Chemical amplification type positive type photosensitive resin composition, photosensitive dry film, and method for producing patterned resist film

Abstract

To provide a chemical amplification type positive type photosensitive resin composition from which a patterned resist film suppressing roughness on its side wall is given, a photosensitive dry film, a method for producing a patterned resist film, a method for manufacturing a substrate with a mold, a method for manufacturing a plated molded article, a method for manufacturing a substrate with a mask for plasma etching, and a substrate etching method.SOLUTION: In a chemical amplification type positive type photosensitive resin composition which contains an optical acid generator (A) for generating acid by irradiation with active rays or radiation, a resin (B) for increasing dissolubility to alkali by action of the acid and an organic solvent (S), the organic solvent (S) contains an organic solvent (S1) having a boiling point under the atmospheric pressure of 210°C or lower or no boiling point under the atmospheric pressure, and an organic solvent (S2) having a boiling point under the atmospheric pressure of lower than 210°C.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a chemically amplified positive photosensitive resin composition, a photosensitive dry film including a photosensitive layer made of the chemically amplified positive photosensitive resin composition, a method for manufacturing a patterned resist film using the aforementioned chemically amplified positive photosensitive resin composition, a method for manufacturing a substrate with a mold, a method for manufacturing an electroformed product, a method for manufacturing a substrate with a mask for plasma etching, and a method for etching a substrate.

Background Art

[0002] Currently, photolithography has become the mainstream of precision microfabrication technology. Photolithography refers to a general term for a technology in which a photoresist composition is applied to the surface of a workpiece to form a photoresist layer, the photoresist layer is patterned by photolithography technology, and chemical etching, electrolytic etching, or electroforming mainly using electroplating is performed using the patterned photoresist layer (photoresist pattern) as a mask to manufacture various precision parts such as semiconductor packages.

[0003] In recent years, with the downsizing of electronic devices, the high-density mounting technology of semiconductor packages has advanced, and improvements in mounting density have been achieved based on multi-pin thin film mounting of packages, miniaturization of package sizes, two-dimensional mounting technology using the flip-chip method, and three-dimensional mounting technology. In such high-density mounting technology, as connection terminals, for example, protruding electrodes (mounting terminals) such as bumps protruding on the package, or metal posts connecting redistribution lines (RDLs) extending from peripheral terminals on the wafer and mounting terminals are arranged on the substrate with high precision.

[0004] A photoresist composition is used in the above-mentioned photolithography. As such a photoresist composition, a positive photoresist composition containing an alkali-soluble novolak resin and a photosensitizer such as a compound having a naphthoquinonediazide group is known (see Patent Document 1, etc.).

[0005] Such positive photoresist compositions are used, for example, in the formation of plating-shaped objects such as bumps, metal posts, and Cu rewiring by plating processes. Specifically, using a positive photoresist composition, a photoresist layer with a desired film thickness is formed on a support such as a metal substrate, exposed through a predetermined mask pattern, developed, and a photoresist pattern is formed as a mold in which the portion for forming the plating-shaped object is selectively removed (peeled off). Then, after filling the removed portion (non-resist portion) with a conductor such as copper by plating, the surrounding photoresist pattern is removed, thereby forming bumps, metal posts, and Cu rewiring. In addition, positive photoresist compositions are also used, for example, in the formation of an etching mask when processing a substrate by etching. Specifically, using a chemically amplified photoresist composition, a photoresist layer with a desired film thickness is formed on the substrate. Then, only the portion corresponding to the etching target location of the photoresist layer is exposed through a predetermined mask pattern, and after that, the exposed photoresist layer is developed to form a photoresist pattern used as an etching mask.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] When forming a patterned resist film using a positive photoresist composition as described in Patent Document 1, roughness may occur on the side surface of the pattern due to the influence of reflection from the substrate. When the roughness on the side surface of the pattern, the patterned resist film is used as a mold for plating or as an etching mask, it has an adverse effect on the shape of the plating-shaped object and the shape of the substrate processed by etching.

[0008] The present invention has been made in view of the above problems, and provides a chemically amplified positive photosensitive resin composition that gives a patterned resist film with suppressed roughness on the side walls, a photosensitive dry film including a photosensitive layer made of the chemically amplified positive photosensitive resin composition, a method for manufacturing a patterned resist film using the above-described chemically amplified positive photosensitive resin composition, a method for manufacturing a substrate with a mold using the above-described chemically amplified positive photosensitive resin composition, a method for manufacturing an electroformed article using the above-described chemically amplified positive photosensitive resin composition, a method for manufacturing a substrate with a mask for plasma etching, and a method for etching a substrate.

Means for Solving the Problems

[0009] As a result of intensive studies to achieve the above object, the present inventors have found that in a chemically amplified positive photosensitive resin composition containing a photoacid generator (A) that generates an acid upon irradiation with actinic rays or radiation, a resin (B) whose solubility in alkali increases by the action of an acid, and an organic solvent (S), by using an organic solvent (S) containing an organic solvent (S1) having a boiling point of 210°C or higher under atmospheric pressure or having no boiling point under atmospheric pressure and an organic solvent (S2) having a boiling point of less than 210°C under atmospheric pressure, the above problems can be solved, and the present invention has been completed. Specifically, the present invention provides the following.

[0010] A first aspect of the present invention includes a photoacid generator (A) that generates an acid upon irradiation with actinic rays or radiation, a resin (B) whose solubility in alkali increases by the action of an acid, and an organic solvent (S), wherein the organic solvent (S) is a chemically amplified positive photosensitive composition containing an organic solvent (S1) having a boiling point of 210°C or higher under atmospheric pressure or having no boiling point under atmospheric pressure and an organic solvent (S2) having a boiling point of less than 210°C under atmospheric pressure.

[0011] The second aspect of the present invention is a photosensitive dry film having 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 photosensitive composition according to the first aspect.

[0012] The third aspect of the present invention is a method for manufacturing a patterned resist film, including a laminating step of laminating a photosensitive layer composed of the chemically amplified positive photosensitive composition according to the first aspect on a substrate, an exposure step of selectively irradiating the photosensitive layer with actinic rays or radiation, and a developing step of developing the exposed photosensitive layer.

[0013] The fourth aspect of the present invention is a method for manufacturing a substrate with a mold, including a laminating step of laminating a photosensitive layer composed of the chemically amplified positive photosensitive composition according to the first aspect on a substrate, an exposure step of selectively irradiating the photosensitive layer with actinic rays or radiation, and a developing step of developing the exposed photosensitive layer to create a mold for forming a plated molded article.

[0014] The fifth aspect of the present invention is a method for manufacturing a plated molded article, including a step of plating a substrate with a mold manufactured by the method for manufacturing a substrate with a mold according to the fourth aspect to form a plated molded article in the mold.

[0015] The sixth aspect of the present invention is a method for manufacturing a substrate with a mask for plasma etching, including a laminating step of laminating a photosensitive layer composed of the chemically amplified positive photosensitive composition according to the first aspect on a substrate, an exposure step of selectively irradiating the photosensitive layer with actinic rays or radiation, and a developing step of developing the exposed photosensitive layer to create a mask for plasma etching.

[0016] The seventh aspect of the present invention is a method for etching a substrate, including performing plasma etching on a substrate with a mask for plasma etching manufactured by the method for manufacturing a substrate with a mask for plasma etching according to the sixth aspect.

Advantages of the Invention

[0017] According to the present invention, there are provided a chemically amplified positive photosensitive resin composition that provides a patterned resist film with suppressed roughness on sidewalls, a photosensitive dry film including a photosensitive layer made of the chemically amplified positive photosensitive resin composition, a method for manufacturing a patterned resist film using the above-described chemically amplified positive photosensitive resin composition, a method for manufacturing a substrate with a mold using the above-described chemically amplified positive photosensitive resin composition, a method for manufacturing an electroformed product using the above-described chemically amplified positive photosensitive resin composition, a method for manufacturing a substrate with a mask for plasma etching, and a method for etching a substrate.

Embodiments for Carrying Out the Invention

[0018] ≪Chemically Amplified Positive Photosensitive Resin Composition≫ The chemically amplified positive photosensitive resin composition (hereinafter, also referred to as the photosensitive resin composition) contains a photoacid generator (A) (hereinafter, also referred to as the photoacid generator (A)) that generates an acid upon irradiation with actinic rays or radiation, a resin (B) (hereinafter, also referred to as the resin (B)) whose solubility in alkali increases by the action of an acid, and an organic solvent (S). The photosensitive resin composition may contain components such as a radical generator (C), an alkali-soluble resin (D), a sulfur-containing compound (E), and an acid diffusion inhibitor (F) that satisfy specific requirements described later, if necessary.

[0019] Hereinafter, the essential or optional components contained in the photosensitive resin composition and the method for manufacturing the photosensitive resin composition will be described.

[0020] <Photoacid Generator (A)> The photoacid generator (A) is a compound that generates an acid upon irradiation with actinic rays or radiation, and is a compound that generates an acid directly or indirectly by light. As the photoacid generator (A), photoacid generators conventionally incorporated in various photosensitive compositions can be used without particular limitation.

[0021] As the photoacid generator (A), a sulfonate-type photoacid generator (A1) which is a nonionic photoacid generator that generates sulfonic acid upon irradiation with actinic rays or radiation, and an onium salt-type photoacid generator (A2) are preferred.

[0022] Examples of the sulfonate-type photoacid generator (A1) include sulfonium ester compounds such as imide sulfonate compounds and oxime sulfonate compounds. The imide sulfonate compound is a compound having a structure represented by >N-O-SO2-, and decomposes at the N-O bond upon irradiation with actinic rays or radiation to generate sulfonic acid. The oxime sulfonate compound is a compound having a structure represented by =N-O-SO2-, and decomposes at the N-O bond upon irradiation with actinic rays or radiation to generate sulfonic acid.

[0023] Examples of the oxime sulfonate compound include compounds represented by the following formula (a1).

Chemical formula

[0024] In the above formula (a1), R 20a represents a monovalent, divalent, or trivalent organic group, R 21a represents a substituted or unsubstituted saturated hydrocarbon group, unsaturated hydrocarbon group, or aromatic group, and n represents the number of repeating units of the structure in parentheses.

[0025] In the above formula (a1), examples of the aromatic group include aryl groups such as a phenyl group and a naphthyl group, and heteroaryl groups such as a furyl group and a thienyl group. These may have one or more appropriate substituents on the ring, such as a halogen atom, an alkyl group, an alkoxy group, a nitro group, etc. Further, R 21a is particularly preferably an alkyl group having 1 to 6 carbon atoms, and examples include a methyl group, an ethyl group, a propyl group, and a butyl group. In particular, a compound in which R 20a is an aromatic group and R 21a is an alkyl group having 1 to 4 carbon atoms is preferred.

[0026] As the acid generator represented by the above formula (a1), when n = 1, R 20a is any of a phenyl group, a methylphenyl group, and a methoxyphenyl group, and R 21a is a methyl group, and specific examples thereof include α-(methylsulfonyloxyimino)-1-phenylacetonitrile, α-(methylsulfonyloxyimino)-1-(p-methylphenyl)acetonitrile, α-(methylsulfonyloxyimino)-1-(p-methoxyphenyl)acetonitrile, and the like. When n = 2, specific examples of the compound represented by the above formula (a1) include compounds represented by the following formulae.

[0027]

Chemical formula

[0028] As the oxime sulfonate compound, the following compounds are also preferable.

Chemical formula

[0029] Examples of the imide sulfonate compound include compounds represented by the following formula (a2).

Chemical formula

[0030] R22a The organic group as such is not particularly limited as long as it does not inhibit the object of the present invention. The organic group may be a hydrocarbon group and may contain heteroatoms such as O, N, S, P, and halogen atoms. Further, the structure of the organic group may be linear, branched, cyclic, or a combination of these structures.

[0031] R 22a Suitable organic groups as such include a halogen atom and / or an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted with an alkylthio group, an aryl group having 6 to 20 carbon atoms which may have a substituent, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, an alkylaryl group having 7 to 20 carbon atoms which may have a substituent, a camphor-10-yl group, and the following formula (a2a): -R 29a -(O) a -R 30a -(O) b -Y 1 -R 31a ···(a2a) (In formula (a2a), Y 1 is a single bond or an alkanediyl group having 1 to 4 carbon atoms. R 29a and R 30a are each an alkanediyl group having 2 to 6 carbon atoms which may be substituted with a halogen atom, or an arylene group having 6 to 20 carbon atoms which may be substituted with a halogen atom. R 31a is an alkyl group having 1 to 18 carbon atoms which may be substituted with a halogen atom, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom, or an aralkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom. a and b are each 0 or 1, and at least one of a and b is 1.) Groups represented by the following formula are exemplified.

[0032] R 22aWhen the organic group as [substituent] has a halogen atom as a substituent, examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom.

[0033] R 22a When the organic group as [substituent] is an alkyl group having 1 to 18 carbon atoms substituted with an alkylthio group, the number of carbon atoms of the alkylthio group preferably ranges from 1 to 18. Examples of the alkylthio group having 1 to 18 carbon atoms include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, a sec-butylthio group, a tert-butylthio group, an isobutylthio group, an n-pentylthio group, an isopentylthio group, a tert-pentylthio group, an n-hexylthio group, an n-heptylthio group, an isoheptylthio group, a tert-heptylthio group, an n-octylthio group, an isooctylthio group, a tert-octylthio group, a 2-ethylhexylthio group, an n-nonylthio group, an n-decylthio group, an n-undecylthio group, an n-dodecylthio group, an n-tridecylthio group, an n-tetradecylthio group, an n-pentadecylthio group, an n-hexadecylthio group, an n-heptadecylthio group, and an n-octadecylthio group.

[0034] R 22a When the organic group as [substituent] 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. Further, the structure of the aliphatic hydrocarbon group is not particularly limited, and it may be linear, branched, cyclic, or a combination of these structures.

[0035] R 22a Preferable examples when the organic group as [substituent] is an alkenyl group include an allyl group and a 2-methyl-2-propenyl group.

[0036] R 22aPreferable examples where the organic group as such is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group, an n-hexyl group, an n-hexan-2-yl group, an n-hexan-3-yl group, an n-heptyl group, an n-heptan-2-yl group, an n-heptan-3-yl group, an isoheptyl group, a tert-heptyl group, an n-octyl group, an isooctyl group, a tert-octyl group, a 2-ethylhexyl group, an n-nonyl group, an isononyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, and an n-octadecyl group.

[0037] R 22a When the organic group as such is 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. As the alicyclic hydrocarbon group, a group obtained by removing one hydrogen atom from these alicyclic hydrocarbons is preferable.

[0038] R 22aPreferable examples where the organic group as such is an aliphatic hydrocarbon group substituted with a halogen atom include a trifluoromethyl group, a pentafluoroethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a heptafluoro-n-propyl group, a 3-bromopropyl group, a nonafluoro-n-butyl group, a tridecafluoro-n-hexyl group, a heptadecafluoro-n-octyl group, a 2,2,2-trifluoroethyl group, a 1,1-difluoroethyl group, a 1,1-difluoro-n-propyl group, a 1,1,2,2-tetrafluoro-n-propyl group, a 3,3,3-trifluoro-n-propyl group, a 2,2,3,3,3-pentafluoro-n-propyl group, a 2-norbornyl-1,1-difluoroethyl group, a 2-norbornyl tetrafluoroethyl group, and a 3-adamantyl-1,1,2,2-tetrafluoropropyl group.

[0039] R 22a Preferable examples where the organic group as such is an aliphatic hydrocarbon group substituted with an alkylthio group include a 2-methylthioethyl group, a 4-methylthio-n-butyl group, and a 2-n-butylthioethyl group.

[0040] R 22a Preferable examples where the organic group as such is an aliphatic hydrocarbon group substituted with a halogen atom and an alkylthio group include a 3-methylthio-1,1,2,2-tetrafluoro-n-propyl group.

[0041] R 22a Preferable examples where the organic group as such is an aryl group include a phenyl group, a naphthyl group, and a biphenylyl group.

[0042] R 22a Preferable examples where the organic group as such is an aryl group substituted with a halogen atom include a pentafluorophenyl group, a chlorophenyl group, a dichlorophenyl group, and a trichlorophenyl group.

[0043] R 22aPreferable examples where the organic group as [the group in question] is an aryl group substituted with an alkylthio group include a 4-methylthiophenyl group, a 4-n-butylthiophenyl group, a 4-n-octylthiophenyl group, and a 4-n-dodecylthiophenyl group.

[0044] R 22a Preferable examples where the organic group as [the group in question] is an aryl group substituted with a halogen atom and an alkylthio group include a 1,2,5,6-tetrafluoro-4-methylthiophenyl group, a 1,2,5,6-tetrafluoro-4-n-butylthiophenyl group, and a 1,2,5,6-tetrafluoro-4-n-dodecylthiophenyl group.

[0045] R 22a Preferable examples where the organic group as [the group in question] is an aralkyl group include a benzyl group, a phenethyl group, a 2-phenylpropan-2-yl group, a diphenylmethyl group, and a triphenylmethyl group.

