CN114967342A

CN114967342A - Positive photosensitive composition and dry film, patterned resist film, substrate with mold, and method for producing plated molded article

Info

Publication number: CN114967342A
Application number: CN202111623546.9A
Authority: CN
Inventors: 桃泽绫
Original assignee: Tokyo Ohka Kogyo Co Ltd
Current assignee: Tokyo Ohka Kogyo Co Ltd
Priority date: 2021-02-25
Filing date: 2021-12-28
Publication date: 2022-08-30
Also published as: KR20220121694A; JP2022129979A; TW202244616A

Abstract

The invention provides a chemical amplification type positive photosensitive composition which has high solid content concentration, good storage stability, and can form a photosensitive layer with excellent resistance to crack and can inhibit repulsion and swelling of a developing solution, a photosensitive dry film with the photosensitive layer formed by the chemical amplification type positive photosensitive composition, a manufacturing method of a patterned resist film using the chemical amplification type positive photosensitive composition, a manufacturing method of a tape casting mould substrate and a manufacturing method of a plated shaped object. The chemically amplified positive photosensitive composition comprises: an acid generator (A) which generates an acid by irradiation with an active light or a radiation; the resin (B) has an increased solubility in alkali due to the action of an acid, and comprises an acrylic resin (B3), wherein the acrylic resin (B3) comprises a specific structural unit, and has a solid content concentration of 25 to 50 mass%.

Description

Positive photosensitive composition, dry film, patterned resist film, substrate with mold, and method for producing plated molded article

Technical Field

The present invention relates to a chemically amplified positive photosensitive composition, a photosensitive dry film including a photosensitive layer formed of the chemically amplified positive photosensitive composition, a method for producing a patterned resist film using the chemically amplified positive photosensitive composition, a method for producing a substrate with a mold, and a method for producing a plated molded article.

Background

At present, photoelectric machining (photofabrication) has become the mainstream of precision microfabrication technology. The photo-electric processing is a general term for a technology for manufacturing various precision parts such as a semiconductor package by applying a photoresist composition to the surface of a workpiece to form a photoresist layer, patterning the photoresist layer by a photolithography technique, and performing chemical etching, electrolytic etching, or electroforming mainly by electroplating using the patterned photoresist layer (photoresist pattern) as a mask.

In recent years, with the miniaturization of electronic devices, high-density mounting technology of semiconductor packages has been advanced, and the mounting density of multi-pin thin-film mounting by packages, miniaturization of package sizes, 2-dimensional mounting technology by flip chip method, and 3-dimensional mounting technology has been improved. In such a high-density mounting technique, for example, a bump electrode (mounting terminal) such as a bump protruding from a package, a metal post connecting a rewiring extending from a peripheral terminal on a wafer and the mounting terminal, or the like is disposed on a substrate as a connection terminal with high accuracy.

A photoresist composition is used in the above-described photoelectric processing, and a chemically amplified photosensitive composition containing an acid generator is known as such a photoresist composition (see patent documents 1 and 2, etc.). The chemically amplified photosensitive composition is a composition in which an acid is generated from an acid generator by irradiation (exposure) with radiation, and diffusion of the acid is promoted by heat treatment, so that an acid-catalyzed reaction is caused with respect to a base resin or the like in the composition, and alkali solubility is changed.

Such a chemically amplified photosensitive composition is used for forming a patterned insulating film or an etching mask, and for forming a plating structure such as a bump, a metal post, or a Cu rewiring by a plating process. Specifically, a photoresist layer having a desired film thickness is formed on a support such as a metal substrate using a chemically amplified photosensitive composition, and is exposed to light through a predetermined mask pattern and developed to form a photoresist pattern used as a mold for selectively removing (peeling off) a portion where a plated shaped article is formed. Then, after a conductor such as copper is embedded in the removed portion (non-resist portion) by plating, a photoresist pattern around the conductor is removed, whereby a bump, a metal post, and a Cu rewiring can be formed.

Documents of the prior art

Patent literature

Patent document 1: japanese patent laid-open No. 9-176112

Patent document 2: japanese laid-open patent publication No. 11-52562

Disclosure of Invention

Technical problem to be solved by the invention

When the formed photoresist layer (photosensitive layer) is thick, a chemically amplified photosensitive composition having an increased solid content concentration may be used.

However, the conventional chemically amplified photosensitive composition has a problem of poor storage stability when the solid content concentration is high. If the storage stability of the chemically amplified photosensitive composition is poor, for example, the viscosity of the chemically amplified photosensitive composition increases with time.

Further, when a conventional chemically amplified photosensitive composition is used, there is a problem that the photoresist layer sometimes repels a developer during development. If the developer is repelled, the developer cannot be brought into sufficient contact with the photosensitive layer, and thus, a pattern formation failure such as a phenomenon that a region where a resist pattern is not formed or a formed resist pattern cannot be formed into a desired shape occurs.

Further, when a conventional positive-type chemically amplified photosensitive composition is used, there is a problem that the exposed photoresist layer comes into contact with a developer during development, and the photoresist layer swells. When the photoresist layer swells during development, unexposed portions may be dissolved. When the photoresist layer swells during development, wrinkles due to swelling, or floating or deformation due to swelling may be observed in unexposed portions of the formed resist pattern.

Further, when a conventional positive-type chemically amplified photosensitive composition is used, there is a problem that cracks may be formed in a formed resist pattern. If a crack is formed in the resist pattern, it is difficult to form a plated shaped object having a desired shape when the resist pattern is used as a mold for forming the plated shaped object, for example. Therefore, it is also desired that the chemically amplified photosensitive composition be inhibited from cracking, i.e., be excellent in crack resistance.

The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a chemically amplified positive photosensitive composition having a high solid content concentration and good storage stability, which is capable of forming a photosensitive layer having excellent resistance to cracking while suppressing repulsion and swelling of a developer, a photosensitive dry film including a photosensitive layer formed of the chemically amplified positive photosensitive composition, a method for producing a patterned resist film using the chemically amplified positive photosensitive composition, a method for producing a substrate with a mold, and a method for producing a plated molded article.

Solution for solving the above technical problem

The present inventors have made intensive studies to achieve the above object, and as a result, have found that the above technical problems can be solved by a chemically amplified positive photosensitive composition comprising: an acid generator (A) which generates an acid by irradiation with an active light or a radiation; and a resin (B) having an increased solubility in alkali due to an action of an acid, wherein the resin (B) comprises an acrylic resin (B3), the acrylic resin (B3) comprises a structural unit represented by the following formula (B3-1), and the chemically amplified positive photosensitive composition has a solid content concentration of 25 to 70 mass%. Specifically, the present invention provides the following technical solutions.

The invention of claim 1 is a chemical amplification type positive photosensitive composition, comprising: an acid generator (A) which generates an acid by irradiation with active light or radiation; a resin (B) whose solubility in alkali is increased by the action of an acid,

the resin (B) comprises an acrylic resin (B3),

the acrylic resin (B3) contains a structural unit represented by the following formula (B3-1),

[ CHEM 1 ]

(in the formula (B3-1), R ^b01 is-O-, -S-, -CO-O-, -CO-NH-or-SO ₂ -，R ^b02 And R ^b03 Each independently is a hydrogen atom or an organic group, R ^b02 And R ^b03 At least one of which is represented by-CO-O-R ^b04 A group represented by R ^b04 Is a hydrogen atom or an organic group, and x1 and x2 are each independently 1 or 2. )

The chemical amplification type positive photosensitive composition has a solid content concentration of 25 to 70 mass%.

The invention of claim 2 is a photosensitive dry film, has a substrate film and formed on the surface of the substrate film photosensitive layer, the photosensitive layer is composed of the 1 st claim of chemical amplification type positive photosensitive composition.

The 3 rd aspect of the present invention is a method for manufacturing a patterned resist film, comprising:

a laminating step of laminating a photosensitive layer composed of the chemically amplified positive photosensitive composition according to claim 1 on a substrate;

an exposure step of irradiating the photosensitive layer with active light or radiation selectively at a position; and

and a developing step of developing the exposed photosensitive layer.

The present invention according to claim 4 is a method for manufacturing a substrate with a mold, including:

a laminating step of laminating a photosensitive layer composed of the chemically amplified positive photosensitive composition according to claim 1 on a substrate having a metal surface;

an exposure step of irradiating the photosensitive layer with active light or radiation; and

and a developing step of developing the exposed photosensitive layer to produce a mold for forming a plated molded article.

The invention according to claim 5 is a method for producing a plated shaped article, comprising a step of plating the molded substrate with a mold produced by the method for producing a molded substrate with a mold according to claim 4 to form a plated shaped article in the mold.

Effects of the invention

The present invention can provide a chemically amplified positive photosensitive composition having a high solid content concentration and good storage stability, and capable of forming a photosensitive layer that is suppressed in repelling and swelling against a developer and excellent in crack resistance, a photosensitive dry film provided with a photosensitive layer composed of the chemically amplified positive photosensitive composition, a method for producing a patterned resist film using the chemically amplified positive photosensitive composition, a method for producing a substrate with a mold, and a method for producing a plated molded article.

Detailed Description

Chemically amplified positive photosensitive composition

The chemically amplified positive photosensitive composition (hereinafter also referred to as a photosensitive composition) contains: an acid generator (a) that generates an acid by irradiation with active light or radiation (hereinafter also referred to as the acid generator (a)); the resin (B) has increased solubility in alkali due to the action of an acid (hereinafter also referred to as resin (B)). The resin (B) contains an acrylic resin (B3), and the acrylic resin (B3) contains a structural unit represented by the following formula (B3-1). The photosensitive resin composition may contain components such as an acid diffusion inhibitor (C), an alkali-soluble resin (D), a sulfur-containing compound (E), a dye (F), and an organic solvent (S), if necessary.

The solid content concentration of the chemically amplified positive photosensitive composition is 25 mass% or more and 70 mass% or less. When the solid content concentration is within this range, a thick photosensitive layer can be easily formed. The solid content concentration of the photosensitive composition may be 30 mass% or more and 60 mass% or less, or 40 mass% or more and 50 mass% or less. The solid component means a component other than the organic solvent (S) and water.

Hereinafter, essential or optional components contained in the photosensitive composition and a method for producing the photosensitive composition will be described.

< acid Generator (A) >

The acid generator (a) is a compound that generates an acid by irradiation of active light or radiation, and is not particularly limited as long as it is a compound that directly or indirectly generates an acid by light. The acid generator (a) is preferably the acid generators of the first to fifth embodiments described below. Hereinafter, preferred embodiments of the acid generator (a) preferably used in the positive photosensitive composition will be described as a first embodiment to a fifth embodiment.

The acid generator (a) may be a compound represented by the following formula (a 1).

[ CHEM 2]

In the above formula (a1), X ^1a A sulfur atom or an iodine atom representing the valence g, g being 1 or 2. h represents the number of repeating units of the structure in parentheses. R ^1a Is equal to X ^1a The bonded organic group represents an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an alkynyl group having 2 to 30 carbon atoms, and R is ^1a May be substituted with at least 1 selected from the group consisting of alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro, and halogen. R ^1a The number of (b) is g + h (g-1) +1, R ^1a May be the same as or different from each other. In addition, 2 or more R ^1a Can be directly bonded to each other or through-O-, -S-, -SO ₂ -、-NH-、-NR ^2a -, -CO-, -COO-, -CONH-, and having 1 carbon atom numberAlkylene or phenylene groups of 3 or more bonded to form a group containing X ^1a The ring structure of (a). R ^2a An alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

X ^2a The structure is represented by the following formula (a 2).

[ CHEM 3 ]

In the above formula (a2), X ^4a X represents a 2-valent group of an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a heterocyclic compound having 8 to 20 carbon atoms ^4a May be substituted with at least 1 kind selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, a hydroxyl group, a cyano group, a nitro group, and a halogen. X ^5a represents-O-, -S-, -SO-, -SO ₂ -、-NH-、-NR ^2a -, -CO-, -COO-, -CONH-, an alkylene group having 1 to 3 carbon atoms, or a phenylene group. h represents the number of repeating units of the structure in parentheses. h + 1X ^4a And h X ^5a May be the same or different. R ^2a As defined above.

X ^3a- Examples of the onium counter ion include a fluoroalkyl fluorophosphate anion represented by the following formula (a17) and a borate anion represented by the following formula (a 18).

[ CHEM 4 ]

[(R ^3a ) _j PF _6-j ] ^- (a17)

In the above formula (a17), R ^3a Represents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms. j represents R ^3a The number of (b) is an integer of 1 to 5 inclusive. j R ^3a May be the same or different.

[ CHEM 5]

In the above formula (a18), R ^4a ～R ^7a Each independently represents a fluorine atom or a phenyl group, and a part or all of hydrogen atoms of the phenyl group may be substituted by at least 1 selected from the group consisting of a fluorine atom and a trifluoromethyl group.

Examples of the onium ion in the compound represented by the formula (a1) include triphenylsulfonium, tri-p-tolylsulfonium, 4- (phenylthio) phenyldiphenylsulfonium, bis [4- (diphenylsulfonium) phenyl ] sulfide, bis [4- { bis [4- (2-hydroxyethoxy) phenyl ] sulfonium } phenyl ] sulfide, bis {4- [ bis (4-fluorophenyl) sulfonium ] phenyl } sulfide, 4- (4-benzoyl-2-chlorophenylthio) phenyl bis (4-fluorophenyl) sulfonium, 7-isopropyl-9-oxo-10-thioxo-9, 10-dihydroanthracen-2-yl-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thioxo-9, 10-dihydroanthracen-2-yl-diphenylsulfonium, and mixtures thereof, 2- [ (diphenyl) sulfonium ] thioxanthone, 4- [4- (4-tert-butylbenzoyl) phenylthio ] phenyl di-p-tolylsulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, diphenylbenzoylmethyl sulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl (1-ethoxycarbonyl) ethyl sulfonium, 4-hydroxyphenylmethylbenzoylmethyl sulfonium, phenyl [4- (4-biphenylthio) phenyl ] 4-biphenylsulfonium, phenyl [4- (4-biphenylthio) phenyl ] 3-biphenylsulfonium, [4- (4-acetylphenylthio) phenyl ] diphenylsulfonium, octadecylmethylbenzoylmethylsulfinium, diphenyliodonium, di-p-tolyliodonium, bis (4-dodecylphenyl) iodonium, and the like, Bis (4-methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyliodonium, bis (4-decyloxy) phenyliodonium, 4- (2-hydroxytetradecyloxy) phenylphenyliodonium, 4-isopropylphenyl (p-tolyl) iodonium, or 4-isobutylphenyl (p-tolyl) iodonium, and the like.

Among the onium ions in the compound represented by the above formula (a1), a preferable onium ion is a sulfonium ion represented by the following formula (a 19).

[ CHEM 6 ]

In the above formula (a19), R ^8a Each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkyloxycarbonyl group, a halogen atom, an aryl group which may have a substituent, and an arylcarbonyl group. X ^2a X in the above formula (a1) ^2a The same meaning is used.

Specific examples of the sulfonium ion represented by the above formula (a19) include 4- (phenylthio) phenyldiphenylsulfonium, 4- (4-benzoyl-2-chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, phenyl [4- (4-biphenylthio) phenyl ] 4-biphenylsulfonium, phenyl [4- (4-biphenylthio) phenyl ] 3-biphenylsulfonium, [4- (4-acetylphenylthio) phenyl ] diphenylsulfonium, and diphenyl [4- (p-terphenylthio) phenyl ] diphenylsulfonium.

In the fluoroalkyl fluorophosphate anion represented by the above formula (a17), R ^3a The alkyl group substituted with a fluorine atom preferably has 1 to 8 carbon atoms, and more preferably has 1 to 4 carbon atoms. Specific examples of the alkyl group include: linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl, and the proportion of hydrogen atoms in the alkyl groups substituted by fluorine atoms is usually 80% or more, preferably 90% or more, and more preferably 100%. When the substitution rate of fluorine atoms is less than 80%, the acid strength of the onium fluoroalkyl fluorophosphate represented by the above formula (a1) is lowered.

Particularly preferred R ^3a A linear or branched perfluoroalkyl group having 1 to 4 carbon atoms and a fluorine atom substitution rate of 100%, and specific examples thereof include CF ₃ 、CF ₃ CF ₂ 、(CF ₃ ) ₂ CF、CF ₃ CF ₂ CF ₂ 、CF ₃ CF ₂ CF ₂ CF ₂ 、(CF ₃ ) ₂ CFCF ₂ 、CF ₃ CF ₂ (CF ₃ )CF、(CF ₃ ) ₃ C。R ^3a The number j of (a) is an integer of 1 to 5, preferably 2 to 4, and particularly preferably 2 or 3.

Specific examples of the preferable fluoroalkylfluorophosphate anion include [ (CF) ₃ CF ₂ ) ₂ PF ₄ ] ^- 、[(CF ₃ CF ₂ ) ₃ PF ₃ ] ^- 、[((CF ₃ ) ₂ CF) ₂ PF ₄ ] ^- 、[((CF ₃ ) ₂ CF) ₃ PF ₃ ] ^- 、[(CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ] ^- 、[(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- 、[((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ^- 、[((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ^- 、[(CF ₃ CF ₂ CF ₂ CF ₂ ) ₂ PF ₄ ] ^- Or [ (CF) ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- Among them, [ (CF) is particularly preferable ₃ CF ₂ ) ₃ PF ₃ ] ^- 、[(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- 、[((CF ₃ ) ₂ CF) ₃ PF ₃ ] ^- 、[((CF ₃ ) ₂ CF) ₂ PF ₄ ] ^- 、[((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ^- Or [ ((CF) ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ^- 。

A preferred specific example of the borate anion represented by the formula (a18) includes tetrakis (pentafluorophenyl) borate ([ B (C) ] ₆ F ₅ ) ₄ ] ^- ) Tetra [ (trifluoromethyl) phenyl group]Borate ([ B (C) ] ₆ H ₄ CF ₃ ) ₄ ] ^- ) Difluoro bis (pentafluorophenyl) borate ([ (C) ₆ F ₅ ) ₂ BF ₂ ] ^- ) Trifluoro-pentafluorophenyl borate ([ (C) ₆ F ₅ )BF ₃ ] ^- ) Tetrakis (difluorophenyl) borate ([ B (C)) ₆ H ₃ F ₂ ) ₄ ] ^- ) And the like. Among these, tetrakis (pentafluorophenyl) borate ([ B (C) is particularly preferable ₆ F ₅ ) ₄ ] ^- )。

Examples of the second mode of the acid generator (A) include 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (2-furyl) vinyl ] s-triazine, 2, 4-bis (trichloromethyl) -6- [2- (5-methyl-2-furyl) vinyl ] s-triazine, 2, 4-bis (trichloromethyl) -6- [2- (5-ethyl-2-furyl) vinyl ] s-triazine, 2, 4-bis (trichloromethyl) -6- [2- (5-propyl-2-furyl) vinyl ] s-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3, 5-dimethoxyphenyl) vinyl ] s-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3, 5-diethoxyphenyl) vinyl ] s-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3, 5-dipropoxyphenyl) vinyl ] s-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3-methoxy-5-ethoxyphenyl) vinyl ] s-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3-methoxy-5-propoxyphenyl) vinyl ] s-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3, 4-methylenedioxyphenyl) vinyl ] s-triazine, 2, 4-bis (trichloromethyl) -6- (3, 4-methylenedioxyphenyl) s-triazine, 2, 4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl s-triazine, 2, 4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl s-triazine, 2, 4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl s-triazine, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1, 3, 5-triazine, 2- (4-methoxynaphthyl) -4, 6-bis (trichloromethyl) -1, 3, 5-triazine, 2- [2- (2-furyl) vinyl ] -4, 6-bis (trichloromethyl) -1, 3, 5-triazine, 2- [2- (5-methyl-2-furyl) vinyl ] -4, 6-bis (trichloromethyl) -1, 3, 5-triazine, 2- [2- (3, 5-dimethoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) -1, 3, 5-triazine, 2- [2- (3, 4-dimethoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) -1, halogen-containing triazine compounds such as 3, 5-triazine, 2- (3, 4-methylenedioxyphenyl) -4, 6-bis (trichloromethyl) -1, 3, 5-triazine, tris (1, 3-dibromopropyl) -1, 3, 5-triazine, tris (2, 3-dibromopropyl) -1, 3, 5-triazine and the like, and halogen-containing triazine compounds represented by the following formula (a3) such as tris (2, 3-dibromopropyl) isocyanurate and the like.

