TW202234152A - Chemically amplified positive-type photosensitive composition, photosensitive dry film, method of manufacturing patterned resist film, method of manufacturing substrate with a template and method of manufacturing plated molded article Provide a chemically amplified positive-type photosensitive composition, that is useful for forming a photosensitive layer with a higher concentration of solid content, good storage stability, capability to form developer-repellent and suppressed swelling properties, and excellent crack resistance. - Google Patents

Abstract

The purpose of this invention is to provide a chemically amplified positive-type photosensitive composition, that is useful for forming a photosensitive layer with a higher concentration of solid content, good storage stability, capability to form developer-repellent and suppressed swelling properties, and excellent crack resistance. The chemically amplified positive photosensitive composition contains a photosensitive dry film of a photosensitive resin layer comprised of the composition. The invention provides a method for manufacturing a patterned resist film using the mentioned chemically amplified positive photosensitive composition and a method for manufacturing a substrate with a template, and a method for manufacturing a plated molded article. The above-mentioned chemically amplified positive-type photosensitive composition comprises: an acid generator (A) that generates an acid upon irradiation with actinic rays or radiation; a resin (B), whose solubility in alkali increases due to the action of acid, contains an acrylic resin (B3), wherein the acrylic resin (B3) contains a specific constituent unit and a solid content concentration is more than 25 mass% and less than 70 mass%.

Description

Chemically amplified positive photosensitive composition, photosensitive dry film, manufacturing method of patterned resist film, manufacturing method of substrate with casting mold, and manufacturing method of plated molding

The present invention relates to a chemically amplified positive photosensitive composition, a photosensitive dry film provided with a photosensitive layer composed of the chemically amplified positive photosensitive composition, and a diagram using the above chemically amplified positive photosensitive composition The manufacturing method of the molded resist film, the manufacturing method of the board|substrate with a casting mold, and the manufacturing method of a plated molding.

At present, photofabrication has become the mainstream of precision microfabrication technology. Photo-etching processing refers to coating the photoresist composition on the surface of the object to be processed to form a photoresist layer, patterning the photoresist layer using photolithography technology, and patterning the photoresist layer ( Photoresist pattern) is used as a mask to perform chemical etching, electrolytic etching, or electroforming mainly by electroplating, etc., to manufacture various precision parts such as semiconductor packages. A general term for the technology.

In addition, in recent years, with the miniaturization of electronic equipment, the high-density mounting technology of semiconductor packages has been advanced, and multi-lead thin-film mounting based on the package, the miniaturization of the package size, and the two-dimensional mounting technology of the flip-chip method are being sought. , The installation density of 3D installation technology is improved. In such a high-density mounting technology, bump electrodes (mounting terminals) such as bumps protruding from the package, or metal posts that connect rewiring extending from peripheral terminals on the wafer to the mounting terminals are used as connection terminals. are arranged on the substrate with high precision.

A photoresist composition is used in the above-mentioned photoetching process, and as such a photoresist composition, a chemically amplified photosensitive composition containing an acid generator is known (see Patent Documents 1, 2, etc.). The chemically amplified photosensitive composition means that an acid is generated from an acid generator by irradiation with radiation (exposure), and the diffusion of the acid is accelerated by heat treatment, thereby causing an acid-catalyzed reaction with respect to the matrix resin in the composition, and making it alkaline Solubility changes.

Such chemically amplified photosensitive compositions are used for forming, for example, bumps, metal pillars, and Cu re-wiring by a plating step, in addition to the formation of insulating films for patterning and etching masks. Dressings, etc. Specifically, a photoresist layer of a desired film thickness is formed on a support such as a metal substrate using a chemically amplified photosensitive composition, exposed through a predetermined mask pattern, and developed to form a selective A photoresist pattern used to remove (peel off) a mold forming a part of a plated molded object. Then, after burying conductors such as copper in the removed portion (non-resist portion) by plating, the surrounding photoresist pattern is removed, whereby bumps, metal pillars, and Cu rewiring can be formed. prior art literature Patent Literature

Patent Document 1: Japanese Patent Application Laid-Open No. 9-176112 Patent Document 2: Japanese Patent Application Laid-Open No. 11-52562

The problem to be solved by the invention

When the photoresist layer (photosensitive layer) formed is thick, etc., the chemically amplified type photosensitive composition whose solid content density|concentration was raised may be used. However, the conventional chemically amplified photosensitive composition has a problem of poor storage stability when the solid content concentration is high. When the storage stability of the chemically amplified photosensitive composition is poor, for example, the viscosity of the chemically amplified photosensitive composition increases with time.

In addition, when a conventional chemically amplified photosensitive composition is used, there is a problem that the resist layer sometimes repels the developer during development. If the developer is repelled, the developer cannot be sufficiently brought into contact with the photosensitive layer, resulting in poor pattern formation. For example, a region where the resist pattern is not formed, or the formed resist pattern is not desired the shape of such a phenomenon.

In addition, when a conventional positive-type chemically amplified photosensitive composition is used, there is a problem that the photoresist layer may be swelled by bringing the exposed photoresist layer into contact with the developer during development. When the resist layer swells during development, the unexposed portion may be dissolved. In addition, when the resist layer swells during development, in the formed resist pattern, wrinkles due to swelling, or floating or deformation due to swelling may be observed in unexposed parts.

In addition, when a conventional positive-type chemically amplified photosensitive composition is used, there is a problem that cracks may be formed in the formed resist pattern. If cracks are formed in the resist pattern, for example, when the resist pattern is used as a mold for forming a plated molding, it becomes difficult to form a plated molding of a desired shape. Therefore, in the chemically amplified photosensitive composition, it is also desired to suppress the occurrence of cracks, that is, it is also desired to be excellent in crack resistance.

The present invention has been made in view of the above-mentioned technical problems, and an object of the present invention is to provide a chemically amplified photosensitive layer that can form a photosensitive layer with high solid content concentration, good storage stability, suppressed repulsion to developing solution and swelling, and excellent crack resistance. Positive type photosensitive composition, photosensitive dry film provided with photosensitive layer composed of the chemically amplified positive type photosensitive composition, patterned resist film using the chemically amplified type positive type photosensitive composition The manufacturing method, the manufacturing method of the board|substrate with a mold, and the manufacturing method of the plated molding. Means for solving the above problems

In order to achieve the above object, the inventors of the present invention have made intensive studies, and as a result, they have found that the above-mentioned technical problems can be solved by the chemically amplified positive type photosensitive composition as follows, and have completed the present invention. The above chemically amplified type positive type photosensitive composition Contains: acid generator (A), which generates acid by irradiation with active light rays or radiation; resin (B), whose solubility in alkali is increased by the action of acid, resin (B) contains acrylic resin (B3), acrylic resin Resin (B3) contains a structural unit represented by the following formula (B3-1), and has a solid content concentration of 25% by mass or more and 70% by mass or less. Specifically, the present invention provides the following technical aspects.

(式(B3-1)中，R ^b01為氫原子或者甲基，R ^b02為單鍵或者連接基，R ^b03為氫原子或者脂肪族烴基，R ^b04以及R ^b05分別獨立地為單鍵或者脂肪族烴基，R ^b04以及R ^b05不同時為單鍵，R ^b06以及R ^b07分別獨立地為氫原子或者脂肪族烴基，R ^b02以及R ^b03中的一方可以與構成丙烯酸樹脂(B3)的主鏈的碳原子鍵結而形成環，R ^b02與R ^b03可以鍵結而形成環，R ^b02與R ^b05可以鍵結而形成環，R ^b06與R ^b07可以鍵結而形成環)。 固體成分濃度為25質量%以上70質量%以下。 A first aspect of the present invention is a chemically amplified positive photosensitive composition comprising: an acid generator (A) that generates an acid by irradiation with actinic rays or radiation; and a resin (B) that has solubility in alkali due to The action of the acid increases, the resin (B) contains the acrylic resin (B3), and the acrylic resin (B3) contains the structural unit represented by the following formula (B3-1),

(In formula (B3-1), R ^b01 is a hydrogen atom or a methyl group, R ^b02 is a single bond or a linking group, R ^b03 is a hydrogen atom or an aliphatic hydrocarbon group, R ^b04 and R ^b05 are each independently a single bond or aliphatic aliphatic hydrocarbon group, R ^b04 and R ^b05 are not single bonds at the same time, R ^b06 and R ^b07 are each independently a hydrogen atom or an aliphatic hydrocarbon group, and one of R ^b02 and R ^b03 may be combined with the main chain of the acrylic resin (B3). Carbon atoms are bonded to form a ring, R ^b02 and R ^b03 may be bonded to form a ring, R ^b02 and R ^b05 may be bonded to form a ring, and R ^b06 and R ^b07 may be bonded to form a ring). The solid content concentration is 25 mass % or more and 70 mass % or less.

A second aspect of the present invention is a photosensitive dry film comprising a base film and a photosensitive layer formed on the surface of the base film, wherein the photosensitive layer is composed of the chemically amplified positive-type photosensitive composition of the first aspect .

A third aspect of the present invention is a method for manufacturing a patterned resist film, comprising: In the lamination step, a photosensitive layer composed of the chemically amplified positive photosensitive composition of the first aspect is laminated on the substrate; an exposing step of selectively irradiating the photosensitive layer with active light rays or radiation; and In the developing step, the exposed photosensitive layer is developed.

A fourth aspect of the present invention is a method for manufacturing a substrate with a mold, comprising: In the lamination step, a photosensitive layer composed of the chemically amplified positive-type photosensitive composition of the first aspect is laminated on a substrate having a metal surface; an exposing step of selectively irradiating the photosensitive layer with active light rays or radiation; and In the development step, the exposed photosensitive layer is developed to prepare a mold for forming a plated molded object.

A fifth aspect of the present invention is a method for producing a plated molded article, comprising forming a plated molded article in the mold by applying plating to a substrate with a mold produced by the method for producing a substrate with a mold of the fourth aspect. A step of. Invention effect

According to the present invention, it is possible to provide a chemically amplified positive-type photosensitive composition capable of forming a photosensitive layer with high solid content concentration, good storage stability, suppressed repellency to developer and swelling, and excellent crack resistance, and having A photosensitive dry film of a photosensitive layer composed of the chemically amplified positive photosensitive composition, a method for producing a patterned resist film using the chemically amplified positive photosensitive composition, and a substrate with a casting mold A manufacturing method and a manufacturing method of a plated molded object. Detailed ways

"Chemical Amplification Type Positive Photosensitive Composition" The chemically amplified positive photosensitive composition (hereinafter also referred to as photosensitive composition) contains an acid generator (A) (hereinafter also referred to as acid generator (A)) that generates acid by irradiation with actinic rays or radiation (hereinafter also referred to as acid generator (A)), Resin (B) (hereinafter also referred to as resin (B)) whose solubility with respect to an alkali is increased by the action of an acid. Moreover, resin (B) contains acrylic resin (B3), and acrylic resin (B3) contains the structural unit represented by following formula (B3-1). The photosensitive resin composition may contain components such as an acid diffusion inhibitor (C), an alkali-soluble resin (D), a sulfur-containing compound (E), a dye (F), and an organic solvent (S) as needed. In addition, the solid content concentration of the chemically amplified positive photosensitive composition is 25 mass % or more and 70 mass % or less. When the solid content concentration is within this range, it is easy to form a thick photosensitive layer. The solid content concentration of the photosensitive composition may be 30 mass % or more and 60 mass % or less, or 40 mass % or more and 50 mass % or less. In addition, the solid content means components other than the organic solvent (S) and water.

Hereinafter, the essential or optional components contained in the photosensitive composition and the manufacturing method of the photosensitive composition will be described.

<acid generator (A)> The acid generator (A) is a compound that generates an acid by irradiation with actinic rays or radiation, and is not particularly limited as long as it is a compound that generates an acid directly or indirectly by light. As an acid generator (A), the acid generator of the 1st - 5th aspect demonstrated below is preferable. Hereinafter, the preferred aspect in the acid generator (A) preferably used in the positive photosensitive composition will be described as the first to fifth aspects.

As a 1st aspect in an acid generator (A), the compound represented by following formula (a1) is mentioned.

In the above formula (a1), X ^1a represents a sulfur atom or an iodine atom with a valence g, and g is 1 or 2. h represents the number of repeating units of the structure in parentheses. R ^1a is an organic group bonded to X ^1a , and represents 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, An alkenyl group having 2 to 30 carbon atoms or an alkynyl group having 2 to 30 carbon atoms, R ^1a may be selected from an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, and an alkoxycarbonyl group , aryloxycarbonyl, arylthiocarbonyl, aryloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl At least one kind of substitution selected from the group consisting of an acyl group, an arylsulfonyl group, an alkyleneoxy group, an amino group, a cyano group, a nitro group, and a halogen group. The number of R ^1a is g+h(g-1)+1, and R ^1a may be the same or different from each other. In addition, two or more R ^1a may be directly bonded to each other or via -O-, -S-, -SO-, -SO ₂ -, -NH-, -NR ^2a -, -CO-, -COO-, - CONH-, an alkylene group or a phenylene group having 1 or more carbon atoms and 3 or less carbon atoms are bonded to form a ring structure including X ^1a . 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 represents an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a heterocyclic compound having 8 to 20 carbon atoms. Divalent group, X ^4a can be selected from an alkyl group with 1 to 8 carbon atoms, an alkoxy group with 1 to 8 carbon atoms, an aryl group with 6 to 10 carbon atoms, a hydroxyl group, a cyano group , each group of nitro, and at least one selected from the group consisting of halogen. X ^5a represents -O-, -S-, -SO-, -SO ₂ -, -NH-, -NR ^2a -, -CO-, -COO-, -CONH-, or those having 1 or more carbon atoms and 3 or less. Alkylene or phenylene. 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 fluoroalkyl 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 hydrogen atoms are substituted with fluorine atoms. j represents the number, and is an integer of 1 or more and 5 or less. The j pieces of R ^3a may be the same or different, respectively.

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

Examples of the onium ion in the compound represented by the above formula (a1) include triphenyl perionium, tris-p-tolyl perionium, 4-(phenylthio)phenyldiphenyl perionium, bis[4-(diphenyl) peryl)phenyl] sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]peryl}phenyl]sulfide, bis{4-[bis(4-fluorobenzene) base) peryl] phenyl} sulfide, 4-(4-benzyl-2-chlorophenylthio) phenyl bis(4-fluorophenyl) peri, 7-isopropyl-9-oxo -10-thio-9,10-dihydroanthracene-2-yl di-p-tolyl perionium, 7-isopropyl-9-oxo-10-thio-9,10-dihydroanthracene-2-yl Diphenyl perionyl, 2-[(diphenyl) peryl] thioxanthone, 4-[4-(4-tert-butylbenzyl) phenylthio] phenyl di-p-tolyl perium, 4- (4-benzyl phenylthio) phenyl diphenyl strontium, diphenyl benzyl sulfamethazine, 4-hydroxyphenylmethyl benzyl sulfite, 2-naphthylmethyl (1-ethoxy) Carbonyl) ethyl strontium, 4-hydroxyphenylmethylbenzyl sulfamethazine, phenyl[4-(4-biphenylthio)phenyl]4-biphenylsulfanium, phenyl[4-(4 -Biphenylthio)phenyl]3-biphenylthio, [4-(4-acetylphenylthio)phenyl]diphenylthio, octadecylmethylbenzylmethyl, two Phenyl iodonium, di-p-tolyl iodonium, bis(4-dodecylphenyl) iodonium, bis(4-methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyl iodonium, bis(4-decyloxy)phenyl iodonium, 4-(2-hydroxytetradecyloxy)phenylphenyl iodonium, 4-isopropylphenyl(p-tolyl) iodonium or 4-isobutylphenyl (p-tolyl) iodonium, etc.

Among the onium ions in the compound represented by the above formula (a1), preferable examples of the onium ions include perium ions represented by the following formula (a19).

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

Specific examples of the pericium ion represented by the above formula (a19) include 4-(phenylthio)phenyldiphenyl perionium and 4-(4-benzyl-2-chlorophenylthio)benzene bis(4-fluorophenyl) peri Phenyl pericynium, phenyl[4-(4-biphenylthio)phenyl]3-biphenyl pericy [4-(p-Terphenylthio)phenyl]diphenylperylium.

In the fluoroalkyl fluorophosphoric acid anion represented by the above formula (a17), R ^3a represents an alkyl group substituted with a fluorine atom, and the preferable number of carbon atoms is 1 or more and 8 or less, and the more preferable number of carbon atoms is 1 or more and 4 or less. Specific examples of the alkyl group include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl. Chain alkyl; also cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and other cycloalkyl groups, etc., the ratio of the hydrogen atom of the alkyl group to be replaced by a fluorine atom is usually more than 80%, preferably more than 90%, More preferably, it is 100%. When the substitution rate of fluorine atoms is less than 80%, the acid strength of the onium fluoroalkyl fluorophosphate represented by the above formula (a1) decreases.

Particularly preferred R ^3a is a linear or branched perfluoroalkyl group having 1 or more carbon atoms and 4 or less carbon atoms and a substitution rate of fluorine atoms of 100%. Specific examples 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 . The number j of R ^3a is an integer of 1 or more and 5 or less, preferably 2 or more and 4 or less, and particularly preferably 2 or 3.

Specific examples of preferable fluoroalkyl fluorophosphate anions include [(CF ₃ CF ₂ ) ₂ PF ₄ ] ^- , [(CF ₃ CF ₂ ) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ^- , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ^- , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ^- , [(CF ₃ CF ₂ CF ₂ CF ₂ ) ₂ PF ₄ ] ^- or [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , among them, [(CF ₃ CF ₂ ) ₃ PF ₃ ] ^- and [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] are particularly preferred ^- , [((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 ] ⁻ .