[0046] R 22a Preferable examples where the organic group as [the group in question] is an aralkyl group substituted with a halogen atom include a pentafluorophenylmethyl group, a phenyldifluoromethyl group, a 2-phenyltetrafluoroethyl group, and a 2-(pentafluorophenyl)ethyl group.

[0047] R 22a Preferable examples where the organic group as [the group in question] is an aralkyl group substituted with an alkylthio group include a p-methylthiobenzyl group.

[0048] R 22a Preferable examples where the organic group as [the group in question] is an aralkyl group substituted with a halogen atom and an alkylthio group include a 2-(2,3,5,6-tetrafluoro-4-methylthiophenyl)ethyl group.

[0049] R 22aPreferable examples where the organic group as such is an alkylaryl group include 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 4-n-butylphenyl group, 4-isobutylphenyl group, 4-tert-butylphenyl group, 4-n-hexylphenyl group, 4-cyclohexylphenyl group, 4-n-octylphenyl group, 4-(2-ethyl-n-hexyl)phenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4-di-tert-butylphenyl group, 2,5-di-tert-butylphenyl group, 2,6-di-tert-butylphenyl group, 2,4-di-tert-pentylphenyl group, 2,5-di-tert-pentylphenyl group, 2,5-di-tert-octylphenyl group, 2-cyclohexylphenyl group, 3-cyclohexylphenyl group, 4-cyclohexylphenyl group, 2,4,5-trimethylphenyl group, 2,4,6-trimethylphenyl group, 2,4,6-triisopropylphenyl group.

[0050] The group represented by formula (a2a) is a group containing an ether group. In formula (a2a), Y 1 Examples of the alkanediyl group having 1 to 4 carbon atoms represented by include methylene group, ethane-1,2-diyl group, ethane-1,1-diyl group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, butane-1,3-diyl group, butane-2,3-diyl group, butane-1,2-diyl group. In formula (a2a), R 29a or R 30aExamples of the alkane diyl group having 2 to 6 carbon atoms represented by include an ethane-1,2-diyl group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a butane-1,3-diyl group, a butane-2,3-diyl group, a butane-1,2-diyl group, a pentane-1,5-diyl group, a pentane-1,3-diyl group, a pentane-1,4-diyl group, a pentane-2,3-diyl group, a hexane-1,6-diyl group, a hexane-1,2-diyl group, a hexane-1,3-diyl group, a hexane-1,4-diyl group, a hexane-2,5-diyl group, a hexane-2,4-diyl group, and a hexane-3,4-diyl group.

[0051] In formula (a2a), R 29a or R 30a When is an alkane diyl group having 2 to 6 carbon atoms substituted with a halogen atom, examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. Examples of the alkane diyl group substituted with a halogen atom include a tetrafluoroethane-1,2-diyl group, a 1,1-difluoroethane-1,2-diyl group, a 1-fluoroethane-1,2-diyl group, a 1,2-difluoroethane-1,2-diyl group, a hexafluoropropane-1,3-diyl group, a 1,1,2,2,-tetrafluoropropane-1,3-diyl group, and a 1,1,2,2,-tetrafluoropentane-1,5-diyl group.

[0052] In formula (a2a), R 29a or R 30aExamples of the case where it is an arylene group include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 2,5-dimethyl-1,4-phenylene group, biphenyl-4,4'-diyl group, diphenylmethane-4,4'-diyl group, 2,2-diphenylpropane-4,4'-diyl group, naphthalene-1,2-diyl group, naphthalene-1,3-diyl group, naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, naphthalene-1,6-diyl group, naphthalene-1,7-diyl group, naphthalene-1,8-diyl group, naphthalene-2,3-diyl group, naphthalene-2,6-diyl group, naphthalene-2,7-diyl group.

[0053] In formula (a2a), R 29a or R 30a When it is an arylene group substituted with a halogen atom, examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. Examples of the arylene group substituted with a halogen atom include 2,3,5,6-tetrafluoro-1,4-phenylene group.

[0054] In formula (a2a), R 31a Examples of the alkyl group having 1 to 18 carbon atoms which may have a branch represented by include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, isopentyl group, tert-pentyl group, n-hexyl group, n-hexan-2-yl group, n-hexan-3-yl group, n-heptyl group, n-heptan-2-yl group, n-heptan-3-yl group, isoheptyl group, tert-heptyl group, n-octyl group, isooctyl group, tert-octyl group, 2-ethylhexyl group, n-nonyl group, isononyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group.

[0055] In formula (a2a), R 31aWhen it is an alkyl group having 1 to 18 carbon atoms substituted with a halogen atom, examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. Examples of the alkyl group substituted with a halogen atom include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoro-n-propyl group, a nonafluoro-n-butyl group, a tridecafluoro-n-hexyl group, a heptadecafluoro-n-octyl group, a 2,2,2-trifluoroethyl group, a 1,1-difluoroethyl group, a 1,1-difluoro-n-propyl group, a 1,1,2,2-tetrafluoro-n-propyl group, a 3,3,3-trifluoro-n-propyl group, a 2,2,3,3,3-pentafluoro-n-propyl group, and a 1,1,2,2-tetrafluorotetradecyl group.

[0056] In formula (a2a), R 31a When it 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, bicyclo[2.2.2]octane, and adamantane. As the alicyclic hydrocarbon group, a group obtained by removing one hydrogen atom from these alicyclic hydrocarbons is preferable.

[0057] In formula (a2a), R 31a When it is an aryl group, a halogenated aryl group, an aralkyl group, or a halogenated aralkyl group, preferable examples of these groups are the same as those when R 22a is these groups.

[0058] Among the groups represented by formula (a2a), a preferable group is a group in which the carbon atom bonded to the sulfur atom among the groups represented by R 29a is substituted with a fluorine atom. The number of carbon atoms of such a preferable group is preferably 2 or more and 18 or less.

[0059] R 22aAs for this, a perfluoroalkyl group having 1 to 8 carbon atoms is preferable. Further, since it is easy to form a highly fine patterned resist film, a camphor-10-yl group is also preferable as R 22a is preferable.

[0060] In formula (a2), R 23a ~R 28a is a hydrogen atom or a monovalent organic group. Further, R 23a and R 24a and, R 24a and R 25a and, R 25a and R 26a and, R 26a and R 27a and, or R 27a and R 28a and may each be bonded to each other to form a ring. For example, R 25a and R 26a are bonded to form a 5-membered ring together with a naphthalene ring, whereby an acenaphthene skeleton may be formed.

[0061] As the monovalent organic group, an alicyclic hydrocarbon group, a heterocyclic group (heterosilyl group), or an alkyl group having 4 to 18 carbon atoms which may be substituted with a halogen atom and may have a branch, an alkoxy group; a heterosilyloxy group; an alicyclic hydrocarbon group, a heterocyclic group (heterosilyl group), or an alkylthio group having 4 to 18 carbon atoms which may be substituted with a halogen atom and may have a branch; a heterosilylthio group; is preferable. Further, a group in which a methylene group at an arbitrary position not adjacent to the oxygen atom of the alkoxy group is substituted with -CO- is also preferable. A group in which the alkoxy group is interrupted by an -O-CO- bond or an -O-CO-NH- bond is also preferable. Note that the left end of the -O-CO- bond and the -O-CO-NH- bond is on the side closer to the naphthoic acid mother nucleus in the alkoxy group. Furthermore, an alkylthio group having 4 to 18 carbon atoms which may be substituted with an alicyclic hydrocarbon group, a heterocyclic group, or a halogen atom and may have a branch is also preferable as R 23a ~R 28a is preferable. A group in which a methylene group at any position not adjacent to the sulfur atom of the alkylthio group is substituted with -CO- is also preferred. A group in which the alkylthio group is interrupted by an -O-CO- bond or an -O-CO-NH- bond is also preferred. The left end of the -O-CO- bond and the -O-CO-NH- bond is the side closer to the naphthoic acid nucleus in the alkylthio group.

[0062] R 23a ~R 28a As for, R 24a is an organic group, and R 23a and R 25a ~R 28a are hydrogen atoms, or R 25a is an organic group, and R 23a , R 24a and R 26a ~R 28a are preferably hydrogen atoms. Also, R 23a ~R 28a may all be hydrogen atoms.

[0063] R 23a ~R 28a Examples of the case where R

[0064] R 23a ~R 28a is an unsubstituted alkyl group include n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, isopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, isoheptyl group, tert-heptyl group, n-octyl group, isooctyl group, tert-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group.Examples of cases where it is an unsubstituted alkoxy group include n-butyloxy group, sec-butyloxy group, tert-butyloxy group, isobutyloxy group, n-pentyloxy group, isopentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, isoheptyloxy group, tert-heptyloxy group, n-octyloxy group, isooctyloxy group, tert-octyloxy group, 2-ethylhexyl group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group.

[0065] R 23a ~R 28a Examples of cases where it is an unsubstituted alkylthio group include n-butylthio group, sec-butylthio group, tert-butylthio group, isobutylthio group, n-pentylthio group, isopentylthio group, tert-pentylthio group, n-hexylthio group, n-heptylthio group, isoheptylthio group, tert-heptylthio group, n-octylthio group, isooctylthio group, tert-octylthio group, 2-ethylhexylthio group, n-nonylthio group, n-decylthio group, n-undecylthio group, n-dodecylthio group, n-tridecylthio group, n-tetradecylthio group, n-pentadecylthio group, n-hexadecylthio group, n-heptadecylthio group, n-octadecylthio group.

[0066] R 23a ~R 28aWhen it is 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. As the alicyclic hydrocarbon group, a group obtained by removing one hydrogen atom from these alicyclic hydrocarbons is preferable.

[0067] R 23a ~R 28a When it is an alkyl group, an alkoxy group or an alkylthio group substituted with a heterocyclic group, or R 23a ~R 28a When it is a heterocyclyloxy group, examples of the heterocyclic ring constituting the main skeleton of the heterocyclic group or the heterocyclyloxy group include pyrrole, thiophene, furan, pyran, thiopyran, imidazole, pyrazole, thiazole, isothiazole, oxazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, pyrrolidine, pyrazolidine, imidazolidine, isoxazolidine, isothiazolidine, piperidine, piperazine, morpholine, thiomorpholine, chroman, thiochroman, isochroman, isothiochroman, indoline, isoindoline, pyrindine, indolizine, indole, indazole, purine, quinolidine, isoquinoline, quinoline, naphthyridine, phthalazine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, perimidine, phenanthroline, carbazole, carboline, phenazine, antiridine, thiadiazole, oxadiazole, triazine, triazole, tetrazole, benzimidazole, benzoxazole, benzothiazole, benzothiadiazole, benzofuroxan, naphthimidazole, benzotriazole, tetraazaindene. In addition, a saturated heterocyclic ring obtained by hydrogenating a ring having a conjugated bond among these heterocyclic rings is also preferable. As the heterocyclic group that substitutes an alkyl group, an alkoxy group or an alkylthio group, or the heterocyclic group contained in a heterocyclyloxy group, a group obtained by removing one hydrogen atom from the above heterocycle is preferable.

[0068] R 23a ~R 28a Examples of the case where R 23a ~R 28a is an alkoxy group containing an alicyclic hydrocarbon group include cyclopentyloxy group, methylcyclopentyloxy group, cyclohexyloxy group, fluorocyclohexyloxy group, chlorocyclohexyloxy group, cyclohexylmethyloxy group, methylcyclohexyloxy group, norbornyloxy group, ethylcyclohexyloxy group, cyclohexylethyloxy group, dimethylcyclohexyloxy group, methylcyclohexylmethyloxy group, norbornylmethyloxy group, trimethylcyclohexyloxy group, 1-cyclohexylbutyloxy group, adamantyloxy group, menthyloxy group, n-butylcyclohexyloxy group, tert-butylcyclohexyloxy group, bornyloxy group, isobornyloxy group, decahydronaphthyloxy group, dicyclopentadienooxy group, 1-cyclohexylpentyloxy group, methyladamantyloxy group, adamantylmethyloxy group, 4-pentylcyclohexyloxy group, cyclohexylcyclohexyloxy group, adamantylethyloxy group, dimethyladamantyloxy group.

[0069] R 23a ~R 28a Examples of the case where R 23a ~R 28a is a heterocyclyloxy group include tetrahydrofuranyloxy group, furfuryloxy group, tetrahydrofurfuryloxy group, tetrahydropyranyloxy group, butyrolactonyloxy group, indryloxy group.

[0070] R 23a ~R 28a Examples of the case where R 23a ~R 28a is an alkylthio group containing an alicyclic hydrocarbon group include cyclopentylthio group, cyclohexylthio group, cyclohexylmethylthio group, norbornylthio group, isonorbornylthio group.

[0071] R 23a ~R 28a Examples of the case where ~R is a heterocyclic thio group include a furfuryl thio group and a tetrahydrofuranyl thio group.

[0072] R 23a ~R 28a Examples of the case where ~R is a group in which a methylene group at any position not adjacent to the oxygen atom of the alkoxy group is substituted with -CO- include a 2-ketobutyl-1-oxy group, a 2-ketopentyl-1-oxy group, a 2-ketohexyl-1-oxy group, a 2-ketoheptyl-1-oxy group, a 2-ketooctyl-1-oxy group, a 3-ketobutyl-1-oxy group, a 4-ketopentyl-1-oxy group, a 5-ketohexyl-1-oxy group, a 6-ketoheptyl-1-oxy group, a 7-ketooctyl-1-oxy group, a 3-methyl-2-ketopentan-4-oxy group, a 2-ketopentan-4-oxy group, a 2-methyl-2-ketopentan-4-oxy group, a 3-ketoheptan-5-oxy group, and a 2-adamantanone-5-oxy group.

[0073] R 23a ~R 28a Examples of the case where ~R is a group in which a methylene group at any position not adjacent to the sulfur atom of the alkylthio group is substituted with -CO- include a 2-ketobutyl-1-thio group, a 2-ketopentyl-1-thio group, a 2-ketohexyl-1-thio group, a 2-ketoheptyl-1-thio group, a 2-ketooctyl-1-thio group, a 3-ketobutyl-1-thio group, a 4-ketopentyl-1-thio group, a 5-ketohexyl-1-thio group, a 6-ketoheptyl-1-thio group, a 7-ketooctyl-1-thio group, a 3-methyl-2-ketopentan-4-thio group, a 2-ketopentan-4-thio group, a 2-methyl-2-ketopentan-4-thio group, and a 3-ketoheptan-5-thio group.

[0074] Specific examples of the compound represented by the formula (a2) include the following compounds.

[0075]

Chemical formula

[0076]

Chem.

[0077]

Chem.

[0078]

Chem.

[0079]

Chem.

[0080]

Chem.

[0081]

Chem.

[0082]

Chem.

[0083]

Chem.

[0084]

Chem.

[0085] Examples of the imidosulfonate compound also include a compound represented by the following formula (a3).

Chem.

[0086] In formula (a3), the aliphatic hydrocarbon group having 1 to 20 carbon atoms as R a1 and R a2 may be linear, branched, cyclic, or a combination of these structures. As the aliphatic hydrocarbon group, an alkyl group is preferred. Preferable specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, and n-decyl group. R a1 and R a2 Examples of the substituent that the aliphatic hydrocarbon group having 1 to 20 carbon atoms as R a1 and R a2Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms and having a substituent as such include a perfluoroalkyl group having 1 to 6 carbon atoms. Specific examples thereof include CF3-, CF3CF2-, (CF3)2CF-, CF3CF2CF2-, CF3CF2CF2CF2-, (CF3)2CFCF2-, CF3CF2(CF3)CF-, and (CF3)3C-.

[0087] In formula (a3), R a1 and R a2 The aromatic group having 5 to 20 ring-constituting atoms and may have a substituent as such may be an aromatic hydrocarbon group or an aromatic heterocyclic group. Examples of the aromatic group include aryl groups such as a phenyl group and a naphthyl group, and heteroaryl groups such as a furyl group and a thienyl group. The substituent that the aromatic group having 5 to 20 ring-constituting atoms may have is the same as the substituent that the aliphatic hydrocarbon group having 1 to 20 carbon atoms and may have a substituent as R a1 and R a2 as such.

[0088] In formula (a3), R a4 as the aromatic group having 5 to 20 ring-constituting atoms and may have a substituent as such is the same as the aromatic group having 5 to 20 ring-constituting atoms and may have a substituent as described for R a1 and R a2 as such. In formula (a3), R a4 as the perfluoroalkyl group having 1 to 6 carbon atoms is the same as the perfluoroalkyl group having 1 to 6 carbon atoms as described for R a1 and R a2 as such. In formula (a3), R a4 Specific examples of the aralkyl group having 7 to 20 carbon atoms and may have a substituent as such include a benzyl group, a phenethyl group, an α-naphthylmethyl group, a β-naphthylmethyl group, a 2-α-naphthylethyl group, and a 2-β-naphthylethyl group. In formula (a3), the heteroarylalkyl group is a group in which some of the carbon atoms constituting the aromatic hydrocarbon ring in the arylalkyl group are substituted with heteroatoms such as N, O, or S. R a4 Specific examples of the heteroarylalkyl group containing an aromatic heterocyclic group having 5 to 20 ring-constituting atoms which may have a substituent as R

[0089] In formula (a3), R a5 The hydrocarbon group having 1 to 6 carbon atoms as R may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof. The aliphatic hydrocarbon group may be linear, branched, cyclic, or a combination of these structures. Examples of the aliphatic hydrocarbon group include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and n-hexyl group. Examples of the aromatic hydrocarbon group include phenyl group.

