured by Dainippon Ink and Chemicals, Inc.), FLORAAD (manufactured by Sumitomo 3M Limited), ASAHIGUARD, and SURFLOON (all manufactured by Asahi Glass Co., Ltd.), PEPOL (manufactured by Toho Chemical Industry Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), and POLYFLOW (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.).

[0201] The amount of surfactant to be added is adjusted appropriately depending on the type of solid component to be used, but is preferably 0 to 49 mass % of the total mass of the solid components, more preferably 0 to 5 mass %, even more preferably 0 to 1 mass %, and particularly preferably 0 mass %.

[0202] (Organic Carboxylic Acid or Phosphorus Oxo Acid or Derivative Thereof) For the purpose of preventing sensitivity degradation or improving resist pattern shape and deposition stability, an organic carboxylic acid or a phosphorus oxo acid or a derivative thereof can be further contained as an optional component. The organic carboxylic acid or the phosphorus oxo acid or a derivative thereof can be used in combination with an acid diffusion controller or alone. Suitable organic carboxylic acids include malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid. Examples of phosphorus oxo acids or derivatives thereof include phosphoric acid, di-n-butyl phosphate, diphenyl phosphate, and other phosphoric acid or ester derivatives thereof; phosphonic acid, dimethyl phosphonate, di-n-butyl phosphonate, phenylphosphonic acid, diphenyl phosphonate, and other phosphonic acid or ester derivatives thereof; phosphinic acid, phenylphosphinic acid, and other phosphinic acid or ester derivatives thereof; and phosphonic acid, phenylphosphinic acid, and other ester derivatives thereof. Of these, phosphonic acid is particularly preferred.

[0203] The organic carboxylic acid, phosphorus oxo acid, or derivative thereof may be used alone or in combination of two or more. The amount of the organic carboxylic acid, phosphorus oxo acid, or derivative thereof is adjusted appropriately depending on the type of compound used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass, of the total mass of the solid components.

[0204] [Other Additives] Furthermore, the composition of this embodiment may contain one or more additives other than the components described above, as needed. Examples of such additives include dyes, pigments, and adhesion promoters. For example, the incorporation of a dye or pigment is preferred because it can visualize the latent image in the exposed area and mitigate the effects of halation during exposure. Furthermore, the incorporation of an adhesion promoter is preferred because it can improve adhesion to the substrate. Further examples of other additives include antihalation agents, storage stabilizers, antifoaming agents, shape modifiers, and the like, specifically 4-hydroxy-4'-methylchalcone.

[0205] In the composition of the present embodiment, the total amount of optional component (F) can be 0 to 99 mass% of the total mass of the solid components, preferably 0 to 49 mass%, more preferably 0 to 10 mass%, even more preferably 0 to 5 mass%, still more preferably 0 to 1 mass%, and particularly preferably 0 mass%.

[0206] To form a resist pattern from the composition of this embodiment, a solution of the composition is applied to a substrate, such as a silicon wafer, metal, plastic, glass, or ceramic, using a suitable coating method such as a spin coater, dip coater, or roller coater, to form a resist film. This may be pre-heated at a temperature of about 50°C to 200°C, and then exposed through a predetermined mask pattern. The thickness of the coating film is, for example, about 0.1 to 20 μm, preferably about 0.3 to 2 μm. Light beams of various wavelengths, such as ultraviolet light and X-rays, can be used for exposure. For example, light sources such as far ultraviolet light (e.g., F2 excimer laser (wavelength 157 nm), ArF excimer laser (wavelength 193 nm), and KrF excimer laser (wavelength 248 nm), extreme ultraviolet light (wavelength 13 nm), X-rays, and electron beams can be appropriately selected and used. Furthermore, exposure conditions, such as the exposure dose, are appropriately selected depending on the formulation of the resin and / or compound, the type of additive, and the like.

[0207] In this embodiment, in order to stably form a highly accurate fine pattern, it is preferable to perform a heat treatment at a temperature of 50 to 200°C for 30 seconds or more after exposure. In this case, if the temperature is less than 50°C, there is a risk of widening the variation in sensitivity depending on the type of substrate. Thereafter, the resist is developed using an alkaline developer typically at 10 to 50°C for 10 to 200 seconds, preferably at 20 to 25°C for 15 to 90 seconds, to form a predetermined resist pattern.

[0208] The alkaline developer is, for example, an alkaline aqueous solution in which an alkaline compound such as an alkali metal hydroxide, aqueous ammonia, alkylamines, alkanolamines, heterocyclic amines, tetraalkylammonium hydroxides, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, or 1,5-diazabicyclo-[4.3.0]-5-nonene is dissolved to a concentration of typically 1 to 10% by weight, preferably 1 to 3% by weight. A water-soluble organic solvent or a surfactant may also be added to the alkaline aqueous developer, as appropriate.

[0209] [Resin Composition] The composition of this embodiment can be resinified to form a resin composition. When the composition of this embodiment is resinified, a polymer (resin) containing a repeating unit represented by formula (C) described below, which is derived from the structure of compound A, can be obtained. That is, the resin composition of this embodiment is a resin made from a composition containing compound A and compound B, and contains a polymer having a repeating unit represented by formula (C1) below. Note that, in the resin composition of this embodiment, compound B is presumed to be preferably present in the vicinity of the polymer containing the repeating unit of formula (C) due to its compatibility or affinity with compound A.

[0210] [Compound A (co)polymer] The resin made from the composition of this embodiment may contain a polymer having a repeating unit represented by the following formula (C1) (hereinafter, may be referred to as a "compound A (co)polymer"). By forming a polymer having a repeating unit represented by the following formula (C1), it is possible to form a polymer containing one or more halogen elements, one or more hydrophilic groups, or one or more decomposable groups. As a result, a resist composition according to this embodiment, which contains a polymer having a repeating unit represented by the following formula (C1) as a resin component, can achieve high sensitivity in the lithography process and high resolution due to an increase in the solubility contrast of the resin during development. In formula (C1), R １ , R ２ , R ３ , A, n １ , n ２ is as defined in the formula (1) above, and the symbol * represents the bonding point to the adjacent repeating unit.

[0211] The compound A (co)polymer represented by the above formula (C1) can be obtained by polymerizing one or more compounds A represented by general formula (1) in this embodiment, or by polymerizing one or more compounds A represented by general formula (1) in this embodiment together with other monomers. However, it is preferable that the other monomers do not include compound B. The compound A (co)polymer can be used as a film-forming material for lithography.

[0212] The repeating units other than the repeating unit represented by the formula (C1) in the compound A copolymer represented by the formula (C1) are not particularly limited, but for example, those described in International Publication WO2016 / 125782, International Publication WO2015 / 115613, JP2015 / 117305, International Publication WO2014 / 175275, and JP2012 / 162498, or compounds represented by the following formulas (C2) and (C3) can be used. (In formula (C2), R Ｃ１１ represents a hydrogen atom or a methyl group; R Ｃ１２ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R Ｃ１３ is R Ｃ１３represents a cycloalkyl or heterocycloalkyl group having 4 to 20 carbon atoms together with the carbon atom to which it is attached, and the dot * represents the bonding point to the adjacent repeating unit. Preferably, R Ｃ１２ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R Ｃ１３ is R Ｃ１３ R is, together with the carbon atom to which it is attached, a cycloalkyl group or heterocycloalkyl group having 4 to 10 carbon atoms. Ｃ１３ may have a substituent (for example, an oxo group). (In formula (C3), R Ｃ２１ represents a hydrogen atom or a methyl group; R Ｃ２２ and R Ｃ２３ each independently represents an alkyl group having 1 to 4 carbon atoms; R Ｃ２４ represents an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms; R Ｃ２２ ~R Ｃ２４ Two or three of these may form an alicyclic structure having 3 to 20 carbon atoms together with the carbon atoms to which they are attached, and the dot * indicates the bonding point to the adjacent repeating unit.) Preferably, R Ｃ２２ represents an alkyl group having 1 to 3 carbon atoms, and R Ｃ２４ is a cycloalkyl group having 5 to 10 carbon atoms. Ｃ２２ ~R Ｃ２４ The alicyclic structure formed by may contain multiple rings such as adamantyl groups, etc. The alicyclic structure may have a substituent (for example, a hydroxyl group or an alkyl group).

[0213] The monomer raw material for the repeating unit represented by general formula (C3) is not limited, but examples thereof include 2-methyl-2-(meth)acryloyloxyadamantane, 2-ethyl-2-(meth)acryloyloxyadamantane, 2-isopropyl-2-(meth)acryloyloxyadamantane, 2-n-propyl-2-(meth)acryloyloxyadamantane, 2-n-butyl-2-(meth)acryloyloxyadamantane, 1-methyl-1-(meth)acryloyloxycyclopentane, 1-ethyl-1-(meth)acryloyloxycyclopentane, 1-methyl Examples of such monomers include 1-(meth)acryloxycyclohexane, 1-ethyl-1-(meth)acryloxycyclohexane, 1-methyl-1-(meth)acryloxycycloheptane, 1-ethyl-1-(meth)acryloxycycloheptane, 1-methyl-1-(meth)acryloxycyclooctane, 1-ethyl-1-(meth)acryloxycyclooctane, 2-ethyl-2-(meth)acryloxydecahydro-1,4:5,8-dimethanonaphthalene, and 2-ethyl-2-(meth)acryloxynorbornane. Commercially available products can be used as these monomers.

