JP2020012900A - Chemically amplified photosensitive composition, photosensitive dry film, method for producing photosensitive dry film, method for producing patterned resist film, sensitizer, and method for sensitizing chemically amplified photosensitive composition - Google Patents

Abstract

To provide a chemically amplified photosensitive composition with high sensitivity, a photosensitive dry film having a photosensitive layer composed of the chemically amplified photosensitive composition, a method for producing the photosensitive dry film, a method for producing a patterned resist film using the chemically amplified photosensitive composition, a sensitizer for the chemically amplified photosensitive composition, and a method for sensitizing the chemically amplified photosensitive composition.SOLUTION: A chemically amplified photosensitive composition has an acid generator (A) that generates acid by irradiation with active rays or radiation rays, the composition further having a predetermined structure sulfur-containing compound (C) having a sulfonic acid ester structure and a mercapto group or an organo thio group.SELECTED DRAWING: None

Description

  The present invention provides a chemically amplified photosensitive composition, a photosensitive dry film including a photosensitive layer comprising the chemically amplified photosensitive composition, a method for producing the photosensitive dry film, and the aforementioned chemically amplified photosensitive composition. The present invention relates to a method for producing a patterned resist film using a composition, a sensitizer for improving the sensitivity of a chemically amplified photosensitive composition, and a method for sensitizing a chemically amplified photosensitive composition.

  At present, 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 technology, and the patterned photoresist layer (photoresist pattern) is used as a mask for chemical etching and electrolytic etching. It is a general term for a technology for manufacturing various precision components such as semiconductor packages by performing etching or electroforming mainly based on electroplating.

  In recent years, with the downsizing of electronic devices, high-density packaging technology for semiconductor packages has advanced, and the use of multi-pin thin-film packaging, miniaturization of package size, flip-chip two-dimensional packaging technology, and three-dimensional packaging technology have been promoted. Based on this, the mounting density is improved. In such a high-density mounting technology, as connection terminals, for example, protruding electrodes (mounting terminals) such as bumps protruding on a package, or metal posts for connecting 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 for the photofabrication as described above, and as such a photoresist composition, a chemically amplified photosensitive composition containing an acid generator is known (Patent Documents 1 and 2). Etc.). In a chemically amplified photosensitive composition, an acid is generated from an acid generator by irradiation (exposure), and diffusion of the acid is promoted by heat treatment, thereby causing an acid-catalyzed reaction on a base resin or the like in the composition. The alkali solubility changes.

  Such a chemically amplified photosensitive composition can be used to form a patterned insulating film, an etching mask, and a plated object such as a bump, a metal post, and a Cu rewiring by a plating process. It is used for Specifically, using a chemically amplified photosensitive composition, a photoresist layer of a desired thickness is formed on a support such as a metal substrate, exposed through a predetermined mask pattern, and developed. A photoresist pattern to be used as a mold from which a part for forming a plated object is selectively removed (stripped) is formed. Then, after a conductor such as copper is buried in the removed portion (non-resist portion) by plating, the photoresist pattern around the conductor is removed, so that bumps, metal posts, and Cu rewiring can be formed. .

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

Generally, when a resist pattern is formed, it is often desired that the cross-sectional shape be rectangular. In particular, in the formation of connection terminals such as bumps and metal posts and the formation of Cu rewiring by the above-described plating process, it is strongly desired that the cross-sectional shape of the non-resist portion of the resist pattern serving as a mold be rectangular. .
Further, when forming a plated object such as a connection terminal or Cu rewiring, a thick resist pattern is often formed as a mold in consideration of the shape and size of the plated object.

As described above, in order to form a resist pattern having a certain thickness and a desired cross-sectional shape, it is desirable that the chemically amplified photosensitive composition used for forming the resist pattern has high sensitivity. It is.
However, the sensitivity of the conventionally known chemically amplified photosensitive composition is not always sufficient, and further improvement is desired.

  The present invention has been made in view of the above problems, a chemically amplified photosensitive composition having high sensitivity, a photosensitive dry film including a photosensitive layer comprising the chemically amplified photosensitive composition, A method for producing a photosensitive dry film, a method for producing a patterned resist film using the aforementioned chemically amplified photosensitive composition, a sensitizer for the chemically amplified photosensitive composition, and a chemically amplified photosensitive composition. A method for sensitizing a composition.

  Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, a sulfonic acid ester was added to a chemically amplified photosensitive composition containing an acid generator (A) that generates an acid upon irradiation with actinic rays or radiation. The inventor has found that the above problem can be solved by blending a sulfur-containing compound (C) having a structure and a predetermined structure having a mercapto group or an organothio group, thereby completing the present invention. Specifically, the present invention provides the following.

（式（Ｃ−Ｉ）中、Ｘ^ｃ１は有機連結基であり、Ｒ^ｃ０１は、水素原子、又はスルホン酸エステル構造を含まない有機基であり、Ｒ^ｃ０２は、炭素原子上に結合手を有する１価の有機基であり、ｎ１は、１以上４以下の整数であり、ｎ２は、１以上４以下の整数であり、Ｒ^ｃ０２は、Ｘ^ｃ１を構成する元素のいずれか１つと結合して環を形成してもよい。）
で表される化合物、及び／又は、下記式（Ｃ−ＩＩ）

（式（Ｃ−ＩＩ）中、Ｘ^ｃ２及びＸ^ｃ３は、それぞれ、有機連結基であり、Ｘ^ｃ４は、単結合、又は２価の有機基であり、Ｒ^ｃ０３及びＲ^ｃ０４は、それぞれ、炭素原子上に結合手を有する１価の有機基であり、ｎ３及びｎ４は、それぞれ、１以上３以下の整数であり、ｎ３＋ｎ４は２以上４以下の整数であり、Ｒ^ｃ０３は、Ｘ^ｃ２を構成する元素のいずれか１つと結合して環を形成してもよく、Ｒ^ｃ０４は、Ｘ^ｃ３を構成する元素のいずれか１つと結合して環を形成してもよい。）
で表される化合物である化学増幅型感光性組成物である。 A first aspect of the present invention comprises an acid generator (A) that generates an acid upon irradiation with actinic rays or radiation, and a sulfur-containing compound (C),
When the sulfur-containing compound (C) has the following formula (C-I):

(In the formula (CI), X ^c1 is an organic linking group, R ^c01 is a hydrogen atom or an organic group not containing a sulfonic acid ester structure, and R ^c02 has a bond on a carbon atom. A monovalent organic group, n1 is an integer of 1 or more and 4 or less, n2 is an integer of 1 or more and 4 or less, and R ^c02 is bonded to any one of the elements constituting X ^c1. (A ring may be formed.)
And / or the following formula (C-II)

(In the formula (C-II), X ^c2 and X ^c3 are each an organic linking group, X ^c4 is a single bond or a divalent organic group, and R ^c03 and R ^c04 are each a carbon atom. A monovalent organic group having a bond on an atom, n3 and n4 are each an integer of 1 or more and 3 or less, n3 + n4 is an integer of 2 or more and 4 or less, and R ^c03 forms X ^{c2 May} form a ring by combining with any one of the following elements, and R ^c04 may form a ring by combining with any one of the elements constituting X ^c3 .)
And a chemically amplified photosensitive composition.

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

  A third aspect of the present invention is a method for producing a photosensitive dry film, comprising applying a chemically amplified photosensitive composition according to the first aspect to a base film to form a photosensitive layer. is there.

According to a fourth aspect of the present invention,
A laminating step of laminating a photosensitive layer comprising the chemically amplified photosensitive composition according to the first embodiment on a substrate;
An exposure step of irradiating the photosensitive layer with actinic rays or radiation in a position-selective manner,
And a developing step of developing the photosensitive layer after exposure.

（式（Ｃ−Ｉ）中、Ｘ^ｃ１は有機連結基であり、Ｒ^ｃ０１は、水素原子、又はスルホン酸エステル構造を含まない有機基であり、Ｒ^ｃ０２は、炭素原子上に結合手を有する１価の有機基であり、ｎ１は、１以上４以下の整数であり、ｎ２は、１以上４以下の整数であり、Ｒ^ｃ０２は、Ｘ^ｃ１を構成する元素のいずれか１つと結合して環を形成してもよい。）
で表される化合物、及び／又は、下記式（Ｃ−ＩＩ）

（式（Ｃ−ＩＩ）中、Ｘ^ｃ２及びＸ^ｃ３は、それぞれ、有機連結基であり、Ｘ^ｃ４は、単結合、又は２価の有機基であり、Ｒ^ｃ０３及びＲ^ｃ０４は、それぞれ、炭素原子上に結合手を有する１価の有機基であり、ｎ３及びｎ４は、それぞれ、１以上３以下の整数であり、ｎ３＋ｎ４は２以上４以下の整数であり、Ｒ^ｃ０３は、Ｘ^ｃ２を構成する元素のいずれか１つと結合して環を形成してもよく、Ｒ^ｃ０４は、Ｘ^ｃ３を構成する元素のいずれか１つと結合して環を形成してもよい。）
で表される化合物を含む、増感剤である。 In a fifth aspect of the present invention, a chemical amplification type photosensitive composition containing an acid generator (A) that generates an acid upon irradiation with actinic rays or radiation is incorporated into a chemically amplified photosensitive composition. Improve sensitivity,
The following formula (CI):

(In the formula (CI), X ^c1 is an organic linking group, R ^c01 is a hydrogen atom or an organic group not containing a sulfonic acid ester structure, and R ^c02 has a bond on a carbon atom. A monovalent organic group, n1 is an integer of 1 or more and 4 or less, n2 is an integer of 1 or more and 4 or less, and R ^c02 is bonded to any one of the elements constituting X ^c1. (A ring may be formed.)
And / or the following formula (C-II)

(In the formula (C-II), X ^c2 and X ^c3 are each an organic linking group, X ^c4 is a single bond or a divalent organic group, and R ^c03 and R ^c04 are each a carbon atom. A monovalent organic group having a bond on an atom, n3 and n4 are each an integer of 1 or more and 3 or less, n3 + n4 is an integer of 2 or more and 4 or less, and R ^c03 forms X ^{c2 May} form a ring by combining with any one of the following elements, and R ^c04 may form a ring by combining with any one of the elements constituting X ^c3 .)
It is a sensitizer containing the compound represented by these.

（式（Ｃ−Ｉ）中、Ｘ^ｃ１は有機連結基であり、Ｒ^ｃ０１は、水素原子、又はスルホン酸エステル構造を含まない有機基であり、Ｒ^ｃ０２は、炭素原子上に結合手を有する１価の有機基であり、ｎ１は、１以上４以下の整数であり、ｎ２は、１以上４以下の整数であり、Ｒ^ｃ０２は、Ｘ^ｃ１を構成する元素のいずれか１つと結合して環を形成してもよい。）
で表される化合物、及び／又は、下記式（Ｃ−ＩＩ）

（式（Ｃ−ＩＩ）中、Ｘ^ｃ２及びＸ^ｃ３は、それぞれ、有機連結基であり、Ｘ^ｃ４は、単結合、又は２価の有機基であり、Ｒ^ｃ０３及びＲ^ｃ０４は、それぞれ、炭素原子上に結合手を有する１価の有機基であり、ｎ３及びｎ４は、それぞれ、１以上３以下の整数であり、ｎ３＋ｎ４は２以上４以下の整数であり、Ｒ^ｃ０３は、Ｘ^ｃ２を構成する元素のいずれか１つと結合して環を形成してもよく、Ｒ^ｃ０４は、Ｘ^ｃ３を構成する元素のいずれか１つと結合して環を形成してもよい。）
で表される化合物を加えることを含む、化学増幅型感光性組成物の増感方法である。 In a sixth aspect of the present invention, a chemically amplified photosensitive composition containing an acid generator (A) that generates an acid upon irradiation with actinic rays or radiation includes the following formula (CI):

(In the formula (CI), X ^c1 is an organic linking group, R ^c01 is a hydrogen atom or an organic group not containing a sulfonic acid ester structure, and R ^c02 has a bond on a carbon atom. A monovalent organic group, n1 is an integer of 1 or more and 4 or less, n2 is an integer of 1 or more and 4 or less, and R ^c02 is bonded to any one of the elements constituting X ^c1. (A ring may be formed.)
And / or the following formula (C-II)

(In the formula (C-II), X ^c2 and X ^c3 are each an organic linking group, X ^c4 is a single bond or a divalent organic group, and R ^c03 and R ^c04 are each a carbon atom. A monovalent organic group having a bond on an atom, n3 and n4 are each an integer of 1 or more and 3 or less, n3 + n4 is an integer of 2 or more and 4 or less, and R ^c03 forms X ^{c2 May} form a ring by combining with any one of the following elements, and R ^c04 may form a ring by combining with any one of the elements constituting X ^c3 .)
A method for sensitizing a chemically amplified photosensitive composition, comprising adding a compound represented by the formula:

  According to the present invention, a chemically amplified photosensitive composition having high sensitivity, a photosensitive dry film including a photosensitive layer composed of the chemically amplified photosensitive composition, and a method for producing the photosensitive dry film, Provided are a method for producing a patterned resist film using the aforementioned chemically amplified photosensitive composition, a sensitizer for the chemically amplified photosensitive composition, and a method for sensitizing the chemically amplified photosensitive composition. can do.