[0090] In formula (a3), R a6 The hydrocarbon group having 1 to 6 carbon atoms as R is the same as the hydrocarbon group having 1 to 6 carbon atoms described for R a5 .

[0091] In formula (a3), R b1 The hydrocarbon group having 1 to 30 carbon atoms as R may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof. The aliphatic hydrocarbon group may be linear, branched, cyclic, or a combination of these structures. Examples of the aliphatic hydrocarbon group include linear aliphatic hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl groups, and cyclic aliphatic hydrocarbon groups (hydrocarbon rings) such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, and norbornyl groups. Examples of the aromatic hydrocarbon group include phenyl and naphthyl groups. Examples of the group formed by combining an aliphatic hydrocarbon group and an aromatic hydrocarbon group include benzyl, phenethyl, and furylmethyl groups. R b1 When the hydrocarbon group as R contains a hydrocarbon ring, examples of the atomic group containing a hetero atom that substitutes at least one of the carbon atoms constituting the hydrocarbon ring include -CO-, -CO-O-, -SO-, -SO2-, -SO2-O-, and -P(=O)-(OR b7 )3. R b7 is a hydrocarbon group having 1 to 6 carbon atoms, and is the same as the hydrocarbon group having 1 to 6 carbon atoms described for R a5 .

[0092] In formula (a3), specific examples of the halogen atom as R b4 and R b5 include chlorine, fluorine, bromine, and iodine atoms.

[0093] In formula (a3), the hydrocarbon group having 1 to 6 carbon atoms as R b6 is the same as the hydrocarbon group having 1 to 6 carbon atoms described for R a5 in formula (a3).

[0094] In formula (a3), the perfluoroalkyl group having 1 to 6 carbon atoms as Q 1 and Q 2 is the same as the perfluoroalkyl group having 1 to 6 carbon atoms described for R a1 and R a2 in formula (a3).

[0095] In the compound represented by the formula (a3), the orientation of the ester bond as L is not particularly limited, and it may be either -CO-O- or -O-CO-.

[0096] The compound represented by the formula (a3) is preferably a compound represented by the following formula (a3-1).

Chemical formula

[0097] R in the formula (a3-1) a1 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and when the aliphatic hydrocarbon group as R a1 contains 1 or more methylene groups, at least a part of the methylene groups may be substituted with a group selected from the group consisting of -O-, -S-, -CO-, -CO-O-, -SO-, -SO2-, and -NR a5 -, and the compound represented by the formula (a3-1) is preferred.

[0098] 〔Onium salt type photoacid generator (A2)〕 As the onium salt type photoacid generator (A2), conventionally known onium salt type photoacid generators such as iodonium salts and sulfonium salts can be used without particular limitation.

[0099] As the onium salt type photoacid generator (A2), onium salts having a naphthalene ring in the cation moiety can be mentioned. This "having a naphthalene ring" means having a structure derived from naphthalene, and means having at least two ring structures and maintaining their aromaticity. This 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. The structure derived from the naphthalene ring may be a monovalent group (having one free valence) or a divalent group (having two or more free valences) or more, but it is preferably a monovalent group (however, in this case, the free valence is counted excluding the portion bonded to the above substituent). The number of naphthalene rings is preferably 1 or more and 3 or less.

[0100] As the cation moiety of such an onium salt having a naphthalene ring in the cation moiety, the structure represented by the following formula (A1) is preferable.

[0101]

Chemical formula

[0102] In the above formula (A1), at least one of R 1a , R 2a , R 3a represents a group represented by the following formula (A2), and the rest represent a linear or branched alkyl group having 1 to 6 carbon atoms, a phenyl group which may have a substituent, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Alternatively, one of R 1a , R 2a , R 3a is a group represented by the following formula (A2), and the remaining two are each independently a linear or branched alkylene group having 1 to 6 carbon atoms, and the ends thereof may be bonded to form a ring. R 1a , R 2a , R 3aSpecific examples of the linear or branched alkyl group having 1 to 6 carbon atoms as the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group. R 1a , R 2a , R 3a Specific examples of the linear or branched alkyl group having 1 to 6 carbon atoms as the aryl group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, an n-pentyloxy group, and an n-hexyloxy group. R 1a , R 2a , R 3a When is a phenyl group which may have a substituent, preferred substituents include a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, and a linear or branched alkyl group having 1 to 6 carbon atoms.

[0103] [ka]

[0104] In the above formula (A2), R 4a , R 5a each independently represents a hydroxyl group, a linear or branched alkoxy group having from 1 to 6 carbon atoms, or a linear or branched alkyl group having from 1 to 6 carbon atoms; R 6a 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 to 2, and l+m is 3 or less. 4a When there are multiple R, they may be the same or different. 5a When multiple are present, they may be the same or different. R 4a , and R 5aSpecific examples of the linear or branched alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, an n-pentyloxy group, and an n-hexyloxy group. R 4a 、and R 5a Specific examples of the linear or branched alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group. R 6a Specific examples of the linear or branched alkylene group having 1 to 6 carbon atoms include a methylene group, an ethane-1,2-diyl group (ethylene group), an ethane-1,1-diyl group, a propane-1,3-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group.

[0105] The above R 1a 、R 2a 、R 3a Among the above, the number of the groups represented by the above formula (A2) is preferably 1 from the viewpoint of the stability of the compound, and the rest are linear or branched alkylene groups having 1 to 6 carbon atoms, and the ends thereof may be bonded to form a cyclic structure. In this case, the above two alkylene groups form a 3- to 9-membered ring including a sulfur atom. The number of atoms (including a sulfur atom) constituting the ring is preferably 5 or more and 6 or less.

[0106] In addition, examples of the substituent that the above alkylene group may have include an oxygen atom (in this case, forming a carbonyl group together with the carbon atom constituting the alkylene group), a hydroxyl group, and the like.

[0107] Examples of the substituent that the phenyl group may have include a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, a linear or branched alkyl group having 1 to 6 carbon atoms, and the like.

[0108] Examples of those suitable as these cation moieties include those represented by the following formulas (A3), (A4-1), and (A4-2), and in particular, the structures represented by the following formulas (A4-1) and (A4-2) are preferred.

[0109]

Chemical formula

[0110] Such a cation moiety may be an iodonium salt or a sulfonium salt, but a sulfonium salt is desirable from the viewpoint of acid generation efficiency and the like.

[0111] Therefore, as a suitable anion moiety of an onium salt having a naphthalene ring in the cation moiety, an anion capable of forming a sulfonium salt is desirable.

[0112] Such an anion moiety of the acid generator is a fluoroalkylsulfonate ion or an arylsulfonate ion in which some or all of the hydrogen atoms are fluorinated.

[0113] The alkyl group in the fluoroalkylsulfonate ion may be linear, branched, or cyclic and have 1 to 20 carbon atoms. From the bulkiness and diffusion distance of the generated acid, it preferably has 1 to 10 carbon atoms. In particular, branched or cyclic ones are preferred because of their short diffusion distance. Also, because they can be synthesized inexpensively, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, etc. can be mentioned as preferred ones.

[0114] 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 or may not be substituted with an alkyl group or a halogen atom. In particular, an aryl group having 6 to 10 carbon atoms is preferable because it can be synthesized at low cost. Specific examples of preferable ones include a phenyl group, a toluenesulfonyl group, an ethylphenyl group, a naphthyl group, and a methylnaphthyl group.

[0115] In the above-mentioned fluoroalkylsulfonic acid ion or arylsulfonic acid ion, when some or all of the hydrogen atoms are fluorinated, the fluorination rate is preferably 10% or more and 100% or less, more preferably 50% or more and 100% or less. In particular, those in which all hydrogen atoms are substituted with fluorine atoms are preferable because the acid strength becomes stronger. Specific examples of such substances include trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctanesulfonate, perfluorobenzenesulfonate, and the like.

[0116] Among these, preferable anion parts include those represented by the following formula (A5).

[0117]

Chemical formula

[0118] In the above formula (A5), R 7a is a group represented by the following formulas (A6), (A7), and (A8).

[0119]

Chemical formula

[0120] In the above formula (A6), x represents an integer of 1 or more and 4 or less. Further, in the above formula (A7), R 8arepresents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkoxy group having 1 to 6 carbon atoms, and y represents an integer of 1 to 3. Among these, trifluoromethanesulfonate and perfluorobutanesulfonate are preferred from the viewpoint of safety.

[0121] Further, as the anion part, those containing nitrogen represented by the following formulas (A9) and (A10) can also be used.

[0122] [Chemical formula]

[0123] In the above formulas (A9) and (A10), X a represents a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, the number of carbon atoms of the alkylene group is 2 to 6, preferably 3 to 5, and most preferably 3 carbon atoms. Also, Y a , Z a each independently represents a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, the number of carbon atoms of the alkyl group is 1 to 10, preferably 1 to 7, and more preferably 1 to 3.

[0124] X a The smaller the number of carbon atoms of the alkylene group of, or Y a , Z a The smaller the number of carbon atoms of the alkyl group of, the better the solubility in the organic solvent, which is preferable.

[0125] Also, the alkylene group of X a or Y a , Z aIn the alkyl group, the larger the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength, which is preferable. The ratio of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate, is preferably 70% or more and 100% or less, more preferably 90% or more and 100% or less, and most preferably, a perfluoroalkylene group or a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.

[0126] Preferred examples of the onium salt having a naphthalene ring in the cationic part include compounds represented by the following formulas (A11-1), (A11-2), and (A12).

[0127] [Chemical formula]

[0128] The total content of the acid generator (A) is preferably 0.01% by mass or more and 20% by mass or less, more preferably 0.03% by mass or more and 10% by mass or less, and particularly preferably 0.05% by mass or more and 8% by mass or less with respect to the total solid content of the photosensitive resin composition. In this specification, the solid content refers to components other than the organic solvent (S) and water.

[0129] [Resin (B)] The resin (B) whose solubility in alkali increases by the action of an acid is not particularly limited, and any resin whose solubility in alkali increases by the action of an acid can be used. Among them, it is preferable to contain at least one resin selected from the group consisting of a novolak resin (B1), a polyhydroxystyrene resin (B2), and an acrylic resin (B3). In the novolak resin (B1) and the polyhydroxystyrene resin (B2), at least a part of the phenolic hydroxyl groups are protected by acid dissociable dissolution inhibiting groups. Further, the acrylic resin (B3) contains a structural unit derived from a (meth)acrylate having an acid dissociable group.

[0130] [Novolak resin (B1)] As the novolak resin (B1), a resin containing a structural unit represented by the following formula (b-11) can be used.

[0131]

Chemical formula

[0132] In the above formula (b-11), R 1b represents an acid dissociable dissolution inhibiting group. As the acid dissociable dissolution inhibiting group, a so-called acetal type protecting group is preferable. R 2b , R 3b each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0133] As the acid dissociable dissolution inhibiting group represented by the above R 1b , a group represented by the following formula (b-12), (b-13), a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, a vinyloxyethyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, or a trialkylsilyl group is preferable.

[0134]

Chemical formula

[0135] In the above formula (b-12), (b-13), R 4b , R 5b each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, R 6b represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, R 7b represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and o represents 0 or 1.

[0136] Examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. Examples of the cyclic alkyl group include cyclopentyl group, cyclohexyl group and the like.

[0137] Here, specific examples of the acid dissociable dissolution inhibiting group represented by the above formula (b-12) include 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-isopropoxyethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1-tert-butoxyethyl group, 1-cyclohexyloxyethyl group, 1-methoxypropyl group, 1-ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1-ethoxy-1-methylethyl group and the like. Specific examples of the acid dissociable dissolution inhibiting group represented by the above formula (b-13) include tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group and the like. Examples of the trialkylsilyl group include groups in which the number of carbon atoms of each alkyl group is 1 or more and 6 or less, such as trimethylsilyl group and tri-tert-butyldimethylsilyl group.

[0138] When using the patterned resist film formed using the photosensitive resin composition as an etching mask, in terms of excellent resistance to the etchant, the acid dissociable dissolution inhibiting group is preferably a polyvalent acid dissociable dissolution inhibiting group derived from a polyvalent vinyl ether compound having two or more vinyloxy groups. The polyvalent acid dissociable dissolution inhibiting group is preferably a divalent acid dissociable dissolution inhibiting group derived from a divinyl ether compound represented by the following formula (I).

[0139] H2C=CH-O-A a1 -O-CH=CH2 ···(I) In the formula (I), A a1 may have a substituent and may contain an ether bond in the main chain, and is an alkylene group having 1 to 10 carbon atoms, or the following formula (II): -(A a2 )nb -A a3 -(A a2 ) nb -···(II) is a group represented by In formula (II), A a2 is an alkylene group having 1 to 10 carbon atoms which may have a substituent, A a3 is a cyclohexylene group, and nb is 0 or 1.

[0140] When both ends of the divinyl ether compound represented by formula (I) react with two of the phenolic hydroxyl groups of the novolak resin, a divalent acid dissociable dissolution inhibiting group derived from the divinyl ether compound represented by formula (I) is formed. The divalent acid dissociable dissolution inhibiting group derived from the divinyl ether compound represented by formula (I) is represented by the following formula (Ia): -CH(CH3)-O-A b1 -O-CH(CH3)-···(Ia) is a group represented by Also, when only one end of the divinyl ether compound represented by formula (I) reacts with the phenolic hydroxyl group of the novolak resin, the following formula (Ib): -CH(CH3)-O-A b1 -O-CH=CH2···(Ib) a monovalent acid dissociable dissolution inhibiting group represented by is formed. A in formula (Ia) and formula (Ib) b1 is the same as A in formula (I) b1 is the same.

[0141] When A in formula (I) b1 is an alkylene group having 1 to 10 carbon atoms which may have a substituent and may contain an ether bond in the main chain, examples of the substituent which the alkylene group may have include halogen atoms such as a chlorine atom, a bromine atom and a fluorine atom, and alkoxy groups such as a methoxy group and an ethoxy group.

[0142] When A in formula (I) b1The alkylene group as [description] may contain an ether bond (-O-) in its chain. A b1 When [description] is an alkylene group that may contain an ether bond in the main chain, the number of carbon atoms thereof is 1 or more and 10 or less, preferably 1 or more and 8 or less, and more preferably 2 or more and 6 or less. A b1 Preferable specific examples of the alkylene group as [description] that may contain an ether bond in the main chain include -CH2CH2CH2CH2-, -CH2CH2-O-CH2CH2-, and -CH2CH2-O-CH2CH2-O-CH2CH2-.

[0143] The divalent group represented by the above formula (II) is also preferable as A b1 In the formula (II), A b3 is a cyclohexylene group. The cyclohexylene group may be any of a cyclohexane-1,4-diyl group, a cyclohexane-1,3-diyl group, and a cyclohexane-1,2-diyl group, and a cyclohexane-1,4-diyl group is preferable. In the formula (II), nb is independently 0 or 1. In the formula (II), A b2 is an alkylene group having 1 to 10 carbon atoms which may have a substituent. The number of carbon atoms of the alkylene group as A b2 is preferably 1 or more and 6 or less, more preferably 1 or more and 4 or less, and still more preferably 1 or 2. Substituents that the alkylene group as A b2 may have include halogen atoms such as a chlorine atom, a bromine atom, and a fluorine atom, and alkoxy groups such as a methoxy group and an ethoxy group. A b2 Preferable specific examples of [description] include a methylene group, an ethane-1,2-diyl group, an ethane-1,1,-diyl group, a propane-1,3-diyl group, and a butane-1,4-diyl group.

[0144] Particularly preferable examples of the divalent group represented by the formula (II) are those in which both nbs are 1, A b3 is a cyclohexane-1,4-diyl group, and two As b2Examples of the group that are both methylene groups are given.

[0145] [Polyhydroxystyrene resin (B2)] As the polyhydroxystyrene resin (B2), a resin containing a structural unit represented by the following formula (b4) can be used.

[0146] [Chemical formula]

[0147] 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 dissociable dissolution inhibiting group.

[0148] The alkyl group having 1 to 6 carbon atoms is, for example, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, etc. Examples of the cyclic alkyl group include a cyclopentyl group, a cyclohexyl group, etc.

[0149] As the acid dissociable dissolution inhibiting group represented by the above R 9b , the same acid dissociable dissolution inhibiting groups as those exemplified in the above formulas (b-12) and (b-13) can be used. Further, the acid dissociable dissolution inhibiting group may be a polyvalent acid dissociable dissolution inhibiting group derived from a polyvalent vinyl ether compound having two or more vinyloxy groups. The polyvalent acid dissociable dissolution inhibiting group is as described above for the novolak resin (B1).

