JP7020953B2 - Chemically amplified positive photosensitive resin composition, photosensitive dry film, photosensitive dry film manufacturing method, patterned resist film manufacturing method, molded substrate manufacturing method, plated molded product manufacturing method, and mercapto Compound - Google Patents

Description

The present invention comprises a chemically amplified positive photosensitive resin composition, a photosensitive dry film comprising a photosensitive resin layer composed of the chemically amplified positive photosensitive resin composition, and a method for producing the photosensitive dry film. A method for producing a patterned resist film using the above-mentioned chemically amplified positive photosensitive resin composition, a method for producing a molded substrate using the above-mentioned chemically amplified positive photosensitive resin composition, and a method for producing a molded substrate. The present invention relates to a method for manufacturing a plated model using a substrate.

Currently, photofabrication is the mainstream of precision microfabrication technology. Photofabrication is a method in which a photoresist composition is applied to the surface of a workpiece to form a photoresist layer, the photoresist layer is patterned by photolithography technology, and the patterned photoresist layer (photoresist pattern) is used as a mask for chemical etching and electrolysis. It is a general term for technologies for manufacturing various precision parts such as semiconductor packages by performing etching or electroforming mainly for electroplating.

In recent years, along with the downsizing of electronic devices, high-density mounting technology for semiconductor packages has advanced, and the packaging has become multi-pin thin film mounting, package size miniaturization, two-dimensional mounting technology by flip chip method, and three-dimensional mounting technology. The mounting density is improved based on this. In such high-density mounting technology, as connection terminals, for example, a protruding electrode (mounting terminal) such as a bump protruding on a package, or a metal post connecting a rewiring extending from a peripheral terminal on a wafer and a mounting terminal. Etc. are arranged on the substrate with high precision.

Photoresist compositions are used for photofabrication as described above, and as such photoresist compositions, chemically amplified photoresist compositions containing an acid generator are known (Patent Documents 1, 2, etc.). See). In the chemically amplified photoresist composition, acid is generated from the acid generator by irradiation (exposure), the diffusion of the acid is promoted by the heat treatment, and an acid catalytic reaction is caused with the base resin or the like in the composition. The alkali solubility changes.

Such a chemically amplified positive photoresist composition is used, for example, for forming a plated object such as a bump, a metal post, and Cu rewiring by a plating step. Specifically, a chemically amplified photoresist composition is used to form a photoresist layer of a desired film thickness on a support such as a metal substrate, exposed through a predetermined mask pattern, developed, and plated. A photoresist pattern is formed in which the portion forming the model is selectively removed (peeled) and used as a mold. Then, by embedding a conductor such as copper in the removed portion (non-resist portion) by plating and then removing the photoresist pattern around the removed portion (non-resist portion), bumps, metal posts, and Cus rewiring can be formed. ..

Japanese Unexamined Patent Publication No. 9-176112 Japanese Unexamined Patent Publication No. 11-52562

In the formation of connection terminals such as bumps and metal posts by the above plating process and the formation of Cu rewiring, it is desired that the cross-sectional shape of the non-resist portion of the resist pattern used as a mold is rectangular.
Therefore, regarding the non-resist portion of the resist pattern, the taper angle formed by the substrate surface and the side surface of the resist portion in the vicinity of the substrate surface is 88 ° or more, preferably 88 ° or more and 92 ° or less. desired.
By doing so, it is possible to sufficiently secure a contact area between the connection terminals such as bumps and metal posts, the bottom surface of Cu rewiring, and the support. Then, it is easy to form a connection terminal or Cu rewiring having good adhesion to the support.

However, using a conventionally known chemically amplified positive resist resist composition as disclosed in Patent Documents 1 and 2, a connection terminal such as a bump and a metal post, and a mold for forming Cu rewiring. When the resist pattern is formed on a metal substrate, the resist portion projects toward the non-resist portion on the contact surface between the substrate surface and the resist pattern, so that the width of the bottom is narrower than the width of the top in the non-resist portion. "Footing" is likely to occur.
In this case, the taper angle described above becomes an acute angle.

As described above, when a conventionally known chemically amplified positive photoresist composition as disclosed in Patent Documents 1 and 2 is used, bumps, metal posts, and Cu rewiring having good adhesion to the substrate are used. It is difficult to form a resist pattern having a desirable cross-sectional shape, which is easy to form such as.

Further, the mold pattern for plating may be formed on a substrate having a warp or a step derived from a substrate such as a polyimide film laminated on the substrate. Therefore, in the chemically amplified positive photoresist composition portion used for forming the mold pattern for plating, a pattern having a desired size and shape can be formed regardless of the degree of flatness of the substrate surface. It is desirable that the margin of focal depth (DOF) is wide.
Depth of focus (DOF) margin is the range of depth of focus that can form a resist pattern with dimensions that deviate from the target size within a predetermined range when the focus is shifted up and down for exposure with the same exposure amount. be. The wider the depth of focus (DOF) margin, the better.

The present invention has been made in view of the above problems, and a resist pattern serving as a template for a plated product is formed on the metal surface of a substrate having a metal surface by using a chemically amplified positive photosensitive resin composition. In this case, for the non-resist portion of the resist pattern, the taper angle, which is the angle between the substrate surface and the side surface of the resist portion, can be set to 88 ° or more in the vicinity of the substrate surface, and the focal depth (DOF) margin can be set. A photosensitive dry film comprising a chemically amplified positive photosensitive resin composition and a photosensitive resin layer composed of the chemically amplified positive photosensitive resin composition, a method for producing the photosensitive dry film, and the above-mentioned method. A method for producing a patterned resist film using a chemically amplified positive photosensitive resin composition, a method for producing a molded substrate using the above-mentioned chemically amplified positive photosensitive resin composition, and a method for producing the molded substrate. It is an object of the present invention to provide a method for manufacturing a plated molded product to be used.

As a result of diligent research to achieve the above object, the present inventors have found that the above-mentioned problems can be solved by containing a mercapto compound having a specific structure in a chemically amplified positive photosensitive resin composition. , The present invention has been completed. Specifically, the present invention provides the following.

The first aspect of the present invention is an acid generator (A) that generates an acid by irradiation with active light or radiation, a resin (B) whose solubility in an alkali is increased by the action of the acid, and a mercapto compound (C). A chemically amplified positive photosensitive resin composition containing
The mercapto compound (C) contains a nitrogen-containing heterocyclic compound having a nitrogen-containing heterocycle having only a carbon atom, a hydrogen atom, and a nitrogen atom as a main skeleton.
In the nitrogen-containing heterocyclic compound, one or more mercapto groups and one or more electron-withdrawing groups are bonded to carbon atoms in the nitrogen-containing heterocycle.
When the nitrogen-containing heterocyclic compound exhibits tautomerism, the nitrogen-containing heterocyclic compound may contain a tautomer in the chemically amplified positive photosensitive resin composition. It is a resin composition.

The second aspect of the present invention has a substrate film and a photosensitive resin layer formed on the surface of the substrate film, and the photosensitive resin layer is chemically amplified positive photosensitive according to the first aspect. A photosensitive dry film made of a resin composition.

A third aspect of the present invention comprises applying the chemically amplified positive photosensitive resin composition according to the first aspect on a substrate film to form a photosensitive resin layer. It is a manufacturing method of.

A fourth aspect of the present invention is
A laminating step of laminating a photosensitive resin layer made of the chemically amplified positive photosensitive resin composition according to the first aspect on a substrate having a metal surface.
An exposure process in which the photosensitive resin layer is regioselectively irradiated with active light rays or radiation,
A method for producing a patterned resist film, comprising a developing step of developing a photosensitive resin layer after exposure.

A fifth aspect of the present invention is
A laminating step of laminating a photosensitive resin layer having a chemically amplified positive photosensitive resin composition according to the first aspect on a substrate having a metal surface.
An exposure process in which the photosensitive resin layer is regioselectively irradiated with active light rays or radiation,
A method for manufacturing a substrate with a mold, which comprises a developing step of developing a photosensitive resin layer after exposure to create a mold for forming a plated model.

A sixth aspect of the present invention is a method for producing a plated molded product, which comprises a step of plating a molded substrate manufactured by the method according to the fifth aspect to form a plated model in the mold. ..

According to the present invention, when a resist pattern serving as a template for a plated product is formed on a metal surface of a substrate having a metal surface by using a chemically amplified positive photosensitive resin composition, the resist pattern is not resisted. Regarding the portion, the taper angle, which is the angle between the substrate surface and the side surface of the resist portion, can be set to 88 ° or more in the vicinity of the substrate surface, and the chemical amplification type positive photosensitive with a wide margin of focal depth (DOF). A photosensitive dry film comprising a resin composition and a photosensitive resin layer composed of the chemically amplified positive photosensitive resin composition, a method for producing the photosensitive dry film, and the above-mentioned chemically amplified positive photosensitive resin composition. A method for producing a patterned resist film using a material, a method for producing a molded substrate using the above-mentioned chemically amplified positive photosensitive resin composition, and a method for producing a plated molded product using the molded substrate. Can be provided.

<< Chemically amplified positive photosensitive resin composition >>
The chemically amplified positive photosensitive resin composition (hereinafter, also referred to as a photosensitive resin composition) is an acid generator (A) (hereinafter, an acid generator (A)) that generates an acid by irradiation with active light or radiation. It contains a resin (B) whose solubility in alkali is increased by the action of an acid (hereinafter, also referred to as a resin (B)), and a mercapto compound (C) having a predetermined structure. The photosensitive resin composition may contain components such as an alkali-soluble resin (D), an acid diffusion inhibitor (E), and an organic solvent (S), if necessary.

The film thickness of the resist pattern formed by using the photosensitive resin composition is not particularly limited. The photosensitive resin composition is preferably used for forming a thick-film resist pattern. Specifically, the film thickness of the resist pattern formed by using the photosensitive resin composition is preferably 0.5 μm or more, more preferably 0.5 μm or more and 300 μm or less, and even more preferably 0.5 μm or more and 150 μm or less. , 0.5 μm or more and 200 μm or less is particularly preferable.
The upper limit of the film thickness may be, for example, 100 μm or less. The lower limit of the film thickness may be, for example, 1 μm or more, or 3 μm or more.

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

<Acid generator (A)>
The acid generator (A) is a compound that generates an acid by irradiation with 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. As the acid generator (A), the acid generator of the first to fifth aspects described below is preferable. Hereinafter, among the acid generators (A) preferably used in the photosensitive resin composition, suitable ones will be described as the first to fifth embodiments.

As the first aspect of the acid generator (A), a compound represented by the following formula (a1) can be mentioned.

In the above formula (a1), X ^1a represents a sulfur atom or an iodine atom having a valence g, and g is 1 or 2. h represents the number of repeating units of the structure in parentheses. R ^1a is an organic group bonded to X ^1a , 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, and the like. Represents an alkenyl group having 2 to 30 carbon atoms or an alkynyl group having 2 to 30 carbon atoms, and R ^1a is alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthio. At least one selected from the group consisting of carbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro groups, and halogens. It may be replaced with a seed. The number of R ^1a is g + h (g-1) + 1, and R ^1a may be the same or different from each other. In addition, two or more R1a directly to each other, or -O-, -S-, ^-SO- , _-SO2- , -NH-, -NR ^2a- , -CO-, -COO-, -CONH- , An alkylene group having 1 or more and 3 or less carbon atoms or a phenylene group may be bonded to form a ring structure containing X ^1a . R ^2a is an alkyl group having 1 or less carbon atoms and 5 or more carbon atoms or an aryl group having 6 or less carbon atoms and 10 or more carbon atoms.

X ^2a has a structure represented by the following formula (a2).

In the above formula (a2), ^X4a comprises an alkylene group having 1 or more and 8 or less carbon atoms, an arylene group having 6 or more and 20 or less carbon atoms, or a divalent group of a heterocyclic compound having 8 or more and 20 or less carbon atoms. Represented, X ^4a is composed of a group consisting of an alkyl having 1 to 8 carbon atoms, an alkoxy having 1 to 8 carbon atoms, an aryl, hydroxy, cyano, and nitro groups having 6 to 10 carbon atoms, and a halogen. It may be substituted with at least one selected. X ^5a is -O-, -S-, -SO-, -SO _2- , -NH-, -NR ^2a- , -CO-, -COO-, -CONH-, alkylene with 1 or more carbon atoms and 3 or less carbon atoms. Represents a group or a phenylene group. h represents the number of repeating units of the structure in parentheses. The h + 1 ^X4a and the h ^X5a may be the same or different, respectively. R ^2a is the same as the above definition.

X ^3a- is a counterion of onium, and examples thereof include a fluorinated alkylfluorophosphate anion represented by the following formula (a17) and a borate anion represented by the following formula (a18).

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 indicates the number thereof, and is an integer of 1 or more and 5 or less. The j ^R3a may be the same or different.

In the above formula (a18), R ^4a to R ^7a independently represent a fluorine atom or a phenyl group, and a part or all of the hydrogen atom of the phenyl group is selected from the group consisting of a fluorine atom and a trifluoromethyl group. It may be replaced with at least one of these.

Examples of the onium ion in the compound represented by the above formula (a1) include triphenylsulfonium, tri-p-tolylsulfonium, 4- (phenylthio) phenyldiphenylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide, and the like. Bis [4- {bis [4- (2-hydroxyethoxy) phenyl] sulfonio} phenyl] sulfide, bis {4- [bis (4-fluorophenyl) sulfonate] phenyl} sulfide, 4- (4-benzoyl-2-) Phenylphenylthio) Phenylbis (4-fluorophenyl) sulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10 -Cheer-9,10-dihydroanthracene-2-yldiphenylsulfonium, 2-[(diphenyl) sulfonate] thioxanthone, 4- [4- (4-tert-butylbenzoyl) phenylthio] phenyldi-p-tolylsulfonium, 4- (4-Benzoylphenylthio) Phenyldiphenylsulfonium, diphenylphenacilsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl (1-ethoxycarbonyl) ethylsulfonium, 4-hydroxyphenylmethylphenacilsulfonium, phenyl [4- (4-Biphenylthio) phenyl] 4-biphenylsulfonium, phenyl [4- (4-biphenylthio) phenyl] 3-biphenylsulfonium, [4- (4-acetophenylthio) phenyl] diphenylsulfonium, octadecylmethylphenacylsulfonium , Diphenyliodonium, di-p-tolyliodonium, bis (4-dodecylphenyl) iodinenium, bis (4-methoxyphenyl) iodinenium, (4-octyloxyphenyl) phenyliodonium, bis (4-decyloxy) phenyliodonium, 4- Examples thereof include (2-hydroxytetradecyloxy) phenylphenyliodonium, 4-isopropylphenyl (p-tolyl) iodonium, 4-isobutylphenyl (p-tolyl) iodonium, and the like.

Among the onium ions in the compound represented by the above formula (a1), preferable onium ions include sulfonium ions represented by the following formula (a19).

In the above formula (a19), R ^8a is independently composed of a hydrogen atom, an alkyl, a hydroxy, an alkoxy, an alkylcarbonyl, an alkylcarbonyloxy, an alkyloxycarbonyl, a halogen atom, and an aryl, an arylcarbonyl, which may have a substituent. Represents a group selected from the group. X ^2a has the same meaning as X ^2a in the above formula (a1).

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) -Acetphenylthio) phenyl] diphenylsulfonium, diphenyl [4- (p-terphenylthio) phenyl] diphenylsulfonium can be mentioned.

In the fluorinated alkylfluorophosphate anion represented by the above formula (a17), R ^3a represents an alkyl group substituted with a fluorine atom, and the preferable number of carbon atoms is 1 or more and 8 or less, and the more preferable number of carbon atoms is 1 or more. It is 4 or less. 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 further cyclopropyl, cyclobutyl and cyclopentyl. , Cycloalkyl groups such as cyclohexyl, and the like, and the ratio of the hydrogen atom of the alkyl group substituted with the fluorine atom is usually 80% or more, preferably 90% or more, and more preferably 100%. When the substitution rate of the fluorine atom is less than 80%, the acid strength of the onium fluorinated alkylfluorophosphate represented by the above formula (a1) decreases.

Particularly preferable R ^3a is a linear or branched perfluoroalkyl group having 1 or more and 4 or less carbon atoms and a substitution rate of 100% of fluorine atoms, and specific examples thereof include CF ₃ and 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 CF CF ₂ , CF ₃ CF ₂ (CF ₃ ) CF, (CF ₃ ) ₃ C Can be mentioned. The number j of R ^3a is an integer of 1 or more and 5 or less, preferably 2 or more and 4 or less, and particularly preferably 2 or 3.

Specific examples of preferred fluorinated alkylfluorophosphate anions 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 these, [(CF 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 CF) CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ^-is particularly preferable.

Preferred specific examples of the borate anion represented by the above formula (a18) are tetrakis (pentafluorophenyl) borate ([B _{(C6 F 5) 4 ] -} ⁾ and tetrakis [(trifluoromethyl) phenyl] borate ( [B (C ₆ H ₄ CF ₃ ) ₄ ] ^- ), difluorobis (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 ₆ F ₅ ) ₄ ] ^- ) is particularly preferable.