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

As a second aspect in the acid generator (A), 2,4-bis(trichloromethyl)-6-pipronyl-1,3,5-triazine, 2,4-bis(trichloromethyl), Chloromethyl)-6-[2-(2-furyl)ethenyl]s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methyl-2-furyl ) vinyl]s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-ethyl-2-furyl)vinyl]s-triazine, 2,4-bis(trichloromethyl) Chloromethyl)-6-[2-(5-propyl-2-furyl)vinyl]s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5- Dimethoxyphenyl)vinyl]s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-diethoxyphenyl)vinyl]s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-dipropoxyphenyl)vinyl]s-triazine, 2,4-bis(trichloromethyl)-6- [2-(3-Methoxy-5-ethoxyphenyl)vinyl]s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3-methoxy-5 -Propoxyphenyl)vinyl]s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-methylenedioxyphenyl)vinyl]s-triazine oxazine, 2,4-bis(trichloromethyl)-6-(3,4-methylenedioxyphenyl)s-triazine, 2,4-bis-trichloromethyl-6-(3- bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis- Trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy) ) styrylphenyl-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)- Naphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(2-furyl)ethenyl]-4,6-bis(trichloromethyl) base)-1,3,5-triazine, 2-[2-(5-methyl-2-furyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5- Triazine, 2-[2-(3,5-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2- (3,4-Dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-methylenedioxy phenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, tris(1,3-dibromopropyl)-1,3,5-triazine, tris(2, Halogen-containing triazine compounds such as 3-dibromopropyl)-1,3,5-triazine and triazine compounds represented by the following formula (a3) such as tris(2,3-dibromopropyl)isocyanurate Halogenated triazine compounds.

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

Moreover, as an aspect in the acid generator (A), α-(p-toluenesulfonyloxyimino)-phenylacetonitrile, α-(benzenesulfonyloxyimino)-2, 4-Dichlorophenylacetonitrile, α-(benzenesulfonyloxyimino)-2,6-dichlorophenylacetonitrile, α-(2-chlorobenzenesulfonyloxyimino)-4-methyl Oxyphenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, and a compound represented by the following formula (a4) containing an oxime sulfonate group.

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

In the above formula (a4), examples of the aromatic group include aryl groups such as phenyl and naphthyl groups, and heteroaryl groups such as furyl groups and thienyl groups. These may have one or more appropriate substituents on the ring, for example, a halogen atom, an alkyl group, an alkoxy group, a nitro group, and the like. In addition, 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 group and R ^13a is an alkyl group having 1 to 4 carbon atoms is preferable.

As the acid generator represented by the above formula (a4), when n=1, R ^12a is any one of a phenyl group, a methylphenyl group, and a methoxyphenyl group, and R ^13a is a methyl group. The compound, specifically, α-(methylsulfonyloxyimino)-1-phenylacetonitrile, α-(methylsulfonyloxyimino)-1-(p-methylbenzene base) acetonitrile, α-(methylsulfonyloxyimino)-1-(p-methoxyphenyl)acetonitrile, [2-(propylsulfonyloxyimino)-2,3-di Hydroxythiophene-3-ylidene](o-tolyl)acetonitrile, etc. When n=2, as an acid generator represented by the said formula (a4), the acid generator represented by the following formula is specifically mentioned.

Moreover, as a 4th aspect in an acid generator (A), the onium salt which has a naphthalene ring in a cation part is mentioned. The "having a naphthalene ring" means having a structure derived from naphthalene, and means having a structure having at least two rings, and their aromaticity is maintained. The naphthalene ring may have substituents such as a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, and a linear or branched alkoxy group having 1 to 6 carbon atoms. . Although the structure derived from the naphthalene ring may be a monovalent group (free valence of 1) or a divalent group (free valence of 2) or more, it is desirably a monovalent group (wherein the above-mentioned substitution is removed in this case) free atomic valences are counted). The number of naphthalene rings is preferably 1 or more and 3 or less.

As a cation part of such an onium salt which has a naphthalene ring in a cation part, the structure represented by 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 represent a linear or branched chain having 1 to 6 carbon atoms. An alkyl group, an optionally substituted 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 other two are independently a linear or branched subgroup having 1 to 6 carbon atoms. Alkyl groups may be bonded to their ends 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 straight chain having 1 to 6 carbon atoms or less. In the chain or branched alkyl group, 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 from each other. Furthermore, in the case where a plurality of R ^18a are present, they may be the same or different from each other.

From the viewpoint of the stability of the compound, the number of groups represented by the above formula (a6) in R ^14a , R ^15a , and R ^16a is preferably one, and the rest are straight groups having 1 to 6 carbon atoms. Chained or branched alkylene groups may be cyclically bonded to their terminals. In this case, the above-mentioned two alkylene groups include a sulfur atom and constitute a three- to nine-membered ring. 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 carbon atom which comprises an alkylene group forms a carbonyl group), a hydroxyl group, etc. are mentioned.

In addition, as the substituent which the phenyl group may have, a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, a linear or branched chain alkyl, etc.

As a structure suitable for these cation moieties, the structure represented by following formula (a7), (a8), etc. are mentioned, and the structure represented by following formula (a8) is especially preferable.

Such a cation moiety may be an iodonium salt or a peryllium salt, but is desirably a peryllium salt from the viewpoint of acid production efficiency and the like.

Therefore, as the anion part of the onium salt which has a naphthalene ring in a cation part preferably an anion which can form a pernium salt.

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

The alkyl group in the fluoroalkylsulfonic acid ion may be a straight-chain, branched-chain or cyclic alkyl group having 1 to 20 carbon atoms, and is preferred from the perspective of the volume of the generated acid and its diffusion distance. The number of carbon atoms is 1 or more and 10 or less. In particular, branched or cyclic alkyl groups are preferred because the diffusion distance is short. Moreover, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, etc. can be mentioned as a preferable group from the point which can synthesize|combine inexpensively.

The aryl group in the arylsulfonic acid ion is an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group which may be substituted or unsubstituted with an alkyl group or a halogen atom. In particular, an aryl group having 6 or more and 10 or less carbon atoms is preferable from the viewpoint of being able to synthesize at low cost. Specific examples of preferable aryl groups include a phenyl group, a tosyl group, an ethylphenyl group, a naphthyl group, a methylnaphthyl group, and the like.

In the above-mentioned fluoroalkylsulfonic acid ion or arylsulfonic acid ion, when a part or all of hydrogen atoms are fluorinated, the fluorination rate is preferably 10% or more and 100% or less, more preferably 50% or more and 100%. % or less, especially those obtained by substituting all hydrogen atoms with fluorine atoms, are preferred because the strength of the acid increases. Specific examples of such substances include trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctanesulfonate, perfluorobenzenesulfonate, and the like.

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

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

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

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

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

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

In addition, 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 fluorine atoms, the stronger the strength of the acid, which is preferable. The ratio of fluorine atoms in the alkylene group or the alkyl group, that is, the fluorination rate is preferably 70% or more and 100% or less, more preferably 90% or more and 100% or less, and most preferably all hydrogen atoms are replaced by fluorine atoms The resulting perfluoroalkylene or perfluoroalkyl.

The compounds represented by the following formulae (a15) and (a16) are exemplified as such preferred compounds of the onium salt having a naphthalene ring in the cation part.

In addition, as the fifth aspect in the acid generator (A), bis(p-toluenesulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, Bis(cyclohexylsulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane and other bissulfonyldiazomethanes; 2-nitrobenzyl p-toluenesulfonate , 2,6-dinitrobenzyl p-toluenesulfonate, nitrobenzyl toluenesulfonate, dinitrobenzyl toluenesulfonate, nitrobenzyl sulfonate, nitrobenzyl carbonate, dinitrobenzyl carbonate Nitrobenzyl derivatives such as esters; pyrogallol trimesylate, pyrogallol trimesylate, benzyl tosylate, benzyl sulfonate, N-methylsulfonyloxysuccinimide Amines, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyloxymaleimide, N-methylsulfonyloxyphthalimide and other sulfonic acid esters class; N-(trifluoromethylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)-1,8-naphthalimide, N-(trifluoromethylsulfonyloxy)-1,8-naphthalimide, N-(trifluoromethylsulfonyloxy)-1,8-naphthalimide Fluoromethylsulfonyloxy)-4-butyl-1,8-naphthalimide and other trifluoromethanesulfonates; diphenyliodonium hexafluorophosphate, (4-methoxybenzene base) phenyl iodonium triflate, bis(p-tert-butylphenyl) iodonium trifluoromethanesulfonate, triphenyl perylene hexafluorophosphate, (4-methoxyphenyl) bis Onium salts such as phenyl perylene trifluoromethanesulfonate, (p-tert-butylphenyl)diphenyl perylene trifluoromethanesulfonate; benzoin toluenesulfonate, α-methylbenzoin toluenesulfonate Benzoin tosylate such as acid esters; other diphenyl iodonium salts, triphenyl peronium salts, phenyl diazonium salts, benzyl carbonate, etc.

(式(a21)中，R ^22a為1價的有機基，R ^23a、R ^24a、R ^25a以及R ^26a分別獨立地為氫原子或者1價的有機基，R ^23a與R ^24a、R ^24a與R ^25a或者R ^25a與R ^26a可以分別相互鍵結而形成環)。 The acid generator (A) is also preferably a naphthene acid derivative represented by the following formula (a21).

(In formula (a21), R ^22a is a monovalent organic group, R ^23a , R ^24a , R ^25a and R ^26a are each independently a hydrogen atom or a monovalent organic group, R ^23a and R ^24a , R ^24a and R ^25a or R ^25a and R ^26a may each be bonded to each other to form a ring).

The organic group as R ^22a is not particularly limited in the range that does not inhibit the object of the present invention. The organic group may be a hydrocarbon group, or may contain hetero atoms such as O, N, S, P, and a halogen atom. In addition, the structure of the organic group may be linear, branched, cyclic, or a combination of these structures.

(式(a21a)中，Y ¹為單鍵或者碳原子數為1以上4以下的烷二基。R ^27a以及R ^28a分別為可以被鹵素原子取代的碳原子數為2以上6以下的烷二基或者可以被鹵素原子取代的碳原子數為6以上20以下的亞芳基。R ^29a為可以被鹵素原子取代的碳原子數為1以上18以下的烷基、碳原子數為3以上12以下的脂環式烴基、可以被鹵素原子取代的碳原子數為6以上20以下的芳基、可以被鹵素原子取代的碳原子數為7以上20以下的芳烷基。a以及b分別為0或者1，a以及b中的至少一個為1)。 Examples of the organic group suitable for R ^22a include aliphatic hydrocarbon groups with 1 to 18 carbon atoms which may be substituted by halogen atoms and/or alkylthio groups, and 6 or more and 20 or less carbon atoms which may have substituents. aryl group, optionally substituted aralkyl group having 7 to 20 carbon atoms, optionally substituted alkylaryl group having 7 to 20 carbon atoms, camphor-10-yl, and the following formula The base represented by (a21a).

(In formula (a21a), Y ¹ is a single bond or an alkanediyl group having 1 or more carbon atoms and 4 or less. R ^27a and R ^28a are respectively alkanediyl group having 2 or more carbon atoms and 6 or less carbon atoms which may be substituted by a halogen atom. group or an arylene group having 6 to 20 carbon atoms which may be substituted by a halogen atom. R ^29a is an alkyl group having 1 to 18 or less carbon atoms that may be substituted by a halogen atom, and 3 to 12 or less carbon atoms alicyclic hydrocarbon group, aryl group with 6 to 20 carbon atoms which may be substituted by halogen atoms, aralkyl group with 7 to 20 or less carbon atoms which may be substituted by halogen atoms. a and b are respectively 0 or 1, at least one of a and b is 1).

When the organic group as R ^22a has a halogen atom as a substituent, the halogen atom may, for example, be a chlorine atom, a bromine atom, an iodine atom or a fluorine atom.

When the organic group as R ^22a is an alkyl group having 1 or more and 18 or less carbon atoms substituted with an alkylthio group, the alkylthio group preferably has 1 or more and 18 or less carbon atoms. Examples of the alkylthio group having 1 to 18 carbon atoms include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, sec-butylthio, tert-butylthio, Isobutylthio, n-pentylthio, isopentylthio, tert-amylthio, n-hexylthio, n-heptylthio, isoheptylthio, tert-heptylthio, n-octylthio, isooctylthio, tertiary Octylthio, 2-ethylhexylthio, n-nonylthio, n-decylthio, n-undecylthio, n-dodecylthio, n-tridecylthio, n-tetradecylthio, n-pentadecylthio, n-hexadecylthio, n-heptadecylthio and n-octadecylthio.

When the organic group as R ^22a is an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted with a halogen atom and/or an alkylthio group, the aliphatic hydrocarbon group may contain an unsaturated double bond. In addition, the structure of the aliphatic hydrocarbon group is not particularly limited, and may be linear, branched, cyclic, or a combination of these structures.

Preferable examples in the case where the organic group as R ^22a is an alkenyl group include an allyl group and a 2-methyl-2-propenyl group.

Preferred examples when the organic group as R ^22a is an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, and isobutyl. base, n-pentyl, isopentyl, tert-amyl, n-hexyl, n-hexane-2-yl, n-hexane-3-yl, n-heptyl, n-heptan-2-yl, n-heptan-3-yl , isoheptyl, tert-heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, n-nonyl, isononyl, n-decyl, n-undecyl, n-dodecyl , n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl and n-octadecyl.

When the organic group as R ^22a is an alicyclic hydrocarbon group, examples of the alicyclic hydrocarbon constituting the main skeleton of the alicyclic hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, and cyclohexane. alkane, cycloheptane, cyclooctane, cyclodecane, bicyclo[2.1.1]hexane, bicyclo[2.2.1]heptane, bicyclo[3.2.1]octane, bicyclo[2.2.2]octane, and Adamantane. The alicyclic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from these alicyclic hydrocarbons.

Preferable examples when the organic group as R ^22a is an aliphatic hydrocarbon group substituted with a halogen atom include trifluoromethyl, pentafluoroethyl, 2-chloroethyl, and 2-bromoethyl base, heptafluoro-n-propyl, 3-bromopropyl, nonafluoro-n-butyl, tridecafluoro-n-hexyl, heptafluoro-n-octyl, 2,2,2-trifluoroethyl, 1,1-difluoro Ethyl, 1,1-difluoro-n-propyl, 1,1,2,2-tetrafluoro-n-propyl, 3,3,3-trifluoro-n-propyl, 2,2,3,3, 3-Pentafluoro-n-propyl, 2-norbornyl-1,1-difluoroethyl, 2-norbornyltetrafluoroethyl and 3-adamantyl-1,1,2,2-tetrafluoro propyl.

Preferred examples in the case where the organic group as R ^22a is an aliphatic hydrocarbon group substituted with an alkylthio group include 2-methylthioethyl, 4-methylthio-n-butyl, and 2-methylthioethyl. - n-Butylthioethyl.

As a preferable example in the case where the organic group as R ^22a is an aliphatic hydrocarbon group substituted with a halogen atom and an alkylthio group, 3-methylthio-1,1,2,2-tetrafluoro can be mentioned. - n-propyl.

Preferred examples when the organic group as R ^22a is an aryl group include a phenyl group, a naphthyl group, and a biphenyl group.

Preferred examples when the organic group as R ^22a is an aryl group substituted with a halogen atom include pentafluorophenyl, chlorophenyl, dichlorophenyl, and trichlorophenyl.

Preferred examples when the organic group as R ^22a is an aryl group substituted with an alkylthio group include 4-methylthiophenyl, 4-n-butylthiophenyl, 4-n-butylthiophenyl Octylthiophenyl, 4-n-dodecylthiophenyl.

1,2,5,6-tetrafluoro-4-methylthiobenzene is mentioned as a preferable example in the case where the organic group as R ^22a is an aryl group substituted with a halogen atom and an alkylthio group base, 1,2,5,6-tetrafluoro-4-n-butylthiophenyl, 1,2,5,6-tetrafluoro-4-n-dodecylthiophenyl.

Preferred examples when the organic group as R ^22a is an aralkyl group include benzyl, phenethyl, 2-phenylpropan-2-yl, diphenylmethyl, and triphenylmethyl. base.

Preferred examples in the case where the organic group as R ^22a is an aralkyl group substituted with a halogen atom include pentafluorophenylmethyl, phenyldifluoromethyl, and 2-phenyltetrafluoro Ethyl, 2-(pentafluorophenyl)ethyl.

A preferred example in the case where the organic group as R ^22a is an aralkyl group substituted with an alkylthio group is a p-methylthiobenzyl group.

2-( ^2,3,5,6 -tetrafluoro-4- 2-(2,3,5,6-tetrafluoro-4- methylthiophenyl)ethyl.

Preferred examples when the organic group as R ^22a is an alkylaryl group include 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, and 3-isopropyl. Phenyl, 4-isopropylphenyl, 4-n-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4-n-hexylphenyl, 4-cyclohexylphenyl, 4 -n-Octylphenyl, 4-(2-ethyl-n-hexyl)phenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl , 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-di-tert-butylphenyl, 2,5-di-tert-butyl Phenyl, 2,6-di-tert-butylphenyl, 2,4-di-tert-amylphenyl, 2,5-di-tert-amylphenyl, 2,5-di-tert-octylphenyl, 2-ring Hexylphenyl, 3-cyclohexylphenyl, 4-cyclohexylphenyl, 2,4,5-trimethylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triiso Propylphenyl.

The group represented by the formula (a21a) is an ether group-containing group. In formula (a21a), as the alkanediyl group represented by Y ¹ and having 1 or more carbon atoms and 4 or less, methylene, ethane-1,2-diyl, ethane-1,1-diyl may, for example, be mentioned. base, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, butane-1,3-diyl, butane-2,3-diyl, Butane-1,2-diyl. In the formula (a21a), as the alkanediyl group represented by R ^27a or R ^28a and having 2 or more carbon atoms and 6 or less, ethane-1,2-diyl, propane-1,3-diyl, Propane-1,2-diyl, butane-1,4-diyl, butane-1,3-diyl, butane-2,3-diyl, butane-1,2-diyl, pentane Alkane-1,5-diyl, pentane-1,3-diyl, pentane-1,4-diyl, pentane-2,3-diyl, hexane-1,6-diyl, hexane Alkane-1,2-diyl, Hexane-1,3-diyl, Hexane-1,4-diyl, Hexane-2,5-diyl, Hexane-2,4-diyl, Hexane Alkane-3,4-diyl.