[0214] Iodine-containing (meth)acrylate (co)polymers represented by general formula (5) obtained from iodine-containing (meth)acrylate compounds represented by general formula (2), iodine-containing (meth)acrylate (co)polymers represented by general formula (6) obtained from iodine-containing (meth)acrylate compounds represented by general formula (3), and iodine-containing (meth)acrylate (co)polymers represented by general formula (6') obtained from iodine-containing (meth)acrylate compounds represented by general formula (3') can also be obtained by similar methods. The iodine-containing (meth)acrylate (co)polymers represented by general formula (5) and general formula (6) are preferred for improving the performance of film-forming materials for lithography. (In formula (5), R １ , n ２ , A, and the symbol * are as defined in formula (C1) above. (In formula (6), B is as defined in formula (3) above, and R１ , n ２ , the symbol * is as defined in formula (C1) above.) (In formula (6'), B' is as defined in formula (3') above, and R １ , n ２ , the symbol * is as defined in formula (C1) above.)

[0215] [Method for Producing Compound A (Co)polymer] Next, a method for producing a Compound A (co)polymer by polymerization reaction will be described. The polymerization reaction is carried out by dissolving the monomers that will become repeating units in a solvent, adding a catalyst, and heating or cooling the mixture. The reaction conditions can be set as desired depending on the type of initiator, the initiation method such as heat or light, the temperature, pressure, concentration, solvent, additives, etc. The Compound A (co)polymer of this embodiment can be produced by known methods, such as radical polymerization using a radical generator such as azoisobutyronitrile or peroxide, or ionic polymerization using a catalyst such as an alkyllithium or a Grignard reagent.

[0216] As the solvent used in the polymerization reaction, commercially available products that are generally available can be used. For example, various solvents such as alcohols, ethers, hydrocarbons, and halogenated solvents can be used as appropriate within the range that does not inhibit the reaction. A mixture of multiple solvents can also be used within the range that does not inhibit the reaction.

[0217] The Compound A (co)polymer obtained by the polymerization reaction can be purified by a known method, specifically by a combination of ultrafiltration, crystallization, microfiltration, acid washing, washing with water having an electrical conductivity of 10 mS / m or less, and extraction.

[0218] [Method for producing resin composition] It is preferable to produce a resin composition by resinifying a composition containing compound A and compound B. It is also preferable that compound B is present in the resin composition independently of the compound A (co)polymer. The resinification method may be the same as the method for producing the compound A (co)polymer.

[0219] [Film-Forming Composition] The film-forming composition of this embodiment is a film-forming composition that contains the above-described composition or the above-described resin composition and is particularly suitable for lithography techniques. Furthermore, a composition containing the film-forming composition may be, for example, a lithography film-forming composition that can be used for forming a film for semiconductor lithography. Furthermore, a composition containing the film-forming composition may be, for example, a resist film-forming composition that can be used for forming a resist film (i.e., a "resist composition"). Furthermore, the film-forming composition can be used for forming an upper layer film (i.e., an "upper layer film-forming composition"), an intermediate layer (i.e., an "intermediate layer-forming composition"), an underlayer film (i.e., an "underlayer film-forming composition"), etc. These compositions can primarily or supplementarily perform optical or electromagnetic radiation functions such as anti-reflection and secondary electron diffusion prevention, and functions to improve pattern quality by preventing pattern collapse, defects, and maintaining pattern shape due to chemical and physical effects, for the purpose of improving the patterning performance of the resist layer in the lithography process. The composition of this embodiment can form a film with high sensitivity and can also provide a good resist pattern shape.

[0220] The composition, resin composition, and film-forming composition of this embodiment can also be used as an optical component-forming composition that applies lithography technology. Optical components are used in film and sheet form, and are useful as plastic lenses (prism lenses, lenticular lenses, microlenses, Fresnel lenses, viewing angle control lenses, contrast enhancement lenses, etc.), retardation films, electromagnetic wave shielding films, prisms, optical fibers, solder resists for flexible printed wiring, plating resists, interlayer insulating films for multilayer printed wiring boards, photosensitive optical waveguides, liquid crystal displays, organic electroluminescence (EL) displays, optical semiconductor (LED) elements, solid-state imaging elements, organic thin-film solar cells, dye-sensitized solar cells, and organic thin-film transistors (TFTs). The composition is particularly suitable for use as a filling film and planarizing film on a photodiode, planarizing films before and after a color filter, microlenses, and planarizing and conformal films on a microlens, which are components of solid-state imaging elements that require a high refractive index.

[0221] The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples in any way.

[0222] [Measurement Method] (1) Compound Structure The compound structure was measured using a Bruker Avance 500III spectrometer under the following conditions: １ The product was confirmed by H-NMR measurement. Frequency: 500 MHz Solvent: CDCl ３ , or d ６ -DMSO Internal standard: TMS Measurement temperature: 23 ° C. Also, １３ C-NMR measurements were carried out using the same apparatus under the following conditions: Frequency: 125 MHz Solvent: CDCl ３ , or d ６ -DMSO Internal standard: Use the solvent used Measurement temperature: 23°C

[0223] (2) Molecular Weight and Molecular Weight Distribution The molecular weight and molecular weight distribution of the copolymer were measured by determining the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene by gel permeation chromatography (GPC), and then calculating the polydispersity (Mw / Mn). Apparatus: Shodex GPC-101 (manufactured by Showa Denko K.K.) Column: KF-80M x 3 Eluent: THF 1 mL / min Temperature: 40°C

[0224] [Synthesis of Compound A]

[0225] (Synthesis of A1) [Protecting Group Introduction Step] Using a 10 L three-necked eggplant flask connected to a reflux condenser, 84 g of A4 (MAC-2H35I) synthesized by the method described below was added to 450 mL of dehydrated dimethylformamide (DMF) under nitrogen flow in an ice bath, and dissolved by stirring with a stirring blade. Next, 29.3 g (1.2 equivalents) of diisopropylethylamine was added over 30 minutes while stirring in an ice bath, and the mixture was stirred for an additional 60 minutes. 21.5 g of chloromethyl ethyl ether (1.2 equivalents relative to the functional group equivalent) was added dropwise to the stirred reaction solution over 60 minutes, and the mixture was stirred for an additional 30 minutes in an ice bath. Then, 900 mL of pure water was added in an ice bath, and the mixture was stirred for 60 minutes, after which the formed precipitate was collected by filtration. The recovered solid was suspended and stirred in 600 mL of methanol in an ice bath for 30 minutes, and then filtered to obtain 90.6 g of the target product A1 (MAC-2H35I-EM) as a white solid. 200 mL of ethyl acetate and 500 mL of pure water were added to the organic phase obtained after filtration, and the mixture was stirred. The organic phase was recovered and concentrated under reduced pressure to obtain 85.8 g of the target product A1 (MAC-2H35I-EM) as a white solid. The yield was 90%.

[0226]

[0227] (Synthesis of A2)

[0228] [Protecting Group Introduction Step] Using a 10 L three-necked eggplant flask connected to a reflux condenser, 84 g of A4 (MAC-4H35I) synthesized by the method described below was added to 450 mL of dehydrated dimethylformamide (DMF) under nitrogen flow in an ice bath, and the mixture was dissolved by stirring with a stirring blade. Next, 29.3 g (1.2 equivalents) of diisopropylethylamine was added over 30 minutes while stirring in an ice bath, and the mixture was stirred for an additional 60 minutes. 21.5 g of chloromethyl ethyl ether (1.2 equivalents relative to the functional group equivalent) was added dropwise to the stirred reaction solution over 60 minutes, and the mixture was stirred for an additional 30 minutes in an ice bath. Then, 900 mL of pure water was added in an ice bath, and after stirring for 60 minutes, the formed precipitate was collected by filtration. The collected solid was suspended and stirred in 600 mL of methanol in an ice bath for 30 minutes, and then filtered to obtain 288.7 g of the target product A as a white solid. To the organic phase, 200 mL of ethyl acetate and 500 mL of pure water were added and stirred, and then the organic phase was recovered and concentrated under reduced pressure to obtain 84.9 g of a white solid as the target product A2 (MAC-4H35I-EM). The yield was 89%.

[0229]

[0230] (Synthesis of A3) 90 g (0.24 mol) of 3,5-diiodosalicylic aldehyde was dissolved in 900 ml of methanol, and NaBH ４ To the mixture, 22.8 g (0.60 mol) of 2-hydroxy-3,5-diiodobenzyl alcohol was added at a temperature below 10°C. The mixture was then stirred for 3 hours under ice-cooling and then stirred at 25°C for 16 hours to allow the reaction to proceed, and the methanol was evaporated under reduced pressure to concentrate the mixture. Water and ethyl acetate were added to the concentrate, and the organic phase was extracted. Magnesium sulfate was added to this organic phase and the mixture was dried, and the solvent was evaporated under reduced pressure to obtain a crude product of 2-hydroxy-3,5-diiodobenzyl alcohol. The obtained crude product of 2-hydroxy-3,5-diiodobenzyl alcohol was purified by column chromatography to obtain 82.5 g (yield 91%) of 2-hydroxy-3,5-diiodobenzyl alcohol shown below.