The second aspect of the acid generator (A) is 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2. -(2-Frill) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methyl-2-furyl) ethenyl] -s-triazine, 2,4-bis ( Trichloromethyl) -6- [2- (5-ethyl-2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-propyl-2-furyl) ethenyl ] -S-Triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-dimethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2 -(3,5-diethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-dipropoxyphenyl) ethenyl] -s-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3-methoxy-5-ethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3-methoxy-) 5-propoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-methylenedioxyphenyl) ethenyl] -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) 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) ethenyl] -4,6-bis ( Trichloromethyl) -1,3,5-triazine, 2- [2- (5-methyl-2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2-[ 2- (3,5- Dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl)- 1,3,5-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 other halogen-containing triazine compounds, and Tris (2,3-dibromopropyl) isocyanurate and the like according to the following formula (a3). Examples thereof include halogen-containing triazine compounds represented by.

In the above formula (a3), R ^9a , R ^10a , and R ^11a each independently represent an alkyl halide group.

In addition, as a third aspect of the acid generator (A), α- (p-toluenesulfonyloxyimine) -phenylacetate, α- (benzenesulfonyloxyimine) -2,4-dichlorophenylnitrile, α- (benzene). Contains sulfonyloxyimino) -2,6-dichlorophenyl acetonitrile, α- (2-chlorobenzenesulfonyloxyimino) -4-methoxyphenyl acetonitrile, α- (ethylsulfonyloxyimino) -1-cyclopentenyl acetonitrile, and oxime sulfonate group Examples thereof include compounds represented by the following formula (a4).

In the above formula (a4), R ^12a represents a monovalent, divalent or trivalent organic group, and R ^13a is a substituted or unsubstituted saturated hydrocarbon group, unsaturated hydrocarbon group, or aromatic group. It represents a compound group, and n represents the number of repeating units of the structure in parentheses.

In the above formula (a4), the aromatic compound group indicates a group of a compound exhibiting physical and chemical properties peculiar to an aromatic compound, for example, an aryl group such as a phenyl group or a naphthyl group, or a frill group. , Heteroaryl groups such as thienyl group. These may have one or more suitable substituents such as a halogen atom, an alkyl group, an alkoxy group, a nitro group and the like on the ring. Further, R ^13a is particularly preferably an alkyl group having 1 or more and 6 or less carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group and a butyl group. In particular, a compound in which R ^12a is an aromatic compound group and R ^13a is an alkyl group having 1 or more and 4 or less carbon atoms is preferable.

As the acid generator represented by the above formula (a4), when n = 1, R ^12a is any of a phenyl group, a methyl phenyl group, and a methoxy phenyl group, and R ^13a is a compound having a methyl group, specifically. Specifically, α- (methylsulfonyloxyimino) -1-phenyl acetonitrile, α- (methylsulfonyloxyimino) -1- (p-methylphenyl) acetonitrile, α- (methylsulfonyloxyimino) -1- (p-). Examples thereof include methoxyphenyl) acetonitrile, [2- (propylsulfonyloxyimino) -2,3-dihydroxythiophene-3-iriden] (o-tolyl) acetonitrile and the like. When n = 2, the acid generator represented by the above formula (a4) specifically includes an acid generator represented by the following formula.

Further, as a fourth aspect of the acid generator (A), an onium salt having a naphthalene ring in the cation portion can be mentioned. By "having a naphthalene ring", it means having a structure derived from naphthalene, and it means that the structure of at least two rings and their aromaticity are maintained. This naphthalene ring has a substituent such as a linear or branched alkyl group having 1 or more and 6 or less carbon atoms, a hydroxyl group, and a linear or branched alkoxy group having 1 or more and 6 or less carbon atoms. May be good. The structure derived from the naphthalene ring may be a monovalent group (one free valence) or a divalent group (two free valences) or more, but it may be a monovalent group. Desirable (however, at this time, the free valence shall be counted except for the portion bonded to the above substituent). The number of naphthalene rings is preferably 1 or more and 3 or less.

As the cation portion of the onium salt having a naphthalene ring in such a cation portion, a structure represented by the following formula (a5) is preferable.

In the above formula (a5), at least one of R ^14a , R ^15a , and R ^16a represents a group represented by the following formula (a6), and the rest are linear or branched with 1 or more and 6 or less carbon atoms. Represents an alkyl group, a phenyl group which may have a substituent, a hydroxyl group, or a linear or branched alkoxy group having 1 or more and 6 or less carbon atoms. Alternatively, one of R ^14a , R ^15a , and R ^16a is a group represented by the following formula (a6), and the remaining two are independently linear or branched with 1 or more and 6 or less carbon atoms. It is an alkylene group of, and these ends may be bonded to form a cyclic.

In the above formula (a6), R ^17a and R ^18a are independently hydroxyl groups, linear or branched alkoxy groups having 1 to 6 carbon atoms, or linear or branched having 1 to 6 carbon atoms. Represents a branched alkyl group, and R ^19a represents a linear or branched alkylene group having 1 to 6 carbon atoms which may have a single bond or a substituent. l and m independently represent integers of 0 or more and 2 or less, and l + m is 3 or less. However, when there are a plurality of R ^17a , they may be the same or different from each other. Further, when a plurality of R ^18a exist, they may be the same or different from each other.

Of the above R ^14a , R ^15a , and R ^16a , the number of groups represented by the above formula (a6) is preferably one from the viewpoint of compound stability, and the rest are direct sequences having 1 or more and 6 or less carbon atoms. It is a chain-shaped or branched alkylene group, and these ends may be bonded to form a cyclic group. In this case, the above two alkylene groups form a 3- to 9-membered ring including a sulfur atom. The number of atoms (including sulfur atoms) constituting the ring is preferably 5 or more and 6 or less.

Examples of the substituent that 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.

The substituents that the phenyl group may have include a hydroxyl group, a linear or branched alkoxy group having 1 or more and 6 or less carbon atoms, and a linear or branched alkoxy group having 1 or more and 6 or less carbon atoms. Alkoxy group and the like can be mentioned.

Suitable examples of these cation portions include those represented by the following formulas (a7) and (a8), and a structure represented by the following formula (a8) is particularly preferable.

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

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

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

The alkyl group in the fluoroalkyl sulfonic acid ion may be linear, branched or cyclic with 1 or more and 20 or less carbon atoms, and has 1 or more and 10 or less carbon atoms from the bulkiness of the generated acid and its diffusion distance. Is preferable. In particular, branched or annular ones are preferable because they have a short diffusion distance. Further, since it can be synthesized at low cost, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group and the like can be mentioned as preferable ones.

Examples of the aryl group in the aryl sulfonic acid ion include an aryl group having 6 to 20 carbon atoms, an alkyl group, a phenyl group which may or may not be substituted with a halogen atom, and a naphthyl group. In particular, an aryl group having 6 or more and 10 or less carbon atoms is preferable because it can be synthesized at low cost. Specific examples of the preferred ones include a phenyl group, a toluenesulfonyl group, an ethylphenyl group, a naphthyl group, a methylnaphthyl group and the like.

In the above fluoroalkyl sulfonic acid ion or aryl sulfonic acid ion, the fluorination rate when a part or all of hydrogen atoms is fluorinated is preferably 10% or more and 100% or less, more preferably 50% or more and 100%. The following is particularly preferable, in which all hydrogen atoms are replaced with fluorine atoms because the acid strength becomes stronger. Specific examples of such a substance include trifluoromethanesulfonate, perfluorobutane sulfonate, perfluorooctane sulfonate, perfluorobenzene sulfonate and the like.

Among these, preferred anion portions include those represented by the following formula (a9).

In the above formula (a9), R ^20a is a group represented by the following formulas (a10), (a11), and (a12).

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

Further, as the anion portion, those containing nitrogen represented by the following formulas (a13) and (a14) can also be used.

In the above formulas (a13) and (a14), Xa represents ^a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the number of carbon atoms of the alkylene group is 2 or more and 6 It is preferably 3 or more and 5 or less, and most preferably the number of carbon atoms is 3. Further, Y ^a and Z ^a each independently represent a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the number of carbon atoms of the alkyl group is 1 or more and 10 or less. It is preferably 1 or more and 7 or less, and more preferably 1 or more and 3 or less.

The smaller the number of carbon atoms of the alkylene group of ^Xa or the number of carbon atoms of the alkyl group of ^Ya and ^Za , the better the solubility in an organic solvent, which is preferable.

Further, in the alkylene group of ^Xa or the alkyl group of ^Ya and ^Za , the larger the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength is, which is preferable. The ratio of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate is preferably 70% or more and 100% or less, more preferably 90% or more and 100% or less, and most preferably all hydrogen atoms are fluorine. It is a perfluoroalkylene group or a perfluoroalkyl group substituted with an atom.

Preferred as an onium salt having a naphthalene ring in such a cation portion include compounds represented by the following formulas (a15) and (a16).

The fifth aspect of the acid generator (A) includes bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, and bis (2,4-). Dimethylphenylsulfonyl) Bissulfonyldiazomethanes such as diazomethane; p-toluenesulfonic acid 2-nitrobenzyl, p-toluenesulfonic acid 2,6-dinitrobenzyl, nitrobenzyltosylate, dinitrobenzyltosylate, nitrobenzylsulfonate, nitro Nitrobenzyl derivatives such as benzylcarbonate, dinitrobenzylcarbonate; pyrogalloltrimesylate, pyrogalloltritosylate, benzyltosylate, benzylsulfonate, N-methylsulfonyloxysuccinimide, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyl Sulfonic acid esters such as oxymaleimide and N-methylsulfonyloxyphthalimide; N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) -1,8-naphthalimide, N- (trifluoromethyl) Trifluoromethanesulfonic acid esters such as sulfonyloxy) -4-butyl-1,8-naphthalimide; diphenyliodonium hexafluorophosphate, (4-methoxyphenyl) phenyliodonium trifluoromethanesulfonate, bis (p-tert-butyl) Onium salts such as phenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (p-tert-butylphenyl) diphenylsulfonium trifluoromethanesulfonate; benzointoshi Benzointosilates such as late and α-methylbenzointosylate; other diphenyliodonium salts, triphenylsulfonium salts, phenyldiazonium salts, benzylcarbonate and the like can be mentioned.

This acid generator (A) may be used alone or in combination of two or more. The content of the acid generator (A) is preferably 0.1% by mass or more and 10% by mass or less, and 0.5% by mass or more and 3% by mass or less, based on the total mass of the photosensitive resin composition. Is more preferable. By setting the amount of the acid generator (A) to be used in the above range, it is easy to prepare a photosensitive resin composition having good sensitivity, a uniform solution, and excellent storage stability.

<Resin (B)>
The resin (B) whose solubility in an alkali is increased by the action of an acid is not particularly limited, and any resin whose solubility in an alkali is increased by the action of an acid can be used. Among them, it is preferable to contain at least one resin selected from the group consisting of novolak resin (B1), polyhydroxystyrene resin (B2), and acrylic resin (B3).

[Novolak resin (B1)]
As the novolak resin (B1), a resin containing a structural unit represented by the following formula (b1) can be used.

In the above formula (b1), R ^1b represents an acid dissociative dissolution inhibitory group, and R ^2b and R ^3b each independently represent a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms.

Examples of the acid dissociative dissolution inhibitor group represented by R ^1b include a group represented by the following formulas (b2) and (b3), and a linear, branched, or cyclic alkyl having 1 or more and 6 or less carbon atoms. It is preferably a group, a vinyloxyethyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, or a trialkylsilyl group.

In the above formulas (b2) and (b3), R ^4b and R ^5b each independently represent a hydrogen atom or a linear or branched alkyl group having 1 or more and 6 or less carbon atoms, and R ^6b is carbon. Represents a linear, branched, or cyclic alkyl group having 1 or more and 10 or less atoms, and ^R7b represents a linear, branched, or cyclic alkyl group having 1 or more and 6 or less carbon atoms. 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, a neopentyl group and the like. .. Examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group.

Here, as the acid dissociative dissolution inhibitory group represented by the above formula (b2), specifically, a methoxyethyl group, an ethoxyethyl group, an n-propoxyethyl group, an isopropoxyethyl group, an n-butoxyethyl group, Examples thereof include isobutoxyethyl group, tert-butoxyethyl group, cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1-ethoxy-1-methylethyl group and the like. Specific examples of the acid dissociable dissolution inhibitory group represented by the above formula (b3) include a tert-butoxycarbonyl group and a tert-butoxycarbonylmethyl group. Examples of the trialkylsilyl group include groups having 1 or more and 6 or less carbon atoms in each alkyl group such as a trimethylsilyl group and a tri-tert-butyldimethylsilyl group.

[Polyhydroxystyrene resin (B2)]
As the polyhydroxystyrene resin (B2), a resin containing a structural unit represented by the following formula (b4) can be used.

In the above formula (b4), R ^8b represents a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms, and R ^9b represents an acid dissociative dissolution inhibitory group.

The alkyl group having 1 or more and 6 or less carbon atoms is, for example, a linear, branched, or cyclic alkyl group having 1 or more and 6 or less carbon atoms. 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, a neopentyl group and the like. Examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group.

As the acid dissociative dissolution inhibitor represented by R ^9b , the same acid dissociative dissolution inhibitor as those exemplified in the formulas (b2) and (b3) can be used.

Further, the polyhydroxystyrene resin (B2) can contain another polymerizable compound as a constituent unit for the purpose of appropriately controlling the physical and chemical properties. Examples of such a polymerizable compound include known radically polymerizable compounds and anionic polymerizable compounds. Examples of such polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; 2-methacryloyloxyethyl succinic acid, 2-. Methacrylic acid derivatives having carboxy groups and ester bonds such as methacryloyloxyethyl maleic acid, 2-methacryloyloxyethylphthalic acid, 2-methacryloxyethyl hexahydrophthalic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (Meth) acrylic acid alkyl esters such as (meth) acrylate; (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; phenyl (meth) acrylate, (Meta) acrylic acid aryl esters such as benzyl (meth) acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, Vinyl group-containing aromatic compounds such as α-methylhydroxystyrene and α-ethylhydroxystyrene; Vinyl group-containing aliphatic compounds such as vinyl acetate; Conjugate diolefins such as butadiene and isoprene; Examples thereof include nitrile group-containing polymerizable compounds; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; and amide bond-containing polymerizable compounds such as acrylamide and methacrylamide; and the like.

[Acrylic resin (B3)]
The acrylic resin (B3) is not particularly limited as long as it is an acrylic resin whose solubility in an alkali is increased by the action of an acid and has been conventionally blended in various photosensitive resin compositions.
The acrylic resin (B3) preferably contains, for example, a constituent unit (b-3) derived from an acrylic acid ester containing a _—SO2 -containing cyclic group or a lactone-containing cyclic group. In such a case, when forming a resist pattern, it is easy to form a resist pattern having a preferable cross-sectional shape.

(-SO ₂ -containing cyclic group)
Here, "-SO ₂ -containing cyclic group" means a cyclic group containing a ring containing -SO _2- in its ring skeleton, and specifically, a sulfur atom (specifically, -SO ₂ -containing ring group) in -SO 2-. S) is a cyclic group forming a part of the cyclic skeleton of the cyclic group. A ring containing -SO _2- in its ring skeleton is counted as the first ring, and if it is the ring alone, it is a monocyclic group, and if it has another ring structure, it is a polycyclic group regardless of its structure. It is called. -SO ₂ -The contained cyclic group may be monocyclic or polycyclic.

-SO ₂ -containing cyclic groups are particularly cyclic groups containing -O-SO ₂ -in their cyclic skeleton, that is, -OS- in -O-SO _2- contains a part of the cyclic skeleton. It is preferably a cyclic group containing a sultone ring to be formed.

The number of carbon atoms of the _—SO2 -containing cyclic group is preferably 3 or more and 30 or less, more preferably 4 or more and 20 or less, further preferably 4 or more and 15 or less, and particularly preferably 4 or more and 12 or less. 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.

The —SO ₂ -containing cyclic group may be a —SO ₂ -containing aliphatic cyclic group or a —SO ₂ -containing aromatic cyclic group. It is preferably a _—SO2 -containing aliphatic cyclic group.

As the -SO ₂ -containing aliphatic cyclic group, a hydrogen atom is obtained from an aliphatic hydrocarbon ring in which a part of carbon atoms constituting the ring skeleton is substituted with -SO _2- or -O-SO _2- . Examples include groups excluding at least one. More specifically, a group in which at least one hydrogen atom is removed from an aliphatic hydrocarbon ring in which -CH _2- is substituted with -SO _2- , which constitutes the ring skeleton, constitutes the ring-CH _2- . Examples thereof include a group in which at least one hydrogen atom is removed from an aliphatic hydrocarbon ring in which CH ₂ -is substituted with —O _— SO2-.

The number of carbon atoms in the alicyclic hydrocarbon ring is preferably 3 or more and 20 or less, and more preferably 3 or more and 12 or less. The alicyclic hydrocarbon ring may be a polycyclic type or a monocyclic type. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane having 3 or more and 6 or less carbon atoms is preferable. Examples of the monocycloalkane include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon ring is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane having 7 or more and 12 or less carbon atoms, and specifically, the polycycloalkane is adamantane or norbornane. , Isobornane, tricyclodecane, tetracyclododecane and the like.

