JP7125253B2 - A chemically amplified positive photosensitive resin composition, a photosensitive dry film, a method for producing a photosensitive dry film, a method for producing a patterned resist film, a method for producing a substrate with a template, and a method for producing a plated model, and Mercapto compound - Google Patents

Description

The present invention provides a chemically amplified positive photosensitive resin composition, a photosensitive dry film comprising a photosensitive resin layer made of the chemically amplified positive photosensitive resin composition, a method for producing the photosensitive dry film, A method for producing a patterned resist film using the chemically amplified positive photosensitive resin composition described above, a method for producing a substrate with a template using the chemically amplified positive photosensitive resin composition described above, and with the template and a method for manufacturing a plated model using a substrate.

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

In recent years, with the downsizing of electronic equipment, high-density mounting technology for semiconductor packages has progressed. Based on this, the improvement of the mounting density is attempted. In such high-density mounting technology, connection terminals include protruding electrodes (mounting terminals) such as bumps protruding from the package, and metal posts that connect rewiring extending from peripheral terminals on a wafer to mounting terminals. etc. are arranged on the substrate with high precision.

A photoresist composition is used in the photofabrication as described above. As such a photoresist composition, a chemically amplified photoresist composition containing an acid generator is known (Patent Documents 1 and 2, etc.). ). In a chemically amplified photoresist composition, radiation (exposure) generates an acid from an acid generator, and heat treatment promotes the diffusion of the acid, causing an acid catalytic reaction with the base resin and the like in the composition. Alkali solubility is changed.

Such a chemically amplified positive photoresist composition is used, for example, in the formation of plated objects such as bumps and metal posts by a plating process. Specifically, using a chemically amplified photoresist composition, a photoresist layer having a desired thickness is formed on a support such as a metal substrate, exposed through a predetermined mask pattern, developed, and bumps. A photoresist pattern used as a mold is formed from which portions for forming metal posts and metal posts are selectively removed (exfoliated). Then, after embedding a conductor such as copper in the removed portion (non-resist portion) by plating, the photoresist pattern around it is removed to form bumps and metal posts.

JP-A-9-176112 JP-A-11-52562

In the formation of connection terminals such as bumps and metal posts by the above plating process, the width of the bottom (surface side of the support) is larger than the width of the top (surface side of the resist layer) for the non-resist part of the resist pattern that serves as the mold. Larger is preferred. By doing so, the contact area between the bottom surface of the connection terminal such as a bump or 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 photoresist composition as disclosed in Patent Documents 1 and 2, etc., a resist pattern serving as a mold for forming bumps, metal posts, etc. is formed on a metal substrate. When forming the resist pattern, the resist portion protrudes toward the non-resist portion at the contact surface between the substrate surface and the resist pattern, and as a result, the width of the bottom of the non-resist portion is narrower than the width of the top, resulting in "footing". .
For this reason, when using a conventionally known chemically amplified positive photoresist composition as disclosed in Patent Documents 1, 2, etc., the non-resist portion where the bottom width is larger than the top width on the metal substrate It is difficult to form a resist pattern with

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

The present inventors have made intensive studies to achieve the above objects, and as a result, found that the above problems can be solved by incorporating a mercapto compound having a specific structure into a chemically amplified positive photosensitive resin composition. , have completed the present invention. Specifically, the present invention provides the following.

（式（Ｃ１－１）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、Ｒ^ｃ４は炭化水素基であり、Ｒ^ｃ２、Ｒ^ｃ３、及びＲ^ｃ４が結合する炭素原子は、第３級炭素原子であり、Ｒ^ｃ３とＲ^ｃ４とは、互いに結合して環を形成してもよく、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、エーテル結合、スルフィド結合、及びカルボニル基から選択される１種以上の２価基を含む脂肪族環ＣＡを有する１価の有機基、水酸基、又は水酸基含有基で置換された脂肪族環ＣＨを有する１価の有機基、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ＣＡ、脂肪族環ＣＨ、脂肪族環ＣＬ、脂肪族環ＣＳ、又は脂肪族環ＣＰを形成している。）

（式（Ｃ１－２）中、Ｒ^ｃ１、Ｒ^ｃ２、Ｒ^ｃ３、ｎ１、及びｎ２は、式（Ｃ１－１）と同様であり、Ｒ^ｃ５は、Ｒ^ｃ６、及びＲ^ｃ７は、それぞれ独立に水素原子、又はアルキル基であり、Ｒ^ｃ５及びＲ^ｃ６は、互いに結合して環を形成してもよく、
ただし、Ｒ^ｃ２及びＲ^ｃ３の少なくとも一方が、脂肪族環ＣＡを有する１価の有機基、脂肪族環ＣＨを有する１価の有機基、脂肪族環ＣＬを有する１価の有機基、脂肪族環ＣＳを有する１価の有機基、又は脂肪族環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ＣＡ、脂肪族環ＣＨ、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。 A first aspect of the present invention comprises an acid generator (A) that generates an acid upon irradiation with an actinic ray or radiation, a resin (B) that increases solubility in alkali by the action of the acid, and the following formula (C1- 1), or (C1-2):

(In formula (C1-1), R ^c1 is a (n1+n2)-valent organic group, R ^c1 is bonded to a carbonyl group via a C—C bond, and is bonded to a mercapto group via a C—S bond, and R ^c2 and R ^c3 are each independently a hydrogen atom or a monovalent organic group, R ^c4 is a hydrocarbon group, and the carbon atom to which R ^c2 , R ^c3 and R ^c4 are bonded is a tertiary carbon an atom, R ^c3 and R ^c4 may be bonded to each other to form a ring, n1 is an integer of 1 or more and 4 or less, n2 is an integer of 1 or more and 4 or less,
provided that at least one of R ^c2 and R ^c3 is a monovalent organic group having an aliphatic ring CA containing one or more divalent groups selected from an ether bond, a sulfide bond, and a carbonyl group in the ring structure , a hydroxyl group, or a monovalent organic group having an aliphatic ring CH substituted with a hydroxyl group-containing group, a monovalent ring having an aliphatic ring CL containing a divalent group represented by -CO-O- in the ring structure an organic group, a monovalent organic group having an aliphatic ring CS containing a divalent group represented by —SO ₂ — in the ring structure, or the following formula in the ring structure:

Is a monovalent organic group having an aliphatic ring CP containing a trivalent group represented by
R ^c2 and R ^c3 combine to form an aliphatic ring CA, an aliphatic ring CH, an aliphatic ring CL, an aliphatic ring CS, or an aliphatic ring CP. )

(In formula (C1-2), R ^c1 , R ^c2 , R ^c3 , n1, and n2 are the same as in formula (C1-1), and R ^c5 , R ^c6 , and R ^c7 are each independently a hydrogen atom or an alkyl group, and R ^c5 and R ^c6 may be bonded to each other to form a ring,
provided that at least one of R ^c2 and R ^c3 is a monovalent organic group having an aliphatic ring CA, a monovalent organic group having an aliphatic ring CH, a monovalent organic group having an aliphatic ring CL, an aliphatic a monovalent organic group having a ring CS or a monovalent organic group having an aliphatic ring CP;
R ^c2 and R ^c3 combine to form an aliphatic ring CA, an aliphatic ring CH, an aliphatic ring CL, an aliphatic ring CS, or an aliphatic ring CP. )
A chemically amplified positive photosensitive resin composition containing a mercapto compound (C) represented by

A second aspect of the present invention has a substrate film and a photosensitive resin layer formed on the surface of the substrate film, wherein the photosensitive resin layer is a chemically amplified positive photosensitive film 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 coating a substrate film with the chemically amplified positive photosensitive resin composition according to the first aspect to form a photosensitive resin layer. is a manufacturing method.

A fourth aspect of the present invention is
A lamination 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 step of position-selectively irradiating the photosensitive resin layer with actinic rays or radiation;
and a developing step of developing the exposed photosensitive resin layer.

A fifth aspect of the present invention is
A lamination 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 step of position-selectively irradiating the photosensitive resin layer with actinic rays or radiation;
and a developing step of developing a photosensitive resin layer after exposure to form a mold for forming a plated molded article.

A sixth aspect of the present invention is a method for producing a plated modeled article, including the step of plating the substrate with a mold manufactured by the method according to the fifth aspect to form a plated modeled article in the mold. .

（式（Ｃ１－１）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、Ｒ^ｃ４は炭化水素基であり、Ｒ^ｃ２、Ｒ^ｃ３、及びＲ^ｃ４が結合する炭素原子は、第３級炭素原子であり、Ｒ^ｃ３とＲ^ｃ４とは、互いに結合して環を形成してもよく、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、エーテル結合、スルフィド結合、及びカルボニル基から選択される１種以上の２価基を含む脂肪族環ＣＡを有する１価の有機基、水酸基、又は水酸基含有基で置換された脂肪族環ＣＨを有する１価の有機基、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ＣＡ、脂肪族環ＣＨ、脂肪族環ＣＬ、脂肪族環ＣＳ、又は脂肪族環ＣＰを形成している。）

（式（Ｃ１－２）中、Ｒ^ｃ１、Ｒ^ｃ２、Ｒ^ｃ３、ｎ１、及びｎ２は、式（Ｃ１－１）と同様であり、Ｒ^ｃ５は、Ｒ^ｃ６、及びＲ^ｃ７は、それぞれ独立に水素原子、又はアルキル基であり、Ｒ^ｃ５及びＲ^ｃ６は、互いに結合して環を形成してもよく、
ただし、Ｒ^ｃ２及びＲ^ｃ３の少なくとも一方が、脂肪族環ＣＡを有する１価の有機基、脂肪族環ＣＨを有する１価の有機基、脂肪族環ＣＬを有する１価の有機基、脂肪族環ＣＳを有する１価の有機基、又は脂肪族環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ＣＡ、脂肪族環ＣＨ、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 (C1-1) or (C1-2):

(In formula (C1-1), R ^c1 is a (n1+n2)-valent organic group, R ^c1 is bonded to a carbonyl group via a C—C bond, and is bonded to a mercapto group via a C—S bond, and R ^c2 and R ^c3 are each independently a hydrogen atom or a monovalent organic group, R ^c4 is a hydrocarbon group, and the carbon atom to which R ^c2 , R ^c3 and R ^c4 are bonded is a tertiary carbon an atom, R ^c3 and R ^c4 may be bonded to each other to form a ring, n1 is an integer of 1 or more and 4 or less, n2 is an integer of 1 or more and 4 or less,
provided that at least one of R ^c2 and R ^c3 is a monovalent organic group having an aliphatic ring CA containing one or more divalent groups selected from an ether bond, a sulfide bond, and a carbonyl group in the ring structure , a hydroxyl group, or a monovalent organic group having an aliphatic ring CH substituted with a hydroxyl group-containing group, a monovalent ring having an aliphatic ring CL containing a divalent group represented by -CO-O- in the ring structure an organic group, a monovalent organic group having an aliphatic ring CS containing a divalent group represented by —SO ₂ — in the ring structure, or the following formula in the ring structure:

Is a monovalent organic group having an aliphatic ring CP containing a trivalent group represented by
R ^c2 and R ^c3 combine to form an aliphatic ring CA, an aliphatic ring CH, an aliphatic ring CL, an aliphatic ring CS, or an aliphatic ring CP. )

(In formula (C1-2), R ^c1 , R ^c2 , R ^c3 , n1, and n2 are the same as in formula (C1-1), and R ^c5 , R ^c6 , and R ^c7 are each independently a hydrogen atom or an alkyl group, and R ^c5 and R ^c6 may be bonded to each other to form a ring,
provided that at least one of R ^c2 and R ^c3 is a monovalent organic group having an aliphatic ring CA, a monovalent organic group having an aliphatic ring CH, a monovalent organic group having an aliphatic ring CL, an aliphatic a monovalent organic group having a ring CS or a monovalent organic group having an aliphatic ring CP;
R ^c2 and R ^c3 combine to form an aliphatic ring CA, an aliphatic ring CH, an aliphatic ring CL, an aliphatic ring CS, or an aliphatic ring CP. )
is a mercapto compound represented by

According to the present invention, using a chemically amplified positive photosensitive resin composition, when forming a resist pattern that serves as a template for a plated model on the metal surface of a substrate having a metal surface, the top in the non-resist portion A chemically amplified positive photosensitive resin composition that can suppress the occurrence of "footing" in which the width of the bottom (surface side of the support) is narrower than the width (surface side of the resist layer), and the chemically amplified positive photosensitive resin composition A photosensitive dry film comprising a photosensitive resin layer made of a type photosensitive resin composition, a method for producing the photosensitive dry film, and a patterned resist film using the chemically amplified positive type photosensitive resin composition described above. It is possible to provide a production method, a method for producing a substrate with a template using the photosensitive resin composition described above, and a method for producing a plated model using the substrate with the template.

FIG. 10 is a diagram schematically showing a cross section of a resist pattern observed when measuring a footing amount in a non-resist portion in the resist pattern in Examples and Comparative Examples;

<<Chemical amplification type positive photosensitive resin composition>>
A chemically amplified positive photosensitive resin composition (hereinafter also referred to as a photosensitive resin composition) contains an acid generator (A) (hereinafter also referred to as an acid generator (A)) that generates an acid upon exposure to actinic rays or radiation. ), a resin (B) whose solubility in alkali increases under the action of acid (hereinafter also referred to as 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 using the photosensitive resin composition is not particularly limited. The photosensitive resin composition is preferably used for forming a thick resist pattern. Specifically, the film thickness of the resist pattern formed using the photosensitive resin composition is preferably 0.5 μm or more, more preferably 0.5 μm or more and 300 μm or less, even more preferably 1 μm or more and 150 μm or less, particularly Most preferably, the thickness is 3 μm or more and 100 μm or less.