≪Chemically amplified photosensitive composition≫
The chemically amplified photosensitive composition (hereinafter also referred to as a photosensitive composition) is referred to as an acid generator (A) that generates an acid upon irradiation with actinic rays or radiation (hereinafter also referred to as an acid generator (A)). , A sulfur-containing compound (C). The sulfur-containing compound (C) has a predetermined structure containing a sulfonic acid ester bond, as described later.
When such a photosensitive composition is exposed, first, the acid generator (A) generates an acid. Then, by the action of the acid generated by the acid generator (A), the sulfonic ester bond in the sulfur-containing compound (C) is cleaved to generate a sulfonic acid group. The decomposition product of the sulfur-containing compound (C) having a sulfonic acid group cleaves a sulfonic ester bond in another sulfur-containing compound (C), and the decomposition product of the sulfur-containing compound (C) having a sulfonic acid group is further separated. Generate.
For such a reason, the photosensitive composition containing the acid generator (A) and the sulfur-containing compound (C) generates an acid with high efficiency by irradiation with actinic rays or radiation. Therefore, the photosensitive composition containing the acid generator (A) and the sulfur-containing compound (C) has high sensitivity.

  In addition, the above-described chemically amplified photosensitive composition has favorable sensitivity, but also has an advantage that the blending of the sulfur-containing compound (C) hardly causes a decrease in the transparency of the patterned resist film.

As the chemically amplified photosensitive composition, a conventionally known composition containing an acid generator (A) except that it contains a combination of an acid generator (A) and a sulfur-containing compound (C) having a predetermined structure. It is the same as the chemically amplified photosensitive composition.
The chemically amplified photosensitive composition may be a positive photosensitive resin composition in which solubility in a developer is increased by the action of an acid generated by exposure, and by the action of an acid generated by exposure, A negative photosensitive resin composition having reduced solubility in a developing solution may be used.

As the positive chemically amplified photosensitive composition, a tert-butyl group, a tert-butoxycarbonyl group, a tetrahydropyranyl group, an acetal group, and a trimethylsilyl are used together with the acid generator (A) and the sulfur-containing compound (C). And a photosensitive composition containing a resin (B) having an alkali-soluble group protected by a group which is deprotected by the action of an acid represented by a group, and having increased solubility in alkali by the action of an acid. .
As the negative type chemically amplified photosensitive composition, a condensing agent such as methylolmelamine and a resin which can be cross-linked by a condensing agent such as a novolak resin are used together with the acid generator (A) and the sulfur-containing compound (C). And a photosensitive composition containing the same. When the photosensitive composition is exposed to light, the photosensitive composition is cured by a crosslinking reaction caused by an acid generated by the exposure.
As the negative chemically amplified photosensitive composition, a photosensitive composition containing an epoxy compound together with the acid generator (A) and the sulfur-containing compound (C) is also preferable. When such a photosensitive composition is exposed, cationic polymerization of the epoxy compound by an acid generated by the exposure proceeds, and as a result, the photosensitive composition is cured.

  Among these chemically amplified photosensitive compositions, it is particularly easy to increase the sensitivity to a desired degree, and the type of the structural unit of the resin (B) whose solubility in alkali is increased by the action of an acid. It is easy to impart desired properties to the patterned resist film by adjusting the ratio of the structural units and the proportion of the structural units. For example, the acid generator (A) and the resin (B) having increased alkali solubility due to the action of an acid. ), And a chemically amplified positive photosensitive resin composition containing the sulfur-containing compound (C).

Hereinafter, as typical examples of the photosensitive composition, an acid generator (A), a resin (B) whose solubility in alkali is increased by the action of an acid (hereinafter also referred to as a resin (B)), and a sulfur-containing compound ( C) and a chemically amplified positive photosensitive resin composition (hereinafter, also referred to as a positive photosensitive resin composition) containing essential or optional components and a method for producing the photosensitive resin composition. explain.
The acid generator (A) and the sulfur-containing compound (C) described below can be applied to photosensitive compositions other than the positive photosensitive resin composition described below.

<Acid generator (A)>
The acid generator (A) is a compound that generates an acid by 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 by light. As the acid generator (A), the acid generators of the first to fifth embodiments described below are preferable. Hereinafter, preferred acid generators (A) suitably used in the positive photosensitive resin composition will be described as first to fifth embodiments.

  The first embodiment of the acid generator (A) includes a compound represented by the following formula (a1).

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

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

In the formula (a2), X ^4a represents 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. And X ^4a is a 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, and halogen. It may be substituted with at least one selected from. X ^5a is _{-O -, - S -, -} SO -, - SO 2 -, - NH -, - NR 2a -, - CO -, - COO -, - CONH-, carbon atom number of 1 to 3 alkylene Represents a phenylene group or a phenylene group. h represents the number of repeating units of the structure in parentheses. h + 1 X ^4a and h X ^5a may be the same or different, respectively. R ^2a 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 the formula (a17), R ^3a represents an alkyl group in which 80% or more of the hydrogen atoms have been substituted with fluorine atoms. j represents the number and is an integer of 1 or more and 5 or less. The j R ^3a may be the same or different.

In the 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 of 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 above.

  Examples of the onium ion in the compound represented by the above formula (a1) include triphenylsulfonium, tri-p-tolylsulfonium, 4- (phenylthio) phenyldiphenylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide, 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-dihydroanthracene 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, octadecy Methylphenacylsulfonium, diphenyliodonium, di-p-tolyliodonium, bis (4-dodecylphenyl) iodonium, bis (4-methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyliodonium, bis (4-decyloxy) phenyl Examples thereof include iodonium, 4- (2-hydroxytetradecyloxy) phenylphenyliodonium, 4-isopropylphenyl (p-tolyl) iodonium, and 4-isobutylphenyl (p-tolyl) iodonium.

  Among the onium ions in the compound represented by the formula (a1), a preferred onium ion is a sulfonium ion represented by the following formula (a19).

In the formula (a19), R ^8a independently represents a hydrogen atom, an alkyl, a hydroxy, an alkoxy, an alkylcarbonyl, an alkylcarbonyloxy, an alkyloxycarbonyl, a halogen atom, an aryl optionally having a substituent, an arylcarbonyl. Represents a group selected from the group consisting of: X ^2a represents the same meaning as ^{X 2a} in the formula (a1).

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

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

Particularly preferred R ^3a is a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms and a 100% fluorine atom substitution rate, and specific examples thereof include CF ₃ , CF ₃ CF ₂ , (CF ₃ ) ₂ CF, CF ₃ CF ₂ CF ₂ , CF ₃ CF ₂ CF ₂ CF ₂ , (CF ₃ ) ₂ CFCF ₂ , CF ₃ CF ₂ (CF ₃ ) CF, (CF ₃ ) ₃ C No. 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, particularly preferably 2 or 3.

Specific examples of preferable fluorinated alkylfluorophosphate anions include [(CF ₃ CF ₂ ) ₂ PF ₄ ] ⁻ , [(CF ₃ CF ₂ ) ₃ PF ₃ ] ⁻ , and [((CF ₃ ) ₂ CF) _2. PF ₄ ] ⁻ , [(CF ₃ ) ₂ CF) ₃ PF ₃ ] ⁻ , [(CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ] ⁻ , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ⁻ , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ⁻ , [(CF ₃ CF ₂ CF ₂ CF ₂ ) ₂ PF ₄ ] ⁻ , or [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , of 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 above formula (a18) include tetrakis (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ⁻ ) and tetrakis [(trifluoromethyl) phenyl] borate ( [B (C ₆ H ₄ CF ₃ ) ₄ ] ⁻ ), difluorobis (pentafluorophenyl) borate ([(C ₆ F ₅ ) ₂ BF ₂ ] ⁻ ), trifluoro (pentafluorophenyl) borate ([(C ^{_{6 F 5) BF 3] -}} ), tetrakis (difluorophenyl) borate _{([B (C 6 H 3} F 2) 4] -) , and the like. Among them, tetrakis (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ⁻ ) is particularly preferred.

  As the 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-diethoxyf Nyl) 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- Lichloromethyl-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, halogen-containing triazine compounds such as tris (2,3-dibromopropyl) -1,3,5-triazine and the following formula (a3) such as tris (2,3-dibromopropyl) isocyanurate And a halogen-containing triazine compound represented by the formula:

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

  Further, as a third embodiment of the acid generator (A), α- (p-toluenesulfonyloxyimino) -phenylacetonitrile, α- (benzenesulfonyloxyimino) -2,4-dichlorophenylacetonitrile, α- (benzene Contains sulfonyloxyimino) -2,6-dichlorophenylacetonitrile, α- (2-chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, and an oxime sulfonate group A compound represented by the following formula (a4):

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

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

As the acid generator represented by the formula (a4), when n = 1, a compound in which R ^12a is any one of a phenyl group, a methylphenyl group, and 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.

  The fourth embodiment of the acid generator (A) includes an onium salt having a naphthalene ring in a cation portion. The expression “having a naphthalene ring” means having a structure derived from naphthalene, which 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, and a linear or branched alkoxy group having 1 to 6 carbon atoms. Is also good. The structure derived from the naphthalene ring may be a monovalent group (having one free valence) or a divalent group (having two free valences) or more. Desirable (however, at this time, the free valence is counted except for the portion bonded to the substituent). The number of naphthalene rings is preferably from 1 to 3.

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

In the 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 is a linear or branched group having 1 to 6 carbon atoms. Represents an alkyl group, a phenyl group which may have a substituent, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Alternatively, one of R ^14a , R ^15a , and R ^16a is a group represented by the following formula (a6), and the other two are each independently a linear or branched group having 1 to 6 carbon atoms. And these terminals may be bonded to form a ring.

In the 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. It represents a branched alkyl group, and R ^19a represents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms which may have a substituent. l and m each independently represent an integer of 0 or more and 2 or less, and 1 + m is 3 or less. However, when a plurality of R ^17a are present, they may be the same or different. When a plurality of R ^18a are present, they may be the same or different.

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

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

  Examples of the substituent 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 alkoxy group having 1 to 6 carbon atoms. And the like.

  Examples of suitable cation moieties include those represented by the following formulas (a7) and (a8), and particularly preferred is a structure represented by the following formula (a8).

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

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

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

  The alkyl group in the fluoroalkylsulfonic acid ion may be linear, branched or cyclic having 1 to 20 carbon atoms, and having 1 to 10 carbon atoms in view of the bulk of the generated acid and its diffusion distance. Is preferred. In particular, a branched or annular one is preferable because the diffusion distance is short. Further, 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, such as an alkyl group, a phenyl group which may or may not be substituted with a halogen atom, and a naphthyl group. In particular, an aryl group having 6 to 10 carbon atoms is preferable because it can be synthesized at low cost. Specific examples of preferred examples include a phenyl group, a toluenesulfonyl group, an ethylphenyl group, a naphthyl group, and a methylnaphthyl group.

  In the above fluoroalkyl sulfonate ion or aryl sulfonate ion, when a part or all of the hydrogen atoms are fluorinated, the fluorination rate is preferably from 10% to 100%, more preferably from 50% to 100%. The following are preferred, particularly those in which all hydrogen atoms are replaced with fluorine atoms, since the strength of the acid is increased. Specific examples of such a material include trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctanesulfonate, perfluorobenzenesulfonate and the like.

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

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

In the above formula (a10), x represents an integer of 1 or more and 4 or less. In the formula (a11), R ^21a represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkyl group having 1 to 6 carbon atoms. 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.

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

The formula (a13), (a14) in, X ^a represents a linear or branched alkylene group having at least one hydrogen atom is substituted with a fluorine atom, the number of carbon atoms of the alkylene group 2 to 6 Or less, preferably 3 or more and 5 or less, and 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 by a fluorine atom, and the alkyl group has 1 to 10 carbon atoms. , Preferably 1 or more and 7 or less, more preferably 1 or more and 3 or less.

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

Further, an alkylene group or Y ^a of X ^a, the alkyl groups of Z ^a, the larger the number of hydrogen atoms substituted with fluorine atoms is large, preferred because the acid strength increases. The ratio of fluorine atoms in the alkylene group or the alkyl group, that is, the fluorination ratio 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. A perfluoroalkylene group or a perfluoroalkyl group substituted with an atom.

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

  In the fifth embodiment 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, nitrobenzyl sulfonate, nitro Nitrobenzyl derivatives such as benzyl carbonate and dinitrobenzyl carbonate; pyrogallol trimesylate, pyrogallol tritosylate, benzyl tosylate, benzylsulfonate, N-methylsulfonyloxysuccinine Sulfonic acid esters such as amide, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyloxymaleimide, N-methylsulfonyloxyphthalimide; N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) Trifluoromethanesulfonic acid esters such as -1,8-naphthalimide and N- (trifluoromethylsulfonyloxy) -4-butyl-1,8-naphthalimide; diphenyliodonium hexafluorophosphate, (4-methoxyphenyl) Phenyliodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate Onium salts such as (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate and (p-tert-butylphenyl) diphenylsulfonium trifluoromethanesulfonate; benzoin tosylate such as benzoin tosylate and α-methylbenzoin tosylate; and others Diphenyliodonium salt, triphenylsulfonium salt, phenyldiazonium salt, benzyl carbonate and the like.

  The acid generator (A) may be used alone or in combination of two or more. Further, the content of the acid generator (A) is preferably from 0.1% by mass to 10% by mass, and more preferably from 0.2% by mass to 6% by mass, based on the total solid content of the positive photosensitive resin composition. It is more preferably at most 0.5% by mass, particularly preferably at least 0.5% by mass and at most 3% by mass. By setting the amount of the acid generator (A) to be in the above range, it is easy to prepare a positive photosensitive resin composition having good sensitivity, a uniform solution, and excellent storage stability.

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

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

In the formula (b1), R ^1b represents an acid dissociable, dissolution inhibiting group, and R ^2b and R ^3b each independently represent 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), and linear, branched, or cyclic alkyl having 1 to 6 carbon atoms. It is preferably a group, a vinyloxyethyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, or a trialkylsilyl group.