The _—SO2 -containing cyclic group may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, an oxygen atom (= O), -COOR ", -OC (= O) R", a hydroxyalkyl group, a cyano group and the like. Can be mentioned.

As the alkyl group as the substituent, an alkyl group having 1 or more and 6 or less carbon atoms is preferable. The alkyl group is preferably linear or branched. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group and the like. Be done. Among these, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.

As the alkoxy group as the substituent, an alkoxy group having 1 or more and 6 or less carbon atoms is preferable. The alkoxy group is preferably linear or branched. Specific examples thereof include a group in which an alkyl group mentioned as the above-mentioned alkyl group as a substituent is bonded to an oxygen atom (—O—).

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 halogenated alkyl group of the substituent include a group in which a part or all of the hydrogen atom of the above-mentioned alkyl group is substituted with the above-mentioned halogen atom.

Examples of the alkyl halide group as the substituent include a group in which a part or all of the hydrogen atom of the alkyl group mentioned as the alkyl group as the above-mentioned substituent is substituted with the above-mentioned halogen atom. As the halogenated alkyl group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.

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

When R "is a linear or branched alkyl group, the number of carbon atoms of the chain alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, 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 or more and 15 or less, more preferably 4 or more and 12 or less, and particularly preferably 5 or more and 10 or less. Specifically, a fluorine atom. , Or monocycloalkanes that may or may not be substituted with a fluorinated alkyl group, and polycycloalkanes such as bicycloalkanes, tricycloalkanes, tetracycloalkanes, etc., except for one or more hydrogen atoms. More specifically, one or more hydrogen atoms can be obtained from monocycloalkanes such as cyclopentane and cyclohexane, and polycycloalkyls such as adamantan, norbornan, isobornane, tricyclodecane and tetracyclododecane. Examples include the excluded groups.

As the hydroxyalkyl group as the substituent, a hydroxyalkyl group having 1 or more and 6 or less carbon atoms is preferable. Specifically, a group in which at least one of the hydrogen atoms of the alkyl group mentioned as the alkyl group as the above-mentioned substituent is substituted with a hydroxyl group can be mentioned.

（式中、Ａ’は酸素原子若しくは硫黄原子を含んでいてもよい炭素原子数１以上５以下のアルキレン基、酸素原子又は硫黄原子であり、ｚは０以上２以下の整数であり、Ｒ^１０ｂはアルキル基、アルコキシ基、ハロゲン化アルキル基、水酸基、－ＣＯＯＲ”、－ＯＣ（＝Ｏ）Ｒ”、ヒドロキシアルキル基、又はシアノ基であり、Ｒ”は水素原子、又はアルキル基である。） -SO ₂ -Containing cyclic groups include, more specifically, groups represented by the following formulas (3-1) to (3-4).

(In the formula, A'is an alkylene group, an oxygen atom or a sulfur atom having 1 or more and 5 or less carbon atoms which may contain an oxygen atom or a sulfur atom, z is an integer of 0 or more and 2 or less, and R ^10b . Is an alkyl group, an alkoxy group, a halogenated alkyl group, a hydroxyl group, -COOR ", -OC (= O) R", a hydroxyalkyl group, or a cyano group, and R "is a hydrogen atom or an alkyl group.)

In the above formulas (3-1) to (3-4), A'is an alkylene group having 1 or more and 5 or less carbon atoms which may contain an oxygen atom (-O-) or a sulfur atom (-S-). , Oxygen atom, or sulfur atom. As the alkylene group having 1 or more and 5 or less carbon atoms in A', a linear or branched alkylene group is preferable, 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 in which —O— or —S— is interposed between the terminal or carbon atom of the above-mentioned alkylene group, for example, —O—. Examples thereof include CH _2- , -CH ₂ -O-CH _2- , -S-CH _2- , -CH ₂ -S-CH _2- , and the like. As A', an alkylene group having 1 or more and 5 or less carbon atoms or —O— is preferable, an alkylene group having 1 or more and 5 or less carbon atoms is more preferable, and a methylene group is most preferable.

z may be any of 0, 1, and 2, with 0 being most preferred. When z is 2, the plurality of R ^10b may be the same or different.

The alkyl group, alkoxy group, alkyl halide group, -COOR ", -OC (= O) R", and hydroxyalkyl group in R ^10b may each have a _-SO2 -containing cyclic group. Examples of the substituents include an alkyl group, an alkoxy group, an alkyl halide group, -COOR ", -OC (= O) R", and a hydroxyalkyl group similar to those described above.

Hereinafter, specific cyclic groups represented by the above-mentioned formulas (3-1) to (3-4) will be illustrated. In addition, "Ac" in the formula indicates an acetyl group.

As the _—SO2 -containing cyclic group, among the above, the group represented by the above-mentioned formula (3-1) is preferable, and the above-mentioned chemical formulas (3-1-1) and (3-1-18) are preferable. , (3-3-1), and at least one selected from the group consisting of the groups represented by (3-4-1) are more preferable, and the above-mentioned chemical formula (3-1-1) is used. The groups that are used are most preferred.

(Cronide-containing cyclic group)
The “lactone-containing cyclic group” refers to a cyclic group containing a ring (lactone ring) containing —O—C (= O) —in its ring skeleton. The lactone ring is counted as the first ring, and when it has only a lactone ring, it is called a monocyclic group, and when it has another ring structure, it is called a polycyclic group regardless of its structure. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group.

As the lactone cyclic group in the structural unit (b-3), any one can be used without particular limitation. Specifically, the lactone-containing monocyclic group is a group obtained by removing one hydrogen atom from a 4- to 6-membered ring lactone, for example, a group obtained by removing one hydrogen atom from β-propionolactone, or γ-butyrolactone. Examples thereof include a group from which one hydrogen atom has been removed, a group from which one hydrogen atom has been removed from δ-valerolactone, and the like. Examples of the lactone-containing polycyclic group include a bicycloalkane having a lactone ring, a tricycloalkane, and a group obtained by removing one hydrogen atom from a tetracycloalkane.

The structural unit (b-3) is not particularly limited as long as it has a _—SO2 -containing cyclic group or a lactone-containing cyclic group, but the structure of the other portion is not particularly limited, but it is bonded to the carbon atom at the α-position. A structural unit derived from an acrylic acid ester in which a hydrogen atom may be substituted with a substituent (b-3-S) containing a _—SO2 -containing cyclic group, and a carbon atom at the α-position. It is selected from the group consisting of a structural unit (b-3-L) which is a structural unit derived from an acrylic acid ester in which a hydrogen atom bonded to is optionally substituted with a substituent and contains a lactone-containing cyclic group. At least one structural unit is preferred.

[Constituent unit (b-3-S)]
As an example of the structural unit (b-3-S), more specifically, a structural unit represented by the following formula (b-S1) can be mentioned.

（式中、Ｒは水素原子、炭素原子数１以上５以下のアルキル基、又は炭素原子数１以上５以下のハロゲン化アルキル基であり、Ｒ^１１ｂは－ＳＯ_２－含有環式基であり、Ｒ^１２ｂは単結合、又は２価の連結基である。）

(In the formula, R is a hydrogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, or an alkyl halide group having 1 or more and 5 or less carbon atoms, and R ^11b is a _−SO2 -containing cyclic group. R ^12b is a single bond or a divalent linking group.)

In the formula (b-S1), R is the same as described above.
R ^11b is the same as the _—SO2 -containing cyclic group mentioned above.
R ^12b may be either a single bond or a divalent linking group. Since the effect of the present invention is excellent, it is preferably a divalent linking group.

The divalent linking group in R ^12b is not particularly limited, and examples thereof include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a heteroatom, and the like.

-Divalent hydrocarbon group which may have a substituent The hydrocarbon group as a divalent linking group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated. Saturated hydrocarbon groups are usually preferred. More specific examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group having a ring in its structure, and the like.

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

As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable. Specifically, methylene group [-CH _2- ], ethylene group [-(CH ₂ ) _2- ], trimethylene group [-(CH ₂ ) _3- ], tetramethylene group [-(CH ₂ ) _4- ]. , Pentamethylene group [-(CH ₂ ) _5- ] and the like.

As the branched-chain aliphatic hydrocarbon group, a branched-chain alkylene group is preferable. Specifically, -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 -etc. Alkylmethylene groups; -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- , etc. Alkylethylene groups; -CH (CH ₃ ) CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH ₂ -etc. Alkyltrimethylene groups; -CH (CH ₃ ) CH ₂ CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH ₂ CH _2- Examples thereof include an alkylalkylene group such as an alkyltetramethylene group and the like. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 or more and 5 or less carbon atoms is preferable.

The linear or branched aliphatic hydrocarbon group may or may not have a substituent (a group or atom other than a hydrogen atom) that replaces a hydrogen atom. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 or more and 5 or less carbon atoms substituted with a fluorine atom, an oxo group (= O), and the like.

As the aliphatic hydrocarbon group containing a ring in the above structure, a cyclic aliphatic hydrocarbon group which may contain a substituent containing a hetero atom in the ring structure (two hydrogen atoms are removed from the aliphatic hydrocarbon ring). Group), a group in which the cyclic aliphatic hydrocarbon group is bonded to the terminal of a linear or branched aliphatic hydrocarbon group, or a cyclic aliphatic hydrocarbon group in a linear or branched chain. Examples thereof include groups intervening in the middle of the aliphatic hydrocarbon group. Examples of the above-mentioned linear or branched-chain aliphatic hydrocarbon group include the same as described above.

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

The cyclic aliphatic hydrocarbon group may be a polycyclic type or a monocyclic type. As the monocyclic aliphatic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferable. The number of carbon atoms of the monocycloalkane is preferably 3 or more and 6 or less. Specific examples thereof include cyclopentane and cyclohexane. As the polycyclic aliphatic hydrocarbon group, a group obtained by removing two hydrogen atoms from a polycycloalkane is preferable. The number of carbon atoms of the polycycloalkane is preferably 7 or more and 12 or less. Specific examples thereof include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

The cyclic aliphatic hydrocarbon group may or may not have a substituent (a group or atom other than a hydrogen atom) that substitutes for a hydrogen atom. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, an oxo group (= O) and the like.

As the alkyl group as the above-mentioned substituent, an alkyl group having 1 or more carbon atoms and 5 or less carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are more preferable.

As the alkoxy group as the above-mentioned substituent, an alkoxy group having 1 or more and 5 or less carbon atoms is preferable, and a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group. Is more preferable, and a methoxy group and an ethoxy group are particularly preferable.

Examples of the halogen atom as the above-mentioned 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 above-mentioned alkyl halide group as a substituent include a group in which a part or all of the hydrogen atom of the above-mentioned alkyl group is substituted with the above-mentioned halogen atom.

The cyclic aliphatic hydrocarbon group may have a part of carbon atoms constituting its ring structure substituted with —O— or —S—. As the substituent containing the heteroatom, —O—, —C (= O) —O—, —S—, —S (= O) _2- , —S (= O) ₂ -O— are preferable.

The aromatic hydrocarbon group as a divalent hydrocarbon group is a divalent hydrocarbon group having at least one 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 π electrons, and may be a monocyclic type or a polycyclic type. The number of carbon atoms in the aromatic ring is preferably 5 or more and 30 or less, more preferably 5 or more and 20 or less, further preferably 6 or more and 15 or less, and particularly preferably 6 or more and 12 or less. However, the number of carbon atoms does not include the number of carbon atoms of the substituent.

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

Specifically, as an aromatic hydrocarbon group as a divalent hydrocarbon group, a group obtained by removing two hydrogen atoms from the above-mentioned aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); A group obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (for example, biphenyl, fluorene, etc.); a group obtained by removing one hydrogen atom from the above aromatic hydrocarbon ring or aromatic heterocycle (for example, a group obtained by removing one hydrogen atom from the above aromatic hydrocarbon ring or aromatic heterocycle). A group in which one of the hydrogen atoms of an aryl group or heteroaryl group is substituted with an alkylene group (for example, a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, 2- A group obtained by removing one hydrogen atom from an aryl group in an arylalkyl group such as a naphthylethyl group); and the like.

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

In the above aromatic hydrocarbon group, the hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent. For example, the hydrogen atom bonded to the 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, an alkyl halide group, a hydroxyl group, an oxo group (= O) and the like.

As the alkyl group as the above-mentioned substituent, an alkyl group having 1 or more carbon atoms and 5 or less carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, an n-butyl group and a tert-butyl group are more preferable.

As the alkoxy group as the above-mentioned substituent, an alkoxy group having 1 or more and 5 or less carbon atoms is preferable, and a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group. Is preferable, and a methoxy group and an ethoxy group are more preferable.

Examples of the halogen atom as the above-mentioned 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 above-mentioned alkyl halide group as a substituent include a group in which a part or all of the hydrogen atom of the above-mentioned alkyl group is substituted with the above-mentioned halogen atom.

-Bivalent linking group containing a hetero atom The hetero atom in the divalent linking group containing a hetero atom is an atom other than a carbon atom and a hydrogen atom, and is, for example, an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. And so on.

As a divalent linking group containing a heteroatom, specifically, -O-, -C (= O)-, -C (= O) -O-, -OC (= O) -O-, -S-, -S (= O) _2- , -S (= O) ₂ -O-, -NH-, -NH-C (= O)-, -NH-C (= NH)-, = N Examples thereof include a non-hydrocarbon-based linking group such as −, a combination of at least one of these non-hydrocarbon-based linking groups and a divalent hydrocarbon group, and the like. Examples of the divalent hydrocarbon group include the same as the divalent hydrocarbon group which may have the above-mentioned substituent, and a linear or branched aliphatic hydrocarbon group is preferable. ..

Of the above, H in -NH-, -NH-, and -NH-C (= NH)-in -C (= O) -NH- is substituted with a substituent such as an alkyl group or an acyl group, respectively. It may have been done. The number of carbon atoms of the substituent is preferably 1 or more and 10 or less, more preferably 1 or more and 8 or less, and particularly preferably 1 or more and 5 or less.

As the divalent linking group in R ^12b , a linear or branched alkylene group, a cyclic aliphatic hydrocarbon group, or a divalent linking group containing a hetero atom is particularly preferable.

When the divalent linking group in R ^12b is a linear or branched alkylene group, the number of carbon atoms of the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and 1 or more and 4 or less. Is particularly preferable, and 1 or more and 3 or less are most preferable. Specifically, in the description of the above-mentioned "divalent hydrocarbon group which may have a substituent" as the divalent linking group, it is mentioned as a linear or branched aliphatic hydrocarbon group. Examples thereof include a linear alkylene group and a branched alkylene group.

When the divalent linking group in R ^12b is a cyclic aliphatic hydrocarbon group, the cyclic aliphatic hydrocarbon group may have a "substituent" as the above-mentioned divalent linking group. In the description of "divalent hydrocarbon group", the same group as the cyclic aliphatic hydrocarbon group mentioned as "aliphatic hydrocarbon group containing a ring in the structure" can be mentioned.

As the cyclic aliphatic hydrocarbon group, a group in which two or more hydrogen atoms are removed from cyclopentane, cyclohexane, norbornane, isobornane, adamantane, tricyclodecane, or tetracyclododecane is particularly preferable.

When the divalent linking group in R ^12b is a divalent linking group containing a heteroatom, the preferred linking groups are -O-, -C (= O) -O-, and -C (= O). )-, -OC (= 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-, general formula-Y ¹ -O-Y ² -,-[Y ¹ -C (= O) -O] _m A group represented _by' -Y ^2- or -Y ¹ -OC (= O) -Y _2- [Even if Y ¹ and Y ² in the formula each have an independent substituent. It is a good divalent hydrocarbon group, O is an oxygen atom, and m'is an integer of 0 or more and 3 or less. ] And so on.

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

Equation-Y ¹ -O-Y ² -,-[Y ¹ -C (= O) -O] _m' -Y ^2- , or -Y ¹ -OC (= O) -Y ² -Medium, Y ¹ and Y ² are divalent hydrocarbon groups that may independently have a substituent. Examples of the divalent hydrocarbon group include the same as the "divalent hydrocarbon group which may have a substituent" mentioned in the description as the divalent linking group.

As Y1, ^a linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a linear alkylene group having 1 or more carbon atoms and 5 or less carbon atoms is more preferable, and a methylene group and ethylene are preferable. Groups are particularly preferred.

As Y ² , a linear or branched aliphatic hydrocarbon group is preferable, and a methylene group, an ethylene group, and an alkyl methylene group are more preferable. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 or more and 5 or less carbon atoms, more preferably a linear alkyl group having 1 or more and 3 or less carbon atoms, and particularly preferably a methyl group.

In the group represented by the formula- [Y1 ^- C (= O) -O] _m' ^- Y2-, m'is an integer of 0 or more and 3 or less, preferably an integer of 0 or more and 2 or less, 0 or 1 is more preferable, and 1 is particularly preferable. That is, the group represented by the formula- [Y1 ^- C (= O) -O] _m' ^{- Y2-} is represented by the formula-Y1 ^- C (= O) -OY2-. Groups are particularly preferred. Of these, a group represented by the formula- (CH ₂ ) _a' -C (= O) -O- (CH ₂ ) _b' -is preferable. In the formula, a'is an integer of 1 or more and 10 or less, preferably an integer of 1 or more and 8 or less, more preferably 1 or more and 5 or less, further preferably 1 or 2, and most preferably 1. b'is an integer of 1 or more and 10 or less, preferably an integer of 1 or more and 8 or less, more preferably an integer of 1 or more and 5 or less, still more preferably 1 or 2, and most preferably 1.

