JP6931310B2 - Chemically amplified positive photosensitive resin composition, photosensitive dry film, method for producing photosensitive dry film, method for producing a patterned resist film, method for producing a substrate with a mold, and method for producing a plated molded product, 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 the 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 work piece 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 by 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. Based on this, the mounting density has been improved. In such a 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 polyether 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 model such as a bump or a metal post in a plating process. 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 bumped. Or a photoresist pattern used as a mold in which the portion forming the metal post is selectively removed (peeled) is formed. Then, after embedding a conductor such as copper in the removed portion (non-resist portion) by plating, a bump or a metal post can be formed by removing the photoresist pattern around the conductor.

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, the width of the bottom (support surface side) is larger than the width of the top (resist layer surface side) of the non-resist portion of the resist pattern used as a mold. It is desirable that the size is larger. By doing so, the contact area between the bottom surface of the connection terminal such as a bump or a metal post and the support is increased, and the adhesion between the connection terminal and the support is improved.

However, using a conventionally known chemically amplified positive resist composition as disclosed in Patent Documents 1 and 2, a resist pattern serving as a template for forming bumps, metal posts and the like is formed on a metal substrate. When forming, the resist portion projects toward the non-resist portion on the contact surface between the substrate surface and the resist pattern, so that "footing" in which the width of the bottom is narrower than the width of the top is likely to occur in the non-resist portion. ..
Therefore, when a conventionally known chemically amplified positive photoresist composition as disclosed in Patent Documents 1 and 2 is used, a non-resist portion having a bottom width larger than a top width on a metal substrate. It is difficult to form a resist pattern comprising.

The present invention has been made in view of the above problems, and a resist pattern serving as a template for a plated model is formed on a metal surface of a substrate having a metal surface by using a chemically amplified positive photosensitive resin composition. A chemically amplified positive photosensitive resin that can suppress the occurrence of "footing" in which the width of the bottom (support surface side) is narrower than the width of the top (surface side of the resist layer) in the non-resist portion. A photosensitive dry film comprising the 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. An object of the present invention is to provide a method for producing a patterned resist film using the above, a method for producing a molded substrate using the above-mentioned photosensitive resin composition, and a method for producing a plated molded product using the molded substrate. do.

As a result of intensive studies to achieve the above object, the present inventors have found that the above problems can be solved by incorporating 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.

（式（Ｃ１）中、Ｒ^ｃ１は（ｎ１＋ｎ２）価の有機基であり、Ｒ^ｃ１は、Ｃ−Ｃ結合によってカルボニル基と結合し、且つＣ−Ｓ結合によってメルカプト基と結合し、Ｒ^ｃ２及びＲ^ｃ３は、それぞれ独立に水素原子、又は１価の有機基であり、ｎ１は、１以上４以下の整数であり、ｎ２は、１以上４以下の整数であり、
ただし、Ｒ^ｃ２及びＲ^ｃ３の少なくとも一方が、環構造中に−ＣＯ−Ｏ−で表される２価基を含む脂肪族環ＣＬを有する１価の有機基、環構造中に−ＳＯ_２−で表される２価基を含む脂肪族環ＣＳを有する１価の有機基、又は環構造中に下記式：

で表される３価基を含む脂肪族環ＣＰを有する１価の有機基であるか、Ｒ^ｃ２とＲ^ｃ３とが結合して、脂肪族環ＣＬ、脂肪族環ＣＳ、又は脂肪族環ＣＰを形成している。）
で表されるメルカプト化合物（Ｃ）と、を含有する化学増幅型ポジ型感光性樹脂組成物である。 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 the following formula (C1). :

(In the formula (C1), R ^c1 is a (n1 + n2) valent organic group, and R ^c1 is bonded to a carbonyl group by a CC bond and a mercapto group by a CS bond, and R ^c2 and R ^c3 is independently a hydrogen atom or a monovalent organic group, n1 is an integer of 1 or more and 4 or less, and n2 is an integer of 1 or more and 4 or less.
However, ^{at least one of R c2} and R ^c3 is a monovalent organic group having an aliphatic ring CL containing a divalent group represented by -CO-O- in the ring structure, and -SO _{2- in the ring structure.} A monovalent organic group having an aliphatic ring CS containing a divalent group represented by, or the following formula in the ring structure:

It is a monovalent organic group having an aliphatic ring CP containing a trivalent group represented by, or R ^c2 and R ^c3 are combined to form an aliphatic ring CL, an aliphatic ring CS, or an aliphatic ring CP. Is forming. )
A chemically amplified positive photosensitive resin composition containing the mercapto compound (C) represented by.

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

A third aspect of the present invention is a photosensitive dry film comprising applying the chemically amplified positive photosensitive resin composition according to the first aspect on a base 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, which comprises 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,
It is a method for manufacturing a substrate with a mold, which includes a developing step of developing a photosensitive resin layer after exposure to prepare a mold for forming a plated molded product.

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

（式（Ｃ１）中、Ｒ^ｃ１は（ｎ１＋ｎ２）価の有機基であり、Ｒ^ｃ１は、Ｃ−Ｃ結合によってカルボニル基と結合し、且つＣ−Ｓ結合によってメルカプト基と結合し、Ｒ^ｃ２及びＲ^ｃ３は、それぞれ独立に水素原子、又は１価の有機基であり、ｎ１は、１以上４以下の整数であり、ｎ２は、１以上４以下の整数であり、
ただし、Ｒ^ｃ２及びＲ^ｃ３の少なくとも一方が、環構造中に−ＣＯ−Ｏ−で表される２価基を含む脂肪族環ＣＬを有する１価の有機基、環構造中に−ＳＯ_２−で表される２価基を含む脂肪族環ＣＳを有する１価の有機基、又は環構造中に下記式：

で表される３価基を含む脂肪族環ＣＰを有する１価の有機基であるか、Ｒ^ｃ２とＲ^ｃ３とが結合して、脂肪族環ＣＬ、脂肪族環ＣＳ、又は脂肪族環ＣＰを形成している。）
で表される、メルカプト化合物である。 A seventh aspect of the present invention is the following formula (C1):

(In the formula (C1), R ^c1 is a (n1 + n2) valent organic group, and R ^c1 is bonded to a carbonyl group by a CC bond and a mercapto group by a CS bond, and R ^c2 and R ^c3 is independently a hydrogen atom or a monovalent organic group, n1 is an integer of 1 or more and 4 or less, and n2 is an integer of 1 or more and 4 or less.
However, ^{at least one of R c2} and R ^c3 is a monovalent organic group having an aliphatic ring CL containing a divalent group represented by -CO-O- in the ring structure, and -SO _{2- in the ring structure.} A monovalent organic group having an aliphatic ring CS containing a divalent group represented by, or the following formula in the ring structure:

It is a monovalent organic group having an aliphatic ring CP containing a trivalent group represented by, or R ^c2 and R ^c3 are combined to form an aliphatic ring CL, an aliphatic ring CS, or an aliphatic ring CP. Is forming. )
It is a mercapto compound represented by.