The essential or optional components contained in the photosensitive resin composition and the method for producing the photosensitive resin composition are described below.

<Acid generator (A)>
The acid generator (A) is a compound that generates an acid upon irradiation with actinic rays or radiation, and is not particularly limited as long as it is a compound that directly or indirectly generates an acid upon exposure to light. As the acid generator (A), the acid generators of the first to fifth embodiments described below are preferred. Among the acid generators (A) that are preferably used in the photosensitive resin composition, preferable ones are described below as the first to fifth aspects.

A first aspect of the acid generator (A) includes compounds represented by the following formula (a1).

In formula (a1) above, X ^1a represents a sulfur atom or an iodine atom with a valence of g, where 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 , and is an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, represents an alkenyl group having 2 to 30 carbon atoms or an alkynyl group having 2 to 30 carbon atoms, and R ^1a is alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthio at least one selected from the group consisting of carbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, and nitro groups, and halogen seeds may be substituted. The number of R ^1a is g+h(g−1)+1, and each R ^1a may be the same or different. Two or more R ^1a may be directly connected to each other, or —O—, —S—, —SO—, —SO ₂ —, —NH—, —NR ^2a —, —CO—, —COO—, —CONH— , an alkylene group having 1 to 3 carbon atoms, or a phenylene group to form a ring structure containing X ^1a . R ^2a is an alkyl group having 1 to 5 carbon atoms or aryl group having 6 to 10 carbon atoms.

^X2a is a structure represented by the following formula (a2).

In the above formula (a2), X ^4a is 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. X ^4a is selected from the group consisting of alkyl having 1 to 8 carbon atoms, alkoxy having 1 to 8 carbon atoms, aryl having 6 to 10 carbon atoms, hydroxy, cyano, nitro groups, and halogen It may be substituted with at least one selected. X ^5a is -O-, -S-, -SO-, -SO ₂ -, -NH-, -NR ^2a -, -CO-, -COO-, -CONH-, alkylene having 1 to 3 carbon atoms; group, or a phenylene group. h represents the number of repeating units of the structure in parentheses. The h+1 X ^4a and the h X ^5a may be the same or different. ^R2a is the same as defined above.

X ^3a- is a counter ion of onium, and includes a fluorinated alkylfluorophosphate anion represented by the following formula (a17) or a borate anion represented by the following formula (a18).

In formula (a17) above, R ^3a represents an alkyl group in which 80% or more of the hydrogen atoms are substituted with fluorine atoms. j indicates the number and is an integer of 1 or more and 5 or less. j R ^3a may be the same or different.

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

The onium ion in the compound represented by the formula (a1) includes triphenylsulfonium, tri-p-tolylsulfonium, 4-(phenylthio)phenyldiphenylsulfonium, 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-dihydroanthracen-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10 -thia-9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(diphenyl)sulfonio]thioxanthone, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4- (4-benzoylphenylthio)phenyldiphenylsulfonium, diphenylphenacylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, 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- (2-hydroxytetradecyloxy)phenylphenyliodonium, 4-isopropylphenyl(p-tolyl)iodonium, 4-isobutylphenyl(p-tolyl)iodonium, and the like.

Of the onium ions in the compound represented by formula (a1) above, preferred onium ions include sulfonium ions represented by formula (a19) below.

In the above formula (a19), each R ^8a is independently from a hydrogen atom, alkyl, hydroxy, alkoxy, alkylcarbonyl, alkylcarbonyloxy, alkyloxycarbonyl, halogen atom, optionally substituted aryl, arylcarbonyl, represents a group selected from the group consisting of X ^2a has the same meaning as X ^2a in formula (a1) above.

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 -acetophenylthio)phenyl]diphenylsulfonium, 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, preferably has 1 or more and 8 or less carbon atoms, more preferably 1 or more carbon atoms. 4 or less. Specific examples of alkyl groups include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl and tert-butyl; and cyclopropyl, cyclobutyl and cyclopentyl. , cycloalkyl groups such as cyclohexyl, etc., and the ratio of hydrogen atoms in the alkyl groups substituted with fluorine atoms is usually 80% or more, preferably 90% or more, more preferably 100%. If the substitution rate of fluorine atoms is less than 80%, the acid strength of the onium fluorinated alkylfluorophosphate represented by formula (a1) is lowered.

Particularly preferred R ^3a is a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms and having a fluorine atom substitution rate of 100%, and specific examples thereof include CF ₃ and CF ₃ CF. ₂ , _{( CF3} ) _2CF , _CF3CF2CF2 , _{CF3CF2CF2CF2 , ( CF3} ) _{2CFCF2 , CF3CF2 ( CF3} )CF _{, ( CF3} ) _3C 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 ] ⁻ , [ _{( ( CF3} ) _2CFCF2 ) _2PF4 ] ^- _, [ _{( ( CF3} ) _2CFCF2 ) _{3PF3 ]} ^- , [ _{( CF3CF2CF2CF2} ) _{2PF4 ]} ^- , or [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , among which [(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 CFCF ₂ ) ₂ PF ₄ ] ^- is particularly preferred.

Preferred specific examples of the borate anion represented by the formula (a18) include 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 preferred.

As a second embodiment of the acid generator (A), 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2 -(2-furyl)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, etc. of the following formula (a3) Halogen-containing triazine compounds represented by are mentioned.

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

Further, as a third aspect of the acid generator (A), α-(p-toluenesulfonyloxyimino)-phenylacetonitrile, α-(benzenesulfonyloxyimino)-2,4-dichlorophenylacetonitrile, α-(benzene sulfonyloxyimino)-2,6-dichlorophenylacetonitrile, α-(2-chlorobenzenesulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, and oximesulfonate groups and a compound represented by the following formula (a4).

In formula (a4) above, R ^12a represents a monovalent, divalent, or trivalent organic group, and R ^13a represents a substituted or unsubstituted saturated hydrocarbon group, an unsaturated hydrocarbon group, or an aromatic 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 refers to a group of compounds exhibiting physical and chemical properties peculiar to aromatic compounds. , and heteroaryl groups such as thienyl groups. These may have one or more suitable substituents such as halogen atoms, alkyl groups, alkoxy groups, nitro groups, etc. on the ring. Further, R ^13a is particularly preferably an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group and a butyl group. Particularly preferred are compounds in which R ^12a is an aromatic compound group and R ^13a is an alkyl group having 1 to 4 carbon atoms.

As the acid generator represented by the above formula (a4), when n=1, R ^12a is any one of a phenyl group, a methylphenyl group, or a methoxyphenyl group, and R ^13a is a methyl group. Specifically, α-(methylsulfonyloxyimino)-1-phenylacetonitrile, α-(methylsulfonyloxyimino)-1-(p-methylphenyl)acetonitrile, α-(methylsulfonyloxyimino)-1-(p- methoxyphenyl)acetonitrile, [2-(propylsulfonyloxyimino)-2,3-dihydroxythiophen-3-ylidene](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.

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

As the cation moiety of such an onium salt having a naphthalene ring in the cation moiety, 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 having 1 to 6 carbon atoms , 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 each independently linear or branched having 1 to 6 carbon atoms and these terminals may be combined to form a ring.

In the above formula (a6), R ^17a and R ^18a each independently represent a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Represents a branched alkyl group, and R ^19a represents a single bond or an optionally substituted linear or branched alkylene group having 1 to 6 carbon atoms. 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 multiple R ^17a are present, they may be the same or different. Moreover, when multiple R ^18a are present, they may be the same or different from each other.

Among R ^14a , R ^15a , and R ^16a , the number of groups represented by the above formula (a6) is preferably one from the viewpoint of the stability of the compound, and the rest are straight groups having 1 to 6 carbon atoms. It is a chain or branched alkylene group, and these terminals may be combined to form a ring. In this case, the 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.

Further, examples of the substituent that the alkylene group may have include an oxygen atom (in this case, forming a carbonyl group together with the carbon atoms constituting the alkylene group), a hydroxyl group, and the like.

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

Preferred examples of these cation moieties include those represented by the following formulas (a7) and (a8), and the structures represented by the following formula (a8) are particularly preferred.

Such a cation moiety may be an iodonium salt or a sulfonium salt, but a sulfonium salt is preferable from the viewpoint of acid generation efficiency.

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

The anion part of such an acid generator is a fluoroalkylsulfonate ion or an arylsulfonate ion in which some or all of the hydrogen atoms are fluorinated.

The alkyl group in the fluoroalkylsulfonate ion may be linear, branched, or cyclic, having 1 to 20 carbon atoms, and the number of carbon atoms should be 1 to 10, considering the bulkiness of the generated acid and its diffusion distance. is preferred. In particular, branched or ring-shaped ones are preferable because they have a short diffusion distance. Moreover, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, and the like can be mentioned as preferable ones because they can be synthesized at low cost.

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

In the above fluoroalkylsulfonate ion or arylsulfonate ion, when some or all of the hydrogen atoms are fluorinated, the fluorination rate is preferably 10% or more and 100% or less, more preferably 50% or more and 100%. It is below, and it is particularly preferable to replace all the hydrogen atoms with fluorine atoms because the strength of the acid increases. Specific examples of such compounds include trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctane sulfonate, and perfluorobenzenesulfonate.

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

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

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

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

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

The smaller the number of carbon atoms in the alkylene group of X ^a or the number of carbon atoms in the alkyl groups of ^Ya and ^Za , the better the solubility in organic solvents, which is preferable.

Moreover, in the alkylene group of X ^a or the alkyl group of Y ^a or Z ^a , the greater 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 atom-substituted perfluoroalkylene group or perfluoroalkyl group.

Preferable onium salts having a naphthalene ring in the cation moiety 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- bissulfonyldiazomethanes such as dimethylphenylsulfonyl)diazomethane; 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, nitrobenzyl tosylate, dinitrobenzyl tosylate, nitrobenzylsulfonate, nitro Nitrobenzyl derivatives such as benzyl carbonate and dinitrobenzyl carbonate; 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 trifluoromethanesulfonate; benzoin tosylates such as benzoin tosylate and α-methylbenzoin tosylate; other diphenyliodonium salts, triphenylsulfonium salts, phenyldiazonium salts, benzyl carbonate and the like.

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, relative to the total mass of the photosensitive resin composition. is more preferable. By adjusting the amount of the acid generator (A) to be used within the above range, it is easy to prepare a photosensitive resin composition that has good sensitivity, is a uniform solution, and has excellent storage stability.

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

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

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

Examples of the acid dissociable, dissolution inhibiting group represented by R ^1b include groups represented by the following formulas (b2) and (b3), linear, branched, or cyclic alkyl groups having 1 to 6 carbon atoms. 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 to ⁶ carbon atoms; represents a linear, branched or cyclic alkyl group having 1 to 10 atoms, R ^7b represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; represents 0 or 1.

Examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. . Moreover, a cyclopentyl group, a cyclohexyl group, etc. are mentioned as said cyclic alkyl group.

Here, specific examples of the acid dissociable, dissolution inhibiting group represented by the above formula (b2) include a methoxyethyl group, an ethoxyethyl group, an n-propoxyethyl group, an isopropoxyethyl group, an n-butoxyethyl group, isobutoxyethyl group, tert-butoxyethyl group, cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1-ethoxy-1-methylethyl group and the like. Specific examples of the acid-dissociable, dissolution-inhibiting 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 to 6 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 formula (b4) above, R ^8b represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ^9b represents an acid dissociable, dissolution inhibiting group.

The alkyl group having 1 to 6 carbon atoms is, for example, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. Linear or branched alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. A cyclopentyl group, a cyclohexyl group, etc. are mentioned as a cyclic alkyl group.

As the acid-dissociable, dissolution-inhibiting group represented by ^R9b , the same acid-dissociable, dissolution-inhibiting groups as exemplified in the above formulas (b2) and (b3) can be used.

Furthermore, the polyhydroxystyrene resin (B2) can contain other polymerizable compounds as structural units for the purpose of appropriately controlling physical and chemical properties. Examples of such polymerizable compounds include known radically polymerizable compounds and anionically 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-methacryloyloxyethylsuccinic acid, 2- Methacrylic acid derivatives having a carboxy group and an ester bond such as methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylic acid alkyl esters such as (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and other (meth) acrylic acid hydroxyalkyl esters; phenyl (meth) acrylate, (meth)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; conjugated diolefins such as butadiene and isoprene; nitrile group-containing polymerizable compounds; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylamide;

[Acrylic resin (B3)]
The acrylic resin (B3) is not particularly limited as long as it is an acrylic resin whose solubility in alkali increases under the action of an acid and which is conventionally blended in various photosensitive resin compositions.
The acrylic resin (B3) preferably contains a structural unit (b-3) derived from an acrylic acid ester containing, for example, a —SO ₂ —containing cyclic group or a lactone-containing cyclic group. In such a case, when forming a resist pattern, it is easy to suppress the occurrence of footing.