Regarding the divalent linking group in R ^12b , as the divalent linking group containing a hetero atom, an organic group composed of a combination of at least one non-hydrocarbon group and a divalent hydrocarbon group is preferable. Among them, 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 formulas-Y1 ^{- OY2} -,-[Y1 ^- C (=) O) -O] A group represented by _m' ^- Y2- or ^{-Y1 -} OC (= O) -Y2- is more preferable, and the above-mentioned formula- [Y1 ^- C (= O). -O] A group represented by _m' -Y ^2- or -Y ¹ -OC (= O) -Y ^2- is particularly preferable.

The divalent linking group in R ^12b preferably contains an alkylene group or an ester bond (-C (= O) -O-).

The alkylene group is preferably a linear or branched alkylene group. Suitable examples of the linear aliphatic hydrocarbon group include methylene group [-CH _2- ], ethylene group [-(CH ₂ ) _2- ], trimethylene group [-(CH ₂ ) _3- ], Examples thereof include a tetramethylene group [-(CH ₂ ) _4- ], a pentamethylene group [-(CH ₂ ) _5- ], and the like. Suitable examples of this branched alkylene group are -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, -C (CH ₃ ) _2- , -C (CH ₃ ) (CH ₂ ). Alkylmethylene groups such as CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) _2- , etc .; -CH (CH ₃ ) CH _2- , -CH ( Alkylene ethylene such as 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- , etc. Group; -CH (CH ₃ ) CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH _2- , etc. Alkyltrimethylene group; -CH (CH ₃ ) CH ₂ CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH ₂ An alkyl alkylene group such as an alkyl tetramethylene group such as CH _2- or the like can be mentioned.

As the divalent linking group containing an ester bond, in particular, the formula: —R ^13b −C (= O) —O— [in the formula, R ^13b is a divalent linking group. ] Is preferred. That is, the structural unit (b-3-S) is preferably a structural unit represented by the following formula (b-S1-1).

（式中、Ｒ、及びＲ^１１ｂはそれぞれ前記と同様であり、Ｒ^１３ｂは２価の連結基である。）

(In the formula, R and R ^11b are the same as described above, and R ^13b is a divalent linking group.)

The R ^13b is not particularly limited, and examples thereof include the same as the above-mentioned divalent linking group in R ^12b .
As the divalent linking group of R ^13b , a linear or branched alkylene group, an aliphatic hydrocarbon group containing a ring in the structure, or a divalent linking group containing a hetero atom is preferable, and the divalent linking group is linear. Alternatively, a branched alkylene group or a divalent linking group containing an oxygen atom as a hetero atom is preferable.

As the linear alkylene group, a methylene group or an ethylene group is preferable, and a methylene group is particularly preferable. As the branched alkylene group, an alkylmethylene group or an alkylethylene group is preferable, and -CH (CH ₃ )-, -C (CH ₃ ) _2- , or -C (CH ₃ ) ₂ CH _2- is particularly preferable. preferable.

As the divalent linking group containing an oxygen atom, an ether bond or a divalent linking group containing an ester bond is preferable, and the above-mentioned ^−Y1 −O ⁻ Y2-, − [Y1 ^- C (= O). ) -O] _m' ^- Y2- or -Y1 ^- OC (= O) ^-Y2- is more preferable. Y ¹ and Y ² are divalent hydrocarbon groups that may independently have substituents, and m'is an integer of 0 or more and 3 or less. Of these, -Y1 ^- OC (= O) -Y2- is preferable, and the group represented _{by-(CH 2) c-OC (= O)-(CH 2} ⁾ _{d - is} particularly preferable. .. c is an integer of 1 or more and 5 or less, preferably 1 or 2. d is an integer of 1 or more and 5 or less, preferably 1 or 2.

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

（式中、Ｒ、Ａ’、Ｒ^１０ｂ、ｚ、及びＲ^１３ｂはそれぞれ前記と同じである。）

(In the formula, R, A', R ^10b , z, and R ^13b are the same as described above, respectively.)

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

As R ^13b , a linear or branched alkylene group or a divalent linking group containing an oxygen atom is preferable. The linear or branched alkylene group and the divalent linking group containing an oxygen atom in R ^13b include the above-mentioned linear or branched alkylene group and a divalent linking group containing an oxygen atom, respectively. The same can be mentioned.

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

（式中、Ｒ、及びＡ’はそれぞれ前記と同じであり、ｃ～ｅはそれぞれ独立に１以上３以下の整数である。）

(In the formula, R and A'are the same as described above, and c to e are independently integers of 1 or more and 3 or less.)

[Constituent unit (b-3-L)]
Examples of the structural unit (b-3-L) include, for example, those in which R ^11b in the above-mentioned formula (b-S1) is replaced with a lactone-containing cyclic group, and more specifically, the following formula (b) Examples thereof include structural units represented by b-L1) to (b-L5).

（式中、Ｒは水素原子、炭素原子数１以上５以下のアルキル基、又は炭素原子数１以上５以下のハロゲン化アルキル基であり；Ｒ’はそれぞれ独立に水素原子、アルキル基、アルコキシ基、ハロゲン化アルキル基、水酸基、－ＣＯＯＲ”、－ＯＣ（＝Ｏ）Ｒ”、ヒドロキシアルキル基、又はシアノ基であり、Ｒ”は水素原子、又はアルキル基であり；Ｒ^１２ｂは単結合、又は２価の連結基であり、ｓ”は０以上２以下の整数であり；Ａ”は酸素原子若しくは硫黄原子を含んでいてもよい炭素原子数１以上５以下のアルキレン基、酸素原子、又は硫黄原子であり；ｒは０又は１である。）

(In the formula, R is a hydrogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, or an alkyl halide group having 1 or more and 5 or less carbon atoms; R'is an independent hydrogen atom, an alkyl group and an alkoxy group, respectively. , Alkyl halide group, hydroxyl group, -COOR ", -OC (= O) R", hydroxyalkyl group, or cyano group, where R "is a hydrogen atom or alkyl group; R ^12b is a single bond or It is a divalent linking group, where s "is an integer of 0 or more and 2 or less; A" is an alkylene group having 1 or more and 5 or less carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom, or sulfur. It is an atom; r is 0 or 1.)

R in the formulas (b-L1) to (b-L5) is the same as described above.
The alkyl group, alkoxy group, alkyl halide group, -COOR ", -OC (= O) R", and hydroxyalkyl group in R'may each have a _-SO2 -containing cyclic group. Examples of the substituent include an alkyl group, an alkoxy group, an alkyl halide group, -COOR ", -OC (= O) R", and a hydroxyalkyl group similar to those described above.

R'is preferably a hydrogen atom in consideration of industrial availability and the like.
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 or more and 10 or less, and more preferably 1 or more and 5 or less.
When R "is a cyclic alkyl group, the number of carbon atoms is preferably 3 or more and 15 or less, more preferably 4 or more and 12 or less, and most preferably 5 or more and 10 or less. Specifically, one or more polycycloalkanes such as monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane which may or may not be substituted with a fluorine atom or a fluorinated alkyl group. Examples thereof include groups excluding hydrogen atoms. Specifically, one or more monocycloalkanes such as cyclopentane and cyclohexane, and polycycloalkanes such as adamantan, norbornan, isobornane, tricyclodecane and tetracyclododecane. Examples include groups excluding hydrogen atoms.
As A ", the same as A'in the above-mentioned formula (3-1) can be mentioned. A" is an alkylene group having 1 or more and 5 or less carbon atoms, an oxygen atom (—O—) or a sulfur atom. It is preferably (—S—), and more preferably an alkylene group having 1 or more and 5 or less carbon atoms, or —O—. As the alkylene group having 1 or more and 5 or less carbon atoms, a methylene group or a dimethylmethylene group is more preferable, and a methylene group is most preferable.

R ^12b is the same as R ^12b in the above formula (b-S1).
In the formula (b-L1), s "is preferably 1 or 2.
Hereinafter, specific examples of the structural units represented by the above-mentioned equations (b-L1) to (b-L3) will be illustrated. In each of the following formulas, R ^α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

As the structural unit (b-3-L), at least one selected from the group consisting of the structural units represented by the above-mentioned formulas (b-L1) to (b-L5) is preferable, and the structural unit (b-L1) is preferably one. )-(B-L3), at least one selected from the group consisting of the structural units represented by the above-mentioned formula (b-L1) or (b-L3) is more preferable. At least one selected from the group is particularly preferred.
Among them, the above-mentioned formulas (b-L1-1), (b-L1-2), (b-L2-1), (b-L2-7), (b-L2-12), (b-L2). -14), (b-L3-1), and at least one selected from the group consisting of the structural units represented by (b-L3-5) are preferable.

式（ｂ－Ｌ６）及び（ｂ－Ｌ７）中、Ｒ及びＲ^１２ｂは前述と同様である。 Further, as the structural unit (b-3-L), the structural unit represented by the following formulas (b-L6) to (b-L7) is also preferable.

In the formulas (b-L6) and (b-L7), R and R ^12b are the same as described above.

Further, the acrylic resin (B3) is a structural unit represented by the following formulas (b5) to (b7) having an acid dissociating group as a structural unit that enhances the solubility of the acrylic resin (B3) in an alkali by the action of an acid. including.

In the above formulas (b5) to (b7), R ^14b and R ^18b to R ^23b are independently hydrogen atoms, linear or branched alkyl groups having 1 to 6 carbon atoms, fluorine atoms, or fluorine atoms, respectively. Represents a linear or branched fluorinated alkyl group having 1 or more and 6 or less carbon atoms, and ^R15b to ^R17b are independently linear or branched alkyl groups having 1 or more and 6 or less carbon atoms. Represents a linear or branched fluorinated alkyl group having 1 or more and 6 or less carbon atoms, or an alicyclic group having 5 or more and 20 or less carbon atoms, and each independently has a linear number of 1 or more and 6 or less carbon atoms. Represents a linear or branched alkyl group or a linear or branched fluorinated alkyl group having 1 or more and 6 or less carbon atoms, and R ^16b and R ^17b are bonded to each other, and both are bonded carbon atoms. Together with this, a hydrocarbon ring having 5 or more and 20 or less carbon atoms may be formed, Y ^b represents an aliphatic cyclic group or an alkyl group which may have a substituent, and p is 0 or more and 4 or less. It represents an integer and q represents 0 or 1.

Examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. Can be mentioned. Further, the fluorinated alkyl group is one in which a part or all of the hydrogen atom of the above alkyl group is substituted with a fluorine atom.
Specific examples of the aliphatic cyclic group include groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. Specifically, a group obtained by removing one hydrogen atom from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantan, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Can be mentioned. In particular, a group obtained by removing one hydrogen atom from cyclohexane or adamantane (which may further have a substituent) is preferable.

When the R ^16b and R ^17b do not bond with each other to form a hydrocarbon ring, the carbon atoms of the R ^15b , R ^16b , and R ^17b are high in contrast and have good resolution, depth of focus, and the like. It is preferably a linear or branched alkyl group having a number of 2 or more and 4 or less. The R ^19b , R ^20b , R ^22b , and R ^23b are preferably hydrogen atoms or methyl groups.

The above R ^16b and R ^17b may form an aliphatic cyclic group having 5 or more and 20 or less carbon atoms together with the carbon atom to which both are bonded. Specific examples of such an aliphatic cyclic group include groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. Specifically, one or more hydrogen atoms were removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantan, norbornane, isobornane, tricyclodecane, and tetracyclododecane. The group is mentioned. In particular, a group obtained by removing one or more hydrogen atoms from cyclohexane or adamantane (which may further have a substituent) is preferable.

Further, when the aliphatic cyclic group formed by R ^16b and R ^17b has a substituent on its ring skeleton, examples of the substituent include a hydroxyl group, a carboxy group, a cyano group, and an oxygen atom (= O). ) And the like, and linear or branched alkyl groups having 1 or more and 4 or less carbon atoms can be mentioned. As the polar group, an oxygen atom (= O) is particularly preferable.

The Y ^b is an aliphatic cyclic group or an alkyl group, and examples thereof include groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. .. Specifically, one or more hydrogen atoms were removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantan, norbornane, isobornane, tricyclodecane, and tetracyclododecane. The basis etc. can be mentioned. In particular, a group obtained by removing one or more hydrogen atoms from adamantane (which may further have a substituent) is preferable.

Further, when the aliphatic cyclic group of Y ^b has a substituent on its ring skeleton, examples of the substituent include polar groups such as a hydroxyl group, a carboxy group, a cyano group and an oxygen atom (= O). Examples thereof include a linear or branched alkyl group having 1 or more and 4 or less carbon atoms. As the polar group, an oxygen atom (= O) is particularly preferable.

When Y ^b is an alkyl group, it is preferably a linear or branched alkyl group having 1 or more and 20 or less carbon atoms, preferably 6 or more and 15 or less. Such an alkyl group is particularly preferably an alkoxyalkyl group, and examples of such an alkoxyalkyl group include 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, and 1-isopropoxy. Ethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1-tert-butoxyethyl group, 1-methoxypropyl group, 1-ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1 -Ethyl-1-methylethyl group and the like can be mentioned.

As a preferable specific example of the structural unit represented by the above formula (b5), those represented by the following formulas (b5-1) to (b5-33) can be mentioned.

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

As a preferable specific example of the structural unit represented by the above formula (b6), those represented by the following formulas (b6-1) to (b6-26) can be mentioned.

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

As a preferable specific example of the structural unit represented by the above formula (b7), those represented by the following formulas (b7-1) to (b7-15) can be mentioned.

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

Among the structural units represented by the formulas (b5) to (b7) described above, the structural unit represented by the formula (b6) is preferable from the viewpoint of easy synthesis and relatively high sensitivity. Further, among the structural units represented by the formula (b6), a structural unit in which Y ^b is an alkyl group is preferable, and a structural unit in which one or both of R ^19b and R ^20b is an alkyl group is preferable.

Further, the acrylic resin (B3) is a resin composed of a copolymer containing the structural units represented by the above formulas (b5) to (b7) and the structural units derived from the polymerizable compound having an ether bond. Is preferable.

Examples of the polymerizable compound having an ether bond include a radically polymerizable compound such as a (meth) acrylic acid derivative 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) Examples thereof include 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 in combination of two or more.

Further, the acrylic resin (B3) can contain other polymerizable compounds as a constituent unit for the purpose of appropriately controlling the physical and chemical properties. Examples of such a polymerizable compound include known radically polymerizable compounds and anionic polymerizable compounds.

Examples of such polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; 2-methacryloyloxyethyl succinic acid and 2-methacryloyloxy. Methacrylic acid derivatives having carboxy groups and ester bonds such as ethylmaleic acid, 2-methacryloyloxyethylphthalic acid, 2-methacryloyloxyethylhexahydrophthalic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth). ) (Meth) acrylic acid alkyl esters such as acrylates and cyclohexyl (meth) acrylates; (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylates and 2-hydroxypropyl (meth) acrylates; phenyl ( (Meta) acrylic acid aryl esters such as meth) acrylates and benzyl (meth) acrylates; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene , Hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene and other vinyl group-containing aromatic compounds; Vinyl acetate and other vinyl group-containing aliphatic compounds; butadiene, isoprene and other conjugated diolefins; acrylonitrile, methacrylic acid (B) nitrile group-containing polymerizable compounds such as nitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylic amide; and the like can be mentioned.

As described above, the acrylic resin (B3) may contain a structural unit derived from a polymerizable compound having a carboxy group, such as the monocarboxylic acids and dicarboxylic acids described above. However, the acrylic resin (B3) does not substantially contain a structural unit derived from a polymerizable compound having a carboxy group because it is easy to form a resist pattern including a non-resist portion having a good rectangular cross-sectional shape. Is preferable. Specifically, the ratio of the structural units derived from the polymerizable compound having a carboxy group in the acrylic resin (B3) is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 5% by mass or less. preferable.
In the acrylic resin (B3), the acrylic resin containing a relatively large amount of the structural unit derived from the polymerizable compound having a carboxy group contains or does not contain a small amount of the structural unit derived from the polymerizable compound having a carboxy group. It is preferable to use it in combination with an acrylic resin.

Examples of the polymerizable compound include (meth) acrylic acid esters having an acid non-dissociable aliphatic polycyclic group, vinyl group-containing aromatic compounds and the like. As the acid non-dissociative aliphatic polycyclic group, a tricyclodecanyl group, an adamantyl group, a tetracyclododecanyl group, an isobornyl group, a norbornyl group and the like are particularly preferable because they are easily available industrially. These aliphatic polycyclic groups may have a linear or branched alkyl group having 1 or more and 5 or less carbon atoms as a substituent.

Specific examples of the (meth) acrylic acid esters having an acid-non-dissociating aliphatic polycyclic group include those having the structures of the following formulas (b8-1) to (b8-5). can.