In the formula (a21a), when R ^27a or R ^28a is an alkanediyl group having 2 or more carbon atoms and 6 or less carbon atoms, which is substituted by a halogen atom, the halogen atom may, for example, be a chlorine atom, a bromine atom, or an iodine atom. atoms and fluorine atoms. Examples of the alkanediyl group substituted with a halogen atom include tetrafluoroethane-1,2-diyl, 1,1-difluoroethane-1,2-diyl, and 1-fluoroethane -1,2-diyl, 1,2-difluoroethane-1,2-diyl, hexafluoropropane-1,3-diyl, 1,1,2,2,-tetrafluoropropane-1, 3-diyl, 1,1,2,2,-tetrafluoropentane-1,5-diyl.

In formula (a21a), as an example when R ^27a or R ^28a is an arylene group, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 2,5-Dimethyl-1,4-phenylene, biphenyl-4,4'-diyl, diphenylmethane-4,4'-diyl, 2,2,-diphenylpropane -4,4'-diyl, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6 -diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl.

In the formula (a21a), when R ^27a or R ^28a is an arylene group substituted with a halogen atom, the halogen atom may, for example, be a chlorine atom, a bromine atom, an iodine atom, or a fluorine atom. As an example of the arylene group substituted with a halogen atom, 2,3,5,6- tetrafluoro- 1,4- phenylene group is mentioned.

In formula (a21a), as the alkyl group having 1 to 18 carbon atoms which may have a branch represented by R ^29a , methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, isopentyl, tert-amyl, n-hexyl, n-hexane-2-yl, n-hexane-3-yl, n-heptyl, n-heptane-2 -yl, n-heptane-3-yl, isoheptyl, tert-heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, n-nonyl, isononyl, n-decyl, n- Undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl.

In the formula (a21a), when R ^29a is an alkyl group having 1 to 18 carbon atoms substituted with a halogen atom, the halogen atom includes a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. . Examples of the alkyl group substituted with a halogen atom include trifluoromethyl, pentafluoroethyl, heptafluoro-n-propyl, nonafluoro-n-butyl, tridecafluoro-n-hexyl, and heptadecafluoro-n-octyl. , 2,2,2-trifluoroethyl, 1,1-difluoroethyl, 1,1-difluoro-n-propyl, 1,1,2,2-tetrafluoro-n-propyl, 3,3 ,3-trifluoro-n-propyl, 2,2,3,3,3-pentafluoro-n-propyl, 1,1,2,2-tetrafluorotetradecyl.

In formula (a21a), when R ^29a is an alicyclic hydrocarbon group having 3 to 12 carbon atoms, examples of the alicyclic hydrocarbon constituting the main skeleton of the alicyclic hydrocarbon group include cyclopropane. , cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, bicyclo[2.1.1]hexane, bicyclo[2.2.1]heptane, bicyclo[3.2.1]octane alkane, bicyclo[2.2.2]octane, and adamantane. The alicyclic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from these alicyclic hydrocarbons.

In the formula (a21a), when R ^29a is an aryl group, a halogenated aryl group, an aralkyl group, or a halogenated aralkyl group, preferred examples of these groups are the same as when R ^22a is these groups.

Among the groups represented by the formula (a21a), a preferable group is a group in which a carbon atom bonded to a sulfur atom in the group represented by R ^27a is substituted with a fluorine atom. The number of carbon atoms of the above-mentioned preferable group is preferably 2 or more and 18 or less.

R ^22a is preferably a perfluoroalkyl group having 1 or more and 8 or less carbon atoms. Furthermore, camphor-10-yl is also preferable as R ^22a from the viewpoint of easily forming a high-definition resist pattern.

In formula (a21), R ^23a to R ^26a are a hydrogen atom or a monovalent organic group. In addition, R ^23a and R ^24a , R ^24a and R ^25a , or R ^25a and R ^26a may each be bonded to each other to form a ring. For example, an acenaphthene skeleton can be formed by bonding R ^24a and R ^25a to form a five-membered ring together with a naphthalene ring.

The monovalent organic group is preferably an alkyl group and an alkoxy group having 4 to 18 carbon atoms which may be substituted by an alicyclic hydrocarbon group, a heterocyclyl group or a halogen atom and may have a branched chain; Epoxy group; an alkylthio group having 4 or more and 18 or less carbon atoms which may be substituted by an alicyclic hydrocarbon group, a heterocyclyl group or a halogen atom and which may have a branched chain; a heterocyclic thio group. Moreover, it is also preferable that the methylene group in the arbitrary position which is not adjacent to an oxygen atom of this alkoxy group is substituted by -CO-. Also preferred is a group in which the alkoxy group is interrupted by a -O-CO- bond or a -O-CO-NH- bond. In addition, the left end of the -O-CO- bond and the -O-CO-NH- bond is the side close to the parent nucleus of naphthoic acid in the alkoxy group. Furthermore, an alkylthio group having 4 or more and 18 or less carbon atoms which may be substituted by an alicyclic hydrocarbon group, a heterocyclic group or a halogen atom and which may have a branch is also preferable as R ^23a to R ^26a . The alkylthio group is also preferably a group obtained by substituting a methylene group at any position not adjacent to a sulfur atom in the alkylthio group by -CO-. Also preferred is a group in which the alkylthio group is interrupted by a -O-CO- bond or a -O-CO-NH- bond. In addition, the left end of the -O-CO- bond and the -O-CO-NH- bond is the side close to the naphthoic acid parent nucleus in the alkylthio group.

As R ^23a to R ^26a , preferably R ^23a is an organic group, R ^24a to R ^26a are hydrogen atoms, or R ^24a is an organic group and R ^23a , R ^25a and R ^26a are hydrogen atoms. In addition, all of R ^23a to R ^26a may be hydrogen atoms.

Examples in the case where R ^23a to R ^26a are unsubstituted alkyl groups include n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, isopentyl, tert-amyl, n-hexyl base, n-heptyl, isoheptyl, tert-heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl base, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl.

Examples in the case where R ^23a to R ^26a are unsubstituted alkoxy groups include n-butoxy, sec-butoxy, tert-butoxy, isobutoxy, n-pentoxy, and isopentyloxy base, tert-pentyloxy, n-hexyloxy, n-heptyloxy, isoheptyloxy, tert-heptyloxy, n-octyloxy, isooctyloxy, tert-octyloxy, 2-ethylhexyl, n-nonyloxy base, n-decyloxy, n-undecyloxy, n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, n-hexadecyloxy, n- Heptadecyloxy, n-octadecyloxy.

Examples in the case where R ^23a to R ^26a are unsubstituted alkylthio groups include n-butylthio, sec-butylthio, tert-butylthio, isobutylthio, n-pentylthio, and isopentylthio. base, tert-amylthio, n-hexylthio, n-heptylthio, isoheptylthio, tert-heptylthio, n-octylthio, isooctylthio, tert-octylthio, 2-ethylhexylthio, n- Nonylthio, n-decylthio, n-undecylthio, n-dodecylthio, n-tridecylthio, n-tetradecylthio, n-pentadecylthio, n-hexadecylthio , n-heptadecylthio, n-octadecylthio.

When R ^23a to R ^26a are an alkyl group, an alkoxy group, or an alkylthio group substituted with an alicyclic hydrocarbon group, examples of the alicyclic hydrocarbon constituting the main skeleton of the alicyclic hydrocarbon group include Cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, bicyclo[2.1.1]hexane, bicyclo[2.2.1]heptane, bicyclo[3.2.1 ]octane, bicyclo[2.2.2]octane, and adamantane. The alicyclic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from these alicyclic hydrocarbons.

When R ^23a to R ^26a are an alkyl group substituted with a heterocyclic group, an alkoxy group, or an alkylthio group, or when R ^23a to R ^26a are a heterocyclic group, they are used as a constituent heterocyclic group. Alternatively, examples of the heterocyclic ring of the main skeleton of the heterocyclyloxy group include pyrrole, thiophene, furan, pyran, thiopyran, imidazole, pyrazole, thiazole, isothiazole, oxazole, isoxazole, pyridine, pyridine oxazine, pyrimidine, pyridazine, pyrrolidine, pyrazolidine, imidazolidine, isoxazolidine, isothiazolidine, oxidine, oxazine, morpholine, thiomorpholine, chroman, thiochroman, isochroman, Isothiochroman, indoline, isoindoline, 4-indolizine, indolizine, indole, indazole, purine, quinazine, isoquinoline, quinoline, naphthyridine, phthalazine, quinoxaline , quinazoline, cinnoline, pteridine, acridine, pyridine, phenanthroline, quinazoline, quinoline, phenazine, anthyridine, thiadiazole, oxadiazole, triazine, triazole , tetrazole, benzimidazole, benzoxazole, benzothiazole, benzothiadiazole, benzoflurane, naphthimidazole, benzotriazole, tetraazaindene. Moreover, the saturated heterocyclic ring obtained by hydrogenating the ring which has a conjugated bond among these heterocyclic rings is also preferable. The heterocyclic group substituted for the alkyl group, the alkoxy group, or the alkylthio group, or the heterocyclic group contained in the heterocyclic oxy group is preferably a group obtained by removing one hydrogen atom from the above-mentioned heterocyclic ring.

Examples in the case where R ^23a to R ^26a are alkoxy groups containing an alicyclic hydrocarbon group include cyclopentyloxy, methylcyclopentyloxy, cyclohexyloxy, fluorocyclohexyloxy, chlorocyclohexyloxy, cyclohexylmethyloxy, methylcyclohexyloxy, norbornyloxy, ethylcyclohexyloxy, cyclohexylethyloxy, dimethylcyclohexyloxy, methyl Cyclohexylmethyloxy, norbornylmethyloxy, trimethylcyclohexyloxy, 1-cyclohexylbutyloxy, adamantyloxy, menthyloxy, n-butylcyclohexyloxy , tert-butylcyclohexyloxy, bornyloxy, isobornyloxy, decalinyloxy, dicyclopentadienyloxy, 1-cyclohexylpentyloxy, methyladamantyloxy group, adamantylmethyloxy, 4-pentylcyclohexyloxy, cyclohexylcyclohexyloxy, adamantylethyloxy, dimethyladamantyloxy.

As examples in the case where R ^23a to R ^26a are heterocyclicoxy groups, tetrahydrofuranyloxy, furfuryloxy, tetrahydrofurfuryloxy, tetrahydropyranyloxy, butyrolactoneoxy base, indolyloxy.

Examples in the case where R ^23a to R ^26a are alkylthio groups containing an alicyclic hydrocarbon group include cyclopentylthio, cyclohexylthio, cyclohexylmethylthio, norbornylthio, isonor Bornylthio group.

As an example in the case where R ^23a to R ^26a are a heterocyclic thio group, a furfurylthio group and a tetrahydrofuranylthio group may, for example, be mentioned.

2-ketobutyl-1- is an example in the case where R ^23a to R ^26a are groups in which the methylene group at any position not adjacent to the oxygen atom of the alkoxy group is substituted by -CO- Oxy, 2-ketopentyl-1-oxy, 2-ketohexyl-1-oxy, 2-ketoheptyl-1-oxy, 2-ketooctyl-1-oxy, 3-ketobutan yl-1-oxyl, 4-ketopentyl-1-oxyl, 5-ketohexyl-1-oxyl, 6-ketoheptyl-1-oxyl, 7-ketooctyl-1-oxyl, 3-Methyl-2-ketopentan-4-oxy, 2-ketopentan-4-oxy, 2-methyl-2-ketopentan-4-oxy, 3-ketoheptane-5 -oxy, 2-adamantanone-5-oxy.

2-ketobutyl-1- is an example in the case where R ^23a to R ^26a are groups in which a methylene group at any position not adjacent to a sulfur atom of an alkylthio group is substituted by -CO- Sulfanyl, 2-ketopentyl-1-sulfanyl, 2-ketohexyl-1-sulfanyl, 2-ketoheptyl-1-sulfanyl, 2-ketooctyl-1-sulfanyl, 3-ketobutanyl base-1-sulfanyl, 4-ketopentyl-1-sulfanyl, 5-ketohexyl-1-sulfanyl, 6-ketoheptyl-1-sulfanyl, 7-ketooctyl-1-sulfanyl, 3-Methyl-2-ketopentane-4-sulfanyl, 2-ketopentane-4-sulfanyl, 2-methyl-2-ketopentane-4-sulfanyl, 3-ketoheptane-5 -Sulfur group.

Specific examples of the compound represented by the formula (a21) include the following compounds.

The acid generator (A) may be used alone or in combination of two or more. In addition, the content of the acid generator (A) is preferably 0.1 mass % or more and 10 mass % or less, more preferably 0.2 mass % or more and 6 mass % or less, particularly preferably 0.2 mass % or more with respect to the total solid content of the photosensitive composition. Preferably, it is 0.5 mass % or more and 3 mass % or less. By making the usage-amount of an acid generator (A) into the said range, it becomes easy to prepare the photosensitive composition which has favorable sensitivity, is a uniform solution, and is excellent in storage stability.

<Resin (B)> In the photosensitive composition, an acrylic resin (B3) is contained as an essential component as a resin (B) whose solubility to an alkali is increased by the action of an acid. And the acrylic resin (B3) contains the structural unit represented by Formula (B3-1). The photosensitive composition may contain the acrylic resin (B3) and any resin other than the acrylic resin (B3) whose solubility in alkalis is increased by the action of an acid. Among them, the ratio of the mass of the acrylic resin (B3) to the mass of the resin (B) is preferably 50 mass % or more, more preferably 70 mass % or more, further preferably 90 mass % or more, particularly preferably 100 mass % or more quality%. Examples of any resins other than the acrylic resin (B3) whose solubility in alkalis are increased by the action of acids include novolak resins (B1) in which the solubility in alkalis is increased by the action of acids, novolak resins (B1), The solubility of polyhydroxystyrene resin (B2) and the acrylic resin other than acrylic resin (B3) whose solubility is increased by the action of an acid is increased by the action of an acid. Hereinafter, each resin will be specifically described.

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

In the above formula (b1), R ^1b represents an acid-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.

As the acid dissociable dissolution inhibiting group represented by the above R ^1b , a group represented by the following formulae (b2) and (b3), a linear, branched or cyclic group having 1 to 6 carbon atoms is preferable Alkyl, vinyloxyethyl, tetrahydropyranyl, tetrahydrofuranyl or trialkylsilyl.

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 represents a carbon number of A linear, branched or cyclic alkyl group with 1 or more and 10 or less, R ^7b represents a linear, branched or cyclic alkyl group with 1 or more carbon atoms and 6 or less, and o 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 Base et al. Moreover, as said cyclic alkyl group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned.

Here, specific examples of the acid dissociable dissolution inhibiting group represented by the above formula (b2) include methoxyethyl, ethoxyethyl, n-propoxyethyl, isopropoxyethyl, n-propoxyethyl, Butoxyethyl, isobutoxyethyl, tert-butoxyethyl, cyclohexyloxyethyl, methoxypropyl, ethoxypropyl, 1-methoxy-1-methyl- ethyl, 1-ethoxy-1-methylethyl, etc. Moreover, as an acid-dissociable dissolution-inhibiting group represented by the said formula (b3), a t-butoxycarbonyl group, a t-butoxycarbonylmethyl group, etc. are mentioned specifically,. Moreover, as said trialkylsilyl group, the carbon number of each alkyl group, such as a trimethylsilyl group and a tri-tert-butyldimethylsilyl group, is 1 or more and 6 or less, for example.

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

In the above formula (b4), R ^8b represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ^9b represents an acid-dissociative dissolution inhibiting group.

The above-mentioned 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. etc., as a cyclic alkyl group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned.

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

Furthermore, for the purpose of appropriately controlling physical and chemical properties, the polyhydroxystyrene resin (B2) can contain another polymerizable compound as a structural unit. As such a polymerizable compound, a well-known radical polymerizable compound and an anion polymerizable compound are mentioned. In addition, 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-methacryloyloxy ethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid Formic acid and other methacrylic acid derivatives with carboxyl and ester bonds; (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate; ( (Meth) hydroxyalkyl acrylates such as 2-hydroxyethyl meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc.; (meth) phenyl acrylate, benzyl (meth)acrylate, etc. acrylic acid aryl esters; diethyl maleate, dibutyl fumarate and other dicarboxylic acid diesters; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, Vinyl toluene, hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene and other vinyl-containing aromatic compounds; vinyl acetate and other vinyl-containing aliphatic compounds; butadiene, Conjugated dienes such as isoprene; nitrile-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; acrylamide, methacrylonitrile Polymeric compounds containing amide bonds, such as amines, etc.

(式(B3-1)中，R ^b01為氫原子或者甲基，R ^b02為單鍵或者連接基，R ^b03為氫原子或者脂肪族烴基，R ^b04以及R ^b05分別獨立地為單鍵或者脂肪族烴基，R ^b04以及R ^b05不同時為單鍵，R ^b06以及R ^b07分別獨立地為氫原子或者脂肪族烴基，R ^b02以及R ^b03中的一方可以與構成丙烯酸樹脂(B3)的主鏈的碳原子鍵結而形成環，R ^b02與R ^b03可以鍵結而形成環，R ^b02與R ^b05可以鍵結而形成環，R ^b06與R ^b07可以鍵結而形成環)。 [Acrylic resin (B3)] The acrylic resin (B3) which is a resin (B) whose solubility to an alkali is increased by the action of an acid contains a structural unit represented by the following formula (B3-1).