（式（Ｃ１−ｄ）中、Ｒ^ｃ１は（ｎ１＋ｎ２）価の有機基であり、Ｒ^ｃ１は、Ｃ−Ｃ結合によってカルボニル基と結合し、且つＣ−Ｓ結合によってメルカプト基と結合し、Ｒ^ｃ２及びＲ^ｃ３は、それぞれ独立に水素原子、又は１価の有機基であり、Ｘ^ｃはＲ^ｘ１−（Ｃ＝Ｏ）−で表される基であり、Ｒ^ｘ１は１価の炭化水素基であり、ｎ１は、１以上４以下の整数であり、ｎ２は、１以上４以下の整数であり、
ただし、Ｒ^ｃ２及びＲ^ｃ３の少なくとも一方が、環構造中に−ＣＯ−Ｏ−で表される２価基を含む脂肪族環ＣＬを有する１価の有機基、環構造中に−ＳＯ_２−で表される２価基を含む脂肪族環ＣＳを有する１価の有機基、又は環構造中に下記式：

で表される３価基を含む脂肪族環ＣＰを有する１価の有機基であるか、Ｒ^ｃ２とＲ^ｃ３とが結合して、脂肪族環ＣＬ、脂肪族環ＣＳ、又は脂肪族環ＣＰを形成している。）
で表される化合物である。 An eighth aspect of the present invention is the following formula (C1-d):

(In the formula (C1-d), R ^c1 is a (n1 + n2) valent organic group, and R ^c1 is bonded to a carbonyl group by a CC bond and a mercapto group by a CS bond, and is R. ^c2 and R ^c3 are independently hydrogen atoms or monovalent organic groups, X ^c is ^{a group represented by R x1-} (C = O)-, and R ^x1 is a monovalent hydrocarbon group. N1 is an integer of 1 or more and 4 or less, and n2 is an integer of 1 or more and 4 or less.
However, ^{at least one of R c2} and R ^c3 is a monovalent organic group having an aliphatic ring CL containing a divalent group represented by -CO-O- in the ring structure, and -SO _{2- in the ring structure.} A monovalent organic group having an aliphatic ring CS containing a divalent group represented by, or the following formula in the ring structure:

It is a monovalent organic group having an aliphatic ring CP containing a trivalent group represented by, or R ^c2 and R ^c3 are combined to form an aliphatic ring CL, an aliphatic ring CS, or an aliphatic ring CP. Is forming. )
It is a compound represented by.

（式（Ｃ１−ｆ）中、Ｒ^ｃ１は（１＋ｎ２）価の有機基であり、Ｒ^ｃ１は、Ｃ−Ｃ結合によってカルボニル基と結合し、且つＣ−Ｓ結合によって硫黄原子と結合し、Ｒ^ｃ２及びＲ^ｃ３は、それぞれ独立に水素原子、又は１価の有機基であり、ｎ２は、１以上４以下の整数であり、
ただし、Ｒ^ｃ２及びＲ^ｃ３の少なくとも一方が、環構造中に−ＣＯ−Ｏ−で表される２価基を含む脂肪族環ＣＬを有する１価の有機基、環構造中に−ＳＯ_２−で表される２価基を含む脂肪族環ＣＳを有する１価の有機基、又は環構造中に下記式：

で表される３価基を含む脂肪族環ＣＰを有する１価の有機基であるか、Ｒ^ｃ２とＲ^ｃ３とが結合して、脂肪族環ＣＬ、脂肪族環ＣＳ、又は脂肪族環ＣＰを形成している。）
で表される化合物である。 A ninth aspect of the present invention is the following formula (c1-f):

(In the formula (C1-f), R ^c1 is a (1 + n2) -valent organic group, and R ^c1 is bonded to a carbonyl group by a CC bond and a sulfur atom by a CS bond. ^c2 and R ^c3 are independently hydrogen atoms or monovalent organic groups, and n2 is an integer of 1 or more and 4 or less.
However, ^{at least one of R c2} and R ^c3 is a monovalent organic group having an aliphatic ring CL containing a divalent group represented by -CO-O- in the ring structure, and -SO _{2- in the ring structure.} A monovalent organic group having an aliphatic ring CS containing a divalent group represented by, or the following formula in the ring structure:

It is a monovalent organic group having an aliphatic ring CP containing a trivalent group represented by, or R ^c2 and R ^c3 are combined to form an aliphatic ring CL, an aliphatic ring CS, or an aliphatic ring CP. Is forming. )
It is a compound represented by.

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 top in the non-resist portion. A chemically amplified positive photosensitive resin composition capable of suppressing the occurrence of "footing" in which the width of the bottom (support surface side) is narrower than the width of the (resist layer surface side), and the chemically amplified positive A photosensitive dry film provided with a photosensitive resin layer composed of a type photosensitive resin composition, a method for producing the photosensitive dry film, and a patterned resist film using the above-mentioned chemically amplified positive type photosensitive resin composition. It is possible to provide a manufacturing method, a method for manufacturing a molded substrate using the above-mentioned photosensitive resin composition, and a method for manufacturing a plated molded product using the molded substrate.

It is a figure which shows typically the cross section of the resist pattern observed at the time of measuring the footing amount in the non-resist part in a resist pattern in an Example and a comparative example.

<< 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) that generates an acid by irradiation with active light or radiation (hereinafter, also referred to as an acid generator (A)). 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, particularly preferably 1 μm or more and 150 μm or less, and 3 μm or more. Most preferably 100 μm or less.

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, the suitable acid generator (A) preferably used in the photosensitive resin composition will be described as the first to fifth aspects.

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 of 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} , which includes an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, and an alkyl group having 1 to 30 carbon atoms. 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, asyloxy, 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. Also, directly with each other two or more ^{R 1a,} or _{-O -, - S -, -} SO -, - SO 2 -, - 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), X ^4a contains an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a divalent group of a heterocyclic compound having 8 to 20 carbon atoms. Represented, X ^4a consists 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 replaced with at least one selected. X ^5a is _{-O -, - S -, -} SO -, - SO 2 -, - NH -, - NR 2a -, - CO -, - COO -, - CONH-, carbon atom number of 1 to 3 alkylene 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 R ^3a 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 atoms of the phenyl group are 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, and bis [4- (diphenylsulfonio) phenyl] sulfide. Bis [4- {bis [4- (2-hydroxyethoxy) phenyl] sulfonio} phenyl] sulfide, bis {4- [bis (4-fluorophenyl) sulfonio] phenyl} sulfide, 4- (4-benzoyl-2-) Chlorophenylthio) Phenylbis (4-fluorophenyl) sulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10 -Thia-9,10-dihydroanthracene-2-yldiphenylsulfonium, 2-[(diphenyl) sulfonio] 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) iodonium, bis (4-methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyliodonium, bis (4-decyloxy) phenyliodonium, 4- Examples thereof include (2-hydroxytetradecyloxy) phenylphenyl iodonium, 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 represents the same meaning as ^{X 2a} in the 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) Examples thereof include −acetophenylthio) phenyl] diphenylsulfonium and diphenyl [4- (p-terphenylthio) phenyl] diphenylsulfonium.

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 group such as sikuhexyl, 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 fluorine atom substitution rate of 100%. 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 CFCF 2, CF 3 CF 2 (CF 3) CF, is _{(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.

Specific preferred examples of the borate anion represented by the formula (a18), tetrakis (pentafluorophenyl) borate _{([B (C 6 F 5} ) 4] -), 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.

Further, as a third aspect of the acid generator (A), α- (p-toluenesulfonyloxyimino) -phenylaceterminate, α- (benzenesulfonyloxyimino) -2,4-dichlorophenylnitrile, α- (benzene) Contains sulfonyloxyimino) -2,6-dichlorophenylacetoform, α- (2-chlorobenzenesulfonyloxyimino) -4-methoxyphenylnitrile, 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 can be mentioned. 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 carbon atoms 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 substituents such as a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, and a linear or branched alkoxy group having 1 to 6 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 to 6 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 to 6 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 to 6 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, respectively. It 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 each independently represent an integer 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 is directly formed with 1 or more and 6 or less carbon atoms. It is a chain 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. Moreover, 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 to 10 carbon atoms is preferable because it can be synthesized at low cost. Specific examples of preferable 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 strength of the acid becomes stronger. Specific examples thereof include trifluoromethanesulfonate, perfluorobutane sulfonate, perfluorooctane sulfonate, and perfluorobenzene sulfonate.

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 perfluorobutane sulfonate 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.

The formula (a13), (a14) in, X ^a represents a linear or branched alkylene group having at least one hydrogen atom is substituted with a fluorine atom, the number of carbon atoms of the alkylene group 2 to 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.

X ^a number of carbon atoms of the alkylene group, or Y ^a, soluble enough in organic solvents the number of carbon atoms in the alkyl group of Z ^a is less preferred because it is excellent.