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

When the acrylic resin (B3) contains a structural unit (b-3) containing a _—SO2 -containing cyclic group or a lactone-containing cyclic group, the structural unit (b-3) in the acrylic resin (B3) The content is preferably 5% by mass or more, more preferably 10% by mass or more, particularly preferably 10% by mass or more and 50% by mass or less, and most preferably 10% by mass or more and 30% by mass or less. When the photosensitive resin composition contains a structural unit (b-3) in an amount within the above range, it is easy to achieve both good developability and good pattern shape.

Further, the acrylic resin (B3) preferably contains 5% by mass or more of the structural units represented by the above formulas (b5) to (b7), more preferably 10% by mass or more, and 10% by mass or more. It is particularly preferable to contain 50% by mass or less.

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

The acrylic resin (B3) preferably contains a structural unit derived from the (meth) acrylic acid esters having the above-mentioned acid non-dissociative aliphatic polycyclic group. The content of the structural unit derived from the (meth) acrylic acid ester having an acid non-dissociative aliphatic polycyclic group in the acrylic resin (B3) is preferably 0% by mass or more and 50% by mass or less, 5 More preferably, it is by mass or more and 30% by mass or less.

As long as the photosensitive resin composition contains a predetermined amount of the acrylic resin (B3), an acrylic resin other than the acrylic resin (B3) described above can also be used as the resin (B). The acrylic resin other than the acrylic resin (B3) is not particularly limited as long as it is a resin containing the structural units represented by the above-mentioned formulas (b5) to (b7).

The polystyrene-equivalent mass average molecular weight of the resin (B) described above is preferably 10,000 or more and 600,000 or less, more preferably 20,000 or more and 400,000 or less, and further preferably 30,000 or more and 300,000 or less. By setting such a mass average molecular weight, sufficient strength of the photosensitive resin layer can be maintained without deteriorating the peelability from the substrate, and further, swelling of the profile and generation of cracks during plating can be prevented. can.

Further, the dispersity of the resin (B) is preferably 1.05 or more. Here, the degree of dispersion is a value obtained by dividing the mass average molecular weight by the number average molecular weight. By setting such a degree of dispersion, it is possible to avoid problems such as stress resistance to the desired plating and the tendency of the metal layer obtained by the plating treatment to swell.

The content of the resin (B) is preferably 5% by mass or more and 60% by mass or less with respect to the total mass of the photosensitive resin composition.

<Mercapto compound (C)>
The photosensitive resin composition contains a mercapto compound (C) containing a nitrogen-containing heterocyclic compound having a predetermined structure. Therefore, when forming a resist pattern using the photosensitive resin composition, the non-resist portion of the resist pattern has a taper angle which is an angle formed by the substrate surface and the side surface of the resist portion in the vicinity of the substrate surface. It can be 88 ° or more. Further, since the photosensitive composition contains the mercapto compound (C), the margin of the depth of focus (DOF) of the photosensitive composition is wide.

Further, when the photosensitive composition contains a nitrogen-containing heterocyclic compound having a predetermined structure, the sensitivity of the photosensitive composition tends to be excellent. Therefore, when a photosensitive composition containing a mercapto compound (C) containing a nitrogen-containing heterocyclic compound having a predetermined structure is used, Cu is likely to have a cross-sectional shape defect such as footing when forming a resist pattern. Even when a metal substrate such as the above is used, it is easy to form a resist pattern having a desired shape and size.

The mercapto compound (C) contains a nitrogen-containing heterocyclic compound having a nitrogen-containing heterocycle consisting only of a carbon atom, a hydrogen atom, and a nitrogen atom as a main skeleton.
Then, in the nitrogen-containing heterocyclic compound, one or more mercapto groups and one or more electron-withdrawing groups are bonded to carbon atoms in the nitrogen-containing heterocycle.
When the nitrogen-containing heterocyclic compound exhibits tautomerism, the nitrogen-containing heterocyclic compound may contain a tautomer in the chemically amplified positive photosensitive resin composition.

The number of each of the mercapto group and the electron-withdrawing group contained in the nitrogen-containing heterocyclic compound per molecule is not particularly limited as long as the object of the present invention is not impaired.
The number of mercapto groups contained in the nitrogen-containing heterocyclic compound per molecule is preferably 1 or more and 3 or less, and more preferably 1 or 2.
The number of electron-withdrawing groups contained in the nitrogen-containing heterocyclic compound per molecule is preferably 1 or more and 3 or less, and more preferably 1 or 2.
As the nitrogen-containing heterocyclic compound, a compound having one mercapto group and one electron-withdrawing group in one molecule is preferable.
When the mononitrogen heterocyclic compound has a plurality of electron-withdrawing groups in one molecule, the plurality of electron-withdrawing groups may be the same as or different from each other.

The nitrogen-containing heterocyclic compound has an electron-withdrawing group attached to a carbon atom in the nitrogen-containing heterocycle. The electron-withdrawing group is not particularly limited as long as it is a group generally recognized by those skilled in the art as an electron-withdrawing group.
Typically, an electron-withdrawing group is defined as a substituent in which the Hammett substituent constant σ _m value is a positive value. Regarding the σ _m value of Hammett, for example, a review article by Yusuke Tono (Organic Synthetic Chemistry Vol. 23, No. 8 (1965) p631-642), translated by Yasuhide Yukawa, "Clam Organic Chemistry [II] 4th Edition" p. It is explained in detail in 656 (Hirokawa Bookstore) and the like.

As the electron-withdrawing group having a positive σ _m value, an alkoxy group such as a methoxy group (σ _m value: 0.12); a hydroxyl group (σ _m value: 0.12); a fluorine atom (σ _m value: 0). .34), Halogen atoms such as chlorine atom (σ _m value: 0.37), bromine atom (σ _m value: 0.39), and iodine atom (σ _m value: 0.35); trifluoromethyl group (trifluoromethyl group) Alkoxy halide group such as σ _m value: 0.43); acyloxy group such as acetoxy group (σ _m value: 0.37); acyl group such as acetyl group (σ _m value: 0.38); methoxycarbonyl group Alkoxycarbonyl group such as (σ _m value: 0.37); cyano group (σ _m value: 0.56); nitro group (σ _m value: 0.71); methylsulfonyl group (σ _m value: 0.60) ) And the like.

The alkoxy group may be linear or branched. The number of carbon atoms of the alkoxy group is not particularly limited, and is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less.
Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, a sec-butyloxy group, a tert-butyloxy group, an n-pentyloxy group and an isopentyloxy group. Examples thereof include a neopentyloxy group and a 2-methylbutyloxy group.

The acyl group may be an aliphatic acyl group, an aromatic acyl group, or an acyl group containing an aliphatic group and an aromatic group. The number of carbon atoms of the acyl group is not particularly limited, and is preferably 2 or more and 20 or less, more preferably 2 or more and 10 or less, and particularly preferably 2 or more and 6 or less.
Specific examples of the acyl group include an acetyl group, a propionyl group, a butanoyl group, a pivaloyl group, and a benzoyl group.

The alkyl halide group may be linear or branched. The number of carbon atoms of the alkyl halide group is not particularly limited, and is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less.
Examples of the halogen atom contained in the alkyl halide group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. As the halogen atom, a fluorine atom, a chlorine atom, and a bromine atom are preferable, and a fluorine atom and a chlorine atom are preferable.
The alkyl halide group may contain a plurality of two or more kinds of halogen atoms in combination.
The halogenated alkyl group may be a group in which a part of the hydrogen atom in the alkyl group is substituted with a halogen atom, or a group in which the entire hydrogen atom is substituted with a halogen atom.
Specific examples of the alkyl halide group include chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2. , 2-Trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, and per Fluorodecyl group and the like can be mentioned.

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

The acyloxy group may be an aliphatic asyloxy group, an aromatic asyloxy group, or an asyloxy group containing an aliphatic group and an aromatic group. The number of carbon atoms of the acyloxy group is not particularly limited, and is preferably 2 or more and 20 or less, more preferably 2 or more and 10 or less, and particularly preferably 2 or more and 6 or less.
Specific examples of the asyloxy group include an acetyloxy group, a propionyloxy group, a butanoyloxy group, a pivaloyloxy group, a benzoyloxy group and the like.

The sulfonyl group may be an aliphatic sulfonyl group, an aromatic sulfonyl group, or a sulfonyl group containing an aliphatic group and an aromatic group. The number of carbon atoms of the sulfonyl group is not particularly limited, and is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less.
Specific examples of the sulfonyl group include a methanesulfonyl group, a benzenesulfonyl group, a toluenesulfonyl group, a trifluoromethanesulfonyl group, a difluoromethanesulfonyl group and the like.

Among the electron-withdrawing groups described above, the molecular weight of the nitrogen-containing heterocyclic compound is not excessively large, and it is easy to obtain a good effect by using a small amount of the nitrogen-containing heterocyclic compound, and the nitrogen-containing complex in the photosensitive composition. At least one selected from the group consisting of a halogen atom, a cyano group, a nitro group, an alkyl halide group, and a group represented by -CO- ^{OR c0} because the ring compound has good solubility and the like. Can be mentioned.

The above-mentioned R ^c0 is a hydrocarbon group having 1 or more and 10 or less carbon atoms. Specific examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl group. Alkyl such as sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, and n-decyl group. Groups; Cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, and cyclodecyl group; phenyl group, naphthalene-1-yl group, and naphthalene-2- Aromatic hydrocarbon groups such as an yl group; aralkyl groups such as a benzyl group and a phenethyl group can be mentioned.

In the nitrogen-containing heterocyclic compound as the mercapto compound (C), the nitrogen-containing heterocycle which is the main skeleton may be a nitrogen-containing aliphatic heterocycle or a nitrogen-containing aromatic heterocycle. As the nitrogen-containing heterocycle in the nitrogen-containing heterocyclic compound, a nitrogen-containing aromatic heterocycle is preferable because a desired effect on the pattern shape and the depth of focus can be easily obtained.

The nitrogen-containing heterocycle may be a monocyclic ring or a condensed ring in which two or more rings are condensed. When the nitrogen-containing heterocycle is a condensed ring, and the condensed ring is composed of only an aliphatic ring, the nitrogen-containing heterocycle is referred to as a nitrogen-containing aliphatic heterocycle. On the other hand, when the mononitrogen heterocycle is a condensed ring containing one or more aromatic monocycles, the nitrogen-containing heterocycle is referred to as a nitrogen-containing aromatic heterocycle.

The type of the nitrogen-containing heterocycle is not particularly limited as long as it satisfies the above-mentioned predetermined requirements. Preferable specific examples of the nitrogen-containing aromatic heterocycle include imidazole, pyrazole, 1,2,3-triazole, 1,2,4-triazole, pyridine, pyrimidine, pyridazine, pyrazine, 1,2,3-triazine, 1 , 2,4-Triazine, 1,3,5-triazine, indol, indazole, benzimidazole, quinoline, isoquinoline, cinnoline, phthalazine, quinazoline, quinoxalin, and 1,8-naphthylidine.

Regarding the nitrogen-containing heterocyclic compound as the mercapto compound (C), since it is easy to obtain the desired effects on the pattern shape and the focal depth in the nitrogen-containing heterocycle, it is assigned to at least one of the carbon atoms to which the mercapto group is bonded. It is preferable that a nitrogen atom is present at an adjacent position.

Since it is easy to obtain the desired effects on the pattern shape and the margin of focal depth (DOF), the nitrogen-containing heterocyclic compounds described above are substituted with 2-mercaptoimidazole substituted with an electron-withdrawing group and electron-withdrawing group 3 as described above. -Mercapto-1,2,4-triazole, 2-mercaptopyridine substituted with electron-withdrawing group, 2-mercapto-1,3,5-triazine substituted with electron-withdrawing group, substituted with electron-withdrawing group 2 -Mercaptopyrimidine and 4-mercaptopyrimidine substituted with an electron-withdrawing group are preferred.

The nitrogen-containing heterocyclic compound as the mercapto compound (C) includes the following formula (CI):
(HS) _m1 -A- (EWG) _m2 ... (CI)
(In the formula (CI), A is a (n1 + n2) -valent nitrogen-containing heterocyclic group consisting of only a carbon atom, a hydrogen atom, and a nitrogen atom, EWG is an electron-withdrawing group, and m1 is 1 or more and 4 or less. Is an integer of, and m2 is 1 or 2.)
The compound represented by is preferable.

As the nitrogen-containing heterocycle as A, as described above, imidazole, pyrazole, 1,2,3-triazole, 1,2,4-triazole, pyridine, pyrimidine, pyridazine, pyrazine, 1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine, indol, indazole, benzimidazole, quinoline, isoquinoline, cinnoline, phthalazine, quinazoline, quinoxalin, and 1,8-naphthylidine are preferred.
Further, as the EWG, as described above, a halogen atom, a cyano group, a nitro group, an alkyl halide group, and a group represented by —CO—O—R ^c0 are preferable.

In the formula (CI), m1 and m2 are preferably 1 respectively. That is, as the nitrogen-containing heterocyclic compound represented by the above formula (CI), the nitrogen-containing heterocyclic compound represented by the following formula (C-II) is preferable.
HS-A-EWG ... (C-II)
(In the formula (C-II), A and EWG are the same as those in the formula (CI).)

The following compounds are preferable as the nitrogen-containing heterocyclic compound represented by the formula (C-II).

Preferred specific examples of the nitrogen-containing heterocyclic compound described above include the following compounds.

A pattern using a positive photosensitive resin composition containing an acid generator (A) that generates an acid by irradiation with active light or radiation and a resin (B) whose solubility in an alkali is increased by the action of the acid. When forming, it is considered that the acid generated from the acid generator (A) at the time of exposure is deactivated near the surface of the substrate.
In particular, in the vicinity of the boundary between the exposed portion and the unexposed portion where the acid concentration is low, footing is likely to occur due to the influence of acid deactivation on the substrate surface. When footing occurs, the taper angle formed by the surface of the substrate and the side surface of the resist portion tends to be an acute angle of less than 88 ° in the vicinity of the surface of the substrate.
In this respect, when the photosensitive resin composition contains the nitrogen-containing heterocyclic compound satisfying the above-mentioned predetermined requirements as the mercapto compound (C), it is easy to suppress the deactivation of the acid on the substrate surface, and as a result, it is desired. It is easy to form a resist pattern with a cross-sectional shape.

The nitrogen-containing heterocyclic compound described above has a mercapto group and a highly polar nitrogen-containing heterocycle in its molecule. Therefore, in the vicinity of the interface between the substrate surface and the coating film, the nitrogen-containing heterocyclic compound tends to be oriented so that the mercapto group is located on the substrate surface side and the highly polar nitrogen-containing heterocycle is located on the coating film side. .. This is because the resin (B) and the like contained in the photosensitive resin composition usually have a high polarity to some extent.

For the reasons described above, when the photosensitive resin composition containing the nitrogen-containing heterocyclic compound having the above-mentioned predetermined structure as the mercapto compound (C) is used, the taper angle is 88 ° or more due to the influence of the suppression of footing and the like. It is easy to form a resist pattern having such a preferable cross-sectional shape.

（式（Ｃ１）中、Ａ^０は１以上の置換基を有してもよく、ヘテロ原子を含んでいてもよい、（ｎ１＋ｎ２）価の環式基であり、Ｒ^ｃ１はそれぞれ独立に、水素原子、炭化水素基、又は酸解離性基であり、ｎ１は１以上４以下の整数であり、ｎ２は１又は２であり、Ｒ^ｃ１の少なくとも１つは、水素原子、又は酸解離性基である。
ただし、Ａ^０は、炭素原子、水素原子、及び窒素原子のみからなる含窒素複素環基ではない。）
なお、Ｒ^ｃ１としての炭化水素基は、酸解離性基に該当しない基であると定義する。 Preferred examples of other mercapto compounds that can be used as the mercapto compound (C) together with the above-mentioned nitrogen-containing heterocyclic compound include a compound represented by the following formula (C1).

(In the formula (C1), A ⁰ is a (n1 + n2) -valent cyclic group which may have one or more substituents and may contain a hetero atom, and R ^c1 is independently hydrogen. It is an atom, a hydrocarbon group, or an acid dissociative group, n1 is an integer of 1 or more and 4 or less, n2 is 1 or 2, and at least one of R ^c1 is a hydrogen atom or an acid dissociative group. be.
However, ^A0 is not a nitrogen-containing heterocyclic group consisting only of a carbon atom, a hydrogen atom, and a nitrogen atom. )
The hydrocarbon group as R ^c1 is defined as a group that does not correspond to an acid dissociative group.

A ⁰ is a (n1 + n2) valent cyclic group which may have one or more substituents and may contain a heteroatom. The heteroatom contained in the cyclic group as A ⁰ is not particularly limited as long as it does not impair the object of the present invention. Preferable examples of heteroatoms include nitrogen atoms, oxygen atoms, sulfur atoms, phosphorus atoms, boron atoms, and silicon atoms. Among these, a nitrogen atom, an oxygen atom, and a sulfur atom are preferable.

^A0 may be a cyclic hydrocarbon group or a heterocyclic group. ^A0 may be an aromatic group or an aliphatic cyclic group. When A is an aliphatic cyclic group, the aliphatic cyclic group may be a saturated aliphatic cyclic group or an unsaturated aliphatic cyclic group. When A ⁰ is an aliphatic cyclic group, A ⁰ is preferably a saturated aliphatic cyclic group.