(In formula (B3-1), R ^b01 is a hydrogen atom or a methyl group, R ^b02 is a single bond or a linking group, R ^b03 is a hydrogen atom or an aliphatic hydrocarbon group, R ^b04 and R ^b05 are each independently a single bond or aliphatic aliphatic hydrocarbon group, R ^b04 and R ^b05 are not single bonds at the same time, R ^b06 and R ^b07 are each independently a hydrogen atom or an aliphatic hydrocarbon group, and one of R ^b02 and R ^b03 may be combined with the main chain of the acrylic resin (B3). Carbon atoms are bonded to form a ring, R ^b02 and R ^b03 may be bonded to form a ring, R ^b02 and R ^b05 may be bonded to form a ring, and R ^b06 and R ^b07 may be bonded to form a ring).

In addition, in this specification, "acrylic resin" refers to a resin in which the ratio of the structural unit derived from a monomer having a (meth)acryloyloxy group to all the structural units constituting the resin is 50 mol % Above, preferably 70 mol% or more, more preferably 90 mol% or more. In addition, in this specification, "(meth)acrylic acid" means both "acrylic acid" and "methacrylic acid". "(meth)acrylate" means both "acrylate" and "methacrylate". "(meth)acryloyloxy" means both "acryloyloxy" and "methacryloyloxy".

In formula (B3-1), -COO-, -OCO-, -CONH-, -O-, hydrocarbon group, and combinations thereof can be exemplified as the linking group of R ^b02 . As the hydrocarbon group, an aliphatic hydrocarbon group having 1 to 10 carbon atoms may, for example, be mentioned. R ^b02 is preferably a group in which -COO- and a hydrocarbon group are bonded or -COO-. A group in which -COO- is bonded to a hydrocarbon group may be a bond between a carbon atom of -COO- and a carbon atom constituting the main chain of the acrylic resin (B3), or a carbon atom of a hydrocarbon group may be bonded to a carbon atom constituting the acrylic resin (B3). ) are bonded to the carbon atoms of the main chain.

In formula (B3-1), as the aliphatic hydrocarbon group for R ^b03 , an aliphatic hydrocarbon group having 1 or more and 10 or less carbon atoms may be mentioned. As the aliphatic hydrocarbon group, linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl.

In formula (B3-1), as the aliphatic hydrocarbon group of R ^b04 and R ^b05 , an aliphatic hydrocarbon group having 1 or more and 4 or less carbon atoms may be mentioned. As the aliphatic hydrocarbon group, linear or branched alkylene groups such as methylene, ethane-1,2-diyl, propane-1,3-diyl, propane-1,2-diyl can be exemplified Two bases.

In formula (B3-1), as the aliphatic hydrocarbon group of R ^b06 and R ^b07 , an aliphatic hydrocarbon group having 1 or more and 10 or less carbon atoms may be mentioned. As the aliphatic hydrocarbon group, linear, branched or cyclic alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tertiary Butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclohexyl.

A ring formed by bonding one of R ^b02 and R ^b03 to a carbon atom constituting the main chain of the acrylic resin (B3), a ring formed by bonding R ^b02 and R ^b03 , and a ring formed by bonding R ^b02 and R ^b05 The ring formed by bonding R ^b06 and R ^b07 may, for example, be an aliphatic hydrocarbon ring. The aliphatic hydrocarbon ring may have a monocyclic structure or a polycyclic structure. Examples of the aliphatic hydrocarbon ring include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, and a cyclododecane ring. , Norbornane ring.

(式(B3-2)中，R ^b01、R ^b03、R ^b04、R ^b05、R ^b06以及R ^b07與上述式(B3-1)中的這些相同，R ^b010為單鍵或者烴基，R ^b05與R ^b010可以鍵結而形成環)。 The structural unit represented by the formula (B3-1) is preferably a structural unit represented by the following formula (B3-2).

(In formula (B3-2), R ^b01 , R ^b03 , R ^b04 , R ^b05 , R ^b06 and R ^b07 are the same as those in the above formula (B3-1), R ^b010 is a single bond or a hydrocarbon group, R ^b05 is a R ^b010 may bond to form a ring).

In formula (B3-2), as the hydrocarbon group for R ^b010 , an aliphatic hydrocarbon group having 1 or more and 10 or less carbon atoms is exemplified. As the aliphatic hydrocarbon group, linear or branched alkylene groups such as methylene, ethane-1,2-diyl, propane-1,3-diyl, propane-1,2-diyl can be exemplified Two bases.

In formula (B3-2), preferably, R ^b03 is a hydrogen atom or an alkyl group having 1 to 4 or less carbon atoms, R ^b04 and R ^b05 are each independently a single bond or a methylene group, R ^b06 and R ^{b07 is} each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ^b010 is a methylene group.

(式(B3-3)以及式(B3-4)中，R ^b01、R ^b03、R ^b06、R ^b07以及R ^b010與上述式(B3-2)中的這些相同)。 The structural unit represented by the formula (B3-2) is preferably a structural unit represented by the following formula (B3-3) or formula (B3-4).

(In formula (B3-3) and formula (B3-4), R ^b01 , R ^b03 , R ^b06 , R ^b07 and R ^b010 are the same as those in the above formula (B3-2)).

(式中，R ^b01～R ^b07與上述式(B3-1)中的這些相同)。 The structural unit represented by the formula (B3-1) can be introduced into the acrylic resin (B3) by using, for example, a monomer corresponding to the formula (B3-1), that is, the following compound as a polymerization or copolymerization component.

(In the formula, R ^b01 to R ^b07 are the same as those in the above formula (B3-1)).

(式中，R ^b01與上述式(B3-1)中的R ^b01相同。) As a specific example of the structural unit represented by Formula (B3-1), the following structural unit is mentioned.

(In the formula, R ^b01 is the same as R ^b01 in the above formula (B3-1).)

When the solid content concentration is high, the storage stability is poor, for example, the viscosity of the photosensitive composition tends to change with time. However, as the resin (B), the acrylic resin (B3) containing the structural unit represented by the formula (B3-1) can be used, and the solid content concentration can be in the range of 25 mass % or more and 70 mass % or less. A photosensitive composition having excellent storage stability even if the solid content concentration is high. For example, set the viscosity at the time of measuring the photosensitive composition at 25°C using an E-type viscometer as V1, leave the photosensitive composition at 40°C for 2 weeks, and measure the viscosity after the standing at 25°C using an E-type viscometer. When the viscosity at the time of a photosensitive composition is made into V2, V2/V1 can be made smaller than 1.1. Since the solid content concentration of the photosensitive composition is high, it is easy to form a photosensitive layer with a thick film (eg, 70 μm or more). Therefore, the photosensitive composition can be preferably used for, for example, formation of a plated molded object.

Moreover, the photosensitive layer formed using the said photosensitive composition can suppress the repelling with respect to the developing solution after exposure. Therefore, for example, the developer can be brought into contact with the entire photosensitive layer, and a resist pattern of a desired shape corresponding to a mask or the like can be formed in the entire region where the photosensitive layer is provided.

Moreover, the photosensitive layer formed using the said photosensitive composition can suppress swelling at the time of image development after exposure. Therefore, for example, in the obtained resist pattern, wrinkles due to swelling, dissolution of unexposed parts, and floating or deformation are suppressed.

In addition, the photosensitive layer formed using the above-mentioned photosensitive composition can suppress the occurrence of cracks, that is, is excellent in crack resistance. Therefore, for example, when the obtained resist pattern is used as a mold for forming a plated molding, it becomes easy to form a plated molding of a desired shape.

The amount of the structural unit represented by the formula (B3-1) in the acrylic resin (B3) is not particularly limited, and the ratio of the mass of the structural unit represented by the formula (B3-1) to the mass of the acrylic resin (B3) is preferable It is 5 mass % or more and 50 mass % or less, More preferably, it is 10 mass % or more and 40 mass % or less, More preferably, it is 10 mass % or more and 30 mass % or less.

The acrylic resin (B3) may also contain a structural unit (b-3) derived from an acrylate containing, for example, a -SO ₂ --containing cyclic group or a lactone-containing cyclic group. In this case, when forming a resist pattern, it is easy to form a resist pattern having a preferable cross-sectional shape. However, when it has a -SO ₂ --containing cyclic group or a lactone-containing cyclic group, the storage stability of the photosensitive composition is deteriorated, so it is preferable not to contain -SO ₂ --containing cyclic group and lactone-containing cyclic group Cyclic group, or the content is less.

(-SO ₂ --containing cyclic group) Here, "-SO ₂ --containing cyclic group" means a cyclic group containing a ring containing -SO ₂ - in its ring skeleton, and specifically, -SO ₂ A cyclic group in which the sulfur atom (S) in the cyclic group forms part of the ring skeleton of the cyclic group. In this ring skeleton, the ring containing -SO ₂ - is counted as the first ring, and when there is only this ring, it is called a monocyclic group, and when there are other ring structures, it is called a monocyclic group regardless of its structure. is a polycyclic base. The -SO ₂ --containing cyclic group may be monocyclic or polycyclic.

The -SO ₂ --containing cyclic group is particularly preferably a cyclic group containing -O-SO ₂ - in its ring skeleton, that is, a sulfonic acid containing -OS- in -O-SO ₂ - as a part of the ring skeleton Cyclic radical of the sultone ring.

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

The -SO ₂ --containing cyclic group may be an -SO ₂ --containing aliphatic cyclic group or an -SO ₂ --containing aromatic cyclic group. Preferably, it is an aliphatic cyclic group containing -SO ₂ -.

The -SO ₂ --containing aliphatic cyclic group may, for example, be at least one removed from an aliphatic hydrocarbon ring in which a part of carbon atoms constituting the ring skeleton is substituted with -SO ₂ - or -O-SO ₂ - A base derived from a hydrogen atom. More specifically, a group obtained by removing at least one hydrogen atom from an aliphatic hydrocarbon ring in which -CH ₂ - constituting the ring skeleton is substituted with -SO ₂ -, and -CH ₂ - constituting the ring are exemplified. -CH ₂ - A group obtained by removing at least one hydrogen atom from the aliphatic hydrocarbon ring substituted with -O-SO ₂ -, and the like.

The number of carbon atoms in the alicyclic hydrocarbon ring is preferably 3 or more and 20 or less, and more preferably 3 or more and 12 or less. The alicyclic hydrocarbon ring may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocyclic alkane having 3 or more and 6 or less carbon atoms. As the monocycloalkane, cyclopentane, cyclohexane and the like can be exemplified. The polycyclic alicyclic hydrocarbon ring is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane having 7 or more and 12 or less carbon atoms. Specifically, as the polycyclic alkane, there may be exemplified Examples include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like.

The -SO ₂ --containing cyclic group may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, an oxygen atom (=O), -COOR", -OC(=O)R", a hydroxyalkyl group, a cyano group Wait.

The alkyl group of 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, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, etc. may be mentioned. Among these, a methyl group or an ethyl group is preferable, and a methyl group is especially preferable.

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

As a halogen atom of this substituent, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, and a fluorine atom is preferable.

The halogenated alkyl group of the substituent may, for example, be a group obtained by substituting a part or all of the hydrogen atoms of the above-mentioned alkyl group with the above-mentioned halogen atom.

As the haloalkyl group of the substituent group, a part or all of the hydrogen atoms of the alkyl group exemplified as the alkyl group of the substituent group are substituted with the above-mentioned halogen atom, for example. As the haloalkyl group, a fluoroalkyl group is preferable, and a perfluoroalkyl group is particularly preferable.

R" in the above-mentioned -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 chain alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, particularly preferably 1 or 2.

When R" is a cyclic alkyl group, the carbon number of the cyclic alkyl group is preferably 3 or more and 15 or less, more preferably 4 or more and 12 or less, particularly preferably 5 or more and 10 or less. Specifically For example, it can be exemplified that one or more hydrogen atoms are removed from monocycloalkanes which may be substituted or unsubstituted by fluorine atoms or fluoroalkyl groups, or from polycycloalkanes such as bicycloalkanes, tricycloalkanes, and tetracycloalkanes. derived groups, etc. More specifically, monocycloalkanes such as cyclopentane and cyclohexane, or adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. may be mentioned. A group obtained by removing one or more hydrogen atoms from a polycycloalkane, etc.

The hydroxyalkyl group of the substituent is preferably a hydroxyalkyl group having 1 or more and 6 or less carbon atoms. Specifically, a group in which at least one hydrogen atom of the alkyl group exemplified as the alkyl group of the above-mentioned substituent is substituted with a hydroxyl group is exemplified.

(式中，A’為可以含有氧原子或硫原子的碳原子數為1以上5以下的亞烷基、氧原子或者硫原子，z為0以上2以下的整數，R ^10b為烷基、烷氧基、鹵代烷基、羥基、 -COOR”、-OC(=O)R”、羥基烷基或者氰基，R”為氫原子或者烷基)。 As the -SO ₂ --containing cyclic group, more specifically, groups represented by the following formulae (3-1) to (3-4) can be mentioned.

(in the formula, A' is an alkylene group, an oxygen atom or a sulfur atom having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, z is an integer of 0 to 2 or less, R ^10b is an alkyl group, an alkane oxy, haloalkyl, hydroxy, -COOR", -OC(=O)R", hydroxyalkyl or cyano, R" is a hydrogen atom or an alkyl group).

In the above formulae (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-), oxygen or sulfur atom. The alkylene group having 1 to 5 carbon atoms in A' is preferably a linear or branched alkylene group, and examples thereof include methylene, ethylene, n-propylene, isopropylidene, and isopropylidene. Propylene etc.

When the alkylene group contains an oxygen atom or a sulfur atom, specific examples thereof include groups in which -O- or -S- is interposed between the ends of the aforementioned alkylene groups or between carbon atoms. 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 or -O- having 1 to 5 carbon atoms is preferable, an alkylene group having 1 to 5 or less carbon atoms is more preferable, and a methylene group is most preferable.

z may be any one of 0, 1, and 2, and is preferably 0. When z is 2, the plurality of R ^10bs may be the same or different, respectively.

Examples of the alkyl group, alkoxy group, haloalkyl group, -COOR", -OC(=O)R", and hydroxyalkyl group in R ^10b are the same as those described above as the -SO ₂ --containing cyclic group, respectively. The substituents which have the same group as an alkyl group, an alkoxy group, a haloalkyl group, -COOR", -OC(=O)R", and a hydroxyalkyl group are exemplified.

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

The -SO ₂ --containing cyclic group is preferably a group represented by the aforementioned formula (3-1), and more preferably a group represented by the aforementioned chemical formulas (3-1-1) and (3-1- 18), (3-3-1) and (3-4-1) at least one selected from the group consisting of groups represented by any one of the above-mentioned chemical formula (3-1-1) base.

(containing lactone cyclic group) "Lactone-containing cyclic group" means containing in its ring skeleton A cyclic group of a ring (lactone ring) of -O-C(=O)-. The lactone ring is referred to as the first ring, and when there is only a lactone ring, it is called a monocyclic group, and when it has other ring structures, it is called a polycyclic group regardless of the structure. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group.

The lactone-containing cyclic group in the structural unit (b-3) is not particularly limited, and any lactone-containing cyclic group can be used. Specifically, as a lactone-containing monocyclic group, a group obtained by removing one hydrogen atom from a four- to six-membered ring lactone, for example, a group obtained by removing one hydrogen atom from β-propiolactone can be mentioned. , a group obtained by removing one hydrogen atom from γ-butyrolactone, a group obtained by removing one hydrogen atom from δ-valerolactone, and the like. Moreover, as a lactone-containing polycyclic group, the group obtained by removing one hydrogen atom from the bicycloalkane, tricycloalkane, and tetracycloalkane which have a lactone ring is mentioned.

As the structural unit (b-3), as long as it is a structural unit having a -SO ₂ --containing cyclic group or a lactone-containing cyclic group, the structure of other parts is not particularly limited, and it is preferably from the α-position An acrylate-derived structural unit in which the carbon atom-bonded hydrogen atom may be substituted by a substituent, a structural unit (b-3-S) containing a -SO ₂ -cyclic group, and as a structural unit derived from a carbon atom in the α position At least one kind of structural unit selected from the group consisting of the structural unit containing a lactone cyclic group (b-3-L) of the acrylate-derived structural unit in which the hydrogen atom to be bonded may be substituted with a substituent.

[Structural unit (b-3-S)] As an example of a structural unit (b-3-S), the structural unit represented by following formula (b-S1) is mentioned more specifically.

(式中，R為氫原子、碳原子數為1以上5以下的烷基或者碳原子數為1以上5以下的鹵代烷基，R ^11b為含-SO ₂-環式基，R ^12b為單鍵或者2價的連接基)。

(in the formula, R is a hydrogen atom, an alkyl group having 1 to 5 or less carbon atoms, or a halogenated alkyl group having 1 to 5 or less carbon atoms, R ^11b is a -SO ₂ --containing cyclic group, and R ^12b is a single bond or a 2-valent linker).

In formula (b-S1), R is the same as above. R ^11b is the same as the above-exemplified -SO ₂ --containing cyclic group. R ^12b may be either a single bond or a divalent linking group.

Although it does not specifically limit as a divalent linking group in ^R12b , As a preferable example, the divalent hydrocarbon group which may have a substituent, the divalent linking group containing a heteroatom, etc. are mentioned.

･A divalent hydrocarbon group which may have a substituent The hydrocarbon group as the divalent linking group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group without aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated. Saturated hydrocarbon groups are generally preferred. As the aliphatic hydrocarbon group, more specifically, a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group having a ring in the structure, and the like can be exemplified.

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, methylene [-CH ₂ -], ethylene [-(CH ₂ ) ₂ -], propylene [-(CH ₂ ) ₃ -], butylene [-(CH ₂ ] may, for example, be mentioned. ) ₄ -], pentylene [-(CH ₂ ) ₅ -] and the like.

