TW202219088A - Polymer, resist composition containing said polymer, method for manufacturing member using same, pattern formation method, and method for forming reversal pattern - Google Patents

Abstract

Provided are: a polymer used in a resist composition which has high absorption efficiency and which is superior in the characteristics of sensitivity, resolution, and pattern performance, and whereby the effects of decreased sensitivity and worsening of pattern roughness that occur due to a decrease in energy application density are mitigated in patterning formed by particles and irradiation with electromagnetic waves or a particle beam having high photon energy; a resist composition containing the polymer; and a method for manufacturing a member using the polymer and the resist composition. The polymer includes: a unit A that has an onium salt structure and generates acid by irradiating a particle beam or an electromagnetic wave; and a unit B having a structure that bonds as a result of acid catalyst reaction. The unit A is indicated by formula (1). (In general formula (1), R1 is any one selected from the group consisting of a hydrogen atom, a linear, branched, or cyclic C1-6 alkyl group, and a linear, branched, or cyclic C1-6 alkenyl group. At least one hydrogen atom in an alkyl group or alkenyl group in R1 can be substituted with a substituent. L is any one selected from the group consisting of a direct bond, a carbonyl oxy group, a carbonyl amino group, a phenylene diyl group, a naphthalene diyl group, a phenylene diyl oxy group, a naphthalene diyl oxy group, a phenylene diyl carbonyl oxy group, a naphthalene diyl carbonyl oxy group, a phenylene diyl oxy carbonyl group, and a naphthalene diyl oxy carbonyl group. Sp is a direct bond, a linear, branched, or cyclic C1-6 alkylene group that may have a substituent, or a linear, branched, or cyclic C1-6 alkenylene group that may have a substituent. At least one methylene group among the Sp can be substituted by a divalent heteroatom-containing group. M+ represents a sulfonium ion or an iodonium ion. X- represents a monovalent anion having an organic group including at least one selected from the group consisting of a hydroxyl group and a sulfonyl group.).

Description

Polymer, resist composition containing the polymer, manufacturing method of parts using the resist composition, pattern forming method, and reverse pattern forming method

Several aspects of the present invention relate to polymers used in resist compositions. In addition, some aspects of the present invention relate to a resist composition containing the above-mentioned polymer, a method for producing a member using the resist composition, a method for forming a pattern, and a method for forming a reverse pattern.

In recent years, photolithography has been actively employed in the manufacture of display devices such as liquid crystal displays (LCDs) and organic EL displays (OLEDs) and formation of semiconductor elements using photoresists. Lights such as i-rays with a wavelength of 365 nm, h-rays (405 nm), and g-rays (436 nm) with longer wavelengths are widely used as active energy rays in the above-mentioned electronic components and electronic product packaging.

With the high integration of equipment, the requirements for the miniaturization of lithography technology are getting higher and higher. There are KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), extreme ultraviolet (EUV, wavelength of 13.5 nm) and short-wavelength light such as electron beam (EB) is used for exposure. Photolithography techniques using these short wavelengths of light, in particular, EUV or electron beams, have enabled single-pattern fabrication, so resist compositions exhibiting high sensitivity to EUV or electron beams will be increasingly required in the future.

With the shortening of the wavelength of the exposure light source, the resist composition is required to improve the lithography characteristics so as to have high sensitivity to the exposure light source and a resolution capable of reproducing the formation of fine-scale patterns. As a resist composition satisfying such a requirement, a chemically amplified resist using a photoacid generator is known (Patent Document 1). However, with conventional chemically amplified resists, it is difficult to sufficiently suppress the collapse of the resist pattern and the reduction in the line width roughness (LWR) of the line pattern as the resolution line width of the resist is reduced.

It is well known that in order to reduce the LWR of a resist and achieve high resolution, there is a method to reduce the diffusion of acid due to heat by using an acid generator with a bulky acid anion having a large molecular weight or an acid anion bound to a polymer . (Patent Documents 2 and 3)

In order to suppress the collapse of the resist pattern, it has been proposed to increase the crosslinking density of the negative-type chemically enhanced resist. However, there are cases where defects such as bridges are generated due to swelling during development, and it is very difficult to increase the crosslink density with high sensitivity while maintaining resolution and pattern performance. [Prior Art Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 9-90637 Patent Document 2: Japanese Patent Laid-Open No. 2011-53622 Patent Document 3: Japanese Patent Laid-Open No. 2010-276910

[The problem to be solved by the invention]

The subject of some aspects of the present invention is to provide a polymer for a resist composition that can significantly suppress acid diffusion and has excellent resolution and pattern characteristics, which is not only a polymer using particle beams or electromagnetic waves, especially In addition to the acid generated from the acid generator by irradiation with electron beams, EUV, or the like, reactions caused by irradiation with electron beams, EUV, or the like, which are simultaneously caused by the acid-catalyzed reaction, are directly utilized. The subject of some aspects of this invention is to provide the resist composition containing the said polymer, the manufacturing method of the member using this resist composition, the pattern formation method, and the formation method of an inversion pattern. [Scheme for problem solving]

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that by using a polymer containing a unit A having a specific onium salt structure and a unit B having a specific structure as a polymer of a resist composition, it is possible to obtain high Sensitivity and suppression of line width roughness (LWR), thus accomplishing several modes of the present invention, wherein the unit A has a monovalent organic group in the anion, the monovalent organic group has at least one selected from a hydroxyl group and a sulfonamide group . More specifically, the following conclusions were obtained by irradiating the resist composition containing the above-mentioned polymer with particle beams or electromagnetic waves. First, the above-mentioned unit A decomposes to generate a large polarity switch from ionic to non-ionic. At the same time, an intramolecular crosslinking reaction occurs between the acid generated by the decomposition of the unit A, the hydroxyl group of the unit B, and/or between the unit A and the unit B. When the anion of the onium salt structure of the above unit A is an anion having an organic group containing a hydroxyl group or a sulfonamide group, a part of the above anion is combined with the above unit B through an acid-catalyzed reaction from the hydroxyl group or sulfonamide group in the anion to enter the polymer. The acid that becomes the polymer anion. Therefore, the resist composition containing the above-mentioned polymer can suppress acid diffusion, has high sensitivity, and can suppress line width roughness (LWR).

One aspect of the present invention for solving the above-mentioned problems is a polymer comprising a unit A that generates an acid by irradiation with a particle beam or an electromagnetic wave, and a unit B having a structure bonded by an acid-catalyzed reaction, wherein the unit A is an anion. A specific onium salt structure having a monovalent organic group having at least one selected from a hydroxyl group and a sulfonamide group. In addition, the said unit A is represented by following General formula (1).

(1) [hua 1]

(1)

(In the above general formula (1), R ¹ is selected from a hydrogen atom; a linear, branched or cyclic alkyl group with 1 to 6 carbon atoms; and a linear, branched or cyclic carbon atom number Any one of the alkenyl groups of 1 to 6, at least one hydrogen atom in the above-mentioned alkyl group and the alkenyl group in this R ¹ can be replaced by a substituent, and L is selected from the group consisting of direct bonding, carbonyloxy, carbonylamino, phenylenediyl , any one of naphthalenediyl, phenylenedioxy, naphthalenedioxy, phenylenedicarbonyloxy, naphthalenedicarbonyloxy, phenylenedioxycarbonyl and naphthalenedioxycarbonyl, and Sp is a direct bond; A linear, branched or cyclic alkylene group having 1 to 6 carbon atoms; and a linear, branched or cyclic alkenylene group having 1 to 6 carbon atoms that may have a substituent In any of the above-mentioned Sp, at least one methylene group may be substituted by a divalent heteroatom-containing group, M ⁺ is a sulfonium ion or an iodide ion, X ^- is a monovalent anion having a monovalent organic group in the anion, and the monovalent organic The group has at least one selected from a hydroxyl group and a sulfonamide group.)

One embodiment of the present invention is a resist composition containing the above-mentioned polymer. In addition, one aspect of the present invention is a method for manufacturing a component, comprising the steps of: a resist film forming step of forming a resist film on a substrate using the above-mentioned resist composition; and exposing the above-mentioned resist film using a particle beam or an electron beam The photolithography step; the pattern forming step of developing the exposed resist film to obtain a photolithography resist pattern.

One aspect of the present invention is a pattern forming method, which includes the following steps: a resist film forming step of forming a resist film on a substrate using the resist composition; photolithography exposing the resist film using particle beams or electromagnetic waves step; a pattern forming step of developing the exposed resist film to obtain a photolithography resist pattern.

One aspect of the present invention is a method for forming an inversion pattern, which includes the following steps: a resist film forming step of forming a resist film on a substrate using the resist composition; and exposing the resist film using particle beams or electromagnetic waves lithography step; obtaining a pattern forming step of developing the lithography resist pattern on the exposed resist film; etching the obtained photolithography resist pattern by coating the composition for inversion pattern to cover at least the concave part of the lithography resist pattern The step of coating a film to expose the surface of the above-mentioned photolithography resist pattern; the step of removing the above-mentioned exposed part of the resist film on the surface of the resist pattern to obtain a reverse pattern. [Effect of invention]

When the polymer according to some aspects of the present invention is used as a resist composition, an acid is generated in addition to the polarity conversion caused by the decomposition from ionicity to nonionicity by irradiation with particle beams, electromagnetic waves, or the like. Due to the generation of the acid, an intramolecular crosslinking reaction occurs between the hydroxyl groups of the unit B and/or between the unit A and the unit B. In addition, the anion in the generated acid has at least one of a hydroxyl group and a sulfonamide group, and reacts with the unit B in the polymer to become an acid of the polymer anion. Therefore, by using the acid of the polymer anion, the intramolecular crosslinking reaction of the acid-diffused polymer can be suppressed even if the bulky anion is not used. Thus, when a pattern is formed using the polymer according to some aspects of the present invention, the characteristics such as sensitivity and line width roughness (LWR) are excellent.

In the present invention, "particle beam or electromagnetic wave" refers not only to electron beams and extreme ultraviolet rays, but also to ultraviolet rays and the like, but is preferably electron beams or extreme ultraviolet rays. In the present invention, "irradiation with particle beams or electromagnetic waves" means irradiating at least a part of the polymer with particle beams or electromagnetic waves. Active species are generated by exciting or ionizing a specific part of the polymer by irradiating a local part of the polymer with a particle beam or electromagnetic wave. The active species decomposes a part of the above-mentioned unit, or the active species attaches to the above-mentioned unit, and the active species causes at least any one of secondary reactions, such as desorption of hydrogen from the above-mentioned unit, to generate a free radical or an acid. Here, "active species" refers to radical cations, radicals, electrons, and the like. The present invention will be specifically described below, but the present invention is not limited thereto.

<1> Polymer A polymer of some embodiments of the present invention is a polymer comprising an acid-generating unit A having a specific onium salt structure, and a unit B having a structure bonded by an acid-catalyzed reaction.

The polymer containing the unit A and the unit B is irradiated with a particle beam or an electromagnetic wave to at least a part of the polymer, whereby an anion and a first radical are generated from the unit A by the reduction of the unit A. A part of the generated anion is synthesized as an acid by bonding with a proton. After the acid becomes a catalyst, a crosslinking reaction is caused by etherification or thioetherification by the reaction between the above-mentioned units B and/or between the above-mentioned units A and the above-mentioned units B. In addition, when a unit other than the above-mentioned unit B has at least one of a hydroxyl group and a sulfonamide group, at least one of the hydroxyl group and sulfonamide group of the unit and at least one of the hydroxyl group and sulfonamide group of the above-mentioned unit B and/or the above-mentioned unit A can also cause a cross-linking reaction. A part of the acid anion generated above or the anion of the unit A may be bonded to the unit B through the acid and at least one of the hydroxyl group and the sulfonamide group of the anion to form a polymer acid.

In addition, the first radical generated from the unit A forms a bond between the first radicals and/or the second radical generated when the polymer contains a radical-generating unit and the first radical, and the above-mentioned It is obtained by causing an intramolecular crosslinking reaction between the units A and/or between the units A and the units that generate radicals (for example, the units C described later). The above-mentioned polymer is excellent in LWR characteristics because at least one of the hydroxyl group and the sulfonamide group forming the anion from the above-mentioned acid is bonded to the above-mentioned unit B, since acid diffusion can be suppressed.

(Unit A) The above-mentioned unit A has a specific onium salt structure. Specifically, the onium salt structure is polarized by irradiating at least a part of the polymer with particle beams or electromagnetic waves, and the anion part of the onium salt preferably has an organic group including at least one of a hydroxyl group and a sulfonamide group. That is, the onium salt structure has at least one of a hydroxyl group and a sulfonamide group in the anion moiety, and an acid is generated by reduction of the onium salt is not particularly limited. Specifically, what is represented by the following general formula (1) is mentioned, for example. In the present invention, "polarity conversion" refers to directly or indirectly changing the polarity from ionic to nonionic by irradiation with particle beams or electromagnetic waves.

(1) [hua 2]

(1)

In the above general formula (1), M ⁺ is a sulfonium ion or an iodide ion, and X ⁻ is a monovalent anion having an organic group including at least one selected from a hydroxyl group and a sulfonamide group.

L is not particularly limited as long as it can bond the main chain constituting the polymer to the above-mentioned onium salt structure, and examples thereof include direct bonding, carbonyloxy, carbonylamino, phenylene, naphthalene, and Any of oxy, naphthalenedioxy, phenylenedicarbonyloxy, naphthalenedicarbonyloxy, phenylenedioxycarbonyl, and naphthalenedioxycarbonyl. L is preferably a carbonyloxy group or the like from the viewpoint of ease of synthesis.

Sp is not particularly limited as long as it can serve as a spacer between the above-mentioned L and the above-mentioned onium salt. For example, it may be a direct bond; a linear, branched or cyclic alkylene having 1 to 6 carbon atoms which may have a substituent and any of linear, branched or cyclic alkenylene groups having 1 to 6 carbon atoms which may have substituents, and at least one methylene group in the above Sp may be substituted by a divalent heteroatom-containing group.

As a C1-C6 linear alkylene group of Sp, a methylene group, an ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, etc. are mentioned. Examples of the branched alkylene group having 1 to 6 carbon atoms in Sp include isopropylene, isobutylene, tert-butylene, isopentylene, tert-pentylene, 2-ethylhexenyl, and the like. .

As a C1-C6 cyclic alkylene group of Sp, a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, etc. are mentioned. At least one methylene group in Sp may be substituted with a divalent heteroatom-containing group. The divalent heteroatom is selected from the group consisting of -O-, -CO-, -COO-, -OCO-, -O-CO-O-, -NHCO-, -CONH-, -NH-CO-O- , -O-CO-NH-, -NH-, -N(R ^Sp )-, -N(Ar ^Sp )-, -S-, -SO-, and SO ₂ ^- and other groups. Examples of RSp include linear, branched, or cyclic alkyl groups having 1 to 12 carbon atoms, and examples of Ar ^Sp include phenyl and naphthyl groups having 12 or less carbon atoms, and examples include aryl groups. In addition, the carbon number of the alkylene group of the said Sp does not include the carbon number of the substituent which Sp may have.

Examples of the substituent that Sp may have (hereinafter referred to as "the first substituent") include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a hydroxyl group; a linear or cyclic carbon number of 1 to 1 to The alkyl group of 12; at least one methylene group in place of the alkyl group is a skeleton containing a group selected from -O-, -CO-, -COO-, -OCO-, -O-CO-O-, -NHCO-, -CONH-, -NH-CO-O-, -O-CO-NH-, -NH-, -N(R ^Sp )-, -N(Ar ^Sp )-, -S-, -SO- and SO ₂ ^- a heteroatom containing radical alkyl; aryl; and heteroaryl and the like. Examples of the alkyl group containing the first substituent of Sp in the skeleton and the alkyl group of the heteroatom-containing group include the alkylene groups in which the above-mentioned Sp alkylene group is a monovalent group. As the aryl group of the first substituent of Sp, the same options as described above for Ar ^Sp can be mentioned. Examples of the heteroaryl group as the first substituent of Sp include groups having skeletons such as furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, and pyrazine. Sp may be directly bonded, but from the viewpoint of radical rebonding between units A and the viewpoint of crosslinking reaction between units B, it is preferably a spacer structure in which molecules are easily movable. Preferably, an alkylene group, an alkyleneoxy group, an alkylenecarbonyloxy group, etc. are mentioned.

R ¹ is selected from a hydrogen atom; a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; and any one of a linear, branched or cyclic alkenyl group having 1 to 6 carbon atoms , at least one hydrogen atom in the above-mentioned alkyl group and alkenyl group in R1 may be substituted by a substituent. As a substituent which R ¹ may have, the same options as those of the above-mentioned first substituent can be exemplified.

Examples of the straight-chain alkyl group having 1 to 6 carbon atoms in R ¹ include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and the like. Examples of the branched alkyl group having 1 to 6 carbon atoms in R ¹ include isopropyl, isobutyl, tert-butyl, isopentyl, tert-amyl, 2-ethylhexyl and the like. Examples of the cyclic alkyl group having 1 to 6 carbon atoms in R ¹ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like.

Examples of the straight-chain, branched-chain or cyclic alkenyl group having 1 to 6 carbon atoms for R ¹ include at least one of the carbon-carbon single bonds of the straight-chain alkyl group, branched-chain alkyl group, and cyclic alkyl group shown above. One is substituted by a carbon-carbon double bond. In addition, fluorinated alkyl groups and fluorinated alkenyl groups in which at least one hydrogen atom of the above-mentioned alkyl group and alkenyl group of R ¹ may be substituted by a fluorine atom. All hydrogen atoms may be substituted with the above-mentioned first substituent. As the fluorinated alkyl group, trifluoromethyl and the like are preferable.

Preferred examples of the unit A include those in the formula (1) where R ¹ is a hydrogen atom or a straight-chain alkyl group, and L is a carbonyloxy group, a carbonylamino group, or a phenylene group. In addition, from the viewpoint of LWR, it is preferable that L is a carbonyloxy group or a carbonylamino group, Sp is a direct bond, R ¹ is a methyl group, and the methyl group has 1 to 4 carbon atoms in the first substituent. A unit of at least any one of an alkyl group, a halogen atom and an aryl group. As R ¹ having the above-mentioned first substituent, ethyl group, isopropyl group, butyl group, halogenated methyl group (fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, etc.), benzyl group, and the like are particularly preferable.

Examples of M ⁺ include a sulfur cation or an iodine cation having a bonding hand bonded to Sp, and are specifically shown in the following general formulae (a1) and (a2).

(a1)               (a2) [hua 3]

(a1) (a2)

In the above general formula, R ^6a is selected from a straight-chain, branched or cyclic alkylene group with 1 to 6 carbon atoms that may have a substituent; a straight-chain, branched or cyclic carbon atom that may have a substituent Alkenylene group with 1 to 6 atoms; arylene group with 6 to 14 carbon atoms which may have substituents; heteroarylene groups with 4 to 12 carbon atoms which may have substituents; . The linear, branched or cyclic alkylene group of R ^6a includes the same options as the alkylene group of Sp above. The linear, branched or cyclic alkenylene group of R ^6a includes the same options as the alkenylene group of Sp above.

The arylene group having 6 to 14 carbon atoms in R ^6a includes a phenylene group, a naphthylene group, and the like. Examples of the heteroarylene group having 4 to 12 carbon atoms in R ^6a include furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, indole, purine, quinoline, isoquinoline, chromene, Thianthrene, dibenzothiophene, phenothiazine, phenoxazine, xanthene, acridine, phenazine, carbazole and other skeleton divalent groups, etc. The alkylene group, alkenyl group, aryl group and heteroaryl group of R ^6b include the above-mentioned alkylene group, alkenylene group, arylene group and heteroarylene group of R ^6a , which are monovalent.

Examples of the substituents of R ^6a and R ^6b include the same substituents as the first substituents which the above-mentioned Sp may have. In the above formula (a1), any two of R ^6a and 2 R ^6b can be directly or via a single bond selected from oxygen atoms, sulfur atoms, divalent nitrogen atom-containing groups and any one of methylene groups, and These bonded sulfur atoms form a ring structure. The above-mentioned divalent nitrogen atom-containing group includes those containing a nitrogen atom in the above-mentioned divalent heteroatom-containing group, and specifically, -NHCO-, -CONH-, -NH-CO-O-, -O-CO-NH- , -NH-, -N(R ^Sp )-, and N(Ar ^Sp )-, etc.

As a sulfide cation of M ⁺ , for example, it has the structure shown below, and has the bonding hand which couple|bonded with the said Sp at arbitrary positions. In addition, the compound shown below may have the same substituent as the 1st substituent at the site|part corresponding to the said R ^6a and R ^6b .

[hua 4]

X ^- is a monovalent anion having an organic group including at least one of a hydroxyl group and a sulfonamide group. Preferably, the hydroxyl group is derived from any one selected from the group consisting of primary, secondary, and tertiary alcohols, and the sulfonamide group is derived from any one selected from the group consisting of primary thiol, secondary thiol, and tertiary thiol. From the viewpoint of the space where the above-mentioned hydroxyl group is bonded to the above-mentioned unit B, it is preferably derived from any one selected from the group consisting of a primary alcohol, a secondary alcohol, a primary thiol, and a secondary thiol. From the viewpoint of reactivity with the unit B via an acid catalyst, it is preferable that the above-mentioned hydroxyl group is not a phenolic hydroxyl group.