In the 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, and R ^6b represents a carbon atom. 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 a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. . Examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl 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, Examples thereof include an isobutoxyethyl group, a tert-butoxyethyl group, a cyclohexyloxyethyl group, a methoxypropyl group, an ethoxypropyl group, a 1-methoxy-1-methyl-ethyl group, and a 1-ethoxy-1-methylethyl group. 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 the formula (b4), 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. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. Examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group.

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

  Further, the polyhydroxystyrene resin (B2) can contain another polymerizable compound as a structural unit for the purpose of appropriately controlling physical and chemical properties. Examples of such a polymerizable compound include known radically polymerizable compounds and anionic polymerizable compounds. Examples of such a polymerizable compound include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; 2-methacryloyloxyethyl succinic acid; Methacrylic acid derivatives having a carboxy group and an ester bond, such as methacryloyloxyethylmaleic acid, 2-methacryloyloxyethylphthalic acid, and 2-methacryloyloxyethylhexahydrophthalic acid; methyl (meth) acrylate, ethyl (meth) acrylate, and butyl Alkyl (meth) acrylates such as (meth) acrylate; hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; phenyl (meth) (Meth) acrylic acid aryl esters such as acrylate and benzyl (meth) acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxy Vinyl group-containing aromatic compounds such as styrene, α-methylhydroxystyrene and α-ethylhydroxystyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; acrylonitrile and methacrylonitrile And the like. Nitrile group-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 due to the action of an acid and is conventionally blended in various photosensitive resin compositions.
Acrylic resin (B3) is, for example, -SO 2 _- containing cyclic group, or preferably contains a structural unit (b-3) derived from an acrylate ester containing a lactone-containing cyclic group. In such a case, when forming the resist pattern, it is easy to form a resist pattern having a preferable cross-sectional shape.

(-SO ₂ - containing cyclic group)
Here, "- SO 2 _- containing cyclic group" means, -SO 2 _- within the ring skeleton thereof shows a cyclic group containing a ring containing, in particular, -SO 2 _- in the sulfur atom ( S) is a cyclic group forming a part of the cyclic skeleton of the cyclic group. The ring containing —SO ₂ — in the ring skeleton is counted as the first ring, and if the ring alone is a monocyclic group, and if it has another ring structure, it is a polycyclic group regardless of the structure. Called. The —SO ₂ —-containing cyclic group may be monocyclic or polycyclic.

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

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

-SO ₂ - containing cyclic group, -SO ₂ - may be a containing aliphatic cyclic group, -SO ₂ - may be a containing aromatic cyclic group. Preferably -SO ₂ - containing aliphatic cyclic group.

As the —SO ₂ —-containing aliphatic cyclic group, a hydrogen atom is derived from an aliphatic hydrocarbon ring in which part of carbon atoms constituting the ring skeleton is substituted with —SO ₂ — or —O—SO ₂ —. At least one group is excluded. More specifically, -CH 2 constituting the ring skeleton _- -CH ₂ constituting at least one group formed by removing a substituted hydrogen atom from an aliphatic hydrocarbon ring, the ring _- is -SO 2 - A group in which at least one hydrogen atom has been removed from an aliphatic hydrocarbon ring in which CH ₂ — has been 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. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane having 3 to 6 carbon atoms is preferable. Examples of the monocycloalkane include cyclopentane and cyclohexane. As the polycyclic alicyclic hydrocarbon ring, a group obtained by removing two hydrogen atoms from a polycycloalkane having 7 to 12 carbon atoms is preferable, 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 the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxygen atom (＝ O), —COOR ″, —OC (＝ O) R ″, a hydroxyalkyl group, a cyano group, 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 a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, and an n-hexyl group. Can be Among these, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.

  As the alkoxy group as the substituent, an alkoxy group having 1 to 6 carbon atoms is preferable. The alkoxy group is preferably linear or branched. Specifically, a group in which the above-described alkyl group as the substituent as the substituent is bonded to an oxygen atom (—O—) is exemplified.

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

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

  Examples of the halogenated alkyl group as the substituent include groups in which part or all of the hydrogen atoms of the above-described alkyl group as the alkyl group as the substituent have been substituted with the aforementioned 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 a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms.

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

  When R ″ is a cyclic alkyl group, the cyclic alkyl group preferably has 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and particularly preferably 5 to 10 carbon atoms. Specifically, a fluorine atom Or one or more hydrogen atoms may be removed from a monocycloalkane, which may or may not be substituted with a fluorinated alkyl group, or a polycycloalkane such as bicycloalkane, tricycloalkane, or tetracycloalkane. More specifically, one or more hydrogen atoms can be obtained from monocycloalkanes such as cyclopentane and cyclohexane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Excluded groups and the like.

  As the hydroxyalkyl group as the substituent, a hydroxyalkyl group having 1 to 6 carbon atoms is preferable. Specifically, a group in which at least one hydrogen atom of the alkyl group mentioned as the alkyl group as the substituent described above 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 specifically, examples of the —SO ₂ —-containing cyclic group include groups represented by the following formulas (3-1) to (3-4).

(In the formula, 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 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. As the alkylene group having 1 to 5 carbon atoms in A ', a linear or branched alkylene group is preferable, and examples thereof include a methylene group, an ethylene group, an n-propylene group, and an isopropylene group.

When the alkylene group contains an oxygen atom or a sulfur atom, specific examples thereof include a group in which -O- or -S- is interposed between the terminal or the carbon atom of the above-described alkylene group. _{CH 2 -, - CH 2 -O} -CH 2 -, - S-CH 2 -, - CH 2 -S-CH 2 - , and the like. A ′ is preferably an alkylene group having 1 to 5 carbon atoms or —O—, more preferably an alkylene group having 1 to 5 carbon atoms, and most preferably a methylene group.

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

As the alkyl group, the alkoxy group, the halogenated alkyl group, -COOR ", -OC (= O) R", and the hydroxyalkyl group for R ^10b , each may have a -SO ₂ -containing cyclic group. As the alkyl group, alkoxy group, halogenated alkyl group, -COOR ", -OC (= O) R", and hydroxyalkyl group mentioned as the substituent, the same as those described above can be mentioned.

  Hereinafter, specific cyclic groups represented by the above formulas (3-1) to (3-4) will be exemplified. Note that “Ac” in the formula represents an acetyl group.

As the —SO ₂ —-containing cyclic group, among the above, a group represented by the above formula (3-1) is preferable, and the above 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 any of the groups represented by the aforementioned chemical formulas (3-1-1). Are most preferred.

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

  The lactone cyclic group in the structural unit (b-3) is not particularly limited, and any lactone cyclic group can be used. Specifically, as the lactone-containing monocyclic group, 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 γ-butyrolactone Examples thereof include a group in which one hydrogen atom has been removed, and a group in which one hydrogen atom has been removed from δ-valerolactone. Examples of the lactone-containing polycyclic group include groups obtained by removing one hydrogen atom from bicycloalkane, tricycloalkane, and tetracycloalkane having a lactone ring.

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

[Structural unit (b-3-S)]
More specifically, examples of the structural unit (b-3-S) include a structural unit 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 the formula (b-S1), R is the same as described above.
R ^11b is the same as the above-mentioned —SO ₂ —-containing cyclic group.
R ^12b may be a single bond or a divalent linking group. From the viewpoint of excellent effects of the present invention, a divalent linking group is preferable.

The divalent linking group for R ^12b is not particularly limited, but preferred examples thereof include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.

-Divalent hydrocarbon group which may have a substituent The hydrocarbon group as a divalent linking group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated. Usually, a saturated hydrocarbon group is preferred. Specific examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group and an aliphatic hydrocarbon group having a ring in the structure.

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

As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable. Specifically, a methylene group _[-CH 2 -], an ethylene group _{[- (CH 2) 2 -} ], a trimethylene group _{[- (CH 2) 3 -} ], a tetramethylene group _{[- (CH 2) 4 -} ] And a pentamethylene group [-(CH ₂ ) _5- ].

As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable. _{Specifically, -CH (CH 3) -,} - CH (CH 2 CH 3) -, - C (CH 3) 2 -, - C (CH 3) (CH 2 CH 3) -, - C (CH _{3) (CH 2 CH 2 CH} 3) -, - C (CH 2 CH 3) 2 - alkyl groups such _{as; -CH (CH 3) CH 2} -, - CH (CH 3) CH (CH 3) - _{, -C (CH 3) 2 CH} 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH 2 CH 3) 2 -CH 2 - alkyl groups such as; -CH _(CH 3) CH Alkyl trimethylene groups such as ₂ CH ₂ — and —CH ₂ CH (CH ₃ ) CH ₂ —; —CH (CH ₃ ) CH ₂ CH ₂ CH ₂ — and —CH ₂ CH (CH ₃ ) CH ₂ CH ₂ — And the like, an alkylalkylene group such as an alkyltetramethylene group. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

  The above-mentioned linear or branched aliphatic hydrocarbon group may or may not have a substituent (a group or atom other than a hydrogen atom) for substituting a hydrogen atom. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom, and an oxo group (＝ O).

  Examples of the aliphatic hydrocarbon group containing a ring in the above structure include a cyclic aliphatic hydrocarbon group which may contain a substituent containing a hetero atom in the ring structure (excluding two hydrogen atoms from the aliphatic hydrocarbon ring). Group), a group in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, or a group in which the cyclic aliphatic hydrocarbon group is linear or branched. And a group interposed in the middle of the aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include the same as those described above.

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

  The 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 of 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 a polycycloalkane is preferable. The polycycloalkane preferably has 7 to 12 carbon atoms. Specific examples include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like.

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

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

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

  Examples of the halogen atom as the above substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, 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 groups have been substituted with the aforementioned halogen atoms.

In the cyclic aliphatic hydrocarbon group, some of the carbon atoms constituting the ring structure may be substituted with -O- or -S-. As the substituent containing a hetero atom, -O-, -C (= O) -O-, -S-, -S (= O) _2- , and -S (= O) _2- O- are preferable.

  The aromatic hydrocarbon group as a divalent hydrocarbon group is a divalent hydrocarbon group having at least one aromatic ring, and may have a substituent. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be 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 the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; an aromatic heterocyclic ring in which a part of carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom; And the like. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, a nitrogen atom and the like. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.

  Specific examples of the aromatic hydrocarbon group as the divalent hydrocarbon group include groups in which two hydrogen atoms have been removed from the above aromatic hydrocarbon ring or aromatic heterocyclic ring (arylene group or heteroarylene group); A group in which two hydrogen atoms have been removed from an aromatic compound containing two or more aromatic rings (eg, biphenyl, fluorene, etc.); a group in which one hydrogen atom has been removed from the above aromatic hydrocarbon ring or aromatic heterocyclic ring ( A group in which one of the hydrogen atoms of an aryl group or a heteroaryl group is substituted with an alkylene group (for example, a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, A group in which one hydrogen atom has been further removed from an aryl group in an arylalkyl group such as a naphthylethyl group);

  The number of carbon atoms of the alkylene group bonded to the above-mentioned aryl group or heteroaryl group is preferably 1 or more, 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 (ＯO).

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

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

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

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

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

Specific examples of the divalent linking group containing a hetero atom 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 connecting groups with a divalent hydrocarbon group. Examples of the divalent hydrocarbon group include the same as the above-described divalent hydrocarbon group which may have a substituent, and a linear or branched aliphatic hydrocarbon group is preferable. .

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

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

When the divalent linking group for R ^12b is a linear or branched alkylene group, the number of carbon atoms of the alkylene group is preferably 1 or more, 10 or less, more preferably 1 or more and 6 or less, and 1 or more and 4 or less. Is particularly preferable, and 1 to 3 is most preferable. Specifically, in the description of the “divalent hydrocarbon group which may have a substituent” as the above-mentioned divalent linking group, it is exemplified as a linear or branched aliphatic hydrocarbon group. And the same as the above-mentioned linear alkylene group and branched 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 described above for the divalent linking group. In the description of the “divalent hydrocarbon group”, the same as the cyclic aliphatic hydrocarbon group mentioned as the “aliphatic hydrocarbon group containing a ring in the structure” can be mentioned.

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

When the divalent linking group for R ^12b is a divalent linking group containing a hetero atom, 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 ^{-Y 1 -O-C (= O} ) -Y 2 - group represented by wherein, ^{Y 1,} and even ^{Y 2} is substituted independently 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 an acyl. The number of carbon atoms of the substituent (such as an alkyl group or an acyl group) 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.

In the formulas -Y ¹ -O-Y ² -,-[Y ¹ -C (＝ O) -O] _{m ′} -Y ^2- , or -Y ¹ -OC (＝ O) -Y ^2- , Y ¹ and Y ² are each independently a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include the same as the “divalent hydrocarbon group which may have a substituent” described in the description of the divalent linking group.

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

As Y ² , a linear or branched aliphatic hydrocarbon group is preferable, and a methylene group, an ethylene group, and an alkylmethylene group are more preferable. 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 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, the formula _{- (CH 2) a '-C} (= O) -O- (CH 2) b' - a group represented by are preferred. In the formula, a ′ is an integer of 1 or more and 10 or less, preferably 1 or more and 8 or less, more preferably 1 or more and 5 or less, still more preferably 1 or 2, and most preferably 1. b ′ is an integer of 1 or more and 10 or less, preferably an integer of 1 or more and 8 or less, more preferably an integer of 1 or more and 5 or less, further preferably 1 or 2, and most preferably 1.