As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred. Specifically, -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CH ₃ )(CH ₂ CH ₃ )-, -C may be mentioned. (CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ - and other alkylmethylene; -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 - and other alkyl ethylene; -CH( CH ₃ )CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ - and other alkyl propylene; -CH(CH ₃ )CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ CH ₂ - such as alkyl butylene, such as alkyl alkylene, etc. The alkyl group in the alkylalkylene group is preferably a straight-chain alkyl group having 1 or more and 5 or less carbon atoms.

The above-mentioned linear or branched aliphatic hydrocarbon group may have a substituent (group or atom other than a hydrogen atom) substituted for a hydrogen atom, or may not have a substituent. As the substituent, a fluorine atom, a fluoroalkyl group having 1 to 5 carbon atoms and substituted by a fluorine atom, an oxo group (=O), and the like can be exemplified.

Examples of the above-mentioned aliphatic hydrocarbon group having a ring in the structure include a cyclic aliphatic hydrocarbon group (a cyclic aliphatic hydrocarbon group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), which may contain a substituent, having a hetero atom in the ring structure. group), a group in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, the cyclic aliphatic hydrocarbon group is interposed between a linear or branched aliphatic hydrocarbon group bases between hydrocarbon groups, etc. As the above-mentioned linear or branched aliphatic hydrocarbon group, the same groups as described above may be mentioned.

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

The cyclic aliphatic hydrocarbon group may be polycyclic or monocyclic. The monocyclic aliphatic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocyclic alkane. The number of carbon atoms of the monocycloalkane is preferably 3 or more and 6 or less. Specifically, cyclopentane, cyclohexane, etc. are mentioned. The polycyclic aliphatic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycyclic alkane. The number of carbon atoms of the polycycloalkane is preferably 7 or more and 12 or less. Specifically, adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. are mentioned.

The cyclic aliphatic hydrocarbon group may have a substituent (group or atom other than a hydrogen atom) substituted for a hydrogen atom, or may not have a substituent. As this substituent, an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, an oxo group (=O) etc. are mentioned.

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

The alkoxy group of the above-mentioned substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and Tert-butoxy, methoxy and ethoxy are particularly preferred.

As a halogen atom of the said substituent, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, Preferably it is a fluorine atom.

The halogenated alkyl group of the above-mentioned substituent may, for example, be a group obtained by substituting a part or all of the hydrogen atoms of the above-mentioned alkyl group with the above-mentioned halogen atom.

In the cyclic aliphatic hydrocarbon group, a part of the carbon atoms constituting the ring structure may be substituted with -O- or -S-. The heteroatom-containing substituent is preferably -O-, -C(=O)-O-, -S-, -S(=O) ₂ -, and -S(=O) ₂ -O-.

The aromatic hydrocarbon group which is a divalent hydrocarbon group is a divalent hydrocarbon group having at least one aromatic ring, and may have a substituent. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 or more and 30 or less, more preferably 5 or more and 20 or less, still more preferably 6 or more and 15 or less, and particularly preferably 6 or more and 12 or less. However, the number of carbon atoms does not include the number of carbon atoms of the substituent.

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

As the aromatic hydrocarbon group of the divalent hydrocarbon group, specifically, a group obtained by removing two hydrogen atoms from the above-mentioned aromatic hydrocarbon ring or aromatic heterocyclic ring (arylene group or heteroarylene group); A group obtained by removing two hydrogen atoms from an aromatic compound having two or more aromatic rings (for example, biphenyl, fluorene, etc.); a group obtained by removing one hydrogen atom from the above-mentioned aromatic hydrocarbon ring or aromatic heterocyclic ring ( A group in which one hydrogen atom of an aryl group or a heteroaryl group is substituted with an alkylene group (for example, from benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl) A group obtained by removing one hydrogen atom from an aryl group in an arylalkyl group such as 2-naphthylethyl group) and the like.

The number of carbon atoms of the alkylene group bonded to the aryl group or the heteroaryl group is preferably 1 or more and 4 or less, more preferably 1 or more and 2 or less, and particularly preferably 1.

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

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

As the alkoxy group of the above-mentioned substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, and methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and tert-butoxy, more preferably methoxy and ethoxy.

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

As the halogenated alkyl group of the above-mentioned substituent, a part or all of the hydrogen atoms of the above-mentioned alkyl group are substituted by the above-mentioned halogen atoms, for example.

･Divalent linking group containing heteroatom The heteroatom in the heteroatom-containing divalent linking group refers to an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom, and the like.

Specific examples of the heteroatom-containing divalent linking group include -O-, -C(=O)-, -C(=O)-O-, -OC(=O)-O-, -S-, -S(=O) ₂ -, -S(=O) ₂ -O-, -NH-, -NH-C(=O)-, -NH-C(=NH)-, =N - etc. non-hydrocarbon linking groups, a combination of at least one of these non-hydrocarbon linking groups and a divalent hydrocarbon group, and the like. The divalent hydrocarbon group may, for example, be the same as the aforementioned divalent hydrocarbon group which may have a substituent, and a linear or branched aliphatic hydrocarbon group is preferred.

In the above, in -C(=O)-NH-, -NH-, -NH-, The H in -NH-C(=NH)- can be substituted by substituents such as alkyl and acyl, respectively. The number of carbon atoms of the substituent is preferably 1 or more and 10 or less, more preferably 1 or more and 8 or less, and particularly preferably 1 or more and 5 or less.

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

When the divalent linking group in R ^12b is a linear or branched alkylene group, the number of carbon atoms of the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, 1 or more and 4 or less are especially preferable, and 1 or more and 3 or less are most preferable. Specifically, the linear or branched aliphatic hydrocarbon group exemplified in the description of the "divalent hydrocarbon group which may have a substituent" as the aforementioned divalent linking group can be exemplified. The same group as the alkylene group and the branched alkylene group.

In the case where the divalent linking group in R ^12b is a cyclic aliphatic hydrocarbon group, the cyclic aliphatic hydrocarbon group may, for example, be the same as the above-mentioned divalent linking group " may have a substituent. In the description of the "valent hydrocarbon group", the same groups as the cyclic aliphatic hydrocarbon group exemplified as "the aliphatic hydrocarbon group containing a ring in the structure".

As the cyclic aliphatic hydrocarbon group, it is particularly preferable to remove two or more hydrogen atoms from cyclopentane, cyclohexane, norbornane, isobornane, adamantane, tricyclodecane, or tetracyclododecane The base obtained.

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

When the divalent linking group in R ^12b is -NH-, the hydrogen atom in -NH- may be substituted with a substituent such as an alkyl group and an acyl group. The number of carbon atoms of the substituent (alkyl group, acyl group, etc.) is preferably 1 or more and 10 or less, more preferably 1 or more and 8 or less, and particularly preferably 1 or more and 5 or less.

In the formula -Y ¹ -OY ² -, -[Y ¹ -C(=O)-O] _m' -Y ² - or -Y ¹ -OC(=O)-Y ² -, Y ¹ and Y ² are respectively It is independently a divalent hydrocarbon group which may have a substituent. The divalent hydrocarbon group may, for example, be the same as the "divalent hydrocarbon group which may have a substituent" exemplified in the description of the aforementioned divalent linking group.

As Y ¹ , a straight-chain aliphatic hydrocarbon group is preferred, a straight-chain alkylene group is more preferred, a straight-chain alkylene group having 1 to 5 carbon atoms is more preferred, and methylene is particularly preferred. group and ethylene.

As Y ² , a linear or branched aliphatic hydrocarbon group is preferable, and a methylene group, an ethylene group, and an alkylmethylene group are more preferable. The alkyl group in the alkylmethylene group is preferably a straight-chain alkyl group having 1 to 5 or less carbon atoms, more preferably a straight-chain alkyl group having 1 to 3 or less carbon atoms, particularly preferably methyl.

In the group represented by the formula -[Y ¹ -C(=O)-O] _m' -Y ² -, m' is an integer of 0 or more and 3 or less, preferably 0 or more and 2 or less, more preferably is 0 or 1, particularly preferably 1. That is, as a group represented by formula -[Y ¹ -C(=O)-O] _m' -Y ² -, a group represented by formula -Y ¹ -C(=O)-OY ² - is particularly preferable. Among them, a group represented by the formula -(CH ₂ ) _a' -C(=O)-O-(CH ₂ ) _b' - is preferable. In this formula, a' is an integer of 1 or more and 10 or less, preferably 1 or more and 8 or less, more preferably 1 or more and 5 or less, still more preferably 1 or 2, and most preferably 1. b' is an integer of 1 or more and 10 or less, preferably 1 or more and 8 or less, more preferably 1 or more and 5 or less, still more preferably 1 or 2, and most preferably 1.

The divalent linking group in R ^12b is preferably an organic group composed of a combination of at least one non-hydrocarbon group and a divalent hydrocarbon group as the heteroatom-containing divalent linking group. Among them, a straight-chain group having an oxygen atom as a heteroatom is preferable, for example, a group containing an ether bond or an ester bond, more preferably the aforementioned formula -Y ¹ -OY ² -, -[Y ¹ -C(=O )-O] _m' -Y ² - or a group represented by -Y ¹ -OC(=O)-Y ² -, particularly preferably the aforementioned formula -[Y ¹ -C(=O)-O] _m' A base represented by -Y ² - or -Y ¹ -OC(=O)-Y ² -.

The divalent linking group in R ^12b is preferably an alkylene group or a divalent linking group containing an ester bond (-C(=O)-O-).

The alkylene group is preferably a linear or branched alkylene group. Preferable examples of the linear aliphatic hydrocarbon group include methylene [-CH ₂ -], ethylene [-(CH ₂ ) ₂ -], and propylene [-(CH ₂ ) ₃ ] -], butylene [-(CH ₂ ) ₄ -] and pentylene [-(CH ₂ ) ₅ -] and the like. Preferred examples of the branched alkylene group include -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) ₂ -, and -C(CH ₃ ) (CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ - and other alkylmethylene; -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 - -CH(CH ₃ )CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ -isoalkyl propylene; -CH(CH ₃ )CH ₂ CH ₂ CH ₂ - , -CH ₂ CH(CH ₃ )CH ₂ CH ₂ - such as alkylene such as alkylene, etc.

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

(式中，R以及R ^11b分別與上述相同，R ^13b是2價的連接基)。

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

Although it does not specifically limit as ^R13b , For example, the same group as the divalent linking group in the above-mentioned ^R12b is mentioned. The divalent linking group of 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 heteroatom, more preferably A linear or branched alkylene group or a divalent linking group containing an oxygen atom as a heteroatom.

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

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

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

(式中，R、A’、R ^10b、z以及R ^13b分別與上述相同)。

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

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

As R ^13b , a linear or branched alkylene group or a divalent linking group containing an oxygen atom is preferable. Examples of the linear or branched alkylene group and the divalent linking group containing an oxygen atom in R ^13b include the above-mentioned linear or branched alkylene group, a group containing an oxygen atom, respectively. The divalent linking group is the same group.

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

(式中，R以及A’分別與上述相同，c～e分別獨立地為1以上3以下的整數)。

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

[Structural unit (b-3-L)] Examples of the structural unit (b-3-L) include, for example, substitution of R ^11b in the aforementioned formula (b-S1) with a lactone-containing cyclic group. The obtained structural unit, more specifically, the structural unit represented by following formula (b-L1) - (b-L5) is mentioned.

(式中，R為氫原子、碳原子數為1以上5以下的烷基或者碳原子數為1以上5以下的鹵代烷基；R’分別獨立地為氫原子、烷基、烷氧基、鹵代烷基、羥基、-COOR”、 -OC(=O)R”、羥基烷基或者氰基，R”為氫原子或者烷基；R ^12b為單鍵或者2價的連接基，s”為0以上2以下的整數；A”為可以含有氧原子或硫原子的碳原子數為1以上5以下的亞烷基、氧原子或者硫原子；r為0或者1)。

(in the formula, R is a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a haloalkyl group with 1 to 5 or less carbon atoms; R' is each independently a hydrogen atom, an alkyl group, an alkoxy group, an alkyl halide group, hydroxyl, -COOR", -OC(=O)R", hydroxyalkyl or cyano group, R" is a hydrogen atom or an alkyl group; R ^12b is a single bond or a divalent linking group, s" is 0 or more An integer of 2 or less; A" is an alkylene group, an oxygen atom or a sulfur atom with a carbon number of 1 or more and 5 or less which may contain an oxygen atom or a sulfur atom; r is 0 or 1).

R in formulae (b-L1) to (b-L5) is the same as above. As the alkyl group, alkoxy group, haloalkyl group, -COOR", -OC(=O)R", and hydroxyalkyl group in R', the substituents which may be substituted as the -SO ₂ --containing cyclic group can be exemplified, respectively. The group exemplified by the group is the same as the group described above about the alkyl group, the alkoxy group, the haloalkyl group, -COOR", -OC(=O)R", and hydroxyalkyl group.

Considering industrial availability, etc., 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 the number of carbon atoms is more preferably 1 or more and 5 or less. When R" is a cyclic alkyl group, the number of carbon atoms is preferably 3 or more and 15 or less, more preferably 4 or more and 12 or less, and the most preferably carbon number is 5 or more and 10 or less. Specifically, It can be exemplified that one or more hydrogen atoms are removed from monocyclic alkanes which may be substituted or unsubstituted by fluorine atoms or fluoroalkyl groups, or from polycyclic alkanes such as bicycloalkanes, tricyclic alkanes, and tetracycloalkanes. Specifically, it can be exemplified from monocyclic alkanes such as cyclopentane and cyclohexane, or from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like. A group obtained by removing one or more hydrogen atoms from a cycloalkane, etc. As A", the same group as that of A' in the aforementioned formula (3-1) can be mentioned. A" is preferably an alkylene group having 1 or more and 5 or less carbon atoms, an oxygen atom (-O-), or sulfur. Atom (-S-), more preferably an alkylene group having 1 or more and 5 or less carbon atoms or -O-. As the alkylene group having from 1 to 5 carbon atoms, a methylene group or a dimethylmethylene group is more preferable, and a methylene group is most preferable.

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

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

式(b-L6)以及(b-L7)中，R以及R ^12b與上述相同。 Moreover, as a structural unit (b-3-L), the structural unit represented by following formula (b-L6) - (b-L7) is also preferable.

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

In addition, in the acrylic resin (B3), the structure represented by the following formulae (b5) to (b7) having an acid dissociable group is included as a structural unit that improves the solubility of the acrylic resin (B3) to an alkali due to the action of an acid unit.

In the above formulae (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 A linear or branched fluoroalkyl group having 1 to 6 carbon atoms, and R ^15b to R ^17b each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms , a linear or branched fluoroalkyl group with 1 to 6 or less carbon atoms, or an aliphatic cyclic group with 5 to 20 or less carbon atoms, R ^16b and R ^17b may be mutually bonded to The carbon atoms to which the two are bonded together form a hydrocarbon ring with 5 to 20 carbon atoms, Y ^b represents an optionally substituted aliphatic cyclic group or an alkyl group, p represents an integer from 0 to 4, and q represents 0 or 1.

Moreover, as said linear or branched alkyl group, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, Neopentyl et al. In addition, the fluoroalkyl group refers to a group in which a part or all of the hydrogen atoms of the above-mentioned alkyl group are substituted with fluorine atoms. Specific examples of the aliphatic cyclic group include groups obtained by removing one or more hydrogen atoms from monocycloalkanes or polycycloalkanes such as bicycloalkanes, tricycloalkanes, and tetracycloalkanes. Specifically, monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, or adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc., can be exemplified. A group obtained by removing one hydrogen atom from a polycyclic alkane such as an alkane. In particular, a group obtained by removing one hydrogen atom from cyclohexane and adamantane (which may further have a substituent) is preferable.

When the above-mentioned R ^16b and R ^17b are not bonded to each other to form a hydrocarbon ring, from the viewpoints of high contrast, high resolution, good depth of focus, and the like, the above-mentioned R ^15b , R ^16b and R ^17b are preferably carbon atoms. A linear or branched alkyl group having 1 or more and 4 or less, more preferably a linear or branched alkyl group having 2 or more and 4 or less carbon atoms. As the above-mentioned R ^19b , R ^20b , R ^22b and R ^23b , a hydrogen atom or a methyl group is preferable.

The above-mentioned R ^16b and R ^17b may form an aliphatic cyclic group having 5 or more and 20 or less carbon atoms together with the carbon atoms to which they are bonded. Specific examples of such aliphatic cyclic groups include groups obtained by removing one or more hydrogen atoms from monocycloalkanes or from polycycloalkanes such as bicycloalkanes, tricycloalkanes, and tetracycloalkanes. Specifically, monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, or adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc., can be exemplified. A group obtained by removing one or more hydrogen atoms from a polycyclic alkane such as an alkane. In particular, a group obtained by removing one or more hydrogen atoms from cyclohexane and adamantane (which may further have a substituent) is preferable.

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

The above-mentioned Y ^b is an aliphatic cyclic group or an alkyl group, and examples thereof include a group obtained by removing one or more hydrogen atoms from a monocycloalkane or a polycycloalkane such as a bicycloalkane, a tricycloalkane, and a tetracycloalkane. . Specifically, monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, or adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc., can be exemplified. A group obtained by removing one or more hydrogen atoms from a polycyclic alkane such as an alkane, etc. A group obtained by removing one or more hydrogen atoms from adamantane (which may further have a substituent) is particularly preferable.

Furthermore, when the aliphatic cyclic group of Y ^b has a substituent on its ring skeleton, examples of the substituent include polar groups such as a hydroxyl group, a carboxyl group, a cyano group, an oxygen atom (=O), and the like. Or a linear or branched alkyl group having 1 or more and 4 or less carbon atoms. As a polar group, an oxygen atom (=O) is especially preferable.

