JP2020003622A - Chemically amplified positive photosensitive resin composition, photosensitive dry film, method for manufacturing photosensitive dry film, method for manufacturing patterned resist film, method for manufacturing substrate with template, method for manufacturing plated molded article, and nitrogen-containing heterocyclic compound - Google Patents

Abstract

To provide a chemically amplified positive photosensitive resin composition from which a resist pattern having a rectangular cross-sectional shape can be easily formed, a photosensitive dry film including a photosensitive resin layer formed of the chemically amplified positive photosensitive resin composition, a method for manufacturing the photosensitive dry film, a method for manufacturing a patterned resist film using the above chemically amplified positive photosensitive resin composition, a method for manufacturing a substrate with a template using the above chemically amplified positive photosensitive resin composition, a method for manufacturing a plated molded article using the above substrate with a template, and a new nitrogen-containing heterocyclic compound.SOLUTION: The chemically amplified positive photosensitive resin composition is a chemically amplified positive photosensitive resin composition comprising an acid generator (A) that generates an acid by irradiation with active rays or radiation and a resin (B) that increases the solubility with an alkali by an action of an acid, into which a nitrogen-containing heterocyclic compound (C) having a specific structure and a LogS value of -4.00 or lower is incorporated.SELECTED DRAWING: None

Description

  The present invention is a chemically amplified positive photosensitive resin composition, a photosensitive dry film including a photosensitive resin layer composed of the chemically amplified positive photosensitive resin composition, a method for producing the photosensitive dry film, A method for producing a patterned resist film using the aforementioned chemically amplified positive photosensitive resin composition, a method for producing a substrate with a mold using the aforementioned chemically amplified positive photosensitive resin composition, The present invention relates to a method for producing a plated molded article using a substrate, and a nitrogen-containing heterocyclic compound which can be preferably added to the above-mentioned chemically amplified positive photosensitive resin 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 a photolithography technique, and the patterned photoresist layer (photoresist pattern) is used as a mask for chemical etching and electrolysis. 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, the high-density packaging technology of semiconductor packages has been 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 a connection terminal, for example, a bump electrode (mounting terminal) such as a bump protruding on a package, or a metal post for connecting a rewiring extending from a peripheral terminal on a wafer to the mounting terminal. 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 photoresist composition containing an acid generator is known (Patent Documents 1, 2 and the like). See). In a chemically amplified photoresist composition, an acid is generated from an acid generator by irradiation (exposure), and the diffusion of the acid is promoted by heat treatment, thereby causing an acid-catalyzed reaction on a base resin and the like in the composition. The alkali solubility changes.

  Such a chemically amplified positive photoresist composition is used, for example, for forming a plated product such as a bump, a metal post, and a Cu rewiring by a plating process. Specifically, using a chemically amplified photoresist composition, a photoresist layer of a desired thickness is formed on a support such as a metal substrate, exposed through a predetermined mask pattern, developed, and plated. A photoresist pattern to be used as a mold from which a part forming a model is selectively removed (stripped) is formed. Then, after a conductor such as copper is buried in the removed portion (non-resist portion) by plating, a photoresist pattern around the conductor is removed, whereby a bump, a metal post, and a Cu rewiring can be formed. .

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 plating process, it is strongly desired that the non-resist part of the resist pattern serving as a mold has a rectangular cross-sectional shape. .
In the process of forming the plated object, the non-resist portion of the resist pattern serving as a mold has a rectangular cross-sectional shape, so that the connection terminals such as bumps and metal posts, the bottom surface of the Cu rewiring, and the contact between the support and the support. A sufficient area can be secured. Then, it is easy to form connection terminals and Cu rewiring having good adhesion to the support. Further, if the cross-sectional shape of the non-resist part of the resist pattern serving as a mold is rectangular, it is possible to form a flat (planar) connection terminal or Cu rewiring whose tip is not widened (not rounded).

However, when a resist pattern is formed using a conventionally known chemically amplified positive photoresist composition as disclosed in Patent Documents 1 and 2, it is difficult to form a resist pattern having a rectangular cross-sectional shape. There are often.
As described above, when a conventionally known chemically amplified positive photoresist composition as disclosed in Patent Documents 1 and 2 is used, it is difficult to form a resist pattern having a desirable cross-sectional shape.

  The present invention has been made in view of the above problems, and a chemically amplified positive photosensitive resin composition which is easy to form a resist pattern having a rectangular cross-sectional shape, and the chemically amplified positive photosensitive resin composition A photosensitive dry film comprising a photosensitive resin layer consisting of, a method for producing the photosensitive dry film, a method for producing a patterned resist film using the aforementioned chemically amplified positive photosensitive resin composition, A method for manufacturing a substrate with a mold using the chemically amplified positive photosensitive resin composition of the present invention, a method for manufacturing a plated molded article using the substrate with the template, and preferably compounded with the aforementioned chemically amplified positive photosensitive resin composition It is an object of the present invention to provide a nitrogen-containing heterocyclic compound which can be used.

  The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that an acid generator (A) that generates an acid upon irradiation with actinic rays or radiation and a resin whose solubility in an alkali increases due to the action of an acid. (B) and a nitrogen-containing heterocyclic compound (C), which is a nitrogen-containing heterocyclic compound having a specific structure and a LogS value of -4.00 or less, in a chemically amplified positive photosensitive resin composition containing (C). It has been found that the above-mentioned problems can be solved by including the compound, and the present invention has been completed. Specifically, the present invention provides the following.

で表される含窒素複素環基であり、
Ａ^１及びＡ^２は、それぞれ独立に、単結合、又は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＮＨＣＯＮＨ−、−Ｓ−、−ＳＯ−、及び−ＳＯ_２−からなる群より選択される２価の基であり、
Ｗ^１は、単結合又は置換基を有してもよい２価の環式基であり、
Ｘ^１は、水素原子、置換基を有してもよい脂肪族炭化水素基又は置換基を有してもよい芳香族炭化水素基であり、
式（ｃ２）中、Ｒ^１、Ｒ^２及びＲ^４は、それぞれ独立に、置換基を有してもよい脂肪族炭化水素基又は置換基を有してもよい芳香族炭化水素基であり、Ｒ^３及びＲ^５は、それぞれ独立に、水素原子、置換基を有してもよい脂肪族炭化水素基又は置換基を有してもよい芳香族炭化水素基であり、
Ｙ^１〜Ｙ^３のうちのいずれか１つが下記式（ｃ３）又は式（ｃ４）：

で表される３価の基であり、当該３価の基が有する３つの結合手のうち一つの結合手がＡ^１に連結され、
式（ｃ３）中、Ｒ^６は、水素原子、置換基を有してもよい脂肪族炭化水素基又は置換基を有してもよい芳香族炭化水素基であり、
Ｙ^１〜Ｙ^３のうちの２つが、それぞれ独立に、−ＣＲ^７Ｒ^８−、−ＮＲ^９−、−Ｏ−及び−Ｓ−からなる群より選択される２価の基であり、
Ｒ^７、Ｒ^８及びＲ^９は、それぞれ独立に、水素原子、置換基を有してもよい脂肪族炭化水素基又は置換基を有してもよい芳香族炭化水素基である。）
で表される化合物であり、
含窒素複素環化合物（Ｃ）の溶解度Ｓの常用対数値ＬｏｇＳが−４．００以下である、化学増幅型ポジ型感光性樹脂組成物。 The first aspect of the present invention relates to an acid generator (A) that generates an acid upon irradiation with actinic rays or radiation, a resin (B) whose solubility in an alkali increases by the action of an acid, and a nitrogen-containing heterocyclic compound. (C) and
The nitrogen-containing heterocyclic compound (C) has the following formula (c1):
Z ¹ -A ¹ -W ¹ -A ² -X ¹ (c1)
(In the formula (c1), Z ¹ is the following formula (c2):

Is a nitrogen-containing heterocyclic group represented by
A ¹ and A ² are each independently a single bond or —O—, —CO—, —COO—, —OCO—, —OCOO—, —NH—, —CONH—, —NHCO—, —NHCONH -, - S -, - SO- , and -SO ₂ - is a divalent radical selected from the group consisting of,
W ¹ is a single bond or a divalent cyclic group which may have a substituent,
X ¹ is a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent,
In the formula (c2), R ¹ , R ² and R ⁴ are each independently an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent, R ³ and R ⁵ are each independently a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent,
Any one of Y ^{1 to} Y ³ is represented by the following formula (c3) or formula (c4):

Wherein one of the three bonds possessed by the trivalent group is linked to A ¹ ,
In the formula (c3), R ⁶ is a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent,
Two of Y ^{1 to} Y ³ are each independently a divalent group selected from the group consisting of —CR ⁷ R ⁸ —, —NR ⁹ —, —O— and —S—,
R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent. )
Is a compound represented by
A chemically amplified positive photosensitive resin composition having a common logarithm LogS of solubility S of the nitrogen-containing heterocyclic compound (C) of -4.00 or less.

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

  A third aspect of the present invention is a photosensitive dry film, comprising applying a chemically amplified positive photosensitive resin composition according to the first aspect on a base film to form a photosensitive resin layer. Is a manufacturing method.

According to a fourth aspect of the present invention,
A laminating step of laminating a photosensitive resin layer composed of the chemically amplified positive photosensitive resin composition according to the first embodiment on a substrate having a metal surface;
An exposure step of irradiating the photosensitive resin layer with position-selective irradiation with actinic rays or radiation, and
And a developing step of developing the photosensitive resin layer after exposure.

According to a fifth aspect of the present invention,
A laminating step of laminating a photosensitive resin layer composed of the chemically amplified positive photosensitive resin composition according to the first embodiment on a substrate having a metal surface;
An exposure step of irradiating the photosensitive resin layer with position-selective irradiation with actinic rays or radiation, and
And a developing step of developing the photosensitive resin layer after exposure to form a mold for forming a plated molded article.

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

で表される含窒素複素環基であり、
Ａ^１及びＡ^２は、それぞれ独立に、単結合、又は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＮＨＣＯＮＨ−、−Ｓ−、−ＳＯ−、及び−ＳＯ_２−からなる群より選択される２価の基であり、
Ｗ^２は、置換基を有してもよい２価の環式基であり、
Ｘ^１は、水素原子、置換基を有してもよい脂肪族炭化水素基又は置換基を有してもよい芳香族炭化水素基であり、
式（ｃ２）中、Ｒ^１、Ｒ^２及びＲ^４は、それぞれ独立に、置換基を有してもよい脂肪族炭化水素基又は置換基を有してもよい芳香族炭化水素基であり、Ｒ^３及びＲ^５は、それぞれ独立に、水素原子、置換基を有してもよい脂肪族炭化水素基又は置換基を有してもよい芳香族炭化水素基であり、
Ｙ^１〜Ｙ^３のうちのいずれか１つが下記式（ｃ３）又は式（ｃ４）：

で表される３価の基であり、当該３価の基が有する３つの結合手のうち一つの結合手がＡ^１に連結され、
式（ｃ３）中、Ｒ^６は、水素原子、置換基を有してもよい脂肪族炭化水素基又は置換基を有してもよい芳香族炭化水素基であり、
Ｙ^１〜Ｙ^３のうちの２つが、それぞれ独立に、−ＣＲ^７Ｒ^８−、−ＮＲ^９−、−Ｏ−及び−Ｓ−からなる群より選択される２価の基であり、
Ｒ^７、Ｒ^８及びＲ^９は、それぞれ独立に、水素原子、置換基を有してもよい脂肪族炭化水素基又は置換基を有してもよい芳香族炭化水素基である。）
で表される、含窒素複素環化合物。 According to a seventh aspect of the present invention,
The following formula (c1-a):
Z ¹ -A ¹ -W ² -A ² -X ¹ (c1-a)
(In the formula (c1-a), Z ¹ is the following formula (c2):

Is a nitrogen-containing heterocyclic group represented by
A ¹ and A ² are each independently a single bond or —O—, —CO—, —COO—, —OCO—, —OCOO—, —NH—, —CONH—, —NHCO—, —NHCONH -, - S -, - SO- , and -SO ₂ - is a divalent radical selected from the group consisting of,
W ² is a divalent cyclic group which may have a substituent,
X ¹ is a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent,
In the formula (c2), R ¹ , R ² and R ⁴ are each independently an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent, R ³ and R ⁵ are each independently a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent,
Any one of Y ^{1 to} Y ³ is represented by the following formula (c3) or formula (c4):

Wherein one of the three bonds possessed by the trivalent group is linked to A ¹ ,
In the formula (c3), R ⁶ is a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent,
Two of Y ^{1 to} Y ³ are each independently a divalent group selected from the group consisting of —CR ⁷ R ⁸ —, —NR ⁹ —, —O— and —S—,
R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent. )
A nitrogen-containing heterocyclic compound represented by the formula:

  According to the present invention, a chemically amplified positive photosensitive resin composition which is easy to form a resist pattern having a rectangular cross section, and a photosensitive resin comprising a photosensitive resin layer composed of the chemically amplified positive photosensitive resin composition Dry film, a method for producing the photosensitive dry film, a method for producing a patterned resist film using the aforementioned chemically amplified positive photosensitive resin composition, and a method for producing the aforementioned chemically amplified positive photosensitive resin Provided is a method for producing a substrate with a mold using the composition, a method for producing a plated molded article using the substrate with the mold, and a nitrogen-containing heterocyclic compound that can be preferably blended with the aforementioned chemically amplified positive photosensitive resin composition. can do.