Regarding the divalent linking group represented by R ^12b, an organic group including a combination of at least one non-hydrocarbon group and a divalent hydrocarbon group is preferable as the divalent linking group containing a hetero atom. Among them, a linear group having an oxygen atom as a hetero atom, for example, a group containing an ether bond or an ester bond is preferable, and the above-mentioned formulas -Y ¹ -O-Y ² -,-[Y ¹ -C (= O) —O] _{m ′} —Y ² — or —Y ¹ —O—C (＝ O) —Y ² — is more preferable, and a group represented by the above formula — [Y ¹ —C (前述 O) is preferred. —O] _{m ′} —Y ² — or —Y ¹ —OC (＝ O) —Y ² — is particularly preferable.

As the divalent linking group for R ^12b , an alkylene group or a group containing an ester bond (—C (＝ O) —O—) is preferable.

The alkylene group is preferably a linear or branched alkylene group. Suitable examples of the linear aliphatic hydrocarbon group include a methylene group _[-CH 2 -], an ethylene group _{[- (CH 2) 2 -} ], a trimethylene group _{[- (CH 2) 3 -} ], a tetramethylene group _{[- (CH 2) 4 -} ], and a pentamethylene group _{[- (CH 2) 5 -} ] , and the like. Suitable examples of this branched chain alkylene _{group, -CH (CH 3) -,} - CH (CH 2 CH 3) -, - C (CH 3) 2 -, - C (CH 3) (CH 2 _{CH 3) -, - C (} CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - alkyl groups such _{as; -CH (CH 3) CH 2} -, - CH ( _{CH 3) CH (CH 3)} -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH 2 CH 3) 2 -CH 2 - alkyl ethylene such as _{group; -CH (CH 3) CH 2} CH 2 -, - CH 2 CH (CH 3) CH 2 - alkyl trimethylene groups such _{as; -CH (CH 3) CH 2} CH 2 CH 2 -, - CH 2 CH _{(CH 3) CH 2 CH 2} - alkyl, such as alkyl tetramethylene group such as Such as an alkylene group, and the like.

As the divalent linking group containing an ester bond, in particular, 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 described above, and R ^13b is a divalent linking group.)

R ^13b is not particularly limited, and includes, for example, those similar to the divalent linking group for R ^12b described above.
As the divalent linking group for R ^13b, a linear or branched alkylene group, an aliphatic hydrocarbon group containing a ring in the structure, or a divalent linking group containing a hetero atom is preferable. Alternatively, a branched alkylene group or a divalent linking group containing an oxygen atom as a hetero atom is preferable.

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

As the divalent linking group containing an oxygen atom, a divalent linking group containing an ether bond or an ester bond is preferable, and the above-described -Y ¹ -O-Y ² -,-[Y ¹ -C (= O ^{_{) -O] m '-Y 2 -}} , or ^{-Y 1 -O-C (= O} ) -Y 2 - is more preferable. Y ¹ and Y ² are 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 preferable, and a group represented by-(CH ₂ ) _c -OC (= O)-(CH ₂ ) _d- is particularly preferable. . c is an integer of 1 or more and 5 or less, preferably 1 or 2. d is an integer of 1 or more and 5 or less, and 1 or 2 is preferable.

  As the structural unit (b-3-S), a structural unit represented by the following formula (b-S1-11) or (b-S1-12) is particularly preferable, and in the formula (b-S1-12) The constituent units represented 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。）

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

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

As R ^13b , a linear or branched alkylene group or a divalent linking group containing an oxygen atom is preferable. ^Examples of the linear or branched alkylene group and the oxygen-containing divalent linking group represented by R ^13b include the aforementioned linear or branched alkylene group and the oxygen-containing divalent linking group, respectively. And the same.

  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。）

(In the formula, R and A ′ are the same as described 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, for example, those in which R ^11b in the above formula (b-S1) is substituted with a lactone-containing cyclic group, and more specifically, the following formula ( and structural units represented by (b-L1) to (b-L5).

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

(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. R ^12b is a single bond, or a halogenated alkyl group, a hydroxyl group, —COOR ″, —OC (＝ O) R ″, a hydroxyalkyl group, or a cyano group; R ″ is a hydrogen atom or an alkyl group; A divalent linking group, s "is an integer of 0 to 2; 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; Is an atom; r is 0 or 1.)

R in the formulas (b-L1) to (b-L5) is the same as described above.
The alkyl group in R ', alkoxy group, halogenated alkyl group, -COOR ", - OC (= O) R", The hydroxyalkyl group, respectively, -SO ₂ - may have the containing cyclic group The same alkyl groups, alkoxy groups, halogenated alkyl groups, -COOR ", -OC (= O) R", and hydroxyalkyl groups as those described above as the substituents can be used.

R 'is preferably a hydrogen atom in view of industrial availability and the like.
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, and 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, it may be substituted with a fluorine atom or a fluorinated alkyl group, and may or may not be substituted with one or more monocycloalkanes, bicycloalkanes, tricycloalkanes, polycycloalkanes such as tetracycloalkanes, etc. Examples thereof include groups excluding hydrogen atoms, etc. Specifically, one or more monocycloalkanes such as cyclopentane and cyclohexane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane are exemplified. Examples thereof include groups excluding a hydrogen atom.
A "is 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. As the alkylene group having 1 to 5 carbon atoms, a methylene group or a dimethylmethylene group is more preferable, and a methylene group is most preferable.

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

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

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

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

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

In the formulas (b5) to (b7), R ^14b and R ^{18b to} R ^23b each independently represent 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, and independently represents a linear chain having 1 to 6 carbon atoms. A branched 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 And Moni may form a 5 carbon atoms to 20 hydrocarbon ring, Y ^b represents an aliphatic cyclic group or an alkyl group which may have a substituent, p is 0 to 4 And q represents 0 or 1.

In addition, examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. No. Further, the fluorinated alkyl group is a group in which part or all of the hydrogen atoms of the above-mentioned alkyl group have been substituted with fluorine atoms.
Specific examples of the aliphatic cyclic group include groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as a monocycloalkane, a bicycloalkane, a tricycloalkane, and a tetracycloalkane. Specifically, a group obtained by removing one hydrogen atom from a monocycloalkane such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Is mentioned. In particular, a group in which one hydrogen atom has been removed from cyclohexane or adamantane (and may further have a substituent) is preferred.

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

R ^16b and R ^17b may form an aliphatic cyclic group having 5 to 20 carbon atoms together with the carbon atom to which both are bonded. Specific examples of such an aliphatic cyclic group include groups obtained by removing one or more hydrogen atoms from a polycycloalkane such as a monocycloalkane, a bicycloalkane, a tricycloalkane, and a tetracycloalkane. 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, a group in which one or more hydrogen atoms have been removed from cyclohexane or adamantane (which may further have a substituent) is preferable.

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

^Yb is an aliphatic cyclic group or an alkyl group, and examples thereof include groups in which one or more hydrogen atoms have been removed 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 in which one or more hydrogen atoms have been removed from adamantane (which may further have a substituent) is preferable.

Furthermore, the alicyclic group of the abovementioned Y ^b is, if they have a substituent on the ring skeleton, examples of the substituents include a hydroxyl group, a carboxyl group, a cyano group, an oxygen atom (= O) polar groups such as And a linear or branched alkyl group having 1 to 4 carbon atoms. As the polar group, an oxygen atom (＝ O) is particularly preferable.

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 an alkyl group is particularly preferably an alkoxyalkyl group, such as a 1-methoxyethyl group, a 1-ethoxyethyl group, a 1-n-propoxyethyl group, and a 1-isopropoxy group. 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.

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

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

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

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

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

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

  Further, the acrylic resin (B3) is a resin comprising a copolymer containing a structural unit 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 a radical polymerizable compound having an ether bond and an ester bond, such as a (meth) acrylic acid derivative. Specific examples thereof 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) Examples include acrylate, methoxypolypropylene glycol (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate. The polymerizable compound having an ether bond is preferably 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, or methoxytriethylene glycol (meth) acrylate. These polymerizable compounds may be used alone or in combination of two or more.

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

  Examples of such a polymerizable compound include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; 2-methacryloyloxyethyl succinic acid and 2-methacryloyloxy Methacrylic acid derivatives having a carboxy group and an ester bond such as ethylmaleic acid, 2-methacryloyloxyethylphthalic acid, and 2-methacryloyloxyethylhexahydrophthalic acid; methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) ) Acrylates, alkyl (meth) acrylates such as cyclohexyl (meth) acrylate; hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate Esters; aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloro Vinyl group-containing aromatic compounds such as methylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene Classes: Nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; Chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; and amide bond-containing polymerizable compounds such as acrylamide and methacrylamide. That.

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

  Examples of the polymerizable compound include (meth) acrylic esters having an acid non-dissociable aliphatic polycyclic group, and aromatic compounds containing a vinyl group. As the acid non-dissociable aliphatic polycyclic group, a tricyclodecanyl group, an adamantyl group, a tetracyclododecanyl group, an isobornyl group, a norbornyl group, and the like are particularly preferable from the viewpoint 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 the (meth) acrylates having an acid non-dissociable aliphatic polycyclic group include those having the structures of the following formulas (b8-1) to (b8-5). it can.

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

When the acrylic resin (B3) contains a structural unit (b-3) containing a —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% by mass or more, more preferably 10% by mass or more, particularly preferably 10% by mass or more and 50% by mass or less, most preferably 10% by mass or more and 30% by mass or less. When the positive 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 a good pattern shape.

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

  The acrylic resin (B3) preferably contains a structural unit derived from the above 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 from 0% by mass to 50% by mass, more preferably from 5% by mass to 30% by mass.

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

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

  The mass average molecular weight in terms of polystyrene of the resin (B) described above is preferably from 10,000 to 600,000, more preferably from 20,000 to 400,000, and still more preferably from 30,000 to 300,000. By having such a mass average molecular weight, it is possible to maintain a sufficient strength of the photosensitive layer composed of the positive photosensitive resin composition without deteriorating the releasability from the substrate, and furthermore, swelling of the profile during plating and the like. And the occurrence of cracks can be prevented.

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

  The content of the resin (B) is preferably 5% by mass or more and 60% by mass or less based on the total solid content of the positive photosensitive resin composition.

（式（Ｃ−Ｉ）中、Ｘ^ｃ１は有機連結基であり、Ｒ^ｃ０１は、水素原子、又はスルホン酸エステル構造を含まない有機基であり、Ｒ^ｃ０２は、炭素原子上に結合手を有する１価の有機基であり、ｎ１は、１以上４以下の整数であり、ｎ２は、１以上４以下の整数であり、Ｒ^ｃ０２は、Ｘ^ｃ１を構成する元素のいずれか１つと結合して環を形成してもよい。）
で表される化合物、及び／又は、下記式（Ｃ−ＩＩ）：

（式（Ｃ−ＩＩ）中、Ｘ^ｃ２及びＸ^ｃ３は、それぞれ有機連結基であり、Ｘ^ｃ４は、単結合、又は２価の有機基であり、Ｒ^ｃ０３及びＲ^ｃ０４は、それぞれ、炭素原子上に結合手を有する１価の有機基であり、ｎ３及びｎ４は、それぞれ、１以上３以下の整数であり、ｎ３＋ｎ４は２以上４以下の整数であり、Ｒ^ｃ０３は、Ｘ^ｃ２を構成する元素のいずれか１つと結合して環を形成してもよく、Ｒ^ｃ０４は、Ｘ^ｃ３を構成する元素のいずれか１つと結合して環を形成してもよい。）
で表される化合物である。 <Sulfur-containing compound (C)>
The positive photosensitive resin composition contains a sulfur-containing compound (C). When the positive photosensitive resin composition contains the sulfur-containing compound (C) having the following predetermined structure, a highly sensitive photosensitive resin composition can be easily obtained. The sulfur-containing compound (C) has the following formula (C-I):

(In the formula (CI), X ^c1 is an organic linking group, R ^c01 is a hydrogen atom or an organic group not containing a sulfonic acid ester structure, and R ^c02 has a bond on a carbon atom. A monovalent organic group, n1 is an integer of 1 or more and 4 or less, n2 is an integer of 1 or more and 4 or less, and R ^c02 is bonded to any one of the elements constituting X ^c1. (A ring may be formed.)
And / or the following formula (C-II):

(In the formula (C-II), X ^c2 and X ^c3 are each an organic linking group, X ^c4 is a single bond or a divalent organic group, and R ^c03 and R ^c04 are each a carbon atom A monovalent organic group having a bond above, n3 and n4 are each an integer of 1 or more and 3 or less, n3 + n4 is an integer of 2 or more and 4 or less, and R ^c03 constitutes X ^c2 (A ring may be formed by bonding with any one of the elements, and R ^c04 may be bonded with any one of the elements constituting X ^c3 .)
It is a compound represented by these.

In the formula (CI), R ^c01 is a hydrogen atom or an organic group containing no sulfonic acid ester structure. The organic group containing no sulfonic acid ester structure may be a hydrocarbon group or an organic group containing a hetero atom such as O, S, N, P, B, Si, and a halogen atom.
R ^c01 is preferably a hydrogen atom, a hydrocarbon group, or an acyl group from the viewpoint of easy synthesis and availability of the compound represented by the formula (CI). The number of carbon atoms of the hydrocarbon group and the acyl group is, for example, preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 4 or less.

The hydrocarbon group as R ^c01 may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. When R ^c01 is an aliphatic hydrocarbon group, the structure of the aliphatic hydrocarbon group may be linear, branched, or cyclic, or a combination of these structures. You may. When R ^c01 is an aliphatic hydrocarbon group, the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group.