Further, when Y ^b is an alkyl group, it is preferably a linear or branched alkyl group having 1 or more and 20 or less carbon atoms, more preferably 6 or more and 15 or less. Such an alkyl group is particularly preferably an alkoxyalkyl group, and examples of such an alkoxyalkyl group include 1-methoxyethyl, 1-ethoxyethyl, and 1-n-propoxyethyl. , 1-isopropoxyethyl, 1-n-butoxyethyl, 1-isobutoxyethyl, 1-tert-butoxyethyl, 1-methoxypropyl, 1-ethoxy propyl, 1-methoxy-1-methyl-ethyl, 1-ethoxy-1-methylethyl, and the like.

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

In the above formulae (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), the structural unit represented by following formula (b6-1) - (b6-26) can be mentioned.

In the above formulae (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), the structural unit represented by following formula (b7-1) - (b7-15) can be mentioned.

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

Among the structural units represented by the formulae (b5) to (b7) described above, the structural unit represented by the formula (b6) is preferred from the viewpoints of easy synthesis and relatively easy high sensitivity. Further, in the structural unit represented by the formula (b6), Y ^b is preferably a structural unit of an alkyl group, and one or both of R ^19b and R ^20b is preferably a structural unit of an alkyl group.

Further, the acrylic resin (B3) is preferably a resin composed of a copolymer containing the structural unit represented by the above formulae (b5) to (b7) and containing a structural unit derived from a polymerizable compound having an ether bond.

As the above-mentioned polymerizable compound having an ether bond, a radically polymerizable compound such as a (meth)acrylic acid derivative having an ether bond and an ester bond can be exemplified, and 2-methoxy (meth)acrylic acid can be mentioned as a specific example. Ethyl ethyl ester, 2-ethoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol ( Meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, (meth) Tetrahydrofurfuryl acrylate, etc. In addition, the polymerizable compound having the above ether bond is preferably 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and methoxytriethylene glycol (methyl) Acrylate. These polymerizable compounds may be used alone or in combination of two or more.

Furthermore, for the purpose of appropriately controlling physical and chemical properties, the acrylic resin (B3) can contain another polymerizable compound as a structural unit. As such a polymerizable compound, a well-known radical polymerizable compound and an anion polymerizable compound are mentioned.

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-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, etc. Methacrylic acid derivatives with carboxyl group and ester bond; (meth)methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, etc. Alkyl acrylates; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and other hydroxyalkyl (meth)acrylates; phenyl (meth)acrylate, (meth)acrylate ) (meth) aryl acrylates such as benzyl acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene , chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene and other vinyl-containing aromatic compounds; vinyl acetate and other vinyl-containing aliphatic compounds Compounds; conjugated dienes such as butadiene and isoprene; nitrile-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; propylene Polyamide bond-containing polymerizable compounds such as amide, methacrylamide, etc.

As described above, the acrylic resin (B3) may contain a structural unit derived from a polymerizable compound having a carboxyl group such as the above-mentioned monocarboxylic acids or dicarboxylic acids. However, the ratio of the structural unit derived from the polymerizable compound having a carboxyl group in the acrylic resin (B3) is preferable from the viewpoint of easily forming a resist pattern including a non-resistor portion having a more favorable rectangular cross-sectional shape It is less than 20 mass %, More preferably, it is 0.1 mass % or more and 15 mass % or less, Especially preferably, it is 1 mass % or more and 10 mass % or less.

Moreover, as a polymerizable compound, the (meth)acrylates which have an acid non-dissociable aliphatic polycyclic group, vinyl group-containing aromatic compounds, etc. are mentioned. From the viewpoint of industrial availability, etc., the acid non-dissociative aliphatic polycyclic group is particularly preferably a tricyclodecyl group, an adamantyl group, a tetracyclododecyl group, an isobornyl group, and a norbornyl group Wait. These aliphatic polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.

As (meth)acrylates which have an acid non-dissociable aliphatic polycyclic group, the compound of the structure of following formula (b8-1) - (b8-5) can be illustrated specifically,.

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

In the case where the acrylic resin (B3) contains a structural unit (b-3) containing a -SO ₂ --containing cyclic group or a lactone cyclic group, the amount of the structural unit (b-3) in the acrylic resin (B3) The content is preferably 50% by mass or less, more preferably 30% by mass or less.

Further, the acrylic resin (B3) preferably contains 5% by mass or more, more preferably 10% by mass or more, particularly preferably 10% by mass or more and 50% by mass or less of the structures represented by the above formulae (b5) to (b7) unit.

The acrylic resin (B3) preferably contains a structural unit derived from the above-mentioned polymerizable compound having an ether bond. In the acrylic resin (B3), the content of the structural unit derived from the polymerizable compound having an ether bond is preferably 0 mass % or more and 50 mass % or less, more preferably 5 mass % or more and 40 mass % or less, still more preferably 5 mass % or more and 30 mass % or less.

The acrylic resin (B3) preferably contains a structural unit derived from (meth)acrylates having the above-mentioned acid-non-dissociable aliphatic polycyclic group. In the acrylic resin (B3), the content of the structural unit derived from (meth)acrylates having an acid-non-dissociable aliphatic polycyclic group is preferably 0 mass % or more and 60 mass % or less, more preferably 5 mass % or more and 50 mass % or less, more preferably 5 mass % or more and 30 mass % or less.

As long as the photosensitive composition contains a predetermined amount of the acrylic resin (B3), an acrylic resin other than the acrylic resin (B3) described above can also be used as the resin (B). As an acrylic resin other than such an acrylic resin (B3), if it is resin containing the structural unit represented by the said formula (b5)-(b7), it will not specifically limit.

The polystyrene-equivalent mass average molecular weight of the resin (B) described above is preferably 10,000 or more and 600,000 or less, more preferably 20,000 or more and 400,000 or less, and still more preferably 30,000 or more and 300,000 or less. By setting such a mass average molecular weight, it is possible to maintain sufficient strength of the photosensitive layer composed of the photosensitive composition without reducing the peelability of the photosensitive layer from the substrate, and it is possible to easily prevent the appearance ( profile) expansion or the occurrence of cracks.

Moreover, it is preferable that the molecular weight distribution coefficient of resin (B) is 1.05 or more. Here, the molecular weight distribution coefficient refers to a value obtained by dividing the mass average molecular weight by the number average molecular weight. By setting such a molecular weight distribution coefficient, the desired stress resistance to plating can be obtained, or the problem that the metal layer obtained by the plating process tends to swell can be avoided.

The content of the resin (B) is preferably 5% by mass or more and 70% by mass or less with respect to the total mass of the photosensitive composition. Moreover, 5 mass % or more and 99 mass % or less are preferable with respect to the total solid content mass of a photosensitive composition, and, as for content of resin (B), 50 mass % or more and 99 mass % or less are more preferable.

<Acid diffusion inhibitor (C)> The photosensitive composition preferably further contains an acid diffusion inhibitor (C) in order to improve the shape of the resist pattern, the stationary stability of the photosensitive resin film, and the like. The acid diffusion inhibitor (C) is preferably a nitrogen-containing compound (C1), and can further contain an organic carboxylic acid, or a phosphorus oxo acid or a derivative (C2) thereof as necessary.

[Nitrogen-containing compound (C1)] Examples of the nitrogen-containing compound (C1) include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tri-n-pentylamine, tribenzylamine, diethanolamine, triethanolamine, n-hexylamine, n-heptylamine Amine, n-octylamine, n-nonylamine, ethylenediamine, N,N,N',N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diamine Diphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, formamide, N-methyl methyl Acetamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, benzylamide, pyrrolidone, N- Methylpyrrolidone, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, imidazole, Benzimidazole, 4-methylimidazole, 8-hydroxyquinoline, acridine, purine, pyrrolidine, pyridine, 2,4,6-tris(2-pyridyl)s-triazine, morpholine, 4-methyl morpholine, oxazine, 1,4-dimethyloxazine, 1,4-diazabicyclo[2.2.2]octane, pyridine, etc. These may be used alone or in combination of two or more.

In addition, ADK STAB LA-52, ADK STAB LA-57, ADK STAB LA-63P, ADK STAB LA-68, ADK STAB LA-72, ADK STAB LA-77Y, ADK STAB LA-77G, ADK STAB LA -81, ADK STAB LA-82 and ADK STAB LA-87 (all manufactured by ADEKA) or commercially available hindered amine compounds such as 4-hydroxy-1,2,2,6,6-pentamethylpyridine derivatives Alternatively, pyridine in which the 2,6-position, such as 2,6-diphenylpyridine and 2,6-di-tert-butylpyridine, was substituted with a substituent such as a hydrocarbon group at the 2,6-position was used as the nitrogen-containing compound (C1).

The nitrogen-containing compound (C1) is usually used in the range of 0 mass parts or more and 5 mass parts or less with respect to 100 mass parts of the total mass of the above-mentioned resin (B) and the following alkali-soluble resin (D), particularly preferably 0 mass parts. It is used in the range of not less than 3 parts by mass and not more than 3 parts by mass.

[Organic carboxylic acid, or phosphorus oxyacid or derivative (C2)] Among the organic carboxylic acids, or phosphorus oxyacids or derivatives thereof (C2), as the organic carboxylic acids, specifically, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid are preferred. acid etc., especially salicylic acid is preferable.

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

The amount of organic carboxylic acid or phosphorus oxo acid or derivative (C2) thereof is usually 0 to 5 parts by mass relative to 100 parts by mass of the total mass of the above-mentioned resin (B) and the following alkali-soluble resin (D) It is especially preferable to use it in the range of 0 mass parts or more and 3 mass parts or less.

In addition, in order to form a salt and stabilize it, it is preferable to use an organic carboxylic acid or a phosphorus oxo acid or its derivative (C2) in an amount equivalent to that of the nitrogen-containing compound (C1).

<Alkali-soluble resin (D)> The photosensitive composition may not contain the alkali-soluble resin (D), or may contain the alkali-soluble resin (D). Here, the alkali-soluble resin means that a resin film having a thickness of 1 μm is formed on a substrate with a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by mass, and immersed in a 2.38% by mass TMAH aqueous solution for 1 μm. Resin of 0.01 μm or more is dissolved in minutes, and refers to a resin that does not belong to the above-mentioned resin (B) (typically, it refers to a resin whose alkali solubility does not substantially change even by the action of an acid). The alkali-soluble resin (D) is preferably at least one resin selected from the group consisting of a novolac resin (D1), a polyhydroxystyrene resin (D2), and an acrylic resin (D3).

[Novolak resin (D1)] A novolak resin is obtained, for example, by addition-condensing an aromatic compound having a phenolic hydroxyl group (hereinafter, simply referred to as "phenols") and aldehydes 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 phenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol , 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol , Phloroglucinol, hydroxybiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, β-naphthol, etc. As said aldehyde, formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde, etc. are mentioned, for example. The catalyst in the addition condensation reaction is not particularly limited, and among acid catalysts, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, etc. can be used, for example.

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

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 inhibited, but it is preferably 1,000 or more and 50,000 or less.

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

The mass average molecular weight of the polyhydroxystyrene resin (D2) is not particularly limited as long as the object of the present invention is not inhibited, but it is preferably 1,000 or more and 50,000 or less.

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

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

Examples of the polymerizable compound having a carboxyl 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-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, etc. A compound having a carboxyl group and an ester bond, etc. The polymerizable compound having the above-mentioned carboxyl group is preferably acrylic acid and methacrylic acid. These polymerizable compounds may be used alone or in combination of two or more.

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

When the total of the resin (B) and the alkali-soluble resin (D) is set to 100 parts by mass, the content of the alkali-soluble resin (D) is preferably 0 parts by mass or more and 80 parts by mass or less, more preferably 0 The mass part or more is 60 mass parts or less. By making content of an alkali-soluble resin (D) into the said range, it exists in the tendency which can prevent the film reduction at the time of image development.

<Sulfur-containing compound (E)> When the photosensitive composition is used for a pattern formed on a metal substrate, the photosensitive composition preferably contains a sulfur-containing compound (E). The sulfur-containing compound (E) is a compound containing a sulfur atom that can coordinate with a metal. In addition, with respect to a compound capable of generating two or more tautomers, when at least one tautomer includes a sulfur atom that coordinates with the metal constituting the surface of the metal substrate, the compound is classified as a sulfur-containing compound. When a resist pattern to be used as a mold for plating is formed on a surface made of metal such as Cu, problems in the cross-sectional shape such as feet are likely to occur. However, in the case where the photosensitive composition contains the sulfur-containing compound (E), even when a resist pattern is formed on the surface of the substrate made of metal, it is easy to suppress the inconvenience of the cross-sectional shape such as the foot. occur. In addition, "foot" means that the width of the bottom part in the non-resist part is changed compared to the width of the top part because the resist part protrudes toward the non-resist part side in the vicinity of the contact surface between the substrate surface and the resist pattern. narrow phenomenon. When the photosensitive composition is used for a pattern formed on a substrate other than a metal substrate, the photosensitive composition does not need to contain a sulfur-containing compound in particular. When the photosensitive composition is used for a pattern formed on a substrate other than a metal substrate, the photosensitive composition can be reduced from the viewpoint that the photosensitive composition can be easily produced due to the reduction in the number of components of the photosensitive composition. The photosensitive composition preferably does not contain the sulfur-containing compound (E) from the viewpoint of the production cost of the product and the like. In addition, in particular, the photosensitive composition used for the pattern formed on the substrate other than the metal substrate contains the sulfur-containing compound (E), which does not cause a problem.

Sulfur atoms that can coordinate with metals, e.g. as mercapto groups (-SH), a thiocarboxy group (-CO-SH), a dithiocarboxy group (-CS-SH), a thiocarbonyl group (-CS-), and the like are contained in the sulfur-containing compound. The sulfur-containing compound preferably has a mercapto group from the viewpoint of being easy to coordinate with a metal and having an excellent effect of inhibiting the footing.

(式中，R ^e1以及R ^e2分別獨立地表示氫原子或者烷基，R ^e3表示單鍵或者亞烷基，R ^e4表示可以包含除碳以外的原子的u價的脂肪族基，u表示2以上4以下的整數)。 As a preferable example of the sulfur-containing compound which has a mercapto group, the compound represented by following formula (e1) is mentioned.

(wherein, R ^e1 and R ^e2 each independently represent a hydrogen atom or an alkyl group, R ^e3 represents a single bond or an alkylene group, R ^e4 represents a u-valent aliphatic group that may contain atoms other than carbon, and u represents 2 an integer above 4 or below).

When R ^e1 and R ^e2 are an alkyl group, the alkyl group may be linear or branched, but preferably linear. When R ^e1 and R ^e2 are alkyl groups, the number of carbon atoms of the alkyl groups is not particularly limited within a range that does not inhibit the purpose of the present invention. The number of carbon atoms in the alkyl group is preferably 1 or more and 4 or less, particularly preferably 1 or 2, and most preferably 1. As a combination of ^Re1 and ^Re2 , it is preferable that one is a hydrogen atom and the other is an alkyl group, and it is particularly preferable that one is a hydrogen atom and the other is a methyl group.

When R ^e3 is an alkylene group, the alkylene group may be straight-chain or branched, but straight-chain is preferred. When R ^e3 is an alkylene group, the number of carbon atoms of the alkylene group is not particularly limited in a range that does not inhibit the purpose of the present invention. The number of carbon atoms of the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, particularly preferably 1 or 2, and most preferably 1.

R ^e4 is an aliphatic group having a valence of not less than 2 and not more than 4, which may contain atoms other than carbon. As an atom other than carbon which may be contained in ^Re4 , a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned. The structure of the aliphatic group as R ^e4 may be linear, branched, cyclic, or a combination of these structures.

(式(e2)中，R ^e4以及u與式(e1)同義)。 Among the compounds represented by the formula (e1), the compounds represented by the following formula (e2) are more preferable.

(In formula (e2), R ^e4 and u are synonymous with formula (e1)).

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

(式(e3-L1)～(e3-L7)中，R’、s”、A”以及r與有關丙烯酸樹脂(B3)前述的式(b-L1)～(b-L7)相同)。 The compounds represented by the following formulae (e3-L1) to (e3-L7) are also exemplified as preferred examples of sulfur-containing compounds having a mercapto group.

(In the formulae (e3-L1) to (e3-L7), R', s", A" and r are the same as the above-mentioned formulae (b-L1) to (b-L7) regarding the acrylic resin (B3).

As a preferable specific example of the mercapto compound represented by the said formula (e3-L1) - (e3-L7), the following compounds can be mentioned.

(對於式(e3-1)～(e3-4)中的簡寫符號的定義，與關於丙烯酸樹脂(B3)所述的、對於式(3-1)～(3-4)所述的內容相同)。 The compounds represented by the following formulae (e3-1) to (e3-4) are also exemplified as preferred examples of the sulfur-containing compound having a mercapto group.

(The definitions of the abbreviations in the formulas (e3-1) to (e3-4) are the same as those described for the acrylic resin (B3) and the formulas (3-1) to (3-4) ).

As a preferable specific example of the mercapto compound represented by the said formula (e3-1) - (e3-4), the following compound is mentioned.

(在式(e4)中，R ^e5為從羥基、碳原子數為1以上4以下的烷基、碳原子數為1以上4以下的烷氧基、碳原子數為1以上4以下的烷硫基、碳原子數為1以上4以下的羥基烷基、碳原子數為1以上4以下的巰基烷基、碳原子數為1以上4以下的鹵代烷基以及鹵素原子構成的組中選擇的基，n1為0以上3以下的整數，n0為0以上3以下的整數，在n1為2或者3的情況下，R ^e5可以相同也可以不同)。 Moreover, as a preferable example of the compound which has a mercapto group, the compound represented by following formula (e4) is mentioned.

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

Specific examples in the case where R ^e5 is an alkyl group having from 1 to 4 carbon atoms and which may have a hydroxyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl. , sec-butyl and tert-butyl. Among these alkyl groups, methyl, hydroxymethyl and ethyl are preferred.

Specific examples in the case where R ^e5 is an alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isopropoxy Butoxy, sec-butoxy and tert-butoxy. Among these alkoxy groups, a methoxy group and an ethoxy group are preferable, and a methoxy group is more preferable.