X ^- is preferably selected from the group consisting of an alkyl sulfate anion having at least one hydroxyl group and a sulfonamide group; an aryl sulfate anion having at least one hydroxyl group and a sulfonamide group; an alkylsulfonate having at least one hydroxyl group and a sulfonamide group anions; aryl sulfonate anions with at least one hydroxyl and sulfonamido groups; alkyl carboxylate anions with at least one hydroxyl and sulfonamido groups; aryl carboxylate anions with at least one hydroxyl and sulfonamido groups; Dialkylsulfonimide anions with at least one hydroxyl group and sulfonamido group; and trialkylsulfonic acid methyl ester anions with at least one hydroxyl group and sulfonamido group; tetraphenylboronic acid with at least one hydroxyl group and sulfonamido group any of the salt anions.

In addition, at least one of the hydrogen atoms ^of the alkyl group and the aryl group in X- may be substituted by a fluorine atom and/or an iodine atom, and from the viewpoint of the reactivity of bonding with the unit B described above, a fluorine atom and an iodine atom are preferred. Replace less. X ^- is more preferably either an alkylsulfonate anion having at least one hydroxyl group and a sulfonamide group, or an arylsulfonate anion having at least one hydroxyl group and a sulfonamide group. In addition, at least one hydrogen atom which the alkyl group of the said alkylsulfonate anion and the aryl group of the said arylsulfonate anion have may be substituted by a fluorine atom.

The number of carbon atoms of the alkyl sulfate anion having at least one of the above-mentioned hydroxyl groups is preferably 1 to 12. The number of carbon atoms of the alkyl sulfate anion having at least one sulfonamide group is preferably 1 to 12. The alkyl sulfate anion can have multiple hydroxyl and sulfonamide groups.

The number of carbon atoms of the aryl sulfate anion having at least one hydroxyl group is preferably 4 to 12. The number of carbon atoms of the aryl sulfate anion having at least one sulfonamide group is preferably 4 to 12. The aryl sulfate anion can have multiple hydroxyl and sulfonamide groups.

It is preferable that the number of carbon atoms of the alkylsulfonate anion which has at least one said hydroxyl group is 1-12. The number of carbon atoms of the alkylsulfonate anion having at least one sulfonamide group is preferably 1 to 12. The alkyl sulfonate anion can have multiple hydroxyl and sulfonamide groups.

The number of carbon atoms of the arylsulfonate anion having at least one hydroxyl group is preferably 4 to 12. The number of carbon atoms of the arylsulfonate anion having at least one sulfonamide group is preferably 4 to 12. The arylsulfonate anion may have multiple hydroxyl and sulfonamide groups.

The number of carbon atoms of the alkylcarboxylate anion having at least one of the above-mentioned hydroxyl groups is preferably 2 to 12. The number of carbon atoms of the alkylcarboxylate anion having at least one sulfonamide group is preferably 2 to 12. The alkylcarboxylate anion may have multiple hydroxyl and sulfonamide groups.

The number of carbon atoms of the arylcarboxylate anion having at least one hydroxyl group is preferably 5 to 12. The number of carbon atoms of the arylcarboxylate anion having at least one sulfonamide group is preferably 5 to 12. The arylcarboxylate anion may have multiple hydroxyl and sulfonamide groups.

The number of carbon atoms of the dialkylsulfoimide anion having at least one of the above-mentioned hydroxyl groups is preferably 1 to 12. The number of carbon atoms of the dialkylsulfoimide anion having at least one sulfonamide group is preferably 1 to 12. The dialkylsulfonimide anion may have multiple hydroxyl groups and sulfonamide groups.

The number of carbon atoms of the methyl trialkylsulfonate anion having at least one of the above-mentioned hydroxyl groups is preferably 1 to 12. The number of carbon atoms of the methyl trialkylsulfonate anion having at least one sulfonamide group is preferably 1 to 12. The methyl trialkylsulfonate anion may have a plurality of hydroxyl groups and sulfonamide groups.

The number of carbon atoms of the tetraphenyl borate anion having at least one of the above-mentioned hydroxyl groups is preferably 25 to 30. The number of carbon atoms of the tetraphenylborate anion having at least one sulfonamide group is preferably 25 to 30. The tetraphenylborate anion can have multiple hydroxyl and sulfonamide groups.

As said X ^- , the following are mentioned, for example.

[hua 5]

The above-mentioned unit A is preferably a unit represented by the following general formula (3).

(3) [hua 6]

(3)

In the above general formula (IV), L, Sp and X ^- are respectively the same as L, Sp and X ^- in the above general formula (1), and R ^6a and R ^6b are respectively the same as R ^6a and R in the above general formula (a1) ^6b .

Further, the polymer of one embodiment of the present invention preferably has a unit A in which M ⁺ X ^- in the above general formula (1) is any onium represented by the following general formula (11) or the following general formula (12) salt structure. When the polymer having this structure is used in a resist composition, it is preferable to irradiate the above-mentioned particle beam or electromagnetic wave (hereinafter also referred to as "first active energy ray") and then to expose a second active energy ray having a lower energy than the above-mentioned first active energy ray. Active energy line. It is preferable that the said 2nd active energy is an ultraviolet-ray, a visible light, etc.. The polymer containing the unit A and the unit B is used as a polymer of the resist composition, and the onium salt structure of the unit A is decomposed by irradiating the resist composition having the above-mentioned polymer with the above-mentioned first active energy ray. An acid is generated, wherein the unit A has a specific onium salt structure having an acetal site or a thioacetal site (hereinafter, "acetal site or thioacetal site" is also referred to as "(thio)acetal site"), and unit B Has a structure that is bonded by an acid-catalyzed reaction. When the onium salt structure of the above-mentioned unit A in the above-mentioned composition of the above-mentioned first active energy ray is irradiated with this acid as a catalyst, when the onium salt structure of the above-mentioned unit A has a (sulfur) acetal moiety, the structure is changed by the acid to convert it into the above-mentioned second active energy ray. Absorbed ketone derivatives. By exposing the above-mentioned second active energy ray to the above-mentioned composition produced from the above-mentioned ketone derivative, an acid is efficiently generated, which is called high sensitivity.

In the unit A of the polymer of one embodiment of the present invention, by having a specific structure between the onium salts of the general formulae (11) and (12), the (thio)acetal moiety, and the dibenzothiophene skeleton, it is possible to improve the The decomposition efficiency of the said 1st active energy ray improves, and the said 2nd active energy ray irradiation absorption after the said 1st active energy ray irradiation is high. Further, when the onium salt structure of the unit A of the polymer of one embodiment of the present invention is an onium salt structure represented by the general formulae (11) and (12), the unit A does not have the second active energy ray such as ultraviolet rays or visible light. Significant absorption. On the other hand, the acid generated by the above-mentioned first active energy ray deprotects the (thio)acetal site of the above-mentioned onium salt structure and converts it into a ketone derivative without impairing the above-mentioned onium salt structure as a photoacid generator. Function. The ketone derivative has a dibenzothiophene structure having a condensed ring structure so that the conjugation length becomes longer, and the absorption wavelength tends to be absorbed by the second active energy ray at a longer wavelength. Since the ketone derivative generates an exposed portion in the resist film to which the first active energy ray is irradiated, the amount of acid generation can be increased in the exposed portion of the first active energy ray by further irradiating the second active energy. In addition, in this invention, it is preferable that the said 2nd active energy ray is an ultraviolet-ray, a visible light, etc. which have a wavelength of 365 nm or more. The second active energy ray is preferably 420 nm or less. In addition, the first active energy ray is preferably higher in energy than the second active energy ray, and is not particularly limited as long as active species such as acid can be generated from the onium salt of the unit A, for example, KrF excimer laser, ArF excimer laser radiation, electron beam or extreme ultraviolet (EUV).

[化8]

[hua 7]

[hua 8]

In the above formulas (11) and (12), the above R ¹⁴ are respectively selected from alkyl, hydroxyl, mercapto, alkoxy, aryloxycarbonyl, heteroaryloxycarbonyl, arylsulfanylcarbonyl, heteroarylthio Alkylcarbonyl, arylsulfonamido, heteroarylsulfonamido, alkylsulfonamido, aryl, heteroaryl, aryloxy, heteroaryloxy, (poly)alkyleneoxy, alkylamino and dialkylamino any of the . R ¹⁷ and R ¹⁸ are respectively selected from alkyl, hydroxyl, mercapto, alkoxy, alkylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, aryl sulfanylcarbonyl, heteroarylsulfanylcarbonyl, arylsulfonamido, heteroarylsulfonamido, alkylsulfonamido, aryl, heteroaryl, aryloxy, heteroaryloxy, alkylsulfinyl sulfinyl, arylsulfinyl, heteroarylsulfinyl, alkylsulfonyl, arylsulfonyl, heteroarylsulfonyl, arylsulfonyl, heteroarylsulfonyl, (poly)alkylene Any of an oxy group, an alkylamino group, a dialkylamino group, a nitro group and a halogen atom. When the above-mentioned R ¹⁴ , R ¹⁷ and R ¹⁸ have carbon atoms, the number of carbon atoms is 1 to 12, and when the above-mentioned R ¹⁴ , R ¹⁷ and R ¹⁸ have a hydrogen atom, the hydrogen atom may be a substituent (hereinafter also referred to as "" The second substituent") is substituted.

The alkyl group in R ¹⁴ , R ¹⁷ and R ¹⁸ may be straight chain, branched chain or cyclic, and specifically, the same alkyl group as the alkyl group of Re of the second substituent described below can be mentioned. In addition, the alkyl moiety such as the alkoxy group, alkylcarbonyl group, alkoxycarbonyl group, etc. in R ¹⁴ , R ¹⁷ and R ¹⁸ may be the same as the alkyl group in R 1 . The aryl group and the heteroaryl group of R ¹⁴ , R ¹⁷ and R ¹⁸ are the same as those of the aryl group and the heteroaryl group of R ¹⁹ . The aryl moieties of the above-mentioned arylcarbonyl group and aryloxycarbonyl group in R ¹⁷ and R ¹⁸ are the same as those in the aryl group in R ¹⁹ . The heteroaryl moieties of the above-mentioned heteroarylcarbonyl group, heteroaryloxycarbonyl group, etc. in R ¹⁷ and R ¹⁸ are the same as those of the heteroaryl group in R ¹ . In addition, from the viewpoint of synthesis, R ¹⁷ and R ¹⁸ are preferably substituents that do not have heteroaryl moieties such as the above-mentioned heteroarylcarbonyl group and heteroaryloxycarbonyl group. In addition, when there are two or more R ¹⁴ in the above-mentioned formulas (11) and (12), two of R ¹⁴ may be connected to each other to form a ring structure.

As the (poly)alkyleneoxy group in R ¹⁴ , R ¹⁷ and R ¹⁸ , a polyoxyethylene group, a polypropylene group, and the like can be mentioned. As a halogen atom in ^R17 and ^R18 , a fluorine atom, a chlorine atom, an iodine atom, etc. are mentioned.

When R ¹⁴ , R ¹⁷ and R ¹⁸ have carbon atoms, the number of carbon atoms is preferably 1 to 12, and these may have a second substituent. In addition, the carbon-carbon single bonds in the alkyl groups of R ² , R ³ and R ⁴ may be replaced by carbon-carbon double bonds. Examples of the second substituent that R ¹⁴ , R ¹⁷ and R ¹⁸ may have include a hydroxyl group, a cyano group, a mercapto group, a carboxyl group, an alkyl group (-Re), an alkoxy group (-OR ^e ), an acyl group (-COR ^e ) ), alkoxycarbonyl (-COOR ^e ), aryl (-Ar), aryloxy (-OAr), amino, alkylamino (-NHR ^e ), dialkylamino (-N(R ^e ) ₂ ), Arylamino (-NHAr), diarylamino (-N(Ar) ₂ ), N-alkyl N-arylamino (-NR ^e Ar) phosphino, silyl, halogen atom, trialkylmethyl Silyl group (-Si-(R ^e ) ₃ ), at least one silyl group substituted with Ar in the alkyl group of the trialkylsilyl group, alkylsulfonamido (-SR ^e ), and arylsulfonamido ( -SAr), etc., but not limited thereto. ^Re and Ar will be described below.

The above-mentioned Re in the above-mentioned second substituent is preferably an alkyl group having 1 or more carbon atoms. In addition, the number of carbon atoms is more preferably 20 or less. As specific examples of the alkyl group having 1 or more carbon atoms, for example, a straight chain such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-n-hexyl group, n-octyl group, and n-decyl group is preferably mentioned. Alkyl; branched alkyl groups such as isopropyl, isobutyl, tert-butyl, isopentyl, tert-amyl, 2-ethylhexyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, Alicyclic alkyl groups such as adamantan-1-yl, adamantan-2-yl, norbornan-1-yl and norbornan-2-yl; one hydrogen of these groups is replaced by a trimethylsilyl, Silyl-substituted alkyl groups substituted with trialkylsilyl groups such as triethylsilyl and dimethylethylsilyl; at least one hydrogen atom of these groups is substituted with a cyano group or a fluorine group Alkyl and so on. The carbon-carbon single bond in the above-mentioned alkyl group may be replaced by a carbon-carbon double bond.

Ar in the above-mentioned second substituent is preferably an aryl group or a heteroaryl group. The heteroaryl group is an aryl group containing one or more heteroatoms in the ring structure. Preferable examples of the above-mentioned Ar include a phenyl group, a biphenyl group, a triphenyl group, a tetraphenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a cyclopentadienyl group, an indenyl group, and an indazo group. (indacenyl), acenaphthyl (acenaphthyl), fluorenyl, heptavirenyl, naphthyl, pyrenyl, oxalyl, tetraphenyl, furyl, thienyl, pyranyl, sulfonylpyranyl , pyrrolyl, imidazolyl, oxazolyl, thiazolyl, pyrazolyl, pyridyl, isobenzofuranyl, benzofuranyl, isochromenyl, chromenyl, indolyl, isoindolyl, benzene Groups having 20 or less carbon atoms, such as an imidazolyl group, a xanthene group, an aquadinyl group, and a carbazolyl group.

When R ¹⁴ , R ¹⁷ and R ¹⁸ have the second substituent, the number of carbon atoms of R ¹⁴ , R ¹⁷ and R ¹⁸ is preferably 1 to 12, including the number of carbon atoms of the second substituent.

It is preferable that the onium salt structure concerning the polymer which concerns on one Embodiment of this invention has at least 1 piece of R ^<14> . In addition, at least one R ¹⁴ is preferably hydroxy or alkoxy. In addition, R ¹⁴ is preferably an ortho position or a para position with respect to the bonding position of the (thio)acetal moiety. When R ¹⁴ having a hydroxyl group or an alkoxy group in the ortho or para position, which is an onium salt structure, becomes a ketone derivative, the absorption of the second active energy ray tends to increase. In the case of a hydroxyl group in particular, since the affinity with respect to an alkaline developer improves, and the solubility of an onium salt during image development improves, it is more preferable. In general, when the onium salt cation structure space is enlarged by providing a substituent to the cation of the onium salt structure, the hydrophobicity is improved and the dissolution inhibiting effect is produced at the time of development. Therefore, it is not necessary to have a hydrophobic substituent which tends to have a low affinity for an alkaline developer, and a configuration in which the absorption wavelength of the ketone derivative after the deprotection of the (thio)acetal moiety is increased and the absorption of the second active energy ray is increased is preferable. . In addition, since the substituent showing basicity inactivates the generated acid and suppresses the decomposition of the acid dissociable group, the configuration in which the substituent showing basicity is introduced is not preferable. As described above, the cation of the onium salt structure related to the polymer of one embodiment of the present invention preferably does not have a substituent including an aromatic ring or an alicyclic structure at R ¹⁴ , R ¹⁷ , and R ¹⁸ , and does not have a In addition, the molecular weight of the cationic moiety of the above-mentioned onium salt structure is preferably 500 or less. More preferably, the cation of the onium salt structure related to the polymer of one embodiment of the present invention does not have a basic group such as an amino group in R ¹⁷ and R ¹⁸ including R ¹⁴ . In the case of having a plurality of R ¹⁴ , it is preferable that at least one R ¹⁴ is a hydroxyl group or an alkoxy group, and the bonding position with respect to the (thio)acetal moiety is the ortho position or the para position. In addition, in the case of having a plurality of R ¹⁴ , as long as at least one R ¹⁴ is a hydroxyl group or an alkoxy group, the other R ⁴ may not be a hydroxyl group or an alkoxy group. From the viewpoint of increasing the absorption wavelength of the ketone derivative derived from the acid to a longer wavelength, a substituent which donates an electron to the aromatic ring to which two or more R ¹⁴ are bonded is more preferable. More preferably, it has a hydroxyl group or an alkoxy group as R ¹⁴ at two or more positions of the ortho-position or the para-position with respect to the bonding position of the (thio)acetal site.

R ¹⁹ is a linear, branched or cyclic alkyl group with 1 to 12 carbon atoms that may have a substituent; a linear, branched or cyclic alkyl group with 1 to 12 carbon atoms that may have a substituent Any of an alkenyl group; an optionally substituted aryl group having 6 to 14 carbon atoms; and, an optionally substituted heteroaryl group having 4 to 12 carbon atoms.

Specific examples of the straight-chain, branched-chain or cyclic alkyl group having 1 to 12 carbon atoms in R ¹⁹ include methyl, ethyl, n-propyl, n-butyl, isopropyl, Alkanes such as tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantan-1-yl, adamantan-2-yl, norbornan-1-yl and norbornan-2-yl Base et al.

In the alkyl group of R ¹⁹ , at least one methylene group may be substituted with a divalent heteroatom-containing group. The divalent heteroatom-containing group is selected from -O-, -CO-, -COO-, -OCO-, -O-CO-O-, -NHCO-, -CONH-, -NH-CO-O-, One of -O-CO-NH-, -NH-, -N(R ^e )-, -N(Ar)-, -S-, -SO- and -SO ₂ -. Among these, it is preferable that the sulfur atom (S ⁺ ) of the perium group is not directly bonded to the heteroatom-containing group and is bonded to the above-mentioned divalent hydrocarbon group. ^Re and Ar will be described below. Examples of the alkenyl group for R ¹⁹ include groups in which at least one carbon-carbon single bond of the above-mentioned alkyl group is substituted with a carbon-carbon double bond.

Specific examples of the optionally substituted aryl group having 6 to 14 carbon atoms for R ¹⁹ include a monocyclic aromatic hydrocarbon group; Hydrocarbons etc. These aryl groups may have substituents. As said monocyclic aromatic hydrocarbon group, the group which has a skeleton, such as benzene, is mentioned. As said condensed polycyclic aromatic hydrocarbon group, the group which has a skeleton, such as indene, naphthalene, azulene, anthracene, and a phenanthrene, is mentioned.

Examples of the heteroaryl group having 4 to 12 carbon atoms which may have a substituent in R ¹⁹ include those containing at least one selected from the group consisting of oxygen atoms, nitrogen atoms and sulfur atoms in the skeleton in place of at least one carbon of the above-mentioned aryl group. group of atoms.

Examples of the above-mentioned heteroaryl group include a monocyclic aromatic heterocyclic group; and a condensed polycyclic aromatic group obtained by condensing at least one of the monocyclic aromatic heterocyclic groups with the above-mentioned aromatic hydrocarbon group, aliphatic heterocyclic group, or the like Heterocyclic groups, etc. These aromatic heterocyclic groups may have a substituent. Examples of the monocyclic aromatic heterocyclic group include groups having skeletons such as furan, pyrrole, imidazole, pyran, pyridine, pyrimidine, and pyrazine.

Examples of fused polycyclic aromatic heterocyclic groups include groups having skeletons such as indole, purine, quinoline, isoquinoline, benzopyran, phenoxazine, xanthene, acridine, phenazine, and carbazole. group.

The substituents (hereinafter also referred to as "third substituents") in R ¹⁹ can be exemplified by the same ones as the above-mentioned second substituents.

When the alkyl group of R ¹⁹ or the like has the above-mentioned third substituent and the onium salt is a low molecular compound, the number of carbon atoms of R ¹⁹ is preferably 1 to 20, including the number of carbon atoms of the third substituent.

Any of the above R ¹⁹ , the benzene ring to which the above R ² is bonded, and the benzene ring to which the above R ³ is bonded may be selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom-containing group, and a methylene group directly or via a single bond. Any of these bonded sulfur atoms form a ring structure. Examples of the "nitrogen atom-containing group" include nitrogen atom-containing groups such as aminodiyl (-NH-), alkylaminodiyl (-NR ^e- ), and arylaminodiyl (-NAr-). 2-valent group. ^Re and Ar are the same as ^Re and Ar of the above-mentioned third substituent.

As R ¹⁹ , an aryl group is preferable from the viewpoint of improving stability.

Any one of the benzene ring to which the above-mentioned R ¹⁹ , the above-mentioned R ¹⁸ is bound, and the benzene ring to which the above-mentioned R ¹⁷ is bound can be directly or via a single bond selected from the group consisting of oxygen atoms, sulfur atoms, nitrogen atom-containing groups and methylene groups. Either, with these bonded sulfur atoms form a ring structure.

When the above-mentioned R ¹⁴ , R ¹⁷ and R ¹⁸ have a methylene group, at least one of the methylene groups may be substituted with a divalent heteroatom-containing group. However, continuous linkage without heteroatoms such as -OO-, -SS- and OS- is preferred. Examples of R ¹⁴ , R ¹⁷ and R ¹⁸ in which the at least one methylene group may be substituted by a divalent heteroatom-containing group include 2-methoxyethoxy, 2-ethoxyethoxy, 2-(2 -Polyalkylene oxides such as methoxyethoxy)ethoxy, 2-(2-ethoxyethoxy)ethoxy, 2-methoxypropoxy and 3-methoxypropoxy polyalkylenethio groups such as 2-methylthioethylthio and 2-ethylthioethylthio; and polyalkylene groups such as 2-methylthioethoxy and 2-ethoxyethylthio oxythiol, etc. However, several aspects of the present invention are not limited thereto.