Preferred examples of the hydrocarbon group as R ^c01 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, alkyl groups such as n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, and n-decyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cycloheptyl group, and Cycloalkyl groups such as cyclooctyl group; and aromatic hydrocarbon groups such as phenyl group, naphthalen-1-yl group, and naphthalen-2-yl group.
Preferred examples of the acyl group as R ^c01 include an acetyl group, a propionyl group, a butanoyl group, a pentanoyl group, a hexanoyl group, a heptanoyl group, an octanoyl group, a nonanoyl group, a decanoyl group, and a benzoyl group.

Among the groups described above, R ^c01 is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an acetyl group, and a propionyl group, and a hydrogen atom, a methyl group, an ethyl group, an acetyl group, And a propionyl group are more preferred, and an acetyl group and a propionyl group are still more preferred.

In the formula (CI), R ^c02 is a monovalent organic group having a bond on a carbon atom. Further, R ^c02 may be combined with any one of the elements constituting X ^c1 to form a ring.
R ^c02 may be a hydrocarbon group or an organic group containing a hetero atom such as O, S, N, P, B, Si, and a halogen atom, as long as it has a bond on a carbon atom. Good.
In the compounds of the formula ^(C-I), and ^{X c1,} and _-SO 2 ^-O-, and ^{R c02} is not to form a group having a cyclic group containing _-SO 2 -O- bond In this case, R ^c02 is preferably a hydrocarbon group from the viewpoint of easy synthesis and availability of the compound represented by the formula (C-I).
In this case, preferred examples of the hydrocarbon group as R ^c02 are the same as the preferred examples of the hydrocarbon group as R ^c01.

（式（Ｃ１）中、Ｒ^ｃ０１、ｎ１、及びｎ２は、前記式（Ｃ−Ｉ）と同様であり、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−ＳＲ^ｃ０１で表される基と結合し、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、−ＣＯ−Ｏ−ＣＨ（Ｒ^ｃ２）（Ｒ^ｃ３）で表されるｎ２個の基のそれぞれにおいて、Ｒ^ｃ２及びＲ^ｃ３のうちの少なくとも１つが−Ｒ^ｃ４−ＳＯ_２−Ｏ−Ｒ^ｃ５で表される基であり、Ｒ^ｃ４は２価の有機基であり、Ｒ^ｃ５は炭素原子上に結合手を有する１価の有機基であり、−ＣＯ−Ｏ−ＣＨ（Ｒ^ｃ２）（Ｒ^ｃ３）で表されるｎ２個の基の少なくとも１つにおいて、Ｒ^ｃ２とＲ^ｃ３とが結合して、環構造中に−ＳＯ_２−Ｏ−で表される２価基を含む脂肪族環を形成していてもよい。）
で表される化合物であるのが好ましい。 When the sulfur-containing compound (C) is a compound represented by the formula (C-I), the compound represented by the formula (C-I) is represented by the following formula (C1):

(In the formula (C1), R ^c01 , n1 and n2 are the same as those in the formula (C-I), R ^c1 is an (n1 + n2) ^-valent organic group, and R ^c1 is a C—C bond. R ^c2 and R ^c3 are each independently a hydrogen atom or a monovalent organic group, and are bonded to a carbonyl group and a group represented by —SR ^c01 by a C—S bond. in each of n2 groups represented by ^{-CH (R c2) (R c3} ), a group at least one of ^{R c2} and ^{R c3} represented by ^-R c4 _-SO 2 ^{-O-R c5} R ^c4 is a divalent organic group, R ^c5 is a monovalent organic group having a bond on a carbon atom, and is represented by —CO—O—CH (R ^c2 ) (R ^c3 ) in at least one n2 ^groups, by bonding with ^{R c2} and ^{R c3,} ring structure It may form an aliphatic ring containing divalent group represented by -SO 2 _-O- in.)
Preferably, the compound is represented by

R ^c1 is an (n1 + n2) -valent organic group. The (n1 + n2) -valent organic group as R ^c1 may include a hetero atom. However, in the sulfur-containing compound (C) represented by the formula (C1), R ^c1 binds to a carbonyl group by a CC bond and binds to a group represented by R ^c01 S- by a ^CS bond. I do.
That is, each bond of the organic group as R ^c1 is bonded to a carbon atom in the organic group.
Further, the divalent organic group may have an unsaturated bond.

Examples of the hetero atom that may be contained in the organic group as R ^c1 include a halogen atom, an oxygen atom, a nitrogen atom, a phosphorus atom, and a silicon atom. The hetero atom may be present in a substituent bonded to the main skeleton of the divalent organic group, or may be present as a part of a bond constituting the divalent organic group.

Examples of the substituent containing a hetero atom include a halogen atom, a hydroxyl group, a mercapto group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, and an acyl group. group, an acyloxy group, an acylthio group, an alkoxycarbonyl group, a cycloalkyl group, an aryloxycarbonyl group, an amino group, N- mono-substituted amino group, N, N- disubstituted amino group, a carbamoyl group (-CO-NH ₂ ), N-monosubstituted carbamoyl groups, N, N-disubstituted carbamoyl groups, nitro groups, cyano groups and the like.

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

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

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

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

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

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

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

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

  Although the number of carbon atoms of 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. The alkoxycarbonyl group may be linear or branched. Specific examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propyloxycarbonyl group, an isopropyloxycarbonyl group, an n-butyloxycarbonyl group, an isobutyloxycarbonyl group, a sec-butyloxycarbonyl group, and a tert- Examples include a butyloxycarbonyl group, an n-pentyloxycarbonyl group, and an n-hexyloxycarbonyl group.

  The number of carbon atoms of the cycloalkyloxycarbonyl group is not particularly limited, but is preferably 4 or more and 11 or less, 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, a cyclononyloxycarbonyl group , And cyclodecyloxycarbonyl groups.

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

Regarding the N-mono-substituted amino group and the N, N-di-substituted amino group, the type of the substituent bonded to the nitrogen atom is not particularly limited. Preferable examples of the substituent bonded to the nitrogen atom include a linear or branched alkyl group having 1 to 6 carbon atoms and a cyclo group 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 the N-monosubstituted amino group include a methylamino group, an ethylamino group, an n-propylamino group, an isopropylamino group, an n-butylamino group, an isobutylamino group, a sec-butylamino group, and a 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, naphthalen-1-ylamino group, naphthalen-2-ylamino group, biphenylylamino group, acetylamino group, propionylamino group, butanoylamino group, pentanoylamino group, hexanoylamino group, Octanoylamino group, Nanoiruamino group, decanoyl group, a benzoylamino group, a naphthalene-1-yl carbonylamino group, and naphthalene-2-yl carbonylamino group.
Preferred examples of the N, N-disubstituted amino group include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, a diisobutylamino group, and a disec-butylamino group. Ditert-butylamino group, di-n-pentylamino group, di-n-hexylamino group, dicyclopentylamino group, dicyclohexylamino group, diphenylamino group, diacetylamino group, dipropionylamino group, and dibenzoylamino group No.

Regarding the N-monosubstituted carbamoyl group and the N, N-disubstituted carbamoyl group, the type of the substituent bonded to the nitrogen atom is not particularly limited. Preferred examples of the substituent bonded to the nitrogen atom are the same as those described for the N-monosubstituted amino group and the N, N-disubstituted amino group.
Preferred specific examples of the N-monosubstituted aminocarbamoyl group include N-methylcarbamoyl, N-ethylcarbamoyl, Nn-propylcarbamoyl, N-isopropylcarbamoyl, Nn-butylcarbamoyl, -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-na Taren-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 -2-ylcarbonylcarbamoyl group.
Preferred examples of the N, N-disubstituted carbamoyl group include N, N-dimethylcarbamoyl, N, N-diethylcarbamoyl, N, N-di-n-propylcarbamoyl, N, N-diisopropylcarbamoyl, N, N-di-n-butylcarbamoyl group, N, N-diisobutylcarbamoyl group, N, N-disec-butylcarbamoyl group, N, N-ditert-butylcarbamoyl group, N, N-din-pentylcarbamoyl Group, N, N-di-n-hexylcarbamoyl group, N, N-dicyclopentylcarbamoyl group, N, N-dicyclohexylcarbamoyl group, N, N-diphenylcarbamoyl group, N, N-diacetylcarbamoyl group, N, N- Examples include a dipropionylcarbamoyl group and an N, N-dibenzoylcarbamoyl group.

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

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 particularly 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, and is preferably linear.

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

When R ^c1 is a saturated aliphatic hydrocarbon group, an alkylene group is preferable as the saturated aliphatic hydrocarbon group because the compound represented by the formula (C1) can be easily synthesized or obtained. Preferred examples of the alkylene group for R ^c1 include a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group. A diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, and a decane-1,10-diyl group. Can be
Among them, methylene group, ethane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, and hexane-1,6 -Diyl group is preferred, methylene group, ethane-1,2-diyl group and propane-1,3-diyl group are more preferred, and methylene group and ethane-1,2-diyl group are particularly preferred.

In the formula (C1), R ^c2 and R ^c3 are each independently a hydrogen atom or a monovalent organic group.
In formula ^{(C1), -CO-O-} CH (R c2) in each of n2 groups represented by ^{(R c3),} at least one of ^{R c2} and ^{R c3 -R} c4 -SO ₂ - It is a group represented by O-R ^c5 .
R ^c4 is a divalent organic group, and R ^c5 is a monovalent organic group having a bond on a carbon atom.
^{Further, -CO-O-CH (R} c2) at least one of n2 groups represented by ^{(R c3),} by bonding with ^{R c2} and ^{R c3,} _-SO 2 -O in the ring An aliphatic ring containing a divalent group represented by-may be formed.

In formula ^{(C1), -CO-O-} CH (R c2) in each of n2 groups represented by ^{(R c3),} at least one of ^{R c2} and ^{R c3 -R} c4 -SO ₂ - When it is a group represented by O-R ^c5 , R ^c5 is the same as R ^c02 described for formula (CI).

（式（３−１）及び式（３−３）中の略号の定義については前述した通りである。） In the formula (C1), in a group represented by —CO—O—CH (R ^c2 ) (R ^c3 ), R ^c2 and R ^c3 are bonded to each other and represented by —SO ₂ —O— in the ring structure. When forming an aliphatic ring containing a divalent group represented by the following formula, examples of the cyclic group formed by the group represented by -CH ( ^Rc2 ) ( ^Rc3 ) include the following formula (3-1) or Examples include a group represented by the formula (3-3).

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

Preferred specific examples of the cyclic groups represented by the above formulas (3-1) and (3-3) include the following groups.

  As the compound represented by the above formula (C1), n1 and n2 are each 1 because of the ease of synthesis and availability of the sulfur-containing compound (C) and the difficulty in generating a residue after development. Preferably it is.

In the formula (C1), when n1 and n2 are each 1 and —CO—O—CH (R ^c2 ) (R ^c3 ) does not form a ring, as a compound represented by the formula (C1), Compounds of the following formula are preferred.
In the following formula, R ^c10 is an acetyl group or a propionyl group. R ^c11 is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or a phenyl group. Ph is an o-phenylene group, an m-phenylene group, or a p-phenylene group, and a p-phenylene group is preferable.
_{^{R c10 S-CH 2 -CO-}} O-CH 2 -SO 2 -O-R c11
R ^c10 S-CH ₂ -CO-O-CH ₂ CH ₂ -SO ₂ -OR ^{c 11
_{R c10 S-CH 2 -CO-}} O-CH (CH 3) -SO 2 -O-R c11
_{^{R c10 S-CH 2 -CO-}} O-CH 2 CH 2 CH 2 -SO 2 -O-R c11
R ^c10 S—CH ₂ —CO—O—CH ₂ CH (CH ₃ ) —SO ₂ —O—R ^{c11
_{R c10 S-CH 2 -CO-}} O-CH (CH 3) CH 2 -SO 2 -O-R c11
R ^c10 S-CH ₂ -CO-O-Ph-SO ₂ -OR ^{c 11
_{R c10 S-CH 2 CH 2}} -CO-O-CH 2 -SO 2 -O-R c11
_{^{R c10 S-CH 2 CH 2}} -CO-O-CH 2 CH 2 -SO 2 -O-R c11
_{^{R c10 S-CH 2 CH 2}} -CO-O-CH (CH 3) -SO 2 -O-R c11
_{^{R c10 S-CH 2 CH 2}} -CO-O-CH 2 CH 2 CH 2 -SO 2 -O-R c11
_{^{R c10 S-CH 2 CH 2}} -CO-O-CH 2 CH (CH 3) -SO 2 -O-R c11
_{^{R c10 S-CH 2 CH 2}} -CO-O-CH (CH 3) CH 2 -SO 2 -O-R c11
R ^c10 S-CH ₂ CH ₂ -CO-O-Ph-SO ₂ -OR ^{c 11
_{R c10 S-CH 2 CH 2}} CH 2 -CO-O-CH 2 -SO 2 -O-R c11
_{^{R c10 S-CH 2 CH 2}} CH 2 -CO-O-CH 2 CH 2 -SO 2 -O-R c11
_{^{R c10 S-CH 2 CH 2}} CH 2 -CO-O-CH (CH 3) -SO 2 -O-R c11
R ^c10 S-CH ₂ CH ₂ CH ₂ —CO—O—CH ₂ CH ₂ CH ₂ —SO ₂ —O—R ^{c11
_{R c10 S-CH 2 CH 2}} CH 2 -CO-O-CH 2 CH (CH 3) -SO 2 -O-R c11
_{^{R c10 S-CH 2 CH 2}} CH 2 -CO-O-CH (CH 3) CH 2 -SO 2 -O-R c11
_{^{R c10 S-CH 2 CH 2}} CH 2 -CO-O-Ph-SO 2 -O-R c11
_{^{R c10 S-CH 2 CH 2}} CH 2 CH 2 -CO-O-CH 2 -SO 2 -O-R c11
_{^{R c10 S-CH 2 CH 2}} CH 2 CH 2 -CO-O-CH 2 CH 2 -SO 2 -O-R c11
_{^{R c10 S-CH 2 CH 2}} CH 2 CH 2 -CO-O-CH (CH 3) -SO 2 -O-R c11
R ^c10 S-CH ₂ CH ₂ CH ₂ CH ₂ -CO-O-CH ₂ CH ₂ CH ₂ -SO ₂ -OR ^{c 11
_{R c10 S-CH 2 CH 2}} CH 2 CH 2 -CO-O-CH 2 CH (CH 3) -SO 2 -O-R c11
_{^{R c10 S-CH 2 CH 2}} CH 2 CH 2 -CO-O-CH (CH 3) CH 2 -SO 2 -O-R c11
_{^{R c10 S-CH 2 CH 2}} CH 2 CH 2 -CO-O-Ph-SO 2 -O-R c11

In the compound represented by the formula (C1), n1 and n2 are each 1, and in the group represented by —CO—O—CH ( ^Rc2 ) ( ^Rc3 ), ^Rc2 and ^Rc3 are bonded. When forming an aliphatic ring containing a divalent group represented by —SO ₂ —O— in the ring structure, a preferred example of the compound represented by the formula (C1) is represented by the following formula: Compounds.
In the following formula, R ^c10 is an acetyl group or a propionyl group, and R ^c12 is a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, or a butane-1,4-diyl. Group.