Specific examples in the case where R ^e5 is an alkylthio group having 1 to 4 carbon atoms include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isopropylthio Butylthio, sec-butylthio and tert-butylthio. Among these alkylthio groups, a methylthio group and an ethylthio group are preferable, and a methylthio group is more preferable.

Specific examples in the case where R ^e5 is a hydroxyalkyl group having 1 to 4 carbon atoms include hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 3-hydroxy-n-propyl, and 4-hydroxyethyl group. -Hydroxyn-butyl, etc. Among these hydroxyalkyl groups, a hydroxymethyl group, a 2-hydroxyethyl group, and a 1-hydroxyethyl group are preferable, and a hydroxymethyl group is more preferable.

Specific examples in the case where R ^e5 is a mercaptoalkyl group having 1 to 4 carbon atoms include mercaptomethyl, 2-mercaptoethyl, 1-mercaptoethyl, 3-mercapto-n-propyl, and 4-mercaptomethyl. -Mercapto-n-butyl, etc. Among these mercaptoalkyl groups, mercaptomethyl, 2-mercaptoethyl, and 1-mercaptoethyl are preferred, and mercaptomethyl is more preferred.

When R ^e5 is a haloalkyl group having 1 to 4 carbon atoms, the halogen atom contained in the haloalkyl group may, for example, be fluorine, chlorine, bromine or iodine. Specific examples in the case where R ^e5 is a haloalkyl group having 1 to 4 carbon atoms include chloromethyl, bromomethyl, iodomethyl, fluoromethyl, dichloromethyl, and dibromomethyl. , difluoromethyl, trichloromethyl, tribromomethyl, trifluoromethyl, 2-chloroethyl, 2-bromoethyl, 2-fluoroethyl, 1,2-dichloroethyl, 2, 2-difluoroethyl, 1-chloro-2-fluoroethyl, 3-chloro-n-propyl, 3-bromo-n-propyl, 3-fluoro-n-propyl and 4-chloro-n-butyl, etc. Among these haloalkyl groups, chloromethyl, bromomethyl, iodomethyl, fluoromethyl, dichloromethyl, dibromomethyl, difluoromethyl, trichloromethyl, tribromomethyl and Trifluoromethyl, more preferably chloromethyl, dichloromethyl, trichloromethyl and trifluoromethyl.

Specific examples in the case where R ^e5 is a halogen atom include fluorine, chlorine, bromine or iodine.

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

In the compound represented by the formula (e4), the substitution position of R ^e5 on the benzene ring is not particularly limited. The substitution position of R ^e5 on the benzene ring is preferably the meta position or the para position with respect to the bonding position of -(CH ₂ ) _n0 -SH.

The compound represented by the formula (e4) is preferably a compound having at least one group selected from the group consisting of an alkyl group, a hydroxyalkyl group, and a mercaptoalkyl group as R ^e5 , more preferably a compound having one group selected from an alkyl group, a mercaptoalkyl group, and a mercaptoalkyl group. A group selected from the group consisting of a hydroxyalkyl group and a mercaptoalkyl group is used as a compound of R ^e5 . When the compound represented by the formula (e4) has one group selected from the group consisting of an alkyl group, a hydroxyalkyl group, and a mercaptoalkyl group as R ^e5 , the benzene ring of the alkyl group, the hydroxyalkyl group, or the mercaptoalkyl group The substitution position on -(CH 2 ) n0 -SH is preferably meta-position or para-position, more preferably para-position relative to the bonding position of -(CH ₂ ) _n0 -SH.

In formula (e4), n0 is an integer of 0 or more and 3 or less. From the viewpoint of easier preparation and acquisition of the compound, n0 is preferably 0 or 1, more preferably 0.

Specific examples of the compound represented by the formula (e4) include p-mercaptophenol, p-thiocresol, m-thiocresol, 4-(methylthio)benzenethiol, and 4-methoxybenzenethiol. Alcohol, 3-methoxybenzenethiol, 4-ethoxybenzenethiol, 4-isopropoxybenzenethiol, 4-tert-butoxybenzenethiol, 3,4-dimethoxybenzenethiol Alcohol, 3,4,5-trimethoxybenzenethiol, 4-ethylbenzenethiol, 4-isopropylbenzenethiol, 4-n-butylbenzenethiol, 4-tert-butylbenzenethiol, 3-ethylbenzenethiol, 3-isopropylbenzenethiol, 3-n-butylbenzenethiol, 3-tert-butylbenzenethiol, 3,5-dimethylbenzenethiol, 3,4- Dimethylbenzenethiol, 3-tert-butyl-4-methylbenzenethiol, 3-tert-4-methylbenzenethiol, 3-tert-butyl-5-methylbenzenethiol, 4-tert-butylbenzenethiol Butyl-3-methylbenzenethiol, 4-mercaptobenzyl alcohol, 3-mercaptobenzyl alcohol, 4-(mercaptomethyl)phenol, 3-(mercaptomethyl)phenol, 1,4-bis(mercaptomethyl) ) phenol, 1,3-bis(mercaptomethyl)phenol, 4-fluorobenzenethiol, 3-fluorobenzenethiol, 4-chlorobenzenethiol, 3-chlorobenzenethiol, 4-bromobenzenethiol, 4-iodobenzenethiol, 3-bromobenzenethiol, 3,4-dichlorobenzenethiol, 3,5-dichlorobenzenethiol, 3,4-difluorobenzenethiol, 3,5-difluorobenzene Benzenethiol, 4-mercaptocatechol, 2,6-di-tert-butyl-4-mercaptophenol, 3,5-di-tert-butyl-4-methoxybenzenethiol, 4-bromo-3-methyl Benzenethiol, 4-(trifluoromethyl)benzenethiol, 3-(trifluoromethyl)benzenethiol, 3,5-bis(trifluoromethyl)benzenethiol, 4-methylthiobenzene Thiol, 4-ethylthiobenzenethiol, 4-n-butylthiobenzenethiol, and 4-tert-butylthiobenzenethiol, etc.

Moreover, as a sulfur-containing compound which has a mercapto group, the compound containing the nitrogen-containing aromatic heterocycle substituted by a mercapto group, and the tautomer of the compound containing the nitrogen-containing aromatic heterocycle substituted by a mercapto group are mentioned. Preferable specific examples of nitrogen-containing aromatic heterocycles include imidazole, pyrazole, 1,2,3-triazole, 1,2,4-triazole, oxazole, thiazole, pyridine, pyrimidine, and pyridine. oxazine, pyrazine, 1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine, indole, indazole, benzimidazole, benzoxazole, benzothiazole , 1H-benzotriazole, quinoline, isoquinoline, cinnoline, phthalazine, quinazoline, quinoxaline and 1,8-naphthyridine.

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

When the photosensitive composition contains the sulfur-containing compound (E), the usage amount thereof is preferably 0.01 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total mass of the resin (B) and the alkali-soluble resin (D). , more preferably 0.02 parts by mass or more and 3 parts by mass or less, particularly preferably 0.05 parts by mass or more and 2 parts by mass or less.

<Dye (F)> The photosensitive composition may contain a dye (F). As the dye (F), azo compounds and curcumin may, for example, be mentioned, and other dyes may be used. Specific examples of the dye (F) include 2-phenylazo-4-methylphenol, 2,2',4,4'-tetrahydroxybenzophenone, 4-dimethylamino-2 ',4'-Dihydroxybenzophenone, 5-amino-3-methyl-1-phenyl-4-(4-hydroxyphenylazo)pyrazole, 4-dimethylamino-4 '-Hydroxyazobenzene, 4-diethylamino-4'-ethoxyazobenzene, 4-diethylaminoazobenzene, curcumin, 1,7-bis(3-methoxy -4-Hydroxyphenyl)-1,6-heptadiene-3,5-dione, 5-hydroxy-4-(4-methoxyphenylazo)-3-methyl-1-phenyl Pyrazole etc.

When the photosensitive composition contains the dye (F), the usage amount thereof is preferably 0.0005 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total mass of the resin (B) and the alkali-soluble resin (D), and more Preferably it is 0.001 mass part or more and 3 mass parts or less, Especially preferably, it is 0.003 mass part or more and 1 mass part or less.

<Organic solvent (S)> The photosensitive composition preferably contains an organic solvent (S). The type of the organic solvent (S) is not particularly limited within a range that does not inhibit the purpose of the present invention, and can be appropriately selected and used from organic solvents conventionally used for photosensitive 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 and ethylene glycol monoacetate. , diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monoacetate monomethyl ether, monoethyl ether, monopropylene Ether, monobutyl ether, monophenyl ether and other polyols and their derivatives; cyclic ethers such as dioxane; ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate Esters, Methyl Pyruvate, Methyl Acetate, Ethyl Acetate, Ethyl Pyruvate, Ethoxyethyl Ethoxylate, Methyl Methoxypropionate, Ethoxyethylpropionate, 2-Hydroxy Methyl propionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methyl propionate, methyl 2-hydroxy-3-methyl butyrate, 3-methoxybutyl acetate, Esters such as 3-methyl-3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene. These may be used alone or in combination of two or more.

The organic solvent is used within the range where the solid content concentration of the photosensitive composition is 25 mass % or more and 70 mass % or less, preferably 30 mass % or more and 60 mass % or less, more preferably 40 mass % or more and 50 mass % or less. (S).

＜Other ingredients＞ In order to improve plasticity, the photosensitive composition may further contain polyethylene resin. Specific examples of the polyethylene resin include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinyl benzoic acid, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl Vinyl alcohol, polyvinyl pyrrolidone, polyvinyl phenol and their copolymers, etc. From the viewpoint of a low glass transition point, the polyethylene resin is preferably polyvinyl methyl ether.

The photosensitive composition may contain a Lewis acidic compound. By making the photosensitive composition contain the Lewis acidic compound, it becomes easy to obtain a highly sensitive photosensitive composition, and it becomes easier to form a resist pattern with a rectangular cross-sectional shape using the photosensitive composition. In addition, when a pattern is formed using a photosensitive composition, when the time required for each step or the time required between the steps in forming the pattern is long, it may be difficult to form a desired pattern. Undesirable effects of pattern of shape or size, or deterioration of developability. However, by blending the Lewis acid compound in the photosensitive composition, such an adverse effect on the pattern shape or developability can be alleviated, and the process margin can be widened.

Here, the Lewis acidic compound means "a compound which has an vacant orbital that can accept at least one electron pair and functions as an electron pair acceptor". The Lewis acidic compound is not particularly limited as long as it belongs to the above-mentioned definition and is recognized as a Lewis acidic compound by those skilled in the art. As the Lewis acidic compound, a compound not belonging to the Bronsted acid (protonic acid) is preferably used. Specific examples of Lewis acidic compounds include boron fluoride and ether complexes of boron fluoride (eg, BF ₃ -Et ₂ O, BF ₃ -Me ₂ O, BF ₃ -THF, etc. Et is an ethyl group) , Me is methyl, THF is tetrahydrofuran), organic boron compounds (such as tri-n-octyl borate, tri-n-butyl borate, triphenyl borate and triphenyl boron, etc.), titanium chloride, aluminum chloride, bromide Aluminum, Gallium Chloride, Gallium Bromide, Indium Chloride, Thallium Trifluoroacetate, Tin Chloride, Zinc Chloride, Zinc Bromide, Zinc Iodide, Zinc Triflate, Zinc Acetate, Zinc Nitrate, Tetrafluoro Zinc borate, manganese chloride, manganese bromide, nickel chloride, nickel bromide, nickel cyanide, nickel acetylacetonate, cadmium chloride, cadmium bromide, stannous chloride, stannous bromide, stannous sulfate and Stannous tartrate, etc. In addition, other specific examples of the Lewis acid compound include chlorides, bromides, sulfates, nitrates, carboxylates, or triflates of rare earth metal elements; and cobalt chloride, chlorine Ferrous and yttrium chloride. Here, the rare earth metal elements include, for example, lanthanum, cerium, pyrite, neodymium, samarium, europium, gadolinium, abium, dysprosium, ∥, erbium, ytterbium, ytterbium, and the like.

The Lewis acidic compound preferably contains a Lewis acidic compound containing an element of Group 13 of the periodic table from the viewpoint of easy availability and good effect by its addition. Here, boron, aluminum, gallium, indium, and thallium may, for example, be mentioned as a Group 13 element of the periodic table. Among the above-mentioned elements of Group 13 of the periodic table, boron is preferred in view of the easiness of obtaining a Lewis acid compound and the particularly excellent addition effect. That is, it is preferable that the Lewis acidic compound contains a Lewis acidic compound containing boron.

Examples of the Lewis acidic compound containing boron include boron fluoride, ether complexes of boron fluoride, boron halides such as boron chloride and boron bromide, and various organic boron compounds. As the Lewis acidic compound containing boron, the organic boron compound is preferable in that the content ratio of the halogen atom in the Lewis acidic compound is reduced and the photosensitive composition can be easily applied to applications requiring a low halogen content. .

(式(f1)中，R ^f1以及R ^f2分別獨立地為碳原子數為1以上20以下的烴基，前述烴基可以具有1個以上的取代基，t1為0以上3以下的整數，在存在多個R ^f1的情況下，多個R ^f1中的2個可以相互鍵結而形成環，在存在多個OR ^f2的情況下，多個OR ^f2中的2個可以相互鍵結而形成環)。 感光性組成物較佳包含1種以上的以上述式(f1)表示的硼化合物作為路易士酸性化合物。 As a preferable example of an organoboron compound, the boron compound represented by following formula (f1) is mentioned.

(In the formula (f1), R ^f1 and R ^f2 are each independently a hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group may have one or more substituents, t1 is an integer of 0 to 3, and in the presence of multiple In the case of a plurality of R ^f1s , two of the plurality of R ^f1s may be bonded to each other to form a ring, and when a plurality of OR ^f2s exist, two of the plurality of OR ^f2s may be bonded to each other to form a ring). The photosensitive composition preferably contains one or more boron compounds represented by the above formula (f1) as the Lewis acidic compound.

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

Preferable specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthalene-1-yl group, a naphthalene-2-yl group, a 4-phenylphenyl group, a 3-phenylphenyl group, and a 2-phenylphenyl group. Among them, a phenyl group is preferred.

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

The hydrocarbon group as R ^f1 and R ^f2 may have one or more substituents. Examples of the substituent include a halogen atom, a hydroxyl group, an alkyl group, an aralkyl group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, Arylthio, aralkylthio, acylthio, acyloxy, acylthio, alkoxycarbonyl, cycloalkoxycarbonyl, aryloxycarbonyl, amine, N-monosubstituted amine, N,N -Disubstituted amino, aminocarboxy (-CO-NH ₂ ), N-monosubstituted aminocarboxy, N,N-disubstituted aminocarboxy, nitro and cyano, etc. The number of carbon atoms of the substituent is not particularly limited as long as it does not inhibit the object of the present invention, but is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less.

Preferred specific examples of the organoboron compound represented by the above formula (f1) include the following compounds. In addition, in the following formula, Pen represents a pentyl group, Hex represents a hexyl group, Hep represents a heptyl group, Oct represents an octyl group, Non represents a nonyl group, and Dec represents a decyl group.

With respect to 100 parts by mass of the total mass of the resin (B) and the alkali-soluble resin (D), the Lewis acid compound is preferably used in a range of 0.01 part by mass to 5 parts by mass, and more preferably 0.01 part by mass or more. It is used in the range of 3 mass parts or less, and it is more preferable to use it in the range of 0.05 mass part or more and 2 mass parts or less.

In addition, when the photosensitive composition is used to form a pattern as a mold for forming a plated molded object, in order to improve the adhesion between the mold formed using the photosensitive composition and the metal substrate, the photosensitive composition also Adhesion aids may be included.

In addition, the photosensitive composition may further contain a surfactant in order to improve coating properties, defoaming properties, leveling properties, and the like. As the surfactant, for example, a fluorine-based surfactant or a silicone-based surfactant is preferably used. Specific examples of fluorine-based surfactants include BM-1000, BM-1100 (all manufactured by BM Chemical Co., Ltd.), MEGAFAC F142D, MEGAFAC F172, MEGAFAC F173, and MEGAFAC F183 (all manufactured by Dainippon Ink Chemical Co., Ltd.) ), Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431 (all manufactured by Sumitomo 3M), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Commercially available fluorosurfactants such as Surflon S-145 (all manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (all manufactured by Toray Silicone Co., Ltd.) , but not limited to these. As the silicone-based surfactant, unmodified silicone-based (polysiloxane) surfactants, polyether-modified silicone-based surfactants, polyester-modified silicone-based surfactants, Alkyl-modified silicone surfactants, aralkyl-modified silicone-based surfactants, and reactive silicone-based surfactants, etc. As the silicone-based surfactant, commercially available silicone-based surfactants can be used. Specific examples of commercially available silicone-based surfactants include PAINTADD M (manufactured by Toray Dow Corning), Tepica K1000, Tepica K2000, Tepica K5000 (all manufactured by Takachiho Sangyo Co., Ltd.), XL- 121 (polyether-modified silicone-based surfactant, manufactured by Clariant), BYK-310 (polyester-modified silicone-based surfactant, manufactured by BYK Chemicals), etc.

In addition, the photosensitive composition may further contain an acid or an acid anhydride in order to finely adjust the solubility with respect to the developer.

Specific examples of acids and acid anhydrides include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid, and cinnamic acid; lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid, syringic acid and other hydroxyl groups Monocarboxylic 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, butanetetracarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, 1,2,5,8-Naphthalenetetracarboxylic acid and other polycarboxylic acids; itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarboxylic anhydride, maleic anhydride, hexahydrophthalic anhydride , Methyltetrahydrophthalic anhydride, Nadic anhydride, 1,2,3,4-butanetetracarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride , benzophenone tetracarboxylic anhydride, ethylene glycol bis-trimellitic anhydride, glycerol trimellitic anhydride and other acid anhydrides.