The above-mentioned R ¹⁵ and R ¹⁶ are respectively preferably a straight-chain, branched or cyclic alkyl group with 1 to 12 carbon atoms that may have a substituent; a straight-chain, branched or cyclic carbon number that may have a substituent group Alkenyl of 1 to 12; aryl of 6 to 14 carbon atoms that may have substituents and heteroaryl groups of 4 to 12 of carbon atoms that may have substituents, these are preferably selected from the same as each above-mentioned R ¹⁹ options. Examples of the substituents of R ¹⁵ and R ¹⁶ (hereinafter also referred to as "fourth substituents") include the same substituents as those of the second substituents described above. The above-mentioned R ¹⁵ and R ¹⁶ can form a ring structure by a single bond directly or through any one selected from an oxygen atom, a sulfur atom and a methylene group, and at least one methylene group in the above-mentioned R ¹⁵ and R ¹⁶ can be a divalent Heteroatom group substitution. From the viewpoint of synthesis, the above-mentioned R ¹⁵ and R ¹⁶ are preferably the same.

L ³ is selected from direct bond; linear, branched or cyclic alkylene group with 1 to 12 carbon atoms; alkenylene group with 2 to 12 carbon atoms; sulfinyl, sulfonyl and carbonyl any of the .

The hydrogen atom of any one of R ¹⁴ , R ¹⁸ , and R ¹⁹ is replaced by a bond with Sp in the above-mentioned general formula (1).

Y is an oxygen atom or a sulfur atom.

q is an integer of 0 to 4, f is an integer of 0 to 3, g is an integer of 1 to 5, j is an integer of 0 to 2, and k is an integer of 1 to 4. However, when any one of the above-mentioned R ¹⁹ , the benzene ring to which the above-mentioned R ¹⁸ is bound, and the above-mentioned benzene ring to which the above R ¹⁷ is bound forms a ring structure with the above-mentioned sulfur atom, in the general formula (11), q is 0 to 3 or j is 0~2, in the above general formula (12), q is 0~3 or j is 0~1. At least one of the benzene rings in the above-mentioned general formulae (11) and (12) may be a six-membered heteroaromatic ring having a heteroatom in the ring, and may be bonded to the above-mentioned general formulae (11) and (12). When the benzene ring of R14 is the above-mentioned heteroaromatic ring, k may be ^0-4 . When there are two or more R ¹⁴ in the above-mentioned general formulae (11) and (12), the two R ¹⁴ may be connected to each other to form a ring structure. X ^- is selected from the same options as X ^- of the above-mentioned general formula (1).

The onium salt structure contained in the unit A in the polymers of some embodiments of the present invention can be exemplified by those having the perionium cation shown below. The wavy line in the perionium cation shown below indicates a bonding site to Sp in the above formula (1), and when there are a plurality of wavy lines in the same structure, it is bonded to any one of the above-mentioned Sp. However, several aspects of the present invention are not limited thereto.

[Chemical 9]

The anion of the above-mentioned unit A is preferably an anion with high hydrophilicity from the viewpoint of improving the contrast in the formation of a photoresist pattern. Specifically, an alkyl sulfate anion, an aryl sulfate anion, an alkylsulfonate anion, an arylsulfonate anion, an alkylcarboxylate anion, an arylcarboxylate anion, etc. are mentioned. These anions have at least one hydroxyl group and a sulfonamide group

The polymer of one embodiment of the present invention may have two or more types of the above-mentioned units A in the above-mentioned polymer. For example, it is preferable to use one photoacid generator unit A (hereinafter also referred to as "unit A1") and the other as the photodegradable base unit A (hereinafter also referred to as "unit A2"). X ^- of the said photodegradable base unit A2 is preferably an alkylcarboxylate anion or an arylcarboxylate anion. It is preferable to use the said photodegradable alkali unit A2 in combination with the said photoacid generator unit A1. In addition, when the said polymer has the unit A2, it has the effect of reducing LWR, and it is effective when high resolution is required. Moreover, when the said polymer has 2 or more types of the said unit A, the unit which M ⁺ X ^- part is the same and the substituent such as R ¹ or L is different can be used.

It is preferable that the molar extinction coefficient at 365 nm of the onium salt related to the polymer of some aspects of the present invention is less than 1.0×10 ⁵ cm ² /mol, and more preferably less than 1.0×10 ⁴ cm ² /mol. In addition, the ketone derivative of the deprotected (thio)acetal moiety of the onium salt related to the polymer of some embodiments of the present invention preferably has a molar extinction coefficient at 365 nm of 1.0×10 ⁵ cm ² /mol or more, more preferably 1.0× 10 ⁶ cm ² /mol or more. The molar extinction coefficient at 365 nm of the above-mentioned ketone derivative is preferably 5 times or more, more preferably 10 times or more, and still more preferably 20 times or more. In order to obtain the above-mentioned properties, an onium salt represented by the above formula (11) or (12) can be used.

(Synthesis method of monomer for unit A) A method for synthesizing the perylene salt structure contained in the unit A of the polymer of one embodiment of the present invention will be described. The present invention is not limited to this.

In the case of a (meth)acrylate monomer in which the target perylene salt structure does not contain a (thio)acetal moiety, for example, the following synthesis methods can be mentioned. First, a Friedel-Crafts reaction is carried out between diarylidene with R ^6b group and benzene with hydroxyl group (R ^6a group) using Bronsted acid to obtain hydroxyaryl diarylidene . Next, using a basic catalyst and (meth)acryloyl chloride, the target pernium salt is obtained. In this case, even if the above-mentioned R ¹ , R ^6a and R ^6b are substituents not exemplified here, as long as they are within the ranges of the above-mentioned R ¹ , R ^6a and R ^6b , the same target perylene salt can be obtained.

[Chemical 10]

In the case where the target perylene salt structure does not contain an ethylene or isopropylene monomer having a (thio)acetal moiety, for example, the following synthesis methods can be mentioned. First, any use of diarylidene with R ^6b group and vinyl or Grignard reagent with isopropenyl group (R ^6a group) is made to react with the arylene body with R ^6b group to form a perylium salt structure. , using a salt with the corresponding anion to perform salt exchange to obtain the target perionium salt structure. In this case, even if the above-mentioned R ¹ , R ^6a and R ^6b are substituents not exemplified here, as long as they are within the ranges of the above-mentioned R ¹ , R ^6a and R ^6b , the same target perylene salt can be obtained.

[Chemical 11]

When the target perylene salt structure includes a (thio)acetal moiety, for example, the following synthesis methods can be mentioned. First, any of the dibenzothiophenes having R ¹⁷ groups and R ¹⁸ groups and benzyl chloride (i=1 in the following general formula) having R ¹⁴ groups were subjected to Friedel-Claat using Lewis acid. Futz reaction to obtain benzophenone derivatives. Next, after oxidizing the sulfide into sulfite, benzene having a hydroxyl group and Brinell's acid are subjected to a Friedel-Crafts reaction to form peronium, and the carbonyl group is acetalized using an acid catalyst and an alcohol (R ¹⁵ OH). Next, the target onium salt is obtained using a basic catalyst and (meth)acryloyl chloride. In this case, even if the above-mentioned R ¹⁴ , R ¹⁵ , R ¹⁷ and R ¹⁸ are substituents not exemplified here, as long as they are within the ranges of the above-mentioned R ¹⁴ , R ¹⁵ , R ¹⁷ and R ¹⁸ , the same target perylene salt can be obtained.

[Chemical 12]

When the target perylene salt structure includes a (thio)acetal moiety, for example, the following synthesis methods can be mentioned. First, a Friedel-Crafts reaction is carried out by using a Lewis acid to carry out a Friedel-Crafts reaction between a dibenzothiophene having an arbitrary R ¹⁷ group and a R ¹⁸ group and a benzyl chloride having an R ¹⁴ group (i=1 in the following general formula), A benzophenone derivative is obtained. Next, after oxidizing the sulfide into sulfite, benzene having a hydroxyl group and Brinell's acid are converted into peronium through a Friedel-Crafts reaction, and the carbonyl group is acetalized using an acid catalyst and an alcohol (R ¹⁵ OH). Next, using a Grignard reagent to form a perylium salt structure, salt exchange is performed with a salt having the corresponding anion to obtain the target perylium salt structure.

[Chemical 13]

(Unit B) The above-mentioned unit B is not particularly limited as long as it has a structure in which two molecules are bonded by an acid-catalyzed reaction. A unit to which the Sp group of the formula (1) is bonded. A compound in which at least any one of the compounds represented by the following general formula (I) or (II) is bonded to the * moiety of the following formula (2) at any position of the compound is contained in the polymer as the unit B. When the above-mentioned polymer contains the above-mentioned unit B, the sensitivity to particle beams or electromagnetic waves can be improved.

(I)

(II) [Chemical 14]

(I)

(II)

(2) [Chemical 15]

(2)

In the above formula (2), R ¹ , L and Sp are the same as the above general formula (1).

In the above general formula (I), R ² and R ³ are each independently selected from any one of a hydrogen atom; an electron donating group; and an electron withdrawing group. When at least one of R ² and R ³ is the above-mentioned electron donating group, acid reactivity can be improved, which is preferable. E is preferably any one selected from a direct bond; an oxygen atom; a sulfur atom; and a methylene group.

n ¹ is an integer of 0 or 1, n ⁴ and n ⁵ are an integer of 1 to 2, respectively, and n ⁴ +n ⁵ is 2 to 4. When n ⁴ is 1, n ² is an integer from 0 to 4, and when n ⁴ is 2, n ² is an integer from 0 to 6. When n ⁵ is 1, n ³ is an integer from 0 to 4, and when n ⁵ is 2, n ³ is an integer from 0 to 6. When n ² is 2 or more and R ² is an electron-donating group or an electron-withdrawing group, two R ² can be selected from the group consisting of oxygen atom, sulfur atom, divalent nitrogen atom-containing group and methylene group directly or through a single bond Either one of them forms a ring structure with each other. When n ³ is 2 or more and R ³ is an electron-donating group or an electron-withdrawing group, two R ³ can be selected from the group consisting of oxygen atom, sulfur atom, divalent nitrogen atom-containing group and methylene group directly or through a single bond Either one of them forms a ring structure with each other. The divalent nitrogen atom-containing group used to form the ring structure in the above formula (I) is the same as the divalent nitrogen atom-containing group in the above formula (a1).

In the above general formula (II), R ⁴ is each independently any one selected from a hydrogen atom; an electron donating group; and an electron withdrawing group. Preferably, at least one of R ⁴ is the electron donating group, thereby increasing acid reactivity. R ⁵ is any one selected from a hydrogen atom; an optionally substituted alkyl group; and an optionally substituted alkenyl group, and at least one methylene group in the above R ⁵ may be substituted with a divalent heteroatom-containing group. In addition, R ⁵ may form a ring structure together with the benzene ring to which the hydroxymethylene group having the R ⁵ is bonded.

Examples of the alkyl group for R ⁵ include linear, branched, or cyclic alkyl groups having 1 to 12 carbon atoms. Specifically, the same alkyl group as R ^6b can be mentioned. Examples of the substituent which R ⁵ has include the same substituents as the first substituent which the above-mentioned Sp has.

n ⁶ is an integer from 0 to 7, n ⁷ is 1 or 2, n ⁶ is an integer from 0 to 5 when n ⁷ is 1, and n ⁶ is an integer from 0 to 7 when n ⁷ is 2.

When n ⁶ is 2 or more and R ⁴ is an electron-donating group or an electron-withdrawing group, two R ⁴ can be selected from the group consisting of oxygen atom, sulfur atom, divalent nitrogen atom-containing group and methylene group directly or through a single bond Either one of them forms a ring structure with each other. As the divalent nitrogen atom-containing group forming the ring structure in the above formula (II), the same divalent nitrogen atom-containing groups as in the above formula (a1) can be exemplified.

Examples of electron donating groups for R ² , R ³ and R ⁴ include an alkyl group (-R ¹³ ) and an alkenyl group in which at least one carbon-carbon single bond of the alkyl group (-R ¹³ ) is substituted with a carbon-carbon double bond; And the alkoxy group (-OR ¹³ ), the alkylthio group (-SR ¹³ ), etc., which are bonded to the ortho-position or para-position of the aromatic ring to which the methine carbon to which the hydroxyl group is bonded is bonded.

The above R ¹³ is preferably an alkyl group having 1 or more carbon atoms. Specific examples of the alkyl group having 1 or more carbon atoms are preferably linear alkanes such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, and n-decyl. branched-chain alkyl groups such as isopropyl, isobutyl, tert-butyl, isopentyl, tert-amyl, 2-ethylhexyl, etc.; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, diamond cycloaliphatic alkyl groups such as alk-1-yl, adamantan-2-yl, norbornan-1-yl and norbornan-2-yl; one of these hydrogens consists of trimethylsilyl, triethyl Trialkylsilyl-substituted silyl-substituted alkyl groups such as silyl groups and dimethylethylsilyl groups; the above-mentioned alkyl groups are not directly bonded to the aromatic compounds possessed by the above-mentioned compounds (I) or (II) An alkyl group or the like in which at least one hydrogen atom contained in a carbon atom of the ring is substituted with a cyano group, a fluorine group, or the like. The above-mentioned R ¹³ preferably has 4 or less carbon atoms.

Examples of electron withdrawing groups for R ² , R ³ and R ⁴ include: -C(=O)R ^13a (R ^13a is an optionally substituted linear, branched or cyclic carbon number of 1 to 12 Alkyl.);-C(=O)R ^13b (R ^13b is an aryl group having 6 to 14 carbon atoms which may have a substituent.);-C(=O)OR ^13a ;-SO ₂ R ^13a ;- SO ₂ R ^13b ; nitro; -OR ^13a substituted at the meta position of nitroso, trifluoromethyl, hydroxyl; -OR ^13b substituted at the meta position of hydroxyl; -SR ^13a substituted at the meta position of hydroxyl; -SR ^13b substituted at the meta position of the hydroxyl group; and at least one of the carbon-carbon single bonds in the above -C(=O)R ^13a , -C(=O)OR ^13a , -SO ₂ R ^13a and SR ^13a is composed of carbon A carbon-carbon double bond-substituted group or a carbon-carbon triple bond-substituted group. As a substituent which R ^13a and R ^13b may have, the same options as the above-mentioned first substituent which Sp have above are exemplified.

Specific examples of the compound represented by the general formula (I) or (II) include the compounds shown below.

[Chemical 16]

One embodiment of the polymer of the present invention is a polymer in which any one of the compounds represented by the general formula (I) or (II) is a unit bonded to the * moiety of the above formula (2) at any position of the compound. B is contained in the polymer. In this case, the position of bonding to the * moiety of the above formula (2) is preferably any one of R ² , R ³ and R ⁴ . For example, in the case of the compound represented by the aforementioned general formula (I), it is preferable to have a bonding hand bonded to the * moiety of the aforementioned formula (2) instead of one H in R ² .

The above-mentioned unit B preferably includes a unit in which R ¹ in the above formula (2) is a hydrogen atom or a straight-chain alkyl group, an L carbonyloxy group, a carbonylamino group, or a phenylene group. In addition, from the viewpoint of LWR, it is preferable that L is a carbonyloxy group or a carbonylamino group, Sp is a direct bond, R ¹ is a methyl group, and the methyl group has 1 to 4 carbon atoms in the first substituent. At least any one or more units of an alkyl group, a halogen atom, and an aryl group. R ¹ having the above-mentioned first substituent is particularly preferably an ethyl group, an isopropyl group, a butyl group, a halogenated methyl group (fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, etc.), a benzyl group, and the like. The polymer of one aspect of the present invention may have two or more types of the above-mentioned unit B in the above-mentioned polymer.

(Unit C) The above-mentioned unit C is a unit having a radical generating structure containing at least one multiple bond selected from multiple bonds of carbon atoms and carbon atoms and multiple bonds of carbon atoms and heteroatoms, as long as at least in the polymerization The particle beam or electromagnetic wave is locally irradiated on the object to generate the second radical, and there is no particular limitation. An intramolecular crosslinking reaction can be induced between the unit A and the unit C by irradiating a particle beam, an electromagnetic wave, or the like. The multiple bonding in the above-mentioned unit C is not particularly limited as long as it can generate radical cations under the influence of particle beams or electromagnetic waves, and the radical cations can be decomposed into second radicals and cations, but they are not included in benzene-based aromatics. And it is preferable that it is at least any one of the bonds shown below. Benzene-based aromatics include aromatics having benzene skeletons such as naphthalene and azulene in addition to benzene. "Multiple bonds not contained in benzene-based aromatics" means multiple bonds not possessed by these aromatics.

[Chemical 17]

Specifically, the radical generating structure containing the above-mentioned multiple bonds has a unit selected from the group consisting of an alkylphenone skeleton, an acyl oxime skeleton, and a benzyl ketal. Having these skeletons may have optional substituents, and the unit having an alkylphenone skeleton includes an α-aminoacetophenone skeleton and the like. More specifically, the structure represented by at least any one of the following general formula (4) is preferable.

(4) [Chemical 18]

(4)

In the above general formula (4), R ¹ , L and Sp are selected from the same options as L and Sp in the above general formula (1), respectively. R ⁷ is each independently selected from a hydrogen atom; a hydroxyl group; -R ^a (R ^a is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent); -OR ^a ; and At least one of the carbon-carbon single bonds in this R ^a is substituted by a carbon-carbon double bond; and any one of -R ^b (R ^b is an aryl group with 6 to 14 carbon atoms that may have a substituent), 2 The above R ³ can form a ring structure by a single bond directly or via any one selected from the group consisting of an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group, and a methylene group. As R ^a , the same options as for the alkyl group of R ^13a can be mentioned. As R ^b , the same options as the aryl group of R ^13b can be mentioned.

As a substituent which Ra and Rb may have, the same options as the substituent which Sp have above can be mentioned. However, three of R ⁷ in the above formula (4) are preferably non-hydrogen atoms. In addition, in the above formula (4), at least one of the three R ⁷ is preferably OH. By having OH as the above-mentioned unit C, a crosslinking reaction between the unit B and the unit C can be induced.

R ⁸ is selected from-R ^a ; ^-Rb ; ^-ORa ; ^-SRa ; ^-ORb ; ^-SRb ;-OC(=O) ^Ra ;-OC(=O) ^Rb ;-C( -C(=O) ^ORb ;-OC(=O) ^ORa ;-OC(=O) ^ORb ;-NHC(=O) ^Ra ; ^-NRaC ( ⁼ O) R ^a ;-NHC(=O) ^Rb ;-NRbC(=O) ^Rb ; ^-NRaC (=O) ^Rb ; ^-NRbC (=O) ^Ra ;-N ^{( Ra} ) ₂ ;-N(R ^b ) ₂ ;-N(R ^a )(R ^b );-SO ₃ R ^a ;-SO ₃ R ^b ;-SO ₂ R ^a ;-SO ₂ R ^b ;the-R ^a A group in which at least one carbon-carbon single bond is substituted by a carbon-carbon double bond; and any of nitro groups. In the above formula (4), when m ¹ is 2 or more, two R ⁸ can form a ring structure by a single bond directly or through any one selected from an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group and a methylene group .

m ² is an integer from 1 to 3. When m ² is 1, m ¹ is an integer from 0 to 4. When m ² is 2, m ¹ is an integer from 0 to 6. When m ² is 3, m ¹ is an integer from 0 to 8. .

The above-mentioned unit C is preferably a unit in which R ¹ is a hydrogen atom or a straight-chain alkyl group, and L is a carbonyloxy group, a carbonylamino group, or a phenylene group in the above-mentioned formula (4). In addition, from the viewpoint of LWR, it is preferable that L is a carbonyloxy group or a carbonylamino group, Sp is a direct bond, R ¹ is a methyl group, and the methyl group has 1 to 4 carbon atoms in the first substituent. At least any one or more units of an alkyl group, a halogen atom, and an aryl group. R ¹ having the above-mentioned first substituent is particularly preferably an ethyl group, an isopropyl group, a butyl group, a halogenated methyl group (fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, etc.), a benzyl group, and the like. The polymer of one embodiment of the present invention may have two or more types of the above-mentioned units C in the above-mentioned polymer.

(Unit D) The polymer of one embodiment of the present invention preferably further contains a unit having an aryloxy group (hereinafter referred to as "unit D") in addition to the units A to C described above. The above-mentioned unit D is preferably a unit in which a phenol structure is bonded to the * part of the above-mentioned formula (2) at any position of the structure. The unit D is not particularly limited as long as it can improve the generation efficiency of the acid generated by the unit A. Specifically, for example, the units shown below are exemplified.