≪Chemically amplified positive photosensitive resin composition≫
A chemically amplified positive photosensitive resin composition (hereinafter also referred to as a photosensitive resin composition) is 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 resin (B) whose solubility in an alkali increases by the action of an acid (hereinafter also referred to as a resin (B)), and a nitrogen-containing heterocyclic compound (C). The photosensitive resin composition may contain components such as an alkali-soluble resin (D), a sulfur-containing compound (E), an acid diffusion inhibitor (F), and an organic solvent (S), if necessary.

The thickness of the resist pattern formed using the photosensitive resin composition is not particularly limited. The photosensitive resin composition is preferably used for forming a thick resist pattern. The thickness of the resist pattern formed using the photosensitive resin composition is specifically, preferably 0.5 μm or more, more preferably 0.5 μm or more and 300 μm or less, and still more preferably 0.5 μm or more and 150 μm or less. , 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.

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

<Acid generator (A)>
The acid generator (A) is a compound that generates an acid by irradiation with 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 aspects described below are preferable. Hereinafter, preferred acid generators (A) suitably used in the 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 from each other. Also, directly with each other two or more ^{R 1a,} or _{-O -, - S -, -} SO -, - SO 2 -, - NH -, - NR 2a -, - CO -, - COO -, - CONH- an alkylene group having 1 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. X ^4a represents 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. 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 indicates 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 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 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 above 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 optionally substituted aryl, an arylcarbonyl, Represents a group selected from the group consisting of: X ^2a has 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 alkylfluorophosphate 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. , Cyclohexyl and the like, and the proportion of the 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. 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 preferred fluorinated alkylfluorophosphate anions include [(CF ₃ CF ₂ ) ₂ PF ₄ ] ⁻ , [(CF ₃ CF ₂ ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ⁻ , [(CF ₃ ) ₂ CF) ₃ PF ₃ ] ⁻ , [(CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ] ⁻ , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ⁻ , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ⁻ , [(CF ₃ CF ₂ CF ₂ CF ₂ ) ₂ PF ₄ ] ⁻ , or [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , 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] -), difluoro (pentafluorophenyl) borate _{([(C 6 F 5)} 2 BF 2] -), trifluoro (pentafluorophenyl) borate ([(C ^{_{6 F 5) BF 3] -}} ), tetrakis (difluorophenyl) borate _{([B (C 6 H 3} F 2) 4] -) , and the like. Among these, tetrakis (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ⁻ ) is particularly preferred.

  As 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 the 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 thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. Particularly, 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 above 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 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.

  Further, as a fourth embodiment of the acid generator (A), an onium salt having a naphthalene ring in a cation portion can be mentioned. The expression "having a naphthalene ring" means having a structure derived from naphthalene, and means that at least two ring structures and their aromaticity are maintained. The naphthalene ring has a substituent such as a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, 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 above 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. 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 l + 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 the 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.

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

  Examples of the substituent which the phenyl group may have include a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, 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, as an anion part of an onium salt having a naphthalene ring in the cation part, an anion capable of forming a sulfonium salt is preferable.

  The anion portion 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 fluoroalkyl sulfonate 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 material 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, a methylnaphthyl group, and the like.

  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 above 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 them, trifluoromethanesulfonate and perfluorobutanesulfonate are preferred from the viewpoint of safety.

  Further, as the anion part, 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 proportion of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate, is preferably 70% or more and 100% or less, more preferably 90% or more and 100% or less, and most preferably all hydrogen atoms are fluorine. 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, benzyltosylate, 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 photosensitive resin composition. The following is more preferable, and it is particularly preferable that the content is 0.5% by mass or more and 3% by mass or less. By setting the amount of the acid generator (A) to be in the above range, it is easy to prepare a photosensitive resin composition having good sensitivity, a uniform solution, and excellent storage stability.

<Resin (B)>
The resin (B) whose solubility in an alkali 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, as the acid dissociable, dissolution inhibiting group represented by the above formula (b2), specifically, a methoxyethyl group, an ethoxyethyl group, an n-propoxyethyl group, an isopropoxyethyl group, an n-butoxyethyl group, Examples thereof include 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 Formulas (b2) and (b3) can be used.

  Furthermore, 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) Aryl (meth) acrylates 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. Chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; and amide bond-containing polymerizable compounds such as acrylamide and methacrylamide.

[Acrylic resin (B3)]
The acrylic resin (B3) is not particularly limited as long as it is an acrylic resin whose solubility in alkali is increased by the action of an acid and has been conventionally compounded 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 when the ring alone is a monocyclic group, and when 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, still more preferably 4 or more and 15 or less, 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 a 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 of 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-mentioned alkyl group as the alkyl group as a 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 monocycloalkanes that may or may not be substituted with a fluorinated alkyl group, or polycycloalkanes such as bicycloalkanes, tricycloalkanes, and tetracycloalkanes. 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).

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

  In the above formulas (3-1) to (3-4), A 'is an alkylene group having 1 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 terminals or carbon atoms 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 of the -SO ₂ -containing cyclic groups may have. 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 aforementioned chemical formulas (3-1-1) and (3-1-18) , (3-3-1) and (3-4-1) are more preferably at least one selected from the group consisting of groups represented by 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 —OC (＝ O) — in the ring skeleton. The lactone ring is counted as the first ring. When only the lactone ring is used, it is called a monocyclic group, and when it has another ring structure, it is called a polycyclic group regardless of its structure. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group.

  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 in which one hydrogen atom has been removed from a 4- to 6-membered lactone, for example, a group in which one hydrogen atom has been removed from β-propionolactone, 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 a lactone may be 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 defined above for the —SO ₂ —-containing cyclic group.
R ^12b may be a single bond or a divalent linking group. A divalent linking group is preferred because the effects of the present invention are excellent.

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 alkylalkylene groups such as alkyltetramethylene groups. 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 having a ring in the above structure include a cyclic aliphatic hydrocarbon group which may contain a substituent having 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, and a group in which the cyclic aliphatic hydrocarbon group is linear or branched. Examples include 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 (＝ O).

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

  The aromatic hydrocarbon group as 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 hydrogen atom 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 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 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 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, and is, 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-mentioned divalent hydrocarbon group which may have a substituent, and a linear or branched aliphatic hydrocarbon group is preferable. .

  Of the above, -NH- in -C (= O) -NH-, H in -NH-, -NH-C (= 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 in R ^12b is a linear or branched alkylene group, the number of carbon atoms of the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and 1 or more and 4 or less. Is particularly preferable, and 1 or more and 3 or less are most preferable. Specifically, in the description of the “divalent hydrocarbon group which may have a substituent” as the above-mentioned divalent linking group, it may be mentioned 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 the above-described 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 ^1b —O—Y ^2b —, — [Y ^1b —C (＝ O) —O] _{m '-Y} ^2b -, or ^{-Y 1b -O-C (= O} ) -Y 2b - group represented by ^{wherein, Y 1b,} and ^{Y 2b} are have independently a substituent 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 ^1b -O-Y ^2b -,-[Y ^1b -C (= O) -O] _{m '} -Y ^2b- , or -Y ^1b -OC (= O) -Y ^2b- , Y ^1b and Y ^2b are each independently a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include those similar to the “divalent hydrocarbon group which may have a substituent” described in the description of the divalent linking group.

As Y ^1b , 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 ^2b , 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.

Formula ^{- [Y 1b -C (= O} ) -O] m '-Y 2b - In the group represented by, m' is an integer of 0 to 3, preferably 0 to 2 integer 0 or 1 is more preferred, and 1 is particularly preferred. That is, the group represented by the formula — [Y ^1b —C (＝ O) —O] _{m ′} —Y ^2b — is represented by the formula —Y ^1b —C (＝ O) —O—Y ^2b —. Groups are particularly preferred. Among them, the formula _{- (CH 2) a '-C} (= O) -O- (CH 2) b' - a group represented by are preferred. In the formula, a ′ is an integer of 1 or more and 10 or less, preferably an integer of 1 or more and 8 or less, more preferably an integer of 1 or more and 5 or less, further preferably 1 or 2, and most preferably 1. b 'is an integer of 1 or more and 10 or less, preferably an integer of 1 or more and 8 or less, more preferably an integer of 1 or more and 5 or less, 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 ^1b -O-Y ^2b -,-[Y ^1b -C (= ^{_{O) -O] m '-Y 2b}} -, or ^{-Y 1b -O-C (= O} ) -Y 2b - more preferably a group represented by the previously described formula ^{- [Y 1b -C (= O} ) —O] _{m ′} —Y ^2b — or —Y ^1b —OC (＝ O) —Y ^2b —.

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 ( Alkyl ethylene such as CH ₃ ) CH (CH ₃ ) —, —C (CH ₃ ) ₂ CH ₂ —, —CH (CH ₂ CH ₃ ) CH ₂ —, and —C (CH ₂ CH ₃ ) ₂ —CH ₂ — _{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.
The divalent linking group for R ^13b is preferably 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. 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-mentioned —Y ^1b —O—Y ^2b —, — [Y ^1b —C (＝ O ^{_{) -O] m '-Y 2b -}} , or ^{-Y 1b -O-C (= O} ) -Y 2b - is more preferable. Y ^1b and Y ^2b 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 1b -O-C (=} O) -Y 2b - is _{preferably, - (CH 2) c -O} -C (= O) - (CH 2) d - is particularly desirable . c is an integer of 1 or more and 5 or less, and 1 or 2 is preferable. d is an integer of 1 to 5, preferably 1 or 2.

  As the structural unit (b-3-S), a structural unit represented by the following formula (b-S1-11) or (b-S1-12) is particularly preferable, and 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 above-described 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 "is a divalent linking group, s" is an integer of 0 or more and 2 or less; A "is an alkylene group having 1 or more and 5 or less carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom, or sulfur 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.
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 polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. Examples thereof include groups excluding hydrogen atoms, etc. Specifically, one or more of monocycloalkanes such as cyclopentane and cyclohexane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane are exemplified. Examples thereof include a group 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 formulas (b-L1) to (b-L5) described above 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 aforementioned 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.

  In addition, 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, each of which is independently 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 to form a carbon atom to which both are bonded. 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 obtained by removing one or more hydrogen atoms 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. Particularly, a group in which one hydrogen atom has been removed from cyclohexane or adamantane (which may have a substituent) is preferable.

When R ^16b and R ^17b do not combine with 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 they are bonded. Specific examples of such an 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, 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 preferred.

^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 preferred.