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

In addition, the above-mentioned photosensitive composition is prepared by mixing and stirring each of the above-mentioned components by a usual method. As an apparatus which can be used when mixing and stirring the said each component, a dissolver, a homogenizer, a three-roll mill, etc. are mentioned. After the above-mentioned components are uniformly mixed, the obtained mixture can be further filtered using a mesh, a membrane filter, or the like.

The above-mentioned photosensitive composition is excellent in storage stability. Therefore, even if a long period of time (for example, 2 weeks) elapses after the preparation of the photosensitive composition, or even if the photosensitive composition is stored at a relatively high temperature (for example, 40° C.), the viscosity change can be suppressed.

"Photosensitive dry film and method for producing photosensitive dry film" The photosensitive dry film has a base film and a photosensitive layer formed on the surface of the base film, and the photosensitive layer is composed of the above-mentioned photosensitive composition.

As a base film, it is preferable to have light transmittance. Specifically, a polyethylene terephthalate (PET) film, a polypropylene (PP) film, a polyethylene (PE) film, etc. can be mentioned, from the viewpoint of achieving an excellent balance between light transmittance and breaking strength See, polyethylene terephthalate (PET) films are preferred.

A photosensitive dry film is produced by coating the above-mentioned photosensitive composition on a base film to form a photosensitive layer. When the photosensitive layer is formed on the base film, the photosensitive composition is applied on the base film using an applicator, a bar coater, a wire bar coater, a roll coater, a curtain coater, or the like and dried so that The film thickness after drying is preferably 0.5 μm or more and 300 μm or less, more preferably 1 μm or more and 300 μm or less, and particularly preferably 3 μm or more and 100 μm or less. Since the solid content concentration of the said photosensitive composition is high, it is suitable to form the photosensitive layer of a thick film (for example, 70 micrometers or more).

The photosensitive dry film may further have a protective film on the photosensitive layer. As this protective film, a polyethylene terephthalate (PET) film, a polypropylene (PP) film, a polyethylene (PE) film, etc. are mentioned.

"Patterned resist film and manufacturing method of substrate with mold" The method of forming a patterned resist film on a board|substrate using the photosensitive composition demonstrated above is not specifically limited. The patterned resist film is preferably used as an insulating film, an etching mask, a mold for forming a plated molding, and the like. The manufacturing method of the patterned resist film comprising the following steps can be exemplified as a preferred method: the lamination step, laminating a photosensitive layer composed of a photosensitive composition on the substrate; In the exposure step, the position of the photosensitive layer is selectively irradiated with active light rays or radiation for exposure; In the developing step, the exposed photosensitive layer is developed. The method for producing a mold-attached substrate provided with a mold for forming a plated molded object includes, in addition to the step of using a substrate having a metal surface as a substrate and laminating a photosensitive layer on the metal surface of the substrate having a metal surface, in the development step The method for producing a patterned resist film is the same as the production method of the patterned resist film, except that a mold for forming a plated molded object is produced by development.

The substrate on which the photosensitive layer is laminated is not particularly limited, and a conventionally known substrate can be used, for example, a substrate for electronic components or a substrate on which a predetermined wiring pattern is formed. As the substrate, a silicon substrate, a glass substrate, or the like can also be used. When manufacturing the board|substrate with a casting_mold|template provided with the casting_mold|template for forming a plated molding, the board|substrate which has a metal surface is used as a board|substrate. As the metal species constituting the metal surface, copper, gold, and aluminum are preferred, and copper is more preferred.

For example, the photosensitive layer is laminated on the substrate as follows. That is, a photosensitive layer having a desired film thickness is formed by applying a liquid photosensitive composition on a substrate and removing the solvent by heating. The thickness of the photosensitive layer is not particularly limited as long as the resist pattern can be formed with a desired film thickness. The film thickness of the photosensitive layer is not particularly limited, but is preferably 0.5 μm or more, more preferably 1 μm or more, still more preferably 10 μm or more, and can also be a thick film of 70 μm or more or 100 μm or more. The upper limit of the film thickness is, for example, 300 μm or less. Since the solid content concentration of the said photosensitive composition is high, a thick photosensitive layer can be formed. Therefore, it can be suitably used, for example, to form a plated molded object.

As a coating method for coating the photosensitive composition on the substrate, a spin coating method, a slit coating method, a roll coating method, a screen printing method, an applicator method, or the like can be used. The photosensitive layer is preferably prebaked. The pre-baking conditions vary depending on the type of each component in the photosensitive composition, the blending ratio, the coating film thickness, etc., but it is usually 70°C or higher and 200°C or lower, preferably 80°C or higher and 150°C or lower. , for more than 2 minutes and less than 120 minutes. The prebaking may be performed multiple times in two or more stages. For example, after prebaking in the first stage at a temperature of 70° C. or higher and 120° C. or lower, prebaking in the second stage may be performed at a temperature higher than that in the first stage.

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

As a radiation source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an argon laser, or the like can be used. In addition, the radiation includes microwaves, infrared rays, visible rays, ultraviolet rays, X rays, gamma rays, electron rays, proton rays, neutron rays, ion rays, and the like. The radiation exposure amount varies depending on the composition of the photosensitive composition, the film thickness of the photosensitive layer, and the like, but is, for example, 100 mJ/cm ² or more and 10000 mJ/cm ² or less. Moreover, in order to generate|occur|produce an acid, the light which activates the acid generator (A) is contained in a radiation.

After exposure, the photosensitive layer is heated (PEB) using a known method to promote acid diffusion, and in the exposed portion of the photosensitive layer, the solubility of the photosensitive layer to a developing solution such as an alkaline developer is changed.

Next, the exposed photosensitive layer is developed according to a conventionally known method to dissolve and remove unnecessary parts, thereby forming a predetermined resist pattern or a mold for forming a plated molded object. At this time, as the developing solution, an alkaline aqueous solution can be used.

The photosensitive layer after exposure formed using the above-mentioned photosensitive composition can suppress repelling to the developer. Therefore, for example, a developer can be brought into contact with the entire photosensitive layer, and a resist pattern corresponding to a mask or the like or a mold for forming a plated molded object can be formed in the entire region where the photosensitive layer is provided. Moreover, the photosensitive layer after exposure formed using the said photosensitive composition can suppress swelling at the time of image development. Therefore, for example, in the obtained resist pattern or a mold for forming a plated molded object, wrinkles due to swelling, dissolution of unexposed parts, and floating or deformation can be suppressed.

As the developer, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium methyl silicate, ammonia water, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyl Diethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, pyridine, 1,8-diazabicyclo[5,4,0]-7-deca Aqueous solutions of bases such as monocarbene and 1,5-diazabicyclo[4,3,0]-5-nonane. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol and ethanol or a surfactant to the aqueous solution of the above-mentioned alkalis can also be used as a developing solution.

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

After development, for example, running water cleaning is performed for 30 seconds to 90 seconds, and drying is performed using an air gun, an oven, or the like. In this way, a resist pattern patterned into a desired shape is formed on the metal surface of the substrate having the metal surface. In addition, in this way, a substrate having a resist pattern on the surface of the substrate can be manufactured. The photosensitive layer formed using the above-mentioned photosensitive composition as described above can suppress the occurrence of cracks. Therefore, for example, when the obtained resist pattern is used as a mold for forming a plated molding, it becomes easy to form a plated molding of a desired shape.

《Method for producing a plated molded article》 In the non-resistor portion (the portion removed by the developer) in the mold of the substrate with the mold formed by the above method, conductors such as metal are embedded by plating, whereby connections such as bumps and metal pillars can be formed. Terminals, or plated moldings such as Cu rewiring. In addition, the plating treatment method is not particularly limited, and various conventionally known methods can be employed. As the plating solution, a solder plating solution, a copper plating solution, a gold plating solution, and a nickel plating solution are particularly preferably used. The remaining mold is finally removed using a stripping liquid or the like according to a conventional method.

[Example]

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

[Examples 1 to 8 and Comparative Examples 1 to 18] In Examples and Comparative Examples, PAG1 and PAG2 of the following formula were used as the acid generator (A).

In Examples and Comparative Examples, the following resins B1 to B4 and B'1 to B'16 were used as resins (resin (B)) whose solubility in alkalis was increased by the action of an acid. The lower right digit of the parenthesis in each structural unit in the following structural formula represents the content (mass %) of the structural unit in the resin. The mass average molecular weight Mw and molecular weight distribution coefficient (Mw/Mn) of each resin are shown in Table 1 below.

In the Examples and Comparative Examples, the following C1 and the compound C2 of the following formula were used as the acid diffusion control agent (C). C1: ADK STAB LA-63P (methyl 1,2,3,4-butanetetracarboxylate with 1,2,2,6,6-pentamethyl-4-piperidinol and β,β,β' , β'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol reaction product) (made by ADEKA).

As the alkali-soluble resin (D), the following D1 (novolak resin (condensate of m-cresol and p-cresol)) was used. The lower right digit of the parenthesis in each structural unit in the following structural formula represents the content (mass %) of the structural unit in the resin. The mass average molecular weight (Mw) of resin D1 was 8000.

In Examples and Comparative Examples, the sulfur-containing compound E1 of the following formula was used as the sulfur-containing compound (E).

In the Examples and Comparative Examples, the following F1 was used as the dye (F). F1: Curcumin

The acid generator (A), resin (B), acid diffusion control agent (C), alkali-soluble resin (D), dye (F), and 0.1 part by mass of the types and parts by mass described in Table 2 were used. E1 of the sulfur-containing compound (E) and 0.02 parts by mass of a surfactant (BYK310, manufactured by BYK) were dissolved in 3-methoxybutyl acetate (organic solvent) so that the solid content concentration would be 48% by mass. (S)), the photosensitive compositions of Examples 1-8 and Comparative Examples 1-18 were obtained. In addition, by adding components other than the organic solvent (S), that is, the resin (B), the acid generator (A), the acid diffusion control agent (C), the alkali-soluble resin (D), the sulfur-containing compound (E), the dye (F) ) and the total mass of the surfactant were divided by the mass of the photosensitive composition to obtain the solid content concentration.

Using the obtained photosensitive composition, evaluation was performed according to the following method. The results are shown in Table 2. [Evaluation of resist pattern (developer repellency, swelling property, and crack resistance)] The photosensitive compositions of Examples and Comparative Examples were coated on a copper film of a copper sputtered silicon wafer substrate (copper film thickness: 200 nm) using a spin coater, and heated on a hot plate at 100° C. for 150 seconds. And it heated at 150 degreeC for 450 second (prebaking), and obtained the photosensitive layer whose thickness is 100 micrometers. After heating (pre-baking), a mask with a square pattern of 30 μm×30 μm and a projection exposure device Prisma GHI5452 (manufactured by Ultratech) were used, and the exposure amount was 1.2 times the minimum exposure amount capable of forming a pattern of a predetermined size. The photosensitive layer is selectively exposed using ghi lines. Next, the substrate was placed on a hot plate and subjected to post-exposure heating (PEB) at 100° C. for 3 minutes. Then, a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution (developer, NMD-3, manufactured by Tokyo Oka Kogyo Co., Ltd.) was added dropwise to the exposed photosensitive layer, and it was left to stand at 23° C. for 60 seconds. (Puddle Development), which was repeated 6 times for development. Then, it wash|cleaned for 60 second with running water, and spin-dried, and obtained the board|substrate with a resist pattern (patterned resist film). For the evaluation of developer repellency, the developer was not repelled at the time of development, and the developer was contained in the entire photosensitive layer, and a square pattern corresponding to the mask was formed in the entire region where the photosensitive layer was provided. It is ○; the developer is repelled during development, so that the developer is not contained on the entire surface of the photosensitive layer, and the formation of the resist pattern is defective (in the case of a region where a square pattern is not formed, or Although a square pattern was formed, it was a case of a shape that was significantly different from the mask), which was evaluated as ×. In the evaluation of swelling property, the photosensitive layer was not swelled during development, no wrinkles were observed in the obtained resist pattern, no dissolution of the unexposed part, and no floating or deformation was observed as ◯. In addition, when the unexposed part of the photosensitive layer swelled at the time of development, and wrinkles were observed in the obtained resist pattern, when the unexposed part was dissolved, or when floating or deformation was observed, it was evaluated as ×. For the evaluation of crack resistance, the obtained resist pattern (square pattern) was observed, the case where cracks were observed at the corners of the square pattern was evaluated as ×, and the case where no cracks were observed at the corners of the square pattern was evaluated. The condition was evaluated as ○.

[Evaluation of storage stability] For the photosensitive compositions of Examples and Comparative Examples, the viscosity was measured using an E-type viscometer at 25° C. immediately after preparation, and the viscosity was measured at 25° C. using an E-type viscometer after standing at 40° C. for 2 weeks. The case where the ratio V2/V1 of the viscosity V1 immediately after preparation and the viscosity V2 after standing at 40° C. for 2 weeks was less than 1.1 was evaluated as ○, and the case of 1.1 or more was evaluated as ×. The results are shown in Table 2.

According to the examples, the following chemically amplified positive-type photosensitive compositions have good storage stability and can form a thick-film photosensitive layer with suppressed repellency and swelling to the developer and excellent crack resistance, that is, including: acid-generating Agent (A), which generates acid by irradiation with actinic rays or radiation; Resin (B), whose solubility in alkali is increased by the action of acid, as resin (B) includes acrylic resin (B3), acrylic resin (B3) ) contains the structural unit represented by formula (B3-1), and the solid content concentration is 25 mass % or more and 70 mass % or less.

On the other hand, according to the comparative example, the storage stability of the chemically amplified positive type photosensitive composition that does not contain the acrylic resin (B3) containing the structural unit represented by the formula (B3-1) as the resin (B) is poor, Alternatively, repelling, swelling, or cracking of the developer occurs in the formed photosensitive layer.

Claims (11)

A chemically amplified positive photosensitive composition, characterized by comprising: an acid generator (A), which generates an acid by irradiation with actinic rays or radiation; a resin (B), whose solubility in alkalis is enhanced by the action of the acid Increase, the aforementioned resin (B) includes an acrylic resin (B3), and the aforementioned acrylic resin (B3) includes a structural unit represented by the following formula (B3-1),

In formula (B3-1), R ^b01 is a hydrogen atom or a methyl group, R ^b02 is a single bond or a linking group, R ^b03 is a hydrogen atom or an aliphatic hydrocarbon group, and R ^b04 and R ^b05 are each independently a single bond or aliphatic Hydrocarbon group, R ^b04 and R ^b05 are not single bonds at the same time, R ^b06 and R ^b07 are each independently a hydrogen atom or an aliphatic hydrocarbon group, and one of R ^b02 and R ^b03 may be combined with the main chain of the acrylic resin (B3). Carbon atoms are bonded to form a ring, R ^b02 and R ^b03 can be bonded to form a ring, R ^b02 and R ^b05 can be bonded to form a ring, R ^b06 and R ^b07 can be bonded to form a ring, the aforementioned chemically amplified positive type The solid content concentration of the photosensitive composition is 25 mass % or more and 70 mass % or less. The chemically amplified positive photosensitive composition according to claim 1, wherein the structural unit represented by the aforementioned formula (B3-1) is a structural unit represented by the following formula (B3-2),

In formula (B3-2), R ^b01 , R ^b03 , R ^b04 , R ^b05 , R ^b06 and R ^b07 are the same as those in the aforementioned formula (B3-1), R ^b010 is a single bond or a hydrocarbon group, R ^b05 and R ^b010 can be bonded to form a ring. The chemically amplified positive type photosensitive composition according to claim 2, wherein, in the formula (B3-2), R ^b03 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ^b04 And R ^b05 is each independently a single bond or a methylene group, R ^b06 and R ^b07 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ^b010 is a methylene group. The chemically amplified positive photosensitive composition according to any one of claims 1 to 3, wherein The ratio of the mass of the structural unit represented by the said formula (B3-1) with respect to the mass of the said acrylic resin (B3) is 5 mass % or more and 50 mass % or less. The chemically amplified positive photosensitive composition according to any one of claims 1 to 4, wherein A sulfur-containing compound (E) containing a sulfur atom capable of coordinating with a metal is also contained. The chemically amplified positive photosensitive composition according to any one of claims 1 to 5, wherein It is used to form a casting mold for forming a plated molding. The chemically amplified positive photosensitive composition according to any one of claims 1 to 6, characterized in that: The viscosity when the chemically amplified positive photosensitive composition was measured at 25°C using an E-type viscometer was set as V1, the chemically amplified positive photosensitive composition was allowed to stand at 40°C for 2 weeks, and the E-type was used. V2/V1 is less than 1.1 when the viscosity when the viscometer measures the chemically amplified positive type photosensitive composition after standing at 25°C is set to V2. A photosensitive dry film, characterized in that: A base film and a photosensitive layer formed on the surface of the base film, wherein the photosensitive layer is composed of the chemically amplified positive-type photosensitive composition according to any one of claims 1 to 7. A method for manufacturing a patterned resist film, comprising: The lamination step is to laminate a photosensitive layer composed of the chemically amplified positive type photosensitive composition according to any one of claims 1 to 7 on a substrate; an exposure step of selectively irradiating the photosensitive layer with active light rays or radiation; and In the developing step, the exposed photosensitive layer is developed. A method for manufacturing a substrate with a mold, comprising: The lamination step is to laminate a photosensitive layer composed of the chemically amplified positive photosensitive composition according to any one of claims 1 to 7 on a substrate having a metal surface; an exposure step of selectively irradiating the photosensitive layer with active light rays or radiation; and In the development step, the exposed photosensitive layer is developed to prepare a mold for forming a plated molded object. A method of manufacturing a plated molded object, characterized in that: The said board|substrate with a casting_mold|template manufactured by the manufacturing method of the board|substrate with a casting_mold|template as described in Claim 10 is included, and the process of forming a plated molded object in the said casting_mold is included.