Further, in the alkylene group of ^{X a or the alkyl group of Y a} and Z ^a , the larger the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength, 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 an atomically substituted perfluoroalkylene group or perfluoroalkyl group.

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

Further, as a fifth aspect of the acid generator (A), bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, 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 and dinitrobenzylcarbonate; pyrogalloltrimesylate, pyrogalloltritosylate, benzyltosylate, benzylsulfonate, N-methylsulfonyloxysuccinimide, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyl Sulfonic acid esters such as oxymaleimide and N-methylsulfonyloxyphthalimide; trifluoromethanesulfonic acid esters such as N-hydroxyphthalimide and N-hydroxynaphthalimide; diphenyliodonium hexafluorophosphate, (4-methoxyphenyl) phenyliodonium Trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (p-tert-butylphenyl) diphenyl Onium salts such as sulfonium trifluoromethane sulfonate; benzointosilates such as benzointosylate 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 alkali is increased by the action of acid is not particularly limited, and any resin whose solubility in alkali is increased by the action of 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), a linear, branched or cyclic alkyl having 1 to 6 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. It represents a linear, branched or cyclic alkyl group having 1 or more and 10 or less atoms, and R ^7b 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 dissociative 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 above 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 radical 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-methacryloyloxyethyl 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.
Acrylic resin (B3) is, for example, -SO 2 _- containing cyclic group, or preferably contains a structural unit (b-3) derived from an acrylate ester containing a lactone-containing cyclic group. In such a case, it is easy to suppress the occurrence of footing when forming the resist pattern.

(-SO ₂ -containing cyclic group)
Here, "- SO 2 _- containing cyclic group" means, -SO 2 _- within the ring skeleton thereof shows a cyclic group containing a ring containing, in particular, -SO 2 _- in the sulfur atom ( 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. The −SO ₂ − containing cyclic group may be monocyclic or polycyclic.

-SO ₂ - containing cyclic group, in particular, -O-SO ₂ - within the ring skeleton cyclic group containing, i.e. -O-SO ₂ - -O-S- medium is a part of the ring skeleton It is preferably a cyclic group containing a sultone ring to be formed.

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

The −SO ₂ -containing cyclic group may be a −SO ₂ -containing aliphatic cyclic group or a −SO ₂ -containing aromatic cyclic group. Preferably -SO ₂ - 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 −CH ₂ − _{constituting the ring skeleton is substituted with −SO 2} − at least one hydrogen atom is removed from the aliphatic hydrocarbon ring, and the ring is composed of −CH ₂ −. Examples thereof include a group obtained by removing at least one hydrogen atom from an aliphatic hydrocarbon ring in which CH ₂ − is substituted with −O−SO _2−.

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 −SO ₂ − 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 to 6 carbon atoms is preferable. The alkyl group is preferably linear or branched. Specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, 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 to 6 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 alkyl halide 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 atoms of the alkyl group listed as the alkyl group as the substituent is substituted with the above-mentioned halogen atom. As the alkyl halide 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-chain or cyclic alkyl group having 1 to 15 carbon atoms.

When R "is a linear or branched alkyl group, the number of carbon atoms of the 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 alkyl fluorinated groups, 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 polycycloalkanes such as adamantan, norbornan, isobornane, tricyclodecane, and tetracyclododecane. Excluded groups and the like can be mentioned.

As the hydroxyalkyl group as the substituent, a hydroxyalkyl group having 1 to 6 carbon atoms is preferable. Specifically, a group in which at least one hydrogen atom 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 group, and more specifically, include groups represented by the following formula (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, an alkyl halide 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. The alkylene group having 1 or more and 5 or less carbon atoms in A'preferably a linear or branched alkylene group, and examples thereof include a methylene group, an ethylene group, an n-propylene group, and an isopropylene group.

When the alkylene group contains an oxygen atom or a sulfur atom, specific examples thereof include a group in which -O- or -S- is interposed between the terminal or carbon atom of the above-mentioned alkylene group, for example, -O-. _{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 to 5 carbon atoms or —O— is preferable, an alkylene group having 1 to 5 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 -SO 2} -containing cyclic group. Examples of the alkyl group, alkoxy group, alkyl halide group, -COOR ", -OC (= O) R", and hydroxyalkyl group mentioned as substituents are the same as those described above.

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

The -SO ₂ - containing cyclic group, among the above, preferably a group represented by the formula (3-1) described above, the aforementioned chemical formula (3-1-1), (3-1-18) , (3-3-1), and (3-4-1), at least one selected from the group consisting of groups represented by any of (3-4-1) is more preferable, and is represented by the above-mentioned chemical formula (3-1-1). The groups that are used are most preferred.

(Lactone-containing cyclic group)
The “lactone-containing cyclic group” refers to a cyclic group containing a ring (lactone ring) containing −OC (= O) − in its cyclic 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 tetracycloalkane from which one hydrogen atom has been removed.

As the structural unit (b-3), -SO 2 - containing cyclic group, or a lactone-containing cyclic structure other parts as long as it has a group is not particularly limited, and bonded to the α-position carbon atom -SO 2 a structural unit is a hydrogen atom are derived substituted from even an acrylate ester with a substituent _- structural unit containing an containing cyclic group (b-3-S), and α-position carbon atom It is selected from the group consisting of a structural unit (b-3-L) derived from an acrylic acid ester in which the hydrogen atom bonded to is optionally substituted with a substituent and containing a lactone-containing cyclic group. At least one structural unit is preferred.

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

（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。）

(Wherein, R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, R ^11b represents a -SO 2 _- 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, -SO ₂ mentioned above - is similar to the containing cyclic group.
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, but a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom and the like are preferable.

-Divalent hydrocarbon group which may have a substituent The hydrocarbon group as the divalent linking group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Aliphatic hydrocarbon groups mean hydrocarbon groups that do not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated. Saturated hydrocarbon groups are usually preferred. More specifically, the aliphatic hydrocarbon group includes a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group having a ring in the 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, a methylene group _[-CH 2 -], an ethylene group _{[- (CH 2) 2 -} ], a trimethylene group _{[- (CH 2) 3 -} ], a 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 − and other alkyl methylene groups; −CH (CH ₃ ) CH ₂ CH ₂ CH ₂ −, −CH ₂ CH (CH ₃ ) CH ₂ CH ₂ − Alkyl alkylene groups such as alkyl tetramethylene groups and the like can be mentioned. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 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) for substituting a hydrogen atom. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and an oxo group (= O).

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 a group 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 those 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 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 alkyl halide group as the above-mentioned 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-. The substituent containing a hetero atom, -O -, - C (= O) -O -, - S -, - S (= O) 2 -, - S (= O) 2 -O- are preferred.

The aromatic hydrocarbon group as the 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 replaced 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 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 more 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 contained in 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 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 alkyl halide group as the above-mentioned 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.

-Divalent 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.

Specific examples of the divalent linking group containing a heteroatom include -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 −, and a combination of at least one of these non-hydrocarbon-based linking groups and a divalent hydrocarbon group. Examples of the divalent hydrocarbon group include those similar to 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- are substituted with substituents such as alkyl groups and acyl groups, 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 divalent linking group containing a linear or branched alkylene group, a cyclic aliphatic hydrocarbon group, or a heteroatom 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 hetero atom, -O-, -C (= O) -O-, -C (= O) are preferable as the linking group. )-, -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 '} Groups represented by −Y ² − or −Y ¹ −OC (= O) −Y ₂₋ [Even if Y ¹ and Y ^{2 in the} formula each have independent substituents. It is a good divalent hydrocarbon group, where O is an oxygen atom and m'is an integer greater than or equal to 0 and less than or equal to 3. ] Etc. can be mentioned.

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 group. 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.