When ^Yb is an alkyl group, it is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 6 to 15 carbon atoms. Such 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 above 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 above 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 above formulas (b7-1) to (b7-15), R ^24b represents a hydrogen atom or a methyl group.

Among the structural units represented by the formulas (b5) to (b7) described above, the structural unit represented by the formula (b6) is preferable in terms 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, phenoxy polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) Examples include acrylate, methoxypolypropylene glycol (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate. Further, the polymerizable compound having an ether bond is preferably 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, or methoxytriethylene glycol (meth) acrylate. These polymerizable compounds may be used alone or in combination of two or more.

  Further, the acrylic resin (B3) can contain 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 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, 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 and 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 include 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-sectional shape. 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) acrylates having an acid non-dissociable aliphatic polycyclic group, and vinyl group-containing aromatic compounds. As the acid non-dissociable aliphatic polycyclic group, a tricyclodecanyl group, an adamantyl group, a tetracyclododecanyl group, an isobornyl group, a norbornyl group, and the like are particularly preferable in terms of 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 acrylic resin (B3) contains a 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 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 a (meth) acrylate 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 from 0% by mass to 50% by mass, and more preferably 5% by mass or less. The content is more preferably from 30% by mass to 30% by mass.

  As long as the photosensitive resin composition contains a predetermined amount of the acrylic resin (B3), an acrylic resin other than the acrylic resin (B3) described above can 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 further preferably from 30,000 to 300,000. By having such a mass average molecular weight, it is possible to maintain sufficient strength of the photosensitive resin layer without lowering the releasability from the substrate, and further to prevent the swelling of the profile during plating and the occurrence of cracks. it can.

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

  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 photosensitive resin composition.

<Nitrogen-containing heterocyclic compound (C)>
The photosensitive resin composition contains a nitrogen-containing heterocyclic compound (C) which is a compound represented by the following formula (c1). Regarding the nitrogen-containing heterocyclic compound (C), a common logarithm value LogS of the solubility S is −4.00 or less. When the photosensitive resin composition contains the nitrogen-containing heterocyclic compound (C) having a LogS value within a predetermined range, it is easy to form a resist pattern having a rectangular cross section using the photosensitive resin composition.

When the nitrogen-containing heterocyclic compound (C) is blended in the photosensitive resin composition, it is easy to obtain a photosensitive resin composition having a wide margin of depth of focus (DOF).
The depth of focus (DOF) margin is a range of a depth of focus at which a resist pattern can be formed with a dimension within which a deviation from a target dimension is within a predetermined range when the exposure is performed by shifting the focus up and down at the same exposure amount. is there. The larger the depth of focus (DOF) margin, the better.
The template pattern for plating may be formed on a substrate having a warp or a step derived from a base material such as a polyimide film laminated on the substrate. Therefore, the chemically amplified positive photoresist composition used to form the template pattern for plating, regardless of the degree of flatness of the substrate surface, so that a pattern of desired dimensions and shape can be formed. It is desired that the margin of depth of focus (DOF) be wide.

  Further, when the photosensitive resin composition contains a nitrogen-containing heterocyclic compound (C), the photosensitive resin composition has good post-exposure stability (PED: post exposure delay) after exposure. When the withdrawal stability over time is good, even if the photosensitive resin layer made of the photosensitive resin composition is withdrawn for a long period of time after the exposure, when the exposed photosensitive resin layer is developed, the pattern is reduced. The shape and pattern dimensions are hardly adversely affected, and a pattern having a desired shape and dimensions is easily formed.

で表される含窒素複素環基であり、
Ａ^１及びＡ^２は、それぞれ独立に、単結合、又は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＮＨＣＯＮＨ−、−Ｓ−、−ＳＯ−、及び−ＳＯ_２−からなる群より選択される２価の基であり、
Ｗ^１は、単結合又は置換基を有してもよい２価の環式基であり、
Ｘ^１は、水素原子、置換基を有してもよい脂肪族炭化水素基又は置換基を有してもよい芳香族炭化水素基であり、
式（ｃ２）中、Ｒ^１、Ｒ^２及びＲ^４は、それぞれ独立に、置換基を有してもよい脂肪族炭化水素基又は置換基を有してもよい芳香族炭化水素基であり、Ｒ^３及びＲ^５は、それぞれ独立に、水素原子、置換基を有してもよい脂肪族炭化水素基又は置換基を有してもよい芳香族炭化水素基であり、
Ｙ^１〜Ｙ^３のうちのいずれか１つが下記式（ｃ３）又は式（ｃ４）：

で表される３価の基であり、当該３価の基が有する３つの結合手のうち一つの結合手がＡ^１に連結され、
式（ｃ３）中、Ｒ^６は、水素原子、置換基を有してもよい脂肪族炭化水素基又は置換基を有してもよい芳香族炭化水素基であり、
Ｙ^１〜Ｙ^３のうちの２つが、それぞれ独立に、−ＣＲ^７Ｒ^８−、−ＮＲ^９−、−Ｏ−及び−Ｓ−からなる群より選択される２価の基であり、
Ｒ^７、Ｒ^８及びＲ^９は、それぞれ独立に、水素原子、置換基を有してもよい脂肪族炭化水素基又は置換基を有してもよい芳香族炭化水素基である。） Z ¹ -A ¹ -W ¹ -A ² -X ¹ (c1)
(In the formula (c1), Z ¹ is the following formula (c2):

Is a nitrogen-containing heterocyclic group represented by
A ¹ and A ² are each independently a single bond or —O—, —CO—, —COO—, —OCO—, —OCOO—, —NH—, —CONH—, —NHCO—, —NHCONH -, - S -, - SO- , and -SO ₂ - is a divalent radical selected from the group consisting of,
W ¹ is a single bond or a divalent cyclic group which may have a substituent,
X ¹ is a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent,
In the formula (c2), R ¹ , R ² and R ⁴ are each independently an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent, R ³ and R ⁵ are each independently a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent,
Any one of Y ^{1 to} Y ³ is represented by the following formula (c3) or formula (c4):

Wherein one of the three bonds possessed by the trivalent group is linked to A ¹ ,
In the formula (c3), R ⁶ is a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent,
Two of Y ^{1 to} Y ³ are each independently a divalent group selected from the group consisting of —CR ⁷ R ⁸ —, —NR ⁹ —, —O— and —S—,
R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent. )

In the formula (c1), A ¹ and A ² each independently represent a single bond or —O—, —CO—, —COO—, —OCO—, —OCOO—, —NH—, —CONH—, -NHCO -, - NHCONH -, - S -, - SO-, and -SO ₂ - is a divalent radical selected from the group consisting of. A ¹ and A ² are each independently preferably a single bond, —O—, —COO—, or —OCO—.

In the formula (c1), W ¹ is a single bond or a divalent cyclic group which may have a substituent.
The ring constituting the divalent cyclic group which may have a substituent as W ¹ may contain a hetero atom other than a nitrogen atom such as O and S.
The number of ring-constituting atoms of the divalent cyclic group which may have a substituent is preferably 4 or more and 15 or less, more preferably 5 or more and 7 or less.
Examples of the divalent cyclic group which may have a substituent as W ¹ include an aliphatic hydrocarbon group which may have a substituent and an aromatic hydrocarbon group which may have a substituent. preferable.
Examples of the aliphatic hydrocarbon group of the aliphatic hydrocarbon group which may have a substituent as a divalent cyclic group include monocycloalkanes and polycycloalkanes such as bicycloalkanes, tricycloalkanes, and tetracycloalkanes. A group obtained by removing two hydrogen atoms from an alkane is exemplified. Specifically, monocycloalkanediyl groups such as cyclopentanediyl group and cyclohexanediyl group; polycycloalkane groups such as adamantanediyl group, norbornenediyl group, isobornenediyl group, tricyclodecanediyl group, and tetracyclododecanediyl group. Alkanediyl groups and the like. Preferably, it is a monocycloalkanediyl group.
Examples of the aromatic hydrocarbon group of the aromatic hydrocarbon group which may have a substituent as a divalent cyclic group include two aromatic rings such as a benzene ring, a naphthalene ring, an anthracene ring, and a fluorene ring. And a group excluding a hydrogen atom. Preferably, it is a phenylene group.
Examples of the substituent which the divalent cyclic group as W ¹ may have include a hydroxyl group, a mercapto group, an amino group, a halogen atom, a nitro group, and a cyano group. Examples of the substituent which the divalent cyclic group as W ¹ may have include a substituent such as a hydroxyl group, a mercapto group, an amino group, a halogen atom, a nitro group, and a cyano group. And organic groups which may contain hetero atoms such as N, O, S, P, Si, B, and halogen atoms. Among these substituents, a hydrocarbon group is preferred.
The hydrocarbon group as a substituent which the divalent cyclic group may have may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aliphatic hydrocarbon group and an aromatic hydrocarbon group. It may be a combination with a hydrocarbon group. The aliphatic hydrocarbon group may be linear, cyclic, or may have a chain structure and a cyclic structure. And may have an unsaturated bond. The number of carbon atoms of the 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 4 or less.
Specific examples of the linear aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group. , Isopentyl group, and neopentyl group. Specific examples of the cyclic aliphatic hydrocarbon group include a cyclic group such as a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, an isobornyl group, and a dicyclopentanyl group.
Examples of the aromatic hydrocarbon group include an aromatic hydrocarbon group containing no hetero atom such as a phenyl group and a naphthyl group, and an aromatic heterocyclic group such as a furyl group, a thienyl group and a pyridyl group.

In the formula (c1), X ¹ is a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent.
The aliphatic hydrocarbon group of the aliphatic hydrocarbon group which may have a substituent as X ¹ has a chain structure or a cyclic structure, including a chain structure and a cyclic structure. Is also good. In the case of a chain, it may be linear or branched. Further, the aliphatic hydrocarbon group may have an unsaturated bond. The number of carbon atoms of the 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.
Specific examples of the linear aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group. , Isopentyl group, and neopentyl group.
Specific examples of the cyclic aliphatic hydrocarbon group include a cyclic group such as a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, an isobornyl group, and a dicyclopentanyl group.
Examples of the aromatic hydrocarbon group of the aromatic hydrocarbon group which may have a substituent as X ¹ include an aromatic hydrocarbon group not containing a hetero atom such as a phenyl group and a naphthyl group, a furyl group, and a thienyl group. And aromatic heterocyclic groups such as a pyridyl group.
More in the X ¹ described, and that tends to lower the value of LOGS, from the point view to obtaining an additive effect desired, an isopropyl group, an isobutyl group, branched-chain alkyl such as sec- butyl and tert- butyl Groups, cyclic aliphatic hydrocarbon groups such as cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, isobornyl group and dicyclopentanyl group, and aromatic hydrocarbon groups such as phenyl group and naphthyl group are preferred.
The substituent of the aliphatic hydrocarbon group which may have a substituent and the aromatic hydrocarbon group which may have a substituent as X ¹ has a divalent cyclic group as W ¹ The same applies to the substituents which may be substituted.

In the formula (c2), R ¹ , R ² and R ⁴ are each independently an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent.
The aliphatic hydrocarbon group which may have a substituent as R ¹ , R ² and R ^{4 is the same} as the aliphatic hydrocarbon group which may have a substituent as X ¹ .
The aromatic hydrocarbon group which may have a substituent as R ¹ , R ² and R ^{4 is the same} as the aromatic hydrocarbon group which may have a substituent as X ¹ .

In the formula (c2), R ³ and R ⁵ are each independently a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent.
The aliphatic hydrocarbon group which may have a substituent as R ³ and R ^{5 is the same} as the aliphatic hydrocarbon group which may have a substituent as X ¹ .
Further, the aromatic hydrocarbon group which may have a substituent as R ³ and R ^{5 is the same} as the aromatic hydrocarbon group which may have a substituent as X ¹ .

In the formula (c2), R ¹ is preferably a methyl group because steric hindrance to R ^{2 to} R ⁵ is small.
In the formula (c2), R ^{2 to} R ⁵ are preferably a methyl group, an ethyl group, or an n-propyl group.
In the formula (c2), R ^{6 to} R ⁹ are preferably a hydrogen atom from the viewpoint of easy synthesis and industrial availability.