[0150] Furthermore, the polyhydroxystyrene resin (B2) can contain other polymerizable compounds as constituent units for the purpose of appropriately controlling physical and chemical properties. Examples of such polymerizable compounds include known radical polymerizable compounds and anionic polymerizable compounds. Examples of such polymerizable compounds also include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives having a carboxy group and an ester bond such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid; alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate; hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate; diester dicarboxylates such as diethyl maleate and dibutyl fumarate; vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylamide; and the like.

[0151] [Acrylic resin (B3)] As the acrylic resin (B3), an acrylic resin whose solubility in alkali increases by the action of an acid is not particularly limited as long as it has been conventionally blended in various photosensitive resin compositions. In the specification and claims of the present application, a resin containing a structural unit derived from (meth)acrylate having an acid dissociable group represented by the following formulas (b5) to (b7) is defined as the acrylic resin (B3). The acrylic resin (B3) preferably contains, for example, a structural unit (b-3) derived from an acrylate ester containing a -SO2-containing cyclic group or a lactone-containing cyclic group. In such a case, when forming a patterned resist film, it is easy to form a patterned resist film having a preferable cross-sectional shape.

[0152] (-SO2-containing cyclic group) Here, the "-SO2-containing cyclic group" refers to a cyclic group containing a ring containing -SO2 in its ring skeleton. Specifically, it is a cyclic group in which the sulfur atom (S) in -SO2 forms part of the ring skeleton of the cyclic group. The ring containing -SO2 in its ring skeleton is counted as the first ring. In the case of only this ring, it is a monocyclic group, and in the case of having another ring structure, it is called a polycyclic group regardless of its structure. The -SO2-containing cyclic group may be monocyclic or polycyclic.

[0153] The -SO2-containing cyclic group is particularly preferably a cyclic group containing a sultone ring in which -O-SO2 in the ring skeleton, that is, -O-S- in -O-SO2, forms part of the ring skeleton.

[0154] The number of carbon atoms of the -SO2-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.

[0155] The -SO2-containing cyclic group may be a -SO2-containing aliphatic cyclic group or a -SO2-containing aromatic cyclic group. Preferably, it is a -SO2-containing aliphatic cyclic group.

[0156] Examples of the -SO2-containing aliphatic cyclic group include a group obtained by removing at least one hydrogen atom from an aliphatic hydrocarbon ring in which a part of the carbon atoms constituting the ring skeleton is substituted with -SO2 or -O-SO2. More specifically, examples include a group obtained by removing at least one hydrogen atom from an aliphatic hydrocarbon ring in which -CH2- constituting the ring skeleton is substituted with -SO2, and a group obtained by removing at least one hydrogen atom from an aliphatic hydrocarbon ring in which -CH2-CH2- constituting the ring is substituted with -O-SO2.

[0157] The number of carbon atoms of the alicyclic hydrocarbon ring is preferably 3 or more and 20 or less, more preferably 3 or more and 12 or less. The alicyclic hydrocarbon ring may be polycyclic or monocyclic. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane having 3 to 6 carbon atoms is preferable. Examples of the monocycloalkane include cyclopentane and cyclohexane. As the polycyclic alicyclic hydrocarbon ring, a group obtained by removing two hydrogen atoms from a polycycloalkane having 7 to 12 carbon atoms is preferable. Specific examples of the polycycloalkane include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0158] The -SO2-containing cyclic group may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxygen atom (=O), -COOR'', -OC(=O)R'', a hydroxyalkyl group, and a cyano group.

[0159] As the alkyl group as the substituent, an alkyl group having 1 to 6 carbon atoms is preferable. The alkyl group is preferably linear or branched. Specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, etc. can be mentioned. Among these, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.

[0160] As the alkoxy group as the substituent, an alkoxy group having 1 to 6 carbon atoms is preferable. The alkoxy group is preferably linear or branched. Specifically, groups in which the alkyl groups mentioned as the alkyl groups as the substituents above are bonded to an oxygen atom (-O-) can be mentioned.

[0161] Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferable.

[0162] Examples of the halogenated alkyl group of the substituent include groups in which some or all of the hydrogen atoms of the alkyl group described above are substituted with the halogen atoms described above.

[0163] Examples of the halogenated alkyl group as the substituent include groups in which some or all of the hydrogen atoms of the alkyl groups mentioned as the alkyl groups as the substituents above are substituted with the halogen atoms described above. As the halogenated alkyl group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.

[0164] In the above-mentioned -COOR” and -OC(=O)R”, each of R” is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms.

[0165] When R” is a linear or branched alkyl group, the number of carbon atoms of the linear alkyl group is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 or 2.

[0166] When “R” is a cyclic alkyl group, the number of carbon atoms of the cyclic alkyl group is preferably 3 or more and 15 or less, more preferably 4 or more and 12 or less, and particularly preferably 5 or more and 10 or less. Specifically, examples include a group obtained by removing one or more hydrogen atoms from a monocycloalkane, bicycloalkane, tricycloalkane, tetracycloalkane, etc., which may or may not be substituted with a fluorine atom or a fluorinated alkyl group. More specifically, examples include a group obtained by removing one or more hydrogen atoms from a monocycloalkane such as cyclopentane and cyclohexane, and a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0167] As the hydroxyalkyl group as the substituent, a hydroxyalkyl group having 1 to 6 carbon atoms is preferable. Specifically, examples include a group in which at least one of the hydrogen atoms of the alkyl group mentioned as the alkyl group as the above-mentioned substituent is substituted with a hydroxyl group.

[0168] As the -SO2-containing cyclic group, more specifically, groups represented by the following formulas (3-1) to (3-4) can be mentioned.

Chemical formula

[0169] In the above formulas (3-1) to (3-4), A’ is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom (-O-) or a sulfur atom (-S-), an oxygen atom, or a sulfur atom. As the alkylene group having 1 to 5 carbon atoms in A’, a linear or branched alkylene group is preferable, and examples thereof include a methylene group, an ethylene group, an n-propylene group, and an isopropylene group.

[0170] 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 terminal or carbon atoms of the aforementioned alkylene group, and examples thereof include -O-CH2-, -CH2-O-CH2-, -S-CH2-, and -CH2-S-CH2-. As A’, an alkylene group having 1 to 5 carbon atoms or -O- is preferable, an alkylene group having 1 to 5 carbon atoms is more preferable, and a methylene group is most preferable.

[0171] z may be any of 0, 1, and 2, and 0 is most preferable. When z is 2, the plurality of R 10b may be the same or different from each other.

[0172] R 10b The alkyl group, alkoxy group, halogenated alkyl group, -COOR”, -OC(=O)R”, and hydroxyalkyl group in are the same as those described above for the alkyl group, alkoxy group, halogenated alkyl group, -COOR”, -OC(=O)R”, and hydroxyalkyl group which may be substituents of the -SO2-containing cyclic group.

[0173] Specific cyclic groups represented by the above formulas (3-1) to (3-4) are exemplified below. In the formulas, “Ac” represents an acetyl group.

[0174]

Chemical formula

[0175] [Chemistry]

[0176] As the -SO2-containing cyclic group, among the above, the group represented by the aforementioned formula (3-1) is preferable, at least one selected from the group consisting of the groups represented by the aforementioned chemical formulas (3-1-1), (3-1-18), (3-3-1), and (3-4-1) is more preferable, and the group represented by the aforementioned chemical formula (3-1-1) is most preferable.

[0177] (Lactone-containing cyclic group) The "lactone-containing cyclic group" refers to a cyclic group containing a ring (lactone ring) containing -O-C(=O)- in its ring skeleton. Counting the lactone ring as the first ring, in the case of only the lactone ring, it is a monocyclic group, and when it further has other ring structures, regardless of the structure, it is called a polycyclic group. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group.

[0178] The lactone cyclic group in the constitutional unit (b-3) is not particularly limited and any one can be used. Specifically, as the lactone-containing monocyclic group, a group obtained by removing one hydrogen atom from a 4- to 6-membered lactone, for example, a group obtained by removing one hydrogen atom from β-propiolactone, a group obtained by removing one hydrogen atom from γ-butyrolactone, a group obtained by removing one hydrogen atom from δ-valerolactone, etc. can be mentioned. Further, as the lactone-containing polycyclic group, a group obtained by removing one hydrogen atom from a bicycloalkane, tricycloalkane, or tetracycloalkane having a lactone ring can be mentioned.

[0179] As the structural unit (b-3), as long as it has a -SO2-containing cyclic group or a lactone-containing cyclic group, the structure of other parts is not particularly limited, but it is a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent and contains a -SO2-containing cyclic group (structural unit (b-3-S)), and a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent and contains a lactone-containing cyclic group (structural unit (b-3-L)), and at least one structural unit selected from the group consisting of these is preferred.

[0180] 〔Structural unit (b-3-S)〕 As an example of the structural unit (b-3-S), more specifically, the structural unit represented by the following formula (b-S1) can be mentioned.

[0181]

Chemical formula

[0182] In formula (b-S1), R is the same as described above. R 11b is the same as the -SO2-containing cyclic group mentioned above. R 12b may be either a single bond or a divalent linking group.

[0183] R 12b The divalent linking group in is not particularly limited, but examples of suitable ones include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom, and the like.

[0184] ·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 having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated. Usually, a saturated hydrocarbon group is preferred. More specifically, examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, and the like.

[0185] 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.

[0186] As the linear aliphatic hydrocarbon group, a linear alkylene group is preferred. Specifically, examples include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], a pentamethylene group [-(CH2)5-], and the like.

[0187] As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred. Specifically, examples include alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-; alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2-, and the like. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 or more and 5 or less carbon atoms is preferred.

[0188] The above linear or branched aliphatic hydrocarbon group may or may not have a substituent (a group or atom other than a hydrogen atom) that replaces a hydrogen atom. Examples of such substituents include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, an oxo group (=O), and the like.

[0189] Examples of the aliphatic hydrocarbon group containing a ring in the above structure include a cyclic aliphatic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring) that may contain a substituent containing a heteroatom in the ring structure, a group in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, a group in which the cyclic aliphatic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, and the like. Examples of the above linear or branched aliphatic hydrocarbon group are the same as those described above.

[0190] 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.

[0191] The cyclic aliphatic hydrocarbon group may be polycyclic or monocyclic. As the monocyclic aliphatic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferable. The number of carbon atoms of the monocycloalkane is preferably 3 or more and 6 or less. Specifically, cyclopentane, cyclohexane, and the like can be mentioned. As the polycyclic aliphatic hydrocarbon group, a group obtained by removing two hydrogen atoms from a polycycloalkane is preferable. The number of carbon atoms of the polycycloalkane is preferably 7 or more and 12 or less. Specifically, adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like can be mentioned.

[0192] The cyclic aliphatic hydrocarbon group may or may not have a substituent (a group or atom other than a hydrogen atom) that replaces a hydrogen atom. Examples of such substituents include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxo group (=O), and the like.

[0193] As the alkyl group as 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, an n-butyl group, and a tert-butyl group are more preferable.

[0194] As the alkoxy group as the above-mentioned substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group are more preferable, and a methoxy group and an ethoxy group are particularly preferable.

[0195] Examples of the halogen atom as the above-mentioned substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, etc., and a fluorine atom is preferable.

[0196] Examples of the halogenated alkyl group as the above-mentioned substituent include groups in which some or all of the hydrogen atoms of the aforementioned alkyl group are substituted with the above-mentioned halogen atoms.

[0197] In the cyclic aliphatic hydrocarbon group, a part of the carbon atoms constituting the ring structure may be substituted with -O- or -S-. As the substituent containing the hetero atom, -O-, -C(=O)-O-, -S-, -S(=O)2-, -S(=O)2-O- are preferable.

[0198] The aromatic hydrocarbon group as the 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 of 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.

[0199] Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocyclic rings in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms; and the like. Examples of the heteroatom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring.

[0200] Specific examples of the aromatic hydrocarbon group as the divalent hydrocarbon group include a group obtained by removing two hydrogen atoms from the above aromatic hydrocarbon ring or aromatic heterocyclic ring (arylene group or heteroarylene group); a group obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (for example, biphenyl, fluorene, etc.); a group in which one hydrogen atom of a group obtained by removing one hydrogen atom from the above aromatic hydrocarbon ring or aromatic heterocyclic ring (aryl group or heteroaryl group) is substituted with an alkylene group (for example, a group obtained by further removing one hydrogen atom from the aryl group in an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, or a 2-naphthylethyl group); and the like.

[0201] The number of carbon atoms of the alkylene group bonded to the above aryl group or heteroaryl group is preferably 1 or more and 4 or less, more preferably 1 or more and 2 or less, and particularly preferably 1.

[0202] In the above aromatic hydrocarbon group, the hydrogen atoms possessed by the aromatic hydrocarbon group may be substituted with substituents. For example, the hydrogen atoms bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted with substituents. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxo group (=O), and the like.

[0203] The alkyl group as the above substituent is preferably an alkyl group having 1 or more and 5 or less carbon atoms, and more preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or a tert-butyl group.

[0204] As the alkoxy group as the above-mentioned substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group are preferable, and a methoxy group and an ethoxy group are more preferable.

[0205] Examples of the halogen atom as the above-mentioned substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferable.

[0206] Examples of the halogenated alkyl group as the above-mentioned substituent include groups in which some or all of the hydrogen atoms of the aforementioned alkyl group are substituted with the aforementioned halogen atoms.

[0207] · Divalent linking group containing a heteroatom The heteroatom in the divalent linking group containing a heteroatom is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.

[0208] Specific examples of the divalent linking group containing a heteroatom include non-hydrocarbon-based linking groups such as -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-O-, -S-, -S(=O)2-, -S(=O)2-O-, -NH-, -NH-C(=O)-, -NH-C(=NH)-, =N-, etc., and combinations of at least one of these non-hydrocarbon-based linking groups and a divalent hydrocarbon group. Examples of the divalent hydrocarbon group include the same ones as the divalent hydrocarbon group that may have the above-mentioned substituents, and a linear or branched aliphatic hydrocarbon group is preferable.

[0209] Among the above, the -NH- in -C(=O)-NH- and the H in -NH- and -NH-C(=NH)- may each be substituted with a substituent such as an alkyl group or an acyl group. The number of carbon atoms of the substituent is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5.

[0210] R 12bAs the divalent linking group in, in particular, a linear or branched alkylene group, a cyclic aliphatic hydrocarbon group, or a divalent linking group containing a hetero atom is preferable.

[0211] R 12b When the divalent linking group in 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, particularly preferably 1 or more and 4 or less, and most preferably 1 or more and 3 or less. Specifically, in the description of the "divalent hydrocarbon group which may have a substituent" as the divalent linking group described above, the same as the linear alkylene group and the branched alkylene group mentioned as the linear or branched aliphatic hydrocarbon group can be mentioned.

[0212] R 12b When the divalent linking group in is a cyclic aliphatic hydrocarbon group, examples of the cyclic aliphatic hydrocarbon group include the same as the cyclic aliphatic hydrocarbon group mentioned as the "aliphatic hydrocarbon group containing a ring in the structure" in the description of the "divalent hydrocarbon group which may have a substituent" as the divalent linking group described above.

[0213] As the cyclic aliphatic hydrocarbon group, a group obtained by removing two or more hydrogen atoms from cyclopentane, cyclohexane, norbornane, isobornane, adamantane, tricyclodecane, or tetracyclododecane is particularly preferable.

[0214] R 12b When the divalent linking group in is a divalent linking group containing a hetero atom, preferable examples of the linking group include -O-, -C(=O)-O-, -C(=O)-, -O-C(=O)-O-, -C(=O)-NH-, -NH- (H may be substituted with a substituent such as an alkyl group or an acyl group), -S-, -S(=O)2-, -S(=O)2-O-, general formula -Y 1b -O-Y 2b -、-[Y 1b -C(=O)-O] m’ -Y 2b -、or -Y 1b -O-C(=O)-Y 2b-represents a group [wherein Y 1b , and Y 2b are each independently a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m' is an integer of 0 or more and 3 or less.], etc. are exemplified.

[0215] R 12b When the divalent linking group in is -NH-, the hydrogen atom in -NH- may be substituted with a substituent such as an alkyl group or 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.

[0216] In the formula -Y 1b -O-Y 2b -, -[Y 1b -C(=O)-O] m’ -Y 2b -, or -Y 1b -O-C(=O)-Y 2b -, Y 1b , and Y 2b are each independently a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include the same ones as those described for the "divalent hydrocarbon group which may have a substituent" as the divalent linking group.

[0217] Y 1b is preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, still more preferably a linear alkylene group having 1 or more and 5 or less carbon atoms, and particularly preferably a methylene group and an ethylene group.

[0218] Y 2b is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group, and an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 or more and 5 or less carbon atoms, more preferably a linear alkyl group having 1 or more and 3 or less carbon atoms, and particularly preferably a methyl group.