Wherein ^{-Y 1 -O-Y 2 -,} - [Y 1 -C (= O) -O] m '-Y 2 -, or ^{-Y 1 -O-C (= O} ) -Y 2 - In, Y ¹ and Y ² are divalent hydrocarbon groups that may independently have substituents. Examples of the divalent hydrocarbon group include the same as the “divalent hydrocarbon group which may have a substituent” mentioned in the explanation as the divalent linking group.

As Y ¹ , a linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a linear alkylene group having 1 or more 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.

Formula ^{- [Y 1 -C (= O} ) -O] m '-Y 2 - In the group represented by, m' is an integer of 0 to 3, preferably 0 to 2 integer 0 or 1 is more preferable, and 1 is particularly preferable. That is, the group represented by the formula − [Y ¹ −C (= O) −O] _{m ′} −Y ² − is represented by the formula −Y ¹ −C (= O) −O−Y ^2−. Groups are particularly preferred. Among them, the formula _{- (CH 2) a '-C} (= O) -O- (CH 2) b' - a group represented by are preferred. 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 an integer of 1 or more and 5 or less, still more 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 containing an oxygen atom, for example, an ether bond, or a group containing an ester bond preferably as a hetero atom, formula ^-Y 1 ^-O-Y 2 described above ^{-, - [Y 1 -C (} = ^{_{O) -O] m '-Y 2}} -, or ^{-Y 1 -O-C (= O} ) -Y 2 - , more preferably a group represented by, the above formula ^{- [Y 1 -C (= O} ) -O] _{m '-Y} ² -, or ^{-Y 1 -O-C (= O} ) -Y 2 - is particularly desirable.

As the ^{divalent linking group in R 12b,} those containing an alkylene group or an ester bond (-C (= O) -O-) are preferable.

The alkylene group is preferably a linear or branched alkylene group. Preferable examples of the linear aliphatic hydrocarbon group include methylene group [−CH ₂ −], ethylene group [− (CH ₂ ) ₂ −], trimethylene group [− (CH ₂ ) ₃ −], a tetramethylene group _{[- (CH 2) 4 -} ], and a pentamethylene group _{[- (CH 2) 5 -} ] , and the like. Preferable examples of the branched alkylene group are -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, -C (CH ₃ ) _2- , -C (CH ₃ ) (CH _2). Alkylene methylene groups such as _{CH 3} )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) _{2- ; -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 - alkyl ethylene such as Group; -CH (CH ₃ ) CH ₂ CH ₂ −, −CH ₂ CH (CH ₃ ) CH ₂ − and other alkyl methylene groups; −CH (CH ₃ ) CH ₂ CH ₂ CH ₂ −, −CH ₂ CH Examples thereof include alkylalkylene groups such as alkyltetramethylene groups such as (CH ₃ ) CH ₂ CH _{2- and the like.}

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 divalent linking group in the above-mentioned 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 −Y ¹ −O−Y ²⁻ , − [Y ¹⁻ C (= O). ^{_{) -O] m '-Y 2 -}} , or ^{-Y 1 -O-C (= O} ) -Y 2 - 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, -Y ^1- OC (= O) -Y ^2- 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 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 those in which R ^11b in the above formula (b-S1) is replaced with a lactone-containing cyclic group, and more specifically, the following formula (b-S1) is used. Examples thereof include the 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 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms; R'is an independent hydrogen atom, alkyl group, and 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, oxygen atom, or sulfur having 1 or more and 5 or less carbon atoms which may contain an oxygen atom or a sulfur atom. 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 in R ', alkoxy group, halogenated alkyl group, -COOR ", - OC (= O) R", The hydroxyalkyl group, respectively, -SO ₂ - may have the 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.

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, tetracycloalkane, which may or may not be substituted with a fluorine atom or an alkyl fluorinated 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.
Examples of A ″ include those similar to A ′ in the above formula (3-1). A ″ is an alkylene group having 1 or more carbon atoms 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-mentioned 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-3-L) is preferably the formula (b-L1). ) To (b-L3), at least one selected from the group consisting of the structural units represented by the above formulas (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). At least one selected from the group consisting of the structural units represented by -14), (b-L3-1), and (b-L3-5) is 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 dissociative group as a structural unit that enhances the solubility of the acrylic resin (B3) in 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 R 15b to} R ^17b 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 to 6 carbon atoms or an aliphatic cyclic group having 5 to 20 carbon atoms, and each independently has a linear chain having 1 to 6 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. May form a hydrocarbon ring having 5 or more and 20 or less carbon atoms, 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 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. Can be mentioned. The fluorinated alkyl group is one in which a part or all of the hydrogen atom of the alkyl group is replaced by 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 adamantane, 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 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 adamantane, 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 other polar groups, and linear or branched alkyl groups having 1 to 4 carbon atoms. 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 adamantane, 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 a 1-methoxyethyl group, a 1-ethoxyethyl group, a 1-n-propoxyethyl group, and a 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 -Ethoxy-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-Esterethyl (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 radical 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) (Meta) acrylic acid alkyl esters such as acrylate and cyclohexyl (meth) acrylate; (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; phenyl ( (Meth) acrylic acid aryl esters such as meta) acrylate and benzyl (meth) acrylate; 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 Binitrile group-containing polymerizable compounds such as bnitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylicamide; 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 rectangular shape having a good 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 preferably used 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-dissociable aliphatic polycyclic group, a tricyclodecanyl group, an adamantyl group, a tetracyclododecanyl group, an isobornyl group, a norbornyl group and the like are particularly preferable in terms of being easily available industrially. These aliphatic polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.

Specific examples of the (meth) acrylic acid esters having an acid-non-dissociable 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.

Acrylic resin (B3) is, -SO ₂ - containing cyclic group, or containing a structural unit containing a lactone-containing cyclic group (b-3), the structural units in the acrylic resin (B3) (b-3) 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-dissociable aliphatic polycyclic group. The content of the structural unit derived from the (meth) acrylic acid ester having an acid-non-dissociable aliphatic polycyclic group in the acrylic resin (B3) is preferably 0% by mass or more and 50% by mass or less. 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 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, it is possible to maintain sufficient strength of the photosensitive resin layer without lowering the peelability from the substrate, and further, it is possible to prevent profile swelling and cracks during plating. can.

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 dispersion degree, 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.

<Mercapt compound (C)>
The photosensitive resin composition contains a mercapto compound (C) represented by the following formula (C1). Therefore, when the resist pattern is formed using the photosensitive resin composition, the occurrence of footing is suppressed.

（式（Ｃ１）中、Ｒ^ｃ１は（ｎ１＋ｎ２）価の有機基であり、Ｒ^ｃ１は、Ｃ−Ｃ結合によってカルボニル基と結合し、且つＣ−Ｓ結合によってメルカプト基と結合し、Ｒ^ｃ２及びＲ^ｃ３は、それぞれ独立に水素原子、又は１価の有機基であり、ｎ１は、１以上４以下の整数であり、ｎ２は、１以上４以下の整数であり、
ただし、Ｒ^ｃ２及びＲ^ｃ３の少なくとも一方が、環構造中に−ＣＯ−Ｏ−で表される２価基を含む脂肪族環ＣＬを有する１価の有機基、環構造中に−ＳＯ_２−で表される２価基を含む脂肪族環ＣＳを有する１価の有機基、又は環構造中に下記式：

で表される３価基を含む脂肪族環ＣＰを有する１価の有機基であるか、Ｒ^ｃ２とＲ^ｃ３とが結合して、脂肪族環ＣＬ、脂肪族環ＣＳ、又は脂肪族環ＣＰを形成している。）
なお、式（Ｃ１）中の−ＣＨＲ^ｃ２Ｒ^ｃ３で表される基は、酸発生剤（Ａ）が露光により発生させる酸により脱離しない基であるのが好ましい。

(In the formula (C1), R ^c1 is a (n1 + n2) valent organic group, and R ^c1 is bonded to a carbonyl group by a CC bond and a mercapto group by a CS bond, and R ^c2 and R ^c3 is independently a hydrogen atom or a monovalent organic group, n1 is an integer of 1 or more and 4 or less, and n2 is an integer of 1 or more and 4 or less.
However, ^{at least one of R c2} and R ^c3 is a monovalent organic group having an aliphatic ring CL containing a divalent group represented by -CO-O- in the ring structure, and -SO _{2- in the ring structure.} A monovalent organic group having an aliphatic ring CS containing a divalent group represented by, or the following formula in the ring structure:

It is a monovalent organic group having an aliphatic ring CP containing a trivalent group represented by, or R ^c2 and R ^c3 are combined to form an aliphatic ring CL, an aliphatic ring CS, or an aliphatic ring CP. Is forming. )
^{The group represented by −CHR c2} R ^c3 in the formula (C1) is preferably a group that is not desorbed by the acid generated by the acid generator (A) by exposure.