[Chemical 19]

Preferably, each of R ¹¹ in the above general formula is independently selected from any one of a hydrogen atom and an alkyl group. The alkyl group of R ¹¹ may have a substituent. Examples of the above-mentioned alkyl group include straight or branched chains having 1 to 5 carbon atoms such as methyl, ethyl, isopropyl, n-isopropyl, sec-butyl, tert-butyl, n-butyl, and pentyl. the alkyl group. As a substituent which the said alkyl group may have, a hydroxyl group, a sulfonyloxy group, an alkoxycarbonyl group, an alkoxycarbonyl group, a cyano group, a methoxy group, an ethoxy group, etc. are mentioned. The substituent which R ¹¹ may have is the same as the above-mentioned first substituent which the above-mentioned Sp has. In the above formula, when two or more R ¹¹ is not a hydrogen atom, the two R ¹¹ where the R ¹¹ is not a hydrogen atom can be selected from the group consisting of an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group and a methylene group directly or via a single bond. either form a ring structure. n ⁸ is 4.

Specifically, the unit D which consists of monomers, such as 4-hydroxyphenyl (meth)acrylate, is mentioned. When the said polymer contains the said unit D, the generation efficiency of an acid can be improved.

The above-mentioned unit D is preferably a unit in which R ¹ is a hydrogen atom or a straight-chain alkyl group, and L is a carbonyloxy group or a phenylene group in the above-mentioned formula (2). In addition, from the viewpoint of LWR, it is preferable that L is a carbonyloxy group or a carbonylamino group, Sp is a direct bond, R ¹ is a methyl group, and the methyl group has an alkane having 1 to 4 carbon atoms in the above-mentioned first substituent. At least any one or more units of a group, a halogen atom and an aryl group. R ¹ having the above-mentioned first substituent is particularly preferably an ethyl group, an isopropyl group, a butyl group, a halogenated methyl group (fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, etc.), a benzyl group, and the like. The polymer of one embodiment of the present invention may have two or more types of the above-mentioned units D in the above-mentioned polymer.

(Unit E) The polymer of one embodiment of the present invention preferably contains, in addition to the units A to D, an organometallic compound-containing unit E (hereinafter referred to as "unit E") having a metal atom selected from Sn, Sb, Ge, Bi, and Te. ”). The metal atom contained in the above-mentioned unit E is not particularly limited as long as it has a high absorption force for EUV or electron beam, and may be an atom of Groups 10 to 16 of the periodic table of elements other than the above-mentioned metal atom. The above-mentioned unit E is preferably an alkyl tin and an aryl tin, an alkyl antimony and an aryl antimony, an alkyl germanium and an aryl germanium, or an alkyl bismuth and an aryl bismuth structure. part of the unit. The secondary electron generation efficiency of the unit E by EUV irradiation is high, and the decomposition efficiency of the above-mentioned unit A and the unit B can be improved. The unit E is not particularly limited as long as it contains the above-mentioned metal atom having a high EUV absorption power, and specifically, the units shown below are exemplified.

[hua 20]

Preferably, each of R ^12a in the above general formula is independently selected from any one of a hydrogen atom and an alkyl group. The alkyl group of R ^12a may have a substituent. Examples of the above-mentioned alkyl group include straight or branched chains having 1 to 5 carbon atoms such as methyl, ethyl, isopropyl, n-isopropyl, sec-butyl, tert-butyl, n-butyl, and pentyl. the alkyl group. As a substituent which the said alkyl group may have, a hydroxyl group, a sulfonyloxy group, an alkoxycarbonyl group, an alkoxycarbonyl group, a cyano group, a methoxy group, an ethoxy group, etc. are mentioned. In the above formula, when two or more R ^12a are not hydrogen atoms, the two R ^12a that are not hydrogen atoms can be selected from the group consisting of oxygen atom, sulfur atom, divalent nitrogen atom-containing group and methylene group directly or ^via a single bond. either form a ring structure. In the above formula, two or more of R ^12b can form a ring structure directly or through any one selected from the group consisting of an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group, and a methylene group by a single bond. n ⁹ is an integer from 0 to 4.

In the above general formula, R ^12b is selected from a straight-chain, branched or cyclic alkyl group with 1 to 6 carbon atoms that can have a substituent; a straight-chain, branched or cyclic carbon atom that can have a substituent Any of an alkenyl group of 1 to 6; an aryl group of 6 to 14 carbon atoms that may have a substituent; a heteroaryl group of 4 to 12 carbon atoms that may have a substituent; and a direct bond. The straight-chain, branched or cyclic alkyl group for R ^12b includes the same options as the alkyl group for R ^2b described above. The straight-chain, branched or cyclic alkenyl group of R ^12b includes the same options as the alkenyl group of R ^2b described above.

The aryl group having 6 to 14 carbon atoms for R ^12b includes the same options as the aryl group for R ^2b described above. The heteroaryl group having 4 to 12 carbon atoms for R ^12b includes the same options as the heteroaryl group for R ^2b described above. Two or more R ^12a may form a ring structure directly or via any one selected from the group consisting of an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group, and a methylene group by a single bond. In addition, any two of the three R ^12b may be bonded to each other and form a ring structure together with these bonded metal atoms. As a substituent which R ^12a and R ^12b may have, the same options as the above-mentioned first substituent which the above-mentioned Sp has can be exemplified.

Specifically, the unit E includes 4-vinylphenyl-triphenyltin, 4-vinylphenyl-tributyltin, 4-isopropenylphenyl-triphenyltin, 4-isopropenylphenyl -Trimethyltin, trimethyltin acrylate, tributyltin acrylate, triphenyltin acrylate, trimethyltin methacrylate, tributyltin methacrylate, triphenyltin methacrylate, 4-vinylphenyl -Diphenylantimony, 4-isopropenylphenyl-diphenylantimony, 4-vinylphenyl-triphenylgermane, 4-vinylphenyl-tributylgermane, 4-isopropenyl A unit composed of monomers such as phenyl-triphenylgermane and 4-isopropenylphenyl-trimethylgermane. By containing the above-mentioned unit E, the above-mentioned polymer can improve the generation efficiency of secondary electrons when irradiated with a particle beam or an electromagnetic wave.

It is preferable that the above-mentioned unit E is that R ¹ in the above-mentioned formula (2) is a hydrogen atom or a straight-chain alkyl group, an L carbonyloxy group, or a phenylene group. In addition, from the viewpoint of LWR, it is preferable that L is a carbonyloxy group or a carbonylamino group, Sp is a direct bond, R ¹ is a methyl group, and the methyl group has 1 to 4 carbon atoms in the first substituent. At least any one or more units of an alkyl group, a halogen atom, and an aryl group. R ¹ having the above-mentioned first substituent is particularly preferably an ethyl group, an isopropyl group, a butyl group, a halogenated methyl group (fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, etc.), a benzyl group, and the like. The polymer of one aspect of the present invention may have two or more of the above-mentioned units E in the above-mentioned polymer.

(Unit F) The polymer of one embodiment of the present invention preferably further has a unit F, and the unit F is represented by the following formula (7) having a halogen atom.

(7) [Chemical 21]

(7)

In the above general formula (7), R ¹ , L and Sp are preferably selected from the same options as R ¹ , L and Sp in the above general formula (2), respectively. R ^h is selected from linear, branched or cyclic alkyl groups with 1 to 12 carbon atoms which may have substituents; linear, branched or cyclic alkyl groups with 1 to 12 carbon atoms which may have substituents Alkyleneoxy; optionally substituted linear, branched or cyclic alkenyl with 1 to 12 carbon atoms; optionally substituted linear, branched or cyclic with 1 to 12 carbon atoms alkenyleneoxy group; aryl group with 6 to 14 carbon atoms which may have substituents; Part or all of them are substituted by fluorine or iodine atoms. The alkylene group of R ^h , the alkenyl group, the alkylene group of the alkyleneoxy group, the alkenylene group of the alkenyleneoxy group, the aryl group, and the heteroaryl group include the same options as the above-mentioned Sp. In addition, as for these substituents, the same options as the substituents for Sp can be exemplified.

Specific examples of the unit F include units derived from the following monomers.

[Chemical 22]

The above-mentioned unit F is preferably one in which R ¹ in the above-mentioned formula (7) is a hydrogen atom or a straight-chain alkyl group, an L carbonyloxy group, a carbonylamino group or a phenylene group. In addition, from the viewpoint of LWR, it is preferable that L is a carbonyloxy group or a carbonylamino group, Sp is a direct bond, R ¹ is a methyl group, and the methyl group has 1 to 4 carbon atoms in the first substituent. At least any one or more units of an alkyl group, a halogen atom, and an aryl group. R ¹ having the above-mentioned first substituent is particularly preferably an ethyl group, an isopropyl group, a butyl group, a halogenated methyl group (fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, etc.), a benzyl group, and the like. The polymer of one aspect of the present invention may have two or more of the above-mentioned units F in the above-mentioned polymer.

(other units) In the range which does not impair the effect of this invention, the polymer of 1 aspect of this invention may have the unit normally used as a resist composition other than the said units A-F. For example, a unit having a skeleton ( Hereinafter referred to as "unit G"). Moreover, the unit which has the skeleton (henceforth "unit H") which has an alcoholic hydroxyl group in the * part of the said formula (2) is mentioned. This unit H is different from the above-mentioned units A to G. The above-mentioned polymer contains the above-mentioned unit H, and it is preferable that there is an inclination to increase the percentage of intramolecular crosslinking reaction. A unit having a skeleton containing an epoxy group, a glycidyl group, an oxetanyl group, or the like is preferable because the acid generated by the unit A is a strong acid because it causes cationic polymerization.

The polymer of one embodiment of the present invention may have a unit I represented by the following general formula (8). Unit I is a different unit from Units A to H described above. When the polymer of one embodiment of the present invention has the unit I, the polymer main chain is easily cut by the action of radicals generated by irradiation with particle beams or electromagnetic waves, and the polymer chain at the exposure boundary can be shortened, thereby reducing LWR. Effect.

(8) [Chemical 23]

(8)

In the above general formula (8), each substituent is preferably as follows: R ¹⁰ is an alkyl group with 1 to 6 carbon atoms selected from linear, branched or cyclic; and, a linear, branched or cyclic carbon Any of the alkenyl groups having 1 to 6 atoms, at least one hydrogen atom in the above-mentioned alkyl group and alkenyl group in the R ¹ may be substituted by a substituent, L ¹⁰ is a direct bond, and R ^c may have the above-mentioned first substitution An aryl group having 6 to 12 carbon atoms in the base. The alkyl group with 1 to 6 carbon atoms and the alkenyl group with 1 to 6 carbon atoms of R ¹⁰ are selected from the same as the alkyl group with 1 to 6 carbon atoms and the alkenyl group with 1 to 6 carbon atoms of the above R ¹ options. Alternatively, R ¹⁰ is a methyl group and the methyl group has at least any one of an alkyl group having 1 to 4 carbon atoms, a halogen atom and an aryl group in the first substituent, L is a carbonyloxy group or a carbonylamino group, and R ^c is A linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a hydrogen atom or the first substituent. In addition, L is a carbonyloxy group or a carbonylamino group, R ^c is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, R ¹⁰ is a methyl group and the methyl group has the above-mentioned first substitution At least one or more units of an alkyl group having 1 to 4 carbon atoms, a halogen atom and an aryl group in the group. R ¹⁰ having the first substituent mentioned above is particularly preferably an ethyl group, an isopropyl group, a butyl group, a halogenated methyl group (fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, etc.), a benzyl group, and the like. It should be noted that the above-mentioned unit I is a unit different from the above-mentioned units A to H.

The above-mentioned unit I is, for example, a unit derived from the following monomers, such as α-methylstyrene derivatives, 2-ethylacrylic acid and its ester derivatives, 2-benzylacrylic acid and its ester derivatives, 2-propylacrylic acid and its ester derivatives, 2-isopropylacrylic acid and its ester derivatives, 2-butylacrylic acid and its ester derivatives, 2-sec-butylacrylic acid and its ester derivatives, 2-fluoromethyl acrylic acid and its ester derivatives, 2-chloromethacrylic acid and its ester derivatives, 2-bromomethacrylic acid and its ester derivatives, 2-iodomethacrylic acid and its ester derivatives, etc. Specific examples of the above-mentioned unit I include units derived from monomers shown below.

[Chemical 24]

The polymer of one embodiment of the present invention may have a unit J represented by the following general formula (9).

(9) [Chemical 25]

(9)

In the above formula (9), R ¹ , L and Sp are selected from the same options as R ¹ , L and Sp in the general formula (2), respectively. R ^d is selected from linear, branched or cyclic alkylsilyl groups with 1 to 12 carbon atoms that may have substituents; 12 alkoxysilyl groups; optionally substituted linear, branched or cyclic alkenylsilyl groups with 1 to 12 carbon atoms; optionally substituted linear, branched or cyclic An alkenyloxysilyl group having 1 to 12 carbon atoms. A siloxane bond may also be included, which is formed by substituting a portion of carbon atoms with silicon atoms and oxygen atoms so that bonded hydrogen or carbon is replaced by oxygen. The above-mentioned unit J can improve the etching resistance of oxygen plasma by containing silicon. Further, when the polymer has a silane structure as the unit J, the above-mentioned unit B reacts under the action of an acid catalyst to generate water, and the water hydrolyzes the unit J to silanol to form a siloxane bond and crosslink, which can improve the sensitivity and The effect of substrate adhesion is preferred. In addition, the said unit J is a different unit from the said unit A-I.

Unit J may be a unit derived from the following monomers, such as 4-trimethylsilylstyrene, 4-trimethoxysilylstyrene, 3-methacryloyloxypropyl Methyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 8-methacryloxyoctyltrimethyl ^{Oxysilane , 3-} (3,5,7,9,11,11,13,15 ^{- heptaisobutylpentacyclo} [ ^{9,5,13,9,15,15,17,13} ]octa Siloxane-1-yl) propyl methacrylate, 3-acryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyl Alkylmethyldimethoxysilane, 8-propenyloxyoctyltrimethoxysilane, 3-(3,5,7,9,11,11,13,15-heptaisobutylpentacyclo[9,5 , 1 ^{3 , 9} , 1 ^{5 , 15} , 1 ^{7 , 13} ] octasiloxane-1-yl) propyl methacrylate and the like.

The resist composition in one aspect of the present invention is characterized in that an intramolecular crosslinking reaction is induced by irradiation with a particle beam or an electromagnetic wave. Therefore, the unit K having an onium salt structure other than the unit A may be included. As the unit K, the anion X- in the above ^- mentioned unit A is changed to the following Y ^- anion. In addition, Y ^- is a monovalent anion which has an organic group which does not contain a hydroxyl group or a sulfonamide group.

Y ^- is preferably selected from the group consisting of alkyl sulfate anions, aryl sulfate anions, alkyl sulfonate anions, aryl sulfonate anions, alkyl carboxylate anions, aryl carboxylate anions, tetrafluoroborate anions any one of an anion, a hexafluorophosphonate anion, a dialkylsulfoimide anion, a methyl trialkylsulfonate anion, a tetraphenylborate anion, and a hexafluoroantimonate anion. In addition, any one selected from the group consisting of a monovalent metal oxonium anion and a hydrogen atomic acid anion containing a monovalent metal oxonium anion can be mentioned as Y ^- . In addition, at least one of the hydrogen atoms ^of the alkyl group and the aryl group in Y- may be substituted with a fluorine atom, and the first one may have a substituent (but the hydroxyl group is excluded). The number of carbon atoms of Y ^- is preferably 1 to 6, including substituents. Examples of the metal oxonium anion include NiO ₂ ^- and SbO ₃ ^- . In addition, compared with VO ₄ ^{3 −} , SeO ₃ ^{2 −} , SeO ₄ ^{2 −} , MoO ₄ ^{2 −} , SnO ₃ ^{2 −} , TeO ₃ ^{2 −} , TeO ₄ ^{2 −} , TaO ₃ ^{2 −} , and WO ₄ ^{2 −} 2 For the ~trivalent metal oxonium anion, H ⁺ , sulfonium ion, iodide ion, and monovalent to divalent metal cations can be appropriately added to make the valence monovalent. The above-mentioned monovalent to divalent metal cations may be general, and examples thereof include Na ⁺ , Sn ^{2 +} , Ni ^{2 +} and the like.

When a strong acid (Y ^- is CF ₃ SO ₃ ^- or the like) is used as the acid generated by the unit K and an organic solvent aqueous solution is used as the developer, it is preferable that the other units do not include units having an acid dissociable group as the polymer in the present invention. unit. The reason for this is that when the other unit includes a unit having an acid dissociable group as the unit of the polymer in the present invention, the polymer tends to be more soluble in a water-soluble developer due to the action of the acid generated by the decomposition of the unit K.

The above-mentioned unit K can be used as a photodegradable base (when the unit K is used as a photodegradable base, it is also referred to as "unit K2"). The anion of the above-mentioned unit K2 is preferably any one selected from the group consisting of an alkylcarboxylate anion and an arylcarboxylate anion in Y ⁻ . It should be noted that these are monovalent anions having an organic group excluding a hydroxyl group or a sulfonamide group, and at least one hydrogen atom contained in the alkyl group of the above-mentioned alkylcarboxylate anion and the aryl group of the above-mentioned arylcarboxylate anion Can be substituted by fluorine atoms. It should be noted that the above-mentioned polymer having the unit K2 has the effect of reducing the LWR, which is effective when high resolution is required.

The polymer of one embodiment of the present invention may have two or more types of the above-mentioned units K in the above-mentioned polymer.

When the unit A is 1, the molar ratios of the polymers in one embodiment of the present invention are, respectively, the unit B is preferably 0.2 to 5, the unit C is preferably 0 to 3, the unit D is preferably 0 to 2, and the unit D is preferably 0 to 2. The unit E is preferably 0~2, the unit F is preferably 0~2, the unit G is preferably 0~2, the unit H is preferably 0~2, the unit I is preferably 0~0.5, and the unit J is preferably 0 ~4, the above-mentioned unit K is preferably 0~2. It should be noted that when the above-mentioned polymer contains at least one selected from the group consisting of unit A1, unit A2 and unit K2 as a photodegradable base, when unit A1 is 1, the total of unit A2 and unit K2 is preferably 0.1 to 1.0 in molar ratio, The molar ratio is more preferably 0.3 to 0.6. The polymer in one aspect of the present invention can be obtained by using the monomer components constituting the above-mentioned respective units as raw materials, and polymerizing them in the above-mentioned mixing ratio by a general method. Alternatively, a polymer containing a unit having an onium salt structure (referred to as a "precursor polymer") may be synthesized first, and the anion moiety of the above-mentioned onium salt structure is salt-exchanged in the precursor polymer as a polymer having a desired anion. A polymer of unit A. The molecular weight of the said polymer in one form of this invention is not specifically limited.

<2> Resist composition A resist composition according to one embodiment of the present invention contains the above-mentioned polymer. In addition to the above polymers, components such as polysubstituted alcohol compounds, organometallic compounds, and organometallic mixtures may be optionally contained. Each component will be described below. It is preferable that the compounding quantity of the said polymer in a resist composition is 70-100 mass % of the total solid content. (polysubstituted alcohol compound) The resist composition of one embodiment of the present invention may have a structure containing only the above-mentioned polymer, or may further contain other components, such as ethylene glycol, triethylene glycol, erythritol, arabinoside, in addition to the above-mentioned polymer. Compounds having two or more hydroxyl groups in the molecule, such as sugar alcohols, 1,4-benzenedimethanol, and 2,3,5,6-tetrafluoro-1,4-benzenedimethanol. By including these components in the resist composition, the efficiency of the crosslinking reaction and the sensitivity to particle beams or electromagnetic waves can be improved.

(Organometallic compounds and organometallic mixtures) The resist composition of one embodiment of the present invention preferably further contains an organometallic compound or an organometallic mixture. In order to sensitize the unit A and the unit B, the metal is preferably selected from the group consisting of Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rh, Pd, Ag, Cd, In, Sn, At least one of Sb, Te, I, Xe, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po, At, Rn and Ra.

The above-mentioned organometallic compound includes tetraaryltin, tetraalkyltin, bis(alkylphosphine)platinum, and the like. Examples of the organometallic mixture include hafnium (IV) acrylate, zirconium (IV) acrylate, bismuth (III) acrylate, bismuth (III) acetate, tin (II) oxalate, and the like. It is preferable that the compounding quantity in the resist composition of the said organometallic compound and organometallic mixture is 0-0.5 molar equivalent with respect to unit A.

(other ingredients) As long as the effects of the present invention are not impaired, the resist composition of one embodiment of the present invention may be mixed with other components in any embodiment. The ingredients that can be mixed are well-known additives, such as those selected from the group consisting of fluorine-containing water-repellent polymers, acid diffusion control agents, organic carboxylic acids, surfactants, fillers, pigments, antistatic agents, flame retardants, light stabilizers, At least one of antioxidants, ion scavengers, organic solvents, and the like. As the above-mentioned fluorine-containing water-repellent polymer, a polymer commonly used in a liquid immersion exposure process can be mentioned, and a polymer having a higher fluorine content than the above-mentioned polymer is preferable. Thus, when a resist film is formed using the resist composition, the water repellency of the fluorine-containing water-repellent polymer enables the fluorine-containing water-repellent polymer to be localized on the surface of the resist film.

The above-mentioned acid diffusion control agent has the effect of suppressing the diffusion phenomenon of the acid generated by the photoacid generator in the resist film and suppressing the undesired chemical reaction in the non-exposed area. Therefore, the storage stability of the obtained resist composition can be further improved, and the resolution as a resist can be further improved, and at the same time, it is possible to suppress the change of the resist pattern due to the fluctuation of the rest time from exposure to development. The line width is changed to obtain a resist composition with excellent process stability.