Wherein ^(c2), the Y 1 to Y ^3, any one of Y 1 to Y ³ is a trivalent group represented by the above formula (c3) or formula (c4), of the trivalent three coupling hands one bond with the group is connected to a ^1. Two of Y ^{1 to} Y ³ are each independently a divalent group selected from the group consisting of —CR ⁷ R ⁸ —, —NR ⁹ —, —O—, and —S—.
For example, when Y ² is a group represented by the formula (c3) and Y ¹ and Y ³ are each —CR ⁷ R ⁸ —, a nitrogen-containing heterocyclic group represented by the formula (c2), (c1) ^{Z 1} in is a monovalent group represented by the formula (c2-1). When Y ² is a group represented by the formula (c4), and Y ¹ and Y ³ are each —CR ⁷ R ⁸ —, the nitrogen-containing heterocyclic group represented by the formula (c2) is represented by the formula It is a monovalent group represented by (c2-2). When Y ¹ is —CR ⁷ R ⁸ —, Y ² is —O—, and Y ³ is a group represented by the formula (c3), the nitrogen-containing complex represented by the formula (c2) The ring group is a monovalent group represented by the formula (c2-3).

In the formula (c3), R ⁶ is a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent.
The aliphatic hydrocarbon group which may have a substituent as R ^{6 is the same} as the aliphatic hydrocarbon group which may have a substituent as X ¹ .
Further, the aromatic hydrocarbon group optionally having a substituent as R ^{6 is the same} as the aromatic hydrocarbon group optionally having a substituent as X ¹ .

R ⁷ , R ⁸ and R ⁹ in Y ^{1 to} Y ³ are each independently a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent. It is.
The aliphatic hydrocarbon group which may have a substituent as R ⁷ , R ⁸ and R ^{9 is the same} as the aliphatic hydrocarbon group which may have a substituent as X ¹ .
The aromatic hydrocarbon group which may have a substituent as R ⁷ , R ⁸ and R ^{9 is the same} as the aromatic hydrocarbon group which may have a substituent as X ¹ .

  The common logarithmic value LogS of the solubility S of the nitrogen-containing heterocyclic compound (C) is -4.00 or less. For example, even if a compound corresponding to the above formula (c1) is used, if LogS is larger than -4.00, the shape becomes poor.

  LogS is the common logarithm of solubility S as described above. LogS is a value calculated by chemdraw (registered trademark) prime (16.0) for Windows (registered trademark). Note that the LogS value may be calculated using software other than the Windows version chemdraw prime (16.0) as long as a value similar to the Windows version chemdraw prime (16.0) can be calculated.

  The LogS value of the nitrogen-containing heterocyclic compound (C) may be -4.00 or less, for example, -4.20 or less. The LogS value of the nitrogen-containing heterocyclic compound (C) is preferably -15.00 or more, and more preferably -8.00 or more.

Specific examples of the nitrogen-containing heterocyclic compound (C) include the following compounds.

In addition, in the specific examples of the above compound, examples in which A ¹ and A ² are —COO—, —OCO—, —CONH—, or —NHCO— have been described; however, in the above compound, —COO—, —OCO -, - CONH -, - the NHCO-, single bond, or, -O -, - CO -, - OCOO -, - NH -, - NHCONH -, - S -, - SO-, or, -SO ₂ - The compound changed to is also a specific example of the compound represented by the formula (c1).

  The nitrogen-containing heterocyclic compound (C) can be synthesized by appropriately combining known reactions. The following shows an example of a method for synthesizing the nitrogen-containing heterocyclic compound (C).

In the formula (c1), A ¹ is —OCO—, A ² is —COO—, and X ¹ has an aliphatic hydrocarbon group or a substituent which may have a substituent. A compound that is a good aromatic hydrocarbon group can be synthesized by a two-step esterification reaction as shown in the following formula.
Specifically, first, an alcohol represented by X ¹ -OH is reacted with a dicarboxylic acid compound represented by W ^1- (COOH) ₂ or an anhydride thereof to carry out esterification, whereby the following reaction is carried out. A monoester compound of a dicarboxylic acid described in the formula (intermediate) is obtained. Then, the target compound is obtained by reacting the monoester compound of dicarboxylic acid described in the following reaction formula with an alcohol represented by Z ¹ -OH. Either of the two-stage esterification reaction may be performed first, and an alcohol represented by Z ¹ -OH and a dicarboxylic acid compound represented by W ^1- (COOH) ₂ or an anhydride thereof are reacted to form an ester. After the conversion, it may be reacted with an alcohol represented by X ¹ -OH.
The dicarboxylic acid monoester compound described in the following reaction formula is represented by the formula (c1), wherein A ¹ is —OCO—, A ² is —COO—, and X ¹ is a hydrogen atom. Compound.

  The esterification method is not particularly limited. A suitable esterification method includes a method in which a carboxylic acid compound and an alcohol are condensed with a condensing agent such as a carbodiimide compound in the presence of a catalyst such as N, N-dimethyl-4-aminopyridine. Alternatively, the carboxylic acid compound may be reacted with a halogenating agent such as thionyl chloride or phosphorus trichloride to form a carboxylic acid halide, and then reacted with an alcohol.

The compound represented by the formula (c1), wherein A ¹ is —NHCO— and A ² is —CONH— can be synthesized by a two-stage amidation reaction as shown in the following formula.
Specifically, first, an amine compound represented by X ¹ —NH ₂ is reacted with a dicarboxylic acid compound represented by W ¹ — (COOH) ₂ or an anhydride thereof to perform amidation, The dicarboxylic acid monoamide compound (intermediate) described in the following reaction formula is obtained. Then, the target compound is obtained by reacting the monoamide compound of dicarboxylic acid described in the following reaction formula with an amine compound represented by Z ¹ -NH ₂ or ammonia. Either of the two-stage amidation reaction may be performed ^first , and an amine compound represented by Z ¹ -NH ₂ is reacted with a dicarboxylic acid compound represented by W ^1- (COOH) ₂ or an anhydride thereof. After performing the amidation by the above, the reaction may be caused to react with an amine compound represented by X ¹ -NH ₂ or ammonia.

  The method of amidation is not particularly limited. As a preferred amidation method, a carboxylic acid compound, a halide of the carboxylic acid compound, or a carboxylic acid compound is reacted with a condensing agent such as a carbodiimide compound in the presence of a catalyst such as N, N-dimethyl-4-aminopyridine. Examples of the method include a method of condensing an acid anhydride of a compound with an amine.

As the raw materials (Z ¹ -OH, Z ¹ -NH _2, etc.) in the above esterification or amidation reaction, commercially available products may be used, or piperidine, piperazine, morpholine, etc. Alternatively, it may be synthesized by applying a coupling reaction and introducing R ^{1 to} R ⁹ depending on the target compound.

As described above, the method for producing the compound represented by the formula (c1) has been described in the case where A ¹ and A ² are ester bonds or carboxylic acid amide bonds. Note that if A ¹ and A ² is a bond other than an ester bond and a carboxylic acid amide is also an ether bond formation reaction, acylation reaction, a carbonate bond forming reaction, N- substituent introduction reaction to an amino group, a urethane bond generated The compound represented by the formula (c1) can be produced by applying a well-known method for a reaction, a thioether bond formation reaction, a sulfoxide bond formation reaction (for example, oxidation of a thioether bond), and a sulfone bond formation reaction. .

  The nitrogen-containing heterocyclic compound (C) is preferably 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 resin (B) and the alkali-soluble resin (D) described later. It is more preferably used in the range of 0.01 part by mass or more and 3 parts by mass or less, and further preferably used in the range of 0.05 part by mass or more and 2 parts by mass or less.

<Alkali-soluble resin (D)>
The photosensitive resin composition preferably further contains an alkali-soluble resin (D) in order to improve crack resistance. Here, the alkali-soluble resin is a resin solution having a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate), 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 at the time of 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.

  The flexibility of the novolak resin can be further improved by using o-cresol, substituting the hydrogen atom of the hydroxyl group in the resin with another substituent, or using a bulky aldehyde. It is.

  The weight 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 from 1,000 to 50,000.

[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-methacryloyloxyethylsuccinic acid, and 2-methacryloyloxy. Compounds having a carboxy group and an ester bond, such as ethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic 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 weight 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, 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 can be easily improved.

<Sulfur-containing compound (E)>
When the photosensitive resin composition is used for forming a pattern on a metal substrate, the photosensitive resin composition preferably contains a sulfur-containing compound (E). The sulfur-containing compound (E) is a compound containing a sulfur atom that can coordinate to a metal. With respect to the compound capable of generating two or more tautomers, when at least one tautomer contains a sulfur atom that coordinates to a metal constituting the surface of the metal substrate, the compound is a sulfur-containing compound. Applicable.
In the case where a resist pattern used as a plating mold is formed on a surface made of a metal such as Cu, a defect in a cross-sectional shape such as footing is likely to occur. However, when the photosensitive resin composition contains the sulfur-containing compound (E), even when a resist pattern is formed on the surface of the substrate made of metal, it is easy to suppress the occurrence of problems in cross-sectional shape such as footing. In addition, "footing" is a phenomenon in which the bottom of the non-resist part is narrower than the top width of the non-resist part because the resist part protrudes toward the non-resist part near the contact surface between the substrate surface and the resist pattern. It is.
When the photosensitive resin composition is used for pattern formation on a substrate other than a metal substrate, it is not particularly necessary that the photosensitive resin composition contains a sulfur-containing compound. When the photosensitive resin composition is used for pattern formation on a substrate other than a metal substrate, the reduction in the number of components of the photosensitive resin composition facilitates the production of the photosensitive resin composition, It is preferable that the photosensitive resin composition does not contain the sulfur-containing compound (E) from the viewpoint that the production cost of the composition can be reduced.
There is no particular problem caused by the photosensitive resin composition used for pattern formation on a substrate other than the metal substrate containing the sulfur-containing compound (E).

Examples of the sulfur atom that can coordinate to a metal include a mercapto group (-SH), a thiocarboxy group (-CO-SH), a dithiocarboxy group (-CS-SH), and a thiocarbonyl group (-CS-). Etc. are included in sulfur-containing compounds.
It is preferable that the sulfur-containing compound has a mercapto group because it is easily coordinated with a metal and has an excellent effect of suppressing footing.

（式中、Ｒ^ｅ１及びＲ^ｅ２は、それぞれ独立に水素原子又はアルキル基を示し、Ｒ^ｅ３は単結合又はアルキレン基を示し、Ｒ^ｅ４は炭素以外の原子を含んでいてもよいｕ価の脂肪族基を示し、ｕは２以上４以下の整数を示す。） Preferred examples of the sulfur-containing compound having a mercapto group include a compound represented by the following formula (e1).

(Wherein, R ^e1 and R ^e2 each independently represent a hydrogen atom or an alkyl group, R ^e3 represents a single bond or an alkylene group, and R ^e4 represents a u-valent fat which may contain an atom other than carbon. And u represents an integer of 2 or more and 4 or less.)

When R ^e1 and R ^e2 are an alkyl group, the alkyl group may be linear or branched, and is preferably linear. When R ^e1 and R ^e2 are alkyl groups, the number of carbon atoms in the alkyl group is not particularly limited as long as the object of the present invention is not hindered. The number of carbon atoms of the alkyl group is preferably 1 or more, 4 or less, particularly preferably 1 or 2, and most preferably 1. As a combination of R ^e1 and R ^e2 , one is preferably a hydrogen atom and the other is an alkyl group, and one is particularly preferably a hydrogen atom and the other is a methyl group.

When ^Re3 is an alkylene group, the alkylene group may be linear or branched, and is preferably linear. When ^Re3 is an alkylene group, the number of carbon atoms of the alkylene group is not particularly limited as long as the object of the present invention is not hindered. The number of carbon atoms in the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, particularly preferably 1 or 2, and most preferably 1.