The structure of the ring constituting A ⁰ may be a monocyclic structure or a polycyclic structure. The structure of the ring constituting A0 is preferably a ^monocyclic structure because it is easy to suppress the generation of residue after development.
The number of ring-constituting atoms in the ring constituting ^A0 is not particularly limited as long as the object of the present invention is not impaired. The number of ring-constituting atoms in the ring constituting A may be typically 3 or more and 50 or less, 4 or more and 30 or less, 5 or more and 20 or less, and 5 or more and 12 or less. It's okay.

When the structure of the ring constituting A ⁰ is a polycyclic structure, the polycyclic structure is a polycyclic structure in which two or more monocycles are condensed, but two or more rings are bonded to each other via a single bond. It may be a polycyclic structure, a polycyclo ring structure which is a bicyclic system, or a polycyclic system having a dicyclic system or more, or a spiro ring structure.

When the structure of the ring constituting A ⁰ is a polycyclic structure, the polycyclic structure may be composed of two or more aromatic monocycles or may be composed of two or more aliphatic monocycles. It may be composed of one or more aromatic monocycles and one or more aliphatic monocycles.
The number of single rings constituting the polycyclic structure is not particularly limited. The number of monocycles constituting the polycyclic structure is, for example, preferably 5 or less, more preferably 3 or less, and particularly preferably 1 or 2.
The number of ring-constituting atoms for a single ring constituting a polycyclic structure is preferably 3 or more and 20 or less, more preferably 4 or more and 16 or less, and particularly preferably 5 or more and 12 or less.

When the structure of the ring constituting ^A0 is a monocyclic structure, specific examples of the monocyclic structure include an aromatic hydrocarbon ring such as a benzene ring; a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring. , Cyclononane ring, cyclodecane ring, cycloundecan ring, cyclododecan ring and other aliphatic hydrocarbon rings; furan ring, thiophene ring, pyran ring, isooxazole ring, isothiazole ring, oxazole ring, and thiazole ring and other aromatics. Heterocycle; Examples thereof include a monocyclic structure composed of an aliphatic heterocycle such as a tetrahydrofuran ring, a tetrahydrothiophene ring, a tetrahydropyran ring, a tetrahydrothiopyran ring, a morpholin ring, and a dioxane ring.

When the structure of the ring constituting A0 is a polycyclic structure, specific examples of the polycyclic structure include aromatic hydrocarbon rings such as a naphthalene ring, a biphenyl ring, an anthracene ring, and a phenylene ring; a decalin ring and a ^hydrindane . Aromatic hydrocarbon rings such as rings, adamantan rings, norbornan rings, isobornan rings, tricyclodecane rings, and tetracyclododecane rings; aliphatic hydrocarbon rings such as tetraline rings, indan rings, cyclopentylbenzene rings, and cyclohexylbenzene rings. And an aromatic hydrocarbon ring; an aromatic heterocycle such as a benzoxazole ring and a benzothiazole ring; an aliphatic heterocycle such as a 7-oxanorbornane ring and a 7-thionorbornan ring; a chroman ring, etc. A ring composed of an aliphatic heterocycle and an aromatic hydrocarbon ring can be mentioned.

^A0 , which is a cyclic group, may be substituted with any kind and any number of substituents as long as the object of the present invention is not impaired. When A ⁰ has a substituent, the number of substituents varies depending on the number of ring-constituting atoms in the cyclic group as A ⁰ , but is preferably 1 or more and 6 or less, more preferably 1 or more and 4 or less, and 1 or 2. Is particularly preferable.

Examples of substituents are halogen atom, hydroxyl group, alkyl group, aralkyl group, alkoxy group, cycloalkyloxy group, aryloxy group, aralkyloxy group, alkylthio group, cycloalkylthio group, arylthio group, aralkylthio group and acyl group. , Acyloxy group, acylthio group, alkoxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, amino group, N-mono-substituted amino group, N, N-di-substituted amino group, carbamoyl group (-CO-NH ₂ ). , N-mono-substituted carbamoyl group, N, N-di-substituted carbamoyl group, nitro group, cyano group and the like.

Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 or more and 6 or less, and more preferably 1 or more and 3 or less. The alkyl group may be linear or branched. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group. Can be mentioned.

The number of carbon atoms of the aralkyl group is not particularly limited, but is preferably 7 or more and 20 or less, and more preferably 7 or more and 13 or less. Specific examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthalene-1-ylmethyl group, a naphthalene-2-ylmethyl group and the like.

The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 or more and 6 or less, and more preferably 1 or more and 3 or less. The alkoxy group may be linear or branched. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, an n-pentyloxy group, and a group. Examples include the n-hexyloxy group.

The number of carbon atoms of the cycloalkyloxy group is not particularly limited, but is preferably 3 or more and 10 or less, and more preferably 3 or more and 8 or less. Specific examples of the cycloalkyloxy group include cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, cyclononyloxy group, and cyclodecyloxy group. Be done.

The number of carbon atoms of the aryloxy group is not particularly limited, but is preferably 6 or more and 20 or less, and more preferably 6 or more and 12 or less. Specific examples of the aryloxy group include a phenoxy group, a naphthalene-1-yloxy group, a naphthalene-2-yloxy group, and a biphenylyloxy group.

The number of carbon atoms of the aralkyloxy group is not particularly limited, but is preferably 7 or more and 20 or less, and more preferably 7 or more and 13 or less. Specific examples of the aralkyloxy group include a benzyloxy group, a phenethyloxy group, a naphthalene-1-ylmethoxy group, a naphthalene-2-ylmethoxy group and the like.

The number of carbon atoms of the acyl group is not particularly limited, and is preferably 2 or more and 20 or less, and more preferably 2 or more and 11 or less. The acyl group may be an aliphatic acyl group or an aromatic acyl group containing an aromatic group. Specific examples of the acyl group include an acetyl group, a propionyl group, a butanoyl group, a pentanoyl group, a hexanoyl group, an octanoyl group, a nonanoyl group, a decanoyl group, a benzoyl group, a naphthalene-1-ylcarbonyl group, and a naphthalene-2-ylcarbonyl. The group is mentioned.

The number of carbon atoms of the acyloxy group is not particularly limited, and is preferably 2 or more and 20 or less, and more preferably 2 or more and 11 or less. The acyloxy group may be an aliphatic acyloxy group or an aromatic acyloxy group containing an aromatic group. Specific examples of the acyloxy group include an acetyloxy group, a propionyloxy group, a butanoyloxy group, a pentanoyloxy group, a hexanoyloxy group, an octanoyloxy group, a nonanoyloxy group, a decanoyyloxy group, a benzoyloxy group, and naphthalene. Examples thereof include 1-ylcarbonyloxy group and naphthalene-2-ylcarbonyloxy group.

Suitable examples of the alkylthio group, cycloalkylthio group, arylthio group, aralkylthio group, and acylthio group include the above-mentioned alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, and suitable group as acyloxy group. , A group in which an oxygen atom is converted into a sulfur atom can be mentioned.

The number of carbon atoms of the alkoxycarbonyl group is not particularly limited, but is preferably 2 or more and 7 or less, and more preferably 2 or more and 4 or less. The alkoxycarbonyl group may be linear or branched. Specific examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propyloxycarbonyl group, an isopropyloxycarbonyl group, an n-butyloxycarbonyl group, an isobutyloxycarbonyl group, a sec-butyloxycarbonyl group, and a tert-. Examples thereof include a butyloxycarbonyl group, an n-pentyloxycarbonyl group, and an n-hexyloxycarbonyl group.

The number of carbon atoms of the cycloalkyloxycarbonyl group is not particularly limited, but is preferably 4 or more and 11 or less, and more preferably 4 or more and 9 or less. Specific examples of the cycloalkyloxycarbonyl group include a cyclopropyloxycarbonyl group, a cyclobutyloxycarbonyl group, a cyclopentyloxycarbonyl group, a cyclohexyloxycarbonyl group, a cycloheptyloxycarbonyl group, a cyclooctyloxycarbonyl group, and a cyclononyloxycarbonyl group. , And cyclodecyloxycarbonyl groups.

The number of carbon atoms of the aryloxycarbonyl group is not particularly limited, but is preferably 7 or more and 21 or less, and more preferably 7 or more and 13 or less. Specific examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a naphthalene-1-yloxycarbonyl group, a naphthalene-2-yloxycarbonyl group, and a biphenylyloxycarbonyl group.

Regarding the N-mono-substituted amino group and the N, N-di-substituted amino group, the type of the substituent bonded to the nitrogen atom is not particularly limited. Preferable examples of the substituent bonded to the nitrogen atom are an alkyl group having 1 or more and 6 or less carbon atoms, which may be linear or branched, and a cyclo having 3 or more and 10 or less carbon atoms. Examples thereof include an alkyl group, an aryl group having 6 to 20 carbon atoms, an aliphatic acyl group having 2 to 7 carbon atoms, and an aromatic acyl group having 7 to 21 carbon atoms.
Suitable specific examples of the N-mono-substituted amino group include methylamino group, ethylamino group, n-propylamino group, isopropylamino group, n-butylamino group, isobutylamino group, sec-butylamino group and tert-. Butylamino group, n-pentylamino group, n-hexylamino group, cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclononylamino group, cyclo Decylamino group, phenylamino group, naphthalene-1-ylamino group, naphthalene-2-ylamino group, biphenylylamino group, acetylamino group, propionylamino group, butanoylamino group, pentanoylamino group, hexanoylamino group, Examples thereof include octanoylamino group, nonanoylamino group, decanoyylamino group, benzoylamino group, naphthalene-1-ylcarbonylamino group, and naphthalene-2-ylcarbonylamino group.
Preferable examples of the N, N-di-substituted amino group are dimethylamino group, diethylamino group, din-propylamino group, diisopropylamino group, din-butylamino group, diisobutylamino group and disec-butylamino group. , Ditert-butylamino group, din-pentylamino group, din-hexylamino group, dicyclopentylamino group, dicyclohexylamino group, diphenylamino group, diacetylamino group, dipropionylamino group, and dibenzoylamino group. Can be mentioned.

Regarding the N-mono-substituted carbamoyl group and the N, N-di-substituted carbamoyl group, the type of the substituent bonded to the nitrogen atom is not particularly limited. Preferable examples of substituents attached to a nitrogen atom are similar to those described for N-mono-substituted amino groups and N, N-di-substituted amino groups.
Suitable specific examples of the N-mono-substituted aminocarbamoyl group include N-methylcarbamoyl group, N-ethylcarbamoyl group, Nn-propylcarbamoyl group, N-isopropylcarbamoyl group, Nn-butylcarbamoyl group and N. -Isobutylcarbamoyl group, N-sec-butylcarbamoyl group, N-tert-butylcarbamoyl group, Nn-pentylcarbamoyl group, Nn-hexylcarbamoyl group, N-cyclopropylcarbamoyl group, N-cyclobutylcarbamoyl group. , N-Cyclopentylcarbamoyl group, N-cyclohexylcarbamoyl group, N-cycloheptylcarbamoyl group, N-cyclooctylcarbamoyl group, N-cyclononylcarbamoyl group, N-cyclodecylcarbamoyl group, N-phenylcarbamoyl group, N-naphthalene. -1-ylcarbamoyl group, N-naphthalen-2-ylcarbamoyl group, N-biphenylylcarbamoyl group, N-acetylcarbamoyl group, N-propionylcarbamoyl group, N-butanoylcarbamoyl group, N-pentanoylcarbamoyl group, N-hexanoylcarbamoyl group, N-octanoylcarbamoyl group, N-nonanoylcarbamoyl group, N-decanoylcarbamoyl group, N-benzoylcarbamoyl group, N-naphthalene-1-ylcarbonylcarbamoyl group, and N-naphthalene- 2-Ilcarbonylcarbamoyl group is mentioned.
Preferable examples of the N, N-di-substituted carbamoyl group include N, N-dimethylcarbamoyl group, N, N-diethylcarbamoyl group, N, N-din-propylcarbamoyl group, N, N-diisopropylcarbamoyl group, N, N-di n-butylcarbamoyl group, N, N-diisobutylcarbamoyl group, N, N-disec-butylcarbamoyl group, N, N-ditert-butylcarbamoyl group, N, N-din-pentylcarbamoyl Group, N, N-din-hexylcarbamoyl group, N, N-dicyclopentylcarbamoyl group, N, N-dicyclohexylcarbamoyl group, N, N-diphenylcarbamoyl group, N, N-diacetylcarbamoyl group, N, N- Examples thereof include a dipropionylcarbamoyl group and an N, N-dibenzoylcarbamoyl group.

^A0 in the formula (C1) is a group obtained by removing (n1 + n2) hydrogen atoms from the monocyclic or polycyclic described above.

In the formula (C1), n1 is an integer of 1 or more and 4 or less, and n2 is 1 or 2. Since the mercapto compound (C) can be easily prepared and obtained, n1 is preferably 1 or 2, and more preferably 1. Therefore, ^A0 in the formula (C1) is preferably a divalent or trivalent group.

Preferable examples of A ⁰ in the case where A ⁰ in the formula (C1) is a divalent or trivalent group include the following groups.

In formula (C1), R ^c1 is a hydrogen atom, a hydrocarbon group, or an acid dissociative group. In the formula (C1), when n2 is 2, the two R ^c1s may be the same or different.
At least one of R ^c1 is a hydrogen atom or an acid dissociative group. Therefore, a photosensitive resin composition containing the acid generator (A), the above-mentioned nitrogen-containing heterocyclic compound, and the mercapto compound represented by the formula (C1) is used to form a coating film, and the coating film is exposed. If so, the mercapto compound represented by the formula (C1) exists as a compound having at least one carboxy group at the exposed portion of the coating film.
When R ^c1 is a hydrogen atom, the mercapto compound represented by the formula (C1) has a carboxy group, and when R ^c1 is an acid dissociating group, the group represented by -COOR ^c1 is an acid generator ( This is because it is converted into a carboxy group by the acid generated from A).

As a result, when the coating film formed by using the photosensitive resin composition is exposed and then developed with an alkaline developer, it is either the mercapto compound (C) itself or is derived from the mercapto compound (C). The mercapto compound having a carboxy group dissolves well in an alkaline developer.
For this reason, when a photosensitive resin composition containing the mercapto compound (C) represented by the above formula (C1) is used, a residue after development is unlikely to occur.

When R ^c1 is a hydrocarbon group in the formula (C1), R ^c1 is preferably a hydrocarbon group having 1 or more and 20 or less carbon atoms, and a saturated aliphatic hydrocarbon group having 1 or more and 20 or less carbon atoms. Aromatic hydrocarbon groups having 6 to 20 carbon atoms are more preferable, saturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms are further preferable, and saturated aliphatic hydrocarbon groups having 1 to 10 carbon atoms are more preferable. Particularly preferable, a saturated aliphatic hydrocarbon group having 1 or more and 6 or less carbon atoms is most preferable.
When R ^c1 is a saturated aliphatic hydrocarbon group, the saturated aliphatic hydrocarbon group may be linear or branched, preferably linear.

When R ^c1 is an aromatic hydrocarbon group, suitable specific examples of the aromatic hydrocarbon group include a negative phenyl group, a naphthalene-1-yl group, a naphthalene-2-yl group, a 4-phenylphenyl group, and 3 -Phenylphenyl group and 2-phenylphenyl group can be mentioned. Of these, a phenyl group is preferred.

When R ^c1 is a saturated aliphatic hydrocarbon group, an alkyl group is preferable as the saturated aliphatic hydrocarbon group because the compound represented by the formula (C1) can be easily synthesized and obtained. For R ^c1 , suitable specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, an n-pentyl group and an n-hexyl group. , N-Heptyl group, n-octyl group, n-nonyl group, and n-decyl group.
Among these, a methyl group, an ethyl group, an n-propyl group and an isopropyl group are preferable, and a methyl group and an ethyl group are more preferable.

When R ^c1 is an acid dissociative group in the formula (C1), the acid dissociative machine may be the same group as the acid dissociative dissolution inhibitor described for the resin (B).
Preferable examples of the acid dissociative group as R ^c1 include a group of the following formula.

（式（Ｃ１－１）中、Ｒ^ｃ１、ｎ１、及びｎ２は、式（Ｃ１）と同様であり、Ａ^ｃは１以上の置換基を有してもよく、ヘテロ原子を含んでいてもよい、（ｎ１＋ｎ２）価の脂肪族環式基である。）
で表される化合物が好ましい。 The mercapto compound (C) represented by the above formula (C1) includes the following formula (C1-1):

(In the formula (C1-1), R ^c1 , n1 and n2 are the same as those in the formula (C1), and ^Ac may have one or more substituents and may contain a heteroatom. , (N1 + n2) -valent aliphatic cyclic group.)
The compound represented by is preferable.

As described above, A in the formula (C1) is preferably a divalent or trivalent group. Therefore, as Ac in the formula ( ^C1-1 ), a divalent or trivalent group is preferable.
The following groups are preferable as the aliphatic cyclic group as ^Ac .