The compound represented by the formula (C1) described above is, for example, a carboxylic acid compound represented by the formula (C1-a) and an alcohol represented by the formula (C1-b) in the following reaction formula: It can be synthesized by esterification according to a well-known method.

Next, the compound represented by the above formula (C-II) will be described. ^{R c03} and ^{R c04} in the formula (C-II) are respectively the same as ^{R c02} in the formula (C-I).
Further, X ^c2 and RX ^c3 in the above formula (C-II) are respectively the same as X ^c1 in the formula (CI).

In the formula (C-II), n3 and n4 are each 1 because of the ease of synthesis and availability of the sulfur-containing compound represented by the formula (C-II), and the difficulty in generating a residue after development. It is preferred that
X ^c4 in the formula (C-II) is a single bond or a divalent organic group. When ^Xc4 is a divalent organic group, the organic group may be an organic group containing O, S, N, P, B, Si, a halogen atom, or the like, or may be a hydrocarbon group. . When ^Xc4 is a divalent organic group, the organic group is preferably a hydrocarbon group.
When X ^c4 is a hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. It may be. When ^Xc4 is an aliphatic hydrocarbon group, the structure of the aliphatic hydrocarbon group may be linear, branched, or cyclic, or a combination of these structures. You may. When ^Xc4 is an aliphatic hydrocarbon group, the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group.

Preferred examples of the hydrocarbon group as ^Xc4 include a methylene group, an ethane-1,2-diyl group, an ethane-1,1-diyl group, a propane-1,3-diyl group, and a propane-1,2-diyl. Group, propane-1,1-diyl group, propane-2,2-diyl group, butane-1,4-diyl group, butane-1,3-diyl group, butane-1,2-diyl group, pentane-1 , 5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, and decane-1,10-diyl Alkylene group such as a group; cyclopentane-1,2-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,2-diyl group, cyclohexane-1,3-diyl group, and hexane-1,4 -Cycloalkyl such as diyl group O-phenylene group, m-phenylene group, p-phenylene group, naphthalene-2,6-diyl group, naphthalene-2,7-diyl group, naphthalene 2,3-diyl group, naphthalene-1,3- And divalent aromatic hydrocarbon groups such as a diyl group and a naphthalene-1,4-diyl group.
As X ^c4 , among the groups described above, a single bond and an alkylene group are preferable, a single bond and an alkylene group having 1 to 10 carbon atoms are preferable, and a single bond, a methylene group, and ethane-1,2- Diyl group, ethane-1,1-diyl group, propane-1,3-diyl group, propane-1,2-diyl group, propane-1,1-diyl group, propane-2,2-diyl group, butane- A 1,4-diyl group, a butane-1,3-diyl group, and a butane-1,2-diyl group are more preferred, and a single bond, a methylene group, and an ethane-1,2-diyl group are still more preferred.

（式（Ｃ２）中、ｎ３及びｎ４は、前記式（Ｃ−ＩＩ）と同様であり、Ｒ^ｃ６は、（ｎ３＋１）価の有機基であり、Ｒ^ｃ７は（ｎ４＋１）価の有機基であり、Ｒ^ｃ６及びＲ^ｃ７は、それぞれ、Ｃ−Ｃ結合によってカルボニル基と結合し、且つＣ−Ｓ結合によってジスルフィド結合と結合し、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、−ＣＯ−Ｏ−ＣＨ（Ｒ^ｃ２）（Ｒ^ｃ３）で表される（ｎ３＋ｎ４）個の基のそれぞれにおいて、Ｒ^ｃ２及びＲ^ｃ３のうちの少なくとも１つが−Ｒ^ｃ４−ＳＯ_２−Ｏ−Ｒ^ｃ５で表される基であり、Ｒ^ｃ４は２価の有機基であり、Ｒ^ｃ５は炭素原子上に結合手を有する１価の有機基であり、−ＣＯ−Ｏ−ＣＨ（Ｒ^ｃ２）（Ｒ^ｃ３）で表される（ｎ３＋ｎ４）個の基の少なくとも１つにおいて、Ｒ^ｃ２とＲ^ｃ３とが結合して、環構造中に−ＳＯ_２−Ｏ−で表される２価基を含む脂肪族環を形成していてもよい。）
で表される化合物であるのが好ましい。 When the sulfur-containing compound (C) is a compound represented by the formula (C-II), the compound represented by the formula (C-II) is represented by the following formula (C2):

(In the formula (C2), n3 and n4 are the same as those in the formula (C-II), R ^c6 is a (n3 + 1) -valent organic group, and R ^c7 is a (n4 + 1) -valent organic group. , R ^c6 and R ^c7 are each bonded to a carbonyl group by a C—C bond and bonded to a disulfide bond by a C—S bond, and R ^c2 and R ^c3 are each independently a hydrogen atom or a monovalent group. an organic ^{group, -CO-O-CH (R} c2) in each represented by (n3 + n4) number of groups ^{(R c3),} at least one of ^{R c2} and ^{R c3 -R} c4 -SO ₂ A group represented by —O—R ^c5 , R ^c4 is a divalent organic group, R ^c5 is a monovalent organic group having a bond on a carbon atom, and —CO—O—CH ( R ^{c2) (represented} by ^{R c3)} (n3 + n4) number of groups In at least ^one, by bonding with ^{R c2} and ^{R c3,} it may form an aliphatic ring containing divalent group represented by _-SO 2 -O- in the ring structure.)
Preferably, the compound is represented by

In Formula (C2), R ^c6 is a (n3 + 1) -valent organic group, and R ^c7 is a (n4 + 1) -valent organic group. The organic groups as R ^c6 and R ^c7 may each include a hetero atom. However, in the sulfur-containing compound (C) represented by the formula (C2), R ^c6 and R ^c7 each bond to a carbonyl group by a CC bond and bond to a disulfide bond by a CS bond.
That is, each bond of the organic group as R ^c6 and R ^c7 is bonded to a carbon atom in the organic group.
Further, the divalent organic group may have an unsaturated bond.

The organic groups as R ^c6 and R ^{c7 are the same} as R ^c1 described for formula (C1).

Further, R ^c2 and R ^{c3 in} the formula (C2) are the same as in the formula (C1).

In Formula (C2), when n3 and n4 are each 1 and -CO-O-CH ( ^Rc2 ) ( ^Rc3 ) does not form a ring, the compound represented by Formula (C2) includes: Compounds of the following formula are preferred.
In the following formula, R ^c10 is an acetyl group or a propionyl group, and R ^c12 is a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, or a butane-1,4-diyl. Group.

In the compound represented by the formula (C1), n3 and n4 are each 1, and in a group represented by -CO-O-CH ( ^Rc2 ) ( ^Rc3 ), ^Rc2 and ^Rc3 are bonded. When forming an aliphatic ring containing a divalent group represented by —SO ₂ —O— in the ring structure, a preferred example of the compound represented by the formula (C2) is represented by the following formula: Compounds.
In the following formula, ^Rc12 is a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, or a butane-1,4-diyl group.

The compound represented by the formula (C2) described above includes, for example, a dicarboxylic acid compound represented by the formula (C2-a) and an alcohol represented by the formula (C2-b) in the following reaction formula: It can be synthesized by esterification according to a well-known method.

  The sulfur-containing compound (C) is used in an amount of 0.01 part by mass or more and 5 parts by mass or less based on 100 parts by mass of the total of the resin (B) and the alkali-soluble resin (D) described below. It is particularly preferable to use it in a range of from 05 parts by mass to 2 parts by mass. When the sulfur-containing compound (C) is used in an amount within the above range, the sensitivity of the positive photosensitive resin composition can be increased to a desired level without deteriorating the patterning characteristics or excessively generating a residue after development. Cheap.

<Alkali-soluble resin (D)>
It is preferable that the positive photosensitive resin composition 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), a 1 μm-thick resin film is formed on a substrate, and a 2.38% by mass TMAH aqueous solution is formed. When immersed for 1 minute, it means that it is dissolved by 0.01 μm or more. The alkali-soluble resin (D) is preferably at least one resin selected from the group consisting of a novolak resin (D1), a polyhydroxystyrene resin (D2), and an acrylic resin (D3).

[Novolak resin (D1)]
The novolak resin is obtained, for example, by subjecting an aromatic compound having a phenolic hydroxyl group (hereinafter, simply referred to as "phenols") and an aldehyde to addition condensation under an acid catalyst.

Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5- Examples include trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, phloroglicinol, 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 used in the addition condensation reaction is not particularly limited. For example, as an acid catalyst, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid and the like are used.

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

  The mass average molecular weight of the novolak 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 the hydroxystyrene-based compound constituting the polyhydroxystyrene resin (D2) include p-hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene, and the like.
Further, the polyhydroxystyrene resin (D2) is preferably a copolymer with a styrene resin. Examples of the styrene compound constituting such a styrene resin include styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, and α-methylstyrene.

  The weight average molecular weight of the polyhydroxystyrene resin (D2) 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.

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

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

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

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

  When the total of the resin (B) and the alkali-soluble resin (D) is 100 parts by mass, the content of the alkali-soluble resin (D) is preferably from 0 to 80 parts by mass, and more preferably from 0 to 60 parts by mass. It is more preferably at most part by mass. When the content of the alkali-soluble resin (D) is in the above range, crack resistance tends to be improved, and film loss during development tends to be prevented.

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

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

  Also, ADK STAB LA-52, ADK STAB LA-57, ADK STAB LA-63P, ADK STAB LA-68, ADK STAB LA-72, ADK STAB LA-77Y, ADK STAB LA-77G, ADK STAB LA-81, ADK STAB LA-82, and ADK STAB LA. Commercially available hindered amine compounds such as -87 (all manufactured by ADEKA), and substitution of a hydrocarbon group at the 2,6-position such as 2,6-diphenylpyridine and 2,6-di-tert-butylpyridine. Pyridine substituted with a group can also be used as the nitrogen-containing compound (E1).

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

[Organic carboxylic acid or phosphorus oxo acid or derivative thereof (E2)]
Among the organic carboxylic acids or phosphorus oxo acids or derivatives thereof (E2), specific examples of the organic carboxylic acids include malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid. , Especially salicylic acid is preferred.

  Phosphorus oxo acids or derivatives thereof include phosphoric acid, phosphoric acid such as phosphoric acid di-n-butyl ester, phosphoric acid diphenyl ester and derivatives thereof such as phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid- Phosphonic acids such as di-n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, phosphonic acid dibenzyl ester and derivatives thereof such as esters; phosphinic acids such as phosphinic acid and 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 the oxo acid of phosphorus or a derivative thereof (E2) is usually present in an amount of from 0 parts by mass to 5 parts by mass based on 100 parts by mass of the resin (B) and the alkali-soluble resin (D) in total. It is particularly preferably used in the range of 0 to 3 parts by mass.

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

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

  Specific examples of the organic solvent (S) include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, and propylene glycol monoacetate. , Dipropylene glycol, polyhydric alcohols such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether and monophenyl ether of dipropylene glycol monoacetate and derivatives thereof; cyclic ethers such as dioxane; ethyl formate, lactic acid Methyl, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, pyrvin Ethyl, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate And esters such as 3-methoxybutyl acetate and 3-methyl-3-methoxybutyl acetate; and aromatic hydrocarbons such as toluene and xylene. 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 hindered. When the positive-type photosensitive resin composition is used for a thick film application in which the thickness of a photosensitive layer obtained by a spin coating method or the like is 5 μm or more, the solid concentration of the positive-type photosensitive resin composition is 30 mass%. It is preferable to use the organic solvent (S) in the range of not less than 55% by mass and not more than 55% by mass.