^Re4 is a divalent to tetravalent aliphatic group which may contain atoms other than carbon. ^Examples of atoms other than carbon that may be included in ^Re4 include a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The structure of the aliphatic group represented by ^Re4 may be linear, branched, cyclic, or a combination of these structures.

（式（ｅ２）中、Ｒ^ｅ４及びｕは、式（ｅ１）と同意である。） Among the compounds represented by the formula (e1), a compound represented by the following formula (e2) is more preferable.

(In the formula (e2), ^Re4 and u are the same as the formula (e1).)

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

（式（ｅ３−Ｌ１）〜（ｅ３−Ｌ７）中、Ｒ’、ｓ”、Ａ”、及びｒは、アクリル樹脂（Ｂ３）について前述した、式（ｂ−Ｌ１）〜（ｂ−Ｌ７）と同様である。） Compounds represented by the following formulas (e3-L1) to (e3-L7) are also preferable examples of the sulfur-containing compound having a mercapto group.

(In the formulas (e3-L1) to (e3-L7), R ′, s ″, A ″, and r are the same as the formulas (b-L1) to (b-L7) described above for the acrylic resin (B3). The same is true.)

Preferred specific examples of the mercapto compounds represented by the above formulas (e3-L1) to (e3-L7) include the following compounds.

（式（ｅ３−１）〜（ｅ３−４）中の略号の定義については、アクリル樹脂（Ｂ３）に関して前述した、式（３−１）〜（３−４）について前述した通りである。） Compounds represented by the following formulas (e3-1) to (e3-4) are also preferable examples of the sulfur-containing compound having a mercapto group.

(The definitions of the abbreviations in the formulas (e3-1) to (e3-4) are as described above for the formulas (3-1) to (3-4) described above with respect to the acrylic resin (B3).)

  Preferred specific examples of the mercapto compounds represented by the above formulas (e3-1) to (e3-4) include the following compounds.

（式（ｅ４）において、Ｒ^ｅ５は、水酸基、炭素原子数１以上４以下のアルキル基、炭素原子数１以上４以下のアルコキシ基、炭素数１以上４以下のアルキルチオ基、炭素数１以上４以下のヒドロキシアルキル基、炭素数１以上４以下のメルカプトアルキル基、炭素数１以上４以下のハロゲン化アルキル基及びハロゲン原子からなる群より選択される基であり、ｎ１は０以上３以下の整数であり、ｎ０は０以上３以下の整数であり、ｎ１が２又は３である場合、Ｒ^ｅ５は同一であっても異なっていてもよい。） Preferred examples of the compound having a mercapto group include a compound represented by the following formula (e4).

(In the formula (e4), R ^e5 represents a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, and an alkylthio group having 1 to 4 carbon atoms. A hydroxyalkyl group, a mercaptoalkyl group having 1 to 4 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms and a halogen atom, wherein n1 is an integer of 0 to 3 And n0 is an integer of 0 or more and 3 or less, and when n1 is 2 or 3, ^Re5 may be the same or different.)

When ^Re5 is an alkyl group which may have a hydroxyl group having 1 to 4 carbon atoms, specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. Group, sec-butyl group, and tert-butyl group. Among these alkyl groups, a methyl group, a hydroxymethyl group, and an ethyl group are preferred.

When ^Re5 is an alkoxy group having 1 to 4 carbon atoms, specific examples include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, and a sec-butyloxy group. And tert-butyloxy groups. Among these alkoxy groups, a methoxy group and an ethoxy group are preferred, and a methoxy group is more preferred.

When ^Re5 is an alkylthio group having 1 to 4 carbon atoms, specific examples include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, an isobutylthio group, and a sec-butylthio group. , And tert-butylthio groups. Among these alkylthio groups, a methylthio group and an ethylthio group are preferred, and a methylthio group is more preferred.

When ^Re5 is a hydroxyalkyl group having 1 to 4 carbon atoms, specific examples thereof include a hydroxymethyl group, a 2-hydroxyethyl group, a 1-hydroxyethyl group, a 3-hydroxy-n-propyl group, and 4 -Hydroxy-n-butyl group and the like. Among these hydroxyalkyl groups, a hydroxymethyl group, a 2-hydroxyethyl group, and a 1-hydroxyethyl group are preferred, and a hydroxymethyl group is more preferred.

When ^Re5 is a mercaptoalkyl group having 1 to 4 carbon atoms, specific examples include mercaptomethyl, 2-mercaptoethyl, 1-mercaptoethyl, 3-mercapto-n-propyl, and 4 -Mercapto-n-butyl group and the like. Among these mercaptoalkyl groups, a mercaptomethyl group, a 2-mercaptoethyl group, and a 1-mercaptoethyl group are preferable, and a mercaptomethyl group is more preferable.

When ^Re5 is a halogenated alkyl group having 1 to 4 carbon atoms, examples of the halogen atom contained in the halogenated alkyl group include fluorine, chlorine, bromine, and iodine. When ^Re5 is a halogenated alkyl group having 1 to 4 carbon atoms, specific examples include a chloromethyl group, a bromomethyl group, an iodomethyl group, a fluoromethyl group, a dichloromethyl group, a dibromomethyl group, a difluoromethyl group, Trichloromethyl group, tribromomethyl group, trifluoromethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-fluoroethyl group, 1,2-dichloroethyl group, 2,2-difluoroethyl group, 1-chloro- Examples include a 2-fluoroethyl group, a 3-chloro-n-propyl group, a 3-bromo-n-propyl group, a 3-fluoro-n-propyl group, and a 4-chloro-n-butyl group. Among these halogenated alkyl groups, chloromethyl group, bromomethyl group, iodomethyl group, fluoromethyl group, dichloromethyl group, dibromomethyl group, difluoromethyl group, trichloromethyl group, tribromomethyl group, and trifluoromethyl group Are preferable, and a chloromethyl group, a dichloromethyl group, a trichloromethyl group, and a trifluoromethyl group are more preferable.

When ^Re5 is a halogen atom, specific examples include fluorine, chlorine, bromine and iodine.

In the formula (e4), n1 is an integer of 0 to 3, and 1 is more preferable. When n1 is 2 or 3, a plurality of ^Re5 may be the same or different.

In the compound represented by the formula (e4), the substitution position of ^Re5 on the benzene ring is not particularly limited. The substitution position of ^{R e5} on the benzene ring are _{- (CH 2)} n0 is preferably meta or para position with respect to the binding position of -SH.

Examples of the compound represented by formula (e4), as R ^e5, alkyl group, hydroxyalkyl group, and a group selected from the group consisting of mercaptoalkyl group, a compound having at least one is preferable, as R ^e5, alkyl Compounds having one group selected from the group consisting of a group, a hydroxyalkyl group, and a mercaptoalkyl group are more preferred. Compounds of formula (e4) is, as R ^e5, alkyl group, hydroxyalkyl group, and optionally having one group selected from the group consisting of mercaptoalkyl group, an alkyl group, a hydroxyalkyl group, or mercaptoalkyl substitution positions on the benzene ring of the group, - (CH ₂₎ is preferably a meta or para position with respect to the binding position of n0 _-SH, and more preferably the para position.

  In the formula (e4), n0 is an integer of 0 or more and 3 or less. N is preferably 0 or 1, and more preferably 0, because the compound is easily prepared and easily available.

  Specific examples of the compound represented by the formula (e4) include p-mercaptophenol, p-thiocresol, m-thiocresol, 4- (methylthio) benzenethiol, 4-methoxybenzenethiol, 3-methoxybenzenethiol, 4-ethoxybenzenethiol, 4-isopropyloxybenzenethiol, 4-tert-butoxybenzenethiol, 3,4-dimethoxybenzenethiol, 3,4,5-trimethoxybenzenethiol, 4-ethylbenzenethiol, 4-isopropylbenzenethiol , 4-n-butylbenzenethiol, 4-tert-butylbenzenethiol, 3-ethylbenzenethiol, 3-isopropylbenzenethiol, 3-n-butylbenzenethiol, 3-tert-butylbenzenethiol, 3,5- Methylbenzenethiol, 3,4-dimethylbenzenethiol, 3-tert-butyl-4-methylbenzenethiol, 3-tert-4-methylbenzenethiol, 3-tert-butyl-5-methylbenzenethiol, 4-tert- Butyl-3-methylbenzenethiol, 4-mercaptobenzyl alcohol, 3-mercaptobenzyl alcohol, 4- (mercaptomethyl) phenol, 3- (mercaptomethyl) phenol, 1,4-di (mercaptomethyl) phenol, 1,3 -Di (mercaptomethyl) phenol, 4-fluorobenzenethiol, 3-fluorobenzenethiol, 4-chlorobenzenethiol, 3-chlorobenzenethiol, 4-bromobenzenethiol, 4-iodobenzenethiol, 3-bromobenzene All, 3,4-dichlorobenzenethiol, 3,5-dichlorobenzenethiol, 3,4-difluorobenzenethiol, 3,5-difluorobenzenethiol, 4-mercaptocatechol, 2,6-di-tert-butyl-4 -Mercaptophenol, 3,5-di-tert-butyl-4-methoxybenzenethiol, 4-bromo-3-methylbenzenethiol, 4- (trifluoromethyl) benzenethiol, 3- (trifluoromethyl) benzenethiol, Examples thereof include 3,5-bis (trifluoromethyl) benzenethiol, 4-methylthiobenzenethiol, 4-ethylthiobenzenethiol, 4-n-butylthiobenzenethiol, and 4-tert-butylthiobenzenethiol.

Examples of the sulfur-containing compound having a mercapto group include a compound containing a nitrogen-containing aromatic heterocycle substituted with a mercapto group and a tautomer of a compound containing a nitrogen-containing aromatic heterocycle substituted with a mercapto group. Can be
Preferred specific examples of the nitrogen-containing aromatic heterocyclic ring include imidazole, pyrazole, 1,2,3-triazole, 1,2,4-triazole, oxazole, thiazole, pyridine, pyrimidine, pyridazine, pyrazine, 1,2,2 3-triazine, 1,2,4-triazine, 1,3,5-triazine, indole, indazole, benzimidazole, benzoxazole, benzothiazole, 1H-benzotriazole, quinoline, isoquinoline, cinnoline, phthalazine, quinazoline, quinoxaline, And 1,8-naphthyridine.

Preferred specific examples of the nitrogen-containing heterocyclic compound suitable as the sulfur-containing compound and the tautomer of the nitrogen-containing heterocyclic compound include the following compounds.

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

<Acid diffusion controller (F)>
It is preferable that the photosensitive resin composition further contains an acid diffusion controller (F) in order to improve the shape of a resist pattern used as a template, the stability of the photosensitive resin film being pulled, and the like. The nitrogen-containing heterocyclic compound (C) contained in the photosensitive resin composition can function as an acid diffusion controller. In the present specification, the acid diffusion controller (F) is defined as a compound other than the nitrogen-containing heterocyclic compound (C). As the acid diffusion controller (F), a nitrogen-containing compound (F1) is preferable, and an organic carboxylic acid or an oxo acid of phosphorus or a derivative thereof (F2) can be further contained as necessary.

[Nitrogen-containing compound (F1)]
Examples of the nitrogen-containing compound (F1) 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, commercially available hindered amine compounds such as 4-hydroxy-1,2,2,6,6-pentamethylpiperidine derivatives, and 2,2 such as 2,6-diphenylpyridine and 2,6-di-tert-butylpyridine. Pyridine substituted at the 6-position with a substituent such as a hydrocarbon group can also be used as the nitrogen-containing compound (F1).

  The nitrogen-containing compound (F1) is generally used in an amount of 0 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), and 0 part by mass or more. It is particularly preferable to use it in a range of 3 parts by mass or less.

[Organic carboxylic acid or phosphorus oxo acid or derivative thereof (F2)]
Among organic carboxylic acids or phosphorus oxo acids or derivatives thereof (F2), specific examples of the organic carboxylic acid include malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid. , Especially salicylic acid is preferred.