（式（Ｃ１－２）中、Ｒ^ｃ１は、式（Ｃ１）と同様であり、Ｒ^ｃ２、及びＲ^ｃ６は、それぞれ独立に水素原子、又はアルキル基であるか、又はＲ^ｃ２とＲ^ｃ６とが、互いに結合して－Ｏ－、－Ｓ－、－ＣＨ_２－、及び－Ｃ（ＣＨ_３）_２－からなる群より選択される２価基を形成してもよく、Ｒ^ｃ３、Ｒ^ｃ４、Ｒ^ｃ５、Ｒ^ｃ７は、それぞれ独立に水素原子、又はメルカプト基であり、Ｒ^ｃ８は、水素原子、又は－ＣＯ－Ｏ－Ｒ^ｃ９で表される基であり、Ｒ^ｃ９は、水素原子、炭化水素基、又は酸解離性基であり、Ｒ^ｃ１、及び^Ｒｃ９の少なくとも一方は、水素原子、又は酸解離性基であり、Ｒ^ｃ３、Ｒ^ｃ４、Ｒ^ｃ５、及びＲ^ｃ７の少なくとも１つはメルカプト基である。）
で表される化合物であるのがより好ましい。 Further, the mercapto compound (C) has the following formula (C1-2) :.

(In the formula (C1-2), R ^c1 is the same as that of the formula (C1), and R ^c2 and R ^c6 are independently hydrogen atoms or alkyl groups, respectively, or R ^c2 and R ^c6 . May combine with each other to form a divalent group selected from the group consisting of -O-, -S-, -CH _2- , and -C (CH ₃ ) _2- , R ^c3 , R ^c4 . , R ^c5 and R ^c7 are independently hydrogen atoms or mercapto groups, R ^c8 is a hydrogen atom or a group represented by -CO-O-R ^c9 , and R ^c9 is a hydrogen atom. A hydrocarbon group or an acid dissociative group, at least one of R ^c1 and ^Rc9 is a hydrogen atom or an acid dissociative group, and at least one of R ^c3 , R ^c4 , R ^c5 , and R ^c7 . It is a mercapto group.)
It is more preferable that the compound is represented by.

In formula (C1-2), R ^c9 is similar to R ^c1 .

Preferable specific examples of the mercapto compound (C), which is the mercapto compound represented by the formula (C1) described above, include the following compounds.

The method for synthesizing the mercapto compound represented by the formula (C1) is not particularly limited. For example, a method for reacting H in a compound represented by (Hal) _n1 -A ^0- (COOR ^c1 ) _n2 (in the formula, Hal is a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom) with NaSH. Alternatively, the mercapto compound represented by the formula (C1) can be obtained by converting it into a mercapto group by a method of reacting with potassium thioacetate and then hydrolyzing.
Further, after synthesizing a compound in which R ^c1 is a hydrogen atom as a mercapto compound represented by the formula (C1) by the above method, the carboxy group is protected by an acid dissociative group or esterified by a well-known method. By doing so, it is possible to obtain a mercapto compound represented by the formula (C1) in which R ^c1 is an acid dissociative group or a hydrocarbon group.

When n1 is 1, (R ^x1 ) _n2 -A ⁰ -S-S-A ^0- (R ^x1 ) _n2 (in the formula, R ^x1 is an alkyl group such as a methyl group and an ethyl group, and acetyl. R ^x1 in a disulfide compound represented by an acyl group such as a group or a formyl group) is oxidized by a well-known method to convert it into a carboxy group, and then the disulfide bond is cleaved according to a well-known method to cleave HS-. The compound represented by A ⁰ − (COOH) _n2 can be obtained as a mercapto compound represented by the formula (C1).
In the compound represented by HS-A ^0- (COOH) _n2 , the carboxy group is protected by an acid dissociable group or esterified by a well-known method, whereby a hydrocarbon group or an acid dissociation is obtained as R ^c1 . A mercapto compound represented by the formula (C1) having a sex group can be obtained.
Further, from the point of view that the yield of the desired mercapto compound is high, the carboxy group is used in the compound represented by (HOOC) _n2 - ^A0 -S-S- ^A0- (COOH) _n2 obtained by the oxidation reaction. A method of cleaving the disulfide bond after protection with an acid dissociative group or esterification by a well-known method is preferable.

Further, in the formula (C1), when n1 is 1 and the cyclic group A is an aliphatic ring or a polycyclic ring containing an aliphatic ring in its structure, the formula (C1) can be used by the following method. The represented compound can be obtained.
In such a method, a compound represented by the following formula (C1-a) is used as the raw material compound. The compound represented by the formula (c1-a) has an n2-valent cyclic group A'containing an unsaturated double bond. By reacting this raw material compound with thioacetic acid (AcSH) in a solvent, thioacetic acid is added to an unsaturated double bond to obtain a compound represented by the following formula (C1-b). The acetylthio group contained in the compound represented by the formula (C1-b) thus obtained is deacetylated according to a conventional method using, for example, sodium hydroxide, and then reacted with an acid as necessary. As a result, the compound represented by the following formula (C1-c) can be obtained as the compound (C) represented by the formula (C1).

In the formula (C1), when n2 is 2 and both R ^c1 are hydrogen atoms, the compound represented by the above formula (C1-a) is replaced with the following formula (C1-a'). The compound represented by the formula (C1) can be obtained by using the dicarboxylic acid anhydride as a raw material.
Regarding this method, the addition of thioacetic acid is the same as the method using the compound represented by the formula (C1-a) as a raw material. By adding thioacetic acid, a compound represented by the following formula (C1-b') is obtained, and then the compound represented by the formula (C1-b') is added to a base such as sodium hydroxide in the presence of water. By reacting with and then with an acid such as hydrochloric acid, deacetylation of the mercapto group and conversion of the acid anhydride group to the carboxy group can be carried out at the same time. By such a reaction, a compound represented by the following formula (C1-c') can be obtained as a compound represented by the formula (C1).

Further, as a preferable example of another mercapto compound that can be used as the mercapto compound (C) together with the above-mentioned nitrogen-containing heterocyclic compound, a compound represented by the following formula (C3) can be mentioned.

In the above equation (c3), Y represents N or CH, s represents an integer of 1 to 3, t represents an integer of 0 to 2, and s + t represents 2 or 3.

Specific examples of the compound represented by the above formula (c3) include 2,4-dimercapto-1,3,5-triazine, 2,4,6-trimercapto-1,3,5-triazine, and 2,4. -Dimercapto-1,3,5-triazine-6-ol, 2-mercapto-1,3,5-triazine-4,6-diol, 2,4-dimercaptopyrimidine, 2-mercaptopyrimidine-4-ol, Examples thereof include 2-mercaptopyrimidine-4,6-diol.

The nitrogen-containing heterocyclic compound satisfying the above-mentioned predetermined requirements is preferably 0.01 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total mass of the resin (B) and the alkali-soluble resin (D) described later. It is used in the range of 0.05 parts by mass or more and 2 parts by mass or less more preferably.
By using the nitrogen-containing heterocyclic compound in an amount within such a range as the mercapto compound (C), it is easy to obtain a desired effect on the pattern shape and the depth of focus.
When another mercapto compound is used together with the nitrogen-containing heterocyclic compound satisfying the above-mentioned predetermined requirements, the total amount of the mercapto compound (C) is the total mass of the resin (B) and the alkali-soluble resin (D) described later. With respect to 100 parts by mass, 0.02 parts by mass or more and 5 parts by mass or less are preferable, and 0.05 parts by mass or more and 2 parts by mass or less are more preferable.

<Alkali-soluble resin (D)>
The photosensitive resin composition preferably further contains an alkali-soluble resin (D) in order to improve crack resistance. Here, the alkali-soluble resin is a resin solution having a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate) to form a resin film having a thickness of 1 μm on a substrate to form a 2.38% by mass TMAH aqueous solution. A substance that dissolves in an amount of 0.01 μm or more when immersed for 1 minute. The alkali-soluble resin (D) is preferably at least one resin selected from the group consisting of novolak resin (D1), polyhydroxystyrene resin (D2), and acrylic resin (D3).

[Novolak resin (D1)]
The novolak resin is obtained, for example, by adding and condensing an aromatic compound having a phenolic hydroxyl group (hereinafter, simply referred to as "phenols") and aldehydes 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- Examples thereof include trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, fluoroxylenol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, β-naphthol and the like.
Examples of the aldehydes include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde and the like.
The catalyst at the time of the addition condensation reaction is not particularly limited, but for example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid and the like are used as the acid catalyst.

It is possible to further improve the flexibility of the novolak resin by using o-cresol, substituting the hydrogen atom of the hydroxyl group in the resin with another substituent, or using bulky aldehydes. Is.

The mass average molecular weight of the novolak resin (D1) is not particularly limited as long as it does not impair the object of the present invention, but is preferably 1000 or more and 50,000 or less.

[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 the styrene resin. Examples of the styrene-based compound constituting such a styrene resin include styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, α-methylstyrene and the like.

The mass average molecular weight of the polyhydroxystyrene resin (D2) is not particularly limited as long as it does not impair the object of the present invention, but is preferably 1000 or more and 50,000 or less.

[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 carboxy group.

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

Examples of the polymerizable compound having a carboxy group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; 2-methacryloyloxyethyl succinic acid and 2-methacryloyloxy. Examples of compounds having a carboxy group and an ester bond such as ethylmaleic acid, 2-methacryloyloxyethylphthalic acid, 2-methacryloyloxyethylhexahydrophthalic acid; and the like can be exemplified. The polymerizable compound having a carboxy group is preferably acrylic acid or methacrylic acid. These polymerizable compounds may be used alone or in combination of two or more.

The mass average molecular weight of the acrylic resin (D3) is not particularly limited as long as it does not impair the object of the present invention, but is preferably 50,000 or more and 800,000 or less.

The content of the alkali-soluble resin (D) is preferably 0 parts by mass or more and 80 parts by mass or less, preferably 0 parts by mass or more and 60 parts by mass when the total of the above resin (B) and the alkali-soluble resin (D) is 100 parts by mass. More preferably, it is by mass or less. By setting the content of the alkali-soluble resin (D) in the above range, the crack resistance tends to be improved and the film loss during development tends to be prevented.

<Acid diffusion control agent (E)>
The photosensitive resin composition preferably further contains an acid diffusion control agent (E) in order to improve the shape of the resist pattern used as a template, the retention stability of the photosensitive resin film, and the like. As the acid diffusion control agent (E), a nitrogen-containing compound (E1) is preferable, and if necessary, an organic carboxylic acid, or a phosphorus oxo acid or a derivative thereof (E2) can be contained.

[Nitrogen-containing compound (E1)]
Examples of the nitrogen-containing compound (E1) include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tri-n-pentylamine, tribenzylamine, diethanolamine, triethanolamine and n-hexylamine. , N-Heptylamine, n-octylamine, n-nonylamine, ethylenediamine, N, N, N', N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4 '-Diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propion Amide, benzamide, pyrrolidone, N-methylpyrrolidone, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, imidazole, benz Imidazole, 4-methylimidazole, 8-oxyquinoline, aclysine, purine, pyrrolidine, piperidine, 2,4,6-tri (2-pyridyl) -S-triazine, morpholine, 4-methylmorpholin, piperazin, 1,4- Examples thereof include dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane, pyridine and the like. These may be used alone or in combination of two or more.

In addition, Adekastab LA-52, Adekastab LA-57, Adekastab LA-63P, Adekastab LA-68, Adekastab LA-72, Adekastab LA-77Y, Adekastab LA-77G, Adekastab LA-81, Adekastab LA-82, and Adekastab LA. Substitution of commercially available hindered amine compounds such as -87 (all manufactured by ADEKA) and 2,6-positions such as 2,6-diphenylpyridine and 2,6-di-tert-butylpyridine with hydrocarbon groups and the like. Pyridine substituted with a group can also be used as the nitrogen-containing compound (E1).

The nitrogen-containing compound (E1) is usually used in a range of 0 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total mass of the resin (B) and the alkali-soluble resin (D), and is 0 parts by mass or more. It is particularly preferable to use it in the range of 3 parts by mass or less.

[Organic carboxylic acid, or phosphorus oxo acid or its derivative (E2)]
Among the organic carboxylic acids, phosphorus oxo acids or derivatives thereof (E2), specifically, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable as the organic carboxylic acid. , Particularly salicylic acid is preferred.

Phosphoric oxo acids or derivatives thereof include phosphoric acids such as phosphoric acid, di-n-butyl ester of phosphoric acid, diphenyl ester of phosphoric acid and derivatives thereof; phosphonic acid, dimethyl phosphonic acid ester, phosphonic acid- Phosphonic acids such as di-n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, phosphonic acid dibenzyl ester and derivatives such as their esters; like phosphinic acid such as phosphinic acid, phenylphosphinic acid and their esters. Derivatives; etc. Of these, phosphonic acid is particularly preferable. These may be used alone or in combination of two or more.

The organic carboxylic acid, or the oxo acid of phosphorus or a derivative thereof (E2) is usually 0 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total mass of the resin (B) and the alkali-soluble resin (D). It is used in a range, and it is particularly preferable to use it in a range of 0 parts by mass or more and 3 parts by mass or less.

Further, in order to form and stabilize the salt, it is preferable to use the same amount of the organic carboxylic acid, or the oxo acid of phosphorus or a derivative thereof (E2) as that of the nitrogen-containing compound (E1).

<Organic solvent (S)>
The photosensitive resin composition contains an organic solvent (S). The type of the organic solvent (S) is not particularly limited as long as it does not impair the object of the present invention, and can be appropriately selected and used from the organic solvents conventionally used in the positive photosensitive resin composition. ..

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

The content of the organic solvent (S) is not particularly limited as long as it does not impair the object of the present invention. When the photosensitive resin composition is used for a thick film application in which the thickness of the photosensitive resin layer obtained by a spin coating method or the like is 10 μm or more, the solid content concentration of the photosensitive resin composition is 30 parts by mass or more 55. It is preferable to use the organic solvent (S) in the range of mass% or less.

<Other ingredients>
The photosensitive resin composition may further contain a polyvinyl resin in order to improve the plasticity. Specific examples of the polyvinyl resin include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinylbenzoic acid, polyvinylmethyl ether, polyvinyl ethyl ether, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylphenol, and copolymers thereof. Can be mentioned. The polyvinyl resin is preferably polyvinyl methyl ether because of its low glass transition point.

Further, the photosensitive resin composition may further contain an adhesive aid in order to improve the adhesiveness between the mold formed by using the photosensitive resin composition and the metal substrate.

Further, the photosensitive resin composition may further contain a surfactant in order to improve 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 surfactants include BM-1000, BM-1100 (all manufactured by BM Chemie), Megafuck F142D, Megafuck F172, Megafuck F173, and Megafuck F183 (all manufactured by Dainippon Ink and Chemicals). , Florard FC-135, Florard FC-170C, Florard FC-430, Florard FC-431 (all manufactured by Sumitomo 3M), Surfron S-112, Surfron S-113, Surfron S-131, Surfron S- Commercially available fluorine-based surfactants such as 141, Surflon S-145 (all manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (all manufactured by Toray Silicone Co., Ltd.) However, it is not limited to these.
Examples of the silicone-based surfactant include unmodified silicone-based surfactants, polyether-modified silicone-based surfactants, polyester-modified silicone-based surfactants, alkyl-modified silicone-based surfactants, aralkyl-modified silicone-based surfactants, and aralkyl-based silicone-based surfactants. A reactive silicone-based surfactant or the like can be preferably used.
As the silicone-based surfactant, a commercially available silicone-based surfactant can be used. Specific examples of commercially available silicone-based surfactants include Paintad M (manufactured by Toray Dow Corning), Topika K1000, Topika K2000, Topika K5000 (all manufactured by Takachiho Sangyo Co., Ltd.), XL-121 (polyester-modified silicone-based). Examples thereof include surfactants (manufactured by Clariant), BYK-310 (polyester-modified silicone-based surfactants, manufactured by Big Chemie) and the like.

Further, the photosensitive resin composition may further contain an acid, an acid anhydride, or a high boiling point solvent in order to finely adjust the solubility in a developing solution.

Specific examples of acids and acid anhydrides include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid and cinnamon acid; lactic acid, 2-hydroxybutyric acid, Hydroxy monocarboxylates such as 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxykatosyl acid, 3-hydroxykatsura acid, 4-hydroxykatsura acid, 5-hydroxyisophthalic acid, syringic acid, etc. Acids; 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-cyclohexanetricarbonate Polyvalent carboxylic acids such as acid, butanetetracarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid; itaconic anhydride, anhydrous Succinic acid, Citraconic anhydride, Dodecenyl succinic acid, Tricarbanyl anhydride, Maleic anhydride, Hexahydrophthalic acid anhydride, Methyltetrahydrophthalic acid anhydride, Hymic acid anhydride, 1,2,3,4-butanetetracarboxylic acid anhydride, Cyclopentanetetracarboxylic acid dianhydride, phthalic acid anhydride, pyromellitic acid anhydride, trimellitic acid anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bis anhydrous trimellitate, glycerintris anhydrous trimellitate and other acid anhydrides; can.

Specific examples of the high boiling point solvent include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and benzyl. Ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, capric acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate , Propylene carbonate, phenyl cellosolve acetone and the like.

Further, the photosensitive resin composition may further contain a sensitizer in order to improve the sensitivity.