[0231] 10 g (27 mmol) of the 2-hydroxy-3,5-diiodobenzyl alcohol obtained above was dissolved in 100 mL of dichloromethane, and 3.1 g (39 mmol) of pyridine was added under ice-cooling, followed by dropwise addition of 4.1 g (27 mmol) of methacrylic anhydride. The mixture was then stirred for 4 hours under ice-cooling and then for 18 hours at room temperature to allow the reaction to proceed. After completion of the reaction, water was added to the reaction solution, which was then washed with an aqueous sodium bicarbonate solution. Magnesium sulfate was added to the organic phase, which was then dried, concentrated, and purified by column chromatography to obtain 9 g (88% yield) of A3 (MAC-2H35I) shown below.

[0232] When the obtained A3 (MAC-2H35I) was subjected to NMR measurement under the above measurement conditions, the following peaks were found, and it was confirmed that it had the chemical structure of A3. δ (ppm) (CDCl ３ ): 7.2 to 8.0 (2H, Ph), 7.6 (1H, -OH), 6.2 (1H, =CH ２ ), 5.7 (1H, =CH ２ ), 5.1 (2H, -CH ２ -), 2.0 (3H, -CH ３ )

[0233] (Synthesis of A4-1) 128 g (0.78 mol) of calcium chloride and NaBH ４ 91.3 g (2.4 mol) of 4-hydroxy-3,5-diiodobenzaldehyde was dissolved in the solution, and 410 g (1.1 mol) of 4-hydroxy-3,5-diiodobenzaldehyde was added to the solution under ice-cooling. After stirring and reacting for 18 hours at 25°C, 10 L of water was added, and the pH was adjusted to 2.5 with hydrochloric acid. The precipitate was filtered, washed with water, and dried to obtain 401 g (yield 97%) of 4-hydroxy-3,5-diiodobenzyl alcohol shown below.

[0234] 400 g (1.06 mol) of the 4-hydroxy-3,5-diiodobenzyl alcohol obtained above was dissolved in 2.8 L of toluene, and 916 g (10.6 mol) of methacrylic acid, 20 g (0.105 mol) of paratoluenesulfonic acid monohydrate, and 13 mg (0.01 mmol) of 4-methoxyphenol were added, followed by stirring for 2 hours under reflux at 110° C. After the reaction, 4 L of water was added, the organic layer was dried, and the mixture was purified by recrystallization twice with hexane to obtain 158 g (yield 33%) of A4 (MAC-4H35I) shown below.

[0235] When the obtained A4 (MAC-4H35I) was subjected to NMR measurement under the above measurement conditions, the following peaks were found, and it was confirmed that it had the chemical structure of A4. δ (ppm) (CDCl ３ ): 9.7 (1H, -OH), 7.8 (2H, Ph), 6.7 (1H, =CH ２ ), 5.0 (1H, =CH ２ ), 5.0 (2H, -CH ２ -), 1.9 (3H, -CH ３ )

[0236] (Synthesis of A4-2) 45.0 g (0.36 mol) of 4-hydroxybenzyl alcohol and 92.4 g (0.36 mol) of iodine were dissolved in 600 mL of methanol, and 6.2 g (0.18 mol) of hydrogen peroxide was added dropwise in a 20°C water bath. The mixture was then stirred at 80°C for 8 hours to allow the reaction to proceed. After cooling, the mixture was washed by a separation treatment using an aqueous sodium thiosulfate solution and brine, and the organic phase was extracted. Magnesium sulfate was added to this organic phase and the mixture was dried, and the solvent was distilled off under reduced pressure to obtain a crude product of 4-hydroxy-3,5-diiodobenzyl alcohol. The obtained crude product of 4-hydroxy-3,5-diiodobenzyl alcohol was purified by column chromatography to obtain 95 g (yield 70%) of 4-hydroxy-3,5-diiodobenzyl alcohol.

[0237] Using the 4-hydroxy-3,5-diiodobenzyl alcohol obtained above, A4 (MAC-4H35I) was obtained in the same manner as in Synthesis-1.

[0238] (Synthesis of A5) 16.8 g (0.1 mol) of 1,3-adamantanediol (manufactured by Mitsubishi Gas Chemical Company) was dissolved in 200 mL of toluene, and 44.9 g (0.2 mol) of 57% aqueous hydrogen iodide solution was added. The mixture was stirred at 80°C for 8 hours to react. After the reaction, 24 g of an 11% aqueous sodium thiosulfate solution was added and stirred for 10 minutes, and then the aqueous phase was drained. The mixture was further washed with 100 g of ion-exchanged water, concentrated to a concentration of 50%, and allowed to cool at -20°C for 2 hours. The precipitated solid was filtered and further rinsed with cold toluene to obtain 12 g of 3-iodo-1-hydroxyadamantane represented by the following formula:

[0239] 2.78 g (10 mmol) of 3-iodo-1-hydroxyadamantane obtained above was dissolved in chloroform, and 0.96 g (12 mmol) of pyridine was added under ice-cooling, followed by dropwise addition of 1.25 g (12 mmol) of methacrylic acid chloride. The mixture was then stirred for 1 hour under ice-cooling and then for 3 hours at room temperature to allow the reaction to proceed. After completion of the reaction, water was added to the reaction solution, which was then washed with a saturated aqueous solution of sodium bicarbonate. Sodium sulfate was added to the organic phase for drying, and the solution was concentrated and then purified by column chromatography to obtain 2.7 g of A5 (MAC-ADI) shown below.

[0240] NMR measurement of the obtained A5 (MAC-ADI) under the above measurement conditions revealed the following peaks, confirming that it had the chemical structure of A5. δ (ppm) (d-DMSO): 6.4-6.5 (2H, ═CH), 1.3-3.2 (17H, Ad-H, -C(CH)═C)

[0241] (Synthesis of A6) 150 g of 1,3,5-adamantanetriol and 1278 g of acetonitrile were placed in a four-necked 10 L separable flask and stirred at 120 rpm for 30 minutes using a half-moon stirring blade at an internal temperature of 25°C to dissolve the contents. 176.9 g (2.0 equivalents) of trimethylsilyl chloride was added dropwise, and stirring was continued at 25°C for 30 minutes. Next, 244.07 g (2.0 equivalents) of sodium iodide was added in portions at a rate of 16 g / min over 15 minutes. Thereafter, the internal temperature was raised to 70°C, and stirring was continued for 6 hours. After allowing to cool, 1625 g of ion-exchanged water was added dropwise while stirring at 120 rpm, and stirring was continued for 10 minutes. 78.7 g of a 10% aqueous solution of sodium sulfite was added dropwise, and the mixture was stirred at an internal temperature of 20°C for 10 minutes. The external temperature was then raised to 40°C, and acetonitrile was removed by distillation under reduced pressure. 700 g of toluene was added, and the mixture was stirred at 25°C for 14 hours. The precipitate was collected by filtration and rinsed twice with 150 mL of acetonitrile. The solid separated by filtration was dried under reduced pressure at 30°C, and 5-iodo-1,3-dihydroxyadamantane (131 g) was obtained.

[0242] 3.5 g of A6 (MAC-ADIOH) was obtained in the same manner as in the synthesis of A5, except that 4.04 g (10 mmol) of 5-iodo-1,3-dihydroxyadamantane obtained above was used instead of 2.78 g of 3-iodo-1-hydroxyadamantane.

[0243] NMR measurement of the obtained A6 (MAC-ADIOH) under the above measurement conditions revealed the following peaks, confirming that it had the chemical structure of A6. δ (ppm) (d-DMSO): 6.4-6.5 (2H, ═CH), 1.5-3.9 (14H, Ad-H, -C(CH)═C), 4.5 (1H, -OH).

[0244] (Synthesis of A7) 2.3 g (12.5 mmol) of 1,3,5-adamantanetriol (manufactured by Mitsubishi Gas Chemical Company) was dissolved in 100 mL of toluene, and 28.1 g (125 mmol) of a 57% aqueous hydrogen iodide solution was added, followed by reaction with stirring for 13 hours at 80° C. After the reaction, water was added and the mixture was washed with sodium hydrogen carbonate. The organic layer was concentrated and then separated and purified by column chromatography, yielding 0.9 g of 3,5-diiodo-1-hydroxyadamantane represented by the following formula.

[0245] 3.5 g of A7 (MAC-ADI2) was obtained in the same manner as in the synthesis of A5, except that 4.04 g (10 mmol) of 3,5-diiodo-1-hydroxyadamantane obtained above was used instead of 2.78 g of 3-iodo-1-hydroxyadamantane.

[0246] NMR measurement of the obtained A7 (MAC-ADI2) under the above measurement conditions revealed the following peaks, confirming that it had the chemical structure of A7. δ (ppm) (d-DMSO): 6.4-6.5 (2H, ═CH), 1.5-3.9 (16H, Ad-H, -C(CH)═C)

[0247] (Synthesis of A11)

[0248] [Protecting Group Introduction Step] Using a 10 L three-necked eggplant flask connected to a reflux condenser, 84 g of MAC-2H35I was added to 168 mL of dehydrated tetrahydrofuran (THF) in an ice bath under nitrogen flow and stirred with a stirring blade to dissolve. Next, 8 g of PPTS (pyridinium-p-toluenesulfonic acid) was added over 30 minutes while stirring in an ice bath, and the mixture was stirred for an additional 60 minutes. 29.4 g of ethyl vinyl ether (1.2 equivalents relative to the functional group equivalent) was added dropwise to the stirred reaction solution over 60 minutes, and the mixture was stirred for an additional 60 minutes at 35°C. 720 mL of pure water was then added in an ice bath, and the mixture was stirred for 60 minutes, after which the organic phase was recovered. 200 mL of ethyl acetate and 500 mL of pure water were added to the recovered organic phase, and the mixture was stirred. The organic phase was then recovered and concentrated under reduced pressure to obtain 87 g of a white solid as the target product, A11 (MAC-2H35I-EE). The yield was 85%.