  Examples of the oxo acid of phosphorus or a derivative thereof include phosphoric acid, phosphoric acid such as di-n-butyl phosphate, diphenyl phosphate, and derivatives such as esters thereof; phosphonic acid, dimethyl phosphonate, 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 (F2) 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 (F2) in an amount equivalent to that of the nitrogen-containing compound (F1).

<Organic solvent (S)>
The photosensitive resin composition contains an organic solvent (S). The type of the organic solvent (S) is not particularly limited as long as 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 as a mixture of two or more.

  The content of the organic solvent (S) is not particularly limited as long as the object of the present invention is not impaired. When the photosensitive resin composition is used for a thick film application in which the thickness of the photosensitive resin layer obtained by a spin coating method or the like is 5 μm or more, the solid content concentration of the photosensitive resin composition is 30% by mass or more and 55% or more. It is preferable to use the organic solvent (S) within the range of not more than mass%.

<Other ingredients>
The 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.

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

Further, the 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 fluorinated surfactant include BM-1000, BM-1100 (all manufactured by BM Chemie), Megafac F142D, Megafac F172, Megafac F173, Megafac F183 (all of Dainippon Ink and Chemicals, Inc.) Co., Ltd.), Florard FC-135, Florard FC-170C, Florard FC-430, Florard FC-431 (all manufactured by Sumitomo 3M), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S- 141, commercially available fluorosurfactants such as Surflon S-145 (all manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (all manufactured by Toray Silicone Co., Ltd.) But are not limited to these.
As the silicone-based surfactant, unmodified silicone-based surfactant, polyether-modified silicone-based surfactant, polyester-modified silicone-based surfactant, alkyl-modified silicone-based surfactant, aralkyl-modified silicone-based surfactant, and A reactive silicone surfactant or the like can be preferably used.
As the silicone-based surfactant, a commercially available silicone-based surfactant can be used. Specific examples of commercially available silicone surfactants include Paintad M (manufactured by Dow Corning Toray), Topica K1000, Topica K2000, 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 photosensitive resin composition may further contain an acid, an acid anhydride, or a high-boiling 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 and 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 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.

  Further, the photosensitive resin composition may further contain a sensitizer for improving sensitivity.

Such an acid generator (A), a resin (B), and a nitrogen-containing heterocyclic compound (C), and if necessary, an alkali-soluble resin (D), a sulfur-containing compound (E), an acid The photosensitive resin composition (chemically amplified positive photosensitive resin composition), which may contain components such as the diffusion inhibitor (F) and the organic solvent (S), is added to the coating film of the photosensitive resin composition. On the other hand, after heating (prebaking) at 130 ° C. for 5 minutes, an operation of contacting with an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide at 23 ° C. for 30 seconds was performed twice at intervals, followed by pure water. It is preferable that the film reduction rate upon rinsing is 0.1 μm / min or more and 0.5 μm / min or less. In addition, the film reduction rate is obtained by the following equation.
Film reduction rate (μm / min) = (film thickness before prebaking operation (μm) −film thickness after two operations (μm)) / contact time of tetramethylammonium hydroxide (min)
(In the formula, “operation” means an operation of contacting with an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide at 23 ° C. for 30 seconds. “Thickness” refers to the thickness of the coating film of the photosensitive resin composition. The contact time is 30 seconds × 2, that is, 1 minute.)

Here, if the film reduction rate is high, the resistance of the pattern formed by using the photosensitive resin composition to the plating solution used when producing a molded object tends to deteriorate. For this reason, conventionally used photosensitive resin compositions are often designed to reduce the film reduction rate.
On the other hand, in the above-mentioned photosensitive resin composition, for example, from the viewpoint of improving the stability over time (PED: post exposure delay) after exposure and from the viewpoint of forming a pattern having a good cross-sectional shape, for example, 0%. It is preferable that the film-removing speed is higher than the film-removing speed of the conventionally used photosensitive resin composition, such as from 0.1 μm / min to 0.5 μm / min.
In this case, it is easy to obtain a photosensitive resin composition having good post-exposure delay (PED: post exposure delay) after exposure. When the exposed photosensitive resin layer is left for a long time, a defect in the pattern shape during development tends to appear near the surface of the photosensitive resin layer. However, if the above-mentioned film reduction rate is set to a higher value within an appropriate range, the surface of the photosensitive resin layer is slightly dissolved at the time of development, so that it is possible to alleviate the problem of the pattern shape after development due to the pull-out.
When such a film reduction rate is adopted, for example, even if the delay time from the exposure to the start of development is set to 9 hours or more, it is easy to make the CD (Critical Dimension) fluctuation as small as 10% or less.

With respect to the photosensitive resin composition, there is no particular limitation on the method for adjusting the film reduction rate within the above preferred range. As a preferable method of adjusting the film reduction rate, a method of adjusting the content of the alkali-soluble resin (D) is exemplified. The larger the content of the alkali-soluble resin (D) in the photosensitive resin composition, the higher the above-mentioned film reduction rate.
Another preferred method of adjusting the film reduction rate is a method of adjusting the amount of units derived from a monomer having an alkali-soluble group in the resin (B). The greater the amount of units derived from the monomer having an alkali-soluble group in the resin (B), the higher the above-mentioned film reduction rate.
Examples of the monomer having an alkali-soluble group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; 2-methacryloyloxyethylsuccinic acid, and 2-methacryloyloxy. Methacrylic acid derivatives having a carboxy group and an ester bond such as ethylmaleic acid, 2-methacryloyloxyethylphthalic acid, and 2-methacryloyloxyethylhexahydrophthalic acid; hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxy Examples thereof include vinyl group-containing aromatic compounds having a phenolic hydroxyl group such as styrene.

<Preparation method of chemically amplified positive photosensitive resin composition>
The chemically amplified positive photosensitive resin composition is prepared by mixing and stirring each of the above-described components in a usual manner. Examples of an apparatus that can be used when 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 resin layer formed on the surface of the base film, and the photosensitive resin layer is made of the above-described photosensitive resin composition.

  As the base film, a film having light transmittance 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 because of its excellent balance of light transmittance and breaking strength.

A photosensitive dry film is produced by applying the above-mentioned photosensitive resin composition on a base film to form a photosensitive resin layer.
When the photosensitive resin layer is formed on the substrate film, the film thickness after drying on the substrate film using an applicator, a bar coater, a wire bar coater, a roll coater, a curtain flow coater, or the like is preferably 0. The photosensitive resin composition is applied to have a thickness of 5 μm or more and 300 μm or less, more preferably 1 μm or more and 300 μm or less, and particularly preferably 3 μm or more and 100 μm or less, and dried.

  The photosensitive dry film may further have a protective film on the photosensitive resin 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 and substrate with mold >>
The method for forming a patterned resist film on a substrate having a metal surface using the above-described photosensitive resin 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 resin layer made of a photosensitive resin composition on a substrate having a metal surface,
An exposure step of irradiating the photosensitive resin layer with position-selective irradiation with actinic rays or radiation, and
A developing step of developing the photosensitive resin layer after exposure,
And a method for producing a patterned resist film.
In a method of manufacturing a substrate with a mold having a mold for forming a plated molded article, a photosensitive resin layer is laminated on a metal surface of a substrate having a metal surface, and in a development step, a plated molded article is formed by development. The method is the same as the method for manufacturing a patterned resist film except that a mold for forming the resist film is formed.

  As the substrate on which the photosensitive resin layer is laminated, a substrate having a metal surface is used. As the metal species constituting the metal surface, copper, gold, and aluminum are preferable, and copper is more preferable. Since the photosensitive resin composition has a wide margin of depth of focus (DOF), various substrates can be used regardless of the flatness of the substrate surface.

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

  As a method for applying the photosensitive resin 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 resin layer. The pre-bake conditions vary depending on the type, blending ratio, coating film thickness, etc. of each component in the photosensitive resin composition, but are usually 70 ° C. to 200 ° C., preferably 80 ° C. to 150 ° C., and are preferably 2 minutes or more. It is about 120 minutes or less.

  The photosensitive resin 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. Is done.

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 and the like of the composition of the photosensitive resin composition and a photosensitive resin layer, for example, in the case of ultra-high pressure mercury lamp used is 100 mJ / cm ² or more 10000 mJ / cm ² or less. 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 resin layer using a known method, and in the exposed portion of the photosensitive resin film, the alkali solubility of the photosensitive resin layer is changed. .

  Next, the exposed photosensitive resin layer is developed according to a conventionally known method, and unnecessary portions are dissolved and removed to form a predetermined resist pattern or a mold for forming a plated 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 (tetramethylammonium hydroxide), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5 An aqueous solution of an alkali such as -diazabicyclo [4,3,0] -5-nonane can be used. In addition, an aqueous solution obtained by adding a suitable amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous solution of the above alkalis can also be used as the developer.

  The development time varies depending on the composition of the photosensitive resin composition, the thickness of the photosensitive resin 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 with a mold having a resist pattern serving as a mold on the metal surface of the substrate having the metal surface can be manufactured.

製造 Manufacturing method for molded objects≫
By embedding a conductor such as a metal by plating in a non-resist part (a part removed by a developing solution) in a mold of a mold-provided substrate formed by the above method, for example, connection terminals such as bumps and metal posts can be formed. In addition, it is possible to form a molded product such as Cu rewiring. The plating method is not particularly limited, and various conventionally known methods can be employed. As the plating solution, solder plating, copper plating, gold plating, and nickel plating solution are particularly preferably used. Finally, the remaining mold is removed using a stripper or the like according to a conventional method.

When manufacturing a plated object, it may be preferable to perform an ashing process on a metal surface exposed in a non-pattern portion of a resist pattern serving as a mold for forming a plated object.
Specifically, for example, this is a case where a plated molded article is formed using a pattern formed using a photosensitive resin composition containing a sulfur-containing compound (E) as a template. In this case, the adhesion of the plated object to the metal surface may be easily impaired. This problem is remarkable when the sulfur-containing compound (E) represented by the above formula (e1) or the sulfur-containing compound (E) represented by the formula (e4) is used.
However, when the above-described ashing treatment is performed, even when a pattern formed using the photosensitive resin composition containing the sulfur-containing compound (E) is used as a mold, a plated molded article that is in good contact with the metal surface is formed. Cheap.
In the case where a compound containing a nitrogen-containing aromatic heterocyclic ring substituted with a mercapto group is used as the sulfur-containing compound (E), the above-mentioned problem relating to the adhesion of the plated molded article is scarce or slight. Therefore, when a compound containing a nitrogen-containing aromatic heterocyclic ring substituted with a mercapto group is used as the sulfur-containing compound (E), a plated molded article having good adhesion to a metal surface is formed without performing an ashing treatment. Cheap.

The ashing process is not particularly limited as long as the method does not damage the resist pattern serving as a mold for forming the plated object to such an extent that a plated object having a desired shape cannot be formed.
A preferable ashing treatment method is a method using oxygen plasma. In order to ash a metal surface on a substrate using oxygen plasma, oxygen plasma may be generated using a known oxygen plasma generator, and the oxygen plasma may be applied to the metal surface on the substrate.

Various gases conventionally used for plasma processing together with oxygen can be mixed with the gas used for generating oxygen plasma within a range not to impair the object of the present invention. Examples of such a gas include a nitrogen gas, a hydrogen gas, and a CF ₄ gas.
The ashing condition using oxygen plasma is not particularly limited as long as the object of the present invention is not impaired, but the processing time is, for example, in a range of 10 seconds to 20 minutes, and preferably in a range of 20 seconds to 18 minutes. And more preferably in the range from 30 seconds to 15 minutes.
By setting the treatment time by the oxygen plasma within the above range, the effect of improving the adhesion of the plated object can be easily obtained without causing a change in the shape of the resist pattern.

  According to the above method, since a resist pattern having a good rectangular cross section can be used as a mold for forming a plated object, it is easy to secure a wide contact area between the plated object and the surface of the substrate. It is possible to produce a plated molded article having excellent adhesion to the substrate.