(—SO ₂ -containing cyclic group)
Here, the “—SO ₂ —containing cyclic group” refers to a cyclic group containing a ring containing —SO ₂ — in its ring skeleton. Specifically, the sulfur atom in —SO ₂ — ( S) is a cyclic group that forms part of the ring skeleton of a cyclic group. A ring containing —SO ₂ — in its ring skeleton is counted as the first ring, and if it contains only the ring, it is a monocyclic group, and if it has another ring structure, it is a polycyclic group regardless of its structure. called. The —SO ₂ —containing cyclic group may be monocyclic or polycyclic.

A —SO ₂ —containing cyclic group is particularly a cyclic group containing —O—SO ₂ — in its ring skeleton, ie, —O—S— in —O—SO ₂ — forms part of the ring skeleton. Preferred are cyclic groups containing a forming sultone ring.

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

The -SO ₂ -containing cyclic group may be an -SO ₂ -containing aliphatic cyclic group or a -SO ₂ -containing aromatic cyclic group. An --SO ₂ --containing aliphatic cyclic group is preferred.

As the —SO ₂ —-containing aliphatic cyclic group, hydrogen atoms are removed from an aliphatic hydrocarbon ring in which some of the carbon atoms constituting the ring skeleton are replaced with —SO ₂ — or —O—SO ₂ —. Groups with at least one removed are included. More specifically, a group obtained by removing at least one hydrogen atom from an aliphatic hydrocarbon ring in which —CH ₂ — constituting the ring skeleton is substituted with —SO ₂ —, or —CH ₂ — constituting the ring. Examples thereof include groups 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, more preferably 3 or more and 12 or less. The alicyclic hydrocarbon ring may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane having 3 or more and 6 or less carbon atoms. 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 to 12 carbon atoms, and specific examples of the polycycloalkane include adamantane and norbornane. , isobornane, tricyclodecane, tetracyclododecane, and the like.

The —SO ₂ —-containing cyclic group may have a substituent. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, halogenated alkyl groups, hydroxyl groups, oxygen atoms (=O), -COOR'', -OC(=O)R'', hydroxyalkyl groups, cyano groups, and the like. is 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 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 preferred, and a methyl group is particularly preferred.

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. Specifically, groups in which the alkyl group exemplified above as the alkyl group as the substituent is bonded to an oxygen atom (--O--) can be mentioned.

A halogen atom as the substituent includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.

Examples of the halogenated alkyl group as the substituent include groups in which some or all of the hydrogen atoms of the aforementioned alkyl group have been substituted with the aforementioned halogen atoms.

Examples of the halogenated alkyl group as the substituent include a group in which some or all of the hydrogen atoms of the alkyl group exemplified above as the alkyl group as the substituent are substituted with the above-described halogen atoms. As the halogenated alkyl group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.

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

When R″ is a linear or branched alkyl group, the number of carbon atoms in 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 in 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. , or removing one or more hydrogen atoms from monocycloalkanes, which may or may not be substituted with fluorinated alkyl groups, and polycycloalkanes such as bicycloalkanes, tricycloalkanes, and tetracycloalkanes. More specifically, one or more hydrogen atoms are added from monocycloalkanes such as cyclopentane and cyclohexane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. groups excepted.

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 exemplified above as the alkyl group as the substituent is substituted with a hydroxyl group is exemplified.

（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。） More specific examples of the —SO ₂ —containing cyclic group include groups represented by the following formulas (3-1) to (3-4).

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

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

When the alkylene group contains an oxygen atom or a sulfur atom, specific examples thereof include groups in which -O- or -S- is interposed between the terminals or carbon atoms 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. A′ is preferably an alkylene group having 1 to 5 carbon atoms or —O—, more preferably an alkylene group having 1 to 5 carbon atoms, and most preferably a methylene group.

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

The alkyl group, alkoxy group, halogenated alkyl group, -COOR'', -OC(=O)R'', and hydroxyalkyl group for R ^10b may each have a -SO ₂ -containing cyclic group. The alkyl group, alkoxy group, halogenated alkyl group, -COOR'', -OC(=O)R'', and hydroxyalkyl group mentioned as substituents are the same as those described above.

Specific examples of the cyclic groups represented by formulas (3-1) to (3-4) are given below. "Ac" in the formula represents an acetyl group.

Among the above, the —SO ₂ —-containing cyclic group is preferably a group represented by the aforementioned formula (3-1), and the aforementioned chemical formulas (3-1-1) and (3-1-18). , (3-3-1), and (3-4-1) are more preferably at least one selected from the group consisting of groups represented by the above chemical formula (3-1-1) are most preferred.

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

Any lactone cyclic group in the structural unit (b-3) can be used without any particular limitation. Specifically, the lactone-containing monocyclic group includes 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, and a group obtained by removing one hydrogen atom from γ-butyrolactone. Examples thereof include a group obtained by removing one hydrogen atom, and a group obtained by removing one hydrogen atom from δ-valerolactone. Examples of lactone-containing polycyclic groups include groups obtained by removing one hydrogen atom from bicycloalkanes, tricycloalkanes, and tetracycloalkanes having a lactone ring.

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

[Structural unit (b-3-S)]
More specific examples of the structural unit (b-3-S) include structural units represented by the following formula (b-S1).

（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 is 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 is a —SO ₂ —containing cyclic group, R ^12b is a single bond or a divalent linking group.)

In formula (b-S1), R is the same as defined above.
R ^11b is the same as the —SO ₂ —containing cyclic group mentioned above.
R ^12b may be either a single bond or a divalent linking group. A divalent linking group is preferable because the effect of the present invention is excellent.

The divalent linking group for R ^12b is not particularly limited, but preferred examples thereof include a divalent hydrocarbon group optionally having a substituent, a divalent linking group containing a hetero atom, and the like.

- Divalent hydrocarbon group optionally having a substituent The hydrocarbon group as the divalent linking group may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group without aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated. A saturated hydrocarbon group is usually preferred. More specifically, the aliphatic hydrocarbon group includes a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in its structure, and the like.

The number of carbon atoms in 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 even more preferably 1 or more and 5 or less.

A linear alkylene group is preferable as the linear aliphatic hydrocarbon group. Specifically, methylene group [-CH ₂ -], ethylene group [-(CH ₂ ) ₂ -], trimethylene group [-(CH ₂ ) ₃ -], tetramethylene group [-(CH ₂ ) ₄ -] , a pentamethylene group [-(CH ₂ ) ₅ -] and the like.

A branched alkylene group is preferable as the branched aliphatic hydrocarbon group. Specifically, -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ ) Alkylmethylene groups such as (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 -, alkylethylene groups such as -CH(CH ₃ )CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ - and other alkyltrimethylene groups; -CH(CH ₃ )CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ CH ₂ - and alkylalkylene groups such as alkyltetramethylene groups such as As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

The straight-chain or branched-chain 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 fluorine-substituted fluorinated alkyl group having 1 to 5 carbon atoms, and an oxo group (=O).

As the aliphatic hydrocarbon group containing a ring in the above structure, a cyclic aliphatic hydrocarbon group (with two hydrogen atoms removed from the aliphatic hydrocarbon ring) which may contain a substituent containing a hetero atom in the ring structure group), a group in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, a group in which the cyclic aliphatic hydrocarbon group is linear or branched Examples thereof include groups interposed in the middle of aliphatic hydrocarbon groups. Examples of the straight-chain or branched-chain aliphatic hydrocarbon group include those mentioned above.

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

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

A cyclic 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 an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and an oxo group (=O).

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

The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, such as 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 preferred, and a methoxy group and an ethoxy group are particularly preferred.

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 preferred.

Examples of the halogenated alkyl group as the above-mentioned substituent include groups in which some or all of the hydrogen atoms of the above-mentioned alkyl group are substituted with the above-mentioned halogen atoms.

In the cyclic aliphatic hydrocarbon group, part of the carbon atoms constituting the ring structure may be substituted with -O- or -S-. Preferred heteroatom-containing substituents are -O-, -C(=O)-O-, -S-, -S(=O) ₂ - and -S(=O) ₂ -O-.

An aromatic hydrocarbon group as a divalent hydrocarbon group is a divalent hydrocarbon group having at least one aromatic ring and may have a substituent. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. 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, still more 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.

Specific examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocyclic rings in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms; etc. The heteroatom in the aromatic heterocycle includes oxygen atom, sulfur atom, nitrogen atom and the like. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings.

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

The number of carbon atoms in the alkylene group bonded to the 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, a hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent. For example, a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and an oxo group (=O).

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

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

The halogen atom as the substituent includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferred.

Examples of the halogenated alkyl group as the substituent include groups in which some or all of the hydrogen atoms of the above-mentioned alkyl group are substituted with the above-mentioned halogen atoms.

- Bivalent linking group containing a hetero atom The hetero atom in the bivalent linking group containing a hetero atom is an atom other than a carbon atom and a hydrogen atom, such as an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. etc.

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 and a combination of at least one of these non-hydrocarbon linking groups and a divalent hydrocarbon group. Examples of the divalent hydrocarbon group include the same divalent hydrocarbon groups that may have a substituent as described above, and a linear or branched aliphatic hydrocarbon group is preferable. .

Among the above, -NH-, -NH- in -C(=O)-NH-, H in -NH-C(=NH)- are substituted with substituents such as alkyl groups and acyl groups, respectively. may have been The number of carbon atoms in 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.

The divalent linking group for R ^12b is particularly preferably a linear or branched alkylene group, a cyclic aliphatic hydrocarbon group, or a heteroatom-containing divalent linking group.

When the divalent linking group for R ^12b is a linear or branched alkylene group, the number of carbon atoms in 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 preferred, and 1 or more and 3 or less is most preferred. Specifically, in the description of the "optionally substituted divalent hydrocarbon group" as the divalent linking group described above, the linear or branched aliphatic hydrocarbon group and the same as the straight-chain alkylene group and branched-chain alkylene group.

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

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

When the divalent linking group for R ^12b is a heteroatom-containing divalent linking group, preferred examples of the linking group include -O-, -C(=O)-O-, -C(=O )-, -OC(=O)-O-, -C(=O)-NH-, -NH- (H may be substituted with a substituent such as an alkyl group or an acyl group), -S-, -S(=O) ₂ -, -S(=O) ₂ -O-, general formula -Y ¹ -O-Y ² -, -[Y ¹ -C(=O)-O] _{m '} -Y ² -, or a group represented by -Y ¹ -OC(=O)-Y ₂ - [wherein Y ¹ and Y ² each independently have a substituent It is a good divalent hydrocarbon group, O is an oxygen atom, and m' is an integer of 0 or more and 3 or less. ] and the like.

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 acyl. The number of carbon atoms in 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.

_Y ^{_ _ _ _ _ _ 1} and Y ² are each independently a divalent hydrocarbon group optionally having a substituent. Examples of the divalent hydrocarbon group include those similar to the "optionally substituted divalent hydrocarbon group" mentioned in the description of the divalent linking group.

Y ¹ is preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 5 carbon atoms, a methylene group, and ethylene groups are particularly preferred.

^Y2 is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group, or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.

In the group represented by the formula -[Y ¹ -C(=O)-O] _m' -Y ² -, m' is an integer of 0 or more and 3 or less, preferably an integer of 0 or more and 2 or less, and 0 or 1 is more preferred, and 1 is particularly preferred. 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, a group represented by the formula -(CH ₂ ) _a' -C(=O)-O-(CH ₂ ) _b' - is 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, 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.

As for the divalent linking group for R ^12b , the heteroatom-containing divalent linking group is preferably an organic group consisting of a combination of at least one non-hydrocarbon group and a divalent hydrocarbon group. Among them, a straight-chain group having an oxygen atom as a heteroatom, such as a group containing an ether bond or an ester bond, is preferred, and the aforementioned formulas -Y ¹ -O-Y ² -, -[Y ¹ -C(= O)—O] _m′ —Y ² — or a group represented by —Y ¹ —OC(=O)—Y ² — is more preferable, and the group represented by the above formula —[Y ¹ —C(=O) A group represented by —O] _m′ —Y ² — or —Y ¹ —O—C(═O)—Y ² — is particularly preferred.

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

The alkylene group is preferably a linear or branched alkylene group. Preferable examples of the linear aliphatic hydrocarbon group include a methylene group [--CH.sub.2--], an ethylene group [-- ₍ CH.sub.2) _.sub.2-- ], a trimethylene group [-- ₍ CH.sub.2) _.sub.3-- ] _, A tetramethylene group [-(CH ₂ ) ₄ -], a pentamethylene group [-(CH ₂ ) ₅ -] and the like can be mentioned. Preferable examples of the branched chain alkylene group include -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CH ₃ )(CH ₂ Alkylmethylene groups such as CH ₃ )—, —C(CH ₃ )(CH ₂ CH ₂ CH ₃ )—, —C(CH ₂ CH ₃ ) ₂ —; —CH(CH ₃ )CH ₂ —, —CH( Alkyl ethylenes such as CH ₃ )CH(CH ₃ )—, —C(CH ₃ ) ₂ CH ₂ —, —CH(CH ₂ CH ₃ )CH ₂ —, —C(CH ₂ CH ₃ ) ₂ —CH ₂ — Alkyltrimethylene groups such as -CH(CH ₃ )CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ -; -CH(CH ₃ )CH ₂ CH ₂ CH ₂ -, -CH ₂ CH and alkylalkylene groups such as alkyltetramethylene groups such as (CH ₃ )CH ₂ CH ₂ —.