Examples of the acid diffusion control agent include compounds having one nitrogen atom in the same molecule, compounds having two nitrogen atoms, and compounds having three nitrogen atoms; amide group-containing compounds; urea compounds; cyclic compounds, etc. The said acid diffusion control agent is used as a monomer which comprises the said polymer unit, and can be contained in the said polymer. In addition, as the acid diffusion control agent, a photodegradable base that generates a weak acid by exposure to light can also be used. As a photodecomposable base, an onium salt compound, an iodonium salt compound, etc. which show acid-diffusion control property by exposure decomposition are mentioned, for example.

Specific examples of acid diffusion control agents include Japanese Patent Publication No. 3577743, Japanese Patent Publication No. 2001-215689, Japanese Patent Publication No. 2001-166476, Japanese Patent Publication No. 2008-102383, Japanese Patent Publication No. 2010-243773, and Japanese Patent Publication No. 2010-243773. No. 2011-37835 and Japanese Patent Laid-Open No. 2012-173505, etc.

The content of the acid diffusion control agent is preferably 0.01 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and even more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polymer component. The above-mentioned surfactants are preferably used to improve coatability. Examples of surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyls, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene Nonionic surfactants such as sorbitol fatty acid esters, fluorosurfactants, organosiloxane polymers, etc. The content of the surfactant is preferably 0.0001 to 12 parts by mass, more preferably 0.0005 to 1 mass %, with respect to 100 parts by mass of the polymer component.

As the organic solvent, for example, ethylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol monomethyl ether propionate are preferable. , propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl β-methoxyisobutyrate, ethyl butyrate, propyl butyrate, methyl isobutyl ketone, ethyl acetate, isoamyl acetate, ethyl lactate, toluene, xylene, cyclohexyl acetate, diacetone alcohol, N-methylpyrrolidone, N,N-dimethylformamide, γ-Butyrolactone, N,N-dimethylacetamide, propylene carbonate, ethylene carbonate, etc. These organic solvents may be used alone or in combination.

<3> Preparation method of resist composition The preparation method of the resist composition of one embodiment of the present invention is not particularly limited, and the above-mentioned polymer and other optional components can be prepared by official methods such as mixing, dissolving, or kneading. The above-mentioned polymers can be synthesized by appropriately polymerizing the monomers constituting the unit A and the unit B, and by a conventional method as necessary, by appropriately polymerizing the monomers constituting the other units. However, the manufacturing method of the polymer which concerns on this invention is not limited to this.

The resist composition component is dissolved in the above-mentioned organic solvent, and the solid content concentration is preferably 1 to 40% by mass. 1-30 mass % is more preferable, and 3-20 mass % is further more preferable. The above-mentioned film thickness can be achieved by setting the solid content concentration in such a range.

The composition of one embodiment of the present invention can be obtained by mixing each component of the above-mentioned composition, and the mixing method is not particularly limited.

<4> Manufacturing method of parts One aspect of the present invention is a method for manufacturing a component, comprising the steps of: forming a resist film on a substrate using the above-mentioned resist composition; exposing the above-mentioned resist film using a particle beam or an electron beam The photolithography step; the pattern forming step of developing the exposed resist film to obtain a photolithography resist pattern. As said member, a device, a mask, etc. are mentioned.

Electron beams and EUV can be exemplified as particle beams or electromagnetic waves used for exposure in the photolithography step, respectively. The irradiation amount of light varies depending on the type and mixing ratio of each component in the photocurable composition, the film thickness of the coating film, and the like, but is preferably 1 J/cm ² or less or 1000 μC/cm ² or less. When the above-mentioned resist composition is contained in the polymer as a sensitizing unit (unit C) or a sensitizing compound, it is preferable to perform secondary exposure using ultraviolet rays or the like after irradiation with particle beams or electromagnetic waves.

Another aspect of the present invention is a method for manufacturing a component, wherein in the photolithography step, the particle beam or electromagnetic wave is exposed and then a second active energy ray lower in energy than the particle beam or electromagnetic wave is irradiated.

As the first active energy ray and the second active energy ray, the onium salts according to the several aspects of the present invention are not particularly limited as long as they do not significantly absorb the second active energy ray, but the wavelength ratio of the first active energy ray is preferably The second active energy ray is short, or the energy of the photon or particle beam is higher than the second active energy ray. The respective active energy rays are exemplified below, but as long as the wavelength of the first active energy ray is shorter than that of the second active energy ray, or the energy of the photon or particle beam is higher than that of the second active energy ray, it is not limited to the following examples. The first active energy ray is not particularly limited as long as active species such as acid can be generated in the resist film after irradiation of the resist film. For example, KrF excimer laser, ArF excimer laser, and electron beam are preferably used. Or extreme ultraviolet (EUV) etc.

As the second active energy ray, the following energy ray may be used. That is, after the irradiation of the first active energy ray, an acid is generated in the resist film, and the (thio)acetal moiety of the onium salt related to the polymers of some embodiments of the present invention is deprotected by the action of the acid generation. A ketone derivative is generated, and the energy ray can activate the ketone derivative to generate active species such as an acid. For example, it refers to KrF excimer laser, UV, visible light, etc., and it is particularly preferable to use light in the region of 365 nm (i-ray) to 436 nm (g-ray) in UV light.

It is preferable that the manufacturing method of the member concerning one aspect of this invention has the process of heating with a heating wire or a laser between the process of irradiating a 1st active energy ray, and the process of irradiating a 2nd active energy ray. By having this step, the decomposition efficiency of the onium salt of the unit A can be improved, and the sensitivity can be further improved. The heating step can be performed on a hot plate or the like, and implementation of pre-baking in the manufacturing method of parts corresponds to this step.

The method for producing a member according to one aspect of the present invention preferably further includes the step of etching a coating film obtained by applying a composition for inversion pattern so as to cover at least the concave portion of the photoresist pattern, thereby making the photoresist The step of exposing the surface of the etching pattern; the step of removing the above-mentioned resist film on the surface portion of the above-mentioned exposed resist pattern to obtain a reversed pattern. As the composition for inversion patterns, known compositions for inversion patterns can be used, and examples thereof include the composition containing a siloxane polymer described in International Publication WO2015/025665.

In addition, one aspect of the present invention is a method for forming an inversion pattern, which includes the following steps: A resist film forming step of forming a resist film on a substrate using the above resist composition; Utilize particle beam or electromagnetic wave, the photolithography step of exposing above-mentioned resist film; The pattern forming step of developing the exposed resist film to obtain a photolithographic resist pattern.

In addition, one aspect of the present invention is a method for forming an inversion pattern, comprising the steps of: forming a resist film on a substrate using the above-mentioned resist composition; exposing the above-mentioned The photolithography step of the resist film; The pattern forming step of developing the exposed resist film to obtain the photolithography resist pattern; The obtained coating film, thereby exposing the surface of the photolithography resist pattern; the step of removing the above-mentioned resist film from the exposed part of the surface of the resist pattern to obtain a reverse pattern. In addition to the use of the above-described resist composition, a general method of forming a reverse pattern can also be used. The above-mentioned substrates are preferably inorganic substrates such as Si, SiO ₂ , SiN, SiON, TiN, WSi, and BPSG (Boron Phosphorus Silicon Glass). For example, in the case of a device manufacturing method, SOG ( Spin on Glass) and other coating-based inorganic substrates, etc. In addition, in the case of the manufacturing method of the mask, the substrate is preferably an inorganic substrate such as Cr, CrO, CrON, MoSi ₂ and SiO ₂ , and more preferably has an EUV absorbing layer such as TaO on the inorganic substrate. The substrate used to make the mask can be of the same structure as the substrate used for the usual mask, for example, in the case of a transmissive mask, it is preferable to be transparent to the transmitted light of the target, and in the case of a reflective mask, it is preferable to be transparent to the light of the target. (Electromagnetic waves such as EUV, etc.) have high reflectivity.

For the development in the pattern forming step, a common developer can be used, and examples of the developer include an alkaline developer, a neutral developer, and an organic solvent developer. Moreover, it is preferable to use the water-soluble developer containing a water-soluble organic solvent as a developer other than the above. The above-mentioned water-soluble organic solvent can be an organic compound having 1 or more carbon atoms mixed with water in any percentage, and specifically, methanol, ethanol, isopropanol, diacetone alcohol, ethylene glycol, ethylene glycol monomethyl can be listed. ether, propylene glycol, propylene glycol monomethyl ether, triethylene glycol, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, diglyme, triglyme, acetonitrile, acetone, N,N-dimethylformamide, dimethylsulfoxide, formic acid, acetic acid, propionic acid, etc.

The above-mentioned water-soluble developer should just be an aqueous solution containing one or more water-soluble organic solvents, and a water-insoluble organic solvent may be further mixed. Examples of the water-insoluble organic solvent include water-immiscible alcohols, water-immiscible ethers, water-immiscible nitriles, water-immiscible ketones, and water-immiscible esters. (eg ethyl acetate) and organohalogen compounds (eg dichloromethane) and the like.

It does not specifically limit as said board|substrate, A well-known board|substrate can be used. For example, substrates made of metals such as silicon, silicon nitride, titanium, tantalum, palladium, copper, chromium, and aluminum; glass substrates and the like can be mentioned. In one embodiment of the present invention, UV, KrF excimer laser, and ArF excimer laser are preferably used as active energy rays used for exposure in a photolithography step for obtaining an interlayer insulating film or the like for LSI production. radiation, electron beam or extreme ultraviolet (EUV).

The irradiation amount of the first active energy ray varies depending on the type and mixing ratio of each component in the photocurable composition, the thickness of the coating film, and the like, but is preferably 1 J/cm ² or less or 1000 μC/cm ² or less. In one embodiment of the present invention, the thickness of the resist film formed from the resist composition is preferably 10 to 200 nm. The above-mentioned resist composition is coated on the substrate by appropriate coating methods such as spin coating, roll coating, flow coating, dip coating, spray coating, blade coating, etc., and is prebaked at 60 to 150 ° C for 1 to 20 minutes, preferably at 80 °C. Pre-bake at ~120°C for 1~10 minutes to form a thin film. The film thickness of the coating film is 5 to 200 nm, preferably 10 to 100 nm. [Example]

Hereinafter, some aspects of the present invention will be described based on examples, but the present invention is not limited by these examples at all.

<Synthesis of compound A1 constituting unit A> (Synthesis Example 1) Synthesis of dibenzothiophene 9-oxide

[Chemical 26]

7.0 g of dibenzothiophenes were dissolved in 21.0 g of formic acid so that the temperature was 35°C. 4.1 g of 35 mass % hydrogen peroxide solution was dripped here, and it stirred for 5 hours at 25 degreeC. After cooling, the reaction was added dropwise to 50 g of pure water to precipitate a solid. The precipitated solid was filtered, washed twice with 20 g of pure water, and then recrystallized with acetone. After filtering and drying, 7.6 g of dibenzothiophene 9-oxides were obtained.

(Synthesis Example 2) Synthesis of 9-(4-hydroxyphenyl)dibenzothiophene iodide

[Chemical 27]

4.0 g of dibenzothiophene 9-oxide and 2.8 g of phenol obtained in the above Synthesis Example 1 were dissolved in 16 g of methanesulfonic acid so that the temperature was 25°C. To this, 1.5 g of phosphorus pentoxide was added, and the mixture was stirred at room temperature for 15 hours. Then, 60 g of pure water was added, and stirring was continued for 5 minutes. The aqueous layer was washed twice with 20 g of ethyl acetate and liquid-separated. 3.6 g of potassium iodide and 30 g of methylene chloride were added, and the mixture was stirred at room temperature for 2 hours. Then, the organic layer obtained by liquid separation was washed four times with 40 g of pure water. The recovered organic layer was concentrated and added dropwise to 100 g of diisopropyl ether to precipitate a solid. The precipitated solid was filtered and dried to obtain 6.6 g of 9-(4-hydroxyphenyl)dibenzothiophene iodide.

(Synthesis Example 3) Synthesis of 9-(4-hydroxyphenyl)dibenzothiophene methyl sulfate

[Chemical 28]

After dissolving 6.0 g of 9-(4-hydroxyphenyl)dibenzothiophene iodide and 2.3 g of dimethyl sulfate obtained in Synthesis Example 2 above in 15 g of methanol to make the temperature at 25°C, and stirring at room temperature for 4 hours, 45 g of ethyl acetate was added to precipitate a solid. The precipitated solid was filtered and dried to obtain 4.9 g of 9-(4-hydroxyphenyl)dibenzothiophene methyl sulfate.

(Synthesis example 4) Synthesis of 9-(4-methacryloyloxyphenyl)dibenzothiophene-methyl sulfate (compound a1)

(化合物a1) [Chemical 29]

(compound a1)

4.0 g of 9-(4-hydroxyphenyl)dibenzothiophene methyl sulfate and 1.9 g of methacrylic acid chloride obtained in the above Synthesis Example 3 were dissolved in 25 g of methylene chloride so that the temperature was 25°C, and trichloromethane was added dropwise. A solution obtained by dissolving 1.4 g of ethylamine in 7 g of dichloromethane was stirred at 25°C for 2 hours. After stirring, 20 g of pure water was added, and stirring was continued for 10 minutes, followed by liquid separation. After the organic layer was washed twice with 20 g of pure water, the organic layer collected by concentration was added dropwise to 60 g of diisopropyl ether to deposit a solid. The precipitated solid was filtered and dried to obtain 3.0 g of 9-(4-methacryloyloxyphenyl)dibenzothiophene-methylsulfate (compound a1).

(Synthesis Example 5) Synthesis of 9-(4-methacryloyloxyphenyl)dibenzothiophene 1,1-difluoro-2-hydroxyethylsulfonate (Compound A1)

(化合物A1) [Chemical 30]

(Compound A1)

4.0 g of methyl 9-(4-methacryloyloxyphenyl)dibenzothiophene sulfate obtained in Synthesis Example 4 above and 3.2 g of sodium 1,1-difluoro-2-hydroxyethanesulfonate were added The mixture was stirred in 25 g of dichloromethane and 20 g of pure water at 25°C for 1 hour. After stirring, liquid separation was performed, and 1.6 g of sodium 1,1-difluoro-2-hydroxysulfonate and 20 g of pure water were further added, and the mixture was stirred at 25° C. for 30 minutes. After stirring, liquid separation was performed, and the recovered organic layer was concentrated. The obtained organic layer was removed by solvent distillation, and purified by column chromatography (dichloromethane/methanol=90/10 (volume ratio)) to obtain 9-(4-methacryloyloxyphenyl)dibenzothiophene 1 , 3.0 g of 1-difluoro-2-hydroxyethyl sulfonate (compound A1).

<Synthesis of compound A2 constituting unit A> (Synthesis example 6) Synthesis of iodine (4-hydroxy)phenyldiphenylsulfonate

[Chemical 31]

The same operation as in Synthesis Example 2 was carried out, except that dibenzothiophene 9-oxide was used instead of diphenyl sulfite, and 5.9 g of iodine (4-hydroxyphenyl)diphenylsulfonate was obtained.

(Synthesis Example 7) Synthesis of (4-methacryloyloxy)phenyldiphenylsulfonic acid-trifluoromethanesulfonate (compound a2)

(化合物a2) [Chemical 32]

(compound a2)

Substitute (4-hydroxyphenyl)diphenylsulfonic acid-methylsulfate for 9-(4-hydroxyphenyl)dibenzothiophene methylsulfate, and use silica gel column chromatography (dichloromethane/methanol=9 /1) The same operation as in Synthesis Example 4 was carried out except that the solid precipitation by diisopropyl ether was replaced, to obtain 9-(4-methacryloyloxyphenyl)dibenzothiophene-trifluoromethanesulfonic acid Acid salt (compound a2) 3.8 g.

(Synthesis Example 8) Synthesis of 9-(4-methacryloyloxyphenyl)diphenyl perionium 1,1-difluoro-2-hydroxyethylsulfonate (Compound A2)

(化合物A2) [Chemical 33]

(Compound A2)

The same synthesis as above was carried out, except that (4-methacryloyloxy)phenyldiphenyl sulfamate methyl sulfate was used instead of 9-(4-methacryloyloxyphenyl)dibenzothiophene methyl sulfate 5 By the same operation, 3.0 g of 9-(4-methacryloyloxyphenyl)diphenyl perionium 1,1-difluoro-2-hydroxyethylsulfonate (compound A2) was obtained.

<Synthesis of compound A3 constituting unit A> (Synthesis Example 9) Synthesis of 9-(4-methacryloyloxyphenyl)diphenyl perionium 1,1,2-trifluoro-3-hydroxypropylsulfonate (Compound A3)

(化合物A3) [Chemical 34]

(Compound A3)

Substitute methyl 9-(4-methacryloyloxyphenyl)dibenzothiophene methyl sulfate with (4-methacryloyloxy)phenyldiphenyl sulfamate methyl sulfate, and use 1,1,2- The same procedure as in Synthesis Example 5 was carried out, except that sodium trifluoro-2-hydroxypropanesulfonate was replaced with sodium 1,1-difluoro-2-hydroxyethanesulfonate to obtain 9-(4-methacryloylidene) Oxyphenyl)diphenyl perionium 1,1,2-trifluoro-3-hydroxypropylsulfonate (compound A3) 3.0 g.

<Synthesis of compound A4 constituting unit A> (Synthesis Example 10) Synthesis of 9-(4-Methacryloyloxyphenyl)diphenylperylium 3-allyloxy-2-hydroxypropylsulfonate (Compound A4)

(化合物A4) [Chemical 35]

(Compound A4)

Substitute (4-methacryloyloxy) phenyldiphenyl perylene sulfate methyl 9-(4-methacryloyloxyphenyl)dibenzothiophene methyl sulfate with 3-allyloxy 9-(4-Methacryloyloxy was obtained by performing the same operations as in Synthesis Example 5 above, except that sodium-2-hydroxypropanesulfonate was used instead of sodium 1,1-difluoro-2-hydroxyethanesulfonate. Phenyl) diphenyl perionium 3-allyloxy 2-hydroxypropyl sulfonate (compound A4) 3.0 g.

<Synthesis of compound A5 constituting unit A> (Synthesis Example 11) Synthesis of 9-(4-methacryloyloxyphenyl)diphenyl perionium-3-mercaptopropylsulfonate (Compound A5)

(化合物A5) [Chemical 36]

(Compound A5)

Substitute methyl 9-(4-methacryloyloxyphenyl)dibenzothiophene methyl sulfate with methyl (4-methacryloyloxy)phenyldiphenylsulfate and use 3-mercaptopropanesulfonic acid The same procedure as in Synthesis Example 5 was carried out except that sodium 1,1-difluoro-2-hydroxyethanesulfonate was replaced with sodium, to obtain 9-(4-methacryloyloxyphenyl)diphenylsulfanium -3-mercaptopropyl sulfonate (compound A5) 3.0 g.

<Synthesis of compound A6 constituting unit A> (Synthesis Example 12) Synthesis of 5-(4-hydroxynaphthyl)tetramethylene perylene-p-toluenesulfonate

[Chemical 37]

5 was obtained in the same manner as in Synthesis Example 2, except that tetramethylene methylene was used instead of dibenzothiophene-9-oxide, 1-naphthol was used instead of phenol, and sodium p-toluenesulfonate was used instead of potassium iodide. -(4-Hydroxynaphthyl)tetramethylene perylene-p-toluenesulfonate 3.5 g.

(Synthesis Example 13) Synthesis of 5-(4-methacryloyloxynaphthyl)tetramethylene perionium-p-toluene perionium

[Chemical 38]

The same procedure as in Synthesis Example 4 was carried out except that 5-(4-hydroxynaphthyl)tetramethylene perylene-trifluoromethanesulfonate was used instead of 9-(4-hydroxyphenyl)dibenzothiophene methyl sulfate. The operation yielded 5.1 g of (5-(4-methacryloyloxynaphthyl)tetramethylene perionium-p-toluene perionium).

(Synthesis Example 14) Synthesis of 5-(4-methacryloyloxynaphthyl)tetramethylene perionium-1,1-difluoro-2-hydroxyethylsulfonate (Compound A6)

(化合物A6) [Chemical 39]

(Compound A6)

Substitute (4-methacryloyloxy) phenyldiphenylsulfate methyl sulfate instead of 9-(4-methacryloyloxyphenyl)dibenzothiophene methyl sulfate, and carry out the same procedure as in Synthesis Example 5 above. , 3.0 g of 9-(4-methacryloyloxyphenyl)diphenyl perionium 1,1-difluoro-2-hydroxyethylsulfonate (compound A6) was obtained.

<Synthesis of compound A7 constituting unit A> (Synthesis Example 15) Synthesis of 2-(4-methoxybenzyl)dibenzothiophene

[Chemical 40]

5.0 g of aluminum chloride was added to 50 g of dichloromethane to make it 0°C, and 5 g of dibenzothiophene was added, and then 4.6 g of 4-methoxybenzyl chloride was dissolved in 9.2 g of dichloromethane and dropped over 30 minutes. add. After the dropwise addition, the mixture was stirred at 25° C. for 1 hour, 60 g of pure water was added, and the mixture was further stirred for 5 minutes, and then washed twice with 20 g of toluene. The obtained organic layer was removed by solvent distillation. The obtained residue was purified by recrystallization using 30 g of acetone to obtain 6.1 g of 2-(4-methoxybenzyl)dibenzothiophene.