[ CHEM 7 ]

In the above formula (a3), R ^9a 、R ^10a 、R ^11a Each independently represents a haloalkyl group.

Further, as a third mode of the acid generator (a), α - (p-toluenesulfonyloxyimino) -phenylacetonitrile, α - (benzenesulfonyloxyimino) -2, 4-dichlorophenylacetonitrile, α - (benzenesulfonyloxyimino) -2, 6-dichlorophenylacetonitrile, α - (2-chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α - (ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, and further, a compound represented by the following formula (a4) containing an oxime sulfonate group may be mentioned.

[ CHEM 8 ]

In the above formula (a4), R ^12a Represents a 1-, 2-or 3-valent organic group, R ^13a Represents a substituted or unsubstituted saturated hydrocarbon group, unsaturated hydrocarbon group or aromatic group, and n represents the number of repeating units of the structure in parentheses.

In the formula (a4), the aromatic group may, for example, be an aryl group such as a phenyl group or a naphthyl group or a heteroaryl group such as a furyl group or a thienyl group. They may have 1 or more suitable substituents on the ring, such as halogen atoms, alkyl groups, alkoxy groups, nitro groups, and the like. In addition, R ^13a The alkyl group having 1 to 6 carbon atoms is particularly preferred, and examples thereof may include a methyl group, an ethyl group, a propyl group and a butyl group. Particular preference is given to R ^12a Is an aromatic group, R ^13a A compound having an alkyl group having 1 to 4 carbon atoms. As the acid generator represented by the above formula (a4), when n is 1, there can be exemplifiedTo take R ^12a Is any one of phenyl, methylphenyl, and methoxyphenyl, and R ^13a Specific examples of the compound having a methyl group include α - (methylsulfonoxyimino) -1-phenylacetonitrile, [ α - (methylsulfonoxyimino) -1- (p-methylphenyl) acetonitrile, [ α - (methylsulfonoxyimino) -1- (p-methoxyphenyl) acetonitrile, [2- (propylsulfonyloxyimino) -2, 3-dihydroxythiophen-3-ylidene ] (o-tolyl) acetonitrile, and the like. When n is 2, specific examples of the acid generator represented by the formula (a4) include those represented by the following formulae.

[ CHEM 9 ]

Further, as a fourth embodiment of the acid generator (a), an onium salt having a naphthalene ring at the cation portion may be mentioned. The "having a naphthalene ring" means having a structure derived from naphthalene, and means having at least 2 rings, and their aromaticity is maintained. The naphthalene ring may have a substituent such as a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Although the structure derived from the naphthalene ring may be a 1-valent group (free valence is 1) or a 2-valent group (free valence is 2) or more, a 1-valent group (in which a portion bonded to the above substituent is removed to count the free valence) is desirable. The number of naphthalene rings is preferably 1 or more and 3 or less.

The cation portion of the onium salt having a naphthalene ring in the cation portion is preferably represented by the following formula (a 5).

[ CHEM 10 ]

In the above formula (a5), R ^14a 、R ^15a 、R ^16a At least 1 of them represents a group represented by the following formula (a6), and the others represent a group having a carbon number ofA linear or branched alkyl group having 1 to 6 carbon atoms, an optionally substituted phenyl group, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Or, R ^14a 、R ^15a 、R ^16a Wherein 1 of the groups is a group represented by the following formula (a6), and the remaining 2 are each independently a linear or branched alkylene group having 1 to 6 carbon atoms, and the terminal of each of the groups may be bonded to form a ring.

[ CHEM 11 ]

In the above formula (a6), R ^17a 、R ^18a Each independently represents a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a linear or branched alkyl group having 1 to 6 carbon atoms, R ^19a Represents a single bond, or a linear or branched alkylene group having 1 to 6 carbon atoms which may have a substituent. l and m each independently represent an integer of 0 to 2, and l + m is 3 or less. Wherein in the presence of a plurality of R ^17a In this case, they may be the same as or different from each other. In addition, in the presence of a plurality of R ^18a In this case, they may be the same as or different from each other.

From the viewpoint of stability of the compound, the above R ^14a 、R ^15a 、R ^16a The number of the groups represented by the formula (a6) in (a) is preferably 1, and the remainder is a linear or branched alkylene group having 1 to 6 carbon atoms, and the ends of the groups may be bonded to form a cyclic group. In this case, the 2 alkylene groups include a sulfur atom to form a three-to nine-membered ring. The number of atoms (including a sulfur atom) constituting the ring is preferably 5 or more and 6 or less.

Examples of the substituent which the alkylene group may have include an oxygen atom (in this case, a carbonyl group is formed together with a carbon atom constituting the alkylene group), a hydroxyl group and the like.

Examples of the substituent which the phenyl group may have include a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, a linear or branched alkyl group having 1 to 6 carbon atoms, and the like.

The structure of the cationic moiety may preferably be represented by the following formula (a7) or (a8), and the structure represented by the following formula (a8) is particularly preferred.

[ CHEM 12 ]

Such a cation portion may be an iodonium salt or a sulfonium salt, and a sulfonium salt is desirable from the viewpoint of acid generation efficiency and the like.

Therefore, as a suitable anion of the anion portion of the onium salt having a naphthalene ring in the cation portion, an anion capable of forming a sulfonium salt is desired.

The anion portion of such an acid generator is a fluoroalkylsulfonic acid ion or arylsulfonic acid ion in which a part or all of hydrogen atoms are fluorinated.

The alkyl group in the fluoroalkylsulfonic acid ion may be a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and preferably has 1 to 10 carbon atoms in view of the volume size of the generated acid and the diffusion distance thereof. In particular, a branched or cyclic alkyl group is preferable because of its short diffusion distance. Further, methyl, ethyl, propyl, butyl, octyl and the like are preferable groups in terms of that synthesis can be performed at low cost.

The aryl group in the arylsulfonic acid ion is an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group, which may be substituted or unsubstituted with an alkyl group or a halogen atom. Particularly, an aryl group having 6 to 10 carbon atoms is preferable because it can be synthesized at low cost. Specific examples of the preferable aryl group include phenyl, tosyl, ethylphenyl, naphthyl and methylnaphthyl.

In the fluoroalkyl sulfonic acid ion or the aryl sulfonic acid ion, the fluorination rate when part or all of the hydrogen atoms are fluorinated is preferably 10% to 100%, more preferably 50% to 100%, and particularly, a substance in which all of the hydrogen atoms are substituted with fluorine atoms is preferable because the strength of the acid is increased. Specific examples thereof include trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctanesulfonate and perfluorobenzenesulfonate.

Among them, preferred examples of the anion portion include an anion portion represented by the following formula (a 9).

[ CHEM 13 ]

R ^20a SO ₃ ^- (a9)

In the above formula (a9), R ^20a Is a group represented by the following formulae (a10), (a11) and (a 12).

[ CHEM 14 ]

In the formula (a10), x represents an integer of 1 to 4. In the formula (a11), R ^21a Represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkoxy group having 1 to 6 carbon atoms, and y represents an integer of 1 to 3. Among them, trifluoromethanesulfonate and perfluorobutanesulfonate are preferable from the viewpoint of safety.

In addition, as the anion portion, a nitrogen-containing anion portion represented by the following formulas (a13) and (a14) can be used.

[ CHEM 15 ]

In the above formulae (a13) and (a14), X ^a Represents a linear or branched alkylene group in which at least 1 hydrogen atom is substituted with a fluorine atom, and the alkylene group has 2 to 6 carbon atoms, preferably 3 to 5 carbon atoms, and most preferably 3 carbon atoms. This is achieved byOuter, Y ^a 、Z ^a Each independently represents a linear or branched alkyl group in which at least 1 hydrogen atom is substituted with a fluorine atom, and the alkyl group has 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, and more preferably 1 to 3 carbon atoms.

X ^a Number of carbon atoms of alkylene group of (2) or Y ^a 、Z ^a The smaller the number of carbon atoms of the alkyl group (b) is, the better the solubility in an organic solvent is, and therefore, the preferable is.

In addition, in X ^a Alkylene or Y of ^a 、Z ^a In the alkyl group of (3), the larger the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength, and thus is preferred. The proportion of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate, is preferably 70% to 100%, more preferably 90% to 100%, and most preferably a perfluoroalkylene group or perfluoroalkyl group in which all hydrogen atoms are replaced with fluorine atoms.

Examples of the preferable compounds of the onium salt having a naphthalene ring in the cation portion include compounds represented by the following formulae (a15) and (a 16).

[ CHEM 16 ]

Further, as the fifth mode of the acid generator (a), bis (p-toluenesulfonyl) diazomethanes, bis (1, 1-dimethylethylsulfonyl) diazomethanes, bis (cyclohexylsulfonyl) diazomethanes, bis (2, 4-dimethylphenylsulfonyl) diazomethanes and other bis (sulfonyl) diazomethanes; nitrobenzyl derivatives such as 2-nitrobenzyl p-toluenesulfonate, 2, 6-dinitrobenzyl p-toluenesulfonate, nitrobenzyl toluenesulfonate, dinitrobenzyl toluenesulfonate, nitrobenzyl sulfonate, nitrobenzyl carbonate and dinitrobenzyl carbonate; sulfonic acid esters such as pyrogallol tricresyl sulfonate, tosylbenzyl ester, benzyl sulfonate, N-methylsulfonyloxy succinimide, N-trichloromethylsulfonyloxy succinimide, N-phenylsulfonyloxy maleimide, and N-methylsulfonyloxy phthalimide; trifluoromethanesulfonic acid esters such as N- (trifluoromethanesulfonyloxy) phthalimide, N- (trifluoromethanesulfonyloxy) -1, 8-naphthalimide, and N- (trifluoromethanesulfonyloxy) -4-butyl-1, 8-naphthalimide; onium salts such as diphenyliodonium hexafluorophosphate, (4-methoxyphenyl) phenyliodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (p-tert-butylphenyl) diphenylsulfonium trifluoromethanesulfonate and the like; benzoin tosylates such as benzoin tosylate and α -methylbenzoin tosylate; other diphenyliodonium salts, triphenylsulfonium salts, phenyldiazonium salts, benzyl carbonate, and the like.

As the acid generator (a), a naphthalenedicarboxylic acid derivative represented by the following formula (a21) is also preferable.

[ CHEM 17 ]

(in the formula (a21), R ^22a Is an organic radical of valency 1, R ^23a 、R ^24a 、R ^25a And R ^26a Each independently is a hydrogen atom or a 1-valent organic radical, R ^23a And R ^24a 、R ^24a And R ^25a Or R ^25a And R ^26a May be bonded to each other to form a ring. )

As R ^22a The organic group (b) is not particularly limited insofar as it does not interfere with the object of the present invention. The organic group may be a hydrocarbon group, and may contain a hetero atom such as O, N, S, P or a halogen atom. The structure of the organic group may be linear, branched, or cyclic, or a combination of these structures.

As appropriate is R ^22a Examples of the organic group of (b) may include an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted with a halogen atom and/or an alkylthio group, an aryl group having 6 to 20 carbon atoms which may have a substituent, and an aryl group having 7 to 20 carbon atoms which may have a substituentAn aralkyl group, an alkylaryl group having 7 to 20 carbon atoms which may have a substituent, a camphor-10-yl group, and a group represented by the following formula (a21 a).

-R ^27a -(O) _a -R ^28a -(O) _b -Y ¹ -R ^29a …(a21a)

(in the formula (a21a), Y ¹ A single bond or an alkanediyl group having 1 to 4 carbon atoms. R ^27a And R ^28a Each of which is an alkanediyl group having 2 to 6 carbon atoms which may be substituted with a halogen atom or an arylene group having 6 to 20 carbon atoms which may be substituted with a halogen atom. R ^29a The alkyl group having 1 to 18 carbon atoms which may be substituted with a halogen atom, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom, or an aralkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom. a and b are 0 or 1, respectively, and at least one of a and b is 1. )

At the position of R ^22a When the organic group (b) has a halogen atom as a substituent, examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom and a fluorine atom.

Under the condition of being R ^22a When the organic group (b) is an alkyl group having 1 to 18 carbon atoms and substituted with an alkylthio group, the carbon atom number of the alkylthio group is preferably 1 to 18.

Examples of the alkylthio group having 1 to 18 carbon atoms include a methylthio group, an ethylthio group, a n-propylthio group, an isopropylthio group, a n-butylthio group, a sec-butylthio group, a tert-butylthio group, an isobutylthio group, a n-pentylthio group, an isopentylthio group, a tert-pentylthio group, a n-hexylthio group, a n-heptylthio group, a tert-heptylthio group, a n-octylthio group, an isooctylthio group, a tert-octylthio group, a 2-ethylhexylthio group, a n-nonylthio group, a n-decylthio group, a n-undecylthio group, a n-dodecylthio group, a n-tridecylthio group, a n-tetradecylthio group, a n-pentadecylthio group, a n-hexadecylthio group, a n-heptadecylthio group and a n-octadecylthio group.

Under the condition of being R ^22a The organic group(s) being optionally substituted by halogen atoms and/or alkylthio groupsWhen the number of carbon atoms of (1) or more and 18 or less is an aliphatic hydrocarbon group, the aliphatic hydrocarbon group may contain an unsaturated double bond.

The structure of the aliphatic hydrocarbon group is not particularly limited, and may be linear, branched, or cyclic, or a combination of these structures.

As at the position of R ^22a Preferable examples of the organic group of (2) include an allyl group and a 2-methyl-2-propenyl group.

As at the position of R ^22a Preferable examples of the organic group of (b) are alkyl groups, and include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, n-hex-2-yl, n-hex-3-yl, n-heptyl, n-hept-2-yl, n-hept-3-yl, isoheptyl, tert-heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, n-nonyl, isononyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl and n-octadecyl.

Under the condition of being R ^22a When the organic group (b) is an alicyclic hydrocarbon group, examples of the alicyclic hydrocarbon constituting the main skeleton of the alicyclic hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane and bicyclo [2.1.1]Hexane, bicyclo [2.2.1 ]]Heptane, bicyclo [3.2.1]Octane, bicyclo [2.2.2]Octane, and adamantane. The alicyclic hydrocarbon group is preferably a group obtained by removing 1 hydrogen atom from these alicyclic hydrocarbons.

As at the position of R ^22a Preferable examples of the organic group(s) of (b) include aliphatic hydrocarbon groups substituted with a halogen atom, for example, trifluoromethyl, pentafluoroethyl, 2-chloroethyl, 2-bromoethyl, heptafluoro-n-propyl, 3-bromopropyl, nonafluoro-n-butyl, tridecfluoro-n-hexyl, heptafluoro-n-octyl, 2, 2, 2-trifluoroethyl, 1-difluoroethyl, 1-difluoro-n-propyl, 1, 2, 2-tetrafluoro-n-propyl, 3, 3, 3-trifluoro-n-propyl, 2, 2, 3, 3, 3-pentafluoro-n-propyl and 2-norbornyl-1, 1-Difluoroethyl, 2-norbornyltetrafluoroethyl and 3-adamantyl-1, 1, 2, 2-tetrafluoropropyl.

As at the position of R ^22a Preferable examples of the organic group of (3) are aliphatic hydrocarbon groups substituted with an alkylthio group, and examples thereof include a 2-methylthioethyl group, a 4-methylthio-n-butyl group and a 2-n-butylthioethyl group.

As at R ^22a A preferable example of the organic group of (3) is an aliphatic hydrocarbon group substituted with a halogen atom and an alkylthio group, and the organic group may, for example, be a 3-methylthio-1, 1, 2, 2-tetrafluoro-n-propyl group.

As at R ^22a Preferable examples of the organic group of (2) include phenyl, naphthyl and biphenyl.

As at the position of R ^22a Preferable examples of the organic group of (3) include aryl groups substituted with a halogen atom, and pentafluorophenyl group, chlorophenyl group, dichlorophenyl group and trichlorophenyl group are mentioned.

As at the position of R ^22a Preferable examples of the organic group of (3) are aryl groups substituted with an alkylthio group, and include a 4-methylthiophenyl group, a 4-n-butylthiophenyl group, a 4-n-octylthiophenyl group and a 4-n-dodecylthiophenyl group.

As at the position of R ^22a Preferable examples of the organic group of (2) include aryl groups substituted with a halogen atom and an alkylthio group, and include 1, 2, 5, 6-tetrafluoro-4-methylthiophenyl group, 1, 2, 5, 6-tetrafluoro-4-n-butylthiophenyl group and 1, 2, 5, 6-tetrafluoro-4-n-dodecylthiophenyl group.

As at R ^22a Preferable examples of the organic group of (3) include aralkyl group, such as benzyl, phenethyl, 2-phenylpropan-2-yl, diphenylmethyl and triphenylmethyl.

As at the position of R ^22a Preferable examples of the organic group of (3) include aralkyl groups substituted with a halogen atom, for example, pentafluorophenylmethyl group, phenyldifluoromethyl group, 2-phenyltetrafluoroethyl group and 2- (pentafluorophenyl) ethyl group.

As at the position of R ^22a The organic group of (A) is an aralkyl group substituted with an alkylthio groupIn the case of (3), a preferred example thereof is p-methylthiobenzyl.

As at the position of R ^22a The organic group of (2) is preferably an aralkyl group substituted with a halogen atom or an alkylthio group, and may, for example, be a 2- (2, 3, 5, 6-tetrafluoro-4-methylthiophenyl) ethyl group.