[0219] In the formula -[Y 1b-C(=O)-O] m’ -Y 2b In the group represented by -, m' is an integer of 0 or more and 3 or less, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, and particularly preferably 1. That is, the formula -[Y 1b -C(=O)-O] m’ -Y 2b As the group represented by -, the group represented by the formula -Y 1b -C(=O)-O-Y 2b - is particularly preferred. Among them, the group represented by the formula -(CH2) a’ -C(=O)-O-(CH2) b’ - is preferred. In the formula, a' is an integer of 1 or more and 10 or less, preferably an integer of 1 or more and 8 or less, more preferably an integer of 1 or more and 5 or less, further preferably 1 or 2, and most preferably 1. b' is an integer of 1 or more and 10 or less, preferably an integer of 1 or more and 8 or less, more preferably an integer of 1 or more and 5 or less, further preferably 1 or 2, and most preferably 1.

[0220] R 12b Regarding the divalent linking group in, as the divalent linking group containing a heteroatom, an organic group composed of a combination of at least one non-hydrocarbon group and a divalent hydrocarbon group is preferred. Among them, a linear group having an oxygen atom as a heteroatom, for example, a group containing an ether bond or an ester bond is preferred. The group represented by the aforementioned formula -Y 1b -O-Y 2b -, -[Y 1b -C(=O)-O] m’ -Y 2b -, or -Y 1b -O-C(=O)-Y 2b - is more preferred. The group represented by the aforementioned formula -[Y 1b -C(=O)-O] m’ -Y 2b -, or -Y 1b -O-C(=O)-Y 2b - is particularly preferred.

[0221] R 12b As the divalent linking group in, an alkylene group or one containing an ester bond (-C(=O)-O-) is preferred.

[0222] The alkylene group is preferably a linear or branched alkylene group. Preferable examples of the linear aliphatic hydrocarbon group include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], and a pentamethylene group [-(CH2)5-], and the like. Preferable examples of the branched alkylene group include alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-; alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2-, and the like, and alkylalkylene groups.

[0223] As the divalent linking group containing an ester bond, in particular, the group represented by the formula: -R 13b -C(=O)-O-[wherein R 13b is a divalent linking group.] is preferable. That is, the constitutional unit (b-3-S) is preferably a constitutional unit represented by the following formula (b-S1-1).

[0224]

Chemical formula

[0225] R 13b is not particularly limited, and for example, the same ones as the divalent linking groups in the aforementioned R 12b can be mentioned. R 13bAs the divalent linking group, a linear or branched alkylene group, an aliphatic hydrocarbon group containing a ring in the structure, or a divalent linking group containing a heteroatom is preferable, and a linear or branched alkylene group or a divalent linking group containing an oxygen atom as the heteroatom is preferable.

[0226] As the linear alkylene group, a methylene group or an ethylene group is preferable, and a methylene group is particularly preferable. As the branched alkylene group, an alkylmethylene group or an alkylethylene group is preferable, and -CH(CH3)-, -C(CH3)2-, or -C(CH3)2CH2- is particularly preferable.

[0227] As the divalent linking group containing an oxygen atom, a divalent linking group containing an ether bond or an ester bond is preferable, and those described above, -Y 1b -O-Y 2b -、-[Y 1b -C(=O)-O] m’ -Y 2b -、 or -Y 1b -O-C(=O)-Y 2b - is more preferable. Y 1b 、 and Y 2b are each independently a divalent hydrocarbon group which may have a substituent, and m' is an integer of 0 or more and 3 or less. Among them, -Y 1b -O-C(=O)-Y 2b - is preferable, and a group represented by -(CH2) c -O-C(=O)-(CH2) d - is particularly preferable. c is an integer of 1 or more and 5 or less, and 1 or 2 is preferable. d is an integer of 1 or more and 5 or less, and 1 or 2 is preferable.

[0228] As the structural unit (b-3-S), in particular, a structural unit represented by the following formula (b-S1-11) or (b-S1-12) is preferable, and a structural unit represented by the formula (b-S1-12) is more preferable.

[0229]

Chemical formula

[0230] In formula (b-S1-11), A' is preferably a methylene group, an oxygen atom (-O-), or a sulfur atom (-S-).

[0231] R 13b is preferably a linear or branched alkylene group or a divalent linking group containing an oxygen atom. R 13b The linear or branched alkylene group and the divalent linking group containing an oxygen atom in R are the same as the linear or branched alkylene group and the divalent linking group containing an oxygen atom described above, respectively.

[0232] As the structural unit represented by formula (b-S1-12), the structural unit represented by the following formula (b-S1-12a) or (b-S1-12b) is particularly preferable.

[0233] [Chemical formula] (In the formula, R and A' are the same as described above, and c to e are each independently an integer of 1 or more and 3 or less.)

[0234] [Structural unit (b-3-L)] Examples of the structural unit (b-3-L) include, for example, those in which R in the above formula (b-S1) 11b is substituted with a lactone-containing cyclic group, and more specifically, the structural units represented by the following formulas (b-L1) to (b-L5) are included.

[0235] [Chemical formula] (In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms; R' are each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogenated alkyl group, a hydroxyl group, -COOR", -OC(=O)R", a hydroxyalkyl group, or a cyano group, and R" is a hydrogen atom or an alkyl group; R 12b is a single bond or a divalent linking group, s" is an integer of 0 or more and 2 or less; A" is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom, or a sulfur atom; r is 0 or 1.)

[0236] R in formulas (b-L1) to (b-L5) is the same as described above. Examples of the alkyl group, alkoxy group, halogenated alkyl group, -COOR", -OC(=O)R", and hydroxyalkyl group in R' are the same as those described above for the alkyl group, alkoxy group, halogenated alkyl group, -COOR", -OC(=O)R", and hydroxyalkyl group which may be a substituent that the -SO2-containing cyclic group has.

[0237] Considering industrial availability and the like, R' is preferably a hydrogen atom. The alkyl group in R" may be linear, branched, or cyclic. When R" is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. When “R” is a cyclic alkyl group, it preferably has 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, examples include groups obtained by removing one or more hydrogen atoms from polycyclic alkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes, which may or may not be substituted with a fluorine atom or a fluorinated alkyl group. Specifically, examples include groups obtained by removing one or more hydrogen atoms from monocycloalkanes such as cyclopentane and cyclohexane, and polycyclic alkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Examples of “A” include the same ones as A’ in the aforementioned formula (3-1). A” is preferably an alkylene group having 1 to 5 carbon atoms, an oxygen atom (-O-), or a sulfur atom (-S-), more preferably an alkylene group having 1 to 5 carbon atoms or -O-. As the alkylene group having 1 to 5 carbon atoms, a methylene group or a dimethylmethylene group is more preferable, and a methylene group is most preferable.

[0238] R 12b is the same as R in the aforementioned formula (b-S1). 12b In the formula (b-L1), s” is preferably 1 or 2. Specific examples of the structural units represented by the aforementioned formulas (b-L1) to (b-L3) are exemplified below. In the following formulas, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0239]

Chemical formula

[0240]

Chemical formula

[0241]

Chemical formula

[0242] As the structural unit (b-3-L), at least one selected from the group consisting of the structural units represented by the aforementioned formulas (b-L1) to (b-L5) is preferable, at least one selected from the group consisting of the structural units represented by the formulas (b-L1) to (b-L3) is more preferable, and at least one selected from the group consisting of the structural units represented by the aforementioned formula (b-L1) or (b-L3) is particularly preferable. Among them, at least one selected from the group consisting of the structural units represented by the aforementioned formulas (b-L1-1), (b-L1-2), (b-L2-1), (b-L2-7), (b-L2-12), (b-L2-14), (b-L3-1), and (b-L3-5) is preferable.

[0243] Further, as the structural unit (b-3-L), the structural units represented by the following formulas (b-L6) to (b-L7) are also preferable.

Chemical formula

[0244] Further, the acrylic resin (B3) contains, as a structural unit that enhances the solubility of the acrylic resin (B3) in alkali by the action of an acid, a structural unit represented by the following formulas (b5) to (b7) having an acid dissociable group.

[0245]

Chemical formula

[0246] In the above formulas (b5) to (b7), R 14b , and R 18b ~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 fluorinated alkyl group having 1 to 6 carbon atoms, and R 15b ~R17b each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched fluorinated alkyl group having 1 to 6 carbon atoms, or an aliphatic cyclic group having 5 to 20 carbon atoms, and R 16b and R 17b may be bonded to each other to form a hydrocarbon ring having 5 to 20 carbon atoms together with the carbon atoms to which they are bonded, and Y b represents an aliphatic cyclic group or an alkyl group which may have a substituent, p represents an integer of 0 or more and 4 or less, and q represents 0 or 1.

[0247] Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and the like. The fluorinated alkyl group is a group in which some or all of the hydrogen atoms of the above 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 polycyclic alkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. Specifically, groups obtained by removing one hydrogen atom from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycyclic alkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane can be mentioned. In particular, groups obtained by removing one hydrogen atom from cyclohexane or adamantane (which may further have a substituent) are preferred.

[0248] When the above R 16b and R 17b do not bond to each other to form a hydrocarbon ring, the above R 15b , R 16b , and R 17b are preferably linear or branched alkyl groups having 2 to 4 carbon atoms from the viewpoints of high contrast, good resolution, depth of focus width, etc. The above R 19b , R 20b , R 22b , R 23bis preferably a hydrogen atom or a methyl group.

[0249] The above R 16b and R 17b may together with the carbon atom to which both are attached form an aliphatic cyclic group having 5 to 20 carbon atoms. Specific examples of such aliphatic cyclic groups include groups obtained by removing one or more hydrogen atoms from polycyclic alkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. Specifically, groups obtained by removing one or more hydrogen atoms from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycyclic alkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane can be mentioned. In particular, groups obtained by removing one or more hydrogen atoms from cyclohexane or adamantane (which may further have a substituent) are preferred.

[0250] Furthermore, when the aliphatic cyclic group formed by the above R 16b and R 17b has a substituent on its ring skeleton, examples of such substituents include polar groups such as a hydroxyl group, a carboxy group, a cyano group, and an oxygen atom (=O), and a linear or branched alkyl group having 1 to 4 carbon atoms. As the polar group, an oxygen atom (=O) is particularly preferred.

[0251] The above Y b is an aliphatic cyclic group or an alkyl group, and examples include groups obtained by removing one or more hydrogen atoms from polycyclic alkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. Specifically, groups obtained by removing one or more hydrogen atoms from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycyclic alkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane can be mentioned. In particular, groups obtained by removing one or more hydrogen atoms from adamantane (which may further have a substituent) are preferred.

[0252] Furthermore, the above Y bWhen the aliphatic cyclic group has a substituent on its ring skeleton, examples of the substituent include polar groups such as a hydroxyl group, a carboxy group, a cyano group, and an oxygen atom (=O), and linear or branched alkyl groups having 1 to 4 carbon atoms. As the polar group, an oxygen atom (=O) is particularly preferable.

[0253] Also, when Y b is an alkyl group, it is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, more preferably 6 to 15 carbon atoms. Such an alkyl group is particularly preferably an alkoxyalkyl group. Examples of such an alkoxyalkyl group include 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-isopropoxyethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1-tert-butoxyethyl group, 1-methoxypropyl group, 1-ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1-ethoxy-1-methylethyl group, and the like.

[0254] Preferable specific examples of the structural unit represented by the above formula (b5) include those represented by the following formulas (b5-1) to (b5-33).

[0255]

Chemical formula

[0256] In the above formulas (b5-1) to (b5-33), R 24b represents a hydrogen atom or a methyl group.

[0257] Preferable specific examples of the structural unit represented by the above formula (b6) include those represented by the following formulas (b6-1) to (b6-26).

[0258]

Chemical formula

[0259] In the above formulas (b6-1) to (b6-26), R24b represents a hydrogen atom or a methyl group.

[0260] Preferable specific examples of the structural unit represented by the above formula (b7) include those represented by the following formulas (b7-1) to (b7-15).

[0261] [Chemical formula]

[0262] In the above formulas (b7-1) to (b7-15), R 24b represents a hydrogen atom or a methyl group.

[0263] Among the structural units represented by the formulas (b5) to (b7) described above, the structural unit represented by the formula (b6) is preferable because it is easy to synthesize and relatively easy to achieve high sensitivity. Further, among the structural units represented by the formula (b6), the structural unit in which Y b is an alkyl group is preferable, and the structural unit in which one or both of R 19b and R 20b are alkyl groups is preferable.

[0264] Furthermore, the acrylic resin (B3) is preferably a resin composed of a copolymer containing a structural unit derived from a polymerizable compound having an ether bond together with the structural units represented by the above formulas (b5) to (b7).

[0265] Examples of the polymerizable compound having the ether bond include radical polymerizable compounds such as (meth)acrylic acid derivatives having an ether bond and an ester bond. Specific examples include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, and the like. Further, the polymerizable compound having the ether bond is preferably 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, or methoxytriethylene glycol (meth)acrylate. These polymerizable compounds may be used alone or in combination of two or more.

[0266] Furthermore, the acrylic resin (B3) may contain other polymerizable compounds as constituent units for the purpose of appropriately controlling physical and chemical properties. Examples of such polymerizable compounds include known radical polymerizable compounds and anionic polymerizable compounds.

[0267] 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; methacrylic acid derivatives having a carboxy group and an ester bond such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid; alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and cyclohexyl (meth)acrylate; hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate; diesters of dicarboxylic acids such as diethyl maleate and dibutyl fumarate; vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylamide; and the like.

[0268] As described above, the acrylic resin (B3) may contain a structural unit derived from a polymerizable compound having a carboxy group such as the above monocarboxylic acids and dicarboxylic acids. However, from the viewpoint of easily forming a patterned resist film including a non-resist portion having a good rectangular cross-sectional shape, the acrylic resin (B3) preferably does not substantially contain a structural unit derived from a polymerizable compound having a carboxy group. Specifically, the ratio of the structural unit derived from a polymerizable compound having a carboxy group in the acrylic resin (B3) is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 5% by mass or less. In the acrylic resin (B3), an acrylic resin containing a relatively large amount of a structural unit derived from a polymerizable compound having a carboxy group is preferably used in combination with an acrylic resin containing only a small amount or no structural unit derived from a polymerizable compound having a carboxy group.

[0269] Examples of the polymerizable compound include (meth)acrylic acid esters having an acid non-dissociable aliphatic polycyclic group, vinyl group-containing aromatic compounds, and the like. As the acid non-dissociable aliphatic polycyclic group, a tricyclodecanyl group, an adamantyl group, a tetracyclododecanyl group, an isobornyl group, a norbornyl group, etc. are particularly preferable in terms of easy availability in industry. These aliphatic polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.

[0270] Specific examples of the (meth)acrylic acid esters having an acid non-dissociable aliphatic polycyclic group include those having the structures of the following formulas (b8-1) to (b8-5).

[0271]

Chemical formula

[0272] In the above formulas (b8-1) to (b8-5), R 25b represents a hydrogen atom or a methyl group.

[0273] When the acrylic resin (B3) contains a structural unit (b-3) containing a -SO2-containing cyclic group or a lactone-containing cyclic group, the content of the structural unit (b-3) in the acrylic resin (B3) is preferably 5% by mass or more, more preferably 10% by mass or more, particularly preferably 10% by mass or more and 50% by mass or less, and most preferably 10% by mass or more and 30% by mass or less. When the photosensitive resin composition contains the structural unit (b-3) in the above range, it is easy to achieve both good developability and a good pattern shape.

[0274] Further, the acrylic resin (B3) preferably contains 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 10% by mass or more and 50% by mass or less of the structural units represented by the aforementioned formulas (b5) to (b7).

[0275] The acrylic resin (B3) preferably contains a structural unit derived from the polymerizable compound having the above ether bond. The content of the structural unit derived from the polymerizable compound having an ether bond in the acrylic resin (B3) is preferably 0% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 30% by mass or less.

[0276] The acrylic resin (B3) preferably contains a structural unit derived from the (meth)acrylic acid esters having the above acid non-dissociable aliphatic polycyclic group. The content of the structural unit derived from the (meth)acrylic acid esters having an acid non-dissociable aliphatic polycyclic group in the acrylic resin (B3) is preferably 0% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 30% by mass or less.