The divalent linking group containing an ester bond is particularly represented by the formula: -R ^13b -C(=O)-O- [wherein R ^13b is a divalent linking group. ] is preferable. 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。）

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

R ^13b is not particularly limited, and includes, for example, the same divalent linking groups for R ^12b described above.
The divalent linking group for R ^13b is preferably a linear or branched alkylene group, an aliphatic hydrocarbon group containing a ring in its structure, or a divalent linking group containing a hetero atom. Alternatively, a branched alkylene group or a divalent linking group containing an oxygen atom as a heteroatom is preferred.

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

^{The divalent} linking group containing an oxygen atom is preferably ^a divalent linking group containing an ether bond or an ester bond. )—O] _m′ —Y ² — or —Y ¹ —O—C(=O)—Y ² — are more preferred. Y ¹ and Y ² are each independently a divalent hydrocarbon group which may have a substituent, and m' is an integer of 0 or more and 3 or less. Among them, -Y ¹ -OC(=O)-Y ² - is preferred, and a group represented by -(CH ₂ ) _c -OC(=O)-(CH ₂ ) _d - is particularly preferred. . 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;

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

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

(Wherein, R, A', R ^10b , z, and R ^13b are the same as above.)

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

R ^13b is preferably a linear or branched alkylene group or a divalent linking group containing an oxygen atom. The straight-chain or branched-chain alkylene group and the divalent linking group containing an oxygen atom for R ^13b are the above-mentioned straight-chain or branched-chain alkylene groups and the divalent linking group containing an oxygen atom, respectively. and similar ones.

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

（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。）

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

[Structural unit (b-3-L)]
Examples of the structural unit (b-3-L) include those obtained by substituting R ^11b in the above formula (b-S1) with a lactone-containing cyclic group, and more specifically, the following formula ( Structural units represented by b-L1) to (b-L5) are exemplified.

（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。）

(Wherein, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms; R 'is each independently a hydrogen atom, an alkyl group, an alkoxy group , a halogenated alkyl group, a hydroxyl group, —COOR″, —OC(═O)R″, a hydroxyalkyl group, or a cyano group, and R″ is a hydrogen atom or an alkyl group; R ^12b is a single bond, or is a divalent linking group, s″ is an integer of 0 or more and 2 or less; A″ is an alkylene group having 1 or more and 5 or less carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom, or sulfur atom; r is 0 or 1.)

R in formulas (b-L1) to (b-L5) is the same as described above.
The alkyl group, alkoxy group, halogenated alkyl group, -COOR'', -OC(=O)R'', and hydroxyalkyl group in R' may each have a -SO ₂ -containing cyclic group. Examples of the alkyl group, alkoxy group, halogenated alkyl group, —COOR″, —OC(═O)R″, and hydroxyalkyl group mentioned above as substituents include the same groups as those described above.

R' is preferably a hydrogen atom in view of industrial availability.
The alkyl group for R″ may be linear, branched or cyclic.
When R″ is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.
When R″ is a cyclic alkyl group, it preferably has 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes, which may or may not be substituted with a fluorine atom or a fluorinated alkyl group, one or more Examples include groups from which a hydrogen atom is removed, etc. Specifically, monocycloalkanes such as cyclopentane and cyclohexane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane, and one or more Groups other than hydrogen atoms are included.
A″ includes the same as A′ in the above formula (3-1). A″ is an alkylene group having 1 to 5 carbon atoms, an oxygen atom (—O—) or a sulfur atom. (-S-) is preferable, and an alkylene group having 1 to 5 carbon atoms or -O- is more preferable. The alkylene group having 1 to 5 carbon atoms is more preferably a methylene group or a dimethylmethylene group, most preferably a methylene group.

R ^12b is the same as R ^12b in formula (b-S1) above.
In formula (b-L1), s″ is preferably 1 or 2.
Specific examples of structural units represented by formulas (b-L1) to (b-L3) are shown below. In each formula below, R ^α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

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

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

In formulas (b-L6) and (b-L7), R and ^R12b are the same as above.

In addition, the acrylic resin (B3) is a structural unit represented by the following formulas (b5) to (b7) having an acid dissociable group as a structural unit that increases the alkali solubility of the acrylic resin (B3) by the action of acid. including.

In the above formulas (b5) to (b7), R ^14b and R ^18b to R ^23b are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom, or represents a linear or branched fluorinated alkyl group having 1 to 6 carbon atoms, and R ^15b to R ^17b each independently represent a linear or branched alkyl group having 1 to 6 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, each independently linear having 1 to 6 carbon atoms a linear or branched alkyl group, or a linear or branched fluorinated alkyl group having 1 to 6 carbon atoms, wherein R ^16b and R ^17b are bonded to each other and the carbon atom to which they are bonded may form a hydrocarbon ring having 5 to 20 carbon atoms together, Y ^b represents an optionally substituted aliphatic cyclic group or an alkyl group, p is 0 to 4 It represents an integer, and q represents 0 or 1.

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

When the above R ^16b and R ^17b do not bind to each other to form a hydrocarbon ring, as the above R ^15b , R ^16b and R ^17b , a carbon atom A linear or branched alkyl group having a number of 2 or more and 4 or less is preferable. R ^19b , R ^20b , R ^22b and R ^23b are preferably hydrogen atoms or methyl groups.

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 atoms to which they are bonded. Specific examples of such aliphatic cyclic groups 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 are removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane. groups. In particular, groups obtained by removing one or more hydrogen atoms from cyclohexane and adamantane (which may further have a substituent) are preferred.

Furthermore, 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 carboxyl group, a cyano group, an oxygen atom (=O ), and linear or branched alkyl groups having 1 to 4 carbon atoms. As the polar group, an oxygen atom (=O) is particularly preferred.

The above ^Yb is an aliphatic cyclic group or an alkyl group, and includes groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. . Specifically, one or more hydrogen atoms are removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane. and the like. In particular, a group obtained by removing one or more hydrogen atoms from adamantane (which may further have a substituent) is preferred.

Furthermore, when the aliphatic cyclic group of ^Yb has a substituent on its ring skeleton, examples of the substituent include a polar group such as a hydroxyl group, a carboxyl group, a cyano group, and an oxygen atom (=O). and linear or branched alkyl groups having 1 to 4 carbon atoms. As the polar group, an oxygen atom (=O) is particularly preferred.

When ^Yb is an alkyl group, it is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 6 to 15 carbon atoms. Such alkyl groups are particularly preferably alkoxyalkyl groups, and examples of such alkoxyalkyl groups include 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 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.

Preferable specific examples of the structural unit represented by the above formula (b5) include those represented by the following formulas (b5-1) to (b5-33).

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

Preferable specific examples of the structural unit represented by the above formula (b6) include those represented by the following formulas (b6-1) to (b6-26).

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

Preferable specific examples of the structural unit represented by the above formula (b7) include those represented by the following formulas (b7-1) to (b7-15).

In formulas (b7-1) to (b7-15) above, 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 because it is easy to synthesize and relatively easy to achieve high sensitivity. Further, among the structural units represented by the formula (b6), structural units in which ^Yb is an alkyl group are preferable, and structural units in which one or both of ^R19b and ^R20b are an alkyl group are preferable.

Furthermore, the acrylic resin (B3) is a resin composed of a copolymer containing structural units derived from a polymerizable compound having an ether bond together with the structural units represented by the above formulas (b5) to (b7). is preferred.

Examples of the polymerizable compound having an ether bond include radically polymerizable compounds such as (meth)acrylic acid derivatives having an ether bond and an ester bond, and specific examples include 2-methoxyethyl (meth)acrylate. , 2-ethoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate Acrylate, methoxypolypropylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate and the like. Moreover, 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.

Furthermore, the acrylic resin (B3) can contain other polymerizable compounds as structural units for the purpose of appropriately controlling physical and chemical properties. Examples of such polymerizable compounds include known radically polymerizable compounds and anionically 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-methacryloyloxyethylsuccinic acid and 2-methacryloyloxy Methacrylic acid derivatives having a carboxy group and an ester bond such as ethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) ) acrylate, cyclohexyl (meth) acrylate and other (meth) acrylic acid alkyl esters; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and other (meth) acrylic acid hydroxyalkyl esters; phenyl ( (meth)acrylic acid aryl esters such as meth)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 group-containing aliphatic compounds such as vinyl acetate; butadiene, isoprene and other conjugated diolefins; acrylonitrile, methacrylic nitrile group-containing polymerizable compounds such as ronitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylamide;

As described above, the acrylic resin (B3) may contain a structural unit derived from a polymerizable compound having a carboxy group such as the above monocarboxylic acids or dicarboxylic acids. However, the acrylic resin (B3) does not substantially contain a structural unit derived from a polymerizable compound having a carboxyl group, because it is easy to form a resist pattern including a non-resist portion having a rectangular cross-sectional shape. is preferred. Specifically, the ratio of structural units derived from a 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 5% by mass or less. preferable.
In the acrylic resin (B3), the acrylic resin containing a relatively large amount of structural units derived from a polymerizable compound having a carboxy group contains only a small amount of structural units derived from a polymerizable compound having a carboxy group, or does not contain 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, adamantyl group, tetracyclododecanyl group, isobornyl group, norbornyl group and the like are particularly preferable in terms of industrial availability. These aliphatic polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.

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

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

When the acrylic resin (B3) contains a structural unit (b-3) containing a —SO ₂ —containing cyclic group or a lactone-containing cyclic group, the structural unit (b-3) in the acrylic resin (B3) The content is preferably 5 mass % or more, more preferably 10 mass % or more, particularly preferably 10 mass % or more and 50 mass % or less, and most preferably 10 mass % or more and 30 mass % or less. When the photosensitive resin composition contains the structural unit (b-3) in an amount within the above range, it is easy to achieve both good developability and good pattern shape.

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

The acrylic resin (B3) preferably contains a structural unit derived from the 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, more preferably 5% by mass or more and 30% by mass or less.

The acrylic resin (B3) preferably contains structural units derived from the (meth)acrylic acid esters having the acid non-dissociable aliphatic polycyclic group. In the acrylic resin (B3), the content of structural units derived from (meth)acrylic acid esters having an acid non-dissociable aliphatic polycyclic group is preferably 0% by mass or more and 50% by mass or less. % by mass or more and 30% by mass or less is more preferable.

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). Such an acrylic resin other than the acrylic resin (B3) is not particularly limited as long as it contains 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 still more preferably 30,000 or more and 300,000 or less. Such a mass average molecular weight allows the photosensitive resin layer to retain sufficient strength without deteriorating the releasability from the substrate, and furthermore prevents profile bulging and cracks from occurring during plating. can.

Moreover, the degree of dispersion of the resin (B) is preferably 1.05 or more. Here, the degree of dispersion is a value obtained by dividing the weight average molecular weight by the number average molecular weight. Such a degree of dispersion makes it possible to avoid the problem of the desired stress resistance to plating and the tendency of the metal layer obtained by plating to swell.

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

<Mercapto compound (C)>
The photosensitive resin composition contains a mercapto compound (C) represented by the following formula (C1-1) or (C1-2). Therefore, when a resist pattern is formed using the photosensitive resin composition, occurrence of footing is suppressed.

（式（Ｃ１－１）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、Ｒ^ｃ４は炭化水素基であり、Ｒ^ｃ２、Ｒ^ｃ３、及びＲ^ｃ４が結合する炭素原子は、第３級炭素原子であり、Ｒ^ｃ３とＲ^ｃ４とは、互いに結合して環を形成してもよく、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、エーテル結合、スルフィド結合、及びカルボニル基から選択される１種以上の２価基を含む脂肪族環ＣＡを有する１価の有機基、水酸基、又は水酸基含有基で置換された脂肪族環ＣＨを有する１価の有機基、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ＣＡ、脂肪族環ＣＨ、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 (C1-1), R ^c1 is a (n1+n2)-valent organic group, R ^c1 is bonded to a carbonyl group via a C—C bond, and is bonded to a mercapto group via a C—S bond, and R ^c2 and R ^c3 are each independently a hydrogen atom or a monovalent organic group, R ^c4 is a hydrocarbon group, and the carbon atom to which R ^c2 , R ^c3 and R ^c4 are bonded is a tertiary carbon an atom, R ^c3 and R ^c4 may be bonded to each other to form a ring, n1 is an integer of 1 or more and 4 or less, n2 is an integer of 1 or more and 4 or less,
provided that at least one of R ^c2 and R ^c3 is a monovalent organic group having an aliphatic ring CA containing one or more divalent groups selected from an ether bond, a sulfide bond, and a carbonyl group in the ring structure , a hydroxyl group, or a monovalent organic group having an aliphatic ring CH substituted with a hydroxyl group-containing group, a monovalent ring having an aliphatic ring CL containing a divalent group represented by -CO-O- in the ring structure an organic group, a monovalent organic group having an aliphatic ring CS containing a divalent group represented by —SO ₂ — in the ring structure, or the following formula in the ring structure:

Is a monovalent organic group having an aliphatic ring CP containing a trivalent group represented by
R ^c2 and R ^c3 combine to form an aliphatic ring CA, an aliphatic ring CH, an aliphatic ring CL, an aliphatic ring CS, or an aliphatic ring CP. )

（式（Ｃ１－２）中、Ｒ^ｃ１、Ｒ^ｃ２、Ｒ^ｃ３、ｎ１、及びｎ２は、式（Ｃ１－１）と同様であり、Ｒ^ｃ５は、Ｒ^ｃ６、及びＲ^ｃ７は、それぞれ独立に水素原子、又はアルキル基であり、Ｒ^ｃ５及びＲ^ｃ６は、互いに結合して環を形成してもよく、
ただし、Ｒ^ｃ２及びＲ^ｃ３の少なくとも一方が、脂肪族環ＣＡを有する１価の有機基、脂肪族環ＣＨを有する１価の有機基、脂肪族環ＣＬを有する１価の有機基、脂肪族環ＣＳを有する１価の有機基、又は脂肪族環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ＣＡ、脂肪族環ＣＨ、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 (C1-2), R ^c1 , R ^c2 , R ^c3 , n1, and n2 are the same as in formula (C1-1), and R ^c5 , R ^c6 , and R ^c7 are each independently a hydrogen atom or an alkyl group, and R ^c5 and R ^c6 may be bonded to each other to form a ring,
provided that at least one of R ^c2 and R ^c3 is a monovalent organic group having an aliphatic ring CA, a monovalent organic group having an aliphatic ring CH, a monovalent organic group having an aliphatic ring CL, an aliphatic a monovalent organic group having a ring CS or a monovalent organic group having an aliphatic ring CP;
R ^c2 and R ^c3 combine to form an aliphatic ring CA, an aliphatic ring CH, an aliphatic ring CL, an aliphatic ring CS, or an aliphatic ring CP. )

The mercapto compound represented by formula (C1-1) and the mercapto compound represented by formula (C1-2) are described below in order.