As at the position of R ^22a Preferable examples of the organic group of (2) include 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 3-isopropylphenyl, 4-n-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4-n-hexylphenyl, 4-cyclohexylphenyl, 4-n-octylphenyl, 4- (2-ethyl-n-hexylphenyl), 2, 3-dimethylphenyl, 2, 4-dimethylphenyl, 2, 5-dimethylphenyl, 2, 6-dimethylphenyl, 3, 4-dimethylphenyl, 3, 5-dimethylphenyl, 2, 4-di-tert-butylphenyl, 2, 5-di-tert-butylphenyl, 2, 6-di-tert-butylphenyl, 2-methylphenyl, 2, 4-di-tert-pentylphenyl group, 2, 5-di-tert-octylphenyl group, 2-cyclohexylphenyl group, 3-cyclohexylphenyl group, 4-cyclohexylphenyl group, 2, 4, 5-trimethylphenyl group, 2, 4, 6-triisopropylphenyl group.

The group represented by formula (a21a) is an ether group-containing group.

In the formula (a21a), as represented by Y ¹ Examples of the alkanediyl group having 1 to 4 carbon atoms include methylene, ethane-1, 2-diyl, ethane-1, 1-diyl, propane-1, 3-diyl, propane-1, 2-diyl, butane-1, 4-diyl, butane-1, 3-diyl, butane-2, 3-diyl and butane-1, 2-diyl.

In the formula (a21a), R is ^27a Or R ^28a Examples of the alkanediyl group having 2 to 6 carbon atoms include ethane-1, 2-diyl group, propane-1, 3-diyl group, propane-1, 2-diyl group, butane-1, 4-diyl group, butane-1, 3-diyl group, butane-2, 3-diyl group, butane-1, 2-diyl group, pentane-1, 5-diyl group and pentane-1, 3-diyl group, pentane-1, 4-diyl, pentane-2, 3-diyl, hexane-1, 6-diyl, hexane-1, 2-diyl, hexane-1, 3-diyl, hexane-1, 4-diyl, hexane-2, 5-diyl, hexane-2, 4-diyl.Hexane-3, 4-diyl.

In the formula (a21a), in R ^27a Or R ^28a In the case of an alkanediyl group having 2 to 6 carbon atoms which is substituted with a halogen atom, examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom and a fluorine atom. Examples of the alkanediyl group which is substituted with a halogen atom include tetrafluoroethane-1, 2-diyl group, 1-difluoroethane-1, 2-diyl group, 1-fluoroethane-1, 2-diyl group, 1, 2-difluoroethane-1, 2-diyl group, hexafluoropropane-1, 3-diyl group, 1, 2, 2-tetrafluoropropane-1, 3-diyl group and 1, 1, 2, 2-tetrafluoropentane-1, 5-diyl group.

In the formula (a21a), as in R ^27a Or R ^28a Examples of the arylene group include a1, 2-phenylene group, a1, 3-phenylene group, a1, 4-phenylene group, a2, 5-dimethyl-1, 4-phenylene group, a biphenyl-4, 4 '-diyl group, a diphenylmethane-4, 4' -diyl group, and a2, -diphenylpropane-4, 4' -diyl, naphthalene-1, 2-diyl, naphthalene-1, 3-diyl, naphthalene-1, 4-diyl, naphthalene-1, 5-diyl, naphthalene-1, 6-diyl, naphthalene-1, 7-diyl, naphthalene-1, 8-diyl, naphthalene-2, 3-diyl, naphthalene-2, 6-diyl and naphthalene-2, 7-diyl.

In the formula (a21a), R is ^27a Or R ^28a In the case of an arylene group substituted with a halogen atom, the halogen atom may, for example, be a chlorine atom, a bromine atom, an iodine atom or a fluorine atom. Examples of the arylene group substituted with a halogen atom may include 2, 3, 5, 6-tetrafluoro-1, 4-phenylene.

In the formula (a21a), R is ^29a Examples of the alkyl group having 1 to 18 carbon atoms which may have a branched chain include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a n-pentyl group, an isopentyl group, a tert-pentyl group, a n-hexyl group, a n-hexane-2-yl group, a n-hexane-3-yl group, a n-heptyl group, a n-heptane-2-yl group, a n-heptane-3-yl group, an isoheptyl group, a tert-heptyl group, a n-octyl group, an isooctyl group, a tert-octyl group, a 2-ethylhexyl group, a n-nonyl group, an isononyl group, a n-decyl group, a n-undecyl group, a n-dodecyl group, a n-tridecyl group, a n-tetradecyl group, a n-pentadecyl group, a n-hexadecyl group, a n-tridecyl groupHeptadecyl and n-octadecyl.

In the formula (a21a), in R ^29a In the case of an alkyl group having 1 to 18 carbon atoms which is substituted with a halogen atom, examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom and a fluorine atom. Examples of the alkyl group which may be substituted with a halogen atom include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoro-n-propyl group, a nonafluoro-n-butyl group, a tridecafluoro-n-hexyl group, a heptafluoro-n-octyl group, a2, 2, 2-trifluoroethyl group, a1, 1-difluoroethyl group, a1, 1-difluoro-n-propyl group, a1, 1, 2, 2-tetrafluoro-n-propyl group, a3, 3, 3-trifluoro-n-propyl group, a2, 2, 3, 3, 3-pentafluoro-n-propyl group and a1, 1, 2, 2-tetrafluorotetradecyl group.

In the formula (a21a), in R ^29a When the alicyclic hydrocarbon group has 3 to 12 carbon atoms, examples of the alicyclic hydrocarbon constituting the main skeleton of the alicyclic hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane and bicyclo [2.1.1]Hexane, bicyclo [2.2.1 ]]Heptane, bicyclo [3.2.1]Octane, bicyclo [2.2.2]Octane, and adamantane. The alicyclic hydrocarbon group is preferably a group obtained by removing 1 hydrogen atom from these alicyclic hydrocarbons.

In the formula (a21a), in R ^29a In the case of aryl, haloaryl, aralkyl, haloaralkyl, preferred examples of these groups are represented by R ^22a The same applies to these groups.

Among the groups represented by the formula (a21a), preferred groups are those represented by R ^27a The group represented is a group in which the carbon atom bonded to the sulfur atom is substituted with a fluorine atom. The number of carbon atoms of the above-mentioned preferred group is preferably 2 to 18.

As R ^22a The perfluoroalkyl group has preferably 1 to 8 carbon atoms. Further, camphor-10-yl is also preferable as R from the viewpoint of easiness in forming a high-definition resist pattern ^22a 。

In the formula (a21), R ^23a ～R ^26a Is a hydrogen atom or a 1-valent organic group. Furthermore, R ^23a And R ^24a 、R ^24a And R ^25a Or R ^25a And R ^26a May be bonded to each other to form a ring. For example, by reacting R ^24a And R ^25a Bonded to form a five-membered ring together with the naphthalene ring, thereby forming an acenaphthene skeleton.

The 1-valent organic group is preferably an alkyl group or alkoxy group having 4 to 18 carbon atoms, which may be substituted with an alicyclic hydrocarbon group, a heterocyclic group (heterocyclic group), or a halogen atom and may have a branch; a heterocyclic oxy group; an alkylthio group which may be substituted with an alicyclic hydrocarbon group, a heterocyclic group (heterocyclic group), or a halogen atom and which may have a branched carbon number of 4 to 18; a heterocyclic thio group.

Further, the alkoxy group is preferably a group in which a methylene group at an arbitrary position not adjacent to an oxygen atom is substituted with-CO-.

Also preferred are groups in which the alkoxy group is interrupted by an-O-CO-bond or an-O-CO-NH-bond. Further, the left end of the-O-CO-bond and the-O-CO-NH-bond is the side near the mother nucleus of naphthalenedicarboxylic acid in the alkoxy group.

Further, an alkylthio group having 4 to 18 carbon atoms which may be substituted with an alicyclic hydrocarbon group, a heterocyclic group or a halogen atom and may have a branch is also preferable as R ^23a ～R ^26a 。

Also preferred is a group wherein a methylene group at any position not adjacent to the sulfur atom in the alkylthio group is substituted with-CO-.

Also preferred are groups in which the alkylthio group is interrupted by an-O-CO-bond or an-O-CO-NH-bond. Further, the left end of the-O-CO-bond and the-O-CO-NH-bond is the side near the mother nucleus of naphthalenedicarboxylic acid in the alkylthio group.

As R ^23a ～R ^26a Preferably R ^23a Is an organic radical, R ^24a ～R ^26a Is a hydrogen atom, or R ^24a Is an organic radical, R ^23a 、R ^25a And R ^26a Is a hydrogen atom. Furthermore, R ^23a ～R ^26a All hydrogen atoms may be used.

As R ^23a ～R ^26a Examples of the unsubstituted alkyl group include n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl and iso-butylPentyl, tert-pentyl, n-hexyl, n-heptyl, isoheptyl, tert-heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl.

As R ^23a ～R ^26a Examples of the unsubstituted alkoxy group include an n-butoxy group, a sec-butoxy group, a tert-butoxy group, an isobutoxy group, a n-pentoxy group, an isopentoxy group, a tert-pentoxy group, an n-hexoxy group, an n-heptoxy group, an isoheptoxy group, a tert-heptoxy group, a n-octoxy group, an isooctoxy group, a tert-octoxy group, a 2-ethylhexyl group, a n-nonoxy group, a n-decyloxy group, a n-undecyloxy group, a n-dodecyloxy group, a n-tridecoxy group, a n-tetradecyloxy group, a n-pentadecyloxy group, a n-hexadecyloxy group, a n-heptadecyloxy group and a n-octadecyloxy group.

As R ^23a ～R ^26a Examples of the unsubstituted alkylthio group include n-butylthio, sec-butylthio, tert-butylthio, isobutylthio, n-pentylthio, isopentylthio, tert-pentylthio, n-hexylthio, n-heptylthio, isoheptylthio, tert-heptylthio, n-octylthio, isooctylthio, tert-octylthio, 2-ethylhexylthio, n-nonylthio, n-decylthio, n-undecylthio, n-dodecylthio, n-tridecylthio, n-tetradecylthio, n-pentadecylthio, n-hexadecylthio, n-heptadecylthio and n-octadecylthio.

At R ^23a ～R ^26a In the case of an alkyl group, alkoxy group or alkylthio group substituted with an alicyclic hydrocarbon group, examples of the alicyclic hydrocarbon constituting the main skeleton of the alicyclic hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane and bicyclo [2.1.1 ] 1]Hexane, bicyclo [2.2.1 ]]Heptane, bicyclo [3.2.1]Octane, bicyclo [2.2.2]Octane, and adamantane. The alicyclic hydrocarbon group is preferably a group obtained by removing 1 hydrogen atom from these alicyclic hydrocarbons.

At R ^23a ～R ^26a Is alkyl, alkoxy or alkylthio substituted by a heterocyclic radicalIn the case of radicals, or in R ^23a ～R ^26a In the case of a heterocyclic oxy group, examples of the heterocyclic ring constituting the main skeleton of the heterocyclic group or the heterocyclic oxy group include pyrrole, thiophene, furan, pyran, thiopyran, imidazole, pyrazole, thiazole, isothiazole, oxazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, pyrrolidine, pyrazolidine, imidazolidine, isoxazolidine, isothiazolidine, piperidine, piperazine, morpholine, thiomorpholine, chroman, thiochroman, isochroman, isothiochroman, indoline, isoindoline, 4-indoline, indolizine, indole, indazole, purine, quinolizine, isoquinoline, quinoline, naphthyridine, phthalazine, quinoxaline, cinnoline, pteridine, acridine, perimidine, phenanthroline, carbazole, carboline, phenazine, antisolvent, thiadiazole, oxadiazole, triazine, triazole, tetrazole, benzimidazole, benzoxazole, benzothiazole, benzothiadiazole, oxadiazole, triazine, triazole, tetrazole, benzimidazole, benzoxazole, benzothiazole, benzothiadiazole, thiadiazole, and thiadiazole, Benzoflurane, naphthoimidazole, benzotriazole, tetraazaindene. In addition, a saturated heterocyclic ring obtained by hydrogenating a ring having a conjugated bond in these heterocyclic rings is also preferable.

The heterocyclic group contained in the heterocyclic group or the heterocyclic group in the heterocyclic oxy group, which is substituted with an alkyl group, an alkoxy group or an alkylthio group, is preferably a group obtained by removing 1 hydrogen atom from the above-mentioned heterocyclic ring.

As R ^23a ～R ^26a Examples of the alkoxy group containing an alicyclic hydrocarbon group include a cyclopentyloxy group, a methylcyclopentyloxy group, a cyclohexyloxy group, a fluorocyclohexyloxy group, a chlorocyclohexyloxy group, a cyclohexylmethyloxy group, a methylcyclohexyloxy group, a norbornyloxy group, an ethylcyclohexyloxy group, a cyclohexylethyloxy group, a dimethylcyclohexyloxy group, a methylcyclohexylmethoxy group, a norbornylmethyloxy group, a trimethylcyclohexyloxy group, a 1-cyclohexylbutyloxy group, an adamantyloxy group, a menthyloxy group, a n-butylcyclohexyloxy group, a t-butylcyclohexyloxy group, a bornyloxy group, an isobornyloxy group, a decahydronaphthyloxy group, a dicyclopentadienyloxy group, a 1-cyclohexylpentyloxy group, a methyladamantyloxy group, an adamantylmethyloxy group, a 4-pentylcyclohexyloxy group, a cyclohexyloxy group, an adamantylethyloxy group, a, Dimethyl adamantyloxy.

As R ^23a ～R ^26a Examples of the heterocyclic oxy group include tetrahydrofuryloxy, furfuryloxy, tetrahydrofuryloxy, tetrahydropyranyloxy, butyllactoyloxy and indolyloxy.

As R ^23a ～R ^26a Examples of the alkylthio group containing an alicyclic hydrocarbon group include a cyclopentylthio group, a cyclohexylthio group, a cyclohexylmethylthio group, a norbornylthio group and an isobornylthio group.

As R ^23a ～R ^26a Examples of the heterocyclic thio group include a furfurylthio group and a tetrahydrofurylthio group.

As R ^23a ～R ^26a Examples of the group resulting from substitution of a methylene group at an arbitrary position not adjacent to the oxygen atom with-CO-in the alkoxy group include 2-ketobutyl-1-oxy group, 2-ketopentyl-1-oxy group, 2-ketohexyl-1-oxy group, 2-ketoheptyl-1-oxy group, 2-ketooctyl-1-oxy group, 3-ketobutyl-1-oxy group, 4-ketopentyl-1-oxy group, 5-ketohexyl-1-oxy group, 6-ketoheptyl-1-oxy group, 7-ketooctyl-1-oxy group, 3-methyl-2-ketopentane-4-oxy group, and the like, 2-methyl-2-ketopentane-4-oxyl, 3-ketoheptane-5-oxyl and 2-adamantanone-5-oxyl.

As R ^23a ～R ^26a Examples of the group obtained by substituting a methylene group at an arbitrary position not adjacent to the sulfur atom of the alkylthio group with-CO-may include 2-ketobutyl-1-thio, 2-ketopentyl-1-thio, 2-ketohexyl-1-thio, 2-ketoheptyl-1-thio, 2-ketooctyl-1-thio, 3-ketobutyl-1-thio, 4-ketopentyl-1-thio, 5-ketohexyl-1-thio, 6-ketoheptyl-1-thio, 7-ketooctyl-1-thio, 3-methyl-2-ketopentane-4-thio, and the like, 2-methyl-2-ketopentane-4-sulfenyl and 3-ketoheptane-5-sulfenyl.

Specific examples of the compound represented by the formula (a21) include the following compounds.

[ CHEM 18 ]

[ CHEM 19 ]

[ CHEM 20 ]

[ CHEM 21 ]

[ CHEM 22 ]

[ CHEM 23 ]

[ CHEM 24 ]

[ CHEM 25 ]

[ CHEM 26 ]

[ CHEM 27 ]

The acid generator (A) may be used alone or in combination of 2 or more. The content of the acid generator (a) is preferably 0.1 mass% or more and 10 mass% or less, more preferably 0.2 mass% or more and 6 mass% or less, and particularly preferably 0.5 mass% or more and 3 mass% or less, based on the total solid content of the photosensitive composition. When the amount of the acid generator (a) used is within the above range, a photosensitive composition having good sensitivity, a uniform solution, and excellent storage stability can be easily prepared.

< resin (B) >

In the photosensitive composition, an acrylic resin (B3) is contained as an essential component as the resin (B) whose solubility in alkali increases by the action of an acid. The acrylic resin (B3) contains a structural unit represented by the formula (B3-1).

The photosensitive composition may contain the acrylic resin (B3) and may contain any resin other than the acrylic resin (B3) whose solubility in alkali is increased by the action of an acid. Among these, the ratio of the mass of the acrylic resin (B3) to the mass of the resin (B) is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, and particularly preferably 100% by mass.

As an arbitrary resin other than the acrylic resin (B3) whose solubility in alkali is increased by the action of an acid, a novolak resin (B1) whose solubility in alkali is increased by the action of an acid, a polyhydroxystyrene resin (B2) whose solubility in alkali is increased by the action of an acid, and an acrylic resin other than the acrylic resin (B3) whose solubility in alkali is increased by the action of an acid can be exemplified.

Hereinafter, each resin will be specifically described.

Novolac resin (B1)

As the novolac resin (B1), a resin containing a structural unit represented by the following formula (B1) can be used.

[ CHEM 28 ]

In the above formula (b1), R ^1b Represents an acid dissociable, dissolution inhibiting group, R ^2b 、R ^3b Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

As with the above R ^1b The acid dissociable, dissolution inhibiting group represented by the formula (b2) or (b3) is preferably a group represented by the formula (b2) or (b3), a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, a vinyloxyethyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, or a trialkylsilyl group.

[ CHEM 29 ]

In the above formulae (b2) and (b3), R ^4b 、R ^5b Each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, R ^6b Represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, R ^7b Represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and o represents 0 or 1.

Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group and a neopentyl group. The cyclic alkyl group may, for example, be a cyclopentyl group or a cyclohexyl group.

Specific examples of the acid dissociable, dissolution inhibiting group represented by formula (b2) include methoxyethyl, ethoxyethyl, n-propoxyethyl, isopropoxyethyl, n-butoxyethyl, isobutoxyethyl, tert-butoxyethyl, cyclohexyloxyethyl, methoxypropyl, ethoxypropyl, 1-methoxy-1-methyl-ethyl, and 1-ethoxy-1-methylethyl. Further, specific examples of the acid dissociable, dissolution inhibiting group represented by the formula (b3) include a tert-butoxycarbonyl group and a tert-butoxycarbonylmethyl group. The trialkylsilyl group may, for example, be a trimethylsilyl group or a tri-tert-butyldimethylsilyl group, each of which has an alkyl group having 1 to 6 carbon atoms.

[ polyhydroxystyrene resin (B2) ]

As the polyhydroxystyrene resin (B2), a resin containing a structural unit represented by the following formula (B4) can be used.