(Synthesis Example 16) Synthesis of 2-(4-methoxybenzyl)dibenzothiophene 5-oxide

[Chemical 41]

6.0 g of 2-(4-methoxybenzyl)dibenzothiophene obtained in Synthesis Example 15 was dissolved in 30 g of formic acid, and 3.5 g of a 35 mass % hydrogen peroxide solution was added dropwise thereto under ice-cooling. Then, it heated up to room temperature and stirred for 5 hours. After stirring, 80 g of pure water was added dropwise to the reaction to precipitate a solid. The precipitated solid was filtered, washed three times with 10 g of pure water, and then dried to obtain crude crystals. The crude crystals were recrystallized with 100 g of acetone and 200 g of ethanol to obtain 4.3 g of 2-(4-methoxybenzyl)dibenzothiophene 5-oxide.

(Synthesis Example 17) Synthesis of 2-[dimethoxy-(4-methoxyphenyl)methyldibenzothiophene-5-oxide

[Chemical 42]

5.0 g of 2-(4-methoxybenzyl)dibenzothiophene 5-oxide obtained in Synthesis Example 16 was added to 20 g of methanol, and 5.0 g of trimethyl orthoformate and 20 mg of concentrated sulfuric acid were added thereto at 60 g. °C was stirred for 3 hours. After stirring, the reaction solution was added to a mixed solution of 60 g of dichloromethane and 10 g of a 3 mass % aqueous sodium bicarbonate solution, and the mixture was stirred for 10 minutes, and the organic layer was recovered. The obtained organic layer was washed with water three times, and then dichloromethane was distilled off to obtain 4.6 g of 2-[dimethoxy-(4-methoxyphenyl)methyldibenzothiophene-5-oxide.

(Synthesis Example 18) 4-vinylphenyl-2-[dimethoxy-(4-methoxyphenyl)methyl]dibenzothiophene-1,1-difluoro-2-hydroxyethanesulfonic acid Synthesis of Salt (Compound A7)

(化合物A7) [Chemical 43]

(Compound A7)

To 4.0 g of 2-[dimethoxy-(4-methoxyphenyl)methyldibenzothiophene-5-oxide obtained in Synthesis Example 17 above, 1.1 g of trimethylchlorosilane and triethylamine were added 1.8 g of the solution was dissolved in 15.5 g of dichloromethane, and 15 ml of a 1.0 mol/L THF solution of 4-vinylphenylmagnesium bromide was added dropwise at 10°C or lower, followed by stirring at 25°C for 1 hour. After stirring, 30 g of a 10 mass % ammonium chloride aqueous solution was added at 5° C. or lower, and after stirring for 10 minutes, 40 g of dichloromethane and 2.7 g of sodium 1,1-difluoro-2-hydroxyethanesulfonate were added at 25° C. Stir for about 2 hours. After the separation was washed three times with water, dichloromethane was distilled off to obtain crude crystals. The crude crystals were purified by silica gel column chromatography (dichloromethane/methanol=90/10 (volume ratio)) to obtain 4-vinylphenyl-2-[dimethoxy-(4-methoxyphenyl) Methyl]dibenzothiophene-1,1-difluoro-2-hydroxyethanesulfonate (compound A7) 2.6 g.

<Synthesis of compound A8 constituting unit A> (Synthesis Example 19) Synthesis of 4-hydroxyphenyl-2-[(4-methoxy)benzyl]dibenzothiophene iodide

用2-(4-甲氧基苯甲醯基)二苯並噻吩5-氧化物代替二苯並噻吩-9-氧化物之外，進行與上述合成例2同樣的操作，得到了4-羥基苯基-2-[(4-甲氧基)苯甲醯基]二苯並噻吩碘化物3.0g。 [Chemical 44]

A 4-hydroxyl group was obtained in the same manner as in Synthesis Example 2, except that 2-(4-methoxybenzyl)dibenzothiophene 5-oxide was used instead of dibenzothiophene-9-oxide. Phenyl-2-[(4-methoxy)benzyl]dibenzothiophene iodide 3.0 g.

(Synthesis Example 20) Synthesis of 4-hydroxyphenyl-2-[(4-methoxy)benzyl]dibenzothiophene-methylsulfate

[Chemical 45]

Substitute 9-(4-hydroxyphenyl)dibenzothiophene iodide with 4-hydroxyphenyl-2-[(4-methoxy)benzyl]dibenzothiophene iodide obtained in Synthesis Example 19 above Other than that, the same operation as the above-mentioned Synthesis Example 3 was carried out to obtain 3.0 g of 4-hydroxyphenyl-2-[(4-methoxy)benzyl]dibenzothiophene-methylsulfate.

(Synthesis Example 21) Synthesis of 4-hydroxyphenyl-2-[dimethoxy-(4-methoxyphenyl)methyl]dibenzothiophene-methyl sulfate

[Chemical 46]

Substitute 4-hydroxyphenyl-2-[(4-methoxy)benzyl]dibenzothiophene-methyl sulfate obtained in Synthesis Example 20 above for 2-(4-methoxybenzyl) ) dibenzothiophene 5-oxide was carried out in the same manner as in Synthesis Example 17 above to obtain 4-hydroxyphenyl-2-[dimethoxy-(4-methoxyphenyl)methyl] Dibenzothiophene-methyl sulfate 3.0 g.

(Synthesis Example 22) Synthesis of 4-methacryloyloxyphenyl-2-[dimethoxy-(4-methoxyphenyl)methyl]dibenzothiophene-methyl sulfate

[Chemical 47]

Substitute 4-hydroxyphenyl-2-[dimethoxy-(4-methoxyphenyl)methyl]dibenzothiophene-methyl sulfate obtained in Synthesis Example 21 above for 9-(4-methyl) 4-Methacrylooxyphenyl-2-[dimethoxy-(4-methacrylooxyphenyl-2-[dimethoxy-(4-methacrylooxyphenyl)-2-[dimethoxy-(4-methacrylooxyphenyl)-2-[dimethoxy-(4-methacrylooxyphenyl) -Methoxyphenyl)methyl]dibenzothiophene-methyl sulfate 3.0 g.

(Synthesis Example 23) 4-Methacryloyloxyphenyl-2-[dimethoxy-(4-methoxyphenyl)methyl]dibenzothiophene-1,1-difluoro-2- Synthesis of Isethionate (Compound A8)

(化合物A8) [Chemical 48]

(Compound A8)

Substitute 9- 4-Methacryloyloxyphenyl 2-[dimethoxyphenyl 2-[dimethoxyphenyl] was obtained in the same manner as in Synthesis Example 5 except for (4-methacryloyloxyphenyl)dibenzothiophene methyl sulfate yl-(4-methoxyphenyl)methyl]dibenzothiophene-1,1-difluoro-2-hydroxyethanesulfonate (compound A8) 3.0 g.

<Synthesis of compound A9 constituting unit A> (Synthesis Example 24) Synthesis of 2-[methoxyphenyl-[1,3]dioxepan-2-yl]dibenzothiophene 5-oxide

[Chemical 49]

2-[methoxyphenyl-[1,3]dioxepan-2-yl] was obtained in the same manner as in Synthesis Example 17 above except that 1,4-butanediol was used in place of methanol. Dibenzothiophene 5-oxide 3.0 g.

(Synthesis Example 25) 4-Vinylphenyl-2-[methoxyphenyl-[1,3]dioxepan-2-yl]dibenzothiophene-1,1-difluoro-2 -Synthesis of hydroxyethanesulfonate (compound A9)

(化合物A9) [Chemical 50]

(Compound A9)

Substitute 2-[dimethoxy-( Except 4-methoxyphenyl) methyldibenzothiophene-5-oxide methanol, the same operation as above-mentioned Synthesis Example 18 was carried out to obtain 4-vinylphenyl-2-[methoxyphenyl -[1,3]Dioxetan-2-yl]dibenzothiophene-1,1-difluoro-2-hydroxyethanesulfonate (Compound A9) 3.0 g.

<Synthesis of compound A10 constituting unit A> (Synthesis Example 26) Synthesis of phenyl-2-[dimethoxy-(4-methoxyphenyl)methyl]dibenzothiophene-bromide

[Chemical 51]

4.0 g of 2-[dimethoxy-(4-methoxyphenyl)methyldibenzothiophene-5-oxide obtained in Synthesis Example 17 above, 1.1 g of trimethylchlorosilane and 1.8 g of triethylamine 15 ml of a 1.0 mol/L THF solution of 4-vinylphenylmagnesium bromide was added dropwise to a solution dissolved in 15.5 g of methylene chloride at 10°C or lower, followed by stirring at 25°C for 1 hour. After stirring, 30 g of a 10 mass % ammonium chloride aqueous solution was added at 5° C. or lower, 40 g of methylene chloride was added after stirring for 10 minutes, and the mixture was stirred at 25° C. for about 2 hours. The liquid separation was washed three times with water, and then dichloromethane was distilled off to obtain crude crystals. The crude crystals were purified by silica gel column chromatography (dichloromethane/methanol = 90/10 (volume ratio)) to obtain phenyl-2-[dimethoxy-(4-methoxyphenyl)methyl] Dibenzothiophene-bromide 3.0 g.

(Synthesis Example 27) Synthesis of phenyl-2-(4-hydroxybenzyl)dibenzothiophene bromide

[Chemical 52]

After adding 3.0 g of phenyl-2-[dimethoxy-(4-methoxyphenyl)methyldibenzothiophene-bromide obtained in Synthesis Example 26 above to 30 ml of acetic acid to make it 110°C, dropwise 2.2 g of a 48% aqueous hydrobromic acid solution was added, and the mixture was stirred for 18 hours. Then, after cooling to 25 degreeC, 60 ml of pure water and 40 g of dichloromethane were added, and it stirred. After separating the liquid and washing with water three times, dichloromethane was distilled off to obtain crude crystals. The crude crystals were purified by silica gel column chromatography (dichloromethane/methanol=80/20 (volume ratio)) to obtain 1.4 g of phenyl-2-(4-hydroxybenzyl)dibenzothiophene bromide.

(Synthesis Example 28) Synthesis of phenyl-2-[dimethoxy-(4-hydroxyphenyl)]methyldibenzothiophene-bromide

[Chemical 53]

Substitute phenyl-2-(4-hydroxybenzyl)dibenzothiophene bromide obtained in Synthesis Example 27 above for 2-(4-methoxybenzyl)dibenzothiophene 5-oxide. Otherwise, the same operation as in Synthesis Example 17 was carried out to obtain 1.5 g of phenyl-2-[dimethoxy-(4-hydroxyphenyl)]methyldibenzothiophene-bromide.

(Synthesis Example 29) Phenyl-2-{dimethoxy-[4-(3-methacryloyloxy)propoxyphenyl]methyl}dibenzothiophene-1,1-difluoro- Synthesis of 2-Hydroxyethanesulfonate (Compound A10)

(化合物A10) [Chemical 54]

(Compound A10)

1.5 g of phenyl-2-[dimethoxy-(4-hydroxyphenyl)]methyldibenzothiophene-bromide obtained in Synthesis Example 28 and 3-trifluoromethanesulfonylpropane methacrylic acid After 1.10 g of ester was dissolved in 10 ml of acetonitrile, 2.1 g of potassium carbonate was added, and the mixture was stirred at 70°C for 3 hours. Then, 30 ml of methylene chloride, 15 m of pure water, and 1.3 g of sodium 1,1-difluoro-2-hydroxyethanesulfonate were added, followed by stirring. The liquid separation was washed three times with water, and the dichloromethane was distilled off to obtain crude crystals. The crude crystals were purified by silica gel column chromatography (dichloromethane/methanol=80/20 (volume ratio)) to obtain phenyl-2-{dimethoxy-[4-(1-ethoxyethyl)oxy] Phenyl]methyl}dibenzothiophene-nonafluorobutanesulfonate (compound A10) 1.0 g.

<Synthesis of compound B1 constituting unit B> (Synthesis Example 30) Synthesis of 2,4-dimethoxy 2-hydroxybenzyl alcohol

[Chemical 55]

6.0 g of 2,4-dimethoxy-4'-hydroxybenzophenone was dissolved in 32 g of THF, 2.2 g of lithium aluminum hydride was added thereto, and the mixture was stirred at room temperature for 3 hours. Then, after adding 6 g of pure water and confirming the generation of hydrogen atoms, the mixture was further stirred for 10 minutes. A 5 mass % sodium oxalate aqueous solution was added, and after stirring for 10 minutes, 30 g of ethyl acetate was added for liquid separation. After washing with 10 g of water three times, the organic layer was concentrated and recovered to obtain 5.9 g of 2,4-dimethoxy 2-hydroxybenzyl alcohol.

(Synthesis Example 31) Synthesis of 2,4-dimethoxy-2'-methacryloyloxyhydroxybenzyl alcohol (Compound B1)

(化合物B1) [Chemical 56]

(Compound B1)

4.0 g of 2,4-dimethoxy-2'-hydroxybenzyl alcohol obtained in Synthesis Example 30 and 4.2 g of methacrylic anhydride were dissolved in 40 g of methylene chloride so that the temperature was 25° C., and triethylamine was added dropwise. 2.8 g of a solution dissolved in 7 g of methylene chloride was stirred at 25° C. for 2 hours, and then 20 g of pure water was added and the mixture was stirred for 10 minutes, followed by liquid separation. After washing the organic layer twice with 20 g of pure water, the recovered organic layer was concentrated, and the obtained organic layer was distilled off with the solvent, and then purified by column chromatography (ethyl acetate/hexane=15/85 (volume ratio)) to obtain 2,4-dimethoxy-2'-methacryloyloxyhydroxybenzyl alcohol (compound B1) 2.6 g.

<Synthesis of compound B2 constituting unit B> (Synthesis Example 32) Synthesis of 2-hydroxybenzyl alcohol

[Chemical 57]

The same operation as in Synthesis Example 30 was carried out except that 2-hydroxybenzophenone was used instead of 2,4-dimethoxy-4'-hydroxybenzophenone to obtain 3.5 g of 2-hydroxybenzyl alcohol.

(Synthesis example 33) Synthesis of 2-methacryloyloxyhydroxybenzyl alcohol (compound B2)

(化合物B2) [Chemical 58]

(Compound B2)

The 2-hydroxybenzyl alcohol obtained in Synthesis Example 32 was used in place of 2,4-dimethoxy-2'-hydroxybenzyl alcohol, and the residue obtained by concentration was subjected to column chromatography (ethyl acetate/hexane=10/ 90 (volume ratio)) was purified, and the same operation as in Synthesis Example 31 was carried out to obtain 3.5 g of 2-methacryloyloxyhydroxybenzyl alcohol (compound B2).

<Synthesis of compound B3 constituting unit B> (Synthesis Example 34) Synthesis of 1-(4-hydroxyphenyl)ethanol

[Chemical 59]

1-(4-hydroxyphenyl)ethanol 2.7 was obtained in the same manner as in Synthesis Example 30 above, except that 4-hydroxyacetophenone was used in place of 2,4-dimethoxy-4'-hydroxybenzophenone g.

(Synthesis Example 35) Synthesis of 1-(4-methacryloyloxyphenyl)ethanol (Compound B3)

(化合物B3) [Chemical 60]

(Compound B3)

The 2-hydroxybenzyl alcohol obtained in Synthesis Example 34 was used in place of 2,4-dimethoxy-2'-hydroxybenzyl alcohol, and the residue obtained by concentration was subjected to column chromatography (ethyl acetate/hexane=10 /90 (volume ratio)), the same operation as in Synthesis Example 31 was carried out to obtain 3.5 g of 2-methacryloyloxyhydroxybenzyl alcohol (compound B3).

<Synthesis of compound B4 constituting unit B> (Synthesis Example 36) Synthesis of 2,4-dimethoxy-4'-(2-vinyloxy)ethoxybenzophenone

[Chemical 61]

4.0 g of 2,4-dimethoxy-4'-hydroxy-benzophenone, 4.8 g of 2-chloroethyl vinyl ether, and 6.4 g of potassium carbonate were dissolved in 24 g of dimethylformamide, and the mixture was Stir at 110°C for 15 hours. Then, the mixture was cooled to 25° C., 60 g of water was added, and the mixture was stirred and extracted with 24 g of toluene. The organic layer recovered after washing with 10 g of water three times was concentrated, and the solvent of the obtained organic layer was distilled off. Ethyl ester/hexane=10/90 (volume ratio)) was purified to obtain 5.4 g of 2,4-dimethoxy-4'-(2-vinyloxy)ethoxybenzophenone.

(Synthesis Example 37) Synthesis of 2,4-dimethoxy-4'-(2-hydroxy)ethoxybenzophenone

[Chemical 62]

5.4 g of 2,4-dimethoxy-4'-(2-vinyloxy)ethoxybenzophenone obtained in Synthesis Example 36, 0.42 g of pyridinium-p-toluenesulfonic acid, and 4.2 g of pure water The mixture was dissolved in 36 g of acetone, and the mixture was stirred at 35° C. for 12 hours. After adding a 3% by mass sodium carbonate aqueous solution, the mixture was continuously stirred and extracted with 42 g of ethyl acetate. The collected organic layer was washed three times with 10 g of water and concentrated. Thus, 4.3 g of 2,4-dimethoxy-4'-(2-hydroxy)ethoxybenzophenone was obtained.

(Synthesis Example 38) Synthesis of 2,4-dimethoxy-4'-(2-hydroxy)ethoxybenzyl alcohol

[Chemical 63]

Except that 2,4-dimethoxy-2'-hydroxybenzyl alcohol was replaced by 2,4-dimethoxy-4'-(2-hydroxy)ethoxybenzophenone obtained in Synthesis Example 37, The same operation as in Synthesis Example 30 was carried out to obtain 2.7 g of 2,4-dimethoxy-4′-(2-hydroxy)ethoxybenzyl alcohol.

(Synthesis Example 39) Synthesis of 2,4-dimethoxy-4'-(2-methacryloyloxy)ethoxybenzyl alcohol (Compound B4)

(化合物B4) [Chemical 64]

(Compound B4)

The 2,4-dimethoxy-4'-(2-hydroxy)ethoxybenzyl alcohol obtained in Synthesis Example 38 was used in place of 2,4-dimethoxy-2'-hydroxybenzyl alcohol, and the mixture was concentrated to give The obtained residue was purified by column chromatography (ethyl acetate/hexane=10/90 (volume ratio)) in the same manner as in Synthesis Example 31 above to obtain 2,4-dimethoxy-4' 3.5 g of -(2-methacryloyloxy)ethoxybenzyl alcohol (compound B4).

<Synthesis of compound B5 constituting unit B> (Synthesis Example 40) Synthesis of 1-(3-hydroxy-4-methoxyphenyl)methanol

[Chemical 65]

The same operation as in Synthesis Example 30 was carried out except that 3-hydroxy-4-methoxybenzaldehyde was used in place of 2,4-dimethoxy-2'-hydroxybenzyl alcohol to obtain 1-(4-hydroxyl phenyl) methanol 2.7 g.

(Synthesis Example 41) Synthesis of 1-(3-methacryloyloxy-4-methoxyphenyl)methanol (Compound B5)

(化合物B5) [Chemical 66]

(Compound B5)

Using 1-(4-hydroxyphenyl)methanol obtained in Synthesis Example 40 in place of 2,4-dimethoxy-2'-hydroxybenzyl alcohol, the mixture was subjected to column chromatography (ethyl acetate/hexane=10/90 ( The obtained residue was purified and concentrated, and the same operation as in Synthesis Example 31 was carried out to obtain 2.1 g of 1-(3-methacryloyloxy-4-methoxyphenyl)methanol (compound B5).

<Synthesis of compound B6 constituting unit B> (Synthesis Example 42) Synthesis of 4-hydroxy-4'-methoxybenzyl alcohol

[Chemical 67]

The same operation as in Synthesis Example 30 above was carried out except that 4-hydroxy-4'-methoxybenzophenone was used instead of 2,4-dimethoxy-4'-hydroxybenzophenone to obtain 4- Hydroxy-4'-methoxybenzyl alcohol 3.5g.

(Synthesis Example 43) Synthesis of 4-methacryloyloxy-4'-methoxybenzophenone (Compound B6)

(化合物B6) [Chemical 68]

(Compound B6)

4-Methacryloyloxy was obtained in the same manner as in Synthesis Example 31, except that 4-hydroxy-4'-methoxybenzyl alcohol obtained in Synthesis Example 42 was used instead of 4-hydroxybenzophenone -4'-Methoxybenzophenone (Compound B6) 3.5 g.

<Synthesis of compound C1 constituting unit C> (Synthesis Example 44) Synthesis of 1-[4-(2-methacryloyloxy)ethoxyphenyl]-2-hydroxy-2-methyl-1-propanone (Compound C1)

(化合物C1) [Chemical 69]

(Compound C1)

4.0 g of 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (Irgacure 2959) and 4.6 g of methacrylic anhydride were dissolved in di 40 g of methyl chloride was adjusted to 25° C., and a solution obtained by dissolving 3.0 g of triethylamine in 7 g of methylene chloride was added dropwise, and the mixture was stirred at 25° C. for 2 hours. Then, 20 g of pure water was added, and the mixture was further stirred for 10 minutes, followed by liquid separation. The organic layer recovered after washing twice with 20 g of pure water was concentrated, the obtained organic layer was distilled off the solvent, and purified by column chromatography (ethyl acetate/hexane=10/90 (volume ratio)) to obtain 1. -[4-(2-Methacryloyloxy)ethoxyphenyl]-2-hydroxy-2-methyl-1-propanone (Compound C1) 4.9 g.