(Mercapto Compound Represented by Formula (C1-1))
In formula (C1-1), 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 formula (C1), R ^c1 is bonded to the carbonyl group via a C—C bond and to the mercapto group via a C—S bond.
That is, each bond of the organic group as R ^c1 is bonded to a carbon atom in the organic group.
In addition, the (n1+n2)-valent organic group may have an unsaturated bond.

Examples of the heteroatom which 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. A heteroatom may be present in a substituent attached to the backbone of a divalent organic group, or may be present as part of a bond that constitutes the divalent organic group.

Examples of substituents containing heteroatoms include halogen atoms, hydroxyl groups, mercapto groups, alkoxy groups, cycloalkyloxy groups, aryloxy groups, aralkyloxy groups, alkylthio groups, cycloalkylthio groups, arylthio groups, aralkylthio groups, acyl group, acyloxy group, acylthio group, alkoxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, amino group, N-monosubstituted amino group, N,N-disubstituted amino group, carbamoyl group (-CO- _NH2 ), N-monosubstituted carbamoyl group, N,N-disubstituted carbamoyl group, nitro group, and cyano group.

Specific examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

Although the number of carbon atoms in the alkoxy group is not particularly limited, it is preferably from 1 to 6, more preferably from 1 to 3. Alkoxy groups can be straight or branched. Specific examples of alkoxy groups include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, n-pentyloxy, and An n-hexyloxy group can be mentioned.

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

Although the number of carbon atoms in the aryloxy group is not particularly limited, it is preferably 6 or more and 20 or less, more preferably 6 or more and 12 or less. Specific examples of aryloxy groups include phenoxy, naphthalen-1-yloxy, naphthalen-2-yloxy, and biphenylyloxy groups.

Although the number of carbon atoms in the aralkyloxy group is not particularly limited, it is preferably 7 or more and 20 or less, more preferably 7 or more and 13 or less. Specific examples of aralkyloxy groups include benzyloxy, phenethyloxy, naphthalen-1-ylmethoxy, and naphthalen-2-ylmethoxy groups.

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

The number of carbon atoms in the acyloxy group is not particularly limited, and is preferably 2 or more and 20 or less, 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 acyloxy groups include acetyloxy, propionyloxy, butanoyloxy, pentanoyloxy, hexanoyloxy, octanoyloxy, nonanoyloxy, decanoyloxy, benzoyloxy, naphthalene- A 1-ylcarbonyloxy group and a naphthalen-2-ylcarbonyloxy group can be mentioned.

Preferred examples of the alkylthio group, cycloalkylthio group, arylthio group, aralkylthio group, and acylthio group include the above-mentioned groups suitable as the alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, and acyloxy group. , a group in which an oxygen atom is changed to a sulfur atom.

Although the number of carbon atoms in the alkoxycarbonyl group is not particularly limited, it is preferably 2 or more and 7 or less, more preferably 2 or more and 4 or less. Alkoxycarbonyl groups may be straight-chain or branched. Specific examples of alkoxycarbonyl groups include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec-butyloxycarbonyl, tert- butyloxycarbonyl, n-pentyloxycarbonyl, and n-hexyloxycarbonyl groups.

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

Although the number of carbon atoms in the aryloxycarbonyl group is not particularly limited, it is preferably 7 or more and 21 or less, more preferably 7 or more and 13 or less. Specific examples of aryloxycarbonyl groups include phenoxycarbonyl groups, naphthalen-1-yloxycarbonyl groups, naphthalen-2-yloxycarbonyl groups, and biphenylyloxycarbonyl groups.

Regarding the N-monosubstituted amino group and the N,N-disubstituted amino group, the type of substituent bonded to the nitrogen atom is not particularly limited. Preferable examples of the substituent bonded to the nitrogen atom include alkyl groups having 1 to 6 carbon atoms which may be linear or branched, cyclo groups having 3 to 10 carbon atoms, Examples 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.
Preferred specific examples of N-monosubstituted amino groups include methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, sec-butylamino, 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, octanoylamino group, nonanoylamino group, decanoylamino group, benzoylamino group, naphthalen-1-ylcarbonylamino group, and naphthalen-2-ylcarbonylamino group.
Preferable examples of N,N-disubstituted amino groups include dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, diisobutylamino group and disec-butylamino group. , di-tert-butylamino group, di-n-pentylamino group, di-n-hexylamino group, dicyclopentylamino group, dicyclohexylamino group, diphenylamino group, diacetylamino group, dipropionylamino group, and dibenzoylamino group mentioned.

There are no particular restrictions on the types of substituents bonded to the nitrogen atoms of the N-monosubstituted carbamoyl group and the N,N-disubstituted carbamoyl group. Preferred examples of substituents bonded to the nitrogen atom are the same as those described for the N-monosubstituted amino group and N,N-disubstituted amino group.
Preferable specific examples of the N-monosubstituted 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-naphthalen-2-ylcarbamoyl group, N-biphenylylcarbamoyl group, N-acetylcarbamoyl group, N-propionylcarbamoyl group, N-butanoylcarbamoyl group, N-pentanoylcarbamoyl group, N-hexanoylcarbamoyl group, N-octanoylcarbamoyl group, N-nonanoylcarbamoyl group, N-decanoylcarbamoyl group, N-benzoylcarbamoyl group, N-naphthalen-1-ylcarbonylcarbamoyl group, and N-naphthalene- A 2-ylcarbonylcarbamoyl group can be mentioned.
Preferable examples of N,N-disubstituted carbamoyl groups include N,N-dimethylcarbamoyl group, N,N-diethylcarbamoyl group, N,N-di-n-propylcarbamoyl group, N,N-diisopropylcarbamoyl group, N,N-di-n-butylcarbamoyl group, N,N-diisobutylcarbamoyl group, N,N-disec-butylcarbamoyl group, N,N-di-tert-butylcarbamoyl group, N,N-di-n-pentylcarbamoyl group group, N,N-di-n-hexylcarbamoyl group, N,N-dicyclopentylcarbamoyl group, N,N-dicyclohexylcarbamoyl group, N,N-diphenylcarbamoyl group, N,N-diacetylcarbamoyl group, N,N- A dipropionylcarbamoyl group and an N,N-dibenzoylcarbamoyl group can be mentioned.

Specific examples of the heteroatom-containing bond that may be contained in the (n1+n2)-valent organic group for R ^c1 include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, urethane bond, imino bond (-N=C(-R)-, -C(=NR)-: R represents a hydrogen atom or an organic group), carbonate bond, sulfonyl bond, sulfinyl bond, azo bond, etc. .

R ^c1 is preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms. 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 group having 1 to 6 carbon atoms is preferable. Hydrogen groups are most preferred.
When R ^c1 is a saturated aliphatic hydrocarbon group, the saturated aliphatic hydrocarbon group may be linear or branched, preferably linear.

When R ^c1 is an aromatic hydrocarbon group, the aromatic hydrocarbon group is preferably a divalent aromatic hydrocarbon group because the compound represented by formula (C1) can be easily synthesized and obtained. Preferred specific examples of divalent aromatic hydrocarbon groups for R ^c1 include p-phenylene group, m-phenylene group, p-phenylene group, naphthalene-2,6-diyl group, naphthalene-2,7- Diyl groups, naphthalene-1,4-diyl groups, and biphenyl-4,4'-diyl groups can be mentioned.
Among these, p-phenylene group, m-phenylene group, naphthalene-2,6-diyl group and biphenyl-4,4'-diyl group are preferred, and p-phenylene group and naphthalene-2,6-diyl group are preferred. , 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 formula (C1) can be easily synthesized and obtained. Preferred specific examples of the alkylene group for R ^c1 include methylene group, ethane-1,2-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4- diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, and decane -1,10-diyl group.
Among these are methylene, ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5- A diyl group and a hexane-1,6-diyl group are preferable, a methylene group, an ethane-1,2-diyl group and a propane-1,3-diyl group are more preferable, and a methylene group and an ethane-1,2-diyl group are preferable. and the propane-1,2-diyl group are particularly preferred.

（式（ｃ１－１－１）中、Ｒ^ｃ２、Ｒ^ｃ３、及びＲ^ｃ４は、式（Ｃ１－１）と同様である。）
で表される基は、露光により酸発生剤（Ａ）が発生させる酸により分解され、カルボキシ基を生じさせる。 In formula (C1-1), R ^c2 and R ^c3 are each independently a hydrogen atom or a monovalent organic group, and R ^c4 is a hydrocarbon group. R ^c3 and R ^c4 may combine with each other to form a ring. Also, the carbon atoms to which R ^c2 , R ^c3 and R ^c4 are bonded are tertiary carbon atoms.
Therefore, the following formula (C1-1-1) in formula (C1-1):

(In formula (c1-1-1), R ^c2 , R ^c3 and R ^c4 are the same as in formula (C1-1).)
The group represented by is decomposed by an acid generated by the acid generator (A) upon exposure to generate a carboxy group.

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ＣＡ、脂肪族環ＣＨ、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 (C1-1), at least one of R ^c2 and R ^c3 has an aliphatic ring CA containing one or more divalent groups selected from an ether bond, a sulfide bond, and a carbonyl group in the ring structure. monovalent organic group having a hydroxyl group, or a monovalent organic group having an aliphatic ring CH substituted with a hydroxyl group-containing group, an aliphatic ring containing a divalent group represented by -CO-O- in the ring structure A monovalent organic group having CL, a monovalent organic group having an aliphatic ring CS containing a divalent group represented by —SO ₂ — in the ring structure, or the following formula in the ring structure:

Is a monovalent organic group having an aliphatic ring CP containing a trivalent group represented by
R ^c2 and R ^c3 combine to form an aliphatic ring CA, an aliphatic ring CH, an aliphatic ring CL, an aliphatic ring CS, or an aliphatic ring CP.

At least one of R ^c2 and R ^c3 is a monovalent organic group having an aliphatic ring CA containing one or more divalent groups selected from an ether bond, a sulfide bond and a carbonyl group in the ring structure. In this case, preferred examples of monovalent organic groups having an aliphatic ring CA include groups obtained by removing one hydrogen atom from the aliphatic rings represented by the following formulas (c-A1) to (c-A6). mentioned.
Further, when R ^c2 and R ^c3 combine to form an aliphatic ring CA, the divalent cyclic group formed by R ^c2 and R ^c3 includes the following formulas (c-A1) to ( Examples thereof include divalent cyclic groups obtained by removing two hydrogen atoms bonded to the same carbon atom from the aliphatic ring represented by c-A6).
However, as described above, in formula (C1-1), the carbon atoms to which R ^c2 , R ^c3 and R ^c4 are bonded are tertiary carbon atoms.
Therefore, the divalent cyclic group formed by R ^c2 and R ^c3 is bound to the same carbon atom from the aliphatic rings represented by the following formulas (c-A1) to (c-A6) 2 In the case of a divalent cyclic group excluding one hydrogen atom, the divalent cyclic group is an aliphatic ring represented by the following formulas (c-A1) to (c-A6), an oxygen atom or sulfur It is not a divalent cyclic group except for two hydrogen atoms attached to the same carbon atom in adjacent positions of the atom.

In formulas (c-A1) to (c-A6), each R ^c7 is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogenated alkyl group, —COOR ^c8 , —OC(=O)R ^c8 , or cyano is a group, R ^c8 is a hydrogen atom or an alkyl group, and n3 is an integer of 0 or more and 2 or less. R ^c7 is the same as R′ in formulas (b-L1) to (b-L7), and R ^c8 is the same as R′ in formulas (b-L1) to (b-L7). be.