<Preparation method of chemically amplified positive photosensitive resin composition>
The chemically amplified positive photosensitive resin composition is prepared by mixing and stirring each of the above components by a usual method. Examples of the device that can be used when mixing and stirring each of the above components include a dissolver, a homogenizer, and a three-roll mill. After uniformly mixing each of the above components, the obtained mixture may be further filtered using a mesh, a membrane filter or the like.

≪Photosensitive dry film≫
The photosensitive dry film has a base film and a photosensitive resin layer formed on the surface of the base film, and the photosensitive resin layer is made of the above-mentioned photosensitive resin composition.

As the base film, a film having light transmission is preferable. Specific examples thereof include polyethylene terephthalate (PET) film, polypropylene (PP) film, polyethylene (PE) film, and the like, and polyethylene terephthalate (PET) film is preferable because it has an excellent balance between light transmission and breaking strength.

A photosensitive dry film is produced by applying the above-mentioned photosensitive resin composition on a base film to form a photosensitive resin layer.
When forming the photosensitive resin layer on the base film, an applicator, a bar coater, a wire bar coater, a roll coater, a curtain flow coater, or the like is used, and the film thickness after drying on the base film is preferably 0. The photosensitive resin composition is applied and dried so as to be 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.

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

<< Manufacturing method of patterned resist film and substrate with mold >>
The method for forming a patterned resist film on the metal surface of a substrate having a metal surface by using the photosensitive resin composition described above is not particularly limited. Such a patterned resist film is suitably used as a mold for forming a plated model.
The preferred method is
A laminating step of laminating a photosensitive resin layer made of a photosensitive resin composition on a metal surface of a substrate having a metal surface, and
An exposure process in which the photosensitive resin layer is exposed by irradiating it with active light or radiation,
A developing process that develops the photosensitive resin layer after exposure,
Examples thereof include a patterned resist film including.
The method for manufacturing a substrate with a mold provided with a mold for forming a plated product is to produce a patterned resist film in the developing process, except for creating a mold for forming the plated product by development. Similar to the method.

The substrate on which the photosensitive resin layer is laminated is not particularly limited, and conventionally known substrates can be used. For example, a substrate for electronic components, a substrate on which a predetermined wiring pattern is formed, and the like are exemplified. be able to. As the substrate, a substrate having a metal surface is used, and as the metal species constituting the metal surface, copper, gold, and aluminum are preferable, and copper is more preferable.

The photosensitive resin layer is laminated on the substrate as follows, for example. That is, a liquid photosensitive resin composition is applied onto a substrate, and the solvent is removed by heating to form a photosensitive resin layer having a desired film thickness. The thickness of the photosensitive resin layer is not particularly limited as long as the resist pattern serving as a mold can be formed with a desired film thickness. The film thickness of the photosensitive resin layer is not particularly limited, but is preferably 0.5 μm or more, more preferably 0.5 μm or more and 300 μm or less, particularly preferably 1 μm or more and 150 μm or less, and most preferably 3 μm or more and 100 μm or less.

As a method for applying the photosensitive resin composition on the substrate, a spin coating method, a slit coating method, a roll coating method, a screen printing method, an applicator method, or the like can be adopted. It is preferable to prebake the photosensitive resin layer. The prebaking conditions vary depending on the type, blending ratio, coating film thickness, etc. of each component in the photosensitive resin composition, but are usually 70 ° C. or higher and 200 ° C. or lower, preferably 80 ° C. or higher and 150 ° C. or lower, for 2 minutes or longer. It takes about 120 minutes or less.

The photosensitive resin layer formed as described above is selectively irradiated (exposed) with active light rays or radiation, for example, ultraviolet rays having a wavelength of 300 nm or more and 500 nm or less, or visible light rays, via a mask having a predetermined pattern. Will be done.

As the radiation source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon gas laser, or the like can be used. Further, the radiation includes microwaves, infrared rays, visible rays, ultraviolet rays, X-rays, γ-rays, electron beams, proton rays, neutron rays, ion rays and the like. The amount of radiation irradiation varies depending on the composition of the photosensitive resin composition, the thickness of the photosensitive resin layer, and the like, but for example, when an ultrahigh pressure mercury lamp is used, it is 100 mJ / cm ² or more and 10,000 mJ / cm ² or less. Further, the radiation includes a light beam that activates the acid generator (A) in order to generate an acid.

After the exposure, the photosensitive resin layer is heated by a known method to promote the diffusion of the acid, and the alkali solubility of the photosensitive resin layer is changed in the exposed portion of the photosensitive resin film. ..

Next, the exposed photosensitive resin layer is developed according to a conventionally known method, and unnecessary portions are dissolved and removed to form a predetermined resist pattern or a mold for forming a plated model. At this time, an alkaline aqueous solution is used as the developing solution.

Examples of the developing solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, and methyldiethylamine. Dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3 0] An aqueous solution of an alkaline substance such as -5-nonane can be used. Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the above alkaline aqueous solution can also be used as a developing solution.

The developing time varies depending on the composition of the photosensitive resin composition, the film thickness of the photosensitive resin layer, and the like, but is usually between 1 minute and 30 minutes or less. The developing method may be any of a liquid filling method, a dipping method, a paddle method, a spray developing method and the like.

After development, wash with running water for 30 seconds or more and 90 seconds or less, and dry using an air gun, an oven, or the like. In this way, a resist pattern patterned in a desired shape is formed on the metal surface of the substrate having the metal surface. Further, in this way, it is possible to manufacture a substrate with a mold having a resist pattern as a mold on the metal surface of the substrate having a metal surface.

≪Manufacturing method of plated objects≫
By embedding a conductor such as metal by plating in the non-resist portion (the portion removed by the developing solution) in the mold of the substrate with a mold formed by the above method, for example, connection terminals such as bumps and metal posts can be formed. , Cu rewiring can form plated objects. The plating treatment method is not particularly limited, and various conventionally known methods can be adopted. As the plating solution, solder plating, copper plating, gold plating, and nickel plating solution are particularly preferably used. The remaining mold is finally removed by a stripping solution or the like according to a conventional method.

According to the above method, for the non-resist portion of the resist pattern, the taper angle formed by the substrate surface and the side surface of the resist portion can be set to 88 ° or more in the vicinity of the substrate surface. Therefore, it is easy to secure a wide contact area between the plated model and the surface of the substrate, and it is possible to manufacture a plated model having excellent adhesion to the substrate.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[Preparation Example 1]
(Synthesis of mercapto compound C8)
In Preparation Example 1, the mercapto compound C8 having the following structure was synthesized.

15.00 g of 7-oxanorborna-5-ene-2,3-dicarboxylic acid anhydride and 150.00 g of tetrahydrofuran were added to the flask and stirred. Then, 7.64 g of thioacetic acid (AcSH) was added to the flask, and the mixture was stirred at room temperature for 3.5 hours. Then, the reaction solution was concentrated to obtain 22.11 g of 5-acetylthio-7-oxanorbornane-2,3-dicarboxylic acid anhydride.
After adding 22.11 g of 5-acetylthio-7-oxanorbornan-2,3-dicarboxylic acid anhydride and 30.11 g of a sodium hydroxide aqueous solution having a concentration of 10% by mass into the flask, the contents of the flask at room temperature. Was stirred for 2 hours. Next, hydrochloric acid (80.00 g) having a concentration of 20% by mass was added into the flask to acidify the reaction solution. Then, extraction with 200 g of ethyl acetate was carried out four times to obtain an extract containing the mercapto compound C2. 25.11 g of tetrahydrofuran (THF) was added to the residue recovered by concentrating the extract and dissolved. Heptane was added dropwise to the obtained THF solution to precipitate the mercapto compound C8, and the precipitated mercapto compound C8 was recovered by filtration. The measurement results of ¹ H-NMR of the mercapto compound C8 are described below.
^{1 1} H-NMR (DMSO-d6): δ12.10 (s, 2H), 4.72 (d, 1H), 4.43 (s, 1H), 3.10 (t, 1H), 3.01 ( d, 1H), 2.85 (d, 1H), 2.75 (d, 1H), 2.10 (t, 1H), 1.40 (m, 1H)

[Examples 1 to 63 and Comparative Examples 1 to 42]
In Examples 1 to 63 and Comparative Examples 1 to 42, the compounds A1 and A2 of the following formula were used as the acid generator (A).

In Examples 1 to 63 and Comparative Examples 1 to 42, the following resins B1 and B2 were used as the resin (resin (B)) whose solubility in alkali was increased by the action of an acid. The number in the lower right of the parentheses in each structural unit in the following structural formula represents the content (mass%) of the structural unit in each resin. The mass average molecular weight Mw of the resin B1 is 40,000, and the dispersity (Mw / Mn) is 2.6. The mass average molecular weight Mw of the resin B2 is 40,000, and the dispersity (Mw / Mn) is 2.6.

As the mercapto compounds (C), in Examples 1 to 63, the following C1 to C7, which are compounds corresponding to the nitrogen-containing heterocyclic compounds satisfying the above-mentioned predetermined requirements, and C8, which is a mercapto compound other than the nitrogen-containing heterocyclic compound, are used. And C9 were used. C8 is the compound obtained in Preparation Example 1. C9 is 2-mercapto-1,3,5-triazine-4,6-diol.

In Comparative Examples 1 to 42, the following C'1 to C'10, which are mercapto compounds not corresponding to the nitrogen-containing heterocyclic compound satisfying the above-mentioned predetermined requirements, were used.

The following resins D1 and D2 were used as the alkali-soluble resin (D).
D1: Polyhydroxystyrene resin (p-hydroxystyrene: styrene = 85: 15 (mass ratio) copolymer, mass average molecular weight (Mw) 2500, dispersity (Mw / Mn) 2.4)
D2: Novolac resin (m-cresol single condensate (mass average molecular weight (Mw) 8000))

In Examples 1 to 63 and Comparative Examples 1 to 42, E1 trypentylamine and LA63-P manufactured by E2ADEKA were used as the acid diffusion inhibitor (E).

The type and amount of the resin (B), the mercapto compound (C), and the alkali-soluble resin (D) shown in Tables 1 to 5, and the acid generator (A) of the type and amount shown in Tables 1 to 5. 0.2 parts by mass of trypentylamine and 0.05 parts by mass of a surfactant (BYK310, manufactured by Big Chemie) are added to 3-methoxybutyl acetate (MA) and propylene so that the solid content concentration is 40% by volume. It was dissolved in a mixed solvent (MA / PM = 6/4 (volume ratio)) with glycol monomethyl ether acetate (PM) to obtain photosensitive resin compositions of Examples and Comparative Examples.

Using the obtained photosensitive resin composition, the shape (cross-sectional shape (taper angle)), the margin of the depth of focus (DOF), and the sensitivity were evaluated according to the following method. The results of these evaluations are shown in Tables 1-5.

[Evaluation of shape (cross-sectional shape (taper angle))]
The photosensitive resin compositions of each Example and Comparative Example were applied onto a copper substrate having a diameter of 8 inches to form a photosensitive resin layer having a film thickness of 7 μm. The photosensitive resin layer was then prebaked at 130 ° C. for 5 minutes. After prebaking, using a line-and-space pattern mask with a line width of 2 μm and a space width of 2 μm and an exposure device Prisma GHI5542 (manufactured by Ultratech), 1.2 times the minimum exposure amount that can form a pattern of a predetermined size. The pattern was exposed with a ghi line at the exposure amount of. Then, the substrate was placed on a hot plate and heated at 90 ° C. for 1.5 minutes after exposure (PEB). Then, a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (developing solution, NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) is dropped onto the exposed photosensitive resin layer and then allowed to stand at 23 ° C. for 30 seconds. Was repeated twice in total. Then, after washing the surface of the resist pattern with running water, nitrogen blow was performed to obtain a resist pattern. The cross-sectional shape of this resist pattern was observed with a scanning electron microscope, and the taper angle, which is the angle formed by the surface of the substrate and the side wall of the resist portion (line), was measured.
When the taper angle was 88 ° or more, it was determined as ◯, and when the taper angle was less than 88 °, it was determined as x.

[Evaluation of Depth of Focus (DOF) Margin]
Using the mask of the line-and-space pattern, the exposure amount was adjusted by the same method as the shape evaluation to form a line-and-space pattern having a line width of 1.5 μm and a space width of 2.5 μm. At this time, the range of focal point in which the pattern can stand independently was investigated.
When the focal range was 28 μm or more, it was determined as ◯, and when the focal range was less than 28 μm, it was determined as ×.

[Evaluation of sensitivity]
Using the mask of the line-and-space pattern, the exposure amount was adjusted by the same method as the shape evaluation to form a line-and-space pattern having a line width of 1.5 μm and a space width of 2.5 μm. The sensitivity was evaluated based on the exposure amount at which a line-and-space pattern having a line width of 1.5 μm and a space width of 2.5 μm could be formed.
When the exposure amount that can form a line-and-space pattern with a line width of 1.5 μm and a space width of 2.5 μm is 700 mJ / cm ² or less, it is judged as ◯, and when it is more than 700 mJ / cm ² and 1000 mJ / cm ² or less, it is judged. It was determined to be Δ, and the case where it was more than 100 mJ / cm ² was determined to be ×.

According to Examples 1 to 63, in addition to the acid generator (A) that generates an acid by irradiation with active light or radiation, and the resin (B) whose solubility in an alkali is increased by the action of the acid, the above-mentioned. When a resist pattern is formed using a positive photosensitive resin composition containing a nitrogen-containing heterocyclic compound satisfying a predetermined requirement as a mercapto compound (C), the angle formed by the surface of the substrate and the side surface of the resist portion is used. It can be seen that a certain taper angle can be set to 88 ° or more, and the depth of focus (DOF) margin is wide.

On the other hand, according to Comparative Examples 1 to 42, when the positive photosensitive resin composition does not contain the nitrogen-containing heterocyclic compound satisfying the above-mentioned predetermined requirements as the mercapto compound (C), the taper angle is 88 ° or more. It can be seen that it is difficult to achieve both the formation of the resist pattern and the wide margin of the depth of focus (DOF).

Claims (11)

Chemically amplified positive photosensitive including an acid generator (A) that generates an acid by irradiation with active light or radiation, a resin (B) whose solubility in an alkali is increased by the action of the acid, and a mercapto compound (C). It is a resin composition
The mercapto compound (C) contains a nitrogen-containing heterocyclic compound having a nitrogen-containing heterocycle having only a carbon atom, a hydrogen atom, and a nitrogen atom as a main skeleton.
The nitrogen-containing heterocycle is 1,2,4-triazole or pyridine.
In the nitrogen-containing heterocyclic compound, one or more mercapto groups and one or more electron-withdrawing groups are bonded to carbon atoms in the nitrogen-containing heterocycle.
When the nitrogen-containing heterocyclic compound exhibits tautomerism, the nitrogen-containing heterocyclic compound may contain a tautomer in the chemically amplified positive photosensitive resin composition. Mold photosensitive resin composition. The chemically amplified positive photosensitive composition according to claim 1 , wherein in the nitrogen-containing heterocycle, a nitrogen atom is present at a position adjacent to at least one of the carbon atoms to which the mercapto group is bonded. The electron-withdrawing group is at least one selected from the group consisting of a halogen atom, a cyano group, a nitro group, an alkyl halide group, and a group represented by —CO—O—R ^c0 , wherein the R ^c0 is. The chemically amplified positive photosensitive composition according to claim 1 or 2 , which is a hydrocarbon group having 1 or more and 10 or less carbon atoms. The nitrogen-containing heterocyclic compound is 3-mercapto-1,2,4-triazole substituted with the electron-withdrawing group, or 2-mercaptopyridine substituted with the electron-withdrawing group, claim 1. The chemically amplified positive photosensitive composition according to any one of 3 to 3 . The chemically amplified positive photosensitive resin composition according to any one of claims 1 to 4 , further comprising an alkali-soluble resin (D). The fifth aspect of claim 5 , wherein the alkali-soluble resin (D) contains at least one resin selected from the group consisting of a novolak resin (D1), a polyhydroxystyrene resin (D2), and an acrylic resin (D3). Chemically amplified positive photosensitive resin composition. It has a substrate film and a photosensitive resin layer formed on the surface of the substrate film, and the photosensitive resin layer is the chemically amplified positive photosensitive according to any one of claims 1 to 6 . A photosensitive dry film made of a resin composition. Production of a photosensitive dry film comprising applying the chemically amplified positive photosensitive resin composition according to any one of claims 1 to 6 onto a base film to form a photosensitive resin layer. Method. A laminating step of laminating a photosensitive resin layer made of the chemically amplified positive photosensitive resin composition according to any one of claims 1 to 6 on a substrate having a metal surface.
An exposure step of regioselectively irradiating the photosensitive resin layer with active light rays or radiation,
A method for producing a patterned resist film, comprising a developing step of developing the photosensitive resin layer after exposure. A laminating step of laminating a photosensitive resin layer made of the chemically amplified positive photosensitive resin composition according to any one of claims 1 to 6 on a substrate having a metal surface.
An exposure step of irradiating the photosensitive resin layer with active light rays or radiation,
A method for manufacturing a substrate with a mold, which comprises a developing step of developing the photosensitive resin layer after exposure to create a mold for forming a plated model. A method for manufacturing a plated molded product, which comprises a step of plating a substrate with a mold manufactured by the method according to claim 10 to form a plated molded product in the mold.