[ CHEM 30 ]

In the above formula (b4), R ^8b Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ^9b Represents an acid dissociable, dissolution inhibiting group.

The alkyl group having 1 to 6 carbon atoms is, for example, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. Examples of the linear or branched alkyl group may include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group and a neopentyl group, and examples of the cyclic alkyl group may include a cyclopentyl group and a cyclohexyl group.

As with the above-mentioned R ^9b As the acid dissociable, dissolution inhibiting group, the same acid dissociable, dissolution inhibiting groups as those exemplified by the formulas (b2) and (b3) can be used.

Further, the polyhydroxystyrene resin (B2) may contain another polymerizable compound as a structural unit for the purpose of appropriately controlling physical and chemical properties. Examples of such polymerizable compounds include known radical polymerizable compounds and anion polymerizable compounds. Examples of the polymerizable compound include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives having a carboxyl group and an ester bond such as 2-methacryloyloxyethylsuccinic acid, 2-methacryloyloxyethylmaleic acid, 2-methacryloyloxyethylphthalic acid, 2-methacryloyloxyethylhexahydrophthalic acid, and the like; alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate; hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; dicarboxylic diesters such as diethyl maleate and dibutyl fumarate; vinyl group-containing aromatic compounds such as styrene, α -methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α -methylhydroxystyrene, and α -ethylhydroxystyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated dienes such as butadiene and isoprene; nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; and amide bond-containing polymerizable compounds such as acrylamide and methacrylamide.

[ acrylic resin (B3) ]

The acrylic resin (B3) as the resin (B) whose solubility in alkali increases by the action of an acid contains a structural unit represented by the following formula (B3-1).

[ CHEM 31 ]

In addition, in the present specification, the "acrylic resin" is a resin: a resin in which the ratio of the total of the structural units represented by the formula (B3-1) and the structural units derived from a monomer having a (meth) acryloyloxy group is 50 mol% or more, preferably 70 mol% or more, and more preferably 90 mol% or more, relative to the total structural units constituting the resin.

In the present specification, "(meth) acrylic acid" means both "acrylic acid" and "methacrylic acid". "(meth) acrylate" means both "acrylate" and "methacrylate". "(meth) acryloyloxy" means both "acryloyloxy" and "methacryloyloxy".

In the formula (B3-1), R ^b01 is-O-, -S-, -CO-O-, -CO-NH-or-SO ₂ -。R ^b01 preferably-O-. That is, the formula (B3-1) is preferably a structure in which a cyclic ether is formed in the main chain.

In the formula (B3-1), R ^b02 And R ^b03 Each independently is a hydrogen atom or an organic group, R ^b02 And R ^b03 At least one of which is represented by-CO-O-R ^b04 The group shown.

As R ^b02 And R ^b03 The organic group of (2) may, for example, be-CO-O-R ^b04 The group shown.

R ^b04 Is a hydrogen atom or an organic group.

As R ^b04 The organic group (b) may, for example, be a hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group having 1 to 20 carbon atoms may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

Examples of the aliphatic hydrocarbon group include straight-chain or branched-chain alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl.

The aromatic hydrocarbon group may, for example, be a phenyl group or a naphthyl group.

In the formula (B3-1), the total of x1 and x2 is preferably 2 or 3 from the viewpoint of a stable cyclic structure. For example, in the formula (B3-1), it is preferable that x1 and x2 are both 1, and R is ^b02 And R ^b03 In (1)One is a hydrogen atom.

For example, the structural unit represented by the formula (B3-1) can be introduced into the acrylic resin (B3) by using the following compound as a monomer corresponding to the formula (B3-1) as a copolymerization component.

[ CHEM 32 ]

Specific examples of the structural unit represented by the formula (B3-1) include the following structural units.

[ CHEM 33 ]

When the solid content concentration is high, the storage stability is poor, and for example, the viscosity of the photosensitive composition is liable to change with time.

However, by using an acrylic resin (B3) containing a structural unit represented by the formula (B3-1) as the resin (B), the solid content concentration can be set to a range of 25 mass% to 70 mass%, and a photosensitive composition having excellent storage stability even at a high solid content concentration can be realized.

For example, when the viscosity of the photosensitive composition measured at 25 ℃ with an E-type viscometer is V1, and the viscosity of the photosensitive composition left standing at 40 ℃ for 2 weeks and measured at 25 ℃ with an E-type viscometer is V2, V2/V1 can be made less than 1.1.

Since the photosensitive composition has a high solid content, a thick (for example, 70 μm or more) photosensitive layer can be easily formed. Therefore, the photosensitive composition can be preferably used for forming a plated shaped article, for example.

Further, the photosensitive layer formed using the photosensitive composition can suppress repulsion to a developer after exposure. Therefore, for example, the developer can be brought into contact with the entire photosensitive layer, and a resist pattern having a desired shape corresponding to a mask or the like can be formed over the entire region where the photosensitive layer is provided.

Further, the photosensitive layer formed using the photosensitive composition can suppress swelling during development after exposure. Therefore, for example, generation of wrinkles, dissolution of unexposed portions, and lifting and deformation of the resulting resist pattern due to swelling can be suppressed.

In addition, the photosensitive layer formed using the photosensitive composition can suppress the generation of cracks, that is, has excellent crack resistance. Therefore, for example, when the obtained resist pattern is used as a mold for forming a plated shaped object, the plated shaped object having a desired shape can be easily formed.

The amount of the structural unit represented by the formula (B3-1) in the acrylic resin (B3) is not particularly limited, and the ratio of the mass of the structural unit represented by the formula (B3-1) to the mass of the acrylic resin (B3) is preferably 5 to 50 mass%, more preferably 10 to 40 mass%, and still more preferably 10 to 30 mass%.

The acrylic resin (B3) may also contain a monomer selected from the group consisting of ₂ -a cyclic group or an acrylate-derived structural unit containing a lactone ring group (b-3). In this case, when forming a resist pattern, a resist pattern having a preferable cross-sectional shape is easily formed. However, if it has a-SO-containing group ₂ the-SO-containing group is preferably not contained because the storage stability of the photosensitive composition is deteriorated when the-cyclic group or the lactone-containing cyclic group is contained ₂ Cyclic groups and lactone-containing cyclic groups or in a smaller amount.

(containing-SO) ₂ -ring type radical)

Here, "contains-SO ₂ The term "cyclic group" means a group containing-SO in its ring skeleton ₂ The cyclic group of the ring of (A) is, specifically, -SO ₂ The sulfur atom (S) in (E) forms a cyclic group which is part of the ring skeleton of the cyclic group. Will contain-SO in the ring skeleton ₂ The ring of (a) is counted as the first ring, and is called a monocyclic group in the case of only the ring, and is called a polycyclic group regardless of the structure in the case of having other ring structures. containing-SO ₂ The cyclic group may be monocyclic or may be monocyclicIs polycyclic.

containing-SO ₂ The cyclic group particularly preferably contains-O-SO in its ring skeleton ₂ Cyclic radicals of (i) containing-O-SO ₂ -O-S-in (a) -forms the cyclic group of the sultone ring forming part of the ring backbone.

containing-SO ₂ The number of carbon atoms of the cyclic group is preferably 3 to 30, more preferably 4 to 20, further preferably 4 to 15, and particularly preferably 4 to 12. The number of carbon atoms is the number of carbon atoms constituting the ring skeleton, and does not include the number of carbon atoms in the substituent.

containing-SO ₂ The-cyclic group may be-SO-containing ₂ The alicyclic group of-may be a group containing-SO ₂ -an aromatic ring radical. Preferably contains-SO ₂ An alicyclic group of (a).

As containing-SO ₂ Examples of the "alicyclic ring" group include those wherein a part of carbon atoms constituting the ring skeleton is replaced with-SO ₂ -or-O-SO ₂ -a group obtained by removing at least 1 hydrogen atom from the aliphatic hydrocarbon ring obtained by substitution. More specifically, the compound may include-CH constituting the ring skeleton thereof ₂ is-by-SO ₂ -a group obtained by removing at least 1 hydrogen atom from the ring of the substituted aliphatic hydrocarbon, -CH constituting the ring ₂ -CH ₂ -by-O-SO ₂ A group obtained by removing at least 1 hydrogen atom from an aliphatic hydrocarbon ring obtained by substitution, and the like.

The number of carbon atoms of the alicyclic hydrocarbon ring is preferably 3 to 20, more preferably 3 to 12. The alicyclic hydrocarbon ring may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing 2 hydrogen atoms from a monocycloparaffin having 3 to 6 carbon atoms. Examples of the monocyclic hydrocarbon include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon ring is preferably a group obtained by removing 2 hydrogen atoms from a polycyclic alkane having 7 to 12 carbon atoms, and specific examples of the polycyclic alkane include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

containing-SO ₂ The cyclic group may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, an oxygen atom (═ O), -COOR ", -OC (═ O) R", a hydroxyalkyl group, and a cyano group.

The alkyl group as the substituent is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably linear or branched. Specifically, the alkyl group may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a neopentyl group or a n-hexyl group. Among these, methyl or ethyl is preferable, and methyl is particularly preferable.

The alkoxy group as the substituent is preferably an alkoxy group having 1 to 6 carbon atoms. The alkoxy group is preferably linear or branched. Specifically, examples of the substituent include alkyl groups in which an oxygen atom (-O-) is bonded to an alkyl group.

Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.

Examples of the "haloalkyl" substituent include those wherein some or all of the hydrogen atoms of the alkyl group are replaced by the halogen atom.

Examples of the "haloalkyl" group as the substituent may include those wherein some or all of the hydrogen atoms of the alkyl group exemplified as the alkyl group as the substituent are substituted with the above-mentioned halogen atom. The haloalkyl group is preferably a fluoroalkyl group, and particularly preferably a perfluoroalkyl group.

R "in the above-mentioned-COOR", -OC (═ O) R "is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms.

When R ″ is a linear or branched alkyl group, the number of carbon atoms of the linear alkyl group is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 or 2.

When R ″ is a cyclic alkyl group, the number of carbon atoms of the cyclic alkyl group is preferably 3 to 15, more preferably 4 to 12, and particularly preferably 5 to 10. Specifically, there can be exemplified a group obtained by removing 1 or more hydrogen atoms from a monocycloparaffin which may be substituted or unsubstituted with a fluorine atom or a fluoroalkyl group, or from a polycycloalkane such as a bicycloalkane, a tricycloalkane or a tetracycloalkane. More specifically, the compound may be obtained by removing 1 or more hydrogen atoms from a monocycloalkane such as cyclopentane or cyclohexane, or a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane.

The hydroxyalkyl group as the substituent is preferably a hydroxyalkyl group having 1 to 6 carbon atoms. Specifically, the alkyl group may have at least 1 hydrogen atom substituted with a hydroxyl group.

As containing-SO ₂ Examples of the "cyclic group" may include groups represented by the following formulae (3-1) to (3-4).

[ CHEM 34 ]

(wherein A' is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, z is an integer of 0 to 2, and R is ^10b Is alkyl, alkoxy, haloalkyl, hydroxy, -COOR ", -OC (═ O) R", hydroxyalkyl or cyano, R "is a hydrogen atom or alkyl. )

In the above formulae (3-1) to (3-4), A' represents an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom (-O-) or a sulfur atom (-S-), an oxygen atom or a sulfur atom. The alkylene group having 1 to 5 carbon atoms in a' is preferably a linear or branched alkylene group, and examples thereof include a methylene group, an ethylene group, an n-propylene group, and an isopropylene group.

When the alkylene group contains an oxygen atom or a sulfur atom, specific examples thereof include a group having-O-or-S-interposed between the terminal or carbon atom of the alkylene group, and examples thereof include-O-CH ₂ -、-CH ₂ -O-CH ₂ -、-S-CH ₂ -、-CH ₂ -S-CH ₂ -and the like. A' is preferably an alkylene group having 1 to 5 carbon atoms or-O-, more preferably an alkylene group having 1 to 5 carbon atoms, and most preferably a methylene group.

z may be any of 0, 1 and 2, most preferably 0. In the case where z is 2, a plurality of R ^10b May be the same or different.

As R ^10b The alkyl group, alkoxy group, haloalkyl group, -COOR ", -OC (═ O) R", and hydroxyalkyl group in (A) may be respectively mentioned as containing-SO ₂ Examples of the "cycloalkyl" group include an alkyl group, an alkoxy group, a haloalkyl group, a "COOR", -OC (═ O) R ", and a hydroxyalkyl group.

Specific cyclic groups represented by the above formulae (3-1) to (3-4) are exemplified below. In the formula, "Ac" represents an acetyl group.

[ CHEM 35 ]

[ CHEM 36 ]

As containing-SO ₂ A cyclic group, preferably a group represented by the formula (3-1) in the above description, more preferably at least one selected from the group consisting of groups represented by any one of the formulae (3-1-1), (3-1-18), (3-3-1) and (3-4-1), and most preferably a group represented by the formula (3-1-1).

(containing a lactone ring group)

The "lactone ring-containing group" refers to a cyclic group containing a ring containing — O — C (═ O) - (lactone ring) in its ring skeleton. The lactone ring is referred to as the first ring, and when the lactone ring is present alone, the lactone ring is referred to as a monocyclic group, and when the lactone ring has another ring structure, the lactone ring is referred to as a polycyclic group regardless of the structure. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group.

The lactone ring-containing group in the structural unit (b-3) is not particularly limited, and any lactone ring-containing group can be used. Specifically, examples of the lactone-containing monocyclic group include groups obtained by removing 1 hydrogen atom from a four-to six-membered cyclic lactone, for example, groups obtained by removing 1 hydrogen atom from β -propiolactone, groups obtained by removing 1 hydrogen atom from γ -butyrolactone, and groups obtained by removing 1 hydrogen atom from δ -valerolactone. The lactone-containing polycyclic group may, for example, be a group obtained by removing 1 hydrogen atom from a bicycloalkane, tricycloalkane or tetracycloalkane having a lactone ring.

The structural unit (b-3) is not particularly limited as long as it has an-SO-containing group ₂ The structure of the other part of the structural unit containing a cyclic group or a lactone-containing cyclic group is not particularly limited, and it is preferable that the structural unit containing an-SO-containing group is derived from an acrylate ester in which a hydrogen atom bonded to the carbon atom at the α -position may be substituted with a substituent ₂ A structural unit (b-3-S) of a cyclic group and at least 1 structural unit selected from the group consisting of a structural unit (b-3-L) containing a lactone-containing cyclic group as a structural unit derived from an acrylate ester in which a hydrogen atom bonded to a carbon atom at the α -position may be substituted with a substituent.

[ structural Unit (b-3-S) ]

More specifically, the structural unit (b-3-S) may, for example, be a structural unit represented by the following formula (b-S1).

[ CHEM 37 ]

(wherein R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a haloalkyl group having 1 to 5 carbon atoms, and R represents ^11b Is containing-SO ₂ -a cyclic group, R ^12b Is a single bond or a 2-valent linking group. )

In the formula (b-S1), R is the same as described above.

R ^11b With the above-exemplifiedcontaining-SO ₂ The cyclic groups are identical.

R ^12b The bond may be a single bond or a 2-valent linking group.

As R ^12b The 2-valent linking group in (2) is not particularly limited, and preferable examples thereof include a 2-valent hydrocarbon group which may have a substituent, a 2-valent linking group containing a hetero atom, and the like.

A 2-valent hydrocarbon group which may have a substituent

The hydrocarbon group as the linking group having a valence of 2 may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group having no aromatic character. The aliphatic hydrocarbon group may be saturated or unsaturated. Saturated hydrocarbon groups are generally preferred. More specifically, the aliphatic hydrocarbon group may, for example, be a straight or branched aliphatic hydrocarbon group or an aliphatic hydrocarbon group having a ring in its structure.

The number of carbon atoms of the linear or branched aliphatic hydrocarbon group is preferably 1 to 10, more preferably 1 to 8, and still more preferably 1 to 5.

The linear aliphatic hydrocarbon group is preferably a linear alkylene group. Specifically, methylene [ -CH ] may be mentioned ₂ -]Ethylene [ - (CH) ₂ ) ₂ -]Propylene [ - (CH) ₂ ) ₃ -]Butylene [ - (CH) ₂ ) ₄ -]- (CH) pentylene [ - (CH) ₂ ) ₅ -]And the like.

The branched aliphatic hydrocarbon group is preferably a branched alkylene group. Specifically, the "CH" (CH) may be mentioned ₃ )-、-CH(CH ₂ CH ₃ )-、-C(CH ₃ ) ₂ -、-C(CH ₃ )(CH ₂ CH ₃ )-、-C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-、-C(CH ₂ CH ₃ ) ₂ -isoalkylmethylene; -CH (CH) ₃ )CH ₂ -、-CH(CH ₃ )CH(CH ₃ )-、-C(CH ₃ ) ₂ CH ₂ -、-CH(CH ₂ CH ₃ )CH ₂ -、-C(CH ₂ CH ₃ ) ₂ -CH ₂ -isoalkylethylene; -CH (CH) ₃ )CH ₂ CH ₂ -、-CH ₂ CH(CH ₃ )CH ₂ -isoalkylpropylene; -CH (CH) ₃ )CH ₂ CH ₂ CH ₂ -、-CH ₂ CH(CH ₃ )CH ₂ CH ₂ An alkylalkylene group such as an alkylbutylene group, etc. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

The above-mentioned linear or branched aliphatic hydrocarbon group may have a substituent (a group or an atom other than a hydrogen atom) in place of a hydrogen atom, or may have no substituent. Examples of the substituent include a fluorine atom, a fluoroalkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom, and an oxo group (═ O).

Examples of the above-mentioned cyclic aliphatic hydrocarbon group having a ring in its structure include a cyclic aliphatic hydrocarbon group which may have a substituent (a group obtained by removing 2 hydrogen atoms from an aliphatic hydrocarbon ring) having a hetero atom in its ring structure, a group obtained by bonding the cyclic aliphatic hydrocarbon group to an end of a linear or branched aliphatic hydrocarbon group, and a group in which the cyclic aliphatic hydrocarbon group is interposed between linear or branched aliphatic hydrocarbon groups. Examples of the linear or branched aliphatic hydrocarbon group may include the same groups as described above.

The number of carbon atoms of the cyclic aliphatic hydrocarbon group is preferably 3 to 20, more preferably 3 to 12.

The cyclic aliphatic hydrocarbon group may be polycyclic or monocyclic. The monocyclic aliphatic hydrocarbon group is preferably a group obtained by removing 2 hydrogen atoms from a monocyclic hydrocarbon group. The number of carbon atoms of the monocycloalkane is preferably 3 to 6. Specifically, the solvent may, for example, be cyclopentane or cyclohexane. The polycyclic aliphatic hydrocarbon group is preferably a group obtained by removing 2 hydrogen atoms from a cycloalkane. The number of carbon atoms of the polycyclic alkane is preferably 7 to 12. Specifically, it may, for example, be adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane.