When at least one of R ^c2 and R ^c3 is a monovalent organic group having the aforementioned aliphatic ring CA, suitable examples of the monovalent organic group include one hydrogen atom from the following aliphatic ring and groups other than
When the divalent cyclic group formed by R ^c2 and R ^c3 is a divalent cyclic group containing the aforementioned aliphatic ring CA, preferred examples of the divalent cyclic group include: Bivalent cyclic groups obtained by removing two hydrogen atoms bonded to the same carbon atom from the following aliphatic rings can be mentioned.

When at least one of R ^c2 and R ^c3 is the aforementioned monovalent organic group having an aliphatic ring CA, suitable examples of the monovalent organic group include the following groups.

When the divalent cyclic group formed by R ^c2 and R ^c3 is a divalent cyclic group containing the aforementioned aliphatic ring CA, preferred examples of the divalent cyclic group include: The following groups may be mentioned.

When at least one of R ^c2 and R ^c3 is a hydroxyl group or a monovalent organic group having an aliphatic ring CH substituted with a hydroxyl group-containing group, preferred examples of the monovalent organic group having an aliphatic ring CH Examples include monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and 1 obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Monovalent organic group having an aliphatic ring CA; Monovalent organic group having an aliphatic ring CL; Monovalent organic group having an aliphatic ring CS; Monovalent organic group having an aliphatic ring CP at least one hydrogen atom of a monovalent aliphatic cyclic group such as an organic group of is substituted with a hydroxyl group or a hydroxyl group-containing group.

The hydroxyl group-containing group is not particularly limited, but is preferably a hydroxyalkyl group or a hydroxyphenyl group. The number of carbon atoms in the hydroxyalkyl group is, for example, preferably 1 or more and 6 or less, more preferably 1 or more and 3 or less. Preferred specific examples of hydroxyalkyl groups include hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, and 2-hydroxypropan-2-yl groups. is mentioned.

The number of hydroxyl groups possessed by the monovalent organic group having an aliphatic ring CH is not particularly limited. Typically, the number of hydroxyl groups is preferably 1 or more and 4 or less, more preferably 1 or 2, and particularly preferably 1.

（式（ｃ－Ｌ１）～（ｃ－Ｌ７）中、Ｒ’、ｓ”、Ａ”、及びｒは、式（ｂ－Ｌ１）～（ｂ－Ｌ７）と同様である。） When at least one of R ^c2 and R ^c3 is the aforementioned monovalent organic group having an aliphatic ring CL, suitable examples of the monovalent organic group having an aliphatic ring CL include the aforementioned formula (b -L1) to (b-L7) include groups obtained by removing one hydrogen atom from an aliphatic ring represented by the following formulas (c-L1) to (c-L7).
Further, when R ^c2 and R ^c3 combine to form an aliphatic ring CL, the divalent cyclic group formed by R ^c2 and R ^c3 includes the following formulas (c-L1) to ( Examples thereof include divalent cyclic groups obtained by removing two hydrogen atoms bonded to the same carbon atom from the aliphatic ring represented by c-L7).
However, as described above, in formula (C1-1), the carbon atoms to which R ^c2 , R ^c3 and R ^c4 are bonded are tertiary carbon atoms.
Therefore, the divalent cyclic group formed by R ^c2 and R ^c3 is bound to the same carbon atom among the aliphatic rings represented by the following formulas (c-L1) to (c-L7). In the case of a divalent cyclic group excluding two hydrogen atoms, the divalent cyclic group is an aliphatic ring represented by the following formulas (c-L1) to (c-L7) to an oxygen atom. It is not a divalent cyclic group except for two hydrogen atoms bonded to adjacent carbon atoms.

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

A group obtained by removing one hydrogen atom from an aliphatic ring represented by the following formula (c-L8) is also preferable as the monovalent organic group having the aforementioned aliphatic ring CL as R ^c2 and R ^c3 .
Furthermore, a divalent cyclic group obtained by removing two hydrogen atoms bonded to the same carbon atom from an aliphatic ring represented by the following formula (c-L8) is also formed by combining R ^c2 and R ^c3 . is preferred as a divalent cyclic group containing an aliphatic ring CL.

（式（（ｃ－Ｌ８）中、Ｒ’は、式（ｂ－Ｌ１）～（ｂ－Ｌ７）と同様である。）

(In formula ((c-L8), R' is the same as in formulas (b-L1) to (b-L7).)

When at least one of R ^c2 and R ^c3 is the aforementioned monovalent organic group having an aliphatic ring CL, preferred examples of the monovalent organic group include one hydrogen atom from the following aliphatic ring and groups other than
When the divalent cyclic group formed by R ^c2 and R ^c3 is a divalent cyclic group containing the aforementioned aliphatic ring CL, preferred examples of the divalent cyclic group include: Bivalent cyclic groups obtained by removing two hydrogen atoms bonded to the same carbon atom from the following aliphatic rings can be mentioned.

When at least one of R ^c2 and R ^c3 is the aforementioned monovalent organic group having an aliphatic ring CL, preferred specific examples of the monovalent organic group include the following groups.

When the divalent cyclic group formed by R ^c2 and R ^c3 is a divalent cyclic group containing the aforementioned aliphatic ring CL, preferred specific examples of the divalent cyclic group include , and the following groups.

When at least one of R ^c2 and R ^c3 is the aforementioned monovalent organic group having an aliphatic ring CS, preferred examples of the monovalent organic group having an aliphatic ring CS include the aforementioned formula (3 -1) to groups represented by (3-4).
Further, when R ^c2 and R ^c3 are combined to form an aliphatic ring CS, the divalent cyclic group formed by R ^c2 and R ^c3 includes the above-mentioned formulas (3-1) to Examples of groups represented by (3-4) include groups in which one hydrogen atom is removed from the carbon atom to which the bond is attached.
However, as described above, in formula (C1-1), the carbon atoms to which R ^c2 , R ^c3 and R ^c4 are bonded are tertiary carbon atoms. Therefore, the bivalent group having an aliphatic ring CS formed by combining ^Rc2 and ^Rc3 is limited to a group satisfying this condition.

（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。）

(The definitions of the abbreviations in formulas (3-1) to (3-4) are as described above.)

When at least one of R ^c2 and R ^c3 is the aforementioned monovalent organic group having an aliphatic ring CS, preferred specific examples of the monovalent organic group having an aliphatic ring CS include the following groups: mentioned.

When the divalent cyclic group formed by R ^c2 and R ^c3 is a divalent cyclic group containing the aforementioned aliphatic ring CS, preferred specific examples of the divalent cyclic group include , and the following groups.

When at least one of R ^c2 and R ^c3 is the aforementioned monovalent organic group having an aliphatic ring CP, preferred examples of the monovalent organic group having an aliphatic ring CP include the following formula (C- A group represented by P1) can be mentioned.
In addition, when R ^c2 and R ^c3 form a divalent cyclic group containing the above-described aliphatic ring CP, the divalent cyclic group satisfies the above-described predetermined conditions for the aliphatic ring CP. is not particularly limited.

In formula (C1-1), R ^c4 is a hydrocarbon group. The number of carbon atoms in the hydrocarbon group is not particularly limited, but is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, even more preferably 1 or more and 8 or less, and particularly preferably 1 or more and 6 or less.
Examples of hydrocarbon groups include alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, aryl groups, aralkyl groups, cycloalkylalkyl groups, and the like.
An alkyl group, an alkenyl group, an aralkyl group, and an alkylene group portion in a cycloalkylalkyl group may be linear or branched.

Specific examples of suitable alkyl groups for R ^c4 include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl and isopentyl. groups, neopentyl groups, and n-hexyl groups.
Preferred specific examples of cycloalkyl groups for R ^c4 include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl groups.
Preferred specific examples of the alkenyl group for R ^c4 include vinyl group, allyl group (2-propenyl group), 3-butenyl group, 4-pentenyl group, 5-hexenyl group and the like.
Preferred specific examples of the cycloalkenyl group for R ^c4 include a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group.
Preferable specific examples of the aryl group for R ^c4 include a phenyl group and a naphthyl group.
Preferred specific examples of aralkyl groups for R ^c4 include benzyl, phenethyl, 3-phenylpropyl, naphthalen-1-ylmethyl and naphthalen-2-ylmethyl groups.
Preferred specific examples of the cycloalkylalkyl group as R ^c4 include a cyclopentylmethyl group, 2-cyclopentylethyl group, 3-cyclopentylpropyl group, cyclohexylmethyl group, 2-cyclohexylmethyl group and 3-cyclohexylpropyl group. be done.

In formula (C1-1), R ^c3 and R ^c4 may combine with each other to form a ring. The ring formed by combining R ^c3 and R ^c4 is not particularly limited as long as the carbon atoms to which R ^c2 , R ^c3 and R ^c4 are bonded are tertiary carbon atoms.
When R ^c3 and R ^c4 are combined to form a cyclic group, the cyclic group is preferably a cycloalkylidene group. Suitable examples of cycloalkylidene groups include cyclopropylidene, cyclobutylidene, cyclopentylidene, and cyclohexylidene groups. Among these, a cyclopentylidene group and a cyclohexylidene group are preferred.

Although the method for producing the mercapto compound represented by formula (C1-1) is not particularly limited, it can be synthesized, for example, 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 with a protecting group X ^c , and then the following formula (C1-b) The carboxylic acid compound represented is obtained. Since the ester bond in the compound represented by formula (C1-1) is cleaved by an acid, a group that can be deprotected under conditions other than acidic conditions is employed as the protecting group ^Xc . Examples of the mercapto group protected with such a protecting group X ^c include groups having structures 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 each independently a hydrogen atom or a hydrocarbon group. As the hydrocarbon group, an alkyl group and an aryl group are preferred. 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. The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, such as a phenyl group, a naphthalene-1-yl group, and a naphthalene-2-yl group. is more preferred, and a phenyl group is particularly preferred.

Next, an ester compound represented by formula (C1-1b) is obtained from a carboxylic acid compound represented by formula (C1-b) and an alcohol represented by formula (C1-1a) below.
The esterification method 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 give the carboxylic acid compound represented by formula (C1-b) and the formula A method of condensation with an alcohol represented by (C1-1a) can be mentioned. Further, after reacting the carboxylic acid compound represented by the formula (C1-b) with a halogenating agent such as thionyl chloride or phosphorus trichloride to produce a carboxylic acid halide, the carboxylic acid halide is converted to the formula (C1-1a ) may be reacted with an alcohol represented by

In the obtained ester compound represented by formula ( ^C1-1b ), the protective group Xc is deprotected to obtain the mercapto compound represented by formula (C1-1). The deprotection method is not particularly limited, and is appropriately selected according to the type of protecting group ^Xc .

<Scheme 1>

In the case of the mercapto compound represented by formula (C1-1), the mercapto compound represented by formula (C1-1) can also be produced by the method described in Scheme 2 below. However, R ^c10 is a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or a methyl group.

In the method described in Scheme 2, an α,β-unsaturated carboxylic acid ester represented by the following formula (C1-1c) undergoes a Michael addition reaction with thioacetic acid to give a carboxylic acid represented by the formula (C1-1d). to obtain an acid ester. Next, the compound represented by the formula (C1-1d) is reacted with a base such as an aqueous ammonia solution to deacetylate, thereby obtaining the mercapto compound represented by the formula (1-1e).
The compound represented by formula (1-1e) is a compound represented by formula (1-1), wherein n1 is 1, n2 is 1, and R ^c1 is —CH ₂ —CH( It is a compound that is a divalent group represented by R ^c10 )—.

<Scheme 2>

In formulas (C1-a), (C1-b), and (C1-1a) to (C1-1e) shown in schemes 1 and 2, R ^c1 , R ^c2 , R ^c3 , R ^c4 , n1, and n2 are synonymous with formula (C1-1).

(Mercapto compound represented by formula (C1-2))
In formula (C1-2), R ^c1 , R ^c2 , R ^c3 , n1, and n2 are as described above.
R ^c5 , R ^c6 and R ^c6 each independently represent a hydrogen atom or an alkyl group. When R ^c5 , R ^c6 and R ^c6 are alkyl groups, the alkyl groups may be linear or branched, preferably linear.
When R ^c5 , R ^c6 , and R ^c6 are alkyl groups, the number of carbon atoms is not particularly limited, and is preferably 1 or more and 6 or less, more preferably 1 or more and 4 or less, further preferably 1 or 2, and particularly 1. preferable.
Preferred examples of alkyl groups for R ^c5 , R ^c6 and R ^c6 include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group. , n-pentyl group, isopentyl group, neopentyl group, and n-hexyl group. Among these groups, a methyl group and an ethyl group are preferred, and a methyl group is more preferred.

The divalent group represented by -CR ^c6 R ^c7 - in formula (C1-2) is preferably a methylene group and an ethane-1,1-diyl group.
The mercapto compound represented by formula (C1-2) has the same structure as the acid-dissociable, dissolution-inhibiting group represented by formula (b2) described above for resin (B), —CR ^c6 R ^c7 —O—. A group represented by CR ^c2 R ^c3 R ^c5 is included in the structure. The group represented by -CR ^c6 R ^c7 -O--CR ^c2 R ^c3 R ^c5 exhibits acid dissociation properties like the group represented by formula (b2).
Therefore, the group represented by —CO—O—CR ^c6 R ^c7 —O—CR ^c2 R ^c3 R ^c5 in the mercapto compound represented by formula (C1-2) is exposed to an acid generator (A ) is decomposed by the generated acid to give a carboxy group.