[0277] As the acrylic resin (B3) described above, in terms of excellent balance of resolution, developability, and plating solution resistance of the formed resist film, a resin containing a structural unit derived from hydroxystyrene and / or a structural unit derived from styrene, and the structural units represented by the aforementioned formulas (b5) to (b7) is also preferred. In this case, the total of the content of the structural unit derived from hydroxystyrene and / or the structural unit derived from styrene in the acrylic resin (B3) and the content of the structural units represented by the aforementioned formulas (b5) to (b7) is preferably 80% by mass or more, more preferably 90% by mass or more, and most preferably 100% by mass based on the mass of the acrylic resin (B3). From the viewpoint of the balance of developability, dimensional accuracy, and plating solution resistance of the resist film formed using the photosensitive resin composition, in the acrylic resin (B3) containing a structural unit derived from hydroxystyrene and / or a structural unit derived from styrene, and a structural unit represented by the formulas (b5) to (b7), the content of the structural unit derived from hydroxystyrene and / or the structural unit derived from styrene is preferably 40% by mass or more and 90% by mass or less, more preferably 50% by mass or more and 90% by mass or less, and even more preferably 60% by mass or more and 90% by mass or less, based on the mass of the acrylic resin (B3). From the viewpoint of improving the developability of the photosensitive resin composition, in the acrylic resin (B3) containing a structural unit derived from hydroxystyrene and / or a structural unit derived from styrene, and a structural unit represented by the formulas (b5) to (b7), the content of the structural unit derived from hydroxystyrene is preferably 40% by mass or more and 70% by mass or less, more preferably 50% by mass or more and 70% by mass or less, based on the mass of the acrylic resin (B3). Further, from the viewpoints of the developability and resolution of the photosensitive resin composition, in the acrylic resin (B3) containing a structural unit derived from hydroxystyrene and / or a structural unit derived from styrene, and a structural unit represented by the formulas (b5) to (b7), the content of the structural unit represented by the formulas (b5) to (b7) is preferably 10% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 40% by mass or less, and even more preferably 10% by mass or more and 30% by mass or less, based on the mass of the acrylic resin (B3).

[0278] As long as the photosensitive resin composition contains a predetermined amount of the acrylic resin (B3), acrylic resins other than the acrylic resin (B3) described above can also be used as the resin (B). Such acrylic resins other than the acrylic resin (B3) are not particularly limited as long as they are resins containing the structural units represented by the aforementioned formulas (b5) to (b7).

[0279] The polystyrene-reduced 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 the mass average molecular weight in this way, sufficient strength of the photosensitive layer can be maintained without reducing the peelability from the substrate, and furthermore, swelling of the profile during plating and generation of cracks can be prevented.

[0280] Also, the dispersity of the resin (B) is preferably 1.05 or more. Here, the dispersity is the value obtained by dividing the mass average molecular weight by the number average molecular weight. By setting the dispersity in this way, problems such as stress resistance to the desired plating and the tendency of the metal layer obtained by the plating treatment to swell can be avoided.

[0281] The content of the resin (B) is preferably 5% by mass or more and 99% by mass or less based on the total solid content of the photosensitive resin composition.

[0282] <Radical generator (C)> The photosensitive resin composition may contain a radical generator (C) having a value of absorption attenuation amount determined by the method including the following i) to vii) of 0.02 or more. The value of the absorption attenuation amount is preferably 0.05 or more, more preferably 0.07 or more, and still more preferably 0.10 or more. The upper limit of the absorption attenuation amount is not particularly limited, and may be, for example, 0.30 or less, or may be 0.20 or less. i) Dissolving 100 parts by mass of a polyhydroxystyrene resin having a weight average molecular weight of 2000 and 3 parts by mass of the radical generator (C) in propylene glycol monomethyl ether to obtain a test solution. ii) Coating the test solution on a glass substrate to form a coating film. iii) Heating the coating film at 100 ° C for 300 seconds to form a resin film having a film thickness of 5 μm. iv) Measuring the absorption Abs1 at a wavelength of 365 nm of the resin film on the glass substrate. v) exposing the resin film with an i-line exposure machine at an exposure dose of 1000 mJ / cm 2 ; vi) measuring Abs2, the absorbance at a wavelength of 365 nm of the exposed resin film; and vii) calculating the absorption attenuation amount as the difference between Abs1 and Abs2.

[0283] When the photosensitive resin composition contains the radical generator (C) described above, the exposure latitude (EL) is large and the resolution is good even when forming a fine pattern.

[0284] As the radical generator (C), an oxime ester compound represented by the following formula (c1) is preferable. [Chemical formula] (In formula (c1), R c1 is a monovalent organic group, a halogen atom, a nitro group, or a cyano group; R c2 is an aliphatic hydrocarbon group; R c3 is an aryl group which may have a substituent; A is S or O; n1 is an integer of 0 or more and 4 or less; n2 is 0 or 1.)

[0285] In formula (c1), A is particularly preferably S in terms of easily obtaining a photopolymerization initiator with excellent sensitivity.

[0286] In formula (c1), R c1 is a monovalent organic group, a halogen atom, a nitro group, or a cyano group. R in formula (c1) c1When it is a monovalent organic group, it can be selected from various organic groups as long as the object of the present invention is not inhibited. As the organic group, a carbon atom-containing group is preferable, and a group composed of one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms is more preferable. The number of carbon atoms of the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, and more preferably 1 or more and 20 or less.

[0287] R c1 Examples of the monovalent organic group suitable as R include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, an amino group substituted with one or two organic groups, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, a cyano group, a substituent represented by HX2C- or H2XC- (wherein X is each independently a halogen atom), etc.

[0288] R c1 When R is an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. Also, R c1 When R is an alkyl group, it may be linear or branched. R c1Specific examples of the case where it is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an n-nonyl group, an isononyl group, an n-decyl group, and an isodecyl group, etc. Further, R c1 When R is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group, etc.

[0289] R c1 When R is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. Further, R c1 When R is an alkoxy group, it may be linear or branched. R c1 Specific examples of the case where R is an alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, an n-pentyloxy group, an isopentyloxy group, a sec-pentyloxy group, a tert-pentyloxy group, an n-hexyloxy group, an n-heptyloxy group, an n-octyloxy group, an isooctyloxy group, a sec-octyloxy group, a tert-octyloxy group, an n-nonyloxy group, an isononyloxy group, an n-decyloxy group, and an isodecyloxy group, etc. Further, R c1 When R is an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxypropyloxy group, etc.

[0290] R c1 When R is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms in the cycloalkyl group or cycloalkoxy group is preferably 3 or more and 10 or less, more preferably 3 or more and 6 or less. R c1 Specific examples of the case where R is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group, etc. R c1 Specific examples of the case where R is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group, etc.

[0291] R c1 When R is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms in the saturated aliphatic acyl group or saturated aliphatic acyloxy group is preferably 2 or more and 21 or less, more preferably 2 or more and 7 or less. R c1 Specific examples of the case where R is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, an n-butanoyl group, a 2-methylpropanoyl group, an n-pentanoyl group, a 2,2-dimethylpropanoyl group, an n-hexanoyl group, an n-heptanoyl group, an n-octanoyl group, an n-nonanoyl group, an n-decanoyl group, an n-undecanoyl group, an n-dodecanoyl group, an n-tridecanoyl group, an n-tetradecanoyl group, an n-pentadecanoyl group, and an n-hexadecanoyl group, etc. R c1 Specific examples of the case where R is a saturated aliphatic acyloxy group include an acetyloxy group, a propanoyloxy group, an n-butanoyloxy group, a 2-methylpropanoyloxy group, an n-pentanoyloxy group, a 2,2-dimethylpropanoyloxy group, an n-hexanoyloxy group, an n-heptanoyloxy group, an n-octanoyloxy group, an n-nonanoyloxy group, an n-decanoyloxy group, an n-undecanoyloxy group, an n-dodecanoyloxy group, an n-tridecanoyloxy group, an n-tetradecanoyloxy group, an n-pentadecanoyloxy group, and an n-hexadecanoyloxy group, etc.

[0292] R c1 When R is an alkoxycarbonyl group, the number of carbon atoms in the alkoxycarbonyl group is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less. R c1 Specific examples of the case where R is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and isodecyloxycarbonyl group.

[0293] R c1 When R is a phenylalkyl group, the number of carbon atoms in the phenylalkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less. Also, R c1 When R is a naphthylalkyl group, the number of carbon atoms in the naphthylalkyl group is preferably 11 or more and 20 or less, more preferably 11 or more and 14 or less. R c1 Specific examples of the case where R is a phenylalkyl group include benzyl group, 2-phenylethyl group, 3-phenylpropyl group, and 4-phenylbutyl group. R c1 Specific examples of the case where R is a naphthylalkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2-(α-naphthyl)ethyl group, and 2-(β-naphthyl)ethyl group. c1 When R is a phenylalkyl group or a naphthylalkyl group, R c1 may further have a substituent on the phenyl group or the naphthyl group.

[0294] R c1 When R is a heterocyclyl group, the heterocyclyl group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. The heterocyclyl group may further have a substituent.

[0295] R c1 When R is a heterocyclyl group, the heterocyclyl group is a 5- or 6-membered monocyclic ring containing one or more N, S, O, or a heterocyclyl group formed by condensation of such monocyclic rings or such monocyclic rings with a benzene ring. When the heterocyclyl group is a condensed ring, the number of rings is up to 3. Examples of the heterocyclic ring constituting such a heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran, etc. R c1 When R is a heterocyclyl group, examples of the substituent that the heterocyclyl group may have include a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, etc.

[0296] R c1 When R is a heterocyclylcarbonyl group, the heterocyclyl group contained in the heterocyclylcarbonyl group is the same as when R c1 is a heterocyclyl group.

[0297] R c1When it is an amino group substituted with one or two organic groups, preferred examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 21 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, and a heterocyclyl group and the like. Specific examples of these preferred organic groups are the same as R c1 as described above. Specific examples of the amino group substituted with one or two organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n-butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, α-naphthoylamino group, and β-naphthoylamino group and the like.

[0298] R c1When the phenyl group, naphthyl group, and heterocyclyl group contained in [the compound] further have substituents, examples of the substituents include substituents containing a group represented by HX2C- or H2XC- (for example, a halogenated alkoxy group containing a group represented by HX2C- or H2XC-, a halogenated alkyl group containing a group represented by HX2C- or H2XC-), an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a benzoyl group, a halogen, a nitro group, and a cyano group, etc. R c1 When the phenyl group, naphthyl group, and heterocyclyl group contained in [the compound] further have substituents, the number of the substituents is not limited as long as it does not inhibit the object of the present invention, and is preferably 1 to 4. R c1 When the phenyl group, naphthyl group, and heterocyclyl group contained in [the compound] have a plurality of substituents, the plurality of substituents may be the same or different.

[0299] R c1 When the benzoyl group contained in [the compound] further has substituents, examples of the substituents include an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a 2-tenoyl group (thiophen-2-ylcarbonyl group), a furan-3-ylcarbonyl group, and a phenyl group, etc.

[0300] Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, etc., and a fluorine atom is preferable.

[0301] Examples of the substituent containing a group represented by HX2C- or H2XC- include a halogenated alkoxy group containing a group represented by HX2C- or H2XC-, a group having a halogenated alkoxy group containing a group represented by HX2C- or H2XC-, a halogenated alkyl group containing a group represented by HX2C- or H2XC-, a group having a halogenated alkyl group containing a group represented by HX2C- or H2XC-, etc. Among them, a halogenated alkoxy group containing a group represented by HX2C- or H2XC- or a group having a halogenated alkoxy group containing a group represented by HX2C- or H2XC- is more preferred.

[0302] Examples of the group having a halogenated alkyl group containing a group represented by HX2C- or H2XC- include an aromatic group (e.g., phenyl group, naphthyl group, etc.) substituted with a halogenated alkyl group containing a group represented by HX2C- or H2XC-, a cycloalkyl group (e.g., cyclopentyl group, cyclohexyl group, etc.) substituted with a halogenated alkyl group containing a group represented by HX2C- or H2XC-, etc. Among them, an aromatic group substituted with a halogenated alkyl group containing a group represented by HX2C- or H2XC- is preferred.

[0303] Examples of the group having a halogenated alkoxy group containing a group represented by HX2C- or H2XC- include an aromatic group (e.g., phenyl group, naphthyl group, etc.) substituted with a halogenated alkoxy group containing a group represented by HX2C- or H2XC-, an alkyl group (e.g., methyl group, ethyl group, n-propyl group, i-propyl group, etc.) substituted with a halogenated alkoxy group containing a group represented by HX2C- or H2XC-, a cycloalkyl group (e.g., cyclopentyl group, cyclohexyl group, etc.) substituted with a halogenated alkoxy group containing a group represented by HX2C- or H2XC-, etc. Among them, an aromatic group substituted with a halogenated alkoxy group containing a group represented by HX2C- or H2XC- is preferred.

[0304] Also, R c1Examples thereof also preferably include a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, and a phenylthioalkyl group which may have a substituent on the aromatic ring. The substituent which the phenoxyalkyl group and the phenylthioalkyl group may have is the same as the substituent which the phenyl group contained in R c1 may have.

[0305] R c1 Among these, a benzoyl group; a naphthoyl group; a benzoyl group substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; a nitro group; and a benzofuranylcarbonyl group which may have a substituent are preferable, and a benzoyl group; a naphthoyl group; a 2-methylphenylcarbonyl group; a 4-(piperazin-1-yl)phenylcarbonyl group; and a 4-(phenyl)phenylcarbonyl group are more preferable.

[0306] Further, in formula (c1), n1 is preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0 or 1. When n1 is 1, the bonding position of R c1 is preferably the para position with respect to the bond to which the phenyl group to which R c1 is bonded is bonded to an oxygen atom or a sulfur atom.

[0307] In formula (c1), the monovalent organic group as R c2 is not particularly limited as long as it does not inhibit the object of the present invention. As the organic group, a carbon atom-containing group is preferable, and a group composed of 1 or more carbon atoms and 1 or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms is more preferable. The number of carbon atoms of the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, and more preferably 1 or more and 20 or less. R c2 Preferable examples of the monovalent organic group as R c1 are the same groups as the monovalent organic group as R c1 in formula (c1). Specific examples of these groups are the same as the groups described for R c1 in formula (c1). Also, R c2 is preferably a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, or a phenylthioalkyl group which may have a substituent on the aromatic ring. The substituents which the phenoxyalkyl group and the phenylthioalkyl group may have are the same as the substituents in the case where the phenyl group, naphthyl group, and heterocyclyl group contained in R c1 in formula (c1) further have substituents.

[0308] Among the organic groups, R c2 is preferably a substituent containing a group represented by the above HX2C- or H2XC-, an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, a cycloalkylalkyl group, or a phenylthioalkyl group which may have a substituent on the aromatic ring. Regarding the number of carbon atoms of the cycloalkyl group contained in the alkyl group, the phenyl group which may have a substituent, or the cycloalkylalkyl group, the number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group, the number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group or the phenylthioalkyl group which may have a substituent on the aromatic ring, or the phenylthioalkyl group which may have a substituent on the aromatic ring, it is the same as R c1 in formula (c1).

[0309] Also, R c2 is preferably a group represented by -A 1 -CO-O-A 2 . A 1 is a divalent organic group, preferably a divalent hydrocarbon group, and preferably an alkylene group. A 2 is a monovalent organic group, preferably a monovalent hydrocarbon group.

[0310] When A 1 is an alkylene group, the alkylene group may be linear or branched, and is preferably linear. When A 1 is an alkylene group, the number of carbon atoms of the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 4 or less.

[0311] A 2 Suitable examples of A include an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. A 2 Specific suitable examples of A include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, a phenyl group, a naphthyl group, a benzyl group, a phenethyl group, an α-naphthylmethyl group, and a β-naphthylmethyl group, etc.

[0312] -A 1 -CO-O-A 2 Specific suitable examples of the group represented by include a 2-methoxycarbonylethyl group, a 2-ethoxycarbonylethyl group, a 2-n-propyloxycarbonylethyl group, a 2-n-butyloxycarbonylethyl group, a 2-n-pentyloxycarbonylethyl group, a 2-n-hexyloxycarbonylethyl group, a 2-benzyloxycarbonylethyl group, a 2-phenoxycarbonylethyl group, a 3-methoxycarbonyl-n-propyl group, a 3-ethoxycarbonyl-n-propyl group, a 3-n-propyloxycarbonyl-n-propyl group, a 3-n-butyloxycarbonyl-n-propyl group, a 3-n-pentyloxycarbonyl-n-propyl group, a 3-n-hexyloxycarbonyl-n-propyl group, a 3-benzyloxycarbonyl-n-propyl group, and a 3-phenoxycarbonyl-n-propyl group, etc.

[0313] Also, R c2 is preferably a group represented by the following formula (c2) or (c3).

Chemical formula

[0314] In formula (c2), R c4 , and R c5 as the monovalent organic group is the same as the monovalent organic group as R c1 in formula (c1). R c4 is preferably a halogenated alkoxy group containing a group represented by HX2C- or H2XC-, a halogenated alkyl group containing a group represented by HX2C- or H2XC-, an alkyl group or a phenyl group. R c4 and R c5 When they combine to form a ring, the ring may be an aromatic ring or an aliphatic ring. As a preferred example of the group represented by formula (c2) in which R c5 and R c5 form a ring, a naphthalen-1-yl group, a 1,2,3,4-tetrahydronaphthalen-5-yl group, etc. may be mentioned. In the above formula (c2), n3 is an integer of 0 or more and 4 or less, preferably 0 or 1, and more preferably 0.

[0315] In the above formula (c3), R c6 is a monovalent organic group. As the monovalent organic group as R c6 is the same as the monovalent organic group as R c1 in formula (c1). Among the organic groups, an alkyl group is preferred. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or more and 3 or less. R c6Examples thereof preferably include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc., and among these, a methyl group is more preferable.