で表される含窒素複素環基であり、
Ａ^１及びＡ^２は、それぞれ独立に、単結合、又は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＮＨＣＯＮＨ−、−Ｓ−、−ＳＯ−、及び−ＳＯ_２−からなる群より選択される２価の基であり、
Ｗ^２は、置換基を有してもよい２価の環式基であり、
Ｘ^１は、水素原子、置換基を有してもよい脂肪族炭化水素基又は置換基を有してもよい芳香族炭化水素基であり、
式（ｃ２）中、Ｒ^１、Ｒ^２及びＲ^４は、それぞれ独立に、置換基を有してもよい脂肪族炭化水素基又は置換基を有してもよい芳香族炭化水素基であり、Ｒ^３及びＲ^５は、それぞれ独立に、水素原子、置換基を有してもよい脂肪族炭化水素基又は置換基を有してもよい芳香族炭化水素基であり、
Ｙ^１〜Ｙ^３のうちのいずれか１つが下記式（ｃ３）又は式（ｃ４）：

で表される３価の基であり、当該３価の基が有する３つの結合手のうち一つの結合手がＡ^１に連結され、
式（ｃ３）中、Ｒ^６は、水素原子、置換基を有してもよい脂肪族炭化水素基又は置換基を有してもよい芳香族炭化水素基であり、
Ｙ^１〜Ｙ^３のうちの２つが、それぞれ独立に、−ＣＲ^７Ｒ^８−、−ＮＲ^９−、−Ｏ−及び−Ｓ−からなる群より選択される２価の基であり、
Ｒ^７、Ｒ^８及びＲ^９は、それぞれ独立に、水素原子、置換基を有してもよい脂肪族炭化水素基又は置換基を有してもよい芳香族炭化水素基である。） The compound represented by the following formula (c1-a) is a novel compound. The compound represented by the following formula (c1-a) is a compound represented by the formula (c1), except that W ¹ is limited to a divalent cyclic group (W ² ) which may have a substituent. The same as formula (c1), Z ¹ , A ¹ , A ² , X ¹ in formula (c1-a), R ^{1 to} R ⁵ , Y ^{1 to} Y ³ in formula (c2), and formula (c3) )), R ⁶ and R ^{7 to} R ⁹ are the same as those in the formula (c1). Further, the divalent cyclic group which may have a substituent as W ² in the formula (c1-a) is a divalent cyclic group which may have a substituent in W ¹ in the formula (c1). It is the same as the cyclic group.
Z ¹ -A ¹ -W ² -A ² -X ¹ (c1-a)
(In the formula (c1-a), Z ¹ is the following formula (c2):

Is a nitrogen-containing heterocyclic group represented by
A ¹ and A ² are each independently a single bond or —O—, —CO—, —COO—, —OCO—, —OCOO—, —NH—, —CONH—, —NHCO—, —NHCONH -, - S -, - SO- , and -SO ₂ - is a divalent radical selected from the group consisting of,
W ² is a divalent cyclic group which may have a substituent,
X ¹ is a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent,
In the formula (c2), R ¹ , R ² and R ⁴ are each independently an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent, R ³ and R ⁵ are each independently a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent,
Any one of Y ^{1 to} Y ³ is represented by the following formula (c3) or formula (c4):

Wherein one of the three bonds possessed by the trivalent group is linked to A ¹ ,
In the formula (c3), R ⁶ is a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent,
Two of Y ^{1 to} Y ³ are each independently a divalent group selected from the group consisting of —CR ⁷ R ⁸ —, —NR ⁹ —, —O— and —S—,
R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent. )

The compound represented by the formula (c1-a) can be contained in a photosensitive resin composition other than the above-described photosensitive resin composition, and can be used for applications other than the photosensitive resin composition.
Although the LogS value of the compound represented by the formula (c1-a) is not limited, it is preferably −4.00 or less from the viewpoint that it can be used in the above-described photosensitive resin composition.

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

[Preparation Example 1]
(Synthesis of Mercapto Compound E1)
In Preparation Example 1, a mercapto compound E1 having the following structure was synthesized as the sulfur-containing compound (E).

In a flask, 15.00 g of 7-oxanorborna-5-ene-2,3-dicarboxylic anhydride and 150.00 g of tetrahydrofuran were added and stirred. Then, 7.64 g of thioacetic acid (AcSH) was added to the flask, and the mixture was stirred at room temperature for 3.5 hours. Thereafter, the reaction solution was concentrated to obtain 22.11 g of 5-acetylthio-7-oxanorbornane-2,3-dicarboxylic anhydride.
22.11 g of 5-acetylthio-7-oxanorbornane-2,3-dicarboxylic anhydride and 30.11 g of a 10% by mass aqueous sodium hydroxide solution were added to the flask, and the contents of the flask were added at room temperature. Was stirred for 2 hours. Next, hydrochloric acid (80.00 g) having a concentration of 20% by mass was added into the flask to make the reaction solution acidic. Thereafter, extraction with 200 g of ethyl acetate was performed four times to obtain an extract containing the mercapto compound E1. The extract was concentrated, and the residue collected was dissolved by adding 25.11 g of tetrahydrofuran (THF). Heptane was dropped into the obtained THF solution to precipitate a mercapto compound E1, and the precipitated mercapto compound E1 was recovered by filtration. The measurement results of ¹ H-NMR of the mercapto compound E1 are described below.
^{1 H-NMR (DMSO-d6} ): δ12.10 (s, 2H), 4.72 (d, 1H), 4.43 (s, 1H), 3.10 (t, 1H), 3.01 ( d, 1H), 2.85 (d, 1H), 2.75 (d, 1H), 2.10 (t, 1H), 1.40 (m, 1H).

[Preparation Example 2]
(Synthesis of nitrogen-containing heterocyclic compound C1)
In Preparation Example 2, the following nitrogen-containing heterocyclic compound C1 was synthesized as the nitrogen-containing heterocyclic compound (C).

After dissolving 1.00 g (6.09 mmol) of 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 10 g of 2-propanol and stirring at 60 ° C. for 6 hours, 2-propanol was added. An intermediate was obtained by distillation under reduced pressure. The intermediate and 4-hydroxy-1,2,2,6,6-pentamethylpiperidine (1.04 g, 6.09 mmol) (manufactured by Tokyo Kasei Kogyo Co., Ltd.) are dissolved in 10 g of methylene chloride, and WSC · HCl (of carbodiimide compound) is dissolved. 1.45 g (7.61 mmol) of hydrochloride) was added, and the mixture was stirred at room temperature for 24 hours. The reaction solution was filtered to remove precipitates, washed once with 1 g of 1% hydrochloric acid, three times with 10 g of pure water, and then washed once with 10 g of a 10% aqueous sodium hydroxide solution and three times with 10 g of pure water. Thereafter, the solvent was distilled off to obtain 1.29 g of the target C1. The measurement results of ¹ H-NMR of C1 are described below. The reaction formula is shown below.
¹ H-NMR (DMSO-d6): δ 6.10 (m, 2H), 4.87-4.72 (m, 2H), 3.23 (m, 2H), 3.10 (m, 2H), 2.15 (s, 3H), 1.73 (m, 2H), 1.35-1.22 (m, 4H), 1.20-1.10 (m, 6H), 1.07 (d, 6H), 0.98 (d, 6H)

[Preparation Example 3]
(Synthesis of nitrogen-containing heterocyclic compound C2)
In Preparation Example 3, the following nitrogen-containing heterocyclic compound C2 was synthesized as the nitrogen-containing heterocyclic compound (C).

Synthesis was performed in the same manner as in Preparation Example 3 except that 1.00 g of 5-norbornene-2,3-dicarboxylic anhydride was changed to 0.902 g of phthalic anhydride, thereby obtaining 1.19 g of C2. The measurement results of ¹ H-NMR of C2 are described below. The reaction formula is shown below.
^{1 H-NMR (DMSO-d6} ): δ7.80-7.60 (m, 4H), 5.20-5.08 (m, 2H), 2.20 (s, 3H), 1.92 (dd , 2H), 1.45 (t, 2H), 1.26 (d, 6H), 1.11 (s, 6H), 1.08 (s, 6H).

[Preparation Example 4]
(Synthesis of nitrogen-containing heterocyclic compound C3)
In Preparation Example 4, the following nitrogen-containing heterocyclic compound C3 was synthesized as the nitrogen-containing heterocyclic compound (C).

In a flask cooled to −20 ° C. under a nitrogen atmosphere, 5.97 mL of a hexane solution of 1.13 M LDA (lithium diisopropylamide) was added. Next, 5.00 g of a THF (tetrahydrofuran) solution in which 0.500 g of t-butyl alcohol was dissolved was dropped into the flask. After stirring the content of the flask at −20 ° C. for 30 minutes, 10.0 g of a THF solution in which 1.00 g (6.75 mmol) of phthalic anhydride was dissolved was dropped into the flask. After the dropwise addition, the content was stirred for 4 hours while the temperature of the content of the flask was raised to room temperature. After stirring, 15 g of water was added to stop the reaction. After recovering the aqueous phase by a liquid separation operation, the recovered aqueous phase was washed three times with 10 g of t-butyl methyl ether. A 10% aqueous hydrochloric acid solution was added to the washed aqueous phase until the pH became 1, followed by extraction with 10 g of methylene chloride three times. After washing the methylene chloride phase with water, the solvent of the methylene chloride phase was distilled off. The obtained crude product was reprecipitated with methylene chloride and heptane to obtain 1.01 g of an intermediate. The intermediate and 4-hydroxy-1,2,2,6,6-pentamethylpiperidine 0.777 g (4.54 mmol) (manufactured by Tokyo Chemical Industry) are dissolved in 10 g of methylene chloride, and 1.08 g of WSC.HCl ( 5.67 mmol) and stirred at room temperature for 24 hours. The reaction solution was filtered to remove precipitates, washed once with 1 g of 1% hydrochloric acid, washed three times with 10 g of pure water, then washed once with 10 g of a 10% aqueous sodium hydroxide solution, and washed three times with 10 g of pure water. Thereafter, the solvent was distilled off to obtain 0.851 g of the target C3. The measurement results of ¹ H-NMR of C3 are described below. The reaction formula is shown below.
^{1 H-NMR (DMSO-d6} ): δ7.80-7.60 (m, 4H), 5.20-5.10 (m, 1H), 2.18 (s, 3H), 1.90 (dd , 2H), 1.47 (t, 2H), 1.20 (s, 9H), 1.10 (s, 6H), 1.05 (s, 6H).

[Preparation Example 5]
(Synthesis of nitrogen-containing heterocyclic compound C'2)
In Preparation Example 5, the following additive C′2 was synthesized.

1.00 g (5.74 mmol) of 4-hydroxy-1,2,2,6,6-pentamethylpiperidine (Tokyo Kasei Kogyo) and 1.00 g of mono-tert-butyl succinate (Tokyo Kasei Kogyo) (5.74 mmol) was dissolved in 10 g of methylene chloride, and 1.37 g (7.17 mmol) of WSC.HCl was added, followed by stirring at room temperature for 24 hours. The reaction solution was filtered to remove precipitates, washed once with 1 g of 1% hydrochloric acid, washed three times with 10 g of pure water, then washed once with 10 g of a 10% aqueous sodium hydroxide solution, and washed three times with 10 g of pure water. Thereafter, the solvent was distilled off to obtain 1.33 g of the target C'2. The results of ¹ H-NMR measurement of C′2 are described below. The reaction formula is shown below.
¹ H-NMR (DMSO-d6): δ 4.93 (m, 1H), 2.44 (m, 4H), 2.13 (s, 3H), 1.78 (dd, 2H), 1.41- 1.31 (m, 11H), 1.08 (s, 6H), 1.05 (s, 6H)

[Examples 1 to 12, and Comparative Examples 1 to 10]
In Examples 1 to 12 and Comparative Examples 1 to 10, the compound A1 represented by the following formula was used as the acid generator (A).

In Examples 1 to 12 and Comparative Examples 1 to 10, the following resins B1, B2, B3 and B4 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 106,000. The weight average molecular weight Mw of the resin B2 is 106,000. The number average molecular weight of the resin B3 is 106,000. The weight average molecular weight Mw of the resin B4 is 40,000, and the degree of dispersion (Mw / Mn) is 2.6.

In Examples 1 to 12, the above C1 to C3 were used as the nitrogen-containing heterocyclic compound (C). In Comparative Examples 1 to 10, the following C′1, C′2 and C′3 were used as alternative additives (C ′) to the nitrogen-containing heterocyclic compound (C).
LogS values of C1, C2, C3, C′1, C′2 and C′3 calculated by the Windows version chemdraw prime (16.0) are as follows.
C1: -4.245
C2: -5.052
C3: -5.384
C'1: -1.473
C'2: -3.370
C'3: -4.222

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)

  The mercapto compound E1 obtained in Preparation Example 1 was used as the sulfur-containing compound (E).

  Acid generator (A), resin (B), nitrogen-containing heterocyclic compound (C) or additive (C ′), and an alkali-soluble resin (D) of the kind and amount shown in Table 1, respectively; 3-methoxybutyl acetate (MA) and propylene glycol monomethyl were mixed with the sulfur-containing compound (E) and 0.05 parts by mass of a surfactant (BYK310, manufactured by BYK-Chemie) so that the solid content concentration became 40% by mass. It was dissolved in a mixed solvent (MA / PM = 6/4 (mass ratio)) with ether acetate (PM) to obtain photosensitive resin compositions of Examples and Comparative Examples.

  Using the obtained photosensitive resin composition, the shape, the depth of focus (DOF) margin, the film reduction rate, and the PED were evaluated according to the following methods. Table 1 shows the results of these evaluations.

[Evaluation of shape]
The photosensitive resin compositions of Examples and Comparative Examples were applied on a copper substrate having a diameter of 8 inches to form a 7 μm-thick photosensitive resin layer (a coating film of the photosensitive resin composition). Next, the photosensitive resin layer was pre-baked at 130 ° C. for 5 minutes. After pre-baking, 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 GHI5452 (Ultratech), it is 1.2 times the minimum exposure amount capable of forming a pattern of a predetermined size. Pattern exposure was performed with ghi-line at the exposure amount. Next, 9 hours after the pattern exposure, the substrate was placed on a hot plate and subjected to post-exposure bake (PEB) at 90 ° C. for 1.5 minutes. Immediately after PEB, a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (developing solution, NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was dropped on the exposed photosensitive resin layer, and the mixture was allowed to stand at 23 ° C. for 30 seconds. This operation was repeated twice in total. Thereafter, the resist pattern surface was washed with running water (rinsed), and then nitrogen was blown to obtain a resist pattern. The cross-sectional shape of the resist pattern was observed with a scanning electron microscope to evaluate the cross-sectional shape of the pattern.
Specifically, the surface (top) of the resist pattern opposite to the surface in contact with the substrate is flat (planar), and the width of the top of the cross section of the resist pattern is the pattern width of the middle part in the thickness direction of the cross section of the resist pattern. When it was almost the same as in the above, it was evaluated as ○. In addition, a case where the top of the resist pattern was rounded (rounded) or the width of the top of the cross section of the resist pattern was significantly different from the pattern width of the middle portion in the thickness direction of the cross section of the resist pattern was evaluated as x. In all the examples, the pattern width at the middle part in the thickness direction of the cross section of the resist pattern was substantially the same as the width (bottom) of the cross section of the resist pattern in contact with the substrate.

[Evaluation of DOF margin]
A line and space pattern having a line width of 2 μm and a space width of 2 μm was formed in the same manner as in [Evaluation of Shape]. At this time, the range of the focus where the pattern can be independently independent was examined.
The case where the focus range was 32 μm or more was judged as ◎, the case where the focus range was 28 μm or more and less than 32 μm was judged as ○, and the case where the focus range was less than 28 μm was judged as x.

[Evaluation of film reduction rate]
The photosensitive resin compositions of Examples and Comparative Examples were applied on a Si substrate to form a 7 μm-thick photosensitive resin layer (a coating film of the photosensitive resin composition). Next, the photosensitive resin layer was pre-baked at 130 ° C. for 5 minutes. After pre-baking, the photosensitive resin layer was twice subjected to an operation of contacting with an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide at 23 ° C. for 30 seconds at 23 ° C., and then the photosensitive resin layer was washed with pure water. Rinsed. After prebaking, the thickness of the photosensitive resin layer before performing an operation of contacting the photosensitive resin layer with an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide at 23 ° C. for 30 seconds, and the photosensitivity after rinsing The thickness of the resin layer was measured, and the value obtained by subtracting the latter from the former was determined as the time during which a 2.38% by weight aqueous solution of tetramethylammonium hydroxide was brought into contact with the photosensitive resin layer (the total contact time of 1 minute). The value obtained by dividing by the above was taken as the film reduction rate. Table 1 shows the results.

[Evaluation of PED]
A line and space pattern having a line width of 2 μm and a space width of 2 μm was formed in the same manner as in [Evaluation of Shape]. At this time, the time until the post-exposure heating (PEB) after pattern exposure was set to 0 hour (PEB immediately after pattern exposure) or 9 hours, respectively, to form resist patterns. With respect to the average value of the uppermost line width of the resist pattern obtained when PEB was performed immediately after the pattern exposure, the resist pattern obtained when the time until the PEB was performed after pattern exposure was set to 9 hours. The ratio of the average value of the upper line width (CD (Critical Dimension) variation rate) was determined.
The case where the CD fluctuation rate was within 10% was judged as ○, and the case where the CD fluctuation rate was more than 10% was judged as ×. Table 1 shows the results.

According to Examples 1 to 12, 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 an alkali increases by the action of an acid, the formula (A) The positive photosensitive resin composition containing the nitrogen-containing heterocyclic compound (C) represented by c1) and having a LogS value of -4.00 or less can form a rectangular resist pattern having a good cross-sectional shape, and It can be seen that the depth of focus (DOF) has a wide margin.
In addition, according to Examples 1 to 9, it can also be seen that the amount of film reduction in the above evaluation was from 0.1 μm / min to 0.5 μm / min.
Further, according to Examples 1 to 9, it is also found that PED is excellent.

  On the other hand, according to Comparative Examples 1 to 10, instead of the nitrogen-containing heterocyclic compound (C), the positive photosensitive resin composition was replaced with a nitrogen-containing heterocyclic compound not corresponding to the nitrogen-containing heterocyclic compound (C). When a certain additive (C ′) is contained, the cross-sectional shape of the top of the resist pattern becomes round, and it is found that it is difficult to form a resist pattern having a good rectangular cross-sectional shape. Further, in Comparative Examples 1 to 10, the range of the focus in the evaluation of the depth of focus (DOF) margin was 24 μm or less, and the depth of focus margin was narrow.

Claims (14)

An acid generator (A) that generates an acid upon irradiation with actinic rays or radiation, a resin (B) whose solubility in an alkali increases by the action of an acid, and a nitrogen-containing heterocyclic compound (C),
The nitrogen-containing heterocyclic compound (C) has the following formula (c1):
Z ¹ -A ¹ -W ¹ -A ² -X ¹ (c1)
(In the formula (c1), Z ¹ is the following formula (c2):

Is a nitrogen-containing heterocyclic group represented by
A ¹ and A ² are each independently a single bond or —O—, —CO—, —COO—, —OCO—, —OCOO—, —NH—, —CONH—, —NHCO—, —NHCONH -, - S -, - SO- , and -SO ₂ - is a divalent radical selected from the group consisting of,
W ¹ is a single bond or a divalent cyclic group which may have a substituent,
X ¹ is a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent,
In the formula (c2), R ¹ , R ² and R ⁴ are each independently an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent, R ³ and R ⁵ are each independently a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent,
Any one of Y ^{1 to} Y ³ is represented by the following formula (c3) or formula (c4):

Wherein one of the three bonds possessed by the trivalent group is linked to A ¹ ,
In the formula (c3), R ⁶ is a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent,
Two of Y ^{1 to} Y ³ are each independently a divalent group selected from the group consisting of —CR ⁷ R ⁸ —, —NR ⁹ —, —O— and —S—,
R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent. )
Is a compound represented by
A chemically amplified positive photosensitive resin composition, wherein a common logarithm LogS of the solubility S of the nitrogen-containing heterocyclic compound (C) is -4.00 or less. The chemically amplified positive photosensitive resin composition according to claim 1, wherein the W ¹ is a divalent cyclic group which may have a substituent. 3. The chemically amplified positive photosensitive material according to claim 1, wherein X ¹ is an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent. 4. Resin composition.   After heating the coating film of the chemically amplified positive-type photosensitive resin composition at 130 ° C. for 5 minutes, it is contacted with an aqueous solution of 2.38 mass% tetramethylammonium hydroxide at 23 ° C. for 30 seconds. The film reduction rate when performing rinsing with pure water after performing the cleaning twice with opening is 0.1 μm / min or more and 0.5 μm / min or less. Chemically amplified positive photosensitive resin composition.   The chemically amplified positive photosensitive resin composition according to any one of claims 1 to 4, further comprising an alkali-soluble resin (D).   The said alkali-soluble resin (D) contains the novolak resin (D1), the polyhydroxystyrene resin (D2), and at least 1 sort (s) of resin selected from the group which consists of acrylic resin (D3). A chemically amplified positive photosensitive resin composition.   The chemically amplified positive photosensitive resin composition according to any one of claims 1 to 6, further comprising a sulfur-containing compound (E) containing a sulfur atom capable of coordinating with a metal.   A chemically amplified positive photosensitive material according to any one of claims 1 to 7, comprising a base film and a photosensitive resin layer formed on a surface of the base film, wherein the photosensitive resin layer is provided. A photosensitive dry film comprising a resin composition.   A method for producing a photosensitive dry film, comprising applying a chemically amplified positive photosensitive resin composition according to any one of claims 1 to 7 onto a base film to form a photosensitive resin layer. Method. A laminating step of laminating a photosensitive resin layer comprising the chemically amplified positive photosensitive resin composition according to any one of claims 1 to 7, on a substrate having a metal surface,
An exposure step of exposing the photosensitive resin layer by irradiating with active light or radiation in a position-selective manner,
And a developing step of developing the photosensitive resin layer after the exposure. A laminating step of laminating a photosensitive resin layer comprising the chemically amplified positive photosensitive resin composition according to any one of claims 1 to 7, on a substrate having a metal surface,
An exposure step of exposing the photosensitive resin layer by irradiating with actinic rays or radiation,
A developing step of developing the photosensitive resin layer after exposure to form a mold for forming a plated molded article.   A method for producing a plated object, comprising a step of plating the substrate with a mold produced by the method according to claim 11 to form a plated object in the mold. The following formula (c1-a):
Z ¹ -A ¹ -W ² -A ² -X ¹ (c1-a)
(In the formula (c1-a), Z ¹ is the following formula (c2):

Is a nitrogen-containing heterocyclic group represented by
A ¹ and A ² are each independently a single bond or —O—, —CO—, —COO—, —OCO—, —OCOO—, —NH—, —CONH—, —NHCO—, —NHCONH -, - S -, - SO- , and -SO ₂ - is a divalent radical selected from the group consisting of,
W ² is a divalent cyclic group which may have a substituent,
X ¹ is a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent,
In the formula (c2), R ¹ , R ² and R ⁴ are each independently an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent, R ³ and R ⁵ are each independently a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent,
Any one of Y ^{1 to} Y ³ is represented by the following formula (c3) or formula (c4):

Wherein one of the three bonds possessed by the trivalent group is linked to A ¹ ,
In the formula (c3), R ⁶ is a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent,
Two of Y ^{1 to} Y ³ are each independently a divalent group selected from the group consisting of —CR ⁷ R ⁸ —, —NR ⁹ —, —O— and —S—,
R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent. )
A nitrogen-containing heterocyclic compound represented by the formula:   14. The nitrogen-containing heterocyclic compound according to claim 13, wherein a common logarithm value LogS of the solubility S is -4.00 or less.