The cyclic aliphatic hydrocarbon group may have a substituent (a group or an atom other than a hydrogen atom) in place of a hydrogen atom, or may have no substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, and an oxo group (═ O).

The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group.

The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group and a tert-butoxy group, and particularly preferably a methoxy group and an ethoxy group.

Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

In the cyclic aliphatic hydrocarbon group, a part of carbon atoms constituting the ring structure thereof may be substituted with-O-or-S-. The heteroatom-containing substituent is preferably-O-, -C (═ O) -O-, -S-, -S (═ O) ₂ -、-S(＝O) ₂ -O-。

The aromatic hydrocarbon group as the 2-valent hydrocarbon group is a 2-valent hydrocarbon group having at least 1 aromatic ring, and may have a substituent. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n +2 pi electrons, and may be monocyclic or polycyclic. The number of carbon atoms of the aromatic ring is preferably 5 to 30, more preferably 5 to 20, further preferably 6 to 15, and particularly preferably 6 to 12. Wherein the number of carbon atoms does not include the number of carbon atoms of the substituent.

Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and an aromatic heterocyclic ring in which a part of carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom. Examples of the hetero atom in the aromatic hetero ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.

Specific examples of the aromatic hydrocarbon group having a 2-valent hydrocarbon group include groups obtained by removing 2 hydrogen atoms from the above aromatic hydrocarbon ring or aromatic heterocyclic ring (arylene group or heteroarylene group); a group obtained by removing 2 hydrogen atoms from an aromatic compound (for example, biphenyl, fluorene, or the like) containing 2 or more aromatic rings; a group (aryl or heteroaryl) obtained by removing 1 hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring, wherein 1 hydrogen atom is substituted with an alkylene group (for example, a group obtained by further removing 1 hydrogen atom from an aryl group in an arylalkyl group such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.), and the like.

The number of carbon atoms of the alkylene group bonded to the aryl group or the heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

In the above aromatic hydrocarbon group, a hydrogen atom of the aromatic hydrocarbon group may be substituted by a substituent. For example, a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, and an oxo group (═ O).

The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and a tert-butyl group.

The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, and is preferably a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a tert-butoxy group, and more preferably a methoxy group and an ethoxy group.

Examples of the "haloalkyl" group as the substituent may include those wherein a part or all of hydrogen atoms of the alkyl group are substituted with the halogen atom.

2-valent linking groups containing hetero atoms

The heteroatom in the heteroatom-containing 2-valent linking group means an atom other than carbon atoms and hydrogen atoms, and examples thereof include oxygen atoms, nitrogen atoms, sulfur atoms, and halogen atoms.

Specific examples of the heteroatom-containing 2-valent linking group include-O-, -C (═ O) -O-, -O-C (═ O) -O-, -S-, -S (═ O) ₂ -、-S(＝O) ₂ And non-hydrocarbon linking groups such as-O-, -NH-C (═ O) -, -NH-C (═ NH) -, ═ N-, or a combination of at least 1 of these non-hydrocarbon linking groups and a 2-valent hydrocarbon group. The 2-valent hydrocarbon group may, for example, be the same as the above-mentioned 2-valent hydrocarbon group which may have a substituent, and is preferably a linear or branched aliphatic hydrocarbon group.

In the above-mentioned groups, H in-NH-, -NH-C (═ NH) -in-C (═ O) -NH-may be substituted with a substituent such as an alkyl group or an acyl group. The number of carbon atoms of the substituent is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5.

As R ^12b The 2-valent linking group in (2) is particularly preferably a linear or branched alkylene group, a cyclic aliphatic hydrocarbon group or a heteroatom-containing 2-valent linking group.

At R ^12b When the linking group having a valence of 2 in (2) is a linear or branched alkylene group, the alkylene group has preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. Specifically, the same groups as those of the linear alkylene group and the branched alkylene group exemplified as the linear or branched aliphatic hydrocarbon group in the description of the "2-valent hydrocarbon group which may have a substituent" as the above-mentioned 2-valent linking group may be mentioned.

At R ^12b In the case where the linking group having a valence of 2 in (2) is a cyclic aliphatic hydrocarbon group, the cyclic aliphatic hydrocarbon group may be the same as the cyclic aliphatic hydrocarbon group exemplified as the "aliphatic hydrocarbon group having a ring in the structure" in the description of the "2-valent hydrocarbon group which may have a substituent" as the linking group having a valence of 2.

The cyclic aliphatic hydrocarbon group is particularly preferably a group obtained by removing two or more hydrogen atoms from cyclopentane, cyclohexane, norbornane, isobornane, adamantane, tricyclodecane, or tetracyclododecane.

At R ^12b In the case where the 2-valent linking group in (2) is a heteroatom-containing 2-valent linking group, preferable examples of the linking group include-O-, -C (═ O) -, -O-C (═ O) -O-, -C (═ O) -NH-, -NH- (H may be substituted with a substituent such as an alkyl group or an acyl group), -S-, -S (═ O) ₂ -、-S(＝O) ₂ -O-in the formula-Y ¹ -O-Y ² -、-[Y ¹ -C(＝O)-O] _m’ -Y ² -or-Y ¹ -O-C(＝O)-Y ₂ A group represented by (wherein Y is) ¹ And Y ² Each independently is a 2-valent hydrocarbon group which may have a substituent, O is an oxygen atom, and m' is an integer of 0 to 3]And the like.

At R ^12b When the linking group having a valence of 2 in (A) is-NH-, the hydrogen atom in the-NH-may be substituted with a substituent such as an alkyl group or an acyl group. The number of carbon atoms of the substituent (such as an alkyl group or an acyl group) is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5.

formula-Y ¹ -O-Y ² -、-[Y ¹ -C(＝O)-O] _m’ -Y ² -or-Y ¹ -O-C(＝O)-Y ² In (Y) ¹ And Y ² Each independently is a 2-valent hydrocarbon group which may have a substituent. Examples of the 2-valent hydrocarbon group may include the same groups as the "2-valent hydrocarbon group which may have a substituent" exemplified in the description of the 2-valent linking group.

As Y ¹ The aliphatic hydrocarbon group is preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, still more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or an ethylene group.

As Y ² The aliphatic hydrocarbon group is preferably a linear or branched aliphatic hydrocarbon group, and more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atomsThe alkyl group in the form of (A) is particularly preferably a methyl group.

In the formula [ Y ] ¹ -C(＝O)-O] _m’ -Y ² In the group represented by-m' is an integer of 0 to 3, preferably 0 to 2, more preferably 0 or 1, and particularly preferably 1. That is, as represented by the formula- [ Y ] ¹ -C(＝O)-O] _m’ -Y ² A group represented by the formula-Y is particularly preferred ¹ -C(＝O)-O-Y ² -a group represented by (a). Among them, preferred is a compound represented by the formula- (CH) ₂ ) _a’ -C(＝O)-O-(CH ₂ ) _b’ -a group represented by (a). In the formula, a' is an integer of 1 to 10, preferably 1 to 8, more preferably 1 to 5, still more preferably 1 or 2, and most preferably 1. b' is an integer of 1 to 10, preferably 1 to 8, more preferably 1 to 5, still more preferably 1 or 2, and most preferably 1.

For R ^12b The 2-valent linking group in (1) is preferably an organic group composed of a combination of at least 1 non-hydrocarbon group and a 2-valent hydrocarbon group as the heteroatom-containing 2-valent linking group. Among these, a linear group having an oxygen atom as a hetero atom, for example, a group containing an ether bond or an ester bond is preferable, and the above-mentioned formula-Y is more preferable ¹ -O-Y ² -、-[Y ¹ -C(＝O)-O] _m’ -Y ² -or-Y ¹ -O-C(＝O)-Y ² A group represented by the formula- [ Y ] ¹ -C(＝O)-O] _m’ -Y ² -or-Y ¹ -O-C(＝O)-Y ² -a group represented by (a).

As R ^12b The linking group having a valence of 2 in (1) is preferably an alkylene group or a linking group having a valence of 2 and containing an ester bond (-C (═ O) -O-).

The alkylene group is preferably a linear or branched alkylene group. Preferable examples of the linear aliphatic hydrocarbon group include methylene [ -CH ₂ -]Ethylene [ - (CH) ₂ ) ₂ -]Propylene [ - (CH) ₂ ) ₃ -]Butylene [ - (CH) ₂ ) ₄ -]And pentylene [ - (CH) ₂ ) ₅ -]And the like. The branched alkylene group is preferablyAn alternative example is-CH (CH) ₃ )-、-CH(CH ₂ CH ₃ )-、-C(CH ₃ ) ₂ -、-C(CH ₃ )(CH ₂ CH ₃ )-、-C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-、-C(CH ₂ CH ₃ ) ₂ -isoalkylmethylene; -CH (CH) ₃ )CH ₂ -、-CH(CH ₃ )CH(CH ₃ )-、-C(CH ₃ ) ₂ CH ₂ -、-CH(CH ₂ CH ₃ )CH ₂ -、-C(CH ₂ CH ₃ ) ₂ -CH ₂ -an isoalkylethylene group; -CH (CH) ₃ )CH ₂ CH ₂ -、-CH ₂ CH(CH ₃ )CH ₂ -isoalkylpropylene; -CH (CH) ₃ )CH ₂ CH ₂ CH ₂ -、-CH ₂ CH(CH ₃ )CH ₂ CH ₂ And an alkylidene group such as an alkylbutylidene group.

As the 2-valent linking group containing an ester bond, the following is particularly preferred: -R ^13b -C (═ O) -O- [ wherein R is ^13b Is a 2-valent linking group]The group shown. That is, the structural unit (b-3-S) is preferably a structural unit represented by the following formula (b-S1-1).

[ CHEM 38 ]

(wherein R and R ^11b Respectively same as above, R ^13b Is a 2-valent linking group. )

As R ^13b The substituent (C) is not particularly limited, and examples thereof include the aforementioned R ^12b The 2-valent linking group in (1) is the same group.

As R ^13b The linking group having a valence of 2 in (b) is preferably a linear or branched alkylene group, an aliphatic hydrocarbon group having a ring in the structure, or a linking group having a valence of 2 containing a heteroatom, and more preferably a linear or branched alkylene group or a linking group having a valence of 2 containing an oxygen atom as a heteroatom.

The linear alkylene group is preferably methyleneThe radical or ethylene radical is particularly preferably methylene. The branched alkylene group is preferably an alkylmethylene group or an alkylethylene group, and particularly preferably-CH (CH) ₃ )-、-C(CH ₃ ) ₂ -or-C (CH) ₃ ) ₂ CH ₂ -。

As the linking group having a valence of 2 containing an oxygen atom, a linking group having a valence of 2 containing an ether bond or an ester bond is preferable, and the group-Y is more preferable ¹ -O-Y ² -、-[Y ¹ -C(＝O)-O] _m’ -Y ² -or-Y ¹ -O-C(＝O)-Y ² -。Y ¹ And Y ² Each independently is a 2-valent hydrocarbon group which may have a substituent, and m' is an integer of 0 to 3 inclusive. Among them, preferred is-Y ¹ -O-C(＝O)-Y ² - (CH) is particularly preferred ₂ ) _c -O-C(＝O)-(CH ₂ ) _d -a group represented by. c is an integer of 1 to 5, preferably 1 or 2. d is an integer of 1 to 5, preferably 1 or 2.

The structural unit (b-3-S) is particularly preferably a structural unit represented by the following formula (b-S1-11) or (b-S1-12), and more preferably a structural unit represented by the following formula (b-S1-12).

[ CHEM 39 ]

(wherein, R, A' and R ^10b Z and R ^13b Respectively, as described above. )

In the formula (b-S1-11), A' is preferably a methylene group, an oxygen atom (-O-), or a sulfur atom (-S-).

As R ^13b The preferable examples of the substituent include a linear or branched alkylene group and a 2-valent linking group containing an oxygen atom. As R ^13b The linear or branched alkylene group and the oxygen atom-containing linking group having a valence of 2 may, for example, be the same groups as those mentioned above for the linear or branched alkylene group and the oxygen atom-containing linking group having a valence of 2.

As the structural unit represented by the formula (b-S1-12), a structural unit represented by the following formula (b-S1-12a) or (b-S1-12b) is particularly preferable.

[ CHEM 40 ]

(wherein R and A' are the same as above, and c to e are each independently an integer of 1 to 3.)

[ structural Unit (b-3-L) ]

Examples of the structural unit (b-3-L) include R in the above-mentioned formula (b-S1) ^11b More specifically, the structural units substituted with a lactone ring-containing group may be structural units represented by the following formulae (b-L1) to (b-L5).

[ CHEM 41 ]

(wherein R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a haloalkyl group having 1 to 5 carbon atoms; R ' represents a hydrogen atom, an alkyl group, an alkoxy group, a haloalkyl group, a hydroxyl group, -COOR ", -OC (═ O) R ', a hydroxyalkyl group or a cyano group, and R ' represents a hydrogen atom or an alkyl group; R represents a hydrogen atom, an alkyl group, a haloalkyl group having 1 to 5 carbon atoms; R represents a halogen atom, and R represents a halogen atom ^12b Is a single bond or a 2-valent linking group, s' is an integer of 0 to 2 inclusive; a' is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom; r is 0 or 1. )

R in the formulae (b-L1) to (b-L5) is the same as described above.

Examples of the alkyl group, alkoxy group, haloalkyl group, -COOR ", -OC (═ O) R", and hydroxyalkyl group in R' may include-SO-containing groups ₂ Examples of the "cycloalkyl" group include the same ones as those illustrated for the alkyl group, alkoxy group, haloalkyl group, -COOR ", -OC (═ O) R", and hydroxyalkyl group.

In view of easy industrial availability, R' is preferably a hydrogen atom.

The alkyl group in R' may be linear, branched or cyclic.

When R ″ is a linear or branched alkyl group, the number of carbon atoms is preferably 1 to 10, and more preferably 1 to 5.

When R ″ is a cyclic alkyl group, the number of carbon atoms is preferably 3 to 15, more preferably 4 to 12, and most preferably 5 to 10. Specifically, a group obtained by removing 1 or more hydrogen atoms from a monocycloparaffin which may be substituted or unsubstituted with a fluorine atom or a fluoroalkyl group, or from a polycycloalkane such as a bicycloalkane, tricycloalkane, and tetracycloalkane can be exemplified. Specifically, the hydrogen atom may be a group obtained by removing 1 or more hydrogen atoms from a monocycloparaffin such as cyclopentane or cyclohexane, or from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane.

Examples of the "A" may include the same groups as those illustrated for A' in the above formula (3-1). A' is preferably an alkylene group having 1 to 5 carbon atoms, an oxygen atom (-O-), or a sulfur atom (-S-), more preferably an alkylene group having 1 to 5 carbon atoms, or-O-. The alkylene group having 1 to 5 carbon atoms is more preferably a methylene group or a dimethylmethylene group, and most preferably a methylene group.

R ^12b And R in said formula (b-S1) ^12b The same is true.

In the formula (b-L1), s "is preferably 1 or 2.

Specific examples of the structural units represented by the above formulae (b-L1) to (b-L3) are shown below. In the following formulae, R ^α Represents a hydrogen atom, a methyl group or a trifluoromethyl group.

[ CHEM 42 ]

[ CHEM 43 ]

[ CHEM 44 ]

As the structural unit (b-3-L), at least 1 selected from the group consisting of the structural units represented by the above-mentioned formulae (b-L1) to (b-L5) is preferable, at least 1 selected from the group consisting of the structural units represented by the above-mentioned formulae (b-L1) to (b-L3) is more preferable, and at least 1 selected from the group consisting of the structural units represented by the above-mentioned formulae (b-L1) or (b-L3) is particularly preferable.

Among them, at least 1 kind selected from the group consisting of the structural units represented by the above-mentioned formulae (b-L1-1), (b-L1-2), (b-L2-1), (b-L2-7), (b-L2-12), (b-L2-14), (b-L3-1) and (b-L3-5) is preferable.

Further, as the structural unit (b-3-L), structural units represented by the following formulae (b-L6) to (b-L7) are also preferable.

[ CHEM 45 ]

In the formulae (b-L6) and (b-L7), R and R ^12b As described above.

Further, the acrylic resin (B3) contains, as a structural unit which improves the solubility of the acrylic resin (B3) in alkali due to the action of an acid, structural units having an acid-dissociable group represented by the following formulae (B5) to (B7).

[ CHEM 46 ]

In the above formulae (b5) to (b7), R ^14b And R ^18b ～R ^23b Each independently represents a hydrogen atom, a carbon atom number of 1 to 6A linear or branched alkyl group, a fluorine atom, or a linear or branched fluoroalkyl group having 1 to 6 carbon atoms, R ^15b ～R ^17b Each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched fluoroalkyl group having 1 to 6 carbon atoms, or an alicyclic group having 5 to 20 carbon atoms, and R is ^16b And R ^17b May be bonded to each other to form a hydrocarbon ring having 5 to 20 carbon atoms together with the carbon atoms bonded to both, Y ^b Represents an alicyclic group or an alkyl group which may have a substituent, p represents an integer of 0 to 4, and q represents 0 or 1.

Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. The fluoroalkyl group is a group in which a part or all of the hydrogen atoms of the alkyl group are replaced with fluorine atoms.

Specific examples of the alicyclic group include groups obtained by removing 1 or more hydrogen atoms from a monocycloparaffin or from a polycycloalkane such as a bicycloalkane, a tricycloalkane or a tetracycloalkane. Specifically, the compound may be one obtained by removing 1 hydrogen atom from a monocycloalkane such as cyclopentane, cyclohexane, cycloheptane or cyclooctane, or a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane. In particular, a group (which may further have a substituent) obtained by removing 1 hydrogen atom from cyclohexane or adamantane is preferable.

In the above-mentioned R ^16b And R ^17b When hydrocarbon rings are not bonded to each other, R is the above-mentioned group ^15b 、R ^16b And R ^17b The alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and more preferably a linear or branched alkyl group having 2 to 4 carbon atoms. As the above-mentioned R ^19b 、R ^20b 、R ^22b 、R ^23b Preferably a hydrogen atom or a methyl group.

R is as defined above ^16b And R ^17b The alicyclic group having 5 to 20 carbon atoms may be formed together with the carbon atoms to which both are bonded. Specific examples of such alicyclic groups include groups obtained by removing 1 or more hydrogen atoms from a monocycloalkane or from a polycycloalkane such as a bicycloalkane, tricycloalkane or tetracycloalkane. Specifically, the hydrogen atom-containing group may be one obtained by removing 1 or more hydrogen atoms from a monocycloalkane such as cyclopentane, cyclohexane, cycloheptane or cyclooctane, or a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane. In particular, a group (which may further have a substituent) obtained by removing 1 or more hydrogen atoms from cyclohexane or adamantane is preferable.