[0316] In the above formula (c3), n5 is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 3 or less, and more preferably 1 or 2. In the above formula (c3), n6 is 0 or more and (n5 + 3) or less, preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0. In the above formula (c3), n4 is an integer of 1 or more and 8 or less, preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 or more and 3 or less, and particularly preferably 1 or 2.

[0317] In formula (c1), R c3 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent. When R c3 is an aliphatic hydrocarbon group, examples of the substituent which it may have preferably include a phenyl group, a naphthyl group, etc.

[0318] In formula (c1), R c3 Examples thereof preferably include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 2-cyclopentylethyl group, a 2-cyclobutylethyl group, a cyclohexylmethyl group, a phenyl group, a benzyl group, a methylphenyl group, a naphthyl group, etc., and among these, a methyl group or a phenyl group is more preferable.

[0319] Preferable specific examples of the compound represented by formula (c1) include the following compounds.

Chemical formula

[0320] As the radical generator (C1), a phosphine oxide compound is also preferable. The phosphine oxide compound is selected from phosphine oxide compounds containing a partial structure represented by the following formula (c9). [Chemical formula] In formula (c4), R c7 , and R c8 are each independently an alkyl group, a cycloalkyl group, an aryl group, an aliphatic acyl group having 2 to 20 carbon atoms, or an aromatic acyl group having 7 to 20 carbon atoms. However, both R c7 , and R c8 are not an aliphatic acyl group or an aromatic acyl group.

[0321] R c7 , and R c8 The number of carbon atoms of the alkyl group as is preferably 1 to 12, more preferably 1 to 8, and even more preferably 1 to 4. R c7 , and R c8 The alkyl group as may be linear or branched. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2,4,4,-trimethylpentyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, and n-dodecyl group.

[0322] R c7 , and R c8 The number of carbon atoms of the cycloalkyl group as is preferably 5 to 12. Specific examples of the cycloalkyl group include cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, and cyclododecyl group.

[0323] R c7 , and R c8The number of carbon atoms of the aryl group as [the aryl group] is preferably 6 or more and 12 or less. The aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and the like. Specific examples of the aryl group include a phenyl group and a naphthyl group.

[0324] R c7 and R c8 The number of carbon atoms of the aliphatic acyl group as [the aliphatic acyl group] is 2 or more and 20 or less, preferably 2 or more and 12 or less, more preferably 2 or more and 8 or less, and still more preferably 2 or more and 6 or less. The aliphatic acyl group may be linear or branched. Specific examples of the aliphatic acyl group include an acetyl group, a propionyl group, a butanoyl group, a pentanoyl group, a hexanoyl group, a heptanoyl group, an octanoyl group, a nonanoyl group, a decanoyl group, an undecanoyl group, a dodecanoyl group, a tridecanoyl group, a tetradecanoyl group, a pentadecanoyl group, a hexadecanoyl group, a heptadecanoyl group, an octadecanoyl group, a nonadecanoyl group, and an icosanoyl group.

[0325] R c7 and R c8 The number of carbon atoms of the aromatic acyl group as [the aromatic acyl group] is 7 or more and 20 or less. The aromatic acyl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and the like. Specific examples of the aromatic acyl group include a benzoyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 2,6-dimethylbenzoyl group, a 2,6-dimethoxybenzoyl group, a 2,4,6-trimethylbenzoyl group, an α-naphthoyl group, and a β-naphthoyl group.

[0326] Preferable specific examples of the phosphine oxide compound containing the structural moiety represented by formula (c4) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide.

[0327] In the photosensitive resin composition, the content of the radical generator (C) is not particularly limited. In the photosensitive resin composition, when the resin (B) is 100 parts by mass, the content of the radical generator (C) is preferably 0.01 part by mass or more and 20 parts by mass or less, more preferably 0.1 part by mass or more and 15 parts by mass or less, and still more preferably 0.5 part by mass or more and 10 parts by mass or less.

[0328] <Alkali-soluble resin (D)> The photosensitive resin composition preferably further contains an alkali-soluble resin (D) in order to improve alkali solubility. Here, the alkali-soluble resin refers to a resin that, when a resin film with a thickness of 1 μm is formed on a substrate using a resin solution with a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate) and immersed in a 2.38% by mass aqueous solution of TMAH (tetramethylammonium hydroxide) for 1 minute, dissolves by 0.01 μm or more and does not correspond to the aforementioned component (B) (typically, it refers to a resin whose alkali solubility does not substantially change even by the action of an acid). As the alkali-soluble resin (D), it is preferably at least one resin selected from the group consisting of a novolak resin (D1), a polyhydroxystyrene resin (D2), and an acrylic resin (D3).

[0329] [Novolak resin (D1)] The novolak resin can be obtained, for example, by subjecting an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as "phenols") and aldehydes to addition condensation under an acid catalyst.

[0330] Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, phloroglucinol, hydroxydiphenyl, bisphenol A, salicylic acid, gallic acid, gallic acid ester, α-naphthol, β-naphthol, and the like. Examples of the aldehydes include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde, and the like. The catalyst during the addition condensation reaction is not particularly limited. For example, in the case of an acid catalyst, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, etc. are used.

[0331] Note that by using o-cresol, substituting the hydrogen atom of the hydroxyl group in the resin with another substituent, or using bulky aldehydes, it is possible to further improve the flexibility of the novolak resin.

[0332] The mass average molecular weight of the novolak resin (D1) is not particularly limited as long as it does not inhibit the object of the present invention, but it is preferably 1000 or more and 50000 or less.

[0333] [Polyhydroxystyrene resin (D2)] Examples of the hydroxystyrene-based compounds constituting the polyhydroxystyrene resin (D2) include p-hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene, and the like. Furthermore, the polyhydroxystyrene resin (D2) is preferably a copolymer with a styrene resin. Examples of the styrenic compound constituting such a styrene resin include styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, α-methylstyrene, and the like.

[0334] The mass average molecular weight of the polyhydroxystyrene resin (D2) is not particularly limited as long as it does not inhibit the object of the present invention, but is preferably 1000 or more and 50000 or less.

[0335] [Acrylic resin (D3)] The acrylic resin (D3) preferably contains a structural unit derived from a polymerizable compound having an ether bond and a structural unit derived from a polymerizable compound having a carboxy group.

[0336] Examples of the polymerizable compound having an ether bond include (meth)acrylic acid derivatives having an ether bond and an ester bond such as 2-methoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate. The polymerizable compound having an ether bond is preferably 2-methoxyethyl acrylate or methoxytriethylene glycol acrylate. These polymerizable compounds may be used alone or in combination of two or more.

[0337] Examples of the polymerizable compound having a carboxy group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; compounds having a carboxy group and an ester bond such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid; and the like. The polymerizable compound having a carboxy group is preferably acrylic acid or methacrylic acid. These polymerizable compounds may be used alone or in combination of two or more.

[0338] The mass average molecular weight of the acrylic resin (D3) is not particularly limited as long as it does not inhibit the object of the present invention, but is preferably 50,000 or more and 800,000 or less.

[0339] When the content of the alkali-soluble resin (D) is based on 100 parts by mass of the total solid content of the photosensitive resin composition, it is preferably 0 parts by mass or more and 80 parts by mass or less, and more preferably 5 parts by mass or more and 70 parts by mass or less.

[0340] <Sulfur-containing compound (E)> When the photosensitive resin composition is used for pattern formation on a metal substrate, the photosensitive resin composition preferably contains a sulfur-containing compound (E). The sulfur-containing compound (E) is a compound containing a sulfur atom capable of coordinating to a metal. For a compound that can generate two or more tautomers, when at least one tautomer contains a sulfur atom that coordinates to the metal constituting the surface of the metal substrate, the compound falls within the category of sulfur-containing compounds. When forming a patterned resist film used as a plating mold on a surface made of a metal such as Cu, defects in the cross-sectional shape such as footing are likely to occur. However, when the photosensitive resin composition contains a sulfur-containing compound (E), even when forming a patterned resist film on the surface made of a metal on the substrate, it is easy to suppress the occurrence of defects in the cross-sectional shape such as footing. Note that "footing" refers to a phenomenon in which the resist portion protrudes toward the non-resist portion side near the contact surface between the substrate surface and the patterned resist film, resulting in the bottom width being narrower than the top width in the non-resist portion. When the photosensitive resin composition is used for pattern formation on a substrate other than a metal substrate, there is no particular need for the photosensitive resin composition to contain a sulfur-containing compound. When the photosensitive resin composition is used for pattern formation on a substrate other than a metal substrate, from the viewpoints that the production of the photosensitive resin composition is easy due to the reduction in the number of components of the photosensitive resin composition and the production cost of the photosensitive resin composition can be reduced, it is preferable that the photosensitive resin composition does not contain a sulfur-containing compound (E). Note that there are no particular problems caused by the photosensitive resin composition used for pattern formation on a substrate other than a metal substrate containing a sulfur-containing compound (E).

[0341] Sulfur atoms that can coordinate to a metal are contained in a sulfur-containing compound, for example, as a mercapto group (-SH), a thiocarboxy group (-CO-SH), a dithiocarboxy group (-CS-SH), and a thiocarbonyl group (-CS-), etc. Since it is easy to coordinate to a metal and has an excellent effect of suppressing footing, it is preferable that the sulfur-containing compound has a mercapto group.

[0342] Preferable examples of the sulfur-containing compound having a mercapto group include compounds represented by the following formula (e1).

Chemical formula

[0343] R e1 and R e2 When they are alkyl groups, the alkyl group may be linear or branched, and is preferably linear. R e1 and R e2 When they are alkyl groups, the number of carbon atoms of the alkyl group is not particularly limited as long as it does not inhibit the object of the present invention. The number of carbon atoms of the alkyl group is preferably 1 or more and 4 or less, particularly preferably 1 or 2, and most preferably 1. R e1 and R e2 As a combination of R

[0344] R e3 When it is an alkylene group, the alkylene group may be linear or branched, and is preferably linear. R e3 When it is an alkylene group, the number of carbon atoms of the alkylene group is not particularly limited as long as it does not inhibit the object 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.

[0345] R e4 is a divalent or more and tetravalent or less aliphatic group which may contain atoms other than carbon. R e4 Examples of the atoms other than carbon which R e4 may contain include a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The structure of the aliphatic group which is R

[0346] Among the compounds represented by formula (e1), the compounds represented by the following formula (e2) are more preferred. [Chemical formula] (In formula (e2), R e4 and u are the same as in formula (e1).)

[0347] Among the compounds represented by the above formula (e2), the following compounds are preferred. [Chemical formula]

[0348] The compounds represented by the following formulas (e3-L1) to (e3-L7) can also be mentioned as preferred examples of the sulfur-containing compounds having a mercapto group. [Chemical formula] (In formulas (e3-L1) to (e3-L7), R', s", A", and r are the same as in formulas (b-L1) to (b-L7) described above for the acrylic resin (B3).)

[0349] Preferable specific examples of the mercapto compounds represented by the above formulas (e3-L1) to (e3-L7) include the following compounds. [Chemical formula]

[0350] The compounds represented by the following formulas (e3-1) to (e3-4) can also be mentioned as preferred examples of the sulfur-containing compounds having a mercapto group. [Chemical formula] (Regarding the definitions of the abbreviations in formulas (e3-1) to (e3-4), they are the same as those described above for formulas (3-1) to (3-4) with respect to the acrylic resin (B3).)

[0351] Preferable specific examples of the mercapto compounds represented by the above formulas (e3-1) to (e3-4) include the following compounds.

[0352]

Chemical formula

[0353] In addition, preferable examples of the compound having a mercapto group include the compound represented by the following formula (e4).

Chemical formula

[0354] R e5 When R is an alkyl group which may have a hydroxyl group having 1 to 4 carbon atoms, specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Among these alkyl groups, a methyl group, a hydroxymethyl group, and an ethyl group are preferable.

[0355] R e5 When R is an alkoxy group having 1 to 4 carbon atoms, specific examples include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, and a tert-butyloxy group. Among these alkoxy groups, a methoxy group and an ethoxy group are preferable, and a methoxy group is more preferable.

[0356] R e5 When R is an alkylthio group having 1 to 4 carbon atoms, specific examples include methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, sec-butylthio group, and tert-butylthio group. Among these alkylthio groups, methylthio group and ethylthio group are preferred, and methylthio group is more preferred.

[0357] R e5 When R is a hydroxyalkyl group having 1 to 4 carbon atoms, specific examples include hydroxymethyl group, 2-hydroxyethyl group, 1-hydroxyethyl group, 3-hydroxy-n-propyl group, and 4-hydroxy-n-butyl group. Among these hydroxyalkyl groups, hydroxymethyl group, 2-hydroxyethyl group, and 1-hydroxyethyl group are preferred, and hydroxymethyl group is more preferred.

[0358] R e5 When R is a mercaptoalkyl group having 1 to 4 carbon atoms, specific examples include mercaptomethyl group, 2-mercaptoethyl group, 1-mercaptoethyl group, 3-mercapto-n-propyl group, and 4-mercapto-n-butyl group. Among these mercaptoalkyl groups, mercaptomethyl group, 2-mercaptoethyl group, and 1-mercaptoethyl group are preferred, and mercaptomethyl group is more preferred.

[0359] R e5 When R is a halogenated alkyl group having 1 to 4 carbon atoms, examples of the halogen atom contained in the halogenated alkyl group include fluorine, chlorine, bromine, iodine, etc. R e5When it is a halogenated alkyl group having 1 to 4 carbon atoms, specific examples include chloromethyl group, bromomethyl group, iodomethyl group, fluoromethyl group, dichloromethyl group, dibromomethyl group, difluoromethyl group, trichloromethyl group, tribromomethyl group, trifluoromethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-fluoroethyl group, 1,2-dichloroethyl group, 2,2-difluoroethyl group, 1-chloro-2-fluoroethyl group, 3-chloro-n-propyl group, 3-bromo-n-propyl group, 3-fluoro-n-propyl group, and 4-chloro-n-butyl group and the like. Among these halogenated alkyl groups, chloromethyl group, bromomethyl group, iodomethyl group, fluoromethyl group, dichloromethyl group, dibromomethyl group, difluoromethyl group, trichloromethyl group, tribromomethyl group, and trifluoromethyl group are preferable, and chloromethyl group, dichloromethyl group, trichloromethyl group, and trifluoromethyl group are more preferable.

[0360] R e5 Specific examples when is a halogen atom include fluorine, chlorine, bromine, or iodine.

[0361] In formula (e4), n1 is an integer of 0 or more and 3 or less, and 1 is more preferable. When n1 is 2 or 3, a plurality of R e5 may be the same or different.

[0362] In the compound represented by 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 -(CH2) n0 -SH.

[0363] As the compound represented by formula (e4), as R e5 , a compound having at least one group selected from the group consisting of an alkyl group, a hydroxyalkyl group, and a mercaptoalkyl group is preferable, and R e5More preferably, the compound has one group selected from the group consisting of an alkyl group, a hydroxyalkyl group, and a mercaptoalkyl group. The compound represented by the formula (e4), R e5 When having one group selected from the group consisting of an alkyl group, a hydroxyalkyl group, and a mercaptoalkyl group, the substitution position of the alkyl group, the hydroxyalkyl group, or the mercaptoalkyl group on the benzene ring is -(CH2) n0 -SH is preferably in the meta or para position relative to the bonding position, more preferably in the para position.

[0364] In the formula (e4), n0 is an integer of 0 or more and 3 or less. Since the compound is easy to prepare and obtain, n0 is preferably 0 or 1, more preferably 0.

[0365] Specific examples of the compound represented by formula (e4) include p-mercaptophenol, p-thiocresol, m-thiocresol, 4-(methylthio)benzenethiol, 4-methoxybenzenethiol, 3-methoxybenzenethiol, 4-ethoxybenzenethiol, 4-isopropyloxybenzenethiol, 4-tert-butoxybenzenethiol, 3,4-dimethoxybenzenethiol, 3,4,5-trimethoxybenzenethiol, 4-ethylbenzenethiol, 4-isopropylbenzenethiol, 4-n-butylbenzenethiol, 4-tert-butylbenzenethiol, 3-ethylbenzenethiol, 3-isopropylbenzenethiol, 3-n-butylbenzenethiol, 3-tert-butylbenzenethiol, 3,5-dimethylbenzenethiol, 3,4-dimethylbenzenethiol, 3-tert-butyl-4-methylbenzenethiol, 3-tert-4-methylbenzenethiol, 3-tert-butyl-5-methylbenzenethiol, 4-tert-butyl-3-methylbenzenethiol, 4-mercaptobenzyl alcohol, 3-mercaptobenzyl alcohol, 4-(mercaptomethyl)phenol, 3-(mercaptomethyl)phenol, 1,4-di(mercaptomethyl)phenol, 1,3-di(mercaptomethyl)phenol, 4-fluorobenzenethiol, 3-fluorobenzenethiol, 4-chlorobenzenethiol, 3-chlorobenzenethiol, 4-bromobenzenethiol, 4-iodobenzenethiol, 3-bromobenzenethiol, 3,4-dichlorobenzenethiol, 3,5-dichlorobenzenethiol, 3,4-difluorobenzenethiol, 3,5-difluorobenzenethiol, 4-mercaptocatechol, 2,6-di-tert-butyl-4-mercaptophenol, 3,5-di-tert-butyl-4-methoxybenzenethiol, 4-bromo-3-methylbenzenethiol, 4-(trifluoromethyl)benzenethiol, 3-(trifluoromethyl)benzenethiol, 3,5-bis(trifluoromethyl)benzenethiol, 4-methylthiobenzenethiol, 4-ethylthiobenzenethiol, 4-n-butylthiobenzenethiol, and 4-tert-butylthiobenzenethiol, etc.