<Synthesis of compound C2 constituting unit C> (Synthesis Example 45) Synthesis of 1-(4-hydroxyphenyl)-2,2-dimethyl-1-propanone

[Chemical 70]

2.0 g of magnesium and 10 g of THF were added to a previously dehydrated flask, and a solution prepared by dissolving 10.0 g of 4-(2-ethoxy)ethoxyphenyl bromide in 50.0 g of THF was added dropwise at room temperature over 1 hour. solution. After the dropwise addition, after stirring at room temperature for 1 hour, the obtained 4-(2-ethoxy)ethoxyphenylmagnesium bromide solution was added dropwise to the pivalic acid chloride to which the pivalic acid chloride had been added over 30 minutes at 5°C. 9.8g and THF40g in a flask. After the dropwise addition, after stirring for 30 minutes, 150 g of 3 mass % hydrochloric acid was added, and stirring was continued for 10 minutes. After that, THF was distilled off, extracted with 150 g of ethyl acetate, liquid-separated, and the obtained organic layer was washed three times with 60 g of pure water. After that, the organic layer obtained by separation was removed by solvent distillation, and then purified by column chromatography (ethyl acetate/hexane=20/80 (volume ratio)) to obtain 1-(4-hydroxyphenyl)-2,2 - 5.8 g of dimethyl-1-propanone.

(Synthesis Example 46) Synthesis of 1-(4-methacryloyloxyphenyl)-2,2-dimethyl-1-propanone (Compound C2)

(化合物C2) [Chemical 71]

(Compound C2)

4.0 g of 1-(4-hydroxyphenyl)-2,2-dimethyl-1-propanone and 4.1 g of methacrylic anhydride obtained in Synthesis Example 45 above were dissolved in 32 g of methylene chloride to make the temperature at 25°C. , a solution obtained by dissolving 2.7 g of triethylamine in 7 g of methylene chloride was added dropwise, and after stirring at 25° C. for 2 hours, 20 g of pure water was added, and stirring was continued for 10 minutes, followed by liquid separation. The organic layer recovered after being washed twice with 20 g of pure water was concentrated, and the organic layer obtained by distilling off the solvent was purified by column chromatography (ethyl acetate/hexane=10/90 (volume ratio)) to obtain 1-( 4-Methacryloyloxyphenyl)-2,2-dimethyl-1-propanone (Compound C2) 4.6 g.

(化合物C3) <Synthesis of compound C3 constituting unit C> (Synthesis example 47) Synthesis of 1-(4-propenyloxyphenyl)-2,2-dimethyl-1-propanone (compound C3) [Chem. 72]

(Compound C3)

The same operation as in Synthesis Example 46 was carried out except that methacrylic anhydride was replaced with acryl chloride to obtain 1-(4-acryloyloxyphenyl)-2,2-dimethyl-1-propanone (Compound C3 ) 5.3g.

<Synthesis of compound C4 constituting unit C> (Synthesis Example 48) Synthesis of 1-(6-hydroxynaphthalen-2-yl)-2,2-dimethyl-1-propanone

[Chemical 73]

The same procedure as in Synthesis Example 45 above was carried out, except that 2-bromo-6-(2-ethoxy)ethoxynaphthalene was used instead of 4-(2-ethoxy)ethoxyphenyl bromide to obtain 1 -(6-Hydroxynaphthalen-2-yl)-2,2-dimethyl-1-propanone 6.9 g.

(Synthesis Example 49) Synthesis of 1-(6-methacryloyloxynaphthalen-2-yl)-2,2-dimethyl-1-propanone (Compound C4)

(化合物C4) [Chemical 74]

(Compound C4)

In addition to replacing 1-(4-hydroxyphenyl)-2,2-dimethyl-1-propanone with 1-(6-hydroxynaphthalen-2-yl)-2,2-dimethyl-1-propanone, The same operation as in Synthesis Example 46 was carried out to obtain 5.3 g of 1-(6-methacryloyloxynaphthalen-2-yl)-2,2-dimethyl-1-propanone (compound C4).

<Synthesis of compound C5 constituting unit C> (Synthesis Example 50) Synthesis of 1-[4-(2-hydroxyethoxy)phenyl]-2,2-dimethyl-1-propanone

[Chemical 75]

The same operation as in Synthesis Example 45 above was carried out except that 4-(2-vinyloxy)ethoxyphenyl bromide was used instead of 4-(2-ethoxy)ethoxyphenyl bromide to obtain 1 -[4-(2-hydroxyethoxy)phenyl]-2,2-dimethyl-1-propanone 6.3 g.

(Synthesis Example 51) Synthesis of 1-[4-(2-methacryloyloxy)ethoxyphenyl]-2,2-dimethyl-1-propanone (Compound C5)

(化合物C5) [Chemical 76]

(Compound C5)

In addition to replacing 1-(4-hydroxyphenyl)-2,2-dimethyl-1-propanone with 1-(2-hydroxyethoxyphenyl)-2,2-dimethyl-1-propanone, The same operation as in Synthesis Example 46 was carried out to obtain 5.6 g of 1-[4-(2-methacryloyloxy)ethoxyphenyl]-2,2-dimethyl-1-propanone (Compound C5) .

<Synthesis of compound C6 constituting unit C> (Synthesis Example 52) Synthesis of phenylglyoxylate chloride

[Chemical 77]

5.0 g of phenylglyoxylic acid was dissolved in 35 g of anisole to make it 50°C, 5.1 g of oxalic chloride was added dropwise over 10 minutes, and the mixture was stirred at 50°C for 2 hours. After the excess oxalyl chloride was distilled off at 70°C, the anisole was distilled off under a reduced pressure environment and concentrated to obtain 26.3 g of an anisole solution of phenylglyoxylate chloride.

(Synthesis Example 53) Synthesis of 1-(4-methoxyphenyl)-2-phenylethanedione

[Chemical 78]

25.0 g of anisole solution of phenylglyoxylate chloride obtained in Synthesis Example 52 was dissolved in 35 g of methylene chloride to make it 0°C, 4.3 g of aluminum chloride was added, and the mixture was stirred at 0°C for 2 hours. After adding 35 g of pure water and stirring for 10 minutes, liquid separation was performed. The organic layer recovered after being washed twice with 30 g of pure water was concentrated, and the organic layer obtained by distilling off the solvent was purified by column chromatography (ethyl acetate/hexane=10/90 (volume ratio)) to obtain 1-(4 -Methoxyphenyl)-2-phenylethanedione 5.6 g.

(Synthesis Example 54) Synthesis of 1-(4-hydroxyphenyl)-2-phenylethanedione

[Chemical 79]

5.0 g of 1-(4-methoxyphenyl)-2-phenylethanedione was dissolved in 95 ml of acetic acid, and 33.2 g of a 48% by mass HBr aqueous solution was added dropwise at 70°C over 10 minutes, followed by stirring at 110°C for 70 minutes. Hour. Then, 150 g of water was added to crystallize, and the crystal was filtered, washed with 250 g of water, and then dried to obtain 4.1 g of 1-(4-hydroxyphenyl)-2-phenylethanedione.

(Synthesis Example 55) Synthesis of 2,2-dimethoxy-1-(4-methacryloyloxyphenyl)ethan-1-one (Compound C6)

(化合物C6) [Chemical 80]

(Compound C6)

4.0 g of 1-(4-hydroxyphenyl)-2-phenylethanedione and 0.10 g of sulfuric acid were dissolved in 12 g of methanol to make the temperature at 25°C, and 2.2 g of trimethyl orthoformate was added dropwise and stirred for 3 hours. After adding 0.6 g of triethylamine at 30° C. and stirring for 5 minutes, the solvent was distilled off. After adding 25 g of acetonitrile, 4.5 g of triethylamine, and 0.11 g of dimethylaminopyridine to the obtained residue, 6.8 g of methacrylic anhydride diluted with 5.0 g of acetonitrile was added dropwise at room temperature. After the dropwise addition, after stirring at 25° C. for 2 hours, 64 g of a 3 mass % NaHCO 3 aqueous solution was added and stirred for 5 minutes. After that, the organic layer recovered after extraction with 32 g of ethyl acetate and 10 g of water was concentrated, and the recovered organic layer was removed by solvent distillation, and then subjected to column chromatography (ethyl acetate/hexane=10/90 (volume ratio)) After purification, 4.3 g of 2,2-dimethoxy-1-(4-methacryloyloxyphenyl)ethan-1-one (compound C6) was obtained.

<Synthesis of compound E1 constituting unit E> (Synthesis Example 56) Synthesis of 4-vinylphenyl-triphenyltin (compound E1)

(化合物E1) [Chemical 81]

(Compound E1)

1.2 g of magnesium and 6 g of THF were put into the flask from which the moisture was removed in advance, and a solution obtained by dissolving 6.0 g of 4-vinylbromobenzene in 12.0 g of THF was added dropwise over 1 hour. After the dropwise addition, the solution was stirred for 1 hour, and the obtained 4-vinylphenylmagnesium bromide solution was added dropwise to the flask to which 7.3 g of triphenyltin chloride and 36 g of THF were added over 30 minutes at 5°C. After the dropwise addition, after stirring for 30 minutes, 600 g of a 1 mass % ammonium chloride aqueous solution was added, and stirring was continued for 10 minutes. After that, THF was distilled off, the organic layer obtained by extracting with 60 g of toluene, and then liquid-separating, was washed three times with 60 g of pure water. After the organic layer obtained by the separation was removed by solvent distillation, it was purified by column chromatography (ethyl acetate/hexane=5/95 (volume ratio)) to obtain 4-vinylphenyl-triphenyltin (compound E1) 5.6 g.

<Synthesis of compound E2 constituting unit E> (Synthesis Example 57) Synthesis of 4-isopropenylphenyl-triphenyltin (compound E2)

(化合物E2) [Chemical 82]

(Compound E2)

7.1 g of 4-isopropenylphenyl-triphenyltin (compound E2) was obtained by carrying out the same operation as the above-mentioned Synthesis Example 56 except that 4-isopropenyl bromobenzene was used instead of 4-vinyl bromobenzene.

<Synthesis of compound E3 constituting unit E> (Synthesis Example 58) Synthesis of 4-vinylphenyl-tributyltin (compound E3)

(化合物E3) [Chemical 83]

(Compound E3)

The same operation as in Synthesis Example 56 was carried out except that tributyltin chloride was used instead of triphenyltin chloride to obtain 5.1 g of 4-vinylphenyl-tributyltin (compound E3).

<Synthesis of compound E4 constituting unit E> (Synthesis Example 59) Synthesis of 4-vinylphenyl-triphenylgermane (compound E4)

(化合物E4) [Chemical 84]

(Compound E4)

The same operation as in Synthesis Example 56 was carried out except that triphenylgermanium chloride was used instead of triphenyltin chloride to obtain 3.1 g of 4-vinylphenyl-tributylgermane (compound E4).

<Synthesis of compound F1 constituting unit F> (Synthesis Example 60) Synthesis of 1-trifluoromethyl-2-bromoethanol

[Chemical 85]

6.0 g of 1-bromo3,3,3-trifluoroacetone was dissolved in 28 g of THF, 0.3 g of lithium aluminum hydride was added, and after stirring at room temperature for 3 hours, 6 g of pure water was added while the generation of hydrogen was confirmed, and stirring was continued for 10 minutes. After adding a 5 mass % sodium oxalate aqueous solution and stirring for 10 minutes, 30 g of ethyl acetate was added for liquid separation, and the organic layer recovered after washing three times with 10 g of water was concentrated to obtain 5.9 g of 1-trifluoromethyl-2-bromoethanol.

(Synthesis Example 61) Synthesis of 1-trifluoromethyl-2-methacryloyloxyethanol (Compound F1)

(化合物F1) [Chemical 86]

(Compound F1)

5.0 g of 1-trifluoromethyl-2-bromoethanol was dissolved in 20 g of DMF, 3.9 g of potassium carbonate and 3.3 g of methacrylic acid were added, and the mixture was stirred at 80° C. for 3 hours, and then 20 g of pure water was added, and stirring was continued for 10 minutes. After adding 30 g of ethyl acetate for liquid separation, the organic layer was washed with 10 g of a 1% by mass aqueous hydrochloric acid solution, and the collected organic layer was washed three times with 10 g of water, and was subjected to column chromatography (ethyl acetate/hexane=10/90 (volume ratio) ) was purified to obtain 4.2 g of 1-trifluoromethyl-2-methacryloyloxyethanol (compound F1).

<Synthesis of compound F2 constituting unit F> (Synthesis Example 62) Synthesis of 1,3,5-triiodo-phenylmethacrylate (Compound F2)

(化合物F2) [Chemical 87]

(Compound F2)

The same procedure as in Synthesis Example 46 was carried out except that 1,3,5-triiodophenol was used instead of 1-(4-hydroxyphenyl)-2,2-dimethyl-1-propanone to obtain 1,3, 4.3 g of 5-triiodo-phenyl methacrylate (compound F2).

<Synthesis of polymer 1> (Synthesis Example 63) Synthesis of polymer a1

(聚合物a1) [Chemical 88]

(polymer a1)

3.0 g of compound a1 constituting unit A, 1.8 g of compound B1 constituting unit B, 2.1 g of compound E1 constituting unit E, and 0.71 g of dimethyl-2,2'- Azobis(2-methylpropionate) and 0.15 g of α-thioglycerol were dissolved in a mixed solution of 9 g of cyclohexanone and 13 g of γ-butyrolactone, and deoxygenated. The above solution was added dropwise to a mixed solution of 4 g of γ-butyrolactone and 4 g of cyclohexanone heated to 80° C. in advance over 4 hours, followed by stirring for 2 hours and then cooling. After cooling, it was reprecipitated by dropwise addition to 90 g of ethyl acetate. After the filtration, 5.3 g of the target polymer 1 was obtained by stirring in 40 g of 20 mass % methanol for 10 minutes, followed by filtration and vacuum drying. The unit ratio of the polymer is disclosed above and below, but the polymer of some embodiments of the present invention is not limited to this.

(聚合物1) (Synthesis Example 64) Synthesis of Polymer 1

(Polymer 1)

2.0 g of the polymer a1 obtained in Synthesis Example 63 and 1.0 g of sodium 2-hydroxysulfonate were added to a mixed solution of 30 g of methylene chloride and 10 g of pure water, and the mixture was stirred at 25° C. for 1 hour. After stirring, liquid separation was performed, and 1.0 g of sodium 2-hydroxysulfonate and 10 g of pure water were further added, and the mixture was stirred at 25° C. for 30 minutes. After repeating this operation three times, liquid separation was performed, and the recovered organic layer was concentrated. After the obtained organic layer was distilled off with the solvent, it was dispersed and washed with isopropanol to obtain 11.5 g of a polymer.

(聚合物2) (Synthesis Example 65) Synthesis of Polymer 2 [Chem. 90]

(Polymer 2)

Except having used 2,3-dihydroxypropanesulfonic acid instead of 2-hydroxysulfonic acid, the same operation as the above-mentioned synthesis example 64 was performed, and the polymer 21.4g was obtained.

(聚合物3) (Synthesis example 66) Synthesis of polymer 3

(Polymer 3)

The same operation as in Synthesis Example 48 was carried out except that 3-[N,N-bis(2-hydroxyethyl)amino]-2-hydroxypropanesulfonic acid was used instead of 2-hydroxypropanesulfonic acid to obtain 1.6 g of polymer item 3.

<Synthesis of polymers 4 to 13 and comparative polymers 1 and 2> (Synthesis Example 67) Synthesis of Polymers 4 to 13 and Comparative Polymers 1 and 2 The above-mentioned compounds A1 to A5, a1 and a2 constituting the unit A, the above-mentioned compounds B1, B2 and B4 constituting the unit B, the above-mentioned compounds C1, C2 and C6 constituting the unit C, and the The following compound D, the aforementioned compounds E1 to E3 constituting the unit E, the aforementioned compounds F1 to F2 constituting the unit F, polymers 4 to 13, and comparative polymers 1 and 2 were synthesized. The details of each polymer synthesized are shown in Table 1. Compound D: 4-hydroxyphenyl methacrylate

[Table 1]

<Preparation of resist composition> Among the above polymers, polymers 1, 4 to 6, 8, and 50 mg of comparative polymer 1 or 2 were dissolved in cyclohexanone, ethyl lactate, and γ-butyrolactone in a ratio of 5:5:1. In the solvent of , the resist composition samples 1 to 7 of Examples 1 to 5 and Comparative Examples 1 to 2 were prepared. The polymers used are shown in Table 2 and Table 3.

<Preparation of developer> The developer was prepared as follows. (1) Using resist composition samples 1 to 7 in which the above-mentioned polymers 1, 4 to 6, and 8 and the comparative polymers 1 to 2 were dissolved, the compositions were applied by spin coating so as to have a film thickness of 100 nm. Prepare the film. (2) An acetonitrile aqueous solution having an acetonitrile concentration of 0 to 80% by mass is prepared. (3) Each film obtained in the above (1) was immersed in each acetonitrile aqueous solution, and the minimum concentration of acetonitrile in the acetonitrile aqueous solution in which the composition applied to the film was completely dissolved within 30 seconds was determined. (4) The acetonitrile aqueous solution obtained in the above (3) was used as a developer for each resist composition sample.

<Evaluation of Electron Beam Sensitivity> The above-mentioned resist composition sample 1 was spin-coated on a silicon wafer. This was prebaked on a hot plate at 110° C. for 1 minute to obtain a substrate on which a coating film having a thickness of 30 nm was formed. The coating film of this board|substrate was drawn with the electron beam of 125keV using the electron beam drawing apparatus (Elionix Inc ELS-F100T), and the 50-nm line pattern of 160-nm pitch was drawn. The board|substrate after electron beam irradiation was used for 90 degreeC hotplate Post Exposure Bake (PEB) for 1 minute. Then, after developing for 1 minute with the developer for patterning in which the acetonitrile concentration of the developer optimized for each polymer was increased by 5% by mass, 50 nm line patterns were obtained by rinsing with pure water. The irradiation dose at this time was set to Emax [μC/cm ² ], and the sensitivity of electron beam irradiation was obtained. The LWR was measured using a scanning electron microscope (SEM) (S-5500 manufactured by Hitachi High-Technologies Corporation) to observe the obtained 50 nm line pattern. The above-mentioned samples 2 to 7 were also evaluated for sensitivity and LWR in the same manner as above. Using the sensitivity and LWR of the resist composition sample 1 (Comparative Example 1) as reference values, the sensitivities and LWRs of the resist composition samples 2 to 7 were compared, and the relative sensitivities and relative LWRs obtained are shown in Table 2.

[Table 2]

From the results of Examples 1 and 2, since the polymers are all polymers having a hydroxyl group in the anion of the unit A, the hydroxyl group of the anion can react with the unit B. Therefore, the reaction efficiency of Examples 1 and 2 was improved, and the sensitivity was increased by 15% or more relative to that of Comparative Example 1. In addition, in the polymer having a hydroxyl group in the anion of the unit A, the acid anion reacts with the unit B to form a part of the polymer, so that the acid diffusion controllability can be greatly improved, and the LWR lower than that of Comparative Example 1 can be reduced by 30% or more.

Examples 3 and 4 have the same cationic structure as that of Comparative Example 2, and compared with Comparative Example 2, the sensitivity can be increased by 15% or more. Compared with Comparative Example 1, the sensitivity of Comparative Example 2 was improved, and the LWR was 20% larger than that of Comparative Example 1. However, Examples 3 and 4 used a polymer having a hydroxyl group in the anion of the unit A, and were also superior in sensitivity compared to Comparative Example 1, and achieved a reduction in LWR of 30% or more.

From the results of Example 5, it can be seen that the anion with a thiol is the same as the anion with a hydroxyl group, and the sensitivity can be improved and the LWR can be reduced compared to the reference example.

<Synthesis of Polymers 14 to 20> (Synthesis Example 68) Synthesis of Polymers 14 to 21 According to the above-mentioned Synthesis Example 46, the above-mentioned compounds A7 to A10 constituting the unit A, the above-mentioned compounds B1, B2 and B4 constituting the unit B, the above-mentioned compounds C1, C2 and C6 constituting the unit C, and the above-mentioned compound E1 constituting the unit E were used. The following compound K of the unit K, synthesized polymers 14 to 21. The details of each polymer synthesized are shown in Table 3. Compound K: 9-(4-Methacryloyloxyphenyl)dibenzothiophene 2,4,6-trifluorobenzoate

[table 3]

[Examples 6 to 13] <Preparation of resist composition> 50 mg of any of the above-mentioned polymers 4 and 14 to 21 was dissolved in cyclohexanone, ethyl lactate and γ-butyrolactone in a ratio of 5:5 : 1 ratio of mixed solvents to prepare resist composition samples 8 to 16 of Examples 6 to 14. The polymers used are shown in Table 4.

<Preparation of developer> A developer was prepared as follows. (1) Using the above-mentioned polymers 4, 14 to 20 and resist composition samples 8 to 15 dissolved, the compositions were applied by spin coating so that the film thickness might be 100 nm to prepare thin films. (2) An acetonitrile aqueous solution having an acetonitrile concentration of 0 to 80% by mass is prepared. (3) Each film obtained in the above (1) was immersed in each acetonitrile aqueous solution, and the minimum concentration of acetonitrile in the acetonitrile aqueous solution in which the composition applied to the film was completely dissolved within 30 seconds was determined. (4) The acetonitrile aqueous solution obtained in the above (3) was used as a developer for each resist composition sample.