Further, in the above R ^16b And R ^17b When the alicyclic group to be formed has a substituent on the ring skeleton, examples of the substituent include a polar group such as a hydroxyl group, a carboxyl group, a cyano group, and an oxygen atom (═ O), or a linear or branched alkyl group having 1 to 4 carbon atoms. As the polar group, an oxygen atom (═ O) is particularly preferable.

Above Y ^b Examples of the alicyclic group or alkyl group include groups obtained by removing 1 or more hydrogen atoms from a monocycloparaffin or from a polycycloalkane such as a bicycloalkane, tricycloalkane or tetracycloalkane. Specifically, the hydrogen atom-containing group may be one obtained by removing 1 or more hydrogen atoms from a monocycloalkane such as cyclopentane, cyclohexane, cycloheptane, or cyclooctane, or a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane. Particularly preferred is a group (which may further have a substituent) obtained by removing 1 or more hydrogen atoms from adamantane.

Further, in the above Y ^b When the alicyclic group in (2) has a substituent on the ring skeleton, examples of the substituent include a polar group such as a hydroxyl group, a carboxyl group, a cyano group, and an oxygen atom (═ O), and a linear or branched alkyl group having 1 to 4 carbon atoms. As the polar group, an oxygen atom (═ O) is particularly preferable.

In addition, in Y ^b In the case of an alkyl group, a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 6 to 15 carbon atoms is preferable. Such an alkyl group is particularly preferably an alkoxyalkyl group, and examples of such an alkoxyalkyl group include a 1-methoxyethyl group, a 1-ethoxyethyl group, a 1-n-propoxyethyl group, a 1-isopropoxyethyl group, a 1-n-butoxyethyl group, a 1-isobutoxyethyl group, a 1-tert-butoxyethyl group, a 1-methoxypropyl group, a 1-ethoxypropyl group, a 1-methoxy-1-methyl-ethyl group, and a 1-ethoxy-1-methylethyl group.

As a preferred specific example of the structural unit represented by the above formula (b5), structural units represented by the following formulae (b5-1) to (b5-33) may be mentioned.

[ CHEM 47 ]

In the above formulae (b5-1) to (b5-33), R ^24b Represents a hydrogen atom or a methyl group.

As a preferred specific example of the structural unit represented by the above formula (b6), structural units represented by the following formulae (b6-1) to (b6-26) may be mentioned.

[ CHEM 48 ]

In the above formulae (b6-1) to (b6-26), R ^24b Represents a hydrogen atom or a methyl group.

As a preferred specific example of the structural unit represented by the above formula (b7), structural units represented by the following formulae (b7-1) to (b7-15) may be mentioned.

[ CHEM 49 ]

In the above formulae (b7-1) to (b7-15), R ^24b To representA hydrogen atom or a methyl group.

Among the structural units represented by the formulae (b5) to (b7) described above, the structural unit represented by the formula (b6) is preferable from the viewpoint of easy synthesis and relatively easy high sensitivity. In addition, in the structural unit represented by the formula (b6), Y is preferably ^b Is a structural unit of an alkyl group, and preferably R ^19b And R ^20b One or both of them are structural units of an alkyl group.

Further, the acrylic resin (B3) is preferably a resin composed of a copolymer containing structural units represented by the above formulae (B5) to (B7) and containing structural units derived from a polymerizable compound having an ether bond.

Examples of the polymerizable compound having an ether bond include radical polymerizable compounds such as (meth) acrylic acid derivatives having an ether bond and an ester bond, and specific examples thereof include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethylcarbitol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate. The polymerizable compound having an ether bond is preferably 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, or methoxytriethylene glycol (meth) acrylate. These polymerizable compounds may be used alone, or 2 or more kinds may be used in combination.

Further, the acrylic resin (B3) may contain another polymerizable compound as a structural unit for the purpose of appropriately controlling physical and chemical properties. Examples of such polymerizable compounds include known radical polymerizable compounds and anion polymerizable compounds.

Examples of such polymerizable compounds include the following compounds: monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives having a carboxyl group and an ester bond, such as 2-methacryloyloxyethylsuccinic acid, 2-methacryloyloxyethylmaleic acid, 2-methacryloyloxyethylphthalic acid, and 2-methacryloyloxyethylhexahydrophthalic acid; alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and cyclohexyl (meth) acrylate; hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; dicarboxylic diesters such as diethyl maleate and dibutyl fumarate; vinyl group-containing aromatic compounds such as styrene, α -methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α -methylhydroxystyrene, and α -ethylhydroxystyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated dienes such as butadiene and isoprene; nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylamide.

As described above, the acrylic resin (B3) may contain a structural unit derived from a polymerizable compound having a carboxyl group such as the monocarboxylic acid or the dicarboxylic acid. However, from the viewpoint of facilitating formation of a resist pattern including a non-resist portion having a more favorable cross-sectional shape, the ratio of the structural unit derived from the polymerizable compound having a carboxyl group in the acrylic resin (B3) is preferably less than 20% by mass, more preferably 0.1% by mass or more and 15% by mass or less, and particularly preferably 1% by mass or more and 10% by mass or less.

Further, the polymerizable compound may, for example, be a (meth) acrylate having an acid-non-dissociative aliphatic polycyclic group, or an aromatic compound containing a vinyl group. From the viewpoint of easy industrial availability, etc., particularly preferred as the acid-non-dissociative aliphatic polycyclic group are tricyclodecyl group, adamantyl group, tetracyclododecyl group, isobornyl group, norbornyl group, and the like. These aliphatic polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.

Specific examples of the (meth) acrylic esters having an acid-non-dissociable aliphatic polycyclic group include compounds having the following formulas (b8-1) to (b 8-5).

[ CHEM 50 ]

In the above formulae (b8-1) to (b8-5), R ^25b Represents a hydrogen atom or a methyl group.

The acrylic resin (B3) contains a monomer containing-SO ₂ In the case of the structural unit (B-3) having a cyclic group or a lactone cyclic group, the content of the structural unit (B-3) in the acrylic resin (B3) is preferably 50% by mass or less, more preferably 30% by mass or less.

The acrylic resin (B3) preferably contains 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 10% by mass or more and 50% by mass or less of the structural units represented by the above formulae (B5) to (B7).

The acrylic resin (B3) preferably contains a structural unit derived from the polymerizable compound having an ether bond. In the acrylic resin (B3), the content of the structural unit derived from the polymerizable compound having an ether bond is preferably 0 mass% or more and 50 mass% or less, more preferably 5 mass% or more and 40 mass% or less, and further preferably 5 mass% or more and 30 mass% or less.

The acrylic resin (B3) preferably contains a structural unit derived from the (meth) acrylate having the acid-nondissociatable aliphatic polycyclic group. In the acrylic resin (B3), the content of the structural unit derived from a (meth) acrylate having an acid-nondissociable aliphatic polycyclic group is preferably 0 mass% or more and 60 mass% or less, more preferably 5 mass% or more and 50 mass% or less, and still more preferably 5 mass% or more and 30 mass% or less.

If the photosensitive composition contains a predetermined amount of the acrylic resin (B3), an acrylic resin other than the acrylic resin (B3) described above can be used as the resin (B). The acrylic resin other than the acrylic resin (B3) is not particularly limited as long as it contains the structural units represented by the above formulae (B5) to (B7).

The polystyrene-equivalent mass average molecular weight of the resin (B) described above is preferably 10000 to 600000, more preferably 20000 to 400000, and still more preferably 30000 to 300000. By setting the mass average molecular weight as described above, it is possible to maintain sufficient strength of the photosensitive layer made of the photosensitive composition without lowering the releasability of the photosensitive layer from the substrate, and further easily prevent the expansion of the outer shape (profile) or the generation of cracks during plating.

The molecular weight distribution coefficient of the resin (B) is preferably 1.05 or more. Here, the molecular weight distribution coefficient is a value obtained by dividing a mass average molecular weight by a number average molecular weight. By setting such a molecular weight distribution coefficient, it is possible to obtain a desired stress resistance against plating or to avoid a problem that a metal layer obtained by plating treatment is likely to swell.

The content of the resin (B) is preferably 5 mass% or more and 70 mass% or less with respect to the total mass of the photosensitive composition.

The content of the resin (B) is preferably 5 mass% or more and 99 mass% or less, and more preferably 50 mass% or more and 99 mass% or less, based on the total solid content mass of the photosensitive composition.

< acid diffusion inhibitor (C) >

The photosensitive composition preferably further contains an acid diffusion inhibitor (C) for the purpose of improving the shape of the resist pattern, the standing stability of the photosensitive resin film, and the like. The acid diffusion inhibitor (C) is preferably a nitrogen-containing compound (C1), and may further contain an organic carboxylic acid, or an oxyacid of phosphorus or a derivative thereof (C2), as required.

[ Nitrogen-containing Compound (C1) ]

Examples of the nitrogen-containing compound (C1) include trimethylamine, diethylamine, triethylamine, di-N-propylamine, tri-N-pentylamine, tribenzylamine, diethanolamine, triethanolamine, N-hexylamine, N-heptylamine, N-octylamine, N-nonylamine, ethylenediamine, N ' -tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4 ' -diaminodiphenylmethane, 4 ' -diaminodiphenyl ether, 4 ' -diaminobenzophenone, 4 ' -diaminodiphenylamine, formamide, N-methylformamide, N-dimethylformamide, acetamide, N-methylacetamide, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone, methylurea, 1-dimethylurea, and mixtures thereof, 1, 3-dimethylurea, 1, 3, 3-tetramethylurea, 1, 3-diphenylurea, imidazole, benzimidazole, 4-methylimidazole, 8-hydroxyquinoline, acridine, purine, pyrrolidine, piperidine, 2, 4, 6-tris (2-pyridyl) s-triazine, morpholine, 4-methylmorpholine, piperazine, 1, 4-dimethylpiperazine, 1, 4-diazabicyclo [2.2.2] octane, pyridine and the like. These may be used alone, or 2 or more of them may be used in combination.

Further, commercially available hindered amine compounds such as ADK STAB LA-52, ADK STAB LA-57, ADK STAB LA-63P, ADK STAB LA-68, ADK STAB LA-72, ADK STAB LA-77Y, ADK STAB LA-77G, ADK STAB LA-81, ADK STAB LA-82 and ADK STAB LA-87 (both manufactured by ADEKA Co., Ltd.), or 4-hydroxy-1, 2, 2, 6, 6-pentamethylpiperidine derivatives, or pyridines in which the 2, 6-position is substituted with a substituent such as a hydrocarbon group, such as 2, 6-diphenylpyridine and 2, 6-di-t-butylpyridine, can also be used as the nitrogen-containing compound (C1).

The nitrogen-containing compound (C1) is used usually in a range of 0 to 5 parts by mass, and particularly preferably in a range of 0 to 3 parts by mass, based on 100 parts by mass of the total of the resin (B) and the alkali-soluble resin (D) described below.

[ organic carboxylic acid, or oxyacid of phosphorus or derivative thereof (C2) ]

Among the organic carboxylic acids or the oxyacids or derivatives thereof of phosphorus (C2), the organic carboxylic acids are specifically preferably malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, etc., and particularly preferably salicylic acid.

Examples of the oxygen acid of phosphorus or a derivative thereof include phosphoric acids such as phosphoric acid, di-n-butyl phosphate and diphenyl phosphate, and derivatives of these acids and esters; phosphonic acids and their ester derivatives such as phosphonic acid, dimethyl phosphonate, di-n-butyl phosphonate, phenylphosphonic acid, diphenyl phosphonate, dibenzyl phosphonate, and the like; phosphinic acids such as phosphinic acid and phenylphosphinic acid, and derivatives such as esters thereof. Among these, phosphonic acid is particularly preferable. These may be used alone, or 2 or more of them may be used in combination.

The organic carboxylic acid, or the phosphorus oxyacid or derivative thereof (C2) is usually used in a range of 0 to 5 parts by mass, particularly preferably in a range of 0 to 3 parts by mass, based on 100 parts by mass of the total of the resin (B) and the alkali-soluble resin (D) described below.

In addition, for the purpose of forming a salt and stabilizing it, it is preferable to use the same amount of the organic carboxylic acid, or the oxyacid of phosphorus or the derivative thereof (C2) as that of the nitrogen-containing compound (C1).

< alkali-soluble resin (D) >

The photosensitive composition may contain no alkali-soluble resin (D), but may contain an alkali-soluble resin (D). Here, the alkali-soluble resin means: a resin film having a film thickness of 1 μm is formed on a substrate by using a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20 mass%, and the resin (B) is a resin which dissolves not less than 0.01 μm when immersed in a 2.38 mass% aqueous TMAH solution for 1 minute and which does not belong to the resin (B) (typically, a resin whose alkali solubility does not substantially change even by the action of an acid). The alkali-soluble resin (D) is preferably at least 1 resin selected from the group consisting of a novolac resin (D1), a polyhydroxystyrene resin (D2), and an acrylic resin (D3).

Novolac resin (D1)

The novolak resin is obtained, for example, by addition-condensing an aromatic compound having a phenolic hydroxyl group (hereinafter, simply referred to as "phenol") and an aldehyde under an acid catalyst.

Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2, 3-xylenol, 2, 4-xylenol, 2, 5-xylenol, 2, 6-xylenol, 3, 4-xylenol, 3, 5-xylenol, 2, 3, 5-trimethylphenol, 3, 4, 5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone monomethyl ether, pyrogallol, m-benzenetriol, hydroxybiphenyl, bisphenol A, gallic acid ester, α -naphthol, and β -naphthol.

Examples of the aldehyde include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde.

The catalyst used in the addition condensation reaction is not particularly limited, and, for example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, and the like can be used as the acid catalyst.

Further, the flexibility of the novolak resin can be further improved by using o-cresol, by substituting a hydrogen atom of a hydroxyl group in the resin with another substituent, or by using an aldehyde having a large volume.

The mass average molecular weight of the novolac resin (D1) is not particularly limited within a range that does not impair the object of the present invention, and is preferably 1000 to 50000.

[ polyhydroxystyrene resin (D2) ]

Examples of the hydroxystyrene compound constituting the polyhydroxystyrene resin (D2) include p-hydroxystyrene, α -methylhydroxystyrene, α -ethylhydroxystyrene and the like.

Further, the polyhydroxystyrene resin (D2) is preferably a copolymer with a styrene resin. Examples of the styrene compound constituting the styrene resin include styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, and α -methylstyrene.

The mass average molecular weight of the polyhydroxystyrene resin (D2) is not particularly limited within a range not interfering with the object of the present invention, and is preferably 1000 to 50000.

[ acrylic resin (D3) ]

The acrylic resin (D3) preferably contains a structural unit derived from a polymerizable compound having an ether bond and a structural unit derived from a polymerizable compound having a carboxyl group.

Examples of the polymerizable compound having an ether bond include (meth) acrylic acid derivatives having an ether bond and an ester bond, such as 2-methoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethylcarbitol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate. The polymerizable compound having an ether bond is preferably 2-methoxyethyl acrylate or methoxytriethylene glycol acrylate. These polymerizable compounds may be used alone, or 2 or more kinds may be used in combination.

Examples of the polymerizable compound having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; and compounds having a carboxyl group and an ester bond such as 2-methacryloyloxyethylsuccinic acid, 2-methacryloyloxyethylmaleic acid, 2-methacryloyloxyethylphthalic acid, and 2-methacryloyloxyethylhexahydrophthalic acid. The polymerizable compound having a carboxyl group is preferably acrylic acid or methacrylic acid. These polymerizable compounds may be used alone, or 2 or more kinds may be used in combination.

The mass average molecular weight of the acrylic resin (D3) is not particularly limited within a range not interfering with the object of the present invention, and is preferably 50000 to 800000.

When the total amount of the resin (B) and the alkali-soluble resin (D) is 100 parts by mass, the content of the alkali-soluble resin (D) is preferably 0 to 80 parts by mass, and more preferably 0 to 60 parts by mass. When the content of the alkali-soluble resin (D) is in the above range, the film reduction during development tends to be prevented.

< Sulfur-containing Compound (E) >

In the case where the photosensitive composition is used for a pattern formed on a metal substrate, the photosensitive composition preferably contains a sulfur-containing compound (E). The sulfur-containing compound (E) is a compound containing a sulfur atom that can coordinate to a metal. In addition, as for a compound that can produce 2 or more tautomers, in the case where at least 1 tautomer includes a sulfur atom that coordinates with a metal constituting the surface of the metal substrate, the compound belongs to a sulfur-containing compound.

When a resist pattern used as a mold for plating is formed on a surface made of a metal such as Cu, defects such as footing are likely to occur in the cross-sectional shape. However, when the photosensitive composition contains the sulfur-containing compound (E), even when a resist pattern is formed on a surface of the substrate made of metal, the occurrence of defects in the cross-sectional shape such as footing is easily suppressed. The "footing" refers to a phenomenon in which the resist portion protrudes toward the non-resist portion side in the vicinity of the contact surface between the substrate surface and the resist pattern, and the width of the bottom portion is narrower than the width of the top portion in the non-resist portion.

In the case where the photosensitive composition is used for a pattern formed on a substrate other than a metal substrate, the photosensitive composition need not particularly contain a sulfur-containing compound. When the photosensitive composition is used for a pattern formed on a substrate other than a metal substrate, the photosensitive composition preferably does not contain the sulfur-containing compound (E) from the viewpoint of ease of production of the photosensitive composition due to a reduction in the number of components of the photosensitive composition, reduction in the production cost of the photosensitive composition, and the like.

In addition, the photosensitive composition for forming a pattern on a substrate other than a metal substrate does not particularly have a problem caused by the inclusion of the sulfur compound (E).

The sulfur atom capable of coordinating to the metal is contained in the sulfur-containing compound as, for example, a mercapto group (-SH), a thiocarboxyl group (-CO-SH), a dithiocarboxyl group (-CS-SH), a thiocarbonyl group (-CS-), and the like.

The sulfur-containing compound preferably has a mercapto group, because it is easily coordinated to a metal and has an excellent effect of inhibiting footing.

Preferable examples of the sulfur-containing compound having a mercapto group include compounds represented by the following formula (e 1).

[ CHEM 51 ]

(in the formula, R ^e1 And R ^e2 Each independently represents a hydrogen atom or an alkyl group, R ^e3 Represents a single bond or alkylene, R ^e4 Represents a u-valent aliphatic group which may contain an atom other than carbon, and u represents an integer of 2 to 4. )

At R ^e1 And R ^e2 In the case of an alkyl group, the alkyl group may be linear or branched, and is preferably linear. At R ^e1 And R ^e2 In the case of an alkyl group, the number of carbon atoms of the alkyl group is not particularly limited within a range that does not impair the object of the present invention. The number of carbon atoms of the alkyl group is preferably 1 to 4, particularly preferably 1 or 2, and most preferably 1. As R ^e1 And R ^e2 In the combination of (3), one is preferably a hydrogen atom and the other is an alkyl group, and particularly preferably one is a hydrogen atom and the other is a methyl group.