R ^c1 is a (n1 + n2) valent organic group. The (n1 + n2) valent organic group as R ^{c1 may contain a heteroatom.} However, in the mercapto compound represented by the formula (C1), R ^c1 is bonded to the carbonyl group by the CC bond and is bonded to the mercapto group by the CS bond.
That is, ^{each bond possessed by the organic group as R c1} is bonded to the carbon atom in the organic group.
Further, the divalent organic group may have an unsaturated bond.

Examples of the hetero atom that the organic group as R ^c1 may contain include a halogen atom, an oxygen atom, a nitrogen atom, a phosphorus atom, a silicon atom and the like. The heteroatom may be present in the substituents attached to the main skeleton of the divalent organic group or as part of the bonds constituting the divalent organic group.

Examples of substituents containing a hetero atom include halogen atom, hydroxyl group, mercapto 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 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 an alkoxy 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 a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group, a cyclononyloxy group, and a 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 decanoyyl 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 acetyloxy group, propionyloxy group, butanoyloxy group, pentanoyloxy group, hexanoyloxy group, octanoyloxy group, nonanoyloxy group, decanoyyloxy group, benzoyloxy group and naphthalene. Examples thereof include 1-ylcarbonyloxy group and naphthalene-2-ylcarbonyloxy group.

Preferable 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 the cyclodecyloxycarbonyl group.

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 to 6 carbon atoms and a cyclo having 3 to 10 carbon atoms, which may be linear or branched. 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.
Preferable 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 N, N-di-substituted amino groups are dimethylamino group, diethylamino group, din-propylamino group, diisopropylamino group, din-butylamino group, diisobutylamino group, 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, 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-naphthalene-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.
Suitable examples of N, N-di-substituted carbamoyl groups 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-di n-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.

Regarding R ^c1 , specific examples of the bond containing a heteroatom which may be contained in a divalent organic group include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, and a urethane bond. , Imino bond (-N = C (-R)-, -C (= NR)-: R indicates a hydrogen atom or an organic group), carbonate bond, sulfonyl bond, sulfinyl bond, azo bond and the like.

As R ^c1 , a hydrocarbon group having 1 to 20 carbon atoms is preferable, and a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferable. Preferably, a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms is more preferable, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms is particularly preferable, and a saturated aliphatic hydrocarbon having 1 to 6 carbon atoms is particularly preferable. Hydrocarbon groups are most preferred.
When R ^c1 is a saturated aliphatic hydrocarbon group, the saturated aliphatic hydrocarbon group may be linear or branched chain, and linear is preferable.

When R ^c1 is an aromatic hydrocarbon group, a divalent aromatic hydrocarbon group is preferable as the aromatic hydrocarbon group because the compound represented by the formula (C1) can be easily synthesized and obtained. Preferable specific examples of the divalent aromatic hydrocarbon group for R ^c1 are p-phenylene group, m-phenylene group, p-phenylene group, naphthalene-2,6-diyl group and naphthalene-2,7-. Examples thereof include a diyl group, a naphthalene-1,4-diyl group, and a biphenyl-4,4'-diyl group.
Among these, p-phenylene group, m-phenylene group, naphthalene-2,6-diyl group, and biphenyl-4,4'-diyl group are preferable, and p-phenylene group, naphthalene-2,6-diyl group. , And biphenyl-4,4'-diyl groups are more preferred.

When R ^c1 is a saturated aliphatic hydrocarbon group, an alkylene group is preferable as the saturated aliphatic hydrocarbon group because the compound represented by the formula (C1) can be easily synthesized and obtained. With ^{respect to R c1} , suitable specific examples of the alkylene group include a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5-. Diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonan-1,9-diyl group, and decan-1,10-diyl group. Be done.
Among these, methylene group, ethane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, and hexane-1,6 The −diyl group is preferable, the methylene group, the ethane-1,2-diyl group, and the propane-1,3-diyl group are more preferable, and the methylene group and the ethane-1,2-diyl group are particularly preferable.

で表される３価基を含む脂肪族環ＣＰを有する１価の有機基であるか、Ｒ^ｃ２とＲ^ｃ３とが結合して、脂肪族環ＣＬ、脂肪族環ＣＳ、又は脂肪族環ＣＰを形成している。 In formula (C1), ^{at least one of R c2} and R ^c3 is a monovalent organic group having an aliphatic ring CL containing a divalent group represented by -CO-O- in the ring structure, in the ring structure. -SO 2 _- 1 monovalent organic group having an aliphatic ring CS containing divalent group represented by, or the following formula in the ring structure:

It is a monovalent organic group having an aliphatic ring CP containing a trivalent group represented by, or R ^c2 and R ^c3 are combined to form an aliphatic ring CL, an aliphatic ring CS, or an aliphatic ring CP. Is forming.

（式（ｃ−Ｌ１）〜（ｃ−Ｌ７）中、Ｒ’、ｓ”、Ａ”、及びｒは、式（ｂ−Ｌ１）〜（ｂ−Ｌ７）と同様である。） Aliphatic when at least one of R ^c2 and R ^c3 is a monovalent organic group having the above-mentioned aliphatic ring CL, or when R ^c2 and R ^c3 are combined to form an aliphatic ring CL. Preferable examples of a monovalent organic group having a ring CL or ^{a cyclic group containing an aliphatic ring CL represented by −CHR c2} R ^c3 are the above-mentioned formulas (b-L1) to (b-L7). Examples of the groups represented by the following formulas (c-L1) to (c-L7) included in.

(In the formulas (c-L1) to (c-L7), R', s ", A", and r are the same as those in the formulas (b-L1) to (b-L7).)

（式（Ｃ２−１）〜（Ｃ２−５）中、Ｒ^ｙは、水素原子、メチル基、又はエチル基であり、ｓは、１又は２である。） The monovalent organic group having an aliphatic ring CL or the ^{cyclic group containing an aliphatic ring CL represented by −CHR c2} R ^c3 is represented by the following formulas (C2-1) to (C2-5). It may be a group other than the group to be used.

(In formulas (C2-1) to (C2-5), ^Ry is a hydrogen atom, a methyl group, or an ethyl group, and s is 1 or 2.)

Aliphatic when at least one of R ^c2 and R ^c3 is a monovalent organic group having the above-mentioned aliphatic ring CL, or when R ^c2 and R ^c3 are combined to form an aliphatic ring CL. Suitable specific examples of a monovalent organic group having a ring CL or a cyclic group containing an aliphatic ring CL represented by ^{−CHR c2} R ^{c3 are described below.} However, among the following groups, the group whose bonder is bonded to the tertiary carbon atom is excluded from the example of the cyclic group containing the aliphatic ring CL represented by ^{−CHR c2} R ^c3.

（式（３−１）〜（３−４）中、の略号の定義については前述した通りである。） Aliphatic when at least one of R ^c2 and R ^c3 is a monovalent organic group having the above-mentioned aliphatic ring CS, or when R ^c2 and R ^c3 are combined to form an aliphatic ring CS. Preferable examples of a monovalent organic group having a ring CS or ^{a cyclic group containing an aliphatic ring CS represented by −CHR c2} R ^c3 are the above-mentioned formulas (3-1) to (3-4). The group represented by is mentioned.