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

The positive photosensitive resin composition preferably also contains a Lewis acidic compound. Since the positive-type photosensitive resin composition contains a Lewis acidic compound, it is easy to obtain a high-sensitivity positive-type photosensitive resin composition, and a rectangular-shaped resist pattern is formed using the positive-type photosensitive resin composition. It's easy to do.
When a pattern is formed using a positive photosensitive resin composition, the time required for each step in forming the pattern, or when the time required between each step is long, a pattern having a desired shape or size is formed. In some cases, adverse effects such as difficulty in developing and deterioration of developability may occur. However, by adding a Lewis acidic compound to the positive photosensitive resin composition, such adverse effects on the pattern shape and developability can be reduced, and the process margin can be widened.

Here, the Lewis acidic compound means “a compound having an empty orbital capable of receiving at least one electron pair and acting as an electron pair acceptor”.
The Lewis acidic compound is not particularly limited as long as it falls under the above definition and is recognized by those skilled in the art as a Lewis acidic compound. As the Lewis acidic compound, a compound that does not correspond to a Bronsted acid (protic acid) is preferably used.
Specific examples of the Lewis acidic compounds, boron fluoride, ether complex of boron fluoride _{(e.g., BF 3 · Et 2 O,} BF 3 · Me 2 O, BF 3 · THF , etc. .Et is an ethyl group, Me Is a methyl group, THF is tetrahydrofuran.), An organic boron compound (for example, tri-n-octyl borate, tri-n-butyl borate, triphenyl borate, triphenyl boron and the like), titanium chloride, chloride Aluminum, aluminum bromide, gallium chloride, gallium bromide, indium chloride, thallium trifluoroacetate, tin chloride, zinc chloride, zinc bromide, zinc iodide, zinc trifluoromethanesulfonate, zinc acetate, zinc nitrate, tetrafluoroborate Zinc acid, manganese chloride, manganese bromide, nickel chloride, nickel bromide, nickel cyanide, nickel Examples include acetylacetonate, cadmium chloride, cadmium bromide, stannous chloride, stannous bromide, stannous sulfate, and stannous tartrate.
Other specific examples of the Lewis acidic compound include rare earth metal elements such as chloride, bromide, sulfate, nitrate, carboxylate, or trifluoromethanesulfonate, and cobalt chloride, ferrous chloride, and yttrium chloride. Can be
Here, examples of the rare earth metal element include lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.

The Lewis acidic compound preferably contains a Lewis acidic compound containing a Group 13 element of the periodic table, because it is easily available and the effect of its addition is good.
Here, examples of Group 13 elements of the periodic table include boron, aluminum, gallium, indium, and thallium.
Among the above elements of Group 13 of the periodic table, boron is preferable because it is easy to obtain a Lewis acidic compound and the addition effect is particularly excellent. That is, the Lewis acidic compound preferably contains a Lewis acidic compound containing boron.

  Examples of the Lewis acidic compound containing boron include boron halides such as boron fluoride, an ether complex of boron fluoride, boron chloride, and boron bromide, and various organic boron compounds. As the Lewis acidic compound containing boron, an organic boron compound is preferable because the content ratio of halogen atoms in the Lewis acidic compound is small, and the photosensitive resin composition is easily applicable to applications in which a low halogen content is required. .

Preferred examples of the organic boron compound include the following formula (f1):
B (R ^f1 ) _t1 (OR ^f2 ) _(3-t1) (f1)
(In the formula (f1), R ^f1 and R ^f2 are each independently a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have one or more substituents, and t1 Is an integer of 0 or more and 3 or less, and when a plurality of R ^f1 are present, two of the plurality of R ^f1 may be bonded to each other to form a ring, and when a plurality of OR ^f2 are present, a plurality of OR ^f Two of ^f2 may combine with each other to form a ring.)
And a boron compound represented by the formula: The photosensitive resin composition preferably contains at least one boron compound represented by the above formula (f1) as a Lewis acidic compound.

When R ^f1 and R ^f2 in the formula (f1) are a hydrocarbon group, the number of carbon atoms of the hydrocarbon group is 1 or more and 20 or less. The hydrocarbon group having 1 to 20 carbon atoms may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a hydrocarbon group composed of a combination of an aliphatic group and an aromatic group. There may be.
As the hydrocarbon group having 1 to 20 carbon atoms, a saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group is preferable. The number of carbon atoms of the hydrocarbon group as R ^f1 and R ^f2 is preferably 1 or more and 10 or less. When the hydrocarbon group is an aliphatic hydrocarbon group, the number of carbon atoms is more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 4 or less.
The hydrocarbon group as R ^f1 and R ^f2 may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and is preferably a saturated hydrocarbon group.
When the hydrocarbon group as R ^f1 and R ^f2 is an aliphatic hydrocarbon group, the aliphatic hydrocarbon group may be linear, branched, or cyclic; A combination of these structures may be used.

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

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

The hydrocarbon group as R ^f1 and R ^f2 may have one or more substituents. Examples of the substituent include a halogen atom, a hydroxyl group, an alkyl group, an aralkyl group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, and an acyl group. , an acyloxy group, an acylthio group, an alkoxycarbonyl group, a cycloalkyl group, an aryloxycarbonyl group, an amino group, N- mono-substituted amino group, N, N- disubstituted amino group, a carbamoyl group _(-CO-NH 2) , An N-monosubstituted carbamoyl group, an N, N-disubstituted carbamoyl group, a nitro group, and a cyano group.
The number of carbon atoms of the substituent is not particularly limited as long as the object of the present invention is not impaired, but is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less.

  Preferable specific examples of the organic boron compound represented by the above formula (f1) include the following compounds. In the following formula, Pen indicates a pentyl group, Hex indicates a hexyl group, Hep indicates a heptyl group, Oct indicates an octyl group, Non indicates a nonyl group, and Dec indicates a decyl group.

  The Lewis acidic compound is used in an amount of preferably 0.01 to 5 parts by mass, more preferably 0 to 5 parts by mass, based on 100 parts by mass of the total of the resin (B) and the alkali-soluble resin (D). It is used in the range of 0.01 to 3 parts by mass, more preferably 0.05 to 2 parts by mass.

  Further, when the positive photosensitive resin composition is used for forming a pattern serving as a mold for forming a plated molded article, the adhesiveness between the mold formed using the positive photosensitive resin composition and the metal substrate is improved. Therefore, it may further contain an adhesion aid.

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

  In addition, the positive photosensitive resin composition may further contain an acid, an acid anhydride, or a high boiling point solvent in order to finely adjust the solubility in a 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 Acid, butanetetracarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentanetetracarbo Polycarboxylic acids such as acid, butanetetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid; itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenylsuccinic anhydride, tricarbanilic anhydride, maleic anhydride; Hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymic anhydride, 1,2,3,4-butanetetracarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, anhydride Acid anhydrides such as trimellitic acid, benzophenone tetracarboxylic anhydride, ethylene glycol bis trimellitate, and glycerin tris trimellitate; and the like.

  Specific examples of the high boiling point solvent 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.

  The positive photosensitive resin composition may further contain a known sensitizer in addition to the sulfur-containing compound (C) in order to improve sensitivity.

<< Preparation Method of Chemically Amplified Photosensitive Composition>
The chemically amplified photosensitive composition is prepared by mixing and stirring the components of the composition by an ordinary method. Examples of an apparatus that can be used for mixing and stirring the above components include a dissolver, a homogenizer, and a three-roll mill. After uniformly mixing the above components, the resulting mixture may be further filtered using a mesh, a membrane filter, or the like.

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

  As the substrate film, a film having optical transparency is preferable. Specifically, a polyethylene terephthalate (PET) film, a polypropylene (PP) film, a polyethylene (PE) film and the like can be mentioned, but a polyethylene terephthalate (PET) film is preferable in that it has an excellent balance between light transmittance and breaking strength.

A photosensitive dry film is produced by applying the above-described photosensitive composition on a base film to form a photosensitive layer.
When forming the photosensitive layer on the substrate film, using an applicator, a bar coater, a wire bar coater, a roll coater, a curtain flow coater, etc., the film thickness after drying on the substrate film is preferably 0.5 μm The photosensitive composition is applied to a thickness of at least 300 μm, more preferably at least 1 μm and at most 300 μm, particularly preferably at least 3 μm and at most 100 μm, and dried.

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

<< Method of manufacturing patterned resist film >>
A method for forming a patterned resist film on a substrate using the above-described photosensitive composition is not particularly limited. Such a patterned resist film is suitably used as an insulating film, an etching mask, a mold for forming a plated object, and the like.
The preferred method is
A laminating step of laminating a photosensitive layer composed of a photosensitive composition on a substrate,
An exposure step of exposing the photosensitive layer by irradiating with actinic rays or radiation,
A developing step of developing the photosensitive layer after exposure,
And a method for producing a patterned resist film.

The substrate on which the photosensitive layer is laminated is not particularly limited, and a conventionally known substrate can be used. Examples thereof include a substrate for an electronic component and a substrate on which a predetermined wiring pattern is formed. Can be. As the substrate, a silicon substrate, a glass substrate, or the like can be used.
When manufacturing a substrate with a mold provided with a mold for forming a plated object, a substrate having a metal surface is used as the substrate. As a metal species constituting the metal surface, copper, gold, and aluminum are preferable, and copper is more preferable.

The photosensitive layer is laminated on the substrate, for example, as follows. That is, a liquid-state photosensitive composition is applied on a substrate, and the solvent is removed by heating to form a photosensitive layer having a desired thickness. The thickness of the photosensitive layer is not particularly limited as long as the resist pattern can be formed with a desired film thickness. The thickness of the photosensitive layer is not particularly limited, but is preferably 0.5 μm or more, more preferably 0.5 μm or more and 300 μm or less, still more preferably 0.5 μm or more and 150 μm or less, and particularly preferably 0.5 μm or more and 200 μm or less.
The upper limit of the film thickness may be, for example, 100 μm or less. The lower limit of the film thickness may be, for example, 1 μm or more, or 3 μm or more.

  As a method for applying the photosensitive composition onto the substrate, a method such as a spin coating method, a slit coating method, a roll coating method, a screen printing method, and an applicator method can be employed. Prebaking is preferably performed on the photosensitive layer. Prebaking conditions vary depending on the type, blending ratio, coating film thickness, etc. of each component in the photosensitive composition, but are usually 70 ° C to 200 ° C, preferably 80 ° C to 150 ° C, and 2 minutes to 120 ° C. Minutes or less.

  The photosensitive layer formed as described above is selectively irradiated (exposed) with actinic rays or radiation, for example, ultraviolet rays or visible rays having a wavelength of 300 nm or more and 500 nm or less through a mask having a predetermined pattern. You.

As a radiation source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon gas laser, or the like can be used. The radiation includes microwaves, infrared rays, visible rays, ultraviolet rays, X-rays, γ-rays, electron beams, proton beams, neutron beams, ion beams, and the like. Dose of radiation varies depending on the film thickness of the composition or a photosensitive layer of a photosensitive composition such as, for example, in the case of ultra-high pressure mercury lamp used is 100 mJ / cm ² or more 10000 mJ / cm ² or less. The radiation includes a light beam that activates the acid generator (A) to generate an acid.

  After exposure, the diffusion of acid is promoted by heating the photosensitive layer using a known method, and in the exposed portion of the photosensitive resin film, the photosensitive layer is exposed to a developing solution such as an alkali developing solution. Alters solubility.

  Next, the exposed photosensitive layer is developed according to a conventionally known method, and unnecessary portions are dissolved and removed to form a predetermined resist pattern or a mold for forming a plated molded product. At this time, an alkaline aqueous solution is used as a 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 obtained 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-mentioned alkalis can also be used as the developer.
Further, depending on the composition of the photosensitive composition, development using an organic solvent can be applied.

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

  After the 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. In this way, a resist pattern patterned into a desired shape is formed on the metal surface of the substrate having the metal surface. Further, in this manner, a substrate having a resist pattern on the metal surface of the substrate can be manufactured.

≪Sensitizer≫
The sensitizer includes a compound represented by the above formula (CI) and / or a compound represented by the above formula (C-II).
As described above, such a sensitizer is added to the chemically amplified photosensitive composition containing the acid generator (A), whereby the sensitivity of the chemically amplified photosensitive composition is favorably improved.
The sensitizer may contain, as necessary, a compound other than the compound represented by the above formula (C-I) and / or the compound represented by the above formula (C-II). As the other components, various components blended in a conventionally known sensitizer for a photosensitive composition can be applied without any particular limitation as long as the object of the present invention is not impaired.

≫Method of sensitizing chemically amplified photosensitive composition≫
The method of sensitizing a chemically amplified photosensitive composition is represented by the above formula (C-I), which is a sulfur-containing compound (C) in a chemically amplified photosensitive composition containing an acid generator (A). And / or adding a compound represented by the formula (C-II).
As described above, the compound represented by the formula (C-I) and / or the compound represented by the formula (C-II) is added to the chemically amplified photosensitive composition containing the acid generator (A). By adding the compound as the sulfur-containing compound (C), the sensitivity of the chemically amplified photosensitive composition can be improved.

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

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

12.0 g of 3,3′-dithiopropionic acid and 120 g of dichloromethane were added to the flask, and the contents of the flask were stirred under a nitrogen atmosphere. Next, 2.79 g of N, N-dimethyl-4-aminopyridine, 24.1 g of a carbodiimide compound, and 20.8 g of an alcohol compound represented by the following formula were added to the flask, and the contents of the flask were stirred for 10 hours. .