<Evaluation of Electron Beam-UV Sensitivity> The above-mentioned resist composition sample 8 was spin-coated on a silicon wafer. This was prebaked on a hot plate at 110° C. for 1 minute to obtain a substrate on which a coating film having a thickness of 30 nm was formed. The coating film of this board|substrate was drawn with the electron beam of 125keV using the electron beam drawing apparatus (Elionix Inc ELS-F100T), and the 50-nm line pattern of 160-nm pitch was drawn. The board|substrate after electron beam irradiation was used for 90 degreeC hotplate Post Exposure Bake (PEB) for 1 minute. Next, full-scale irradiation was performed with a 395 nm UV-LED at an exposure amount of 1000 mJ/cm ² . Then, after developing for 1 minute with the developer for patterning in which the acetonitrile concentration of the developer optimized for each polymer was increased by 5% by mass, 50 nm line patterns were obtained by rinsing with pure water. The irradiation dose at this time was set to Emax [μC/cm ² ], and the sensitivity of electron beam irradiation was obtained. The LWR was measured using a scanning electron microscope (SEM) (S-5500 manufactured by Hitachi High-Technologies Corporation) to observe the obtained 50 nm line pattern. The above-mentioned samples 9 to 16 were also evaluated for sensitivity and LWR in the same manner as above. The sensitivities and LWRs of resist composition samples 9 to 16 were compared with the sensitivity and LWR of resist composition sample 8 as reference values, and the relative sensitivities and relative LWR results obtained are shown in Table 4.

[Table 4]

Example 6 and Examples 7 to 10 in which the composition ratios of units A, B, and E were the same were compared. The hydroxyl group contained in the anions of the compounds A7 to A10 contained in Examples 7 to 10 is bound to the unit B by an acid generated by electron beam irradiation through an acid-catalyzed reaction. In addition, the same units B are also bonded by an acid-catalyzed reaction. In addition, the water generated by the above acid-catalyzed reaction hydrolyzes the acetal moiety of the onium salt in the unit A into a ketone derivative, thereby increasing the wavelength of light absorption, and the polymer is converted to have UV absorption at 395 nm. Therefore, acid is further generated by UV overall exposure after EB irradiation, and even with the same composition as in Example 6, the sensitivity of Examples 7 to 10 is improved.

Comparing Example 6 and Examples 7 to 13, even if the sensitivity to UV irradiation is increased, since the LWR is good, the influence of acid diffusion due to UV irradiation is almost absent. Since patterning was performed with the same level of LWR in Example 6 and Examples 7-13, there was no trade-off between sensitivity and LWR.

Comparing Example 8 and Example 14, it can be seen that since the action of the acid generated by the unit A can be inhibited by adding the unit K, the sensitivity decreases, but the LWR tends to decrease by inhibiting the diffusion of the acid. This works well when high resolution is required. [Industrial Availability]

According to several aspects of the present invention, a polymer and a resist composition containing the polymer can be provided, which have high absorption efficiency for particle beams or electromagnetic waves such as EUV, and are excellent in sensitivity, resolution, and pattern performance.

none

none

Claims (29)

A polymer comprising a polymer of unit A and unit B, wherein unit A has an onium salt structure and an acid is generated by irradiation of particle beams or electromagnetic waves, unit B has a structure bonded by an acid-catalyzed reaction, and said unit A is composed of the following It is represented by the general formula (1). [hua 1]

(1) (In the general formula (1), R ¹ is selected from a hydrogen atom; a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; and, a linear, branched or cyclic alkyl group Any one of the alkenyl groups with 1 to 6 carbon atoms, at least one hydrogen atom in the alkyl group and the alkenyl group described in this R ¹ can be replaced by a substituent, and L is selected from direct bonding, carbonyloxy, carbonylamino, Any one of phenylene diyl, naphthalenediyl, phenylenedioxy, naphthalenedioxy, phenylenedicarbonyloxy, naphthalenedicarbonyloxy, phenylenedioxycarbonyl and naphthalenedioxycarbonyl, Sp is a direct Bonding; linear, branched or cyclic alkylene groups with 1 to 6 carbon atoms that may have substituents; and linear, branched or cyclic alkylene groups with 1 to 6 carbon atoms that may have substituents Any of the alkenylene groups, at least one methylene group in the Sp can be substituted by a divalent heteroatom-containing group, M ⁺ is a sulfonium ion or an iodide ion, X ^- is a monovalent anion with an organic group, the organic group Including at least one selected from hydroxyl and sulfonamide.) The polymer of claim 1, wherein At least one of the hydroxyl groups of the organic group is derived from any one selected from the group consisting of primary alcohols, secondary alcohols and tertiary alcohols, At least one of the sulfonamide groups of the organic group is derived from any one selected from the group consisting of primary thiol, secondary thiol and tertiary thiol. The polymer according to claim 1 or 2, wherein, At least one of the hydroxyl groups of the organic group is derived from any one selected from the group consisting of primary alcohols and secondary alcohols, At least one of the sulfonamide groups in the organic group is derived from any one selected from the group consisting of primary thiol and secondary thiol. The polymer according to any one of claims 1 to 3, wherein X ^- is an alkyl sulfate anion having at least one hydroxyl group and a sulfonamido group; and an aryl sulfate anion having at least one hydroxyl group and a sulfonamido group salt anion; alkyl sulfonate anion having at least one hydroxyl group and sulfonamide group; arylsulfonate anion having at least one hydroxyl group and sulfonamide group; alkylcarboxylate anion having at least one hydroxyl group and sulfonamide group ; Aryl carboxylate anion with at least one hydroxyl group and sulfonamide group; Dialkylsulfonimide anion with at least one hydroxyl group and sulfonamide group; Trialkylsulfonic acid methane with at least one hydroxyl group and sulfonamide group ester anion; and any of tetraphenylborate anions having at least one hydroxyl group and a sulfonamide group, at least one ^of the alkyl group and the hydrogen atom of the aryl group in X- may be substituted by a fluorine atom. The polymer according to claim 4, wherein X ^- is an alkylsulfonate anion having at least one hydroxyl group and a sulfonamido group, and an arylsulfonate anion having at least one hydroxyl group and a sulfonamido group At least one of the hydrogen atoms of any one ^of the alkyl group and the aryl group in X- may be substituted with a fluorine atom. The polymer according to any one of claims 1 to 5, wherein the unit B is a compound represented by the following general formula (I) or (II) at any position of the compound and the following general formula (2) Sp group-bonded unit. [hua 2]

(I)

(II) (in the general formula (I), R ² and R ³ are each independently selected from hydrogen atoms; electron donating groups; and electron withdrawing groups, and E is selected from direct bonding; Oxygen atom; sulfur atom; and any one of methylene groups, n ¹ is an integer of 0 or 1, n ⁴ and n ⁵ are each an integer of 1 to 2, n ⁴ +n ⁵ is 2 to 4, and n ⁴ is 1 When n ² is an integer from 0 to 4, when n ⁴ is 2, n ² is an integer from 0 to 6. When n ⁵ is 1, n ³ is an integer from 0 to 4. When n ⁵ is 2, n ³ is an integer from 0 to 6. Integer, when n ² is 2 or more and R ² is an electron-donating group or an electron-withdrawing group, two R ² can be selected from the group consisting of oxygen atom, sulfur atom, divalent nitrogen atom-containing group and subgroup directly or via a single bond Either one of the methyl groups forms a ring structure with each other, and when n ³ is 2 or more and R ³ is an electron donating group or an electron withdrawing group, two R ³ can be selected from oxygen atoms, sulfur atoms, Any one of the divalent nitrogen atom-containing group and the methylene group forms a ring structure with each other. In the general formula (II), R ⁴ is independently selected from a hydrogen atom; an electron donating group; and an electron withdrawing group Any one, at least one of R ⁴ is the electron-donating group, R ⁵ is selected from a hydrogen atom; an alkyl group that may have a substituent; and any one of an alkenyl group that may have a substituent, at least one of the R ⁵ A methylene group can be substituted by a divalent heteroatom-containing group, and the R ⁵ can form a ring structure together with the benzene ring bonded to the hydroxymethylene group having the R ⁵ , n ⁶ is an integer of 0 to 7, and n ⁷ is 1 or 2, when n ⁷ is 1, n ⁶ is an integer of 0 to 5, when n ⁷ is 2, n ⁶ is an integer of 0 to 7, n ⁶ is 2 or more, and R ⁴ is an electron donating group or an electron withdrawing group In the case of a group, 2 R ⁴ can form a ring structure with each other by a single bond directly or through any one selected from an oxygen atom, a sulfur atom, a group containing a divalent nitrogen atom and a methylene group.) [Chemical 3]

(2) (In the formula (2), R ¹ , L and Sp are selected from the same options as R ¹ , L and Sp in the general formula (1), respectively, and * indicates that the general formula (I) or the bonding site of the compound represented by (II).) The polymer according to any one of claims 1 to 6, wherein, The polymer further comprises units C, The unit C has a radical generating structure containing at least one multiple bond selected from multiple bonds of carbon atoms and carbon atoms and multiple bonds of carbon atoms and heteroatoms, by particle beams or electromagnetic waves. The unit C that generates the second radical is irradiated, The multiple bonds in the radical generating structure are not multiple bonds contained in benzene-based aromatics. The polymer according to claim 7, wherein the multiple bond is at least any one of the bonds shown below. [hua 4]

The polymer according to claim 7 or 8, wherein, The unit C has any one selected from the group consisting of an alkylphenone skeleton, an acyl oxime skeleton, and a benzyl ketal. The polymer according to any one of claims 1 to 9, wherein the unit A is represented by the following general formula (3). [hua 5]

(3) (In the general formula (3), R ¹ , L, Sp and X ^- are selected from the same options as R ¹ , L, Sp and X ^- in the general formula (1), respectively, and R ^6a is Selected from linear, branched or cyclic alkylene groups with 1 to 6 carbon atoms that may have substituents; linear, branched or cyclic alkenes with 1 to 6 carbon atoms that may have substituents base; an arylene group with 6 to 14 carbon atoms that may have a substituent; a heteroarylene group with 4 to 12 carbon atoms that may have a substituent; and any one of direct bonding, at least one of the R ^6a The methylene group can be substituted by a divalent heteroatom-containing group, and R ^6b is respectively selected from a linear, branched or cyclic alkyl group with 1 to 6 carbon atoms that may have a substituent; Chain or cyclic alkenyl group with 1 to 6 carbon atoms; aryl group with 6 to 14 carbon atoms which may have a substituent; , at least one methylene group in the R ^6b can be substituted by a divalent heteroatom-containing group, and two of the R ^6a and 2 R ^6b can be selected from oxygen atoms, sulfur atoms, and divalent nitrogen atoms directly or via a single bond. Any of the group and the methylene group forms a ring structure with the sulfur atom to which these are bonded.) The polymer according to any one of claims 1 to 9, wherein the M ⁺ X ^- is any one represented by the following general formula (11) or the following general formula (12). [hua 6]

[hua 7]

(In the formulas (11) and (12), the R ¹⁴ is independently selected from alkyl, hydroxyl, mercapto, alkoxy, aryloxycarbonyl, heteroaryloxycarbonyl, arylsulfanylcarbonyl , heteroarylsulfanylcarbonyl, arylsulfonamido, heteroarylsulfonamido, alkylsulfonamido, aryl, heteroaryl, aryloxy, heteroaryloxy, (poly)alkyleneoxy, alkane Any one of amino group and dialkylcyano group, R ¹⁷ and R ¹⁸ are independently selected from alkyl, hydroxyl, mercapto, alkoxy, alkylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkoxycarbonyl, Aryloxycarbonyl, Heteroaryloxycarbonyl, Arylsulfanylcarbonyl, Heteroarylsulfanylcarbonyl, Arylsulfamido, Heteroarylsulfamido, Alkylsulfamido, Aryl, Heteroaryl, Aryl Oxy, Heteroaryloxy, Alkylsulfinyl, Arylsulfinyl, Heteroarylsulfinyl, Alkylsulfonyl, Arylsulfonyl, Heteroarylsulfonyl, Arylsulfonyl any one of a group, a heteroarylsulfonyl group, a (poly)alkyleneoxy group, an alkylamino group, a dialkylamino group, a nitro group and a halogen atom, and the number of carbon atoms when the R ¹⁴ , R ¹⁷ and R ¹⁸ have carbon atoms is 1 to 12, and when the R ¹⁴ , R ¹⁷ and R ¹⁸ have a hydrogen atom, the hydrogen atom may be substituted by a substituent, and R ¹⁹ is selected from a linear, branched or cyclic carbon that may have a substituent Alkyl having 1 to 12 atoms; optionally substituted straight-chain, branched or cyclic alkenyl having 1 to 12 carbon atoms; optionally substituted aryl having 6 to 14 carbon atoms; and, Any one of the heteroaryl groups having 4 to 12 carbon atoms that may have a substituent, and any one of the benzene ring to which the R ¹⁹ and the R ¹⁸ are bonded and the benzene ring to which the R ¹⁷ is bonded may be a single bond Form a ring structure directly or through any one selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom-containing group, and a methylene group with the bonded sulfur atom, and when the R ¹⁴ , R ¹⁷ and R ¹⁸ have a methylene group, At least one of the methylene groups may be substituted by a divalent heteroatom-containing group, and the R ¹⁵ and R ¹⁶ are respectively selected from a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent. ; A straight-chain, branched or cyclic alkenyl group with 1 to 12 carbon atoms that may have a substituent; an aryl group with 6 to 14 carbon atoms that may have a substituent; and, a group of carbon atoms that may have a substituent Any of the heteroaryl groups from 4 to 12, the R ¹⁵ and R ¹⁶ can be bonded to each other by a single bond directly or via any one selected from an oxygen atom, a sulfur atom and an alkylene group to form a ring structure, and the R ¹⁵ And at least one methylene group in R ¹⁶ can be substituted by a divalent heteroatom-containing group, L ³ is selected from direct bonding; straight chain, branched chain or cyclic alkylene group with 1 to 12 carbon atoms; carbon number Alkenylene group of 2 to 12; any one of sulfinyl group, sulfonyl group and carbonyl group, any hydrogen atom in R ¹⁴ , R ¹⁸ and R ¹⁹ can be bonded to Sp in the formula (1) Substitution, Y is an oxygen atom or a sulfur atom, q is an integer from 0 to 4, f is an integer from 0 to 3, g is an integer from 1 to 5, and j is 0 an integer of ~2, k is an integer of 1 to 4, (however, any one of the benzene ring to which the R ¹⁹ and the R ¹⁸ are bonded and the benzene ring to which the R ¹⁷ is bonded together form the sulfur atom. In the case of a ring structure, in the formula (11), q is 0 to 3 or j is 0 to 2, and in the formula (12), q is 0 to 3 or j is 0 to 1) The formula (11) and ( In 12), at least one benzene ring may be a six-membered heteroaromatic ring having a heteroatom in the ring, or the benzene ring bonded to R ¹⁴ in the formulas (11) and (12) may be the In the case of a heteroaromatic ring, k is 0 to 4, and when there are two or more R ¹⁴ in the formulas (11) and (12), two of the R ¹⁴ may be linked to each other to form a ring structure, and X ^- is selected from the formula ( 1) X ^- same option. ) The polymer according to any one of claims 7 to 11, wherein the unit C is represented by at least any one of the following general formula (4). [hua 8]

(4) (In the general formula (4), R ¹ , L, Sp and X ^- are selected from the same options as R ¹ , L, Sp and X ^- in the general formula (1), respectively, and R ⁷ are respectively -R ^a (R ^a is a linear, branched or cyclic alkyl group with 1 to 12 carbon atoms that may have substituents, and at least one methylene group in R ^a can be a divalent Heteroatomic group substitution); -OR ^a ; and a group in which at least one carbon-carbon single bond in this R ^a is substituted by a carbon-carbon double bond; and, -R ^b (R ^b is the number of carbon atoms that may have a substituent 6~14 aryl group or any one of the heteroaryl group with 4~12 carbon atoms that may have substituents), 2 R ⁷ can be selected from oxygen atom, sulfur atom, divalent nitrogen directly or through a single bond Either of the atomic group and the methylene group forms a ring structure with each other, and R ⁸ is selected from -R ^a ; -R ^b ;-OR ^a ;-SR ^a ;-OR ^b ;-SR ^b ;-OC(=O)R ^a ;-OC(=O) ^Rb ;-C(=O) ^ORa ;-C(=O) ^ORb ;-OC(=O) ^ORa ;-OC(=O) ^ORb ;-NHC( -NRaC(=O) ^{Ra ;} -NHC(=O) ^Rb ;-NRbC(=O) ^Rb ; ^-NRaC ( ⁼ O ^{)Rb ;} -NR ^b C(=O)R ^a ;-N(R ^a ) ₂ ;-N(R ^b ) ₂ ;-N(R ^a )(R ^b );-SO ₃ R ^a ;-SO ₃ R ^b ;-SO ₂ R ^a ; -SO ₂ R ^b ; a group in which at least one carbon-carbon single bond in the -R ^a is substituted by a carbon-carbon double bond; and any of the nitro groups, m ² is an integer of 1 to 3, When m2 is ¹ , m1 is ^an integer of 0 to 4; when m2 is ² , m1 is ^an integer of 0 to 6 ^; when m2 is ³ , m1 is an integer of 0 to 8; when m1 is ² or more, 2 Each R ⁸ may form a ring structure with each other directly or through any one selected from the group consisting of an oxygen atom, a sulfur atom, a group containing a divalent nitrogen atom, and a methylene group). The polymer according to claim 12, wherein the unit C is represented by the general formula (4), and at least one of R ⁷ in the general formula (4) is a hydroxyl group. The polymer according to any one of claims 1 to 13, wherein, The polymer also contains units D having an aryloxy group. The polymer according to any one of claims 1 to 14, wherein, The polymer further comprises organometallic compound-containing units E having metal atoms selected from Sn, Sb, Ge, Bi and Te. The polymer according to any one of claims 1 to 15, wherein the polymer further includes a unit F represented by the following general formula (7) having a halogen atom. [Chemical 9]

(7) (In the general formula (7), R ¹ , L and Sp are selected from the same options as R ¹ , L and Sp in the general formula (1), respectively, and R ^h is selected from optionally substituted Linear, branched or cyclic alkyl group with 1 to 12 carbon atoms; linear, branched or cyclic alkyleneoxy group with 1 to 12 carbon atoms that may have substituents; Linear, branched or cyclic alkenyl with 1 to 12 carbon atoms; linear, branched or cyclic alkenyleneoxy with 1 to 12 carbon atoms that may have a substituent; An aryl group having 6 to 14 carbon atoms; and any of a heteroaryl group having 4 to 12 carbon atoms that may have a substituent, and a part or all of the hydrogen atoms substituted by carbon atoms are substituted by fluorine atoms or iodine atoms) . A resist composition containing the polymer according to any one of claims 1 to 16. The resist composition according to claim 17, wherein, The resist composition also contains any one of an organometallic compound and an organometallic mixture, The metal is selected from Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, I, Xe, Hf, Ta, At least one of W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po, At, Rn and Ra. A method of manufacturing a component, comprising the steps of: A resist film forming step of forming a resist film on a substrate using the resist composition described in claim 17 or 18; a photolithography step of exposing the resist film using particle beams or electromagnetic waves; The pattern forming step of developing the exposed resist film to obtain a photolithographic resist pattern. A method of manufacturing a component according to claim 19, wherein: The development in the pattern forming step is performed using an aqueous solution containing a water-soluble organic solvent. A method of manufacturing a component according to claim 19 or 20, wherein, In the photolithography step, after exposing the particle beam or electromagnetic wave, a second active energy ray having a lower energy than the particle beam or electromagnetic wave is irradiated. The method for manufacturing a component according to any one of claims 19 to 21, further comprising the steps of: a step of etching a coating film obtained by applying a composition for inversion patterns to cover at least the concave portions of the photoresist pattern, thereby exposing the surface of the photoresist pattern; The step of removing the resist film of the exposed resist pattern surface portion to obtain a reverse pattern. The method for manufacturing a component according to any one of claims 19 to 22, wherein, The particle beam is an electron beam, and the electromagnetic wave is extreme ultraviolet. A pattern forming method comprising the steps of: A resist film forming step of forming a resist film on a substrate using the resist composition described in claim 17 or 18; The photolithography step of exposing the resist film by using particle beams or electromagnetic waves; The pattern forming step of developing the exposed resist film to obtain a photolithographic resist pattern. The pattern forming method according to claim 24, wherein, The development in the pattern forming step is performed using an aqueous solution containing a water-soluble organic solvent. The pattern forming method according to claim 24 or 25, wherein, In the photolithography step, after exposing the particle beam or electromagnetic wave, a second active energy ray having a lower energy than the particle beam or electromagnetic wave is irradiated. A method for forming a reverse pattern, comprising the following steps: A resist film forming step of forming a resist film on a substrate using the resist composition described in claim 17 or 18; The photolithography step of exposing the resist film by using particle beams or electromagnetic waves; The pattern forming step of developing the exposed resist film to obtain a photolithographic resist pattern. a step of etching a coating film obtained by applying a composition for inversion patterns to cover at least the concave portions of the photoresist pattern, thereby exposing the surface of the photoresist pattern; The step of removing the resist film of the exposed surface portion of the photoresist pattern to obtain a reverse pattern. The method for forming an inversion pattern according to claim 27, wherein, The development in the pattern forming step is performed using an aqueous solution containing a water-soluble organic solvent. The method for forming an inversion pattern according to claim 27 or 28, wherein, In the photolithography step, after exposing the particle beam or electromagnetic wave, a second active energy ray having a lower energy than the particle beam or electromagnetic wave is irradiated.