[0249]

[0250] (Synthesis of A12)

[0251] [Protecting Group Introduction Step] Using a 10 L three-necked eggplant flask connected to a reflux condenser, 84 g of MAC-4H35I was added to 168 mL of dehydrated tetrahydrofuran (THF) in an ice bath under nitrogen flow and stirred with a stirring blade to dissolve. Next, 8 g of PPTS (pyridinium-p-toluenesulfonic acid) was added over 30 minutes while stirring in an ice bath, and the mixture was stirred for an additional 60 minutes. 29.4 g of ethyl vinyl ether (1.2 equivalents relative to the functional group equivalent) was added dropwise to the stirred reaction solution over 60 minutes, and the mixture was stirred for an additional 60 minutes at 35°C. 720 mL of pure water was then added in an ice bath, and the mixture was stirred for 60 minutes, after which the organic phase was recovered. 200 mL of ethyl acetate and 500 mL of pure water were added to the recovered organic phase, and the mixture was stirred. The organic phase was then recovered and concentrated under reduced pressure to obtain 83 g of a white solid as the target product A12 (MAC-4H35I-EE). The yield was 81%.

[0252]

[0253] (Synthesis of A21) A 20 L separable flask was prepared, and 4.8 L of dehydrated THF and 1,585 mL of methylmagnesium bromide (1.0 M THF solution) were added. Under N2 flow, the mixture was cooled to an internal temperature of -15°C and stirred at 120 rpm using a half-moon stirring blade for 1 hour. In a separate 3 L flask, 1.2 L of dehydrated THF and 300 g of 4-iodoacetophenone were dissolved to prepare a 4-iodoacetophenone-THF solution. The prepared 4-iodoacetophenone-THF solution was added dropwise to the 20 L separable flask over 1.5 hours, followed by stirring for 1 hour. 281.9 g of methacrylic anhydride was then added dropwise over 1.5 hours. Then, 14.9 g of DMAP was added over 10 minutes, and the internal temperature was returned to 25°C over 20 minutes. Stirring was then continued for 4 hours. After ice-cooling to an internal temperature of 10°C or less, 300 g of saturated aqueous ammonium chloride solution was added dropwise over 10 minutes. Next, 900 g of ion-exchanged water was added dropwise over 30 minutes, and then 3.0 kg of toluene was added. After stirring at 180 rpm for 15 minutes and allowing to stand, the aqueous phase was drained. Furthermore, 1.2 kg of ion-exchanged water was added, and the mixture was stirred at 180 rpm for 15 minutes, then allowed to stand and the aqueous phase was drained. This operation was repeated twice. The recovered organic phase was concentrated by vacuum distillation while blowing in a small amount of air until no solvent components were distilled out, and then the peak containing the target product was separated by column purification using silica gel. The recovered fraction was concentrated and then dissolved in 470 mL of hexane to remove the precipitate, and the filtrate was concentrated and again subjected to column purification using silica gel to obtain the target product A21 (300 g).

[0254] NMR measurement of the obtained A21 under the above measurement conditions revealed the following peaks, confirming that it had the chemical structure of A21: δ (ppm) (d-DMSO): 7.6 (2H, Ph), 7.0 (2H, Ph), 6.5 (1H, ═CH2), 6.4 (1H, ═CH2), 2.0 (3H, —CH3), 1.5 (6H, —CH3).

[0255] (Synthesis of A22) [Reduction Step] A 1 L three-neck flask was prepared, and 24.6 g of 4-iodoacetophenone, 120 g of methanol, and 120 g of toluene were added. Stirring was performed using a half-moon stirring blade. The internal temperature was cooled to 0°C, and 1.5 g (0.4 equivalents) of sodium borohydride was slowly added under N2 flow, followed by stirring for 1 hour. 120 mL of saturated aqueous ammonium chloride solution was added, followed by 120 mL of ion-exchanged water, and stirring for 10 minutes at 180 rpm. 120 mL of ethyl acetate was added and stirred for 10 minutes at 180 rpm, after which the aqueous phase was removed. 150 mL of saturated saline was added and stirred for 10 minutes at 180 rpm, followed by allowing to stand and then removing the aqueous phase. The organic phase was recovered, 50 g of sodium sulfate was added, and the mixture was left to stand for 4 hours. After filtration, the filtrate was concentrated under reduced pressure to obtain the reaction product. The resulting reaction product was purified using a silica gel column to obtain 23.6 g of reaction product. [Protecting Group Introduction Step] A 1 L three-neck flask was prepared, and 23.6 g of the reaction product prepared in the reduction step and 250 mL of ethyl acetate were added. Using a half-moon stirring blade, the flask was cooled to an internal temperature of 0°C and stirred at 120 rpm for 30 minutes to dissolve the product. Under a nitrogen flow, 18.4 g (1.5 equivalents) of diisopropylethylamine and 1.2 g (0.1 equivalents) of dimethylaminopyridine were added, and then 17.6 g (1.2 equivalents) of acetic anhydride was added dropwise while maintaining the internal temperature below 10°C. The mixture was then stirred at 120 rpm for 60 minutes. 160 mL of 1 M hydrochloric acid was gradually added while maintaining the internal temperature below 10°C, and the mixture was stirred at 120 rpm for 1 hour. While maintaining the internal temperature at 25°C or below, an additional 150 mL of ethyl acetate was added, and the mixture was stirred at 180 rpm for 30 minutes, then allowed to stand, and the aqueous phase was removed. Next, 20 mL of saturated aqueous sodium bicarbonate was added, and the mixture was stirred at 180 rpm for 15 minutes, then allowed to stand, and the aqueous phase was removed. 200 mL of saturated saline was then added, and the mixture was stirred at 180 rpm for 15 minutes, then allowed to stand, and the aqueous phase was removed. The organic phase was recovered, and a crude containing the target product was obtained by evaporation under reduced pressure. The target product, A22, was isolated by column purification using silica gel.

[0256] NMR measurement of the obtained A22 under the above measurement conditions revealed the following peaks, confirming that it had the chemical structure of A22. δ (ppm) (d-DMSO): 7.6 (2H, Ph), 7.1 (2H, Ph), 6.5 (1H, ═CH), 6.4 (1H, ═CH), 6.1 (1H, —CH—), 2.0 (3H, —CH), 1.7 (3H, —CH).

[0257] (Synthesis of A23) 2.3 g (12.5 mmol) of 4-methyl-adamantane-1,4-diol was dissolved in 100 mL of toluene, and 11.2 g (50 mmol) of a 57% aqueous hydrogen iodide solution was added, followed by reaction with stirring for 8 hours at 80° C. After the reaction, water was added and the mixture was washed with sodium hydrogen carbonate. The organic layer was concentrated and then separated and purified by column chromatography, yielding 1.1 g of 1-iodo-4-methyl-4-hydroxyadamantane represented by the following formula.

[0258] 3.1 g of A23 (MAC-ADI4H4M) was obtained in the same manner as in the synthesis of A5, except that 2.92 g (10 mmol) of 1-iodo-4-methyl-4-hydroxyadamantane obtained above was used instead of 2.78 g of 3-iodo-1-hydroxyadamantane.

[0259] NMR measurement of the obtained A23 (MAC-ADI4H4M) under the above measurement conditions revealed the following peaks, confirming that it had the chemical structure of A23. δ (ppm) (d-DMSO): 6.4-6.5 (2H, ═CH), 1.2-2.4 (19H, Ad-H, Ad-CH, -C(CH)═C)

[0260] (Synthesis of A24)

[0261] 5.9 g (12.5 mmol) of 2,4,6-triiodophenol was dissolved in 100 mL of methylene chloride, and 1.9 g (12.5 mmol) of methacrylic anhydride and 1.5 g of N,N-dimethylamino-4-aminopyridine were added. The mixture was stirred at the boiling point for 8 hours to react. After the reaction, the mixture was cooled and washed by a separation treatment using water, and then the organic phase was extracted. Magnesium sulfate was added to this organic phase and the mixture was dried, and the solvent was distilled off under reduced pressure to obtain a crude product of A24. The obtained crude product of A24 was purified by column chromatography to obtain 4.0 g of A-24 (yield 60%).

[0262] The obtained A24 was subjected to NMR measurement under the above measurement conditions, and the following peaks were found, confirming that it had the chemical structure of A24. δ (ppm) (d-DMSO): 7.8 (2H, Ph), 6.7 (1H, ═CH ２ ), 5.0 (1H, =CH ２ ), 1.9 (3H, -CH ３ )

[0263] (Synthesis of A25) The same procedure as for A24 was carried out except that 2,4,6-triiodophenol was changed to 4-iodophenol, methacrylic acid anhydride was changed to methacrylic acid chloride, and N,N-dimethylamino-4-aminopyridine was changed to triethylamine, and 2.2 g of A25 was obtained (yield 60%).