In formula (C1-2), R ^c5 and R ^c6 may combine to form a ring. As the ring formed in this case, the aforementioned aliphatic ring CA is preferable.
In the group represented by —CR ^c6 R ^c7 —O—CR ^c2 R ^c3 R ^c5 in formula (C1-2), R ^c5 and R ^c6 are bonded to form an aliphatic ring CA. In this case, preferred examples of the group represented by —CR ^c6 R ^c7 —O—CR ^c2 R ^c3 R ^c5 are the following groups.
In the groups below, all of R ^c2 , R ^c3 and R ^c7 are preferably hydrogen atoms.

As the mercapto compound represented by formula (C1-1) or formula (C1-2) described above, compounds of the following formulas are preferable. In the following formula, R ^x is a group represented by -CR ^c2 R ^c3 R ^c4 or a group represented by -CR ^c6 R ^c7 -O-CR ^c2 R ^c3 R ^c5 .

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

The mercapto compound represented by the formula (C1-2) described above can be prepared according to schemes 1 and 2 in which the method for producing the mercapto compound represented by the formula (C1-1) is described by appropriately changing the starting compound. It can be manufactured by the method described as.

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 an alkali-soluble resin (D) described later. It is particularly preferable to use in the range of 2 parts 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.

Patterning using a positive photosensitive resin composition containing an acid generator (A) that generates an acid upon exposure to actinic rays or radiation, and a resin (B) that increases solubility in alkali under the action of acid. When forming, it is believed that the acid generated from the acid generator (A) during exposure deactivates in the vicinity of the substrate surface.
In particular, near the boundary between the exposed and unexposed areas where the acid concentration is low, footing is likely to occur due to the deactivation of the acid on the substrate surface.
In this respect, when the photosensitive resin composition contains a mercapto compound, it is easy to suppress deactivation of acid on the substrate surface, and as a result, it is easy to suppress footing.
The mercapto compound (C) has a mercapto group in its molecule and a highly polar aliphatic ring such as an aliphatic ring CA, an aliphatic ring CH, an aliphatic ring CL, an aliphatic ring CS, or an aliphatic ring CP. and the formula group. Therefore, in the vicinity of the interface between the substrate surface and the coating film, the mercapto compound (C) is oriented such that the mercapto group is located on the substrate surface side and the highly polar aliphatic cyclic group is located on the coating film side. Cheap. This is because the resin (B) and the like contained in the photosensitive resin composition usually have a relatively high polarity. As a result of the above orientation of the mercapto (C) compound, the mercapto compound (C) is efficiently and uniformly distributed on the substrate surface.
The mercapto compound (C) is oriented so that the mercapto groups are located on the substrate surface side, and the mercapto compound (C) is evenly distributed on the substrate surface. .

In addition, the mercapto compound itself is difficult to dissolve in an alkaline developer, and when the photosensitive resin composition contains the mercapto compound, there arises a problem that a residue tends to be generated during development.
When a residue is generated after development, the residue adheres and accumulates on the surface of the substrate, which may cause pattern shape deterioration similar to footing.
In this regard, the mercapto compound (C) has an acid-labile group in its molecule. Therefore, in the coated film made of the photosensitive resin composition, the acid dissociable group is eliminated in the mercapto compound (C) at the exposed portions, and the mercapto compound (C) is solubilized in the alkaline developer. .
As a result, when the photosensitive resin composition contains the mercapto compound (C), which is the compound represented by formula (C1), deterioration of the pattern shape due to the generation of residues after development is less likely to occur.

For the reason explained above, it is considered that the occurrence of footing is remarkably suppressed when the photosensitive resin composition containing the mercapto compound (C) having the predetermined structure is used.

<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). This refers to the material that dissolves to a thickness 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 resins (D1), polyhydroxystyrene resins (D2), and acrylic resins (D3).

[Novolac resin (D1)]
A novolak resin is obtained, for example, by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as "phenols") and aldehydes in the presence of an acid catalyst.

Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2 ,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5- Trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, phloroglucinol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, β-naphthol and the like.
Examples of the aldehydes include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde.
The catalyst for the addition condensation reaction is not particularly limited, but acid catalysts such as hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid and acetic acid are used.

The flexibility of the novolac resin can be further improved by using o-cresol, substituting the hydrogen atoms of the hydroxyl groups in the resin with other substituents, or using bulky aldehydes. is.

The mass-average molecular weight of the novolac resin (D1) is not particularly limited as long as the object of the present invention is not impaired, but is preferably 1,000 or more and 50,000 or less.

[Polyhydroxystyrene resin (D2)]
Examples of hydroxystyrene-based compounds constituting the polyhydroxystyrene resin (D2) include p-hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene and the like.
Furthermore, the polyhydroxystyrene resin (D2) is preferably a copolymer with a styrene resin. Styrene-based compounds constituting such styrene resins 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 it is preferably 1000 or more and 50000 or less.

[Acrylic resin (D3)]
The acrylic resin (D3) preferably contains structural units derived from a polymerizable compound having an ether bond and structural units 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, ethyl carbitol (meth) acrylate, phenoxypolyethylene glycol ( (Meth)acrylic acid derivatives having an ether bond and an ester bond such as meth)acrylate, methoxypolypropylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and the like can be exemplified. 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-methacryloyloxyethylsuccinic acid and 2-methacryloyloxy compounds having a carboxy group and an ester bond such as ethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid; The polymerizable compound having a carboxyl 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 interfere with the object of the present invention, but it 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, and 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. Part by mass or less is more preferable. By setting the content of the alkali-soluble resin (D) within the above range, there is a tendency that crack resistance can be improved and film reduction during development can be prevented.

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

[Nitrogen-containing compound (E1)]
Nitrogen-containing compounds (E1) include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tri-n-pentylamine, tribenzylamine, diethanolamine, triethanolamine, and n-hexylamine. , n-heptylamine, n-octylamine, n-nonylamine, ethylenediamine, N,N,N',N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4 '-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propion Amide, benzamide, pyrrolidone, N-methylpyrrolidone, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, imidazole, benz imidazole, 4-methylimidazole, 8-oxyquinoline, acridine, purine, pyrrolidine, piperidine, 2,4,6-tri(2-pyridyl)-S-triazine, morpholine, 4-methylmorpholine, piperazine, 1,4- Dimethylpiperazine, 1,4-diazabicyclo[2.2.2]octane, pyridine and the like can be mentioned. 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 used in an amount of 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 oxoacid or derivative thereof (E2)]
Among the organic carboxylic acids and phosphorus oxo acids or derivatives thereof (E2), malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are preferable as the organic carboxylic acids. , especially salicylic acid.

Phosphorus oxoacids or derivatives thereof include phosphoric acid, phosphoric acid such as di-n-butyl phosphate, diphenyl phosphate, and derivatives such as esters thereof; Phosphonic acids such as di-n-butyl ester, phenylphosphonic acid, diphenyl phosphonate, dibenzyl phosphonate and derivatives such as esters thereof; phosphinic acids such as phosphinic acid, phenylphosphinic acid and esters thereof; derivatives; and the like. Among these, phosphonic acid is particularly preferred. These may be used alone or in combination of two or more.

The organic carboxylic acid or phosphorus oxoacid or 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 particularly preferably used in the range of 0 to 3 parts by mass.

In addition, in order to form a salt and stabilize it, it is preferable to use the organic carboxylic acid or phosphorus oxoacid or its derivative (E2) in an amount equivalent to 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 interfere with the object of the present invention, and can be appropriately selected from organic solvents conventionally used in positive photosensitive resin compositions and used. .

Specific examples of the organic solvent (S) include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate. , dipropylene glycol, dipropylene glycol monoacetate monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, monophenyl ether and other polyhydric alcohols and their derivatives; dioxane and other cyclic ethers; ethyl formate, lactic acid Methyl, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate , ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate; esters such as 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 the object of the present invention is not impaired. When the photosensitive resin composition is used for a thick film application in which the film 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. It is preferable to use the organic solvent (S) within the range of mass % or less.

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

In addition, the photosensitive resin composition may further contain an adhesion aid in order to improve the adhesion between the mold formed using the photosensitive resin composition and the metal substrate.

In addition, the photosensitive resin composition may further contain a surfactant in order to improve coating properties, defoaming properties, leveling properties, and the like. Specific examples of surfactants include BM-1000, BM-1100 (all manufactured by BM Chemie), Megafac F142D, Megafac F172, Megafac F173, and Megafac F183 (all manufactured by Dainippon Ink and Chemicals). ), Florado FC-135, Florado FC-170C, Florard FC-430, Florard FC-431 (both manufactured by Sumitomo 3M), Surflon S-112, Surfon S-113, Surfon S-131, Surfon S-141, Surflon S-145 (all manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (all manufactured by Toray Silicone Co., Ltd.) and other commercially available fluorine-based surfactants. but not limited to these.

In addition, the photosensitive resin composition may further contain an acid, an acid anhydride, or a high-boiling solvent in order to finely adjust the solubility in the developer.

Specific examples of acids and acid anhydrides include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid, and cinnamic acid; lactic acid, 2-hydroxybutyric acid, Hydroxymonocarboxylic acids such as 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid and syringic acid 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 acid Polyvalent carboxylic acids such as acids, butanetetracarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid; itaconic anhydride, anhydride succinic acid, citraconic anhydride, dodecenylsuccinic anhydride, tricarbanilic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymic anhydride, 1,2,3,4-butanetetracarboxylic anhydride, acid anhydrides such as cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis anhydride trimellitate, glycerol tris anhydride trimellitate; can.

Further, specific examples of high-boiling solvents include N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzyl Ethyl ether, dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate , propylene carbonate, phenyl cellosolve acetate, and the like.

Moreover, 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-working photosensitive resin composition is prepared by mixing and stirring the above components in a conventional manner. Apparatuses that can be used for mixing and stirring the above components include a dissolver, a homogenizer, a three-roll mill, and the like. After uniformly mixing the above components, the resulting mixture may be filtered using a mesh, membrane filter, or the like.

≪Photosensitive dry film≫
A photosensitive dry film has a substrate film and a photosensitive resin layer formed on the surface of the substrate film, and the photosensitive resin layer is made of the aforementioned photosensitive resin composition.

As the substrate film, one having light transmittance is preferable. Specific examples thereof include polyethylene terephthalate (PET) film, polypropylene (PP) film, polyethylene (PE) film, etc., but polyethylene terephthalate (PET) film is preferred in that it has an excellent balance between light transmittance and breaking strength.

A photosensitive dry film is produced by applying the aforementioned photosensitive resin composition onto a substrate film to form a photosensitive resin layer.
When the photosensitive resin layer is formed on the base film, an applicator, bar coater, wire bar coater, roll coater, curtain flow coater, etc. are used to form the layer so that the film thickness after drying on the base film is preferably 0.5. The photosensitive resin composition is applied to a thickness of 5 to 300 μm, more preferably 1 to 150,300 μm, particularly preferably 3 to 100 μm, and dried.

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

<<Method for manufacturing patterned resist film and substrate with template>>
A method for forming a patterned resist film on a metal surface of a substrate having a metal surface 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.
A suitable method is
A lamination step of laminating a photosensitive resin layer made of a photosensitive resin composition on the metal surface of a substrate having a metal surface;
An exposure step of irradiating and exposing the photosensitive resin layer to actinic rays or radiation;
A developing step of developing the photosensitive resin layer after exposure;
A patterned resist film containing
A method for manufacturing a template-equipped substrate having a template for forming a plated model includes, in a development step, preparing a template for forming the plated model by development, and manufacturing a patterned resist film. 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. be able to. A substrate having a metal surface is used as the substrate, and the metal species constituting the metal surface is preferably copper, gold or aluminum, more preferably copper.

The photosensitive resin layer is laminated on the substrate, for example, as follows. Specifically, a liquid photosensitive resin composition is applied onto a substrate, and the solvent is removed by heating to form a photosensitive resin layer having a desired thickness. The thickness of the photosensitive resin layer is not particularly limited as long as a resist pattern to be a template can be formed with a desired 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 onto the substrate, methods such as spin coating, slit coating, roll coating, screen printing, and applicator method can be employed. It is preferable to pre-bake the photosensitive resin layer. Pre-baking conditions vary depending on the type of each component in the photosensitive resin composition, the mixing ratio, the coating film thickness, etc., but are usually 70° C. or higher and 200° C. or lower, preferably 80° C. or higher and 150° C. or lower, for 2 minutes or more. About 60 minutes or less.

The photosensitive resin layer formed as described above is selectively irradiated (exposure) with actinic rays or radiation such as ultraviolet rays or visible rays having a wavelength of 300 nm or more and 500 nm or less through a mask of a predetermined pattern. be done.

Low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon gas lasers, and the like can be used as radiation sources. Radiation includes microwaves, infrared rays, visible rays, ultraviolet rays, X-rays, γ-rays, electron beams, proton beams, neutron beams, ion beams, and the like. Although the dose of radiation varies depending on the composition of the photosensitive resin composition, the film thickness of the photosensitive resin layer, etc., it is 100 mJ/cm ² or more and 10000 mJ/cm ² or less when using an ultra-high pressure mercury lamp, for example. Radiation also includes light rays that activate the acid generator (A) to generate acid.