(Definition of abbreviations in equations (3-1) to (3-4) is as described above.)

Aliphatic when at least one of R ^c2 and R ^c3 is a monovalent organic group having the above-mentioned aliphatic ring CS, or when R ^c2 and R ^c3 are combined to form an aliphatic ring CS. Suitable specific examples of a monovalent organic group having a ring CS or a cyclic group containing an aliphatic ring CS represented by ^{−CHR c2} R ^{c3 are described below.} However, among the following groups, the group whose bonder is bonded to the tertiary carbon atom is excluded from the example of the cyclic group containing the aliphatic ring CS represented by ^{−CHR c2} R ^c3.

When ^{at least one of R c2} and R ^c3 is a monovalent organic group having the above-mentioned aliphatic ring CP, the monovalent organic group having the aliphatic ring CP is represented by the following formula (C-P1). The groups to be used are mentioned. When R ^c2 and R ^c3 combine to form an aliphatic ring CP, a preferable example of a cyclic group containing an aliphatic ring CP represented by ^{−CHR c2} R ^{c3 is the following formula (C).} The group represented by −P2) can be mentioned.

In formula (C1), R ^c2 and R ^c3 are independently monovalent organic groups. R ^c2 and R ^c3 are neither monovalent organic groups having an aliphatic ring CL, monovalent organic groups having an aliphatic ring CS, or monovalent organic groups having an aliphatic ring CP, and R ^{When c2} and R ^c3 are not bound to each other to form an aliphatic ring CL, an aliphatic ring CS, or an aliphatic ring CP, R ^c2 and R ^c3 may each have a substituent. It is preferably a group. The substituents that the hydrocarbon group may have are the same as the substituents that the divalent hydrocarbon group for ^{R c1 may have.}

As the hydrocarbon group as R ^c2 and R ^c3 , an alkyl group, an alkenyl group, or an aromatic hydrocarbon group is preferable.
The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 or more and 6 or less. Preferable examples of alkyl groups are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and n-hexyl group. Can be mentioned.
The alkenyl group may be linear or branched. The number of carbon atoms of the alkenyl group is preferably 2 or more and 6 or less. Preferable examples of the alkenyl group include a vinyl group, an allyl group (2-propenyl group), a 3-butenyl group, a 4-pentenyl group, and a 5-hexenyl group.
The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 or more and 20 or less, and more preferably 6 or more and 12 or less. Preferable examples of the aromatic hydrocarbon group include a phenyl group, a naphthalene-1-yl group, and a naphthalene-2-yl group.

Among the groups described above, the hydrocarbon groups as R ^c2 and R ^c3 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-pentyl group, n-hexyl group and vinyl. A group, an allyl group, and a phenyl group are preferable, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a vinyl group, and a phenyl group are more preferable.

The method for producing the mercapto compound represented by the formula (C1) is not particularly limited, and for example, it can be synthesized according to Scheme 1 below.
Specifically, first, the mercapto group in the carboxylic acid compound having a mercapto group represented by the following formula (C1-a) is ^{selectively protected by the protecting group Xc} , and the following formula (C1-b) is used. Obtain the carboxylic acid compound represented. Examples of the mercapto group protected by the protecting group X ^c include groups having a structure represented by the following formulas (X-1) to (X-3).
R ^x1 -SS-... (X-1)
R ^x1- (C = O) -S-... (X-2)
R ^x1- S-CR ^x2 R ^x3 -S-... (X-3)
R ^x1 is a hydrocarbon group. R ^x2 and R ^x3 are independently hydrogen atoms or hydrocarbon groups, respectively. As the hydrocarbon group, an alkyl group and an aryl group are preferable. As the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group and an ethyl group are particularly preferable. As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 12 carbon atoms is more preferable, and a phenyl group, a naphthalene-1-yl group, and a naphthalene-2-yl group are preferable. Is more preferable, and a phenyl group is particularly preferable.
As the protecting group X ^{c , a group represented by R x1-} (C = O)-is preferable, an aliphatic acyl group is more preferable, and an acetyl group or a propionyl group is preferable because protection and deprotection are easy. Particularly preferred, most preferred is an acetyl group.

Next, the ester compound represented by the formula (C1-d) is obtained from the carboxylic acid compound represented by the formula (C1-b) and the alcohol represented by the following formula (C1-c).
The method of esterification is not particularly limited. As a suitable esterification method, a carbodiimide compound which is a condensing agent is allowed to act in the presence of a small amount of N, N-dimethyl-4-aminopyridine to form a carboxylic acid compound represented by the formula (C1-b) and a formula. Examples thereof include a method of condensing with an alcohol represented by (C1-c). Further, the carboxylic acid compound represented by the formula (C1-b) is reacted with a halogenating agent such as thionyl chloride or phosphorus trichloride to generate a carboxylic acid halide, and then the carboxylic acid halide is expressed by the formula (C1-c). ) May be reacted with the alcohol.

^{By deprotecting the protecting group Xc in} the obtained ester compound represented by the formula (C1-d), the mercapto compound represented by the formula (C1) can be obtained. The deprotection method is not particularly limited, and is appropriately selected depending on the type of ^{protecting group Xc.}

<Scheme 1>

When n1 is 1 in the mercapto compound represented by the formula (C1), for example, the compound represented by the formula (C1) can be satisfactorily synthesized by the following scheme 2.
In the method described in Scheme 2, a symmetric polycarboxylic acid compound having a disulfide bond in the center, which is represented by the following formula (C1-e), is used as a raw material. First, the polycarboxylic acid compound represented by the formula (C1-e) is reacted with the alcohol represented by the formula (C1-c) to obtain an ester compound represented by the formula (C1-f). This esterification reaction is carried out in the same manner as the reaction between the carboxylic acid compound represented by the formula (C1-b) in Scheme 1 and the alcohol represented by the formula (C1-c).

Then, by cleaving the disulfide bond in the ester compound represented by the formula (C1-f), it is represented by the formula (C1) and represented by the formula (c1-g) as a compound in which n1 is 1. Generate a mercapto compound. The method for cleaving the disulfide bond is not particularly limited. Suitable methods include a method of reacting an ester compound represented by the formula (C1-f) with a base such as triethylamine and dithiothreitol.

In the formulas (C1-a) to (C1-g) shown in Scheme 1 and Scheme 2, R ^c1 , R ^c2 , R ^c3 , n1 and n2 are synonymous with the formula (C1).

<Scheme 2>

As the mercapto compound represented by the formula (C1) described above, the compound of the following formula is preferable. In the following formula, R ^c0 is ^{represented by −CHR c2} R ^c3 and is a cyclic group containing an aliphatic ring CL, an aliphatic ring CS, or an aliphatic ring CP. In R ^c0 , R ^c2 and R ^c3 are coupled to each other to form a ring.

Suitable specific examples of the mercapto compound represented by the formula (C1) are described below.

Further, as described above, the ester compound represented by the following formula (C1-d) and the ester compound having a disulfide bond represented by the formula (C1-f) are intermediate between the compounds represented by the formula (C1). It is preferably used as a body.

（式（Ｃ１−ｄ）中、Ｒ^ｃ１、Ｒ^ｃ２、Ｒ^ｃ３、ｎ１、及びｎ２は式（Ｃ１）と同様であり、Ｘ^ｃはメルカプト基に対する保護基である。）

(In the formula (C1-d), R ^c1 , R ^c2 , R ^c3 , n1, and n2 are the same as those in the formula (C1), and X ^c is a protecting group against the mercapto group.)

（式（Ｃ１−ｆ）中、Ｒ^ｃ１は（１＋ｎ２）価の有機基であり、Ｒ^ｃ１は、Ｃ−Ｃ結合によってカルボニル基と結合し、且つＣ−Ｓ結合によって硫黄原子と結合し、Ｒ^ｃ２、Ｒ^ｃ３、及びｎ２は式（Ｃ１）と同様である。）

(In the formula (C1-f), R ^c1 is a (1 + n2) -valent organic group, and R ^c1 is bonded to a carbonyl group by a CC bond and a sulfur atom by a CS bond. ^c2 , R ^c3 , and n2 are the same as in equation (C1).)

^{As for the protecting group X c} in the formula (C1-d), as ^{described above, the group represented by R x1} − (C = O) − is preferable from the viewpoint of easy protection and deprotection, and the aliphatic acyl group is preferable. Groups are more preferred, acetyl or propionyl groups are particularly preferred, and acetyl groups are most preferred.
Preferable specific examples of the compound represented by the formula (C1-d) include the following compounds.

Preferable specific examples of the compound represented by the formula (C1-f) include the following compounds.

The mercapto compound (C) is used in a range of 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, and is 0.05. It is particularly preferable to use it in the range of 1 part by mass or more and 2 parts by mass or less. When the amount of the mercapto compound (C) added is 0.01 parts by mass or more, it is effective in suppressing footing, and when it is 5 parts by mass or less, a good plated model can be formed.

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 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 effect of acid deactivation on the substrate surface.
In this respect, when the photosensitive resin composition contains a mercapto compound, it is easy to suppress the deactivation of the acid on the surface of the substrate, and as a result, it is easy to suppress the footing.
The mercapto compound (C) has a mercapto group in its molecule and a highly polar cyclic group containing an aliphatic ring CL, an aliphatic ring CS, or an aliphatic ring CP. Therefore, in the vicinity of the interface between the substrate surface and the coating film, the mercapto compound (C) tends to be oriented so that the mercapto group is located on the substrate surface side and the highly polar cyclic group 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. As a result of the orientation of the mercapto (C) compound, the mercapto compound (C) is efficiently and uniformly distributed on the surface of the substrate.
The mercapto compound (C) is oriented so that the mercapto group is located on the surface side of the substrate, and the mercapto compound (C) is uniformly distributed on the surface of the substrate. ..

<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 resin 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, fluoroglycinol, 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.

The flexibility of the novolak resin can be further improved 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 meta) 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-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic 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 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, crack resistance tends to be improved and 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 an oxo acid of phosphorus 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-oxyquinolin, aclysine, purine, pyrrolidine, piperidine, 2,4,6-tri (2-pyridyl) -S-triazine, morpholin, 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.

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 derivative thereof (E2)]
Of the organic carboxylic acid or phosphorus oxo acid or its derivative (E2), the organic carboxylic acid is specifically malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like. , Particularly salicylic acid is preferred.

Phosphonic 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 such as their esters; phosphonic acid, dimethyl phosphonic acid ester, phosphonic acid- Phosphonates such as di-n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, phosphonic acid dibenzyl ester and derivatives such as their esters; such as 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 its derivative (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 from the organic solvents conventionally used in positive photosensitive resin compositions. ..

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 acetate, 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 , Ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate and other esters; 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 in 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 adhesion 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. Specific examples of surfactants include BM-1000 and BM-1100 (all manufactured by BM Chemie), Megafuck F142D, Megafuck F172, Megafuck F173, and Megafuck F183 (all manufactured by Dainippon Ink and Chemicals Co., Ltd.). ), Florard FC-135, Florard FC-170C, Florard FC-430, Florard FC-431 (all manufactured by Sumitomo 3M Ltd.), Surfron S-112, Surfron S-113, Surfron S-131, Surfron S-141, Commercially available fluorine-based surfactants such as 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.) are listed. However, it is not limited to these.

In addition, 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, cinnamic acid; lactic acid, 2-hydroxybutyric acid, Hydroxymonocarboxylics such as 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycaterous acid, 3-hydroxycaterous acid, 4-hydroxycaterous acid, 5-hydroxyisophthalic acid, silingic 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-cyclohexanetricarboxylic Polyvalent carboxylic acids such as acids, butanetetracarboxylic acids, trimellitic acids, pyromellitic acids, cyclopentanetetracarboxylic acids, butanetetracarboxylic acids, 1,2,5,8-naphthalenetetracarboxylic acids; itaconic anhydride, anhydrous Succinic acid, citraconic anhydride, dodecenyl succinic anhydride, tricarbanyl anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymic anhydride, 1,2,3,4-butanetetracarboxylic acid anhydride, Cyclopentanetetracarboxylic acid dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol bis anhydride trimeritat, glycerintris anhydride trimeritate and other acid anhydrides; can.

Specific examples of the high boiling point solvent include N-methylformamide, N, N-dimethylformamide, N-methylformamide, 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, phenylcellosolveacetate and the like.

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

<Method for preparing 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, one having light transmittance is preferable. Specific examples thereof include polyethylene terephthalate (PET) film, polypropylene (PP) film, polyethylene (PE) film, etc., 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 have a thickness of 5 to 300 μm, more preferably 1 to 300 μm, and particularly preferably 3 to 100 μm.

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 containing.
The method for manufacturing a substrate with a mold provided with a mold for forming a plated molded product is to manufacture a patterned resist film in the development process, except for creating a mold for forming the plated molded 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. Examples thereof include substrates for electronic components and substrates on which a predetermined wiring pattern is formed. 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 the 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 used 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 200 ° 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 or radiation, for example, ultraviolet rays having a wavelength of 300 nm or more and 500 nm or less or visible light through 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. Dose of radiation varies depending on the film thickness and the like of the composition of the photosensitive resin composition and a photosensitive resin layer, for example, in the case of ultra-high pressure mercury lamp used is 100 mJ / cm ² or more 10000 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 the insoluble portion is dissolved and removed to form a predetermined resist pattern or a mold for forming a plated object. 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, methyldiethylamine, and the like. 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 alkali 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-mentioned aqueous solution of alkalis 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, it is washed with running water for 30 seconds or more and 90 seconds or less, and dried 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, a substrate with a mold having a resist pattern serving as a mold can be manufactured 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 developer) in the mold of the substrate with a mold formed by the above method, for example, a connection terminal such as a bump or a metal post can be formed. Such a plated model can be formed. 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. Finally, the remaining mold is removed using a stripping solution or the like according to a conventional method.

According to the above method, the width of the bottom (support surface side) becomes narrower than the width of the top (surface side of the resist layer) in the non-resist portion, and the mold can be used while suppressing the occurrence of "footing". A resist pattern is formed. By using the substrate provided with the mold in which the footing is suppressed, which is produced in this manner, it is possible to produce a plated molded product 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 C2)
In Preparation Example 1, the mercapto compound C2 having the following structure was synthesized.

Into the flask, 12.0 g of 3,3'-dithiopropionic acid and 120 g of dichloromethane were added, and the contents of the flask were stirred under a nitrogen atmosphere. Next, 2.79 g of N, N-dimethyl-4-aminopyridine, 24.1 g of the carbodiimide compound, and 20.6 g of the alcohol compound represented by the following formula were added to the flask, and the contents of the flask were stirred for 10 hours. ..

Then, the reaction solution was washed 5 times with 60.0 g of pure water, and then the reaction solution was concentrated to obtain 29.0 g of an intermediate represented by the following formula.