[0264] When the obtained A25 was subjected to NMR measurement under the above measurement conditions, the following peaks were found, and it was confirmed that it had the chemical structure of A25. δ (ppm) (d-DMSO): 7.8 (4H, Ph), 6.7 (1H, ═CH ２ ), 5.0 (1H, =CH ２ ), 1.9 (3H, -CH ３ )

[0265] (Synthesis of A26) 3.5 g (yield 65%) of A26 was obtained in the same manner as A24, except that 2,4,6-triiodophenol was changed to 2,4-diiodobenzyl alcohol and N,N-dimethylamino-4-aminopyridine was changed to triethylamine.

[0266] When the obtained A26 was subjected to NMR measurement under the above measurement conditions, the following peaks were found, and it was confirmed that the compound had the chemical structure of A26. δ (ppm) (d-DMSO): 7.8 (4H, Ph), 6.7 (1H, ═CH ２ ), 5.0 (1H, =CH ２ ), 1.9 (3H, -CH ３ )

[0267] (Synthesis of A27) 30.8 g (0.1 mol) of 5-hydroxy-3-iodo-1-adamantanemethanol (manufactured by Mitsubishi Gas Chemical Company) was dissolved in 250 ml of toluene, and 86 g (1.0 mol) of methacrylic acid and 22.7 g (0.11 mol) of N,N'-dicyclohexylcarbodiimide were added under ice-cooling. The mixture was then stirred at room temperature for 24 hours to allow the reaction to proceed. After completion of the reaction, water was added to the reaction solution, and then an aqueous sodium sulfite solution was added and the mixture was ice-cooled to form a precipitate. The precipitate was recovered by filtration, and then 300 g of ethyl acetate was added to the precipitate to dissolve it. The mixture was then washed five times with 100 g of water and concentrated. After concentration, 200 g of hexane was added under ice-cooling to precipitate crystals. The precipitated crystals were filtered off and dried under reduced pressure at 50°C to obtain 25 g of white crystals A27.

[0268] NMR measurement of the obtained A27 (MAC-ADI) under the above measurement conditions revealed the following peaks, confirming that it had the chemical structure of A27. δ (ppm) (d-DMSO): 6.4-6.5 (2H, ═CH), 4.5 (—OH), 4.0 (—CH), 1.3-3.3 (16H, Ad-H, —C(CH)═C).

[0269] [Synthesis of Compound B]

[0270] (Synthesis of D2) [Iodination Step DML1D]

[0271]

[0272] A 100 L stainless steel reaction vessel connected to a reflux condenser was charged with 700 g of 4-hydroxybenzaldehyde and 4900 ml of methanol, which were dissolved by stirring at 220 rpm for 1 hour under a nitrogen flow. The reaction vessel was ice-cooled, and an aqueous sodium hydroxide solution prepared by dissolving 757 g of sodium hydroxide in 1260 mL of pure water was gradually added to the reaction vessel, followed by the gradual addition of 3200 g of iodine in 10 portions over 60 minutes. The mixture was stirred for 8 hours while maintaining the internal temperature at 60 °C using a water bath. Subsequently, 21 L of a 6 M aqueous hydrochloric acid solution was added dropwise over 1 hour at 120 rpm under ice cooling, followed by 30 minutes of stirring. Next, 2.3 L of a 20% by weight aqueous sodium sulfite solution was added with stirring, followed by 3.5 L of pure water, and the resulting precipitate was collected by filtration. The resulting solid was purified by column chromatography using silica gel to obtain 840 g of DML1D isomer in a yield of 30%.

[0273] [Protecting group introduction step DML1P]

[0274]

[0275] Using a 100 L glass-lined reaction vessel equipped with a reflux condenser, 840 g of DML1D was dissolved in 1680 mL of dehydrated dimethylformamide (DMF) under nitrogen flow in an ice bath. The mixture was then stirred with a stirring blade. Next, 380 g of diisopropylethylamine was added over 30 minutes using a dropping funnel while stirring in the ice bath, followed by an additional 60 minutes of stirring. 255 g of chloromethyl ethyl ether (1.2 equivalents relative to the substrate) was added dropwise to the stirred reaction solution over 60 minutes using a dropping funnel, followed by an additional 30 minutes of stirring in the ice bath. Subsequently, 7.2 L of purified water was added in the ice bath, and after 60 minutes of stirring, the resulting precipitate was collected by filtration. The collected solid was suspended and stirred in 5.8 L of methanol in the ice bath for 30 minutes, after which 996 g of the desired protected DML1P was obtained as a white solid by filtration. The yield was 96%.

[0276] [Reduction step DML1R]

[0277]

[0278] A 20 L separable flask was filled with ethanol (5 L) in an ice bath, and 996 g of the prepared protected DML1P isomer was gradually added and suspended. Under a nitrogen flow, 19 g of sodium borohydride was added in 3 g increments over 60 minutes while stirring. After stirring for 1 hour in an ice bath, 350 g of a 5 wt% aqueous ammonium chloride solution was added dropwise over 15 minutes. Under ice cooling, the resulting reaction solution was gradually added to 8 L of pure water and stirred for 30 minutes. The precipitate that gradually formed during stirring was filtered off and then rinsed with 2 L of pure water. The resulting precipitate was dissolved in 4 L of ethyl acetate and washed three times with 1.5 L of a 10 wt% aqueous NaCl solution. The resulting ethyl acetate solution was recovered, and 80 g of magnesium sulfate was added and suspended for 30 minutes. The filtrate obtained by filtration was concentrated to a concentration of approximately 50% by mass ± 5%, and 9 L of heptane was added to perform crystallization. The filtered crystals were further rinsed with cold heptane and then dried to obtain 701 g of D2 (DML1R isomer) in a yield of 70% and a purity of 99.2%.

[0279] (Synthesis of D1) D1 (DML1RS) was synthesized in the same manner as in the synthesis of D2, except that salicylaldehyde was used in an equimolar amount instead of 4-hydroxybenzaldehyde as a raw material.

[0280]

[0281] (Synthesis of D3) A flask equipped with a reflux condenser and a Dean-Stark reaction system was immersed in an oil bath, and 73 g of compound 3-0 (adamantanediol, 0.43 mol) and 2.5 L of o-xylene were charged into the flask and stirred. Next, 400 g (1.72 mol) of a 55% aqueous solution of hydrogen iodide was added to the flask. The internal temperature was set to 125°C and the reaction was carried out for 3 hours. Thereafter, the mixture was stirred for 1 hour in a water bath at 25°C.

[0282] An additional 2.5 L of ion-exchanged water was added to the reaction vessel, and the mixture was separated into an organic phase and an aqueous phase. After recovering the organic phase, it was washed three times with 1 L of 5% sodium bicarbonate water and then 1 L of ion-exchanged water. After recovering the organic phase, it was concentrated and further purified using a column to obtain D3(DMA0a) (31 g) as a white solid.

[0283] (Synthesis of D4) A flask equipped with a reflux condenser and a Dean-Stark reaction system was immersed in an oil bath, and 80 g of compound 3-1 (adamantanetriol, manufactured by Mitsubishi Gas Chemical Company, Inc., 0.43 mol) and 2.5 L of o-xylene were charged into the flask and stirred. Next, 400 g (1.72 mol) of a 55% aqueous solution of hydrogen iodide was added to the flask. The internal temperature was set to 125°C and a reaction was carried out for 3 hours. Thereafter, the mixture was stirred for 1 hour in a water bath at 25°C.

[0284] An additional 2.5 L of ion-exchanged water was added to the reaction vessel, and the mixture was separated into an organic phase and an aqueous phase. The organic phase was recovered and then washed three times with 1 L of 5% sodium bicarbonate water and then with 1 L of ion-exchanged water. The recovered organic phase was concentrated and further purified using a column to obtain D4 (DMA1a) (33 g) as a white solid.

[0285] (Synthesis of D5) A flask equipped with a stirrer, a condenser, and a Dean-Stark tube was immersed in an oil bath, and 308 g of toluene was added to 21 g of 1,3,5-adamantanetriol. 39.9 g of 55% by mass sulfuric acid and 39.9 g of 55% by mass aqueous hydrogen iodide solution were then added and stirred. After refluxing for 3 hours at 105-110 °C while removing 26 g of distilled water using a Dean-Stark tube, the mixture was cooled to room temperature. 177.5 g of water was added, followed by 10 g of a 10% aqueous sodium sulfite solution. The reaction solution was then filtered, and 31 g of the toluene solution and crystals were separated by filtration. The toluene solution was then washed five times with 88 g of water to obtain 255 g of a toluene solution. 341 g of ethyl acetate was added to 31 g of the separated crystals, and then 85 g of water and 0.4 g of a 10% aqueous sodium sulfite solution were added for separation and washing. Further, separation washing was performed six times with 85 g of water to obtain 316 g of an ethyl acetate solution. 255 g of the toluene solution and 316 g of the ethyl acetate solution in which the crystals had been dissolved were concentrated under reduced pressure, and the precipitated crystals were separated by filtration and then dried under reduced pressure at 50°C to obtain 29.2 g of D5 (DAMA1-tr) as white crystals.

[0286]

[0287] (Synthesis of D6) D6 (DAMA1-x) was obtained in the same manner as in the synthesis of D5, except that meta-xylene was used instead of toluene.

[0288]

[0289] (Synthesis of D7) D7 (DAMA1-eb) was obtained in the same manner as in the synthesis of D5, except that ethylbenzene was used instead of toluene.