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

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

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

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

After development, washing with running water is performed for 30 seconds or more and 90 seconds or less, and drying is performed using an air gun, an oven, or the like. Thus, a resist pattern patterned into a desired shape is formed on the metal surface of the substrate having the metal surface. Moreover, in this way, a substrate with a template provided with a resist pattern serving as a template on the metal surface of a substrate having a metal surface can be manufactured.

≪Manufacturing method of plated model≫
By embedding a conductor such as metal by plating in the non-resist part (the part removed by the developer) in the mold of the substrate with the mold formed by the above method, for example, connection terminals such as bumps and metal posts can be formed. It is possible to form such a plated model. The plating method is not particularly limited, and conventionally known various methods can be employed. Solder plating, copper plating, gold plating, and nickel plating solutions are particularly suitable as the plating solution. The remaining template is finally removed using a stripping solution or the like according to conventional methods.

According to the above method, the mold can be formed while suppressing the occurrence of "footing" in which the width of the bottom (surface side of the support) is narrower than the width of the top (surface side of the resist layer) in the non-resist portion. A resist pattern is formed. By using a substrate provided with a mold with suppressed footing manufactured in this manner, a plated molded article having excellent adhesion to the substrate can be manufactured.

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

[Preparation Example 1]
(Synthesis of mercapto compound C1)
In Preparation Example 1, a mercapto compound C1 having the following structure was synthesized.

Into the flask were added 9.21 g of a methacrylic acid ester represented by the following reaction formula and 91.9 g of tetrahydrofuran (THF), and the contents of the flask were stirred under a nitrogen atmosphere. After adding 7.68 g of lithium thioacetate into the flask, the contents of the flask were stirred at 60°C. Then, after adding n-heptane into the flask, the organic phase was washed 5 times with 91.9 g of pure water, and then the solvent was distilled off from the organic phase to obtain 10.8 g of precursor C1a. .

9.49 g of precursor C1a, 94.9 g of methanol, and 25.5 g of ammonia water having a concentration of 10% by mass were added to the flask and stirred at room temperature for 10 hours. After adding 11.9 g of acetic acid to the reaction solution, 94.9 g of dichloromethane and 94.9 g of pure water were added to the flask. After stirring the contents of the flask, the mixture was allowed to stand still for liquid separation, and the organic phase was recovered. The collected organic layer was washed once with 94.9 g of ammonia water having a concentration of 1% by mass, and then washed with 94.9 g of pure water five times. .87 g was obtained.
¹ H-NMR (600 MHz, DMSO-d6): δ 3.70-3.51 (m, 4H), 3.00-2.15 (m, 3H), 2.05 (t, 2H), 1.75 (t, 2H), 1.53 (s, 3H), 1.25-1.05 (m, 3H)

[Preparation Example 2]
(Synthesis of mercapto compound C2)
In Preparation Example 2, a mercapto compound C2 having the following structure was synthesized.

A mercapto compound C2 was obtained in the same manner as in Preparation Example 1, except that the starting methacrylic acid ester was changed to the following methacrylic acid ester.
¹ H-NMR (600 MHz, DMSO-d6): δ 4.49-4.31 (m, 2H), 3.11 (d, 1H), 3.00-2.60 (m, 2H), 2.57 (d, 2H), 2.22 (m, 1H), 2.08 (t, 1H), 1.90 (s, 3H), 1.25-1.05 (m, 3H)

[Examples 1 to 8 and Comparative Examples 1 to 6]
In Examples and Comparative Examples, a compound of the following formula was used as (A) an acid generator.

In Examples and Comparative Examples, the following resins B1 and B2 were used as resins ((B) resins) whose solubility in alkali increases under the action of acid. The lower right number of parentheses in each structural unit in the following structural formula represents the content (% by mass) of the structural unit in each resin.

As the mercapto compound (C), the mercapto compounds C1 and C2 described above were used in the examples. In Comparative Examples, 3-mercaptopropionic acid was used as mercapto compound C3, and 3-mercaptopropionic acid t-butyl ester was used as mercapto compound C4.

(D) As the alkali-soluble resin, the following resins D1 and D2 were used.
D1: polyhydroxystyrene resin (p-hydroxystyrene: styrene = 85:15 (mass ratio) copolymer, weight average molecular weight (Mw) 2500, degree of dispersion (Mw/Mn) 2.4)
D2: novolak resin (m-cresol homocondensate (mass average molecular weight (Mw) 8000))

Resin (B), mercapto compound (C), and alkali-soluble resin (D) in the types and amounts shown in Table 1, 2.0 parts by mass of acid generator (A), and 0.02 parts by mass of tripentylamine were 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 Table 1 is 0.05 parts by mass or 0.10 parts by mass.

Using the obtained photosensitive resin composition, footing was evaluated according to the following method. These evaluation results are shown in Table 1.

[Evaluation of footing]
The photosensitive resin composition of each example and comparative example was applied onto a copper substrate having a diameter of 8 inches to form a photosensitive resin layer having a thickness of 55 μm. The photosensitive resin layer was then pre-baked at 100° C. for 5 minutes. After pre-baking, using a square pattern mask with a diameter of 30 μm and an exposure apparatus Prisma GHI (manufactured by Ultratech), ghi was exposed at an exposure amount 1.2 times the minimum exposure amount capable of forming a pattern of a predetermined size. A line was pattern-exposed. The substrate was then placed on a hot plate and subjected to post-exposure baking (PEB) at 140° C. for 3 minutes. Thereafter, a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (developer, NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) is added dropwise to the exposed photosensitive resin layer, followed by standing at 23° C. for 60 seconds. was repeated four times in total. Thereafter, the surface of the resist pattern was washed with running water and then blown with nitrogen to obtain a resist pattern. The cross-sectional shape of this resist pattern was observed with a scanning electron microscope to measure the footing amount.
Specifically, the footing amount was measured as follows. FIG. 1 shows a schematic cross-sectional view of a resist portion and a non-resist portion when measuring the amount of footing. In FIG. 1, a resist pattern having resist portions 12 and non-resist portions 13 (holes) is formed on a substrate 11 . First, on the side wall 14 which is the interface between the resist portion 12 and the non-resist portion 13, an inflection point 15 where footing on the side wall 14 starts is determined. A perpendicular line 16 was drawn from the point of inflection 15 toward the surface of the substrate 11 , and the intersection of the perpendicular line 16 and the surface of the substrate 11 was defined as a footing starting point 17 . A footing end point 18 is defined as an intersection point between the curve of the side wall 14 and the surface of the substrate 11 . The width Wf between the footing start point 17 and the footing end point 18 thus determined was taken 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. The degree of footing was evaluated according to the following criteria from the obtained value of the footing amount.
<Footing Evaluation Criteria>
○: 0 μm or more and 1.5 μm or less △: More than 1.5 μm and 2.5 μm or less ×: More than 2.5 μm

According to Examples 1 to 8, in addition to the acid generator (A) that generates acid by irradiation with actinic rays or radiation and the resin (B) that increases the solubility in alkali by the action of acid, a predetermined When a positive photosensitive resin composition containing the mercapto compound (C) having the structure is used to form a resist pattern, it can be seen that footing is suppressed in the resist pattern.

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

11 Substrate 12 Resist portion 13 Non-resist portion 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 upon exposure to actinic rays or radiation, a resin (B) that increases in alkali solubility under the action of the acid, and the following formula (C1-1) or (C1-2): :

(In formula (C1-1), R ^c1 is a (n1+n2)-valent hydrocarbon group having 1 or more and 20 or less carbon atoms , R ^c1 is bonded to a carbonyl group via a C—C bond, and C—S bonded to the mercapto group by a bond, R ^c2 and R ^c3 are each independently a hydrogen atom or a monovalent organic group, R ^c4 is a hydrocarbon group having 1 to 20 carbon atoms , R ^c2 , The carbon atom to which R ^c3 and R ^c4 are bonded is a tertiary carbon atom, R ^c3 and R ^c4 may be bonded to each other to form a ring, 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,
provided that at least one of R ^c2 and R ^c3 is a monovalent organic group having an aliphatic ring CA containing one or more divalent groups selected from an ether bond, a sulfide bond, and a carbonyl group in the ring structure , a hydroxyl group, or a monovalent organic group having an aliphatic ring CH substituted with a hydroxyl group-containing group, a monovalent ring having an aliphatic ring CL containing a divalent group represented by -CO-O- in the ring structure an organic group, a monovalent organic group having an aliphatic ring CS containing a divalent group represented by —SO ₂ — in the ring structure, or the following formula in the ring structure:

is a monovalent organic group having an aliphatic ring CP containing a trivalent group represented,
R ^c2 and R ^c3 are bonded to form the aliphatic ring CA, the aliphatic ring CH, the aliphatic ring CL, the aliphatic ring CS, or the aliphatic ring CP)

(In formula (C1-2), R ^c1 , R ^c2 , R ^c3 , n1, and n2 are the same as in formula (C1-1), R ^c5 , R ^c6 , and R ^c7 are each independently hydrogen atom, or an alkyl group having 1 to 6 carbon atoms , and R ^c5 and R ^c6 may be bonded to each other to form a ring,
provided that at least one of R ^c2 and R ^c3 is a monovalent organic group having the aliphatic ring CA, a monovalent organic group having the aliphatic ring CH, and a monovalent organic group having the aliphatic ring CL , a monovalent organic group having the aliphatic ring CS, or a monovalent organic group having the aliphatic ring CP,
R ^c2 and R ^c3 combine to form the aliphatic ring CP, the aliphatic ring CH, the aliphatic ring CL, the aliphatic ring CS, or the aliphatic ring CP. )
A chemically amplified positive photosensitive resin composition containing a mercapto compound (C) represented by
The monovalent organic group having an aliphatic ring CA is a group obtained by removing one hydrogen atom from an aliphatic ring selected from the following, and the aliphatic ring formed by combining R ^c2 and R ^c3 The divalent cyclic group containing a trivalent ring CA is a divalent cyclic group in which two hydrogen atoms bonded to the same carbon atom are removed from an aliphatic ring selected from the following,

The monovalent organic group having an aliphatic ring CH is one hydrogen from an aliphatic ring selected from cyclopentane, cyclohexane, cycloheptane, cyclooctane, adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane monovalent cyclic group excluding atoms; monovalent organic group having the aliphatic ring CA; monovalent organic group having the aliphatic ring CL; monovalent organic group having the aliphatic ring CS; A group obtained by substituting at least one hydrogen atom of the monovalent organic group having the aliphatic ring CP with a hydroxyl group or a hydroxyl group-containing group,
The monovalent organic group having an aliphatic ring CL is a group in which one hydrogen atom is removed from an aliphatic ring selected from the following, and the aliphatic ring formed by combining R ^c2 and R ^c3 The divalent cyclic group containing a trivalent ring CL is a divalent cyclic group in which two hydrogen atoms bonded to the same carbon atom are removed from an aliphatic ring selected from the following,

The ^monovalent organic group having an aliphatic ring CS is a group represented by the following formulas (3-1) to (3-4), ^and the above A divalent cyclic group containing an aliphatic ring CS, in a group represented by the following formulas (3-1) to (3-4), a group obtained by removing one hydrogen atom from the carbon atom to which the bond is attached and

(Wherein, A′ is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, z is an integer of 0 to 2, and R ^10b is an alkyl group, an alkoxy group, a halogenated alkyl group, a hydroxyl group, -COOR", -OC(=O)R", a hydroxyalkyl group, or a cyano group, and R" is a hydrogen atom or an alkyl group.)
The monovalent organic group having the aliphatic ring CP is a group represented by the following formula (C-P1) and includes the aliphatic ring CP formed by combining R ^c2 and R ^c3 . The divalent cyclic group is a group represented by the following formula (C-P1) in which one hydrogen atom is removed from the carbon atom to which the bond is attached, a chemically amplified positive photosensitive resin composition thing.

2. The chemically amplified positive photosensitive resin composition according to claim 1, further comprising an alkali-soluble resin (D). The alkali-soluble resin (D) according to claim 2, comprising at least one resin selected from the group consisting of a novolac resin (D1), a polyhydroxystyrene resin (D2), and an acrylic resin (D3). A chemically amplified positive photosensitive resin composition. The chemically amplified positive photosensitive material according to any one of claims 1 to 3, comprising a base film and a photosensitive resin layer formed on the surface of the base film, wherein the photosensitive resin layer is A photosensitive dry film made of a resin composition. Manufacture of a photosensitive dry film, comprising forming a photosensitive resin layer by applying the chemically amplified positive photosensitive resin composition according to any one of claims 1 to 3 on a base film. Method. A lamination step of laminating a photosensitive resin layer composed 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 position-selectively irradiating the photosensitive resin layer with actinic rays or radiation;
and a developing step of developing the photosensitive resin layer after exposure. A lamination step of laminating a photosensitive resin layer composed 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 actinic rays or radiation;
and a developing step of developing the exposed photosensitive resin layer to form a mold for forming a plated molded article. A method of manufacturing a plated modeled article, comprising the step of plating the substrate with a template manufactured by the method according to claim 7 to form a plated modeled article in the template.

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