25.1 g of the above intermediate and 251 g of dichloromethane were added to the flask, and the contents of the flask were stirred under a nitrogen atmosphere. Next, 6.90 g of triethylamine and 9.90 g of dithiothreitol were added to the flask, and the mixture was stirred at room temperature for 5 hours.
Then, the reaction solution was diluted with 127 g of dichloromethane. The diluted reaction solution was washed with 127 g of a hydrochloric acid aqueous solution having a concentration of 1% by mass, and then washed 5 times with 127 g of pure water. By concentrating the washed reaction solution, 45.0 g of mercapto compound C2 was obtained.
^{1 1} H-NMR (600 MHz, CDCl3): δ4.80-4.70 (d, 2H), 3.60-3.49 (m, 2H), 2.80 (m, 2H), 2.65 (m) , 2H), 2.60 (s, 1H), 2.20-1.90 (m, 3H), 1.80-1.45 (m, 2H)

[Adjustment example 2]
(Synthesis of mercapto compound C1)
In Adjustment Example 2, 10.0 g of 3-acetylthiopropionic acid and 100 g of dichloromethane were added to the flask in which the following mercapto compound C1 was synthesized, and the contents of the flask were stirred under a nitrogen atmosphere. Next, 1.65 g of N, N-dimethyl-4-aminopyridine, 14.3 g of the carbodiimide compound, and 12.3 g of the alcohol compound represented by the following formula were added to the flask, and the contents of the flask were stirred for 10 hours. ..

Then, the reaction solution was washed 5 times with 50.0 g of pure water, and then the reaction solution was concentrated to obtain 16.0 g of an intermediate represented by the following formula.

15.0 g of the above intermediate and 50 g of methanol were added to the flask, and the contents of the flask were stirred under a nitrogen atmosphere. Next, 10 g of a 10% aqueous hydrochloric acid solution was added to the flask, and the mixture was stirred at room temperature for 5 hours. Then, the reaction solution was extracted twice with 100 g of ethyl acetate, the organic phase was washed 3 times with 50 g of pure water, and then concentrated to obtain 10.5 g of mercapto compound C2.
^{1 1} H-NMR (600 MHz, DMSO-d6): δ5.70 (t, 1H), 5.00 (d, 1H), 4.86 (s, 1H), 4.78 (d, 1H), 4. 17 (m, 1H), 2.67 (m, 4H), 2.50 (m, 1H), 2.39-2.21 (m, 2H)

The following mercapto compounds C3 to C9 were obtained by the same method as in Preparation Example 1.

[Examples 1 to 40 and Comparative Examples 1 to 6]
In Examples and Comparative Examples, the compound of the following formula was used as the (A) acid generator.

In Examples and Comparative Examples, the following resins B1 and B2 were used as the resin ((B) resin) whose solubility in alkali was increased by the action of 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.

As the (C) mercapto compound, the above-mentioned mercapto compounds C1 to C9 were used in Examples. In the comparative example, 3-mercaptopropionic acid was used as the mercapto compound C10, and 3-mercaptopropionate ethyl ester was used as the mercapto compound 11.

As the alkali-soluble resin (D), the following resins D1 and D2 were used.
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))

Tables 1 to 3 show the types and amounts of the resin (B), the mercapto compound (C), and the alkali-soluble resin (D), 2.0 parts by mass of the acid generator (A), and trypentylamine 0. 02 parts by mass was dissolved in methoxybutyl acetate so that the solid content concentration was 53% by mass to obtain photosensitive resin compositions of Examples and Comparative Examples.
The amount of the mercapto compound (C) shown in Tables 1 to 3 is 0.02 parts by mass, 0.05 parts by mass, or 0.10 parts by mass.

Using the obtained photosensitive resin composition, the footing was evaluated according to the following method. The results of these evaluations are shown in Table 1.

[Evaluation of footing]
The photosensitive resin compositions of the respective examples and comparative examples were applied onto a copper substrate having a diameter of 8 inches to form a photosensitive resin layer having a film thickness of 55 μm. Then, the photosensitive resin layer was prebaked at 100 ° C. for 5 minutes. After prebaking, using a mask with a square pattern with a diameter of 30 μm and an exposure device Prisma GHI (manufactured by Ultratech), the exposure amount is 1.2 times the minimum exposure amount that can form a pattern of a predetermined size. The pattern was exposed with lines. Then, the substrate was placed on a hot plate and heated (PEB) after exposure at 140 ° C. for 3 minutes. Then, a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (developing solution, NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) is added dropwise to the exposed photosensitive resin layer, and then the mixture is allowed to stand at 23 ° C. for 60 seconds. Was repeated 4 times 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 to measure the amount of footing.
Specifically, the footing amount was measured as follows. FIG. 1 shows a schematic view of a cross section of a resist portion and a non-resist portion when measuring the footing amount. In FIG. 1, a resist pattern including a resist portion 12 and a non-resist portion 13 (hole) is formed on the substrate 11. First, on the side wall 14 which is the interface between the resist portion 12 and the non-resist portion 13, the inflection point 15 where the footing on the side wall 14 starts is determined. A perpendicular line 16 was drawn from the inflection point 15 toward the surface of the substrate 11, and the intersection of the perpendicular line 16 and the surface of the substrate 11 was set as the footing start point 17. Further, the intersection of the curve of the side wall 14 and the surface of the substrate 11 is set as the footing end point 18. The width Wf between the footing start point 17 and the footing end point 18 defined in this way was defined as the footing amount. The footing amount is a value measured for any one side wall 14 of any one non-resist portion in the resist pattern. From the obtained value of the footing amount, the degree of footing was evaluated according to the following criteria.
<Footing evaluation criteria>
◯: 0 μm or more and 1.5 μm or less Δ: 1.5 μm or more and 2.5 μm or less ×: 2.5 μm or more

According to Examples 1 to 40, 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 alkali is increased by the action of the acid, further described above. It can be seen that when a resist pattern is formed using a positive photosensitive resin composition containing the mercapto compound (C) represented by the formula (C1), footing is suppressed in the resist pattern.

On the other hand, according to Comparative Examples 1 to 6, the positive photosensitive resin composition does not contain the mercapto compound having the structure represented by the formula (C1), or has a structure other than that represented by the formula (C1). It can be seen that when the mercapto compound (C) having a structure is contained, it is difficult to suppress the occurrence of footing.

11 Substrate 12 Resist part 13 Non-resist part 14 Side wall 15 Inflection point 16 Perpendicular line 17 Footing start point 18 Footing end point

Claims (8)

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 the following formula (C1):

(In the formula (C1), R ^c1 is a (n1 + n2) valent organic group, and R ^c1 is bonded to a carbonyl group by a CC bond and a mercapto group by a CS bond, and R ^c2 and R ^c3 is independently a hydrogen atom or a monovalent organic group, n1 is an integer of 1 or more and 4 or less, and n2 is an integer of 1 or more and 4 or less.
However, ^{at least one of R c2} and R ^c3 is a monovalent organic group having an aliphatic ring CL containing a divalent group represented by -CO-O- in the ring structure, and -SO _{2- in the ring structure.} A monovalent organic group having an aliphatic ring CS containing a divalent group represented by, or the following formula in the ring structure:

It is a monovalent organic group having an aliphatic ring CP containing a trivalent group represented by, or R ^c2 and R ^c3 are combined to form the aliphatic ring CL, the aliphatic ring CS, or the fat. It forms a family ring CP. )
A chemically amplified positive photosensitive resin composition containing the mercapto compound (C) represented by. The chemically amplified positive photosensitive resin composition according to claim 1, further comprising an alkali-soluble resin (D). The second aspect of claim 2, 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. The chemically amplified positive photosensitive according to any one of claims 1 to 3, which has a base film and a photosensitive resin layer formed on the surface of the base film. A photosensitive dry film made of a resin composition. Production of a photosensitive dry film, which comprises applying the chemically amplified positive photosensitive resin composition according to any one of claims 1 to 3 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 3 on a substrate having a metal surface.
An exposure step of irradiating the photosensitive resin layer with active rays or radiation in a regioselective manner.
A method for producing a patterned resist film, which comprises a developing step of developing the photosensitive resin layer after exposure. A laminating step of laminating a photosensitive resin layer having a chemically amplified positive photosensitive resin composition according to any one of claims 1 to 3 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 prepare a mold for forming a plated molded product. A method for producing a plated molded product, which comprises a step of plating a substrate with a mold manufactured by the method according to claim 7 to form a plated molded product in the mold.

Images