[0290]

[0291] (Synthesis of D8) D8 (DML2RS) was synthesized by applying the synthesis of D2, except that salicylaldehyde was used in an equimolar amount instead of 4-hydroxybenzaldehyde as a raw material.

[0292]

[0293] (Synthesis of D9) [Reduction step DML1R2]

[0294] A 20 L separable flask was filled with ethanol (5 L) in an ice bath, and 996 g of the prepared protected DML1D isomer was gradually added and suspended. Under a nitrogen flow, 19 g of sodium borohydride was added in 3 g increments over 60 minutes while stirring. After stirring for 1 hour in an ice bath, 350 g of a 5 wt % aqueous ammonium chloride solution was added dropwise over 15 minutes. Under ice cooling, the resulting reaction solution was gradually added to 8 L of pure water and stirred for 30 minutes. The precipitate that gradually formed during stirring was filtered off and then rinsed with 2 L of pure water. The resulting precipitate was dissolved in 4 L of ethyl acetate and washed three times with 1.5 L of a 10 wt % aqueous NaCl solution. The resulting ethyl acetate solution was recovered, and 80 g of magnesium sulfate was added and suspended for 30 minutes. The filtrate obtained by filtration was concentrated to a concentration of approximately 50 wt % ± 5%, and 9 L of heptane was added to perform crystallization. The filtered crystals were further rinsed with cold heptane and then dried to obtain 701 g of D9 (DML1R2 isomer) in a yield of 70% and a purity of 99.2%.

[0295] (Synthesis of D10) A flask equipped with a stirrer, a condenser, and a Dean-Stark tube was immersed in an oil bath, and 308 g of toluene was added to 21 g of 1,3-adamantanediol. 39.9 g of 55% by mass sulfuric acid and 39.9 g of 55% by mass aqueous hydrogen iodide solution were then added and stirred. The mixture was refluxed for 3 hours at 105-110 °C while 26 g of distilled water was removed using a Dean-Stark tube, and then cooled to room temperature. 177.5 g of water was added, followed by 10 g of a 10% aqueous sodium sulfite solution. The reaction solution was then filtered, and 31 g of the toluene solution and crystals were separated by filtration. The toluene solution was then washed five times with 88 g of water to obtain 255 g of a toluene solution. 341 g of ethyl acetate was added to the 31 g of separated crystals, and then 85 g of water and 0.4 g of a 10% aqueous sodium sulfite solution were added for separation and washing. Further, separation washing with 85 g of water was carried out six times to obtain 316 g of an ethyl acetate solution. 255 g of the toluene solution and 316 g of the ethyl acetate solution in which the crystals had been dissolved were concentrated under reduced pressure, and the precipitated crystals were separated by filtration and then dried under reduced pressure at 50°C to obtain 29.2 g of D10 (MAMA1-tr) as white crystals.

[0296]

[0297] (Synthesis of D11)

[0298] Using a 100L stainless steel reaction vessel connected to a reflux condenser, 2500g of salicylic alcohol and 22500g of methanol were charged and dissolved by stirring at 220 rpm for 1 hour under nitrogen flow. The reaction vessel was ice-cooled, and 4089g of iodine was added and stirred to dissolve. Then, 4167g of 34% aqueous iodic acid solution was added dropwise so that the internal temperature was 20 ° C or less, and then the reaction was carried out at 60 ° C for 3 hours. Then, 2500g of 5% aqueous sodium hydrogen sulfite solution was added, followed by 11250g of pure water, and the mixture was further ice-cooled to form a precipitate. After collecting the precipitate by filtration, a silica gel column was used to separate and purify the mixture using ethyl acetate / hexane = 9 / 1 as the added solvent, and 356g of the target D11 (DML11D) was obtained.

[0299] (Synthesis of D12)

[0300] A 100 L stainless steel reactor equipped with a reflux condenser was charged with 2500 g of 4-hydroxybenzyl alcohol and 22,500 g of methanol, and the mixture was dissolved by stirring at 220 rpm for 1 hour under a nitrogen flow. The reactor was cooled on ice, and 4,089 g of iodine was added and dissolved by stirring. Subsequently, 4,167 g of a 34% aqueous iodic acid solution was added dropwise so that the internal temperature was below 20°C, and the mixture was allowed to react at 60°C for 3 hours. Subsequently, 2,500 g of a 5% aqueous sodium bisulfite solution was added, followed by 11,250 g of purified water, and the mixture was further cooled on ice to form a precipitate. The precipitate was collected by filtration and then separated and purified using a silica gel column with ethyl acetate / hexane (9 / 1) as the solvent, yielding 341 g of the target product, D12 (DML12D).

[0301] (Synthesis of D13) D13 (DML2RS) was synthesized in the same manner as in the synthesis of D2, except that salicylaldehyde was used as a raw material in an equimolar amount instead of 4-hydroxybenzaldehyde, the type of protecting agent was ethyl vinyl ether, and the [protecting group introduction step] was changed to the method described below.

[0302]

[0303] [Protecting Group Introduction Step] Using a 100 L glass-lined reaction vessel connected to a reflux condenser, 840 g of DML1D isomer was dissolved in 1680 mL of dehydrated tetrahydrofuran (THF) in an ice bath under nitrogen flow and stirred with a stirring blade. Next, 80 g of PPTS (pyridinium-p-toluenesulfonic acid) was added over 30 minutes while stirring in the ice bath, and the mixture was stirred for an additional 60 minutes. 294 g of ethyl vinyl ether (1.2 equivalents relative to the functional group equivalent) was added dropwise to the stirred reaction solution over 60 minutes and stirred at 35°C for an additional 60 minutes. 7.2 L of pure water was then added in an ice bath, and the mixture was stirred for 60 minutes, after which the organic phase was recovered. 2 L of ethyl acetate and 5 L of pure water were added to the recovered organic phase, and the mixture was stirred. The organic phase was recovered and concentrated under reduced pressure to obtain 833 g of a white solid, the target protected DML2PS isomer. The yield was 81%.

[0304]

[0305] (Synthesis of D14) D14 (DML2R) was synthesized in the same manner as in the synthesis of D2, except that 4-hydroxybenzaldehyde was used as the raw material, the type of protecting agent was ethyl vinyl ether, and the [protecting group introduction step] was changed to the method described below.

[0306]

[0307] [Protecting Group Introduction Step] Using a 100 L glass-lined reaction vessel connected to a reflux condenser, 840 g of DML1D isomer was dissolved in 1680 mL of dehydrated tetrahydrofuran (THF) in an ice bath under nitrogen flow and stirred with a stirring blade. Next, 80 g of PPTS (pyridinium-p-toluenesulfonic acid) was added over 30 minutes while stirring in the ice bath, and the mixture was stirred for an additional 60 minutes. 294 g of ethyl vinyl ether (1.2 equivalents relative to the functional group equivalent) was added dropwise to the stirred reaction solution over 60 minutes and stirred at 35°C for an additional 60 minutes. 7.2 L of pure water was then added in an ice bath, and the mixture was stirred for 60 minutes, after which the organic phase was recovered. 2 L of ethyl acetate and 5 L of pure water were added to the recovered organic phase, and the mixture was stirred. The organic phase was recovered and concentrated under reduced pressure to obtain 833 g of the desired protected DML2P isomer as a white solid. The yield was 81%.

[0308]

[0309] (Synthesis of D15)

[0310] A 20 L separable flask was prepared, and 4.8 L of dehydrated THF and DBN (15.1 g, 0.1 equivalents) were added. Under N2 flow, the flask was cooled to an internal temperature of -15°C and stirred at 120 rpm using a half-moon stirring blade for 1 hour. A 4-iodoacetophenone-THF solution was prepared by dissolving 1.2 L of dehydrated THF and 300 g of 4-iodoacetophenone in a separate 3 L flask. The prepared 4-iodoacetophenone-THF solution was added dropwise to the 20 L separable flask over 1.5 hours, after which the internal temperature was raised to 40°C and stirring was continued for 4 hours. After ice-cooling to an internal temperature of 10°C or below, 300 g of saturated aqueous ammonium chloride solution was added. Next, 900 g of ion-exchanged water was added, followed by an additional 3.0 kg of toluene. The mixture was stirred at 180 rpm for 15 minutes and allowed to stand, after which the aqueous phase was removed. Further, 1.2 kg of ion-exchanged water was added, and the mixture was stirred at 180 rpm for 15 minutes, then allowed to stand and the water tank was drained. This procedure was repeated twice. The recovered organic phase was concentrated by vacuum distillation until no solvent components were distilled out, and then the peak containing the target product was separated by column purification using silica gel. 160 g of D15 (DABP-4I) was obtained.

[0311] NMR measurement of the obtained D15 (DABP-4I) under the above measurement conditions revealed the following peaks, confirming that it had the chemical structure of D15. δ (ppm) (d-DMSO): 8.0 (2H, Ph), 7.6 (2H, Ph), 7.7 (2H, Ph), 7.1 (2H, Ph), 7.3 (1H, -CH=), 2.4 (3H, -CH3).