Thereafter, the reaction solution was washed five times with 60.0 g of pure water, and then the reaction solution was concentrated to obtain 24.1 g of a sulfur-containing compound C1 having the above structure represented by the following formula.
¹ H-NMR (600 MHz, DMSO-d6): δ 5.70 (t, 2H), 5.00 (d, 2H), 4.86 (s, 2H), 4.78 (d, 2H), 4. 17 (m, 2H), 2.67 (m, 8H), 2.51-2.43 (m, 4H)

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

10.0 g of 3-acetylthiopropionic acid and 100 g of dichloromethane were added to the flask, and the contents of the flask were stirred under a nitrogen atmosphere. Next, 1.65 g of N, N-dimethyl-4-aminopyridine, 14.3 g of a carbodiimide compound, and 12.3 g of an alcohol compound represented by the following formula were added to the flask, and the contents of the flask were stirred for 10 hours. .

Thereafter, the reaction solution was washed five times with 50.0 g of pure water, and then the reaction solution was concentrated to obtain 16.0 g of a sulfur-containing compound C2 having the following structure.
^{1 H-NMR (600MHz, DMSO} -d6): δ5.73 (t, 1H), 5.10 (d, 1H), 4.87 (s, 1H), 4.75 (d, 1H), 4. 17 (m, 1H), 2.65 (m, 4H), 2.52-2.20 (m, 5H)

[Examples 1 to 14, and Comparative Examples 1 to 8]
In Examples 1 to 14 and Comparative Examples 1 to 8, compounds A1 and A2 represented by the following formulas were used as the acid generator (A).

In Examples 1 to 14 and Comparative Examples 1 to 8, the following resins B1 and B2 were used as resins (resin (B)) whose solubility in alkali increased by the action of an acid. The number at the lower right of the parenthesis in each structural unit in the following structural formula represents the content (% by mass) of the structural unit in each resin. The weight average molecular weight Mw of the resin B1 is 40,000, and the degree of dispersion (Mw / Mn) is 2.6. The number average molecular weight of the resin B2 is 106,000.

In Examples, the sulfur-containing compounds C1 and C2 obtained in the above Preparation Examples were used as the sulfur-containing compounds (C). In the comparative example, the following C3 and C4 were used.

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

  As the acid diffusion inhibitor (E), E1: tripentylamine and E2: LA63-P manufactured by ADEKA were used.

An acid generator (A), a resin (B), a sulfur-containing compound (C), an alkali-soluble resin (D), and an acid diffusion inhibitor (E) of the types and amounts shown in Tables 1 and 2, respectively; 0.05 parts by mass of a surfactant (BYK310, manufactured by BYK-Chemie) is mixed with 3-methoxybutyl acetate (MA) and propylene glycol monomethyl ether acetate (PM) in a mixed solvent (MA / PM = 6/4 (mass ratio) )) To obtain positive photosensitive resin compositions of Examples and Comparative Examples.
The positive photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 4 used for evaluation at a film thickness of 55 μm described later were prepared such that the solid content concentration was 50% by mass. The positive photosensitive resin compositions of Examples 8 to 14 and Comparative Examples 5 to 8 used for evaluation at a film thickness of 7 μm were prepared such that the solid content concentration was 40% by mass.

  Using the obtained positive photosensitive resin composition, sensitivity and shape were evaluated according to the following methods. In addition, about Examples 1-7 and Comparative Examples 1-4, evaluation was performed at a film thickness of 55 μm. On the other hand, Examples 8 to 14 and Comparative Examples 5 to 8 were evaluated at a film thickness of 7 μm. Tables 1 and 2 show the results of these evaluations.

[Evaluation of sensitivity]
(Evaluation at a film thickness of 55 μm)
The positive photosensitive resin compositions of Examples and Comparative Examples were applied on a copper substrate or a silicon substrate having a diameter of 8 inches to form a photosensitive layer having a thickness of 55 μm. Next, the photosensitive layer was prebaked at 100 ° C. for 5 minutes. After pre-baking, pattern exposure was performed using ghi-rays while changing the exposure amount using a mask having a square pattern capable of forming a rectangular opening of 500 μm × 500 μm and an exposure apparatus Prisma GHI (manufactured by Ultratech). Next, the substrate was placed on a hot plate and subjected to post-exposure bake (PEB) at 100 ° C. for 3 minutes. Thereafter, an operation of dropping a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (developing solution, NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) onto the exposed photosensitive resin layer and then allowing it to stand at 23 ° C. for 60 seconds. Was repeated four times in total. Thereafter, the resist pattern surface was washed with running water, and then nitrogen was blown to obtain a resist pattern. The shape of the resist pattern was observed with a scanning electron microscope, and the amount of exposure at which a square pattern of a predetermined size could be formed was specified.
The sensitivity of the positive photosensitive resin composition was evaluated based on the specified exposure amount.
The case where the exposure amount at which a square pattern of a predetermined size was formed was 300 mJ / cm ² or less was judged as ◎, and the case where the exposure amount was more than 300 mJ / cm ^{2 and} 400 mJ / cm ² or less was judged as ○, and 400 mJ / cm ^2. The case where it was more than was judged as x.

(Evaluation at a film thickness of 7 μm)
The positive-type photosensitive resin compositions of Examples and Comparative Examples were coated on a copper substrate or a silicon substrate having a diameter of 8 inches to form a photosensitive layer having a thickness of 7 μm. Next, the photosensitive resin layer was pre-baked at 130 ° C. for 5 minutes. After prebaking, pattern exposure was performed using ghi lines while changing the exposure amount using a line-and-space pattern mask having a line width of 2 μm and a space width of 2 μm and an exposure apparatus Prism GHI (manufactured by Ultratech). Next, the substrate was placed on a hot plate and subjected to post-exposure bake (PEB) at 90 ° C. for 1.5 minutes. Thereafter, an operation of dropping a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (developing solution, NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) onto the exposed photosensitive resin layer, and then allowing to stand at 23 ° C. for 30 seconds. Was repeated twice in total. Thereafter, the resist pattern surface was washed with running water, and then nitrogen was blown to obtain a resist pattern. The shape of the resist pattern was observed with a scanning electron microscope, and the amount of exposure at which a square pattern of a predetermined size could be formed was specified.
The sensitivity of the positive photosensitive resin composition was evaluated based on the specified exposure amount.
Where exposure that could form a line and space pattern having a predetermined dimension is 80 mJ / cm ² or less was determined ◎, it determines that ○ the case is less than 80 mJ / cm ² ultra 100mJ / cm ^2, 100mJ / A case of more than cm ² was judged as x.

  According to Examples 1 to 14, in addition to the acid generator (A) that generates an acid upon irradiation with actinic rays or radiation and the resin (B) whose solubility in alkali increases by the action of an acid, a predetermined amount It can be seen that the positive photosensitive resin composition containing the sulfur-containing compound (C) having a structure has good sensitivity.

  On the other hand, according to Comparative Examples 1 to 8, the positive photosensitive resin composition does not contain the sulfur-containing compound (C) or contains the sulfur-containing compound (C) having no predetermined structure. In this case, the sensitivity of the photosensitive fat composition is inferior.

Claims (11)

An acid generator (A) that generates an acid upon irradiation with actinic rays or radiation, and a sulfur-containing compound (C),
The sulfur-containing compound (C) has the following formula (C-I):

(In the formula (CI), X ^c1 is an organic linking group, R ^c01 is a hydrogen atom or an organic group not containing a sulfonic acid ester structure, and R ^c02 has a bond on a carbon atom. A monovalent organic group, n1 is an integer of 1 or more and 4 or less, n2 is an integer of 1 or more and 4 or less, and R ^c02 is bonded to any one of the elements constituting X ^c1. (A ring may be formed.)
And / or the following formula (C-II)

(In the formula (C-II), X ^c2 and X ^c3 are each an organic linking group, X ^c4 is a single bond or a divalent organic group, and R ^c03 and R ^c04 are each a carbon atom. A monovalent organic group having a bond on an atom, n3 and n4 are each an integer of 1 or more and 3 or less, n3 + n4 is an integer of 2 or more and 4 or less, and R ^c03 forms X ^{c2 May} form a ring by combining with any one of the following elements, and R ^c04 may form a ring by combining with any one of the elements constituting X ^c3 .)
A chemically amplified photosensitive composition which is a compound represented by the formula: The sulfur-containing compound (C) has the following formula (C1):

(In the formula (C1), R ^c01 , n1 and n2 are the same as those in the formula (C-I), R ^c1 is an (n1 + n2) ^-valent organic group, and R ^c1 is a C—C bond. R ^c2 and R ^c3 are each independently a hydrogen atom or a monovalent organic group, and are bonded to a carbonyl group and a C—S bond to a group represented by —SR ^c01; in each of n2 groups represented by ^{-CH (R c2) (R c3} ), a group at least one of ^{R c2} and ^{R c3} represented by ^-R c4 _-SO 2 ^{-O-R c5} R ^c4 is a divalent organic group, R ^c5 is a monovalent organic group having a bond on a carbon atom, and is represented by —CO—O—CH (R ^c2 ) (R ^c3 ) in at least one n2 ^groups, by bonding with ^{R c2} and ^{R c3,} ring structure It may form an aliphatic ring containing divalent group represented by -SO 2 _-O- in.)
And / or the following formula (C2):

(In the formula (C2), n3 and n4 are the same as those in the formula (C-II), R ^c6 is a (n3 + 1) -valent organic group, and R ^c7 is a (n4 + 1) -valent organic group. , R ^c6 and R ^c7 are each bonded to a carbonyl group by a CC bond, and bonded to a disulfide bond by a C—S bond, and R ^c2 and R ^c3 are each independently a hydrogen atom or a monovalent group. an organic ^{group, -CO-O-CH (R} c2) in each represented by (n3 + n4) number of groups ^{(R c3),} at least one of ^{R c2} and ^{R c3 -R} c4 -SO ₂ A group represented by —O—R ^c5 , R ^c4 is a divalent organic group, R ^c5 is a monovalent organic group having a bond on a carbon atom, and —CO—O—CH ( R ^{c2) (represented} by ^{R c3)} (n3 + n4) number of groups In at least ^one, by bonding with ^{R c2} and ^{R c3,} it may form an aliphatic ring containing divalent group represented by _-SO 2 -O- in the ring structure.)
The chemically amplified photosensitive composition according to claim 1, which is a compound represented by the formula:   The chemically amplified photosensitive composition according to claim 1, which is a positive type.   The chemically amplified photosensitive composition according to claim 3, comprising a resin (B) whose solubility in an alkali is increased by the action of an acid.   The chemically amplified photosensitive composition according to claim 4, further comprising an alkali-soluble resin (D).   The alkali-soluble resin (D) according to claim 5, wherein the alkali-soluble resin (D) includes at least one resin selected from the group consisting of a novolak resin (D1), a polyhydroxystyrene resin (D2), and an acrylic resin (D3). Chemically amplified photosensitive composition.   It has a base film and a photosensitive layer formed on the surface of the base film, and the photosensitive layer is composed of the chemically amplified photosensitive composition according to any one of claims 1 to 6. Photosensitive dry film.   A method for producing a photosensitive dry film, comprising applying a chemically amplified photosensitive composition according to any one of claims 1 to 6 on a base film to form a photosensitive layer. A laminating step of laminating a photosensitive layer comprising the chemically amplified photosensitive composition according to any one of claims 1 to 6 on a substrate,
An exposure step of irradiating the photosensitive layer with actinic rays or radiation in a position-selective manner,
And a developing step of developing the photosensitive layer after exposure. When incorporated into a chemically amplified photosensitive composition containing an acid generator (A) that generates an acid upon irradiation with actinic rays or radiation, the sensitivity of the chemically amplified photosensitive composition is improved.
The following formula (CI):

(In the formula (CI), X ^c1 is an organic linking group, R ^c01 is a hydrogen atom or an organic group not containing a sulfonic acid ester structure, and R ^c02 has a bond on a carbon atom. A monovalent organic group, n1 is an integer of 1 or more and 4 or less, n2 is an integer of 1 or more and 4 or less, and R ^c02 is bonded to any one of the elements constituting X ^c1. (A ring may be formed.)
And / or the following formula (C-II)

(In the formula (C-II), X ^c2 and X ^c3 are each an organic linking group, X ^c4 is a single bond or a divalent organic group, and R ^c03 and R ^c04 are each a carbon atom. A monovalent organic group having a bond on an atom, n3 and n4 are each an integer of 1 or more and 3 or less, n3 + n4 is an integer of 2 or more and 4 or less, and R ^c03 forms X ^{c2 May} form a ring by combining with any one of the following elements, and R ^c04 may form a ring by combining with any one of the elements constituting X ^c3 .)
A sensitizer comprising a compound represented by the formula: A chemically amplified photosensitive composition containing an acid generator (A) that generates an acid upon irradiation with actinic rays or radiation is added to a chemically amplified photosensitive composition represented by the following formula (CI):

(In the formula (CI), X ^c1 is an organic linking group, R ^c01 is a hydrogen atom or an organic group not containing a sulfonic acid ester structure, and R ^c02 has a bond on a carbon atom. A monovalent organic group, n1 is an integer of 1 or more and 4 or less, n2 is an integer of 1 or more and 4 or less, and R ^c02 is bonded to any one of the elements constituting X ^c1. (A ring may be formed.)
And / or the following formula (C-II)

(In the formula (C-II), X ^c2 and X ^c3 are each an organic linking group, X ^c4 is a single bond or a divalent organic group, and R ^c03 and R ^c04 are each a carbon atom. A monovalent organic group having a bond on an atom, n3 and n4 are each an integer of 1 or more and 3 or less, n3 + n4 is an integer of 2 or more and 4 or less, and R ^c03 forms X ^{c2 May} form a ring by combining with any one of the following elements, and R ^c04 may form a ring by combining with any one of the elements constituting X ^c3 .)
A method for sensitizing a chemically amplified photosensitive composition, comprising adding a compound represented by the formula: