JP2019066661A - Chemically amplified positive photosensitive resin composition, photosensitive dry film, production method of photosensitive dry film, production method of patterned resist film, method for manufacturing substrate with template, method for manufacturing plated molded article, and mercapto compound - Google Patents

Abstract

To provide a chemically amplified positive photosensitive resin composition capable of suppressing generation of 'footing', a phenomenon such that when a resist pattern serving as a template for a plated molded article is to be formed on a metal surface of a substrate having the metal surface by using a chemically amplified positive photosensitive resin composition, a width of a bottom (on a support surface side) being smaller than a width of a top (on a resist layer surface side) in a non-resist part, and to provide a photosensitive dry film, a production method of the photosensitive dry film, a production method of a patterned resist film, a method for manufacturing a substrate with a template, and a method for manufacturing a plated molded article using the substrate with a template.SOLUTION: The chemically amplified positive photosensitive resin composition comprises an acid generator (A) that generates an acid by irradiation with active rays or radiation, a resin (B) that shows increase in the solubility with an alkali by an action of an acid, and a mercapto compound having a structure of formula (C1-1) below.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive dry film comprising a chemically amplified positive photosensitive resin composition and a photosensitive resin layer comprising 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 above-described chemically amplified positive photosensitive resin composition, a method for producing a templated substrate using the above-described chemically amplified positive photosensitive resin composition, and the method for producing the same The present invention relates to a method of manufacturing a plated formed article using a substrate.

  Photofabrication is currently the mainstream of precision microfabrication technology. In photofabrication, a photoresist composition is applied to the surface of a workpiece to form a photoresist layer, the photoresist layer is patterned by photolithography, and chemical etching is performed using a patterned photoresist layer (photoresist pattern) as a mask. This is a general term for techniques for manufacturing various precision parts such as semiconductor packages by performing electroforming mainly based on etching or electroplating.

  Also, in recent years, with the downsizing of electronic devices, high-density mounting technology for semiconductor packages has progressed, making the package multi-pin thin film mounting of packages, miniaturizing package size, two-dimensional mounting technology by flip chip method, three-dimensional mounting technology. The mounting density has been improved on the basis of this. In such a high-density mounting technique, for example, protruding electrodes (mounting terminals) such as bumps protruding above the package as connection terminals, and metal posts for connecting rewirings extending from peripheral terminals on a wafer to the mounting terminals Etc. are placed on the substrate with high accuracy.

  Although a photoresist composition is used for photofabrication as described above, a chemically amplified photoresist composition containing an acid generator is known as such a photoresist composition (Patent Documents 1, 2 and the like) See). In the chemically amplified photoresist composition, an acid is generated from the acid generator by irradiation (exposure), diffusion of the acid is promoted by heat treatment, and an acid catalyzed reaction is caused to a base resin etc. in the composition. Alkali solubility changes.

  Such a chemically amplified positive photoresist composition is used, for example, in the formation of a plated object such as a bump or a metal post by a plating process. Specifically, a chemically amplified photoresist composition is used to form a photoresist layer of a desired thickness on a support such as a metal substrate, exposed through a predetermined mask pattern, and developed to form bumps. And a portion for forming a metal post is selectively removed (stripped) to form a photoresist pattern used as a mold. Then, a conductor such as copper is embedded in the removed portion (non-resist portion) by plating, and then the photoresist pattern around it is removed, whereby a bump or a metal post can be formed.

JP-A-9-176112 Japanese Patent Application Laid-Open No. 11-525262

  In the formation of connection terminals such as bumps and metal posts by the above-mentioned plating step, the width of the bottom (support surface side) is wider than the width of the top (surface side of resist layer) for the non-resist portion of the resist pattern to be a mold. It is desirable that it be larger. By doing so, the contact area between the bottom surface of the connection terminal such as the bump and the metal post and the support increases, and the adhesion between the connection terminal and the support is improved.

However, using a conventionally known chemically amplified positive photoresist composition as disclosed in Patent Documents 1 and 2, etc., a resist pattern serving as a mold for forming bumps, metal posts and the like is formed on a metal substrate. When forming, because the resist portion protrudes to the non-resist portion side at the contact surface of the substrate surface and the resist pattern, "footing" in which the bottom width is narrower than the top width tends to occur in the non-resist portion .
For this reason, when using a conventionally known chemically amplified positive photoresist composition as disclosed in Patent Documents 1 and 2, etc., the width of the bottom is larger than the width of the top on the metal substrate. It is difficult to form a resist pattern comprising

  This invention is made in view of the said subject, and forms the resist pattern used as the mold of a plating fabrication thing on the metal surface of the board | substrate which has a metal surface using a chemical amplification type positive photosensitive resin composition. Chemically amplified positive photosensitive resin that can suppress the occurrence of “footing” in which the width of the bottom (support surface side) is narrower than the width of the top (surface side of the resist layer) in the non-resist portion. A photosensitive dry film comprising a composition and a photosensitive resin layer comprising the chemically amplified positive photosensitive resin composition, a method for producing the photosensitive dry film, and the aforementioned chemically amplified positive photosensitive resin composition A method for producing a patterned resist film using the above, a method for producing a templated substrate using the photosensitive resin composition described above, and a method for producing a plated structure using the substrate with a template It aims to provide.

  MEANS TO SOLVE THE PROBLEM As a result of repeating earnest research in order to achieve the said objective, the present inventors find out that the said subject is solvable by making the chemical amplification type positive photosensitive resin composition contain the mercapto compound of a specific structure. The present invention has been completed. Specifically, the present invention provides the following.

The first aspect of the present invention comprises an acid generator (A) that generates an acid upon irradiation with an actinic ray or radiation, a resin (B) that increases the solubility in alkali by the action of the acid, 1) or (C1-2):
(In the formula (C1-1), R ^c1 is an (n1 + n2) -valent organic group, R ^c1 is bonded to a carbonyl group by a C—C bond, and is bonded to a mercapto group by a C—S bond; ^c2 and R ^c3 are each independently a hydrogen atom or a monovalent organic group, R ^c4 is a hydrocarbon group, and the carbon atom to which R ^c2 , R ^c3 and R ^c4 are bonded is a tertiary carbon R ^c3 and R ^c4 may be bonded to each other to form a ring, n1 is an integer of 1 or more and 4 or less, and n2 is an integer of 1 or more and 4 or less,
Provided that at least one of R ^c2 and R ^c3 is a monovalent organic group having an aliphatic ring CA containing at least one divalent group selected from an ether bond, a sulfide bond, and a carbonyl group in a ring structure And a monovalent organic group having an aliphatic ring CH substituted with a hydroxyl group or a hydroxyl group-containing group, an aliphatic ring having an aliphatic ring CL containing a divalent group represented by -CO-O- in the ring structure An organic group, a monovalent organic group having an aliphatic ring CS containing a divalent group represented by —SO ₂ — in the ring structure, or the following formula in the ring structure:
Or a monovalent organic group having an aliphatic ring CP containing a trivalent group represented by
R ^c2 and R ^c3 combine to form an aliphatic ring CA, an aliphatic ring CH, an aliphatic ring CL, an aliphatic ring CS, or an aliphatic ring CP. )
(In formula (C1-2), R ^c1 , R ^c2 , R ^c3 , n1 and n2 are the same as in formula (C1-1), R ^c5 is R ^c6 and R ^c7 are each independently R ^c5 and R ^c6 may be a hydrogen atom or an alkyl group, and may be bonded to each other to form a ring,
However, at least one of R ^c2 and R ^c3 is a monovalent organic group having aliphatic ring CA, a monovalent organic group having aliphatic ring CH, a monovalent organic group having aliphatic ring CL, aliphatic Or a monovalent organic group having a ring CS, or a monovalent organic group having an aliphatic ring CP, or
R ^c2 and R ^c3 combine to form an aliphatic ring CA, an aliphatic ring CH, an aliphatic ring CL, an aliphatic ring CS, or an aliphatic ring CP. )
It is a chemically amplified positive photosensitive resin composition containing the mercapto compound (C) represented by these.

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

  A third aspect of the present invention is a photosensitive dry film, comprising applying the chemical amplification type positive photosensitive resin composition according to the first aspect on a base film to form a photosensitive resin layer. Manufacturing method.

The fourth aspect of the present invention is
A laminating step of laminating a photosensitive resin layer comprising the chemical amplification type positive photosensitive resin composition according to the first aspect on a substrate having a metal surface;
An exposure step of irradiating the photosensitive resin layer selectively with actinic rays or radiation;
And a development step of developing the photosensitive resin layer after exposure.

The fifth aspect of the present invention is
A laminating step of laminating a photosensitive resin layer comprising the chemical amplification type positive photosensitive resin composition according to the first aspect on a substrate having a metal surface;
An exposure step of irradiating the photosensitive resin layer selectively with actinic rays or radiation;
And (d) developing the photosensitive resin layer after exposure to form a mold for forming a plated shaped article.

  A sixth aspect of the present invention is a method for producing a plated shaped article, comprising the steps of plating a mold-coated substrate produced by the method according to the fifth aspect to form a plated shaped article in the mold. .

The seventh aspect of the present invention is a compound represented by the following formula (C1-1) or (C1-2):
(In the formula (C1-1), R ^c1 is an (n1 + n2) -valent organic group, R ^c1 is bonded to a carbonyl group by a C—C bond, and is bonded to a mercapto group by a C—S bond; ^c2 and R ^c3 are each independently a hydrogen atom or a monovalent organic group, R ^c4 is a hydrocarbon group, and the carbon atom to which R ^c2 , R ^c3 and R ^c4 are bonded is a tertiary carbon R ^c3 and R ^c4 may be bonded to each other to form a ring, n1 is an integer of 1 or more and 4 or less, and n2 is an integer of 1 or more and 4 or less,
Provided that at least one of R ^c2 and R ^c3 is a monovalent organic group having an aliphatic ring CA containing at least one divalent group selected from an ether bond, a sulfide bond, and a carbonyl group in a ring structure And a monovalent organic group having an aliphatic ring CH substituted with a hydroxyl group or a hydroxyl group-containing group, an aliphatic ring having an aliphatic ring CL containing a divalent group represented by -CO-O- in the ring structure An organic group, a monovalent organic group having an aliphatic ring CS containing a divalent group represented by —SO ₂ — in the ring structure, or the following formula in the ring structure:
Or a monovalent organic group having an aliphatic ring CP containing a trivalent group represented by
R ^c2 and R ^c3 combine to form an aliphatic ring CA, an aliphatic ring CH, an aliphatic ring CL, an aliphatic ring CS, or an aliphatic ring CP. )
(In formula (C1-2), R ^c1 , R ^c2 , R ^c3 , n1 and n2 are the same as in formula (C1-1), R ^c5 is R ^c6 and R ^c7 are each independently R ^c5 and R ^c6 may be a hydrogen atom or an alkyl group, and may be bonded to each other to form a ring,
However, at least one of R ^c2 and R ^c3 is a monovalent organic group having aliphatic ring CA, a monovalent organic group having aliphatic ring CH, a monovalent organic group having aliphatic ring CL, aliphatic Or a monovalent organic group having a ring CS, or a monovalent organic group having an aliphatic ring CP, or
R ^c2 and R ^c3 combine to form an aliphatic ring CA, an aliphatic ring CH, an aliphatic ring CL, an aliphatic ring CS, or an aliphatic ring CP. )
It is a mercapto compound represented by

  According to the present invention, when forming a resist pattern to be a mold of a plated shaped article on a metal surface of a substrate having a metal surface using a chemical amplification type positive photosensitive resin composition, the top in the non-resist portion Chemically amplified positive photosensitive resin composition capable of suppressing occurrence of "footing" in which the width of the bottom (support surface side) is narrower than the width of the (surface side of resist layer), and the chemically amplified positive resin Photosensitive film comprising a photosensitive resin layer comprising a photosensitive resin composition, a method for producing the photosensitive dry film, and a patterned resist film using the above-mentioned chemically amplified positive photosensitive resin composition The manufacturing method, the manufacturing method of the board | substrate with a mold using the above-mentioned photosensitive resin composition, and the manufacturing method of the metal-plating molded article using the said board | substrate with a mold can be provided.

In an Example and a comparative example, it is a figure which shows typically the cross section of the resist pattern observed when measuring the amount of footing in the non-resist part in a resist pattern.

«Chemically amplified positive photosensitive resin composition»
The chemically amplified positive photosensitive resin composition (hereinafter, also referred to as a photosensitive resin composition) is an acid generator (A) (hereinafter, referred to as an acid generator (A)) that generates an acid upon irradiation with an actinic ray or radiation. And a resin (B) (hereinafter also referred to as a resin (B)) whose solubility in alkali increases by the action of an acid, and a mercapto compound (C) having a predetermined structure. The photosensitive resin composition may contain components, such as an alkali-soluble resin (D), an acid diffusion inhibitor (E), and an organic solvent (S), as necessary.

  The film thickness of the resist pattern formed using the photosensitive resin composition is not particularly limited. The photosensitive resin composition is preferably used for the formation of a thick film resist pattern. Specifically, the film thickness of the resist pattern formed using the photosensitive resin composition is preferably 0.5 μm or more, more preferably 0.5 μm to 300 μm, still more preferably 1 μm to 150 μm, and particularly preferably Preferably, 3 μm to 100 μm is the most preferable.

  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 upon irradiation with an actinic ray or radiation, and is not particularly limited as long as it is a compound that generates an acid directly or indirectly by light. As an acid generator (A), the acid generator of a 1st-5th aspect demonstrated below is preferable. Hereinafter, among the acid generators (A) suitably used in the photosensitive resin composition, preferred ones will be described as the first to fifth embodiments.

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

In the above formula (a1), X ^1a represents a sulfur atom having a valence of g or an iodine atom, 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, R2a 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, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro, and halogen Replaced by species It may be. The number of R ^1a is g + h (g−1) +1, and R ^1a may be the same as 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- And a ring structure containing X ^1a may be formed by bonding via an alkylene group having 1 or more and 3 or less carbon atoms, or a phenylene group. R ^2a is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

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

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

X ^3a- is a counter ion of onium, and examples thereof include a fluorinated alkyl fluorophosphate anion represented by the following formula (a17) or a borate anion represented by the following formula (a18).

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

In formula (a18), each of R ^{4a to} R ^7a independently represents a fluorine atom or a phenyl group, and some or all of the hydrogen atoms of the phenyl group are selected from the group consisting of a fluorine atom and a trifluoromethyl group And at least one of them may be substituted.

  Examples of the onium ion in the compound represented by the above formula (a1) include triphenylsulfonium, tri-p-tolylsulfonium, 4- (phenylthio) phenyldiphenylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide, Bis [4- {bis [4- (2-hydroxyethoxy) phenyl] sulfonio} phenyl] sulfide, bis {4- [bis (4-fluorophenyl) sulfonio] phenyl} sulfide, 4- (4-benzoyl-2-) Chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10 -Thia-9,10-dihydroanthracene 2-yldiphenylsulfonium, 2-[(diphenyl) sulfonio] thioxanthone, 4- [4- (4-tert-butylbenzoyl) phenylthio] phenyldi-p-tolylsulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium Diphenylphenacylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl (1-ethoxycarbonyl) ethylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, phenyl [4- (4-biphenylthio) phenyl] 4- Biphenylsulfonium, phenyl [4- (4-biphenylthio) phenyl] 3-biphenylsulfonium, [4- (4-acetophenylthio) phenyl] diphenylsulfonium, octadecy Methylphenacylsulfonium, diphenyliodonium, di-p-tolyliodonium, bis (4-dodecylphenyl) iodonium, bis (4-methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyliodonium, bis (4-decyloxy) phenyl Examples include iodonium, 4- (2-hydroxytetradecyloxy) phenylphenyl iodonium, 4-isopropylphenyl (p-tolyl) iodonium, or 4-isobutylphenyl (p-tolyl) iodonium, and the like.

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

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

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

In the fluorinated alkyl fluorophosphate anion represented by the above formula (a17), R ^3a represents an alkyl group substituted with a fluorine atom, preferably having 1 to 8 carbon atoms, and more preferably 1 or more carbon atoms It is 4 or less. Specific examples of the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl and tert-butyl; and further cyclopropyl, cyclobutyl and cyclopentyl And the like. The hydrogen atom of the alkyl group is substituted by a fluorine atom, and the proportion thereof is usually 80% or more, preferably 90% or more, and more preferably 100%. When the substitution rate of the fluorine atom is less than 80%, the acid strength of the onium fluorinated alkyl fluorophosphate 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% substitution of fluorine atoms, and specific examples thereof include CF ₃ and CF ₃ CF. ₂ , (CF ₃ ) ₂ CF, CF ₃ CF ₂ CF ₂ , CF ₃ CF ₂ CF ₂ CF ₂ , (CF ₃ ) ₂ CFCF ₂ , CF ₃ CF ₂ (CF ₃ ) CF, (CF ₃ ) ₃ C It can be mentioned. The number j of R ^3a is an integer of 1 or more and 5 or less, preferably 2 or more and 4 or less, and particularly preferably 2 or 3.

Examples of preferred fluorinated alkyl fluorophosphate _{anion, [(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 _{these, [(CF 3 CF 2)} 3 PF 3] -, [(CF 3 CF 2 CF 2) 3 PF 3] -, _{[((CF 3) 2 CF} ) 3 PF 3 ^{_{-, [((CF 3)}} 2 CF) 2 PF 4] -, [((CF 3) 2 CFCF 2) 3 PF 3] -, or _{[((CF 3) 2 CFCF} 2) 2 PF 4] - is Particularly preferred.

Preferable specific examples of the borate anion represented by the above formula (a18) include tetrakis (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ⁻ ) and tetrakis [(trifluoromethyl) phenyl] borate ( [B (C ₆ H ₄ CF ₃ ) ₄ ] ⁻ ), difluorobis (pentafluorophenyl) borate ([(C ₆ F ₅ ) ₂ BF ₂ ] ⁻ ), trifluoro (pentafluorophenyl) borate ([[(C ₆ H ₄ CF ₃ ) ₄ ] ⁻ ) ₆ F ₅ ) BF ₃ ] ⁻ ), tetrakis (difluorophenyl) borate ([B (C ₆ H ₃ F ₂ ) ₄ ] ⁻ ), and the like. Among these, tetrakis (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ⁻ ) is particularly preferable.

  As a second embodiment of the acid generator (A), 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2 -(2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methyl-2-furyl) ethenyl] -s-triazine, 2,4-bis ( Trichloromethyl) -6- [2- (5-ethyl-2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-propyl-2-furyl) ethenyl ] -S-Triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-dimethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2 -(3,5-diethoxy group 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 Halogen-containing triazine compounds such as 3,5-triazine and tris (2,3-dibromopropyl) -1,3,5-triazine; and the following formula (a3) such as tris (2,3-dibromopropyl) isocyanurate And halogen-containing triazine compounds represented by

In said formula (a3), ^R9a , ^R10a , ^R11a respectively independently represents a halogenated alkyl group.

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

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

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

As the acid generator represented by the above formula (a4), when n is 1, a compound wherein R ^12a is any 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- And methoxyphenyl) acetonitrile, [2- (propylsulfonyloxyimino) -2,3-dihydroxythiophen-3-ylidene] (o-tolyl) acetonitrile, and the like. When n = 2, specific examples of the acid generator represented by the above formula (a4) include an acid generator represented by the following formula.

  Moreover, the onium salt which has a naphthalene ring in a cation part is mentioned as a 4th aspect in an acid generator (A). The term "having a naphthalene ring" means having a structure derived from naphthalene, and means that the structure of at least two rings and their aromaticity are maintained. The naphthalene ring has a substituent such as a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. It is also good. The structure derived from the naphthalene ring may be a monovalent group (one free valence) or a divalent group (two free valences), but it is a monovalent group Desirable (however, at this time, free valences are counted excluding the part to be bound to the above-mentioned substituent). The number of naphthalene rings is preferably 1 or more and 3 or less.

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

In the above formula (a5), at least one of R ^14a , R ^15a and R ^16a represents a group represented by the following formula (a6), and the rest are linear or branched having 1 to 6 carbon atoms And a substituted or unsubstituted phenyl group, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Alternatively, one of R ^14a , R ^15a and R ^16a is a group represented by the following formula (a6), and the remaining two are each independently linear or branched having 1 to 6 carbon atoms And the terminal thereof may be bonded to form a ring.

In the above formula (a6), R ^17a and R ^18a each independently represent a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a linear or 1 to 6 carbon atoms R ^19a 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. Moreover, when two or more R ^<18a> exists, they may mutually be same or different.

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

  Moreover, as a substituent which the said alkylene group may have, an oxygen atom (In this case, a carbonyl group is formed with the carbon atom which comprises an alkylene group), a hydroxyl group, etc. are mentioned.

  Moreover, as a substituent which a phenyl group may have, a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, a linear or branched chain having 1 to 6 carbon atoms And alkyl groups of the following.

  As a thing suitable as these cation parts, what is represented by following formula (a7), (a8) etc. can be mentioned, Especially the structure represented by following formula (a8) is preferable.

  As such a cation part, although it may be an iodonium salt or a sulfonium salt, a sulfonium salt is desirable from the point of an acid generation efficiency etc.

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

  As an anion part of such an acid generator, it is fluoroalkyl sulfonate ion or aryl sulfonate ion by which one part or all part of the hydrogen atom was fluorinated.

  The alkyl group in the fluoroalkyl sulfonate ion may be linear, branched or cyclic having 1 to 20 carbon atoms, and has 1 to 10 carbon atoms from the bulkiness of the generated acid and the diffusion distance thereof Is preferred. In particular, branched or cyclic ones are preferable because the diffusion distance is short. In addition, methyl, ethyl, propyl, butyl, octyl and the like can be mentioned as preferable because they can be synthesized inexpensively.

  The aryl group in the aryl sulfonate ion is an aryl group having 6 to 20 carbon atoms, and examples thereof include an alkyl group, and a phenyl group and a naphthyl group which may or may not be substituted with a halogen atom. In particular, an aryl group having 6 to 10 carbon atoms is preferable because it can be synthesized inexpensively. As a specific example of a preferable thing, a phenyl group, a toluene sulfonyl group, an ethylphenyl group, a naphthyl group, a methyl naphthyl group etc. can be mentioned.

  In the above fluoroalkyl sulfonate ion or aryl sulfonate ion, when a part or all of hydrogen atoms are fluorinated, the fluorination ratio is preferably 10% to 100%, more preferably 50% to 100%. The following is preferable, and in particular, substitution of all hydrogen atoms with fluorine atoms is preferable because the strength of the acid increases. Specific examples thereof include trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctanesulfonate, perfluorobenzenesulfonate and the like.

  Among these, as a preferable anion part, what is represented by a following formula (a9) is mentioned.

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

  Moreover, as an anion part, what contains nitrogen represented by following formula (a13) and (a14) can also be used.

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

The smaller the carbon atom number of the alkylene group of X ^a or the carbon atom number of the alkyl group of Y ^a and Z ^a is, the better the solubility in an organic solvent is, and thus it is preferable.

Moreover, in the alkylene group of X ^a or the alkyl group of Y ^a and Z ^a , the larger the number of hydrogen atoms substituted by a fluorine atom, the stronger the acid, which is preferable. The proportion of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination ratio is preferably 70% to 100%, more preferably 90% to 100%, and most preferably all hydrogen atoms are fluorine It is a perfluoroalkylene group or a perfluoroalkyl group substituted by an atom.

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

  Further, as a 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-toluenesulfonic acid, 2,6-dinitrobenzyl p-toluenesulfonic acid, nitrobenzyl tosylate, dinitrobenzyl tosylate, nitrobenzyl sulfonate, nitro Nitrobenzyl derivatives such as benzyl carbonate, dinitrobenzyl carbonate; pyrogallol trimesylate, pyrogallol tritosylate, benzyl tosylate, benzyl sulfonate, N-methylsulfonyl oxysuccin Sulfonic acid esters such as N, trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyloxymaleimide, N-methylsulfonyloxy phthalimide, etc .; trifluoromethane sulfonic acid esters such as N-hydroxy phthalimide, N-hydroxy naphthalimide; Iodonium hexafluorophosphate, (4-methoxyphenyl) phenyliodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl) diphenylsulfonium Trifluoromethanesulfonate, (p-tert-butylphenyl) diphenyl sulfonium trifluoro Onium salts such as Tan sulfonate; benzoin tosylate, benzoin tosylate such as α- methyl benzoin tosylate; other diphenyliodonium salts, triphenylsulfonium salts, phenyldiazonium salts, benzyl carbonate and the like.

  The acid generator (A) may be used alone or in combination of two or more. The content of the acid generator (A) is preferably 0.1% by mass to 10% by mass with respect to the total mass of the photosensitive resin composition, and 0.5% by mass to 3% by mass It is more preferable to By making the usage-amount of an acid generator (A) into said range, it is easy to prepare the photosensitive resin composition which has favorable sensitivity, is a uniform solution, and is excellent in storage stability.

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

[Novolak resin (B1)]
As the novolac 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), linear, branched or cyclic alkyl having 1 to 6 carbon atoms. It is preferably a group, a vinyloxyethyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group or a trialkylsilyl group.

In the above formulas (b2) and (b3), R ^4b and R ^5b each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and R ^6b is carbon O 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, o Represents 0 or 1.

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

  Here, 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, Isobutoxyethyl group, tert-butoxyethyl group, cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1-ethoxy-1-methylethyl group and the like can be mentioned. 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. Moreover, as said trialkyl silyl group, carbon atom number of each alkyl groups, such as a trimethyl silyl group and a tri-tert- butyl dimethyl silyl group, is a group of 1 or more and 6 or less.

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

In 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 linear or branched alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl and neopentyl groups. Examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group.

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

  Furthermore, the polyhydroxystyrene resin (B2) can contain other polymerizable compounds as a constituent unit for the purpose of appropriately controlling physical and chemical properties. Examples of such a polymerizable compound include known radical polymerizable compounds and anionic polymerizable compounds. Moreover, as such a polymerizable compound, for example, monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; 2-methacryloyloxyethyl succinic acid, 2- Methacrylic acid derivatives having a carboxyl group and an ester bond such as methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, etc .; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (Meth) acrylic acid alkyl esters such as (meth) acrylate; (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; phenyl (meth) (Meth) acrylic acid aryl esters such as crylate, benzyl (meth) acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyl toluene, 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, methacrylonitrile And nitrile group-containing polymerizable compounds; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylamide; and the like.

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

(—SO ₂ -containing cyclic group)
Here, the “—SO ₂ -containing cyclic group” refers to a cyclic group containing a ring containing —SO ₂ — in its ring skeleton, and specifically, a sulfur atom in —SO ₂ — ( S) is a cyclic group forming part of the ring skeleton of the cyclic group. The ring containing -SO _{2-in the} ring skeleton is counted as the first ring, and in the case of only the ring, a monocyclic group, and in the case of having another ring structure, a polycyclic group regardless of its structure It is called. The —SO ₂ -containing cyclic group may be monocyclic or polycyclic.

The -SO ₂ -containing cyclic group is, in particular, a cyclic group containing -O-SO ₂ -in its ring skeleton, ie -O-S- in -O-SO ₂ -is a part of the ring skeleton It is preferred that it is a cyclic group containing a sultone ring to be formed.

-SO ₂ - carbon atoms containing cyclic group preferably has 3 to 30, more preferably 4 to 20, more preferably 4 to 15, particularly preferably 4 to 12. The said carbon atom number is the number of carbon atoms which comprise ring structure, and shall not contain the carbon atom number in a substituent.

The -SO ₂ -containing cyclic group may be a -SO ₂ -containing aliphatic cyclic group or a -SO ₂ -containing aromatic cyclic group. Preferred is a —SO ₂ -containing aliphatic cyclic group.

As the -SO ₂ -containing aliphatic cyclic group, a hydrogen atom can be selected from an aliphatic hydrocarbon ring in which a part of carbon atoms constituting the ring structure thereof is substituted by -SO ₂ -or -O-SO _2- At least one removed group is mentioned. More specifically, a group in which at least one hydrogen atom has been removed from an aliphatic hydrocarbon ring in which -CH _2- constituting the ring skeleton is substituted by -SO _2- , -CH _2- constituting the ring CH 2 _- is -O-SO 2 _- or the like at least one group formed by removing a hydrogen atom from the aliphatic hydrocarbon ring substituted with.

  3 or more and 20 or less are preferable, and, as for the carbon atom number of the said alicyclic hydrocarbon ring, 3 or more and 12 or less are more preferable. The alicyclic hydrocarbon ring may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a monocycloalkane having 3 to 6 carbon atoms. Examples of the monocycloalkane include cyclopentane and cyclohexane. As the polycyclic alicyclic hydrocarbon ring, a group in which two hydrogen atoms are removed from a polycycloalkane having 7 to 12 carbon atoms is preferable, and as the polycycloalkane, specifically, adamantane, norbornane and the like can be mentioned. , Isobornane, tricyclodecane, tetracyclododecane and the like.

The —SO ₂ -containing cyclic group may have a substituent. As the substituent, for example, 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, etc. Can be mentioned.

  The alkyl group as the substituent is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably linear or branched. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group etc. are mentioned. Be Among these, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.

  As an alkoxy group as the said substituent, a C1-C6 alkoxy group is preferable. The alkoxy group is preferably linear or branched. Specifically, the group which the alkyl group mentioned as the alkyl group as a substituent mentioned above couple | bonded with the oxygen atom (-O-) is mentioned.

  As a halogen atom as the said substituent, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, A fluorine atom is preferable.

  As a halogenated alkyl group of the said substituent, the group by which one part or all part of the hydrogen atom of the above-mentioned alkyl group was substituted by the above-mentioned halogen atom is mentioned.

  As a halogenated alkyl group as the said substituent, the group by which one part or all part of the hydrogen atom of the alkyl group mentioned as the alkyl group as a substituent mentioned above was substituted by the above-mentioned halogen atom is mentioned. The halogenated alkyl group is preferably a fluorinated alkyl group, particularly preferably a perfluoroalkyl group.

  Each of R "in the aforementioned -COOR" and -OC (= O) R "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 in the linear alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or 2.

  When R ′ ′ is a cyclic alkyl group, the number of carbon atoms in the cyclic alkyl group is preferably 3 or more and 15 or less, more preferably 4 or more and 12 or less, and particularly preferably 5 or more and 10 or less. Or one or more hydrogen atoms are removed from a monocycloalkane which may or may not be substituted with a fluorinated alkyl group, or a polycycloalkane such as a bicycloalkane, tricycloalkane or tetracycloalkane For example, one or more hydrogen atoms are selected from monocycloalkanes such as cyclopentane and cyclohexane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane. The group etc. which were remove | excluded are mentioned.

  As a hydroxyalkyl group as the said substituent, a C1-C6 hydroxyalkyl group is preferable. Specifically, a group in which at least one of the hydrogen atoms of the alkyl group mentioned as the above-mentioned alkyl group as the substituent is substituted by a hydroxyl group can be mentioned.

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 oxygen atom or an alkylene group having 1 to 5 carbon atoms which may contain a sulfur atom, an oxygen atom or a sulfur atom, z is an integer of 0 to 2 and R ^10b Is an alkyl group, an alkoxy group, a halogenated alkyl group, a hydroxyl group, —COOR ′ ′, —OC (OO) 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 an alkylene group having 1 to 5 carbon atoms in A ′, a linear or branched alkylene group is preferable, and a methylene group, an ethylene group, an n-propylene group, an isopropylene group and the like can be mentioned.

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

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

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

  Hereinafter, specific cyclic groups represented by the aforementioned formulas (3-1) to (3-4) will be exemplified. In addition, "Ac" in a formula shows an acetyl group.

Among the above, as the -SO ₂ -containing cyclic group, a group represented by the above-mentioned formula (3-1) is preferable, and the above-mentioned chemical formula (3-1-1), (3-1-18) It is more preferable that at least one selected from the group consisting of a group represented by any one of (3-3-1) and (3-4-1) is selected from the group represented by the above chemical formula (3-1-1). Are most preferred.

(A lactone containing cyclic group)
The “lactone-containing cyclic group” refers to a cyclic group containing a ring (lactone ring) containing —O—C (= O) — in the ring skeleton thereof. The lactone ring is counted as the first ring, and when it has only a lactone ring, it is 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 one may be used. Specifically, as the lactone-containing monocyclic group, a group in which one hydrogen atom is removed from a 4- to 6-membered ring lactone, for example, a group in which one hydrogen atom is removed from β-propionolactone, or γ-butyrolactone Examples thereof include groups in which one hydrogen atom has been removed, and groups in which one hydrogen atom has been removed from δ-valerolactone. Moreover, as a lactone containing polycyclic group, the group which remove | eliminated one hydrogen atom from the bicyclo alkane which has a lactone ring, a tricyclo alkane, and a tetracyclo alkane is mentioned.

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

[Constituent Unit (b-3-S)]
More specifically, examples of the structural unit (b-3-S) include structural units represented by the following formula (b-S1).

(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, and R ^11b is a —SO ₂ -containing cyclic group, R ^12b is a single bond or a divalent linking group.)

In formula (b-S1), R is as defined above.
R ^11b is the same as the —SO ₂ -containing cyclic group mentioned above.
R ^12b may be either a single bond or a divalent linking group. It is preferable that it is a bivalent coupling group from the excellent thing of the effect of this invention.

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

-The bivalent hydrocarbon group which may have a substituent The hydrocarbon group as a bivalent coupling group may be an aliphatic hydrocarbon group, and may be an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated. In general, saturated hydrocarbon groups are preferred. More specifically, as the aliphatic hydrocarbon group, a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, and the like can be mentioned.

  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 a 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 pentamethylene groups [-(CH ₂ ) _5- ] and the like.

As a 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 ) an alkylmethylene group such as (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) _2-, etc .; -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- , -CH ₂ CH (CH ₃ ) CH _2-, etc .; -CH (CH ₃ ) CH ₂ CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH ₂ CH _2- And alkyl alkylene groups such as an alkyl tetramethylene group. As the alkyl group in the alkyl alkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

  The linear or branched aliphatic hydrocarbon group may or may not have a substituent (a group or atom other than a hydrogen atom) replacing a hydrogen atom. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms which is substituted by a fluorine atom, an oxo group (= O), and the like.

  As the aliphatic hydrocarbon group containing a ring in the above structure, a cyclic aliphatic hydrocarbon group which may contain a substituent containing a hetero atom in the ring structure (Excluding two hydrogen atoms from an 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, the cyclic aliphatic hydrocarbon group is linear or branched The group etc. which intervene in the middle of an aliphatic hydrocarbon group are mentioned. Examples of the above linear or branched aliphatic hydrocarbon group include the same as described above.

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

  The cyclic aliphatic hydrocarbon group may be polycyclic or monocyclic. As a 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. Specifically, cyclopentane, cyclohexane and the like can be mentioned. As the polycyclic aliphatic hydrocarbon group, a group obtained by removing two hydrogen atoms from polycycloalkane is preferable. The number of carbon atoms of the polycycloalkane is preferably 7 or more and 12 or less. 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) replacing a hydrogen atom. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxo group (= O) and the like.

  As an alkyl group as said substituent, a C1-C5 alkyl group is preferable, and a methyl group, an ethyl group, a propyl group, n-butyl group, and a tert- butyl group are more preferable.

  As an alkoxy group as said substituent, a C1-C5 alkoxy group is preferable, and a methoxy group, an ethoxy group, n-propoxy group, an iso-propoxy group, n-butoxy group, and a tert- butoxy group are preferable. Is more preferred, and methoxy and ethoxy are particularly preferred.

  As a halogen atom as said substituent, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, A fluorine atom is preferable.

  As a halogenated alkyl group as said substituent, the group by which one part or all part of the hydrogen atom of the above-mentioned alkyl group was substituted by said halogen atom is mentioned.

In the cyclic aliphatic hydrocarbon group, part of 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 a substituent.

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

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

  1 or more and 4 or less are preferable, 1 or more and 2 or less of the carbon atom number of the alkylene group couple | bonded with said aryl group or heteroaryl group is more preferable, and 1 is especially preferable.

  In the above-mentioned aromatic hydrocarbon group, a hydrogen atom of the aromatic hydrocarbon group may be substituted by a substituent. For example, a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted by a substituent. As the said substituent, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxo group (= O) etc. are mentioned, for example.

  As an alkyl group as said substituent, a C1-C5 alkyl group is preferable, and a methyl group, an ethyl group, n-propyl group, n-butyl group, and a tert- butyl group are more preferable.

  As an alkoxy group as said substituent, a C1-C5 alkoxy group is preferable, and a methoxy group, an ethoxy group, n-propoxy group, an iso-propoxy group, n-butoxy group, and a tert- butoxy group are preferable. Are preferred, and methoxy and ethoxy are more preferred.

  As a halogen atom as said substituent, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, A fluorine atom is preferable.

  As a halogenated alkyl group as said substituent, the group by which one part or all part of the hydrogen atom of the above-mentioned alkyl group was substituted by the said halogen atom is mentioned.

-A divalent linking group containing a hetero atom A hetero atom in a divalent linking group containing a hetero atom is an atom other than a carbon atom and a hydrogen atom, for example, an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom Etc.

Specifically, as a divalent linking group containing a hetero atom, -O-, -C (= O)-, -C (= O) -O-, -O-C (= O) -O-, _{-S -, - S (= O} ) 2 -, - S (= O) 2 -O -, - NH -, - NH-C (= O) -, - NH-C (= NH) -, = N And the like, and combinations of at least one of these non-hydrocarbon-based linking groups with a divalent hydrocarbon group, and the like. As the said bivalent hydrocarbon group, the thing similar to the bivalent hydrocarbon group which may have a substituent mentioned above is mentioned, A linear or branched aliphatic hydrocarbon group is preferable .

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

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

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

When the divalent linking group in R ^12b is a cyclic aliphatic hydrocarbon group, the cyclic aliphatic hydrocarbon group may have “a substituent as the divalent linking group described above. In the description of the divalent hydrocarbon group, the same ones as the cyclic aliphatic hydrocarbon groups 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 in R ^12b is a divalent linking group containing a hetero atom, preferred as the linking group is —O—, —C (= O) —O—, —C (= O ), —O—C ((O) —O—, —C (= O) —NH—, and —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-, the formula ^{-Y 1 -O-Y 2 -,} - [Y 1 -C (= O) -O] m A group represented by _' -Y ^2- or -Y ¹ -O-C (= O) -Y _2- [wherein, Y ¹ and Y ² each independently have a substituent It is a good bivalent hydrocarbon group, O is an oxygen atom, and m 'is an integer of 0 or more and 3 or less. Etc.

When the divalent linking group in R ^12b is —NH—, a hydrogen atom in —NH— may be substituted by a substituent such as an alkyl group or acyl. 1 or more and 10 or less are preferable, as for the carbon atom number of the said substituent (an alkyl group, an acyl group, etc.), 1 or more and 8 or less are more preferable, and 1 or more and 5 or less are especially preferable.

Wherein ^{-Y 1 -O-Y 2 -,} - [Y 1 -C (= O) -O] m '-Y 2 -, or ^{-Y 1 -O-C (= O} ) -Y 2 - In, Y ¹ and Y ² are each independently a divalent hydrocarbon group which may have a substituent. As said bivalent hydrocarbon group, the thing similar to "the bivalent hydrocarbon group which may have a substituent" mentioned by the description as said bivalent coupling group is mentioned.

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

As Y ² , a linear or branched aliphatic hydrocarbon group is preferable, and a methylene group, an ethylene group, and an alkylmethylene group are more preferable. The alkyl group in the alkyl methylene 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 1 -C (= O} ) -O] m '-Y 2 - In the group represented by, m' is an integer of 0 to 3, preferably 0 to 2 integer 0 or 1 is more preferable, and 1 is particularly preferable. That is, as a group represented by the formula-[Y ¹ -C (= O) -O] _{m '} -Y ^2-, it is represented by the formula -Y ¹ -C (= O) -O-Y ^2- Groups are particularly preferred. Among them, the formula _{- (CH 2) a '-C} (= O) -O- (CH 2) b' - a group represented by are preferred. In the formula, a ′ is an integer of 1 or more and 10 or less, preferably an integer of 1 or more and 8 or less, more preferably an integer of 1 or more and 5 or less, still more preferably 1 or 2 and most preferably 1. b ′ is an integer of 1 or more and 10 or less, preferably an integer of 1 or more and 8 or less, more preferably an integer of 1 or more and 5 or less, still more preferably 1 or 2 and most preferably 1.

As the divalent linking group containing a hetero atom in the divalent linking group represented by R ^12b, an organic group composed of a combination of at least one non-hydrocarbon group and a divalent hydrocarbon group is preferable. Among them, a linear group having an oxygen atom as a hetero atom, such as an ether bond or a group containing an ester bond, is preferable, and the above-mentioned formula -Y ¹ -O-Y ² -,-[Y ¹ -C (= ^{_{O) -O] m '-Y 2}} -, or ^{-Y 1 -O-C (= O} ) -Y 2 - , more preferably a group represented by, the above formula ^{- [Y 1 -C (= O} ) -O] _{m '-Y} ² -, or ^{-Y 1 -O-C (= O} ) -Y 2 - is particularly desirable.

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

The alkylene group is preferably a linear or branched alkylene group. Preferred examples of the linear aliphatic hydrocarbon group include methylene group [-CH _2- ], ethylene group [-(CH ₂ ) _2- ] and 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 Alkylmethylene groups such as CH ₃ ) —, —C (CH ₃ ) (CH ₂ CH ₂ CH ₃ ) —, —C (CH ₂ CH ₃ ) ₂ — and the like; —CH (CH ₃ ) CH ₂ —, —CH ( _{CH 3) CH (CH 3)} -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH 2 CH 3) 2 -CH 2 - alkyl ethylene such as _{group; -CH (CH 3) CH 2} CH 2 -, - CH 2 CH (CH 3) CH 2 - alkyl trimethylene groups such _{as; -CH (CH 3) CH 2} CH 2 CH 2 -, - CH 2 CH _{(CH 3) CH 2 CH 2} - alkyl, such as alkyl tetramethylene group such as Such as an alkylene group, and the like.

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

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

R ^{13 b} is not particularly limited, and examples thereof include the same ones as the divalent linking group in R ^{12 b} 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, Or a branched alkylene group or a divalent linking group containing an oxygen atom as a hetero atom is preferred.

As a linear alkylene group, a methylene group or ethylene group is preferable, and a methylene group is particularly preferable. As the branched alkylene group, an alkyl methylene group, or an alkyl ethylene group is _{preferable, -CH (CH 3) -,} - C (CH 3) 2 -, or _{-C (CH 3) 2 CH 2} - is particularly preferable.

As the divalent linking group containing an oxygen atom, an ether bond or a divalent linking group containing an ester bond is preferable, and the above-mentioned -Y ¹ -O-Y ² -,-[Y ¹ -C (= O ^{_{) -O] m '-Y 2 -}} , or ^{-Y 1 -O-C (= O} ) -Y 2 - is more preferable. Y ¹ and Y ² are each independently a divalent hydrocarbon group which may have a substituent, and m ′ is an integer of 0 or more and 3 or less. Among them, -Y ¹ -O-C (= O) -Y ² -is preferable, and a group represented by-(CH ₂ ) _c -O-C (= O)-(CH ₂ ) _d- is particularly preferable. . c is an integer of 1 or more and 5 or less, preferably 1 or 2. d is an integer of 1 or more and 5 or less, preferably 1 or 2.

  In particular, as the structural unit (b-3-S), structural units represented by the following formula (b-S1-11) or (b-S1-12) are preferable, and a formula (b-S1-12) is preferable. The structural unit represented is more preferable.

(Wherein, R, A ′, R ^10b , z, and R ^13b are each as defined above)

  In 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. As the linear or branched alkylene group for R ^{13 b and} the divalent linking group containing an oxygen atom, the above-mentioned linear or branched alkylene group and a divalent linking group containing an oxygen atom are mentioned, respectively. The same as those mentioned above.

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

(Wherein, R and A ′ are as defined above, and c to e are each independently an integer of 1 or more and 3 or less)

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

(Wherein R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms; and R ′ each independently represents a hydrogen atom, an alkyl group, or an alkoxy group , 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; R ^12b is a single bond or A divalent linking group, s ′ ′ is an integer of 0 or more and 2 or less; A ′ ′ is an oxygen atom or a sulfur atom-containing alkylene group having 1 to 5 carbon atoms, an oxygen atom, or sulfur Is an atom; r is 0 or 1)

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

In consideration of industrial availability and the like, R ′ is preferably a hydrogen atom.
The alkyl group in R ′ ′ may be linear, branched or cyclic.
When R ′ ′ is a linear or branched alkyl group, the number of carbon atoms is preferably 1 or more and 10 or less, and more preferably 1 or more and 5 or less.
When R ′ ′ is a cyclic alkyl group, it preferably has 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. In particular, one or more of polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes and tetracycloalkanes which may or may not be substituted with a fluorine atom or a fluorinated alkyl group. Groups other than hydrogen atoms can be exemplified, specifically, one or more of monocycloalkanes such as cyclopentane and cyclohexane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane. A group etc. except a hydrogen atom are mentioned.
As A ′ ′, the same as A ′ in the above-mentioned formula (3-1) can be mentioned. 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 an alkylene group having 1 to 5 carbon atoms, a methylene group or a dimethylmethylene group is more preferable, and a methylene group is the most preferable.

R ^12b is the same as ^{R 12b} in the above-mentioned formula (b-S1).
In formula (b-L1), s ′ ′ is preferably 1 or 2.
Below, the specific example of a structural unit represented by above-mentioned Formula (b-L1)-(b-L3) is illustrated. In each of the following formulas, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

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

Moreover, as a structural unit (b-3-L), the structural unit represented by following formula (b-L6)-(b-L7) is also preferable.
In formulas (b-L6) and (b-L7), R and R ^12b are as defined above.

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

In the above 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 R ^{15b to} R ^17b each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms, and each independently represents a linear or branched fluorinated alkyl group having 1 to 6 carbon atoms; A linear or branched fluorinated alkyl group having 1 to 6 carbon atoms or an aliphatic cyclic group having 5 to 20 carbon atoms, each independently having 1 to 6 carbon atoms Or a linear or branched fluorinated alkyl group having 1 to 6 carbon atoms, and R ^16b and R ^17b are bonded to each other, and the carbon atom to which both are bonded And May also form a hydrocarbon ring having 5 to 20 carbon atoms, and Y ^b represents an aliphatic cyclic group or alkyl group which may have a substituent, and p is 0 to 4 And q represents 0 or 1.

Examples of the linear or branched alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl and the like. It can be mentioned. The fluorinated alkyl group is one in which a part or all of hydrogen atoms of the above alkyl group are substituted by a fluorine atom.
Specific examples of the aliphatic cyclic group include groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as a monocycloalkane, bicycloalkane, tricycloalkane or tetracycloalkane. Specifically, a group obtained by removing one hydrogen atom from a monocycloalkane such as cyclopentane, cyclohexane, cycloheptane or cyclooctane, or a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane. Can be mentioned. Particularly preferred are cyclohexane and a group in which one hydrogen atom has been removed from adamantane (which may further have a substituent).

When R ^16b and R ^17b are bonded to each other to form a hydrocarbon ring, carbon atoms are preferable as R ^15b , R ^16b , and R ^{17b because they} have high contrast and good resolution and depth of focus. It is preferable that they are several 2 or more and 4 or less linear or branched alkyl groups. It said ^{R 19b, R 20b, R 22b} , as the ^{R 23b,} is preferably a hydrogen atom or a methyl group.

The R ^16b and R ^17b may form an aliphatic cyclic group having 5 to 20 carbon atoms together with the carbon atom to which both are bonded. Specific examples of such aliphatic cyclic groups include groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as a monocycloalkane, bicycloalkane, tricycloalkane or tetracycloalkane. Specifically, one or more hydrogen atoms are removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, cyclooctane, etc., and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. Groups are mentioned. Particularly preferred are cyclohexane and a group in which one or more hydrogen atoms have been removed from adamantane (which may further have a substituent).

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

The above Y ^b is an aliphatic cyclic group or an alkyl group, and examples thereof include a group in which one or more hydrogen atoms have been removed from a polycycloalkane such as monocycloalkane, bicycloalkane, tricycloalkane, tetracycloalkane or the like. . Specifically, one or more hydrogen atoms are removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, cyclooctane, etc., and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. 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, when the aliphatic cyclic group of Y ^b has a substituent on the ring skeleton thereof, examples of the substituent include polar groups such as a hydroxyl group, a carboxy group, a cyano group and an oxygen atom (等 O). And a linear or branched alkyl group having 1 to 4 carbon atoms. An oxygen atom (は O) is particularly preferred as the polar group.

When Y ^b 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, and as such an alkoxyalkyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-isopropoxy group are preferable. 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 etc. are mentioned.

  As a preferable specific example of the structural unit represented by the said Formula (b5), what is represented by following formula (b5-1)-(b 5-33) can be mentioned.

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

  As a preferable specific example of the structural unit represented by the said Formula (b6), what is represented by following formula (b6-1)-(b6-26) can be mentioned.

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

  As a preferable specific example of the structural unit represented by the said Formula (b7), what is represented by following formula (b7-1)-(b7-15) can be mentioned.

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

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), structural units in which Y ^b is an alkyl group are preferable, and structural units in which one or both of R ^19b and R ^20b are alkyl groups are preferable.

  Furthermore, the acrylic resin (B3) is a resin comprising a copolymer containing a structural unit derived from a polymerizable compound having an ether bond, in addition to the structural units represented by the above formulas (b5) to (b7) Is preferred.

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

  Furthermore, in the acrylic resin (B3), another polymerizable compound can be included as a constituent unit for the purpose of appropriately controlling physical and chemical properties. Examples of such a polymerizable compound include known radical polymerizable compounds and anionic polymerizable compounds.

  Examples of such polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxy Methacrylic acid derivatives having a carboxyl group and an ester bond such as ethylmaleic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, etc .; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) ) (Meth) acrylic acid alkyl esters such as acrylate and cyclohexyl (meth) acrylate; (meth) acrylic acid hydroxyalkyl such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate Esters; (Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate; Dicarboxylic acid diesters such as diethyl maleate and dibutyl fumaric acid; styrene, α-methylstyrene, chlorostyrene, chloro Vinyl group-containing aromatic compounds such as methylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene and the like; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene 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 contain a structural unit derived from a polymerizable compound having a carboxy group such as the above-mentioned monocarboxylic acids and dicarboxylic acids. However, the acrylic resin (B3) substantially does not contain a structural unit derived from a polymerizable compound having a carboxy group, from the viewpoint of easily forming a resist pattern including a non-resist portion having a rectangular shape with a good cross-sectional shape. Is preferred. 20 mass% or less is preferable, and, as for the ratio of the structural unit originating in the polymeric compound which has a carboxy group in an acrylic resin (B3), specifically, 15 mass% or less is more preferable, and 5 mass% or less is especially preferable. preferable.
In the acrylic resin (B3), an acrylic resin containing a relatively large amount of structural units 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. Preferably, it is used in combination with an acrylic resin.

  Moreover, (meth) acrylic acid esters having a non-acid dissociable aliphatic polycyclic group, vinyl group-containing aromatic compounds and the like can be mentioned as the polymerizable compound. As the non-acid 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 and the like. These aliphatic polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.

  Specifically, as the (meth) acrylic acid ester having a non-acid dissociable aliphatic polycyclic group, one having a structure of the following formulas (b8-1) to (b8-5) may be exemplified. it can.

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

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

  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 formulas (b5) to (b7) described above. It is particularly preferable to contain 50% by mass or less.

  The acrylic resin (B3) preferably contains a constituent unit derived from the above-described polymerizable compound having an ether bond. 0 mass% or more and 50 mass% or less are preferable, and, as for content of the structural unit originating in the polymeric compound which has an ether bond in acrylic resin (B3), 5 mass% or more and 30 mass% or less are more preferable.

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

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

  The polystyrene equivalent mass average molecular weight of the resin (B) described above is preferably 10000 or more and 600000 or less, more preferably 20000 or more and 400000 or less, and still more preferably 30000 or more and 300000 or less. By setting it as such a mass average molecular weight, sufficient strength of the photosensitive resin layer can be hold | maintained, without reducing the peelability from a board | substrate, and also it prevents swelling of a profile at the time of plating, and generation of a crack. it can.

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

  It is preferable that content of resin (B) shall be 5 mass% or more and 60 mass% or less with respect to the total mass of the photosensitive resin composition.

<Mercapto compound (C)>
The photosensitive resin composition contains a mercapto compound (C) represented by the following formula (C1-1) or (C1-2). For this reason, when forming a resist pattern using the photosensitive resin composition, generation | occurrence | production of a footing is suppressed.

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

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

  Hereinafter, the mercapto compound represented by Formula (C1-1) and the mercapto compound represented by Formula (C1-2) will be described in order.

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

As a hetero atom which the organic group as R ^c1 may contain, a halogen atom, an oxygen atom, a nitrogen atom, a phosphorus atom, a silicon atom, etc. are mentioned. The heteroatom may be present in a substituent attached to the main skeleton of the divalent organic group, or may be present as part of the bond constituting the divalent organic group.

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

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

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

  Although the carbon atom number of a cycloalkyl oxy group is not specifically limited, 3 or more and 10 or less are preferable, and 3 or more and 8 or less are more preferable. Specific examples of the cycloalkyloxy group include cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, cyclononyloxy group, and cyclodecyloxy group. Be

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

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

  The carbon atom number of an acyl group is not specifically limited, 2 or more and 20 or less are preferable, and 2 or more and 11 or less are more preferable. The acyl group may be an aliphatic acyl group or an aromatic acyl group including an aromatic group. Specific examples of the acyl group include acetyl group, propionyl group, butanoyl group, pentanoyl group, hexanoyl group, octanoyl group, nonanoyl group, decanoyl group, benzoyl group, naphthalene-1-ylcarbonyl group, and naphthalene-2-ylcarbonyl Groups are mentioned.

  The carbon atom number of an acyloxy group is not specifically limited, 2 or more and 20 or less are preferable, and 2 or more and 11 or less are more preferable. The acyloxy group may be an aliphatic acyloxy group or an aromatic acyloxy group containing an aromatic group. Specific examples of the acyloxy group include acetyloxy group, propionyloxy group, butanoyloxy group, pentanoyloxy group, hexanoyloxy group, octanoyloxy group, nonanoyloxy group, decananoyloxy group, benzoyloxy group, naphthalene- 1-yl carbonyloxy group and naphthalen 2-yl carbonyloxy group are mentioned.

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

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

  Although the carbon atom number of a cycloalkyl oxycarbonyl group is not specifically limited, 4 or more and 11 or less are preferable, and 4 or more and 9 or less are more preferable. Specific examples of the cycloalkyloxycarbonyl group are cyclopropyloxycarbonyl group, cyclobutyloxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group, cycloheptyloxycarbonyl group, cyclooctyloxycarbonyl group, cyclononyloxycarbonyl group And cyclodecyloxycarbonyl group.

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

The type of substituent bonded to the nitrogen atom of the N-monosubstituted amino group and the N, N-disubstituted amino group is not particularly limited. Preferable examples of the substituent bonded to the nitrogen atom include an alkyl group having 1 to 6 carbon atoms which may be linear or branched and a cycloalkenyl having 3 to 10 carbon atoms. Examples thereof include an alkyl group, an aryl group having 6 to 20 carbon atoms, an aliphatic acyl group having 2 to 7 carbon atoms, and an aromatic acyl group having 7 to 21 carbon atoms.
Preferred specific examples of the N-monosubstituted amino group include methylamino group, ethylamino group, n-propylamino group, isopropylamino group, n-butylamino group, isobutylamino group, sec-butylamino group, tert- Butylamino group, n-pentylamino group, n-hexylamino group, cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclononylamino group, cyclo Decylamino group, phenylamino group, naphthalene-1-ylamino group, naphthalene-2-ylamino group, biphenylylamino group, acetylamino group, propionylamino group, butanoylamino group, pentanoylamino group, hexanoylamino group, Octanoylamino group, Nanoiruamino group, decanoyl group, a benzoylamino group, a naphthalene-1-yl carbonylamino group, and naphthalene-2-yl carbonylamino group.
Preferred examples of the N, N-disubstituted amino group include dimethylamino, diethylamino, di-n-propylamino, diisopropylamino, di-n-butylamino, di-isobutylamino and di-sec-butylamino. , Di-tert-butylamino group, di-n-pentylamino group, di-n-hexylamino group, dicyclopentylamino group, dicyclohexylamino group, diphenylamino group, diacetylamino group, dipropionylamino group, and dibenzoylamino group It can be mentioned.

The type of substituent bonded to the nitrogen atom of the N-monosubstituted carbamoyl group and the N, N-disubstituted carbamoyl group is not particularly limited. Preferred examples of the substituent bonded to the nitrogen atom are the same as the groups described for the N-monosubstituted amino group and the N, N-disubstituted amino group.
Preferred specific examples of the N-monosubstituted aminocarbamoyl group include N-methylcarbamoyl group, N-ethylcarbamoyl group, Nn-propylcarbamoyl group, N-isopropylcarbamoyl group, Nn-butylcarbamoyl group, N -Isobutylcarbamoyl group, N-sec-butylcarbamoyl group, N-tert-butylcarbamoyl group, Nn-pentylcarbamoyl group, N-n-hexylcarbamoyl group, N-cyclopropylcarbamoyl group, N-cyclobutylcarbamoyl group , N-cyclopentylcarbamoyl group, N-cyclohexylcarbamoyl group, N-cycloheptylcarbamoyl group, N-cyclooctylcarbamoyl group, N-cyclononylcarbamoyl group, N-cyclodecylcarbamoyl group, N-phenylcarbamoyl group, N-na Talen-1-ylcarbamoyl group, N-naphthalen-2-ylcarbamoyl group, N-biphenylylcarbamoyl group, N-acetylcarbamoyl group, N-propionylcarbamoyl group, N-butanoylcarbamoyl group, N-pentanoylcarbamoyl group N-hexanoylcarbamoyl group, N-octanoylcarbamoyl group, N-nonanoylcarbamoyl group, N-decanoylcarbamoyl group, N-benzoylcarbamoyl group, N-naphthalen-1-ylcarbonylcarbamoyl group, and N-naphthalene And -2-ylcarbonylcarbamoyl group.
Preferred examples of the N, N-disubstituted carbamoyl group include N, N-dimethylcarbamoyl group, N, N-diethylcarbamoyl group, N, N-di n-propylcarbamoyl group, N, N-diisopropylcarbamoyl group, N, N-di n-butylcarbamoyl group, N, N-diisobutylcarbamoyl group, N, N-disec-butylcarbamoyl group, N, N-di-tert-butylcarbamoyl group, N, N-di n-pentylcarbamoyl group Group, N, N-di n-hexylcarbamoyl group, N, N-dicyclopentylcarbamoyl group, N, N-dicyclohexylcarbamoyl group, N, N-diphenylcarbamoyl group, N, N-diacetylcarbamoyl group, N, N- Dipropionylcarbamoyl group and N, N-dibenzoylcarbamoyl group can be mentioned.

With regard to R ^c1 , specific examples of the bond containing a hetero atom which may be contained in the (n1 + n2) -valent organic group include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, Urethane bond, imino bond (-N = C (-R)-, -C (= NR)-: R represents a hydrogen atom or an organic group), carbonate bond, sulfonyl bond, sulfinyl bond, azo bond and the like .

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

When R ^c1 is an aromatic hydrocarbon group, a divalent aromatic hydrocarbon group is preferable as the aromatic hydrocarbon group because synthesis and availability of the compound represented by Formula (C1) are easy. Preferred specific examples of the divalent aromatic hydrocarbon group for R ^c1 include p-phenylene group, m-phenylene group, p-phenylene group, naphthalene-2,6-diyl group, naphthalene-2,7- Diyl, naphthalene-1,4-diyl, and biphenyl-4,4'-diyl are included.
Among these, p-phenylene group, m-phenylene group, naphthalene-2,6-diyl group, and biphenyl-4,4'-diyl group are preferable, and p-phenylene group, naphthalene-2,6-diyl group is preferable. And biphenyl-4,4'-diyl groups are more preferred.

When R ^c1 is a saturated aliphatic hydrocarbon group, an alkylene group is preferable as the saturated aliphatic hydrocarbon group because synthesis and availability of the compound represented by Formula (C1) are easy. Preferred specific examples of the alkylene group for R ^c1 include methylene, ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,4- Diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, and decane -1,10-diyl group is mentioned.
Among these, methylene, ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5- Diyl group and hexane-1,6-diyl group are preferred, methylene group, ethane-1,2-diyl group and propane-1,3-diyl group are more preferred, methylene group, ethane-1,2-diyl group Groups and propane-1,2-diyl groups are particularly preferred.

In formula (C1-1), R ^c2 and R ^c3 are each independently a hydrogen atom or a monovalent organic group, and R ^c4 is a hydrocarbon group. R ^c3 and R ^c4 may be combined with each other to form a ring. Also, the carbon atom to which R ^c2 , R ^c3 and R ^c4 are bonded is a tertiary carbon atom.
For this reason, the following formula (C1-1-1) in the formula (C1-1):
(In Formula (c1-1-1), R ^c2 , R ^c3 , and R ^c4 are the same as in Formula (C1-1).)
The group represented by is decomposed by the acid generated by the acid generator (A) upon exposure to give a carboxy group.

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

At least one of R ^c2 and R ^c3 is a monovalent organic group having an aliphatic ring CA containing one or more divalent groups selected from an ether bond, a sulfide bond, and a carbonyl group in a ring structure In the case, as a preferable example of the monovalent organic group having an aliphatic ring CA, a group in which one hydrogen atom is removed from an aliphatic ring represented by the following formulas (c-A1) to (c-A6) is It can be mentioned.
When R ^c2 and R ^c3 combine to form an aliphatic ring CA, ^examples of the divalent cyclic group formed by R ^c2 and R ^c3 include the following formulas (c-A1) to (c) A bivalent cyclic group which remove | eliminated two hydrogen atoms couple | bonded with the same carbon atom from the aliphatic ring represented by c-A6) is mentioned.
However, as described above, in Formula (C1-1), the carbon atom to which R ^c2 , R ^c3 , and R ^c4 are bonded is a tertiary carbon atom.
For this reason, the divalent cyclic group formed by R ^c2 and R ^c3 is bonded to the same carbon atom from the aliphatic ring represented by the following formulas (c-A1) to (c-A6) When it is a bivalent cyclic group except two hydrogen atoms, the bivalent cyclic group is an oxygen atom or a sulfur from the aliphatic ring represented by the following formulas (c-A1) to (c-A6) It is not a divalent cyclic group except for two hydrogen atoms bonded to the same carbon atom at a position adjacent to the atom.

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

When at least one of R ^c2 and R ^c3 is a monovalent organic group having the above-mentioned aliphatic ring CA, preferred examples of the monovalent organic group include one hydrogen atom from the following aliphatic ring: And groups other than.
When the divalent cyclic group formed by R ^c2 and R ^c3 is a divalent cyclic group containing the aforementioned aliphatic ring CA, preferred examples of the divalent cyclic group are: Examples thereof include divalent cyclic groups in which two hydrogen atoms bonded to the same carbon atom have been removed from the following aliphatic ring.

When at least one of R ^c2 and R ^c3 is a monovalent organic group having the above-described aliphatic ring CA, preferable examples of the monovalent organic group include the following groups.

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

When at least one of R ^c2 and R ^c3 is a hydroxyl group or a monovalent organic group having an aliphatic ring CH substituted with a hydroxyl group-containing group, preferable examples of the monovalent organic group having an aliphatic ring CH As a monocycloalkane such as cyclopentane, cyclohexane, cycloheptane, cyclooctane or the like, or one hydrogen atom removed from an aliphatic hydrocarbon ring such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane 1 A monovalent organic group having an aliphatic ring CA; a monovalent organic group having an aliphatic ring CL; a monovalent organic group having an aliphatic ring CS; a monovalent having an aliphatic ring CP The group which substituted at least 1 of the hydrogen atom which monovalent | monohydric aliphatic cyclic groups, such as an organic group, etc. with the hydroxyl group or the hydroxyl-containing group is mentioned.

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

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

When at least one of R ^c2 and R ^c3 is a monovalent organic group having the above-described aliphatic ring CL, a preferred example of the monovalent organic group having the aliphatic ring CL is the above-mentioned formula (b The group which remove | eliminated one hydrogen atom from the aliphatic ring represented by the following formula (c-L1)-(c-L7) contained in-L1)-(b-L7) is mentioned.
When R ^c2 and R ^c3 combine to form an aliphatic ring CL, ^examples of the divalent cyclic group formed by R ^c2 and R ^c3 include the following formulas (c-L1) to (c) and a divalent cyclic group obtained by removing two hydrogen atoms bonded to the same carbon atom from the aliphatic ring represented by c-L7).
However, as described above, in Formula (C1-1), the carbon atom to which R ^c2 , R ^c3 , and R ^c4 are bonded is a tertiary carbon atom.
Therefore, the divalent cyclic group formed by R ^c2 and R ^c3 is bonded to the same carbon atom in the aliphatic ring represented by the following formulas (c-L1) to (c-L7) In the case of a divalent cyclic group from which two hydrogen atoms have been removed, the divalent cyclic group is selected from an aliphatic ring represented by the following formulas (c-L1) to (c-L7) to an oxygen atom It is not a divalent cyclic group except for two hydrogen atoms bonded to carbon atoms at adjacent positions.
(In the formulas (c-L1) to (c-L7), R ′, s ′ ′, A ′ ′, and r are the same as the formulas (b-L1) to (b-L7).)

Moreover, the group which ^{remove |} eliminated one hydrogen atom from the aliphatic ring represented by a following formula (c-L8) is also preferable as a monovalent organic group which has the above-mentioned aliphatic ring CL as ^Rc2 and ^Rc3 .
Furthermore, a divalent cyclic group obtained by removing two hydrogen atoms bonded to the same carbon atom from an aliphatic ring represented by the following formula (c-L8) is also formed by bonding R ^c2 and R ^c3 Preferred as a divalent cyclic group containing a substituted aliphatic ring CL.

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

When at least one of R ^c2 and R ^c3 is a monovalent organic group having the above-mentioned aliphatic ring CL, preferred examples of the monovalent organic group include one hydrogen atom from the following aliphatic ring And groups other than.
When the divalent cyclic group formed by R ^c2 and R ^c3 is a divalent cyclic group containing the aforementioned aliphatic ring CL, preferred examples of the divalent cyclic group are: Examples thereof include divalent cyclic groups in which two hydrogen atoms bonded to the same carbon atom have been removed from the following aliphatic ring.

When at least one of R ^c2 and R ^c3 is a monovalent organic group having the above-mentioned aliphatic ring CL, preferable specific examples of the monovalent organic group include the following groups.

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

When at least one of R ^c2 and R ^c3 is a monovalent organic group having the above-mentioned aliphatic ring CS, a preferred example of the monovalent organic group having the aliphatic ring CS is the above-mentioned formula (3) -1)-(3-4) is mentioned.
When R ^c2 and R ^c3 combine to form an aliphatic ring CS, ^examples of the divalent cyclic group formed by R ^c2 and R ^c3 include the above-described formulas (3-1) to Examples of the group represented by (3-4) include groups in which one hydrogen atom has been removed from the carbon atom to which the bond is attached.
However, as described above, in Formula (C1-1), the carbon atom to which R ^c2 , R ^c3 , and R ^c4 are bonded is a tertiary carbon atom. For this reason, the divalent group having an aliphatic ring CS formed by combining R ^c2 and R ^c3 is limited to a group satisfying this condition.

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

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

When the divalent cyclic group formed by R ^c2 and R ^c3 is a divalent cyclic group containing the above-mentioned aliphatic ring CS, preferred specific examples of the divalent cyclic group are: And the following groups.

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

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

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

In formula (C1-1), R ^c3 and R ^c4 may be bonded to each other to form a ring. Ring and R ^c3 and ^{R c4} are formed by ^bonding, R ^{c2, R c3,} and the carbon atom ^{to which R c4} is bonded is not particularly limited as long as it is a tertiary carbon atom.
When R ^c3 and R ^c4 are bonded to each other to form a cyclic group, the cyclic group is preferably a cycloalkylidene group. Preferred examples of the cycloalkyl dene group include a cyclopropylidene group, a cyclobutylidene group, a cyclopentylidene group, and a cyclohexylidene group. Among these, a cyclopentylidene group and a cyclohexylidene group are preferable.

Although the manufacturing method of the mercapto compound represented by Formula (C1-1) is not specifically limited, For example, it can synthesize | combine according to the following scheme 1.
Specifically, first, the mercapto group in the carboxylic acid compound having a mercapto group represented by the following formula (C1-a) is selectively protected with a protecting group ^{Xc, and is represented} by the following formula (C1-b) The carboxylic acid compound represented is obtained. In addition, since the ester bond in the compound represented by Formula (C1-1) is cleaved by acid, as protecting group ^Xc , group which can be deprotected on conditions other than acidic conditions is employ | adopted. As a mercapto group protected by such a protecting group ^Xc , the group of the structure represented by following formula (X-1)-(X-3) is mentioned, for example.
R ^x1 -S-S- (X-1)
R ^x1- (C = O) -S- (X-2)
R ^x1 -S-CR ^x2 R ^x3 -S- (X-3)
R ^x1 is a hydrocarbon group. Each of R ^x2 and R ^x3 independently is a hydrogen atom or a hydrocarbon group. As a hydrocarbon group, an alkyl group and an aryl group are preferable. As an alkyl group, a C1-C6 alkyl group is preferable, a C1-C4 alkyl group is more preferable, and a methyl group and an ethyl group are especially preferable. As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 12 carbon atoms is more preferable, and a phenyl group, a naphthalene-1-yl group, and a naphthalene-2-yl group Is more preferred, and phenyl is particularly preferred.

Next, an ester compound represented by Formula (C1-1b) is obtained from the carboxylic acid compound represented by Formula (C1-b) and the alcohol represented by the following Formula (C1-1a).
The method of esterification is not particularly limited. As a suitable esterification method, a carbodiimide compound which is a condensing agent is allowed to act in the presence of a small amount of N, N-dimethyl-4-aminopyridine, and a carboxylic acid compound represented by the formula (C1-b) The method of condensing with the alcohol represented by (C1-1a) is mentioned. In addition, after a carboxylic acid compound represented by the formula (C1-b) is reacted with a halogenating agent such as thionyl chloride or phosphorus trichloride to form a carboxylic acid halide, the carboxylic acid halide is reacted with a compound of the formula (C1-1a You may make it react with the alcohol represented by this.

In the obtained ester compound represented by the formula (C1-1b), the mercapto compound represented by the formula (C1-1) is obtained by deprotecting the protecting group ^Xc . The deprotection method is not particularly limited, and may be appropriately selected depending on the type of the protecting group X ^c .

Scheme 1

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

In the method described in Scheme 2, the carboxylic acid represented by the formula (C1 1d) is obtained by the Michael addition reaction of an α, β-unsaturated carboxylic acid ester represented by the following formula (C1-1c) with thioacetic acid An acid ester is obtained. Then, the compound represented by the formula (C1-1d) is reacted with a base such as an aqueous ammonia solution to carry out deacetylation to obtain a mercapto compound represented by the formula (1-1e).
The compound represented by the formula (1-1e) is a compound represented by the formula (1-1), and n1 is 1, n2 is 1, and R ^c1 is -CH ₂ -CH ( It is a compound which is a bivalent group represented by R ^c10 )-.

Scheme 2

In formulas (C1-a), (C1-b), and (C1-1a) to formulas (C1-1e) shown in Scheme 1 and Scheme 2, R ^c1 , R ^c2 , R ^c3 , R ^c4 , N1 and n2 are as defined in the formula (C1-1).

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

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

In the formula (C1-2), R ^c5 and R ^c6 may be combined to form a ring. As a ring formed in this case, the above-mentioned aliphatic ring CA is preferable.
In the group represented by —CR ^c6 R ^c7 —O—CR ^c R ^c3 R ^c5 in formula (C1-2), R ^c5 and R ^c6 are bonded to form an aliphatic ring CA In the case, as preferred examples of the group represented by -CR ^c6 R ^c7 -O-CR ^c2 R ^c3 R ^c5 , the following groups are preferable.
In the following groups, it is preferable that all of R ^c2 , R ^c3 and R ^c7 be a hydrogen atom.

As a mercapto compound represented by Formula (C1-1) or Formula (C1-2) demonstrated above, the compound of a following formula is preferable. In the following formulae, ^Rx is a group represented by -CR ^c2 R ^c3 R ^c4 or a group represented by -CR ^c6 R ^c7 -O-CR ^c2 R ^c3 R ^c5 .

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

  The mercapto compound represented by the formula (C1-2) described above changes the raw material compound as appropriate, and the scheme 1 and the scheme 2 described the method for producing the mercapto compound represented by the formula (C1-1) Can be manufactured by the method described as

  The mercapto compound (C) is used in a range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the total mass of the resin (B) and the alkali-soluble resin (D) described later, 0.05 It is particularly preferable to use in the range of not less than mass part and not more than 2 parts by mass. When the addition amount of the mercapto compound (C) is 0.01 parts by mass or more, the footing can be effectively suppressed, and when the addition amount is 5 parts by mass or less, a good plated shaped article can be formed.

Pattern using a positive photosensitive resin composition comprising an acid generator (A) which generates an acid upon irradiation with actinic rays or radiation, and a resin (B) whose solubility in alkali increases by the action of the acid When forming, it is thought that the acid generated from the acid generator (A) at the time of exposure deactivates in the vicinity of the substrate surface.
In particular, in the vicinity of the boundary between the exposed portion and the unexposed portion where the acid concentration is low, footing is likely to occur due to the influence of the acid deactivation on the substrate surface.
In this respect, when the photosensitive resin composition contains a mercapto compound, it is easy to suppress the deactivation of the acid on the substrate surface, and as a result, it is easy to suppress the footing.
The mercapto compound (C) is a highly polar aliphatic ring such as a mercapto group, aliphatic ring CA, aliphatic ring CH, aliphatic ring CL, aliphatic ring CS, or aliphatic ring CP in the molecule. And a formula group. Therefore, in the vicinity of the interface between the substrate surface and the coating film, the mercapto compound (C) is oriented such that the mercapto group is located on the substrate surface side and the highly polar aliphatic cyclic group is located on the coating film side. Cheap. This is because the resin (B) and the like contained in the photosensitive resin composition usually have high polarity to some extent. As a result of the orientation of the mercapto (C) compound, the mercapto compound (C) is efficiently and uniformly distributed on the substrate surface.
The mercapto compound (C) is oriented such that the mercapto group is located on the substrate surface side, and as a result of the mercapto compound (C) being uniformly distributed on the substrate surface, the deactivation of the acid on the substrate surface is particularly easily suppressed. .

In addition, the mercapto compound itself is difficult to dissolve in an alkaline developer, and if the photosensitive resin composition contains a mercapto compound, a residue is likely to be generated during development.
When the residue is generated after development, adhesion of the residue to the substrate surface and deposition may cause deterioration of the pattern shape similar to the footing.
In this respect, the mercapto compound (C) has an acid dissociable group in its molecule. For this reason, in the coating film made of the photosensitive resin composition, the acid dissociable group is eliminated in the mercapto compound (C) at the exposed portion, and the mercapto compound (C) is solubilized in the alkali developer. .
As a result, when the photosensitive resin composition contains a mercapto compound (C) which is a compound represented by the formula (C1), the pattern shape is hardly deteriorated due to the generation of a residue after development.

  For the reasons described above, it is considered that the occurrence of footing is significantly suppressed when using a photosensitive resin composition containing a mercapto compound (C) having the above-described predetermined structure.

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

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

Examples of the above-mentioned phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2 , 3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5- Trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, phlorogricinol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, β-naphthol and the like.
Examples of the aldehydes include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde and the like.
The catalyst for 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 bulky aldehydes. It is.

  The mass average molecular weight of the novolak resin (D1) is not particularly limited as long as the object of the present invention is not impaired, but it is preferably 1000 or more and 50000 or less.

[Polyhydroxystyrene resin (D2)]
Examples of the hydroxystyrene compound constituting the polyhydroxystyrene resin (D2) include p-hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene and the like.
Furthermore, the polyhydroxystyrene resin (D2) is preferably a copolymer with a styrene resin. As a styrene compound which comprises such a styrene resin, styrene, chlorostyrene, chloromethylstyrene, vinyl toluene, alpha-methylstyrene etc. are mentioned.

  Although the mass mean molecular weight of polyhydroxy styrene resin (D2) is not specifically limited in the range which does not inhibit the object of the present invention, it is preferred that they are 1000 or more and 50000 or less.

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

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

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

  Although the mass mean molecular weight of acrylic resin (D3) is not specifically limited in the range which does not inhibit the object of the present invention, it is preferred that they are 50000 or more and 800000 or less.

  The content of the alkali-soluble resin (D) is preferably 0 parts by mass or more and 80 parts by mass or less, and 0 parts by mass or more and 60 parts by mass, based on 100 parts by mass of the total of the resin (B) and the alkali-soluble resin (D). It is more preferable that the amount is equal to or less by mass. By setting the content of the alkali-soluble resin (D) in the above-mentioned range, it is possible to improve the crack resistance and to prevent film loss during development.

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

[Nitrogen-containing compound (E1)]
As the nitrogen-containing compound (E1), trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tri-n-pentylamine, tribenzylamine, diethanolamine, triethanolamine, 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-diamide Ethylacetamide, 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, 1,4-dimethyl piperazine, 1,4-diazabicyclo [2.2.2] octane, pyridine and the like can be mentioned. These may be used alone or in combination of two or more.

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

[Organic carboxylic acid or oxo acid of phosphorus or derivative thereof (E2)]
Specifically, among organic carboxylic acids or phosphorus oxo acids or derivatives thereof (E2), malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid etc. are preferable as the organic carboxylic acid. Particularly preferred is salicylic acid.

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

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

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

<Organic solvent (S)>
The photosensitive resin composition contains an organic solvent (S). The type of the organic solvent (S) is not particularly limited as long as the object of the present invention is not impaired, and can be appropriately selected and used 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, propylene glycol monoacetate , Polypropylene glycol, monomethyl ether of dipropylene glycol monoacetate, monoethyl ether, monopropyl ether, monobutyl ether, monobutyl ether, monophenyl ether and the like; polyhydric alcohols and derivatives thereof; cyclic ethers such as dioxane; cyclic formates: ethyl formate, lactic acid Methyl, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, pyruvine 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; aromatic hydrocarbons such as toluene and xylene; and the like. These may be used alone or in combination of two or more.

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

<Other ingredients>
The photosensitive resin composition may further contain a polyvinyl resin in order to improve the plasticity. Specific examples of the polyvinyl resin include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinyl benzoic acid, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl phenol, and copolymers of these, etc. Can be mentioned. The polyvinyl resin is preferably polyvinyl methyl ether in view of the low glass transition temperature.

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

  The photosensitive resin composition may further contain a surfactant in order to improve coating properties, defoaming properties, leveling properties, and the like. Specific examples of the surfactant include BM-1000, BM-1100 (all from BM Chemie), Megafac F142D, Megafac F172, Megafac F173, Megafac F183 (all from Dainippon Ink & Chemicals, Inc.) ), Florald FC-135, Florald FC-170C, Florald FC-430, Florald FC-431 (all are manufactured by Sumitomo 3M), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Commercially available fluorosurfactants such as Cerflon S-145 (all manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (all manufactured by Toray Silicone) are listed. Although it is not limited to these.

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

  Specific examples of the acid and acid anhydride 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 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid, hydroxymonocarboxylic acids such as 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, cyclopentanetetracarb Acids, butanetetracarboxylic acid, polyvalent carboxylic acids such as 1,2,5,8-naphthalenetetracarboxylic acid; itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarbanilic anhydride, maleic anhydride, Hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymic acid anhydride, 1,2,3,4-butanetetracarboxylic acid anhydride, cyclopentanetetracarboxylic acid dianhydride, phthalic acid anhydride, pyromellitic acid anhydride, anhydrous And acid anhydrides such as trimellitic acid, benzophenone tetracarboxylic acid anhydride, ethylene glycol bis trimellitate anhydride, and glycerin tris trimellitate anhydride.

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

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

<Method for Preparing Chemically Amplified Positive-type Photosensitive Resin Composition>
The chemically amplified positive photosensitive resin composition is prepared by mixing and stirring the above-mentioned components in a conventional manner. As an apparatus which can be used when mixing and stirring said each component, a dissolver, a homogenizer, 3 roll mill etc. are mentioned. After the above components are uniformly mixed, 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 photosensitive resin composition described above.

  As a base film, what has light transmittance is preferable. Specifically, although a polyethylene terephthalate (PET) film, a polypropylene (PP) film, a polyethylene (PE) film etc. are mentioned, a polyethylene terephthalate (PET) film is preferable at the point which is excellent in the balance of light transmittance and breaking strength.

A photosensitive dry film is manufactured by apply | coating the above-mentioned photosensitive resin composition and forming a photosensitive resin layer on a base film.
When forming a photosensitive resin layer on a base film, the film thickness after drying on a base film is preferably 0. 0 using an applicator, a bar coater, a wire bar coater, a roll coater, a curtain flow coater etc. The photosensitive resin composition is applied and dried so as to be 5 to 300 μm, more preferably 1 to 150,300 μm, and particularly preferably 3 to 100 μm.

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

«Patterned resist film and method of manufacturing templated substrate»
The method for forming a patterned resist film on the metal surface of the substrate having a metal surface using the photosensitive resin composition described above is not particularly limited. Such a patterned resist film is suitably used as a mold for forming a plated shaped article.
The preferred method is
Laminating a photosensitive resin layer made of a photosensitive resin composition on the metal surface of a substrate having a metal surface;
An exposure step of exposing the photosensitive resin layer by irradiation with actinic rays or radiation;
A development step of developing the photosensitive resin layer after exposure;
And patterned resist films.
The method for producing a mold-provided substrate provided with a mold for forming a plated shaped article is a process for producing a patterned resist film except that a mold for forming a plated shaped article is developed by development in a developing step. It is similar to the method.

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

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

  As a method of applying the photosensitive resin composition onto the substrate, methods such as a spin coating method, a slit coating method, a roll coating method, a screen printing method, and an applicator method can be adopted. It is preferable to pre-bake the photosensitive resin layer. Pre-baking conditions vary depending on the type of each component in the photosensitive resin composition, the compounding ratio, the coating film thickness, etc. It is about 60 minutes or less.

  With respect to the photosensitive resin layer formed as described above, actinic rays or radiation, for example, ultraviolet rays or visible rays having a wavelength of 300 nm to 500 nm are selectively irradiated (exposed) through a mask of a predetermined pattern. Be done.

As a radiation source of radiation, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, an argon gas laser or the like can be used. Further, radiation includes microwave, infrared, visible light, ultraviolet, X-ray, γ-ray, electron beam, proton beam, neutron beam, ion beam 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 also includes light that activates the acid generator (A) to generate an acid.

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

  Next, the exposed photosensitive resin layer is developed according to a conventionally known method to dissolve and remove insoluble portions, whereby a mold for forming a predetermined resist pattern or a plated structure is formed. At this time, an alkaline aqueous solution is used as a developer.

  As a developing solution, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyl diethylamine, Dimethyl ethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3, 0] Aqueous solutions of alkalis such as 5-nonane can be used. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to an aqueous solution of the above-mentioned alkalis can also be used as a 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 development method may be any of a liquid deposition method, a dipping method, a paddle method, a spray development method and the like.

  After development, washing with running water is performed for 30 seconds to 90 seconds and dried using an air gun, an oven, or the like. Thus, a resist pattern patterned in a desired shape is formed on the metal surface of the substrate having the metal surface. Also, in this way, it is possible to manufacture a templated substrate provided with a resist pattern to be a template on the metal surface of the substrate having a metal surface.

«Production method of plated shaped object»
By embedding a conductor such as metal in the non-resist portion (portion removed by the developer) in the mold of the substrate with a mold formed by the above method, for example, connection terminals such as bumps and metal posts Such plated shaped objects can be formed. 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. The remaining mold is finally removed using a stripping solution according to a conventional method.

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

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

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

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

In a flask, 9.49 g of a precursor C1a, 94.9 g of methanol, and 25.5 g of ammonia water having a concentration of 10% by mass were added, and the mixture was stirred at room temperature for 10 hours. Next, 11.9 g of acetic acid was added to the reaction solution, and then 94.9 g of dichloromethane and 94.9 g of pure water were added to the flask. After stirring the contents of the flask, it was allowed to stand still to be separated, and the organic phase was recovered. The recovered organic layer is washed once with 94.9 g of 1% by mass ammonia water, and then 5 times with 94.9 g of pure water, and then the solvent is distilled off from the organic phase to obtain a mercapto compound C1 of 7 I got .87g.
¹ H-NMR (600 MHz, DMSO-d6): δ 3.70-3.51 (m, 4 H), 3.00-2.15 (m, 3 H), 2.05 (t, 2 H), 1.75 (T, 2H), 1.53 (s, 3H), 1.25-1.05 (m, 3H)

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

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

[Examples 1 to 8 and Comparative Examples 1 to 6]
In Examples and Comparative Examples, compounds of the following formula were used as the acid generator (A).

In Examples and Comparative Examples, the following resins B1 and B2 were used as resins ((B) resin) in which the solubility in alkali increases by the action of an acid. The numbers at the lower right of the brackets in each structural unit in the following structural formula represent the content (% by mass) of the structural unit in each resin.

  (C) As a mercapto compound, the above-mentioned mercapto compound C1-C2 was used in the Example. In the comparative example, 3-mercaptopropionic acid was used as the mercapto compound C3, and 3-mercaptopropionic acid t-butyl ester was used as the mercapto compound C4.

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

Resin (B), mercapto compound (C) and alkali-soluble resin (D) of the type and amount shown in Table 1, 2.0 parts by mass of acid generator (A), 0.02 parts by mass of tripentylamine Were dissolved in methoxybutyl acetate so that the solid content concentration was 53% by mass, to obtain photosensitive resin compositions of the respective examples and comparative examples.
In addition, the usage-amount of the mercapto compound (C) of Table 1 is 0.05 mass part or 0.10 mass part.

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

[Evaluation of footing]
The photosensitive resin compositions of Examples and Comparative Examples were coated on a copper substrate having a diameter of 8 inches to form a photosensitive resin layer having a thickness of 55 μm. Then, the photosensitive resin layer was prebaked at 100 ° C. for 5 minutes. After prebaking, using a mask of 30 μm diameter square pattern and an exposure apparatus Prisma GHI (manufactured by Ultratech Co., Ltd.), at an exposure amount of 1.2 times the minimum exposure amount capable of forming a pattern of a predetermined size, ghi The pattern was exposed with a line. Then, the substrate was placed on a hot plate and subjected to post-exposure bake (PEB) at 140 ° C. for 3 minutes. Thereafter, a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (developer, NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) is dropped onto the exposed photosensitive resin layer and then allowed to stand at 23 ° C. for 60 seconds Was repeated four times in total. Thereafter, the surface of the resist pattern was washed with running water, and then nitrogen was blown to obtain a resist pattern. The cross-sectional shape of the resist pattern was observed with a scanning electron microscope to measure the amount of footing.
Specifically, the footing amount was measured as follows. A schematic view of a cross section of the resist portion and the non-resist portion at the time of measuring the footing amount is shown in FIG. In FIG. 1, a resist pattern including a resist portion 12 and a non-resist portion 13 (hole) is formed on a substrate 11. First, on the side wall 14 which is an interface between the resist portion 12 and the non-resist portion 13, an inflection point 15 which is a position where footing starts on the side wall 14 was determined. The perpendicular 16 is lowered from the inflection point 15 toward the surface of the substrate 11, and the intersection between the perpendicular 16 and the surface of the substrate 11 is taken as the footing start point 17. Further, a crossing point between the curve of the side wall 14 and the surface of the substrate 11 is defined as a footing end point 18. The width Wf between the footing start point 17 and the footing end point 18 determined in this way is taken as the footing amount. The footing amount is a value measured for any one side wall 14 of any one non-resist portion in the resist pattern. From the value of the footing amount determined, the degree of footing was evaluated according to the following criteria.
<Footing evaluation criteria>
○: 0 μm to 1.5 μm Δ: more than 1.5 μm to 2.5 μm or less ×: 2.5 μm or more

  According to Examples 1 to 8, in addition to the acid generator (A) which generates an acid upon irradiation with an actinic ray or radiation, and the resin (B) whose solubility to an alkali is increased by the action of the acid, In the case of forming a resist pattern using a positive photosensitive resin composition containing a mercapto compound (C) having the structure of the above, it is understood that the footing is suppressed in the resist pattern.

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

11 substrate 12 resist portion 13 non resist portion 14 side wall 15 inflection point 16 vertical line 17 footing start point 18 footing end point

Claims (9)

An acid generator (A) which generates an acid upon irradiation with actinic rays or radiation, a resin (B) whose solubility in alkali increases by the action of the acid, and the following formula (C1-1) or (C1-2) :
(In the formula (C1-1), R ^c1 is an (n1 + n2) -valent organic group, R ^c1 is bonded to a carbonyl group by a C—C bond, and is bonded to a mercapto group by a C—S bond; ^c2 and R ^c3 are each independently a hydrogen atom or a monovalent organic group, R ^c4 is a hydrocarbon group, and the carbon atom to which R ^c2 , R ^c3 and R ^c4 are bonded is a tertiary carbon R ^c3 and R ^c4 may be bonded to each other to form a ring, n1 is an integer of 1 or more and 4 or less, and n2 is an integer of 1 or more and 4 or less,
Provided that at least one of R ^c2 and R ^c3 is a monovalent organic group having an aliphatic ring CA containing at least one divalent group selected from an ether bond, a sulfide bond, and a carbonyl group in a ring structure And a monovalent organic group having an aliphatic ring CH substituted with a hydroxyl group or a hydroxyl group-containing group, an aliphatic ring having an aliphatic ring CL containing a divalent group represented by -CO-O- in the ring structure An organic group, a monovalent organic group having an aliphatic ring CS containing a divalent group represented by —SO ₂ — in the ring structure, or the following formula in the ring structure:
Or a monovalent organic group having an aliphatic ring CP containing a trivalent group represented by
R ^c2 and R ^c3 combine to form the aliphatic ring CA, the aliphatic ring CH, the aliphatic ring CL, the aliphatic ring CS, or the aliphatic ring CP)
(In formula (C1-2), R ^c1 , R ^c2 , R ^c3 , n1 and n2 are the same as in formula (C1-1), R ^c5 is R ^c6 and R ^c7 are each independently R ^c5 and R ^c6 may be a hydrogen atom or an alkyl group, and may be bonded to each other to form a ring,
However, at least one of R ^c2 and R ^c3 is a monovalent organic group having the aliphatic ring CA, a monovalent organic group having the aliphatic ring CH, a monovalent organic group having the aliphatic ring CL Or a monovalent organic group having the aliphatic ring CS, or a monovalent organic group having the aliphatic ring CP,
R ^c2 and R ^c3 combine to form the aliphatic ring CP, the aliphatic ring CH, the aliphatic ring CL, the aliphatic ring CS, or the aliphatic ring CP. )
A chemically amplified positive photosensitive resin composition comprising the mercapto compound (C) represented by   The chemically amplified positive photosensitive resin composition according to claim 1, further comprising an alkali soluble resin (D).   The said alkali-soluble resin (D) contains at least 1 sort (s) of resin selected from the group which consists of novolak resin (D1), polyhydroxystyrene resin (D2), and acrylic resin (D3). Chemical amplification type positive photosensitive resin composition.   It has a base film and the photosensitive resin layer formed in the surface of the said base film, The said photosensitive resin layer is a chemical amplification type positive photosensitive resin of any one of Claims 1-3. Photosensitive dry film comprising a resin composition.   The manufacturing of the photosensitive dry film which apply | coats the chemical amplification type positive photosensitive resin composition of any one of Claims 1-3 on a base film, and forms a photosensitive resin layer. Method. A laminating step of laminating a photosensitive resin layer comprising the chemical amplification type positive photosensitive resin composition according to any one of claims 1 to 3 on a substrate having a metal surface;
An exposure step of irradiating the photosensitive resin layer selectively with an actinic ray or radiation;
And a development step of developing the photosensitive resin layer after exposure. A laminating step of laminating a photosensitive resin layer comprising the chemical amplification type positive photosensitive resin composition according to any one of claims 1 to 3 on a substrate having a metal surface;
Exposing the photosensitive resin layer to an actinic ray or radiation;
And developing the photosensitive resin layer after exposure to form a mold for forming a plated shaped article.   A method for producing a plated formed article, comprising the steps of plating the substrate with a mold produced by the method according to claim 7 to form a plated shaped article in the mold. The following formula (C1-1) or (C1-2):
(In the formula (C1-1), R ^c1 is an (n1 + n2) -valent organic group, R ^c1 is bonded to a carbonyl group by a C—C bond, and is bonded to a mercapto group by a C—S bond; ^c2 and R ^c3 are each independently a hydrogen atom or a monovalent organic group, R ^c4 is a hydrocarbon group, and the carbon atom to which R ^c2 , R ^c3 and R ^c4 are bonded is a tertiary carbon R ^c3 and R ^c4 may be bonded to each other to form a ring, n1 is an integer of 1 or more and 4 or less, and n2 is an integer of 1 or more and 4 or less,
Provided that at least one of R ^c2 and R ^c3 is a monovalent organic group having an aliphatic ring CP containing at least one type of divalent group selected from an ether bond, a sulfide bond, and a carbonyl group in a ring structure And a monovalent organic group having an aliphatic ring CH substituted with a hydroxyl group or a hydroxyl group-containing group, an aliphatic ring having an aliphatic ring CL containing a divalent group represented by -CO-O- in the ring structure An organic group, a monovalent organic group having an aliphatic ring CS containing a divalent group represented by —SO ₂ — in the ring structure, or the following formula in the ring structure:
Or a monovalent organic group having an aliphatic ring CP containing a trivalent group represented by
R ^c2 and R ^c3 combine to form the aliphatic ring CP, the aliphatic ring CH, the aliphatic ring CL, the aliphatic ring CS, or the aliphatic ring CP. )
(In formula (C1-2), R ^c1 , R ^c2 , R ^c3 , n1 and n2 are the same as in formula (C1-1), R ^c5 is R ^c6 and R ^c7 are each independently R ^c5 and R ^c6 may be a hydrogen atom or an alkyl group, and may be bonded to each other to form a ring,
However, at least one of R ^c2 and R ^c3 is a monovalent organic group having the aliphatic ring CP, a monovalent organic group having the aliphatic ring CH, a monovalent organic group having the aliphatic ring CL Or a monovalent organic group having the aliphatic ring CS, or a monovalent organic group having the aliphatic ring CP,
R ^c2 and R ^c3 combine to form the aliphatic ring CP, the aliphatic ring CH, the aliphatic ring CL, the aliphatic ring CS, or the aliphatic ring CP. )
Mercapto compounds represented by