[0312] (Synthesis of D16) A flask equipped with a stirrer, a condenser, and a Dean-Stark tube was immersed in an oil bath, and 308 g of toluene was added to 19 g of 5-hydroxyadamantan-2-one. 39.9 g of 55% by mass sulfuric acid and 39.9 g of 55% by mass aqueous hydrogen iodide solution were then added and stirred. After refluxing for 3 hours at 105-110 °C while extracting 26 g of distilled water using a Dean-Stark tube, the mixture was cooled to room temperature. 177.5 g of water was added, followed by 10 g of a 10% aqueous sodium sulfite solution. The reaction solution was then filtered, and 31 g of the toluene solution and crystals were separated by filtration. The toluene solution was then washed five times with 88 g of water to obtain 255 g of a toluene solution. 341 g of ethyl acetate was added to the 31 g of separated crystals, and then 85 g of water and 0.4 g of a 10% aqueous sodium sulfite solution were added for separation and washing. The mixture was washed six times with 85 g of water to obtain 316 g of an ethyl acetate solution. 255 g of the toluene solution and 316 g of the ethyl acetate solution containing the crystals were concentrated under reduced pressure, and the precipitated crystals were separated by filtration and dried at 50°C under reduced pressure to obtain 29.2 g of D16 (25DHA-tr) as white crystals.

[0313] (Synthesis of D17) The same procedure as for DML1D was carried out except that 4-hydroxybenzaldehyde was changed to 2,4,6-triiodophenol, to obtain 1170 g of D17.

[0314] When the obtained D17 was subjected to NMR measurement under the above measurement conditions, the following peaks were found, confirming that it had the chemical structure of D17. δ (ppm) (d-DMSO): 9.0 (2H, Ph-OH) 7.8 (4H, Ph)

[0315] (Synthesis of D18) The same procedure as for DML1D was carried out except that 4-hydroxybenzaldehyde was changed to 2-iodophenol, to obtain 250 g of D18.

[0316] When the obtained D18 was subjected to NMR measurement under the above measurement conditions, the following peaks were found, confirming that it had the chemical structure of D18. δ (ppm) (d-DMSO): 9.0 (2H, Ph-OH) 7.8 (6H, Ph)

[0317] (Synthesis of D19) The same procedure as for DML1D was carried out except that 4-hydroxybenzaldehyde was changed to 2,5-diiodobenzyl alcohol, to obtain 800 g of D19.

[0318] When the obtained D19 was subjected to NMR measurement under the above measurement conditions, the following peaks were found, confirming that it had the chemical structure of D19. δ (ppm) (d-DMSO): 7.5-8.0 (6H, Ph), 5.3 (2H, —OH), 4.4 (4H, —CH2—)

[0319] (Synthesis of D20) 30.8 g (0.1 mol) of 5-hydroxy-3-iodo-1-adamantanemethanol (manufactured by Mitsubishi Gas Chemical Company) was dissolved in 250 ml of toluene, and 86 g (1.0 mol) of methacrylic acid and 22.7 g (0.11 mol) of N,N'-dicyclohexylcarbodiimide were added under ice cooling. The mixture was then stirred at 120°C for 3 hours to allow the reaction to proceed. After the reaction was completed, the temperature was returned to room temperature, water was added to the reaction solution, and then an aqueous sodium sulfite solution was added and the mixture was ice-cooled to form a precipitate. The precipitate was recovered by filtration, and then 300 g of ethyl acetate was added to the precipitate to dissolve it, followed by washing five times with 100 g of water. After recovery, the solution was concentrated and further purified using a column to obtain 22 g of white solid D20.

[0320] (Synthesis of D21) 30.8 g (0.1 mol) of 5-hydroxy-3-iodo-1-adamantanemethanol (manufactured by Mitsubishi Gas Chemical Company) was dissolved in 250 ml of acetonitrile, and 22.7 g (0.11 mol) of N,N'-dicyclohexylcarbodiimide was added under ice-cooling. The mixture was then stirred at 85°C for 3 hours to allow the reaction to proceed. After the reaction was completed, the mixture was returned to room temperature, water was added to the reaction solution, and then an aqueous sodium sulfite solution was added and the mixture was ice-cooled to form a precipitate. The precipitate was recovered by filtration, and then 300 g of ethyl acetate was added to the precipitate to dissolve it, followed by washing five times with 100 g of water. After recovery, the mixture was concentrated and further purified using a column to obtain 26 g of D21 as a white solid.

[0321] [Preparation of Composition] A composition containing Compound A and Compound B was prepared according to the table below.

[0322] The compound (AR1) used in the resin composition (PSAR1) was as follows.

[0323] [Preparation of Resin Composition 1] (Preparation of Resin Composition PA1) Immediately after preparing composition (PSA1), 4.9 g of composition (PSA1), 3.6 g of 2-ethyl-2-adamantyl methacrylate, 0.8 g of γ-butyrolactone methacrylate, and 0.8 g of hydroxyadamantyl methacrylate were dissolved in 45 mL of tetrahydrofuran, and 0.20 g of azobisisobutyronitrile was added. After refluxing for 12 hours, the reaction solution was added dropwise to 2 L of n-heptane. The precipitated resin was filtered and dried under reduced pressure to obtain a white powdery resin composition (PA1). This resin composition contained an A1 (co)polymer represented by the following chemical formula (P-MAC-2H35I). The molecular weight (Mw) of this A1 (co)polymer was 12,000 and the dispersity (Mw / Mn) was 1.78. Furthermore, the resin composition １３ As a result of C-NMR measurement, the composition ratio (molar ratio) in the following chemical formula (P-MAC-2H35I) was found to be a:b:c:d=45:15:10:20. Note that although the following chemical formula (P-MAC-2H35I) is written in a simplified form to indicate the ratio of each structural unit, P-MAC-2H35I is not a block copolymer in which each structural unit forms an independent block.

[0324]

[0325] (Preparation of Resin Compositions PA2 to PA28c) Resin compositions (PA2) to (PA28c) were obtained using the same method as for preparing resin composition (PA1), except that compositions (PSA2) to (PSA28c), respectively, were used instead of composition (PSA1). The amounts of compositions (PSA2) to (PSA28c) used were such that the amount of compound A contained in each of compositions (PSA2) to (PSA28c) was equimolar to the amount of A1 contained in composition (PSA1) used in the synthesis of resin composition (PA1). The results for the obtained resin compositions are shown in the table below.

[0326] (Preparation of Resin Composition PAR1) Resin composition (PAR1) was obtained using the same method as for preparing resin composition (PA1), except that 4 g of composition (PSAR1), 0.8 g of γ-butyrolactone methacrylate, and 2.2 g of hydroxyadamantyl methacrylate were used instead of composition (PSA1). The amount of composition (PSAR1) used was such that the amount of compound A contained in composition (PSAR1) was equimolar to the amount of compound A1 contained in composition (PSA1) used in the synthesis of resin composition (PA1). The results of the obtained resin composition are shown in the table below. The resin composition also contained an AR (co)polymer represented by the following chemical formula (P-AC-1). The molecular weight (Mw) of this AR (co)polymer was 13,500, and the dispersity (Mw / Mn) was 1.95.

[0327]

[0328] In the formula (P-AC-1), "55", "15", and "30" represent the molar ratios of the respective structural units. Formula (P-AC-1) is written in a simplified manner to indicate the ratios of the respective structural units, but P-AC-1 is not a block copolymer in which the respective structural units form independent blocks.

[0329]

[0330] [Preparation of Resin Composition 2] (Preparation of Resin Composition PB1) After preparing composition (PSA1), composition (PSA1) was stored in a light-shielding bottle and subjected to an accelerated aging test at 40°C for 4 months to prepare composition (PSB1). Thereafter, resin composition (PB1) was prepared using the same method as for preparing resin composition (PA1), except that composition (PSB1) was used instead of composition (PSA1).

[0331] (Preparation of Resin Compositions PB2 to PB28c) Compositions (PSB2) to (PSB28c) and (PBR1) were prepared using the same aging treatment method as for the preparation of resin composition (PSB1), except that compositions (PSA2) to (PSA28c) and (PSAR1) were used instead of composition (PSA1) in the preparation of resin composition PB1. Thereafter, resin compositions (PB2) to (PB28c) and (PBR1) were prepared using the same method as for the preparation of resin composition (PA1), except that compositions (PSB2) to (PSB28c) and (PBR1) were used instead of composition (PSA1), respectively. The amounts of compositions (PSB2) to (PSB28c) used were such that the amount of compound A contained in each of compositions (PSB2) to (PSB28c) was equimolar to the amount of compound A contained in composition (PSA1) used in the synthesis of resin composition (PA1). The amount of composition (PSBR1) used was such that the amount of compound AR1 contained in composition (PSBR1) was equimolar to the amount of AR1 contained in composition (PSAR1) used in the synthesis of resin composition (PAR1). The results of the obtained resin compositions are shown in the table below. The results of the obtained resin compositions are shown in the table below.

[0332]

[0333] [Evaluation of Resin Composition 1] 1. EB Printing (Evaluation of EB Sensitivity, Resolution, and Roughness) [Evaluation Using Resin Composition (PA1)] A resin solution was prepared by blending 5 parts by mass of resin composition (PA1), 1 part by mass of triphenylsulfonium nonafluoromethanesulfonate, 0.1 parts by mass of tributylamine, and 94 parts by mass of PGMEA. The prepared resin solution was then filtered in a clean room using a filter line in which a 15 nm pore size PTFE filter (manufactured by Integris) and a nylon filter (Polyfix nylon (10 nm nylon filter), manufactured by Kitz Microfilter) were connected in series, to obtain a filtered resin solution. The resulting resin solution was applied to a silicon wafer and baked at 110 to 130°C for 60 seconds to form a photoresist layer with a film thickness of 100 nm.