At R ^e3 In the case of an alkylene group, the alkylene group may be linear or branched, and is preferably linear. At R ^e3 In the case of an alkylene group, the number of carbon atoms in the alkylene group is not particularly limited within a range not interfering with the object of the present invention. The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 or 2, and most preferably 1.

R ^e4 Is an aliphatic group having a valence of 2 to 4, which may contain an atom other than carbon. As R ^e4 Examples of the atom which may be contained other than carbon include a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. As R ^e4 The structure of the aliphatic group (b) may be linear, branched or cyclic, or a combination of these structures.

Among the compounds represented by the formula (e1), the compound represented by the following formula (e2) is more preferable.

[ CHEM 52 ]

(in the formula (e2), R ^e4 And u is synonymous with formula (e 1). )

Among the compounds represented by the above formula (e2), the following compounds are preferred.

[ CHEM 53 ]

Compounds represented by the following formulae (e3-L1) to (e3-L7) are also exemplified as preferable examples of the sulfur-containing compound having a mercapto group.

[ CHEM 54 ]

(in the formulae (e3-L1) to (e3-L7), R ', s ', A ' and R are the same as the formulae (B-L1) to (B-L7) described for the acrylic resin (B3.)

As preferable specific examples of the mercapto compound represented by the above formulae (e3-L1) to (e3-L7), the following compounds may be mentioned.

[ CHEM 55 ]

Compounds represented by the following formulae (e3-1) to (e3-4) are also exemplified as preferable examples of the sulfur-containing compound having a mercapto group.

[ CHEM 56 ]

(the same abbreviations as in the formulae (3-1) to (3-4) as in the acrylic resin (B3) are used for the definitions of the symbols in the formulae (e3-1) to (e 3-4))

Preferable specific examples of the mercapto compound represented by the above formulae (e3-1) to (e3-4) include the following compounds.

[ CHEM 57 ]

Further, preferable examples of the compound having a mercapto group include compounds represented by the following formula (e 4).

[ CHEM 58 ]

(in the formula (e4), R ^e5 A group selected from the group consisting of a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, a mercaptoalkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms and a halogen atom, n1 is an integer of 0 to 3, n0 is an integer of 0 to 3, and when n1 is 2 or 3, R is ^e5 May be the same or different. )

As R ^e5 Specific examples of the alkyl group which may have a hydroxyl group and has 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl. Among these alkyl groups, methyl, hydroxymethyl and ethyl groups are preferable.

As R ^e5 Specific examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and the likeAnd tert-butoxy. Among these alkoxy groups, methoxy and ethoxy groups are preferable, and methoxy is more preferable.

As R ^e5 Specific examples of the alkylthio group having 1 to 4 carbon atoms include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, an isobutylthio group, a sec-butylthio group and a tert-butylthio group. Among these alkylthio groups, preferred are methylthio and ethylthio, and more preferred is methylthio.

As R ^e5 Specific examples of the hydroxyalkyl group having 1 to 4 carbon atoms include a hydroxymethyl group, a 2-hydroxyethyl group, a 1-hydroxyethyl group, a 3-hydroxy-n-propyl group, and a 4-hydroxy-n-butyl group. Among these hydroxyalkyl groups, hydroxymethyl, 2-hydroxyethyl and 1-hydroxyethyl are preferable, and hydroxymethyl is more preferable.

As R ^e5 Specific examples of the mercaptoalkyl group having 1 to 4 carbon atoms include a mercaptomethyl group, a 2-mercaptoethyl group, a 1-mercaptoethyl group, a 3-mercapto-n-propyl group, a 4-mercapto-n-butyl group and the like. Among these mercaptoalkyl groups, preferred are mercaptomethyl, 2-mercaptoethyl and 1-mercaptoethyl groups, and more preferred is mercaptomethyl group.

At R ^e5 In the case of a haloalkyl group having 1 to 4 carbon atoms, the halogen atom contained in the haloalkyl group may, for example, be fluorine, chlorine, bromine or iodine. As R ^e5 Specific examples of the haloalkyl group having 1 to 4 carbon atoms include chloromethyl, bromomethyl, iodomethyl, fluoromethyl, dichloromethyl, dibromomethyl, difluoromethyl, trichloromethyl, tribromomethyl, trifluoromethyl, 2-chloroethyl, 2-bromoethyl, 2-fluoroethyl, 1, 2-dichloroethyl, 2-difluoroethyl, 1-chloro-2-fluoroethyl, 3-chloro-n-propyl, 3-bromo-n-propyl, 3-fluoro-n-propyl and 4-chloro-n-butyl. Among these haloalkyl groups, chloromethyl, bromomethyl, iodomethyl, fluoromethyl, dichloromethyl, dibromomethyl, difluoromethyl, trichloromethyl, tribromomethyl and trifluoromethyl groups are preferred, and chloromethyl, dichloromethyl, trichloromethyl and trifluoromethyl groups are more preferred.

As R ^e5 Specific examples of the halogen atom include fluorine, chlorine, bromine and iodine.

In formula (e4), n1 is an integer of 0 to 3, more preferably 1. In the case where n1 is 2 or 3, plural R' s ^e5 May be the same or different.

In the compound represented by the formula (e4), R on the benzene ring ^e5 The substitution position(s) is not particularly limited. R on the benzene ring ^e5 The substitution position of (A) is preferably relative to- (CH) ₂ ) _n0 The bonding position of-SH is a meta position or a para position.

The compound represented by the formula (e4) preferably has at least 1 group selected from the group consisting of alkyl groups, hydroxyalkyl groups and mercaptoalkyl groups as R ^e5 More preferably, the compound of (1) has 1 group selected from the group consisting of alkyl, hydroxyalkyl and mercaptoalkyl as R ^e5 The compound of (1). The compound represented by the formula (e4) has 1 group selected from the group consisting of alkyl, hydroxyalkyl and mercaptoalkyl as R ^e5 In the case of (2), the substitution position on the benzene ring of the alkyl group, hydroxyalkyl group or mercaptoalkyl group is preferably relative to- (CH) ₂ ) _n0 The bonding position of-SH is a meta position or a para position, and more preferably a para position.

In formula (e4), n0 is an integer of 0 to 3. From the viewpoint of easier preparation and availability of the compound, n0 is preferably 0 or 1, more preferably 0.

Specific examples of the compound represented by the formula (e4) include p-mercaptophenol, p-thiocresol, m-thiocresol, 4- (methylthio) benzenethiol, 4-methoxyphenylthiol, 3-methoxyphenylthiol, 4-ethoxybenzenethiol, 4-isopropoxyphenylthiol, 4-tert-butoxybenzenethiol, 3, 4-dimethoxybenzenethiol, 3, 4, 5-trimethoxybenzenethiol, 4-ethylbenzenethiol, 4-isopropylbenzenethiol, 4-n-butylbenzenethiol, 4-tert-butylbenzenethiol, 3-ethylbenzenethiol, 3-isopropylbenzenethiol, 3-n-butylbenzenethiol, 3-tert-butylbenzenethiol, 3, 5-dimethylbenzenethiol, 3, 4-dimethylbenzenethiol, 3-tert-butyl-4-methylphenbenzenethiol, 3-tert-4-methylphenylthiol, 3-tert-butyl-5-methylphenylthiol, 4-tert-butyl-3-methylphenylthiol, 4-mercaptobenzyl alcohol, 3-mercaptobenzyl alcohol, 4- (mercaptomethyl) phenol, 3- (mercaptomethyl) phenol, 1, 4-bis (mercaptomethyl) phenol, 1, 3-bis (mercaptomethyl) phenol, 4-fluorophenylthiol, 3-fluorophenylthiol, 4-chlorobenzenethiol, 3-chlorobenzenethiol, 4-bromobenzenethiol, 4-iodobenzenethiol, 3-bromobenzenethiol, 3, 4-dichlorobenzenethiol, 3, 5-dichlorobenzenethiol, 3, 4-difluorobenzenethiol, 3, 5-difluorobenzenethiol, 4-mercaptocatechol, 2, 6-di-tert-butyl-4-mercaptophenol, 3, 5-di-tert-butyl-4-methoxyphenylthiol, 4-bromo-3-methylphenylthiol, 4- (trifluoromethyl) phenylthiol, 3, 5-bis (trifluoromethyl) phenylthiol, 4-methylthiophenylthiol, 4-ethylthiophenylthiol, 4-n-butylthiophenylthiol, and 4-tert-butylthiophenylthiol.

Examples of the sulfur-containing compound having a mercapto group include a compound containing a nitrogen-containing aromatic heterocycle substituted with a mercapto group and a tautomer of a compound containing a nitrogen-containing aromatic heterocycle substituted with a mercapto group.

Preferred specific examples of the nitrogen-containing aromatic heterocycle include imidazole, pyrazole, 1, 2, 3-triazole, 1, 2, 4-triazole, oxazole, thiazole, pyridine, pyrimidine, pyridazine, pyrazine, 1, 2, 3-triazine, 1, 2, 4-triazine, 1, 3, 5-triazine, indole, indazole, benzimidazole, benzoxazole, benzothiazole, 1H-benzotriazole, quinoline, isoquinoline, cinnoline, phthalazine, quinazoline, quinoxaline and 1, 8-naphthyridine (naphthyridine).

As preferable specific examples of the nitrogen-containing heterocyclic compound and the tautomer of the nitrogen-containing heterocyclic compound, which are suitable as the sulfur-containing compound, the following compounds can be exemplified.

[ CHEMICAL 59 ]

When the photosensitive composition contains the sulfur-containing compound (E), the amount thereof to be used is preferably 0.01 to 5 parts by mass, more preferably 0.02 to 3 parts by mass, and particularly preferably 0.05 to 2 parts by mass, based on 100 parts by mass of the total of the resin (B) and the alkali-soluble resin (D).

< dye (F) >

The photosensitive composition may contain a dye (F).

The dye (F) may, for example, be an azo compound or curcumin, or may be another dye. Specific examples of the dye (F) include 2-phenylazo-4-methylphenol, 2 ', 4, 4' -tetrahydroxybenzophenone, 4-dimethylamino-2 ', 4' -dihydroxybenzophenone, 5-amino-3-methyl-1-phenyl-4- (4-hydroxyphenylazo) pyrazole, 4-dimethylamino-4 '-hydroxyazobenzene, 4-diethylamino-4' -ethoxyazobenzene, 4-diethylaminoazobenzene, curcumin, 1, 7-bis (3-methoxy-4-hydroxyphenyl) -1, 6-heptadiene-3, 5-dione, 5-hydroxy-4- (4-methoxyphenylazo) -3-methyl-1-phenylpyrazole And the like.

When the photosensitive composition contains the dye (F), the amount thereof to be used is preferably 0.0005 parts by mass or more and 5 parts by mass or less, more preferably 0.001 parts by mass or more and 3 parts by mass or less, and particularly preferably 0.003 parts by mass or more and 1 part by mass or less, based on 100 parts by mass of the total of the resin (B) and the alkali-soluble resin (D).

< organic solvent (S) >

The photosensitive composition preferably contains an organic solvent (S). The type of the organic solvent (S) is not particularly limited as long as the object of the present invention is not impaired, and can be appropriately selected from conventional organic solvents used for photosensitive compositions and used.

Specific examples of the organic solvent (S) include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; polyhydric alcohols such as ethylene glycol, ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, propylene glycol monomethyl ether acetate, dipropylene glycol, monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, monophenyl ether of dipropylene glycol monoacetate, and derivatives thereof; cyclic ethers such as dioxane; esters such as ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, and 3-methyl-3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene. These may be used alone, or 2 or more of them may be used in combination.

The organic solvent (S) is used in a range in which the solid content concentration of the photosensitive composition is 25 to 70 mass%, preferably 30 to 60 mass%, and more preferably 40 to 50 mass%.

< other ingredients >

The photosensitive composition may further contain a polyethylene resin in order to improve plasticity. Specific examples of the polyethylene resin include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinyl benzoic acid, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl phenol, and copolymers thereof. The polyethylene resin is preferably polyvinyl methyl ether from the viewpoint of a low glass transition point.

The photosensitive composition may contain a lewis acidic compound. By including a lewis acidic compound in the photosensitive composition, a highly sensitive photosensitive composition can be easily obtained, and a resist pattern having a rectangular cross-sectional shape can be more easily formed using the photosensitive composition.

Further, when a pattern is formed using a photosensitive composition and the time required for each step or the time required between steps in forming the pattern is long, there may be a case where it is difficult to form a pattern having a desired shape or size, or an adverse effect such as deterioration in developability occurs. However, by blending a lewis acidic compound in the photosensitive composition, such adverse effects on the pattern shape and the developability can be alleviated, and the process margin (process margin) can be widened.

Here, the lewis acidic compound is a "compound having an empty orbital capable of accepting at least 1 electron pair and functioning as an electron pair acceptor".

The lewis acidic compound is not particularly limited as long as it is a compound that belongs to the above definition and can be confirmed by a person skilled in the art as a lewis acidic compound. As the lewis acidic compound, a compound other than a bronsted acid (protonic acid) is preferably used.

Specific examples of the Lewis acidic compound include boron fluoride and an ether complex of boron fluoride (for example, BF) ₃ ·Et ₂ O、BF ₃ ·Me ₂ O、BF ₃ THF, etc. Et is ethyl, Me is methyl, THF is tetrahydrofuran), organoboron compounds (e.g., tri-n-octyl borate, tri-n-butyl borate, triphenyl borate, triphenylboron, etc.), titanium chloride, aluminum bromide, gallium chloride, gallium bromide, indium chloride, thallium trifluoroacetate, tin chloride, zinc bromide, zinc iodide, zinc trifluoromethanesulfonate, zinc acetate, zinc nitrate, zinc tetrafluoroborate, manganese chloride, manganese bromide, nickel chloride, nickel bromide, nickel cyanide, nickel acetylacetonate, cadmium chloride, cadmium bromide, stannous chloride, stannous bromide, stannous sulfate, and stannous tartrate, etc.

Further, other specific examples of the lewis acidic compound include chlorides, bromides, sulfates, nitrates, carboxylates, and triflates of rare earth metal elements; and cobalt chloride, ferrous chloride, yttrium chloride, and the like.

Here, examples of the rare earth metal element include lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, and the like.

The lewis acidic compound preferably contains a lewis acidic compound containing an element of group 13 of the periodic table in terms of easy availability and good effect due to addition thereof.

Here, as the group 13 element of the periodic table, boron, aluminum, gallium, indium and thallium may be mentioned.

Among the group 13 elements of the periodic table, boron is preferable from the viewpoint of easiness of obtaining a lewis acidic compound and particularly excellent addition effect. That is, the lewis acidic compound preferably contains a lewis acidic compound containing boron.

Examples of the lewis acidic compound containing boron include boron fluoride, an ether complex of boron fluoride, boron halides such as boron chloride and boron bromide, and various organoboron compounds. As the lewis acidic compound containing boron, an organoboron compound is preferable in that the content of halogen atoms in the lewis acidic compound is small and that the photosensitive composition can be easily applied to applications requiring a low halogen content.

Preferable examples of the organoboron compound include boron compounds represented by the following formula (f 1).

B(R ^f1 ) _t1 (OR ^f2 ) _(3-t1) …(f1)

(in the formula (f1), R ^f1 And R ^f2 Each independently a hydrocarbon group having 1 to 20 carbon atoms, which may have 1 or more substituents, t1 is an integer of 0 to 3, and when a plurality of R's are present ^f1 In the case of (2), a plurality of R ^f1 2 of them may be bonded to each other to form a ring, and a plurality of OR's may be present ^f2 In the case of a plurality of ORs ^f2 2 of them may be bonded to each other to form a ring. )

The photosensitive composition preferably contains 1 or more boron compounds represented by the above formula (f1) as the lewis acidic compound.

In the formula (f1), in R ^f1 And R ^f2 In the case of a hydrocarbon group, the number of carbon atoms in the hydrocarbon group is 1 to 20. The hydrocarbon group having 1 to 20 carbon atoms may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of an aliphatic group and an aromatic group.

The hydrocarbon group having 1 to 20 carbon atoms is preferably a saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group. As R ^f1 And R ^f2 The number of carbon atoms of the hydrocarbon group (2) is preferably 1 to 10. In the case where the hydrocarbon group is an aliphatic hydrocarbon group, carbon thereofThe number of atoms is more preferably 1 to 6, and particularly preferably 1 to 4.

As R ^f1 And R ^f2 The hydrocarbon group (b) may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and is preferably a saturated hydrocarbon group.

Under the condition of being R ^f1 And R ^f2 When the hydrocarbon group (b) is an aliphatic hydrocarbon group, the aliphatic hydrocarbon group may be linear, branched, or cyclic, or a combination of these structures.

Preferable specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthalen-1-yl group, a naphthalen-2-yl group, a 4-phenylphenyl group, a 3-phenylphenyl group and a 2-phenylphenyl group. Among them, phenyl is preferred.

As the saturated aliphatic hydrocarbon group, an alkyl group is preferable. Preferable specific examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a 2-ethylhexyl group, a n-nonyl group and a n-decyl group.

As R ^f1 And R ^f2 The hydrocarbon group (b) may have 1 or more substituents. Examples of the substituent include a halogen atom, a hydroxyl group, an alkyl group, an aralkyl group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, an acyl group, an acyloxy group, an acylthio group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an aryloxycarbonyl group, an amino group, an N-monosubstituted amino group, an N, N-disubstituted amino group, a carbamoyl group (-CO-NH-), and the like ₂ ) N-monosubstituted carbamoyl, N-disubstituted carbamoyl, nitro, cyano and the like.

The number of carbon atoms of the substituent is not particularly limited as long as it does not interfere with the object of the present invention, and is preferably 1 to 10, more preferably 1 to 6.

Specific preferred examples of the organoboron compound represented by the above formula (f1) include the following compounds. In the following formulae, Pen represents pentyl group, Hex represents hexyl group, Hep represents heptyl group, Oct represents octyl group, Non represents nonyl group, and Dec represents decyl group.

[ CHEM 60 ]

[ CHEM 61 ]

[ CHEM 62 ]

[ CHEM 63 ]

[ CHEM 64 ]

The lewis acidic compound is preferably used in a range of 0.01 to 5 parts by mass, more preferably in a range of 0.01 to 3 parts by mass, and still more preferably in a range of 0.05 to 2 parts by mass, based on 100 parts by mass of the total of the resin (B) and the alkali-soluble resin (D).

When the photosensitive composition is used for forming a pattern as a mold for forming a plated shaped article, the photosensitive composition may further contain an adhesion promoter in order to improve adhesion between the mold formed using the photosensitive composition and a metal substrate.

The photosensitive composition may further contain a surfactant for improving coatability, defoaming property, leveling property, and the like. As the surfactant, for example, a fluorine-based surfactant or a silicone-based surfactant is preferably used.

Specific examples of the fluorine-based surfactant include, but are not limited to, commercially available fluorine-based surfactants such as BM-1000, BM-1100 (all manufactured by BM chemical Co., Ltd.), MEGAFAC F142D, MEGAFAC F172, MEGAFAC F173, MEGAFAC F183 (all manufactured by Dainippon ink chemical industries Co., Ltd.), Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431 (all manufactured by Sumitomo 3M Co., Ltd.), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145 (all manufactured by Asahi Nippon Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, and SF-8428 (all manufactured by Toray silicone Co., Ltd.).