[0334] The film was then exposed using an electron beam lithography system (ELS-7500, 100 keV, manufactured by Elionix), baked (PEB) at 105°C for 60 seconds, and puddle-developed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds. After rinsing with pure water, the film was rotated at 1500 rpm for 30 seconds, yielding a positive pattern. The resulting pattern was observed using an SEM (S4800, manufactured by Hitachi, Ltd.) to evaluate the resolution and sensitivity. The results are shown in the table below.

[0335] For the sensitivity evaluation, the lower limit of the exposure dose (mJ / cm2) that enables the formation of a pattern with a line width of 40 nm and a half pitch of 40 nm was determined as the EB sensitivity. The results are shown in the table below.

[0336] Regarding resolution, a pattern with an L (line) / S (space) ratio of 1 / 1 was fabricated using pattern layout condition PL, in which the half pitch was reduced in 1 nm increments from 60 nm, and exposure amount condition D, in which the exposure amount was reduced in 1 mJ / cm increments from 60 mL / cm, and pattern formability was evaluated using a matrix of conditions PL and D to determine the line width at which resolution was minimized. The results are shown in the table below.

[0337] Furthermore, for 10 randomly selected lines from the obtained line patterns, the line width was measured at 30 points at 1 nm intervals per line, and the roughness value was evaluated as three times the standard deviation of the line width values. The results are shown in the table below.

[0338] 2. EUV Sensitivity Evaluation The sensitivity of the resin solutions prepared above to an EUV light source was evaluated by the following method: Each of the prepared resin solutions was applied to a separate silicon wafer using a spin coater, and then heated on a hot plate at 105°C for 60 seconds to form a resist layer with a thickness of 100 nm.

[0339] Next, the entire wafer was subjected to maskless shot exposure using an extreme ultraviolet (EUV) exposure system "EUVES-7000" (product name, manufactured by LithoTech Japan Co., Ltd.), with the exposure dose increasing from 1 mJ / cm² to 80 mJ / cm² in 1 mJ / cm² increments. The wafer was then baked (PEB) for 60 seconds at 105°C and puddle developed for 60 seconds with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH), resulting in a wafer with 80 shots of exposure on the wafer. For each of the resulting shot-exposed areas, the film thickness was measured using an optical interference film thickness meter "VM3200" (product name, manufactured by SCREEN Semiconductor Solutions Co., Ltd.), and profile data on the film thickness versus exposure dose was obtained. The exposure dose at which the slope of the film thickness variation versus exposure dose was greatest was calculated as the sensitivity value (mJ / cm²), which was used as an index of the EUV sensitivity of the resist.

[0340] 3. Evaluation of Plain Film Exposure Defects The resin solution used in the EUV exposure sensitivity measurement was applied to a 12-inch silicon wafer with a 100 nm-thick oxide film formed on the outermost surface, and baked at 105°C for 60 seconds to form a 100 nm-thick photoresist layer. Next, using an extreme ultraviolet (EUV) exposure system "EUVES-7000" (product name, manufactured by Litho Tech Japan Co., Ltd.), the entire wafer was subjected to shot exposure at the same exposure dose as the EUV sensitivity value obtained in the above-mentioned EUV sensitivity evaluation, followed by a 90-second bake (PEB) at 105°C and 60-second paddle development using a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution, yielding a wafer that had been shot-exposed across the entire wafer for 80 shots.

[0341] The exposed wafers thus produced were subjected to an etching process using an etching device "Telius SCCM" (product name, manufactured by Tokyo Electron Limited) with CH4 / CF4 / Ar gas until the oxide film was etched by 60 nm. The wafers produced by etching were subjected to defect evaluation using a defect inspection device "Surfscan SP3" (product name, manufactured by KLA Corporation), and the number of cone defects of 25 nm or more was determined as an index of etching defects. (Evaluation criteria) S: Number of cone defects ≦ 5 A: 5 < Number of cone defects ≦ 20 B: 20 ​​< Number of cone defects ≦ 60 C: 60 < Number of cone defects ≦ 400 D: 400 < Number of cone defects

[0342] The measurement results are shown in the table below.

[0343] [Evaluation of Each Resin Synthesis Example] Resin solutions were prepared in the same manner as when using resin composition (PA1), except that resin composition (PA1) was replaced with resin compositions (PA2) to (PA28c), and photoresist layers were formed using each resin solution. EB sensitivity, resolution, roughness value, EUV sensitivity, and solid film exposure defects were evaluated using the same methods as those used to evaluate resin composition (PA1). The results are shown in the table below.

[0344]

[0345] [Resin Composition Evaluation 2] Resin solutions were prepared in the same manner as in Resin Composition Evaluation 1 using Resin Composition (PA1), except that Resin Composition (PA1) was replaced with Resin Compositions (PB2) to (PB28c), and photoresist layers were formed using each resin solution. The EB sensitivity, resolution, roughness value, EUV sensitivity, and solid film exposure defects were evaluated using the same methods as those used to evaluate Resin Composition (PA1). The results are shown in the table below.

[0346] From the above results, it was found that there is no difference in performance as a resist material between resin compositions (PA1) to (PA28c) and resin compositions (PB1) to (PB28c). From the above, it was found that resin compositions (PB1) to (PB28c) can maintain their performance as a resist material even when stored for a long period of time, and have excellent long-term storage properties.

Claims

1. A composition comprising a compound A represented by the following formula (1) and a compound B represented by the following formula (B1) or formula (BP0-1). (In the formula, R １ is a hydrogen atom, a methyl group or a halogen atom; R ２ , R ３ are each independently a hydrogen atom, a linear organic group having 1 to 20 carbon atoms, a branched organic group having 3 to 20 carbon atoms, or a cyclic organic group having 3 to 20 carbon atoms; A is an organic group having 1 to 30 carbon atoms which may have a protecting group; I is an iodine atom; １ is an integer of 0 or 1; ２ is an integer from 1 to 20. (Wherein, B is a group containing at least one cyclic structure which may have a protecting group, I is an iodine atom, and R ０ is a monovalent functional group having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, R ０ Q is a single bond, a divalent group which may have a substituent, a group containing an alkylene group, a phenylene group, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphoric acid group, -O-CH ２ -, or a group represented by the following formula (B1L), m' is an integer of 0 to 9, n' is an integer of 1 to 19, and n ２ and b is an integer from 1 to 4. (In the formula, R ２ , R ３ is the same as in formula (1); X １ is a divalent group which may have a substituent and which contains an alkylene group, a phenylene group, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group; and n1a is an integer of 0 or 1. (In the formula, B, I, R ０ , m', and n' are defined the same as in formula (B1).

2. The composition according to claim 1, wherein compound B is a compound represented by the following formula (B2): (Wherein, Rx is a hydroxy group or a protecting group; B, I, R ０ , Q has the same meaning as in formula (B1); R ２ , R ３ is the same as in formula (1), R ４ is a protecting group, n １１ is an integer of 0 or 1; ２１ is an integer from 1 to 20; ３１ is an integer from 0 to 19; ４１ is an integer from 0 to 9.

3. The composition according to claim 1, wherein the cyclic structure of B in formula (B1) is benzene, naphthalene, anthracene, pyrene, or a heteroaromatic ring, each of which may have a substituent.

4. The composition according to claim 1, wherein the cyclic structure for B in formula (B1) is a polycyclic alicyclic ring which may have a substituent.

5. The composition according to claim 1, wherein the compound A is a compound represented by the following formula (1'): (In the formula, A, I, R １ , R ２ , R ３ , n １ , n ２ is the same as in formula (1), R ４ is a protecting group, n ３ is between 0 and 19.) 6. The composition according to claim 1, wherein the compound A is a compound represented by the following formula (1″): (In the formula, A, I, R １ , R ２ , R ３ , n １ , n ２ is the same as in formula (1), and R ０ has the same meaning as in formula (B1); R ４ is a protecting group, n ３ is 0 to 19, ４１ is between 0 and 9.) 7. The composition according to claim 1, wherein the organic group for A in formula (1) is benzene, naphthalene, anthracene, pyrene, or a heteroaromatic ring, each of which may have a substituent.

8. The composition according to claim 1, wherein the organic group for A in formula (1) is a polycyclic alicyclic ring which may have a substituent.

9. The composition according to claim 1, wherein the content of said compound B is 10 ppm to 50,000 ppm relative to the total amount of said compound A represented by said formula (1).

10. A resin composition made from the composition according to claim 1, comprising a polymer having a repeating unit represented by the following formula (C1): (In the formula, R １ is a hydrogen atom, a methyl group or a halogen atom; R ２ , R ３ are each independently a hydrogen atom, a linear organic group having 1 to 20 carbon atoms, a branched organic group having 3 to 20 carbon atoms, or a cyclic organic group having 3 to 20 carbon atoms; A is an organic group having 1 to 30 carbon atoms which may have a protecting group; I is an iodine atom; １ is an integer of 0 or 1; ２ is an integer from 1 to 20, and the symbol * represents the bonding point with the adjacent repeating unit.

11. A film-forming composition comprising the composition according to claim 1 or the resin composition according to claim 10.

12. A film-forming composition for semiconductor lithography, comprising the film-forming composition according to claim 11.

13. A composition for forming a resist film for semiconductor lithography, comprising the film-forming composition according to claim 11.