As the silicone surfactant, an unmodified silicone surfactant, a polyether-modified silicone surfactant, a polyester-modified silicone surfactant, an alkyl-modified silicone surfactant, an aralkyl-modified silicone surfactant, a reactive silicone surfactant, and the like can be preferably used.

As the silicone surfactant, commercially available silicone surfactants can be used. Specific examples of commercially available silicone surfactants include PAINTADD M (manufactured by Tooli Dow Corning Co., Ltd.), Tepico card (Japanese No. トピカ) K1000, Tepico card K2000, Tepico card K5000 (manufactured by Kokuku industries Co., Ltd.), XL-121 (polyether modified silicone surfactant, manufactured by Craiden Co., Ltd.), BYK-310 (polyester modified silicone surfactant, manufactured by Bike chemical Co., Ltd.), and the like.

In addition, the photosensitive composition may further contain an acid or an acid anhydride in order to finely adjust the solubility in the developer.

Specific examples of the acid and acid anhydride include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid, and cinnamic acid; hydroxy monocarboxylic acids such as lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid, and syringic acid; polycarboxylic acids such as oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1, 2-cyclohexanedicarboxylic acid, 1, 2, 4-cyclohexanetricarboxylic acid, butanetetracarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, and 1, 2, 5, 8-naphthalenetetracarboxylic acid; itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenylsuccinic anhydride, tricarboxylic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, 1, 2, 3, 4-butanetetracarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitic anhydride, glycerol tristrimellitic anhydride, and the like.

In addition, the photosensitive composition may further contain a known sensitizer for the purpose of improving sensitivity.

The photosensitive composition is prepared by mixing and stirring the above components by a usual method. Examples of the apparatus which can be used for mixing and stirring the above components include a dissolver, a homogenizer, and a three-roll mill. After the above components are uniformly mixed, the obtained mixture may be further filtered using a mesh, a membrane filter, or the like.

The photosensitive composition has excellent storage stability. Therefore, even if a long period (for example, 2 weeks) passes after the photosensitive composition is prepared, or even if the photosensitive composition is stored at a high temperature (for example, 40 ℃), the viscosity change can be suppressed.

Photosensitive dry film and method for producing photosensitive dry film

The photosensitive dry film has a base film and a photosensitive layer formed on the surface of the base film, and the photosensitive layer is composed of the photosensitive composition.

The base film preferably has light transmittance. Specifically, a polyethylene terephthalate (PET) film, a polypropylene (PP) film, a Polyethylene (PE) film, and the like can be mentioned, and a polyethylene terephthalate (PET) film is preferable from the viewpoint of excellent balance between light transmittance and breaking strength.

The photosensitive composition is applied to a base film to form a photosensitive layer, thereby producing a photosensitive dry film.

When forming the photosensitive layer on the base film, the photosensitive composition is applied to the base film by using a coater, a bar coater, a wire bar coater, a roll coater, a curtain coater, or the like, and dried so that the film thickness after drying is preferably 0.5 μm or more and 300 μm or less, more preferably 1 μm or more and 300 μm or less, and particularly preferably 3 μm or more and 100 μm or less.

Since the photosensitive composition has a high solid content concentration, it is suitable for forming a thick (for example, 70 μm or more) photosensitive layer.

The photosensitive dry film may further have a protective film on the photosensitive layer. Examples of the protective film include a polyethylene terephthalate (PET) film, a polypropylene (PP) film, and a Polyethylene (PE) film.

Method for manufacturing patterned resist film and substrate with mold

The method for forming a patterned resist film on a substrate using the photosensitive composition described above is not particularly limited. The patterned resist film is preferably used as an insulating film, an etching mask, a mold for forming a plating molded article, and the like.

A method for producing a patterned resist film including the following steps may be mentioned as a preferable method:

a laminating step of laminating a photosensitive layer made of a photosensitive composition on a substrate;

an exposure step of exposing the photosensitive layer by selectively irradiating the photosensitive layer with active light or radiation;

and a developing step of developing the exposed photosensitive layer.

The method for manufacturing a substrate with a mold having a mold for forming a plated shaped article is the same as the method for manufacturing a patterned resist film, except that the method includes a step of using a substrate having a metal surface as a substrate and laminating a photosensitive layer on the metal surface of the substrate having the metal surface, and the mold for forming the plated shaped article is manufactured by development in a development step.

The substrate on which the photosensitive layer is laminated is not particularly limited, and conventionally known substrates can be used, and examples thereof include substrates for electronic components, substrates on which predetermined wiring patterns are formed, and the like. As the substrate, a silicon substrate, a glass substrate, or the like can also be used.

When manufacturing a substrate with a mold, which is provided with a mold for forming a plated shaped article, a substrate having a metal surface is used as the substrate. The metal species constituting the metal surface is preferably copper, gold, or aluminum, and more preferably copper.

For example, a photosensitive layer is laminated on a substrate as follows. That is, a liquid photosensitive composition is applied onto a substrate, and the solvent is removed by heating, thereby forming a photosensitive layer having a desired film thickness. The thickness of the photosensitive layer is not particularly limited as long as a resist pattern can be formed with a desired film thickness. The thickness of the photosensitive layer is not particularly limited, but is preferably 0.5 μm or more, more preferably 1 μm or more, and even more preferably 10 μm or more, and can be a thick film of 70 μm or more or 100 μm or more. The upper limit of the film thickness is, for example, 300 μm or less.

Since the photosensitive composition has a high solid content concentration, a thick photosensitive layer can be formed. Therefore, it can be preferably used for forming a plated shaped object, for example.

As a coating method for applying the photosensitive composition to the substrate, a spin coating method, a slit coating method, a roll coating method, a screen printing method, a coater method, or the like can be used. The photosensitive layer is preferably pre-baked. The prebaking conditions vary depending on the kind of each component in the photosensitive composition, the blending ratio, the coating film thickness, and the like, but are generally 70 ℃ to 200 ℃ inclusive, preferably 80 ℃ to 150 ℃ inclusive, and are carried out for about 2 minutes to 120 minutes inclusive. The prebaking may be performed a plurality of times in 2 stages or more. For example, after the pre-baking in the 1 st stage is performed at a temperature of 70 ℃ to 120 ℃, the pre-baking in the 2 nd stage may be performed at a higher temperature than the pre-baking in the 1 st stage.

The photosensitive layer formed as described above is selectively irradiated (exposed) with active light or radiation, for example, ultraviolet light or visible light having a wavelength of 300nm to 500nm, through a mask having a predetermined pattern.

As a radiation source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, an argon laser, or the like can be used. The radiation includes microwave, infrared ray, visible ray, ultraviolet ray, X-ray, γ -ray, electron ray, proton ray, neutron ray, ion ray, and the like. The amount of radiation irradiation varies depending on the composition of the photosensitive composition, the film thickness of the photosensitive layer, etc., and is, for example, 100mJ/cm ² Above 10000mJ/cm ² The following. In addition, the radiation contains light that activates the acid generator (a) in order to generate acid.

After exposure, the photosensitive layer is heated (PEB) by a known method to promote diffusion of an acid, and the solubility of the photosensitive layer in a developer such as an alkaline developer is changed in the exposed portion of the photosensitive layer.

Next, the exposed photosensitive layer is developed by a conventionally known method to dissolve and remove unnecessary portions, thereby forming a predetermined resist pattern or a mold for forming a plated shaped article. In this case, an alkaline aqueous solution may be used as the developer.

The photosensitive layer formed by using the photosensitive composition after exposure can inhibit repulsion to a developing solution. Therefore, for example, the developing solution can be brought into contact with the entire photosensitive layer, and a resist pattern corresponding to a mask or the like or a mold for forming a plating shaped object can be formed entirely in the region where the photosensitive layer is provided.

Further, the photosensitive layer after exposure formed using the photosensitive composition can suppress swelling during development. Therefore, for example, in the obtained resist pattern or a mold for forming a plated shaped article, wrinkles due to swelling, dissolution of unexposed portions, and lifting or deformation can be suppressed.

As the developer, for example, an aqueous solution of a base such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium methyl silicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1, 8-diazabicyclo [5, 4, 0] -7-undecene, 1, 5-diazabicyclo [4, 3, 0] -5-nonane, can be used. In addition, an aqueous solution in which a suitable amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added to the alkali aqueous solution can be used as the developer.

The developing time varies depending on the composition of the photosensitive composition, the film thickness of the photosensitive layer, and the like, and is usually 1 minute to 30 minutes. The developing method may be any of a liquid method, a dipping method, a static developing method, a spray developing method, and the like.

After development, for example, the resultant is washed with running water for 30 seconds to 90 seconds, and dried using an air gun, an oven, or the like. In this way, a resist pattern patterned into a desired shape is formed on the metal surface of the substrate having the metal surface. In this way, a substrate having a resist pattern on the surface thereof can be manufactured.

The photosensitive layer formed using the photosensitive composition as described above can suppress the occurrence of cracks. Therefore, for example, when the obtained resist pattern is used as a mold for forming a plated shaped object, the plated shaped object having a desired shape can be easily formed.

Method for producing plated shaped article

In the mold with the mold substrate formed by the above-described method, a conductor such as a metal is embedded by plating in the non-resist portion (portion removed by the developer), and thus, a plated shaped article such as a connection terminal such as a bump or a metal post, or a Cu rewiring can be formed. The plating method is not particularly limited, and various conventionally known methods can be used. As the plating liquid, a solder plating liquid, a copper plating liquid, a gold plating liquid, and a nickel plating liquid are particularly preferably used. The remaining mold is finally removed using a stripping liquid or the like according to a conventional method.

[ examples ] A method for producing a compound

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

[ examples 1 to 6 and comparative examples 1 to 18 ]

In examples and comparative examples, PAG1 and PAG2 of the following formulae were used as the acid generators (a).

[ CHEM 65 ]

In examples and comparative examples, the following resins B1 to B3 and B '1 to B' 16 were used as the resin (B)) whose solubility in alkali was increased by the action of acid. The numerals below and to the right of parentheses in each structural unit in the following structural formula represent the content (mass%) of the structural unit in the resin. The mass average molecular weight Mw and the molecular weight distribution coefficient (Mw/Mn) of each resin are shown in table 1 below.

[ CHEM 66 ]

[ CHEM 67 ]

B′1

B′2

B′3

B′4

B′5

B′6

B′7

B′8

[ CHEM 68 ]

B′9

B′10

B′11

B′14

B′15

B′16

[ TABLE 1 ]

In examples and comparative examples, the following C1 and compound C2 of the following formula were used as the acid diffusion controller (C).

C1: ADK STAB LA-63P (a reaction product of methyl 1, 2, 3, 4-butanetetracarboxylate, 1, 2, 2, 6, 6-pentamethyl-4-piperidinol and β, β, β ', β' -tetramethyl-2, 4, 8, 10-tetraoxaspiro [5.5] undecane-3, 9-diethanol) (manufactured by ADEKA).

[ CHEM 69 ]

C2

As the alkali-soluble resin (D), the following D1 (novolak resin (condensate of m-cresol and p-cresol)) was used. The number below the right of the parentheses in each structural unit in the following structural formula represents the content (mass%) of the structural unit in the resin. The mass average molecular weight (Mw) of D1 was 8000.

[ CHEM 70 ]

D1

In examples and comparative examples, a sulfur-containing compound E1 of the following formula was used as the sulfur-containing compound (E).

[ CHEM 71 ]

E1

In examples and comparative examples, the following F1 was used as the dye (F).

F1: curcumin (curcumin)

The acid generator (a), the resin (B), the acid diffusion controller (C), the alkali-soluble resin (D), and the dye (F) of the types and parts by mass described in table 2 were dissolved in 3-methoxybutylacetate (organic solvent (S)) so that the solid content concentration thereof became 48 mass% in 0.1 part by mass of E1 as the sulfur-containing compound (E) and 0.02 part by mass of a surfactant (BYK310, manufactured by BYK chemical corporation), respectively, to obtain photosensitive compositions of examples 1 to 6 and comparative examples 1 to 18. The solid content concentration is determined by dividing the total mass of the resin (B), the acid generator (a), the acid diffusion controller (C), the alkali-soluble resin (D), the sulfur-containing compound (E), the dye (F), and the surfactant, which are components other than the organic solvent (S), by the mass of the photosensitive composition.

The obtained photosensitive composition was evaluated by the following method. The results are set forth in Table 2.

[ evaluation of resist Pattern (developer repellency, swelling Property, and crack resistance) ]

The photosensitive compositions of examples and comparative examples were applied to a copper film on a copper sputtered silicon wafer substrate (copper film thickness: 200nm) using a spin coater, and heated on a hot plate at 100 ℃ for 150 seconds and at 150 ℃ for 450 seconds (prebaking) to obtain a photosensitive layer having a thickness of 100 μm.

After heating (prebaking), the photosensitive layer was selectively exposed to GHI light at an exposure amount 1.2 times the minimum exposure amount at which a pattern of a predetermined size can be formed, using a 30 μm × 30 μm square pattern mask and a projection exposure apparatus prism GHI5452 (manufactured by Ultratech).

Subsequently, the substrate was placed on a hot plate and subjected to post-exposure heating (PEB) at 100 ℃ for 3 minutes. Thereafter, a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) (developer, NMD-3, manufactured by tokyo chemical industries co., ltd.) was added dropwise to the exposed photosensitive layer, and the resultant was left to stand at 23 ℃ for 60 seconds (puddle development) and then the development was repeated 6 times. Thereafter, the substrate was washed with running water for 60 seconds and spin-dried, thereby obtaining a substrate with a resist pattern (patterned resist film).

As for the evaluation of the repulsion of the developing solution, the evaluation was evaluated as o when the developing solution was contained in the entire photosensitive layer without being repelled during the development and a square pattern corresponding to the mask was formed in the entire region where the photosensitive layer was provided; the case where the developer was repelled during development and the developer was not carried on the entire surface of the photosensitive layer, and poor formation of the resist pattern occurred (the case where there was a region where no square pattern was formed, or the case where the square pattern was formed but the shape differed greatly from the mask) was evaluated as x.

For evaluation of the swelling property, the case where the photosensitive layer did not swell during development, no wrinkles were observed in the obtained resist pattern, the unexposed portion was not dissolved, and no floating or deformation was observed was evaluated as ∘. Further, the case where the unexposed portion of the photosensitive layer swelled upon development and wrinkles were observed, the case where the unexposed portion dissolved, or the case where floating or deformation was observed in the obtained resist pattern was evaluated as x.

For the evaluation of the crack resistance, the obtained resist pattern (square pattern) was observed, and the case where cracks were observed at the corners of the square pattern was evaluated as x, and the case where cracks were not observed at the corners of the square pattern was evaluated as o.

[ evaluation of storage stability ]

For the photosensitive compositions of examples and comparative examples, the viscosity was measured using an E-type viscometer at 25 ℃ immediately after the preparation, and the viscosity was measured using an E-type viscometer at 25 ℃ after standing at 40 ℃ for 2 weeks.

The ratio V2/V1 of the viscosity V1 after the preparation to the viscosity V2 after standing at 40 ℃ for 2 weeks was evaluated as "O" and the ratio of 1.1 or more was evaluated as "X". The results are shown in table 2.

According to the embodiment, the method comprises the following steps: an acid generator (A) which generates an acid upon irradiation with active light or radiation; the chemically amplified positive photosensitive composition has good storage stability and can form a thick photosensitive layer that is suppressed in repulsion and swelling against a developer and has excellent crack resistance, wherein the resin (B) has solubility in an alkali increased by the action of an acid, and the resin (B) contains an acrylic resin (B3) and the acrylic resin (B3) contains a structural unit represented by the formula (B3-1), and the solid content concentration is 25 to 70 mass%.

On the other hand, it is found from the comparative examples that the chemically amplified positive photosensitive composition containing as the resin (B) no acrylic resin (B3) containing a structural unit represented by the formula (B3-1) is inferior in storage stability, or repulsion to a developer, swelling or cracking occurs in the formed photosensitive layer.

[ TABLE 2]

Claims

1. A chemically amplified positive photosensitive composition comprising:

an acid generator (A) which generates an acid by irradiation with active light or radiation; a resin (B) whose solubility in alkali is increased by the action of an acid,

the resin (B) comprises an acrylic resin (B3),

the acrylic resin (B3) comprising a structural unit represented by the following formula (B3-1),

[ CHEM 1 ]

In the formula (B3-1), R ^b01 is-O-, -S-, -CO-O-, -CO-NH-or-SO ₂ -，R ^b02 And R ^b03 Each independently is a hydrogen atom or an organic group, R ^b02 And R ^b03 At least one of which is represented by-CO-O-R ^b04 A group represented by R ^b04 Is a hydrogen atom or an organic group, x1 and x2 are each independently 1 or 2,

2. The chemically amplified positive photosensitive composition according to claim 1,

in the formula (B3-1), x1 and x2 are both 1, R ^b02 And R ^b03 One of them is a hydrogen atom.

3. The chemically amplified positive photosensitive composition according to claim 1 or 2,

the ratio of the mass of the structural unit represented by the formula (B3-1) to the mass of the acrylic resin (B3) is 5 to 50 mass%.

4. The chemically amplified positive photosensitive composition according to claim 1 or 2,

when the viscosity of the chemically amplified positive photosensitive composition measured at 25 ℃ with an E-type viscometer is V1, and the viscosity of the chemically amplified positive photosensitive composition left standing at 40 ℃ for 2 weeks and measured at 25 ℃ with an E-type viscometer after standing is V2, V2/V1 is less than 1.1.

5. The chemically amplified positive photosensitive composition according to claim 1 or 2,

further contains a sulfur-containing compound (E) containing a sulfur atom capable of coordinating with the metal.

6. The chemically amplified positive photosensitive composition according to claim 1 or 2,

for forming a mold for forming a plated molding.

7. A photosensitive dry film characterized in that,

a photosensitive layer comprising the chemically amplified positive photosensitive composition according to any one of claims 1 to 6, and a substrate film, wherein the photosensitive layer is formed on the surface of the substrate film.

8. A method of manufacturing a patterned resist film, comprising:

a laminating step of laminating a photosensitive layer composed of the chemically amplified positive photosensitive composition according to any one of claims 1 to 6 on a substrate;

and a developing step of developing the exposed photosensitive layer.

9. A method for manufacturing a substrate with a mold, comprising:

a laminating step of laminating a photosensitive layer composed of the chemically amplified positive photosensitive composition according to any one of claims 1 to 6 on a substrate having a metal surface;

10. A method for manufacturing a plated molded article, characterized in that,

the method for manufacturing a substrate with a mold according to claim 9, comprising a step of plating the substrate with a mold manufactured by the method for manufacturing a substrate with a mold to form a plated molded article in the mold.