[0366] Examples of the sulfur-containing compound having a mercapto group include a compound containing a nitrogen-containing aromatic heterocyclic ring substituted with a mercapto group, and a tautomer of a compound containing a nitrogen-containing aromatic heterocyclic ring substituted with a mercapto group. Preferable specific examples of the nitrogen-containing aromatic heterocyclic ring include imidazole, pyrazole, 1,2,3-triazole, 1,2,4-triazole, oxazole, thiazole, pyridine, pyrimidine, pyridazine, pyrazine, 1,2,3-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.

[0367] Preferable specific examples of the nitrogen-containing heterocyclic compound suitable as the sulfur-containing compound and the tautomer of the nitrogen-containing heterocyclic compound include the following compounds. [Chemical formula]

[0368] When the photosensitive resin composition contains the sulfur-containing compound (E), its usage amount is preferably 0.01 to 5 parts by mass, more preferably 0.02 to 3 parts by mass, and particularly preferably 0.05 to 2 parts by mass with respect to 100 parts by mass of the total mass of the above resin (B) and the alkali-soluble resin (D).

[0369] [Acid diffusion control agent (F)] The photosensitive resin composition may contain an acid diffusion control agent (F). Examples of the acid diffusion control agent (F) include a nitrogen-containing compound (F1), and if necessary, an organic carboxylic acid, or an oxo acid of phosphorus or its derivative (F2) can be further contained.

[0370] [Nitrogen-containing compound (F1)] Examples of the nitrogen-containing compound (F1) include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tri-n-pentylamine, tribenzylamine, diethanolamine, triethanolamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, ethylenediamine, N,N,N’,N’-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4’-diaminodiphenylmethane, 4,4’-diaminodiphenylether, 4,4’-diaminobenzophenone, 4,4’-diaminodiphenylamine, formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3,-tetramethylurea, 1,3-diphenylurea, imidazole, benzimidazole, 4-methylimidazole, 8-hydroxyquinoline, acridine, purine, pyrrolidine, piperidine, 2,4,6-tri(2-pyridyl)-S-triazine, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo[2.2.2]octane, pyridine, etc. These may be used alone or in combination of two or more.

[0371] In addition, commercially available hindered amine compounds such as AdekaStab LA-52, AdekaStab LA-57, AdekaStab LA-63P, AdekaStab LA-68, AdekaStab LA-72, AdekaStab LA-77Y, AdekaStab LA-77G, AdekaStab LA-81, AdekaStab LA-82, and AdekaStab LA-87 (all manufactured by ADEKA), 4-hydroxy-1,2,2,6,6-pentamethylpiperidine derivatives, etc., and pyridines in which the 2,6-positions are substituted with substituents such as hydrocarbon groups, such as 2,6-diphenylpyridine and 2,6-di-tert-butylpyridine, can also be used as the nitrogen-containing compound (F1).

[0372] The nitrogen-containing compound (F1) is usually used in the range of 0 parts by mass or more and 5 parts by mass or less, and particularly preferably in the range of 0 parts by mass or more and 3 parts by mass or less, based on 100 parts by mass of the total mass of the resin (B) and the following alkali-soluble resin (D).

[0373] [Organic carboxylic acid, or oxo acid of phosphorus or its derivative (F2)] Among the organic carboxylic acid, or oxo acid of phosphorus or its derivative (F2), as the organic carboxylic acid, specifically, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, etc. are suitable, and salicylic acid is particularly preferable.

[0374] Examples of the oxo acid of phosphorus or its derivative include derivatives such as phosphoric acid and its esters like phosphoric acid, dibutyl phosphate, diphenyl phosphate; derivatives such as phosphonic acid and its esters like phosphonic acid, dimethyl phosphonate, di-n-butyl phosphonate, phenylphosphonic acid, diphenyl phosphonate, dibenzyl phosphonate; derivatives such as phosphinic acid and its esters like phosphinic acid, phenylphosphinic acid; etc. Among these, phosphonic acid is particularly preferable. These may be used alone or in combination of two or more.

[0375] The organic carboxylic acid, or oxo acid of phosphorus or its derivative (F2) is usually used in the range of 0 parts by mass or more and 5 parts by mass or less, and particularly preferably in the range of 0 parts by mass or more and 3 parts by mass or less, based on 100 parts by mass of the total mass of the resin (B) and the following alkali-soluble resin (D).

[0376] In addition, in order to form a salt and stabilize it, the organic carboxylic acid, or oxo acid of phosphorus or its derivative (F2) is preferably used in an amount equivalent to that of the above nitrogen-containing compound (F1).

[0377] <Organic solvent (S)> The photosensitive resin composition contains an organic solvent (S). The organic solvent (S) includes an organic solvent (S1) having a boiling point of 210°C or higher under atmospheric pressure or no boiling point under atmospheric pressure, and an organic solvent (S2) having a boiling point of less than 210°C under atmospheric pressure. When the photosensitive resin composition contains the above organic solvent (S1) and the above organic solvent (S2) in combination as the organic solvent (S), the roughness on the sidewalls of the patterned resist film formed using the photosensitive resin composition is suppressed.

[0378] From the ease of removal from the coating film, the boiling point of the organic solvent (S1) under atmospheric pressure is preferably 220°C or higher and 320°C or lower, more preferably 240°C or higher and 300°C or lower. From the viewpoint of achieving both the difficulty of volatilization and the ease of removal from the coating film, the boiling point of the organic solvent (S2) under atmospheric pressure is preferably 50°C or higher and 200°C or lower, more preferably 80°C or higher and 180°C or lower.

[0379] Specific examples of the organic solvent (S) include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butylene glycol, and hexylene glycol; polyols such as glycerin; polyacetates of polyols such as glycerin triacetate (triacetin); monohydric alcohols such as benzyl alcohol and terpineol; monoacetates of glycols such as ethylene glycol monoacetate, diethylene glycol monoacetate, triethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, tripropylene glycol monoacetate, and 1,3-butylene glycol monoacetate; diacetates of glycols such as ethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, tripropylene glycol diacetate, and 1,Diacetates of glycols such as 3-butylene glycol diacetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monophenyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monophenyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monophenyl ether, 1,3-butylene glycol monomethyl ether, 1,3-butylene glycol monoethyl ether, 1,3-butylene glycol monopropyl ether, 1,3-butylene glycol monobutyl ether, and 1,Monoethers of glycols such as 3-butylene glycol monophenyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monophenyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monopropyl ether acetate, triethylene glycol monobutyl ether acetate, triethylene glycol monophenyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monophenyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate, dipropylene glycol monophenyl ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monopropyl ether acetate, tripropylene glycol monobutyl ether acetate, tripropylene glycol monophenyl ether acetate, 1,3-butylene glycol monomethyl ether acetate (3-methoxybutyl acetate), 1,3-butylene glycol monoethyl ether acetate, 1,3-butylene glycol monopropyl ether acetate, 1,3-butylene glycol monobutyl ether acetate, 1,Monoether acetates of glycols such as 3-butylene glycol monophenyl ether acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, and 4-methyl-4-methoxypentyl acetate; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, ethylene glycol diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, diethylene glycol diphenyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dipropyl ether, triethylene glycol dibutyl ether, triethylene glycol diphenyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, propylene glycol diphenyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol dibutyl ether, dipropylene glycol diphenyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dipropyl ether, tripropylene glycol dibutyl ether, tripropylene glycol diphenyl ether, 1,3-butylene glycol dimethyl ether, 1,3-butylene glycol diethyl ether, 1,3-butylene glycol dipropyl ether, 1,3-butylene glycol dibutyl ether, and 1,Diesters of glycols such as 3-butylene glycol diphenyl ether; Ethers such as dioxane and dihexyl ether; Esters such as ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, benzyl acetate, ethyl benzoate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, diethyl maleate, cyclohexanol acetate, gamma-butyrolactone; Aromatic hydrocarbons such as toluene and xylene; etc. can be mentioned. These may be used alone or in combination of two or more.,

[0380] Among the above preferred examples of the organic solvent (S), as the organic solvent (S1) having a boiling point of 210 ° C or higher under atmospheric pressure, diethylene glycol, dipropylene glycol, glycerin, triacetin, terpineol, 1,3-butylene glycol diacetate, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, tripropylene glycol monomethyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monophenyl ether acetate, dipropylene glycol monomethyl ether acetate, dihexyl ether, benzyl acetate, ethyl benzoate, and diethyl maleate are preferred.

[0381] Also, as the organic solvent (S1) having no boiling point under atmospheric pressure, an ionic liquid is preferred. Ionic liquids can be used without particular limitation, especially those used in the field of organic synthesis and as electrolytes for batteries. Ionic liquids are typically salts that can melt in a temperature range of 140°C or lower, and are preferably stable salts that become liquid at 140°C or lower.

[0382] The melting point of the ionic liquid is preferably 120°C or lower, more preferably 100°C or lower, and even more preferably 80°C or lower.

[0383] The ionic liquid preferably consists of an organic cation and an anion. The ionic liquid preferably consists of a nitrogen-containing organic cation, a phosphorus-containing organic cation, or a sulfur-containing organic cation and a counter anion, and more preferably consists of a nitrogen-containing organic cation or a phosphorus-containing organic cation and a counter anion.

[0384] The organic cation constituting the ionic liquid is preferably at least one selected from the group consisting of an alkyl chain quaternary ammonium cation, a piperidinium cation, a pyrimidinium cation, a pyrrolidinium cation, an imidazolium cation, a pyridinium cation, a pyrazolium cation, a guanidinium cation, a morpholinium cation, a phosphonium cation, and a sulfonium cation, more preferably an alkyl chain quaternary ammonium cation, a piperidinium cation, a pyrrolidinium cation, an imidazolium cation, a morpholinium cation, or a phosphonium cation, and even more preferably a pyrrolidinium cation, an imidazolium cation, or a phosphonium cation in terms of the effects of the present invention.

[0385] Specific examples of the above-mentioned alkyl chain quaternary ammonium cations include quaternary ammonium cations represented by the following formula (s1). Specifically, for example, tetramethylammonium cation, ethyltrimethylammonium cation, diethyldimethylammonium cation, triethylmethylammonium cation, tetraethylammonium cation, octyltrimethylammonium cation, hexyltrimethylammonium cation, methyltrioctylammonium cation, etc. can be mentioned. Specific examples of the above-mentioned piperidinium cations include piperidinium cations represented by the following formula (s2). Specifically, for example, 1-propylpiperidinium cation, 1-pentylpiperidinium cation, 1,1-dimethylpiperidinium cation, 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1-methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidinium cation, 1-ethyl-1-propylpiperidinium cation, 1-ethyl-1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, 1,1-dipropylpiperidinium cation, 1-propyl-1-butylpiperidinium cation, 1,1-dibutylpiperidinium cation, etc. can be mentioned. Specific examples of the pyrimidinium cation include, for example, 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,3-dimethyl-1,4-dihydropyrimidinium cation, 1,3-dimethyl-1,6-dihydropyrimidinium cation, 1,2,3-trimethyl-1,4-dihydropyrimidinium cation, 1,2,3-trimethyl-1,6-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1,4-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1,6-dihydropyrimidinium cation, and the like.

[0386] Specific examples of the pyrrolidinium cation include the pyrrolidinium cation represented by the following formula (s3). More specifically, for example, 1,1-dimethylpyrrolidinium cation, 1-ethyl-1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexylpyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1-ethyl-1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium cation, 1-ethyl-1-heptylpyrrolidinium cation, 1,1-dipropylpyrrolidinium cation, 1-propyl-1-butylpyrrolidinium cation, 1,1-dibutylpyrrolidinium cation, and the like. Specific examples of the imidazolium cation include the imidazolium cation represented by the following formula (s5). More specifically, for example, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-propyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3-methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation, 1-butyl-2,3-dimethylimidazolium cation, 1-hexyl-2,3-dimethylimidazolium cation, and the like can be mentioned. Specific examples of the pyridinium cation include the pyridinium cation represented by the following formula (s6). More specifically, for example, 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-3,4-dimethylpyridinium cation, and the like can be mentioned.

[0387] Specific examples of the phosphonium cation include the phosphonium cation represented by the following formula (s4). Specifically, tetraalkylphosphonium cations such as tetrabutylphosphonium cation, tributylmethylphosphonium cation, tributylhexylphosphonium cation, and triethyl(methoxymethyl)phosphonium cation and the like can be mentioned. Specific examples of the sulfonium cation include triethylsulfonium cation, dimethylethylsulfonium cation, triethylsulfonium cation, ethylmethylpropylsulfonium cation, butyldimethylsulfonium cation, 1-methyltetrahydrothiophenium ion, 1-ethyltetrahydrothiophenium cation, 1-propyltetrahydrothiophenium cation, 1-butyltetrahydrothiophenium cation, or 1-methyl-[1,4]-thioxonium cation, etc. Among them, as the sulfonium cation, a sulfonium cation having a cyclic structure such as a 5-membered ring or 6-membered ring of a tetrahydrothiophenium type or hexahydrothiopyrylium type is preferable, and it may have a heteroatom such as an oxygen atom in the cyclic structure.

[0388]

Chemical formula

[0389] In formulas (s1) to (s4), R S1 ~R S4 are each independently an alkyl group having 1 to 20 carbon atoms, or an alkoxyalkyl group represented by R S7 -O-(CH2) Sn -(wherein R S7 represents a methyl group or an ethyl group, and Sn represents an integer of 1 or more and 4 or less). In formula (s5), R S1 ~R S4 are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxyalkyl group represented by R S7 -O-(CH2) Sn -(wherein R S7 represents a methyl group or an ethyl group, and Sn represents an integer of 1 or more and 4 or less), or a hydrogen atom. In formula (s6), R S1 ~R S6 are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxyalkyl group represented by R S7 -O-(CH2) Sn -(wherein R S7represents a methyl group or an ethyl group, and Sn represents an integer of 1 or more and 4 or less), and is a hydrogen atom.

[0390] As the anion constituting the ionic liquid, it may be an organic anion or an inorganic anion, and an organic anion is preferred. As the organic anion, it is preferably at least one selected from the group consisting of carboxylic acid anions, N-acyl amino acid ions, acidic amino acid anions, neutral amino acid anions, alkyl sulfate anions, fluorine-containing compound anions, and phenolic anions, and more preferably a carboxylic acid anion or an N-acyl amino acid ion.

[0391] Specific examples of the above carboxylic acid anions include acetate ion, decanoate ion, 2-pyrrolidone-5-carboxylate ion, formate ion, α-lipoic acid ion, lactate ion, tartrate ion, hippurate ion, N-methylhippurate ion, etc. Among them, acetate ion, 2-pyrrolidone-5-carboxylate ion, formate ion, lactate ion, tartrate ion, hippurate ion, N-methylhippurate ion are preferred, and acetate ion, N-methylhippurate ion, formate ion are more preferred. Specific examples of the above N-acyl amino acid ions include N-benzoylalanine ion, N-acetylphenylalanine ion, aspartate ion, glycine ion, N-acetylglycine ion, etc. Among them, N-benzoylalanine ion, N-acetylphenylalanine ion, N-acetylglycine ion are preferred, and N-acetylglycine ion is more preferred.

[0392] Specific examples of the above acidic amino acid anions include aspartate ion, glutamate ion, etc., and specific examples of the above neutral amino acid anions include glycine ion, alanine ion, phenylalanine ion, etc. Specific examples of the above alkyl sulfate anions include methanesulfonate ions and the like. Specific examples of the above fluorine-containing compound anions include trifluoromethanesulfonate ions, hexafluorophosphonate ions, trifluorotris(pentafluoroethyl)phosphonate ions, bis(fluoroalkylsulfonyl)imide ions (for example, bis(trifluoromethanesulfonyl)imide ions), trifluoroacetate ions, tetrafluoroborate ions, and the like. Specific examples of the above phenolic anions include phenol ions, 2-methoxyphenol ions, 2,6-di-tert-butylphenol ions, and the like.

[0393] As the above inorganic anion, F - , Cl - , Br - , I - , BF4 - , PF6 - and N(SO2F)2 - It is preferably at least one selected from the group consisting of, more preferably BF4 - , PF6 - or N(SO2F)2 - , and even more preferably BF4 - or PF6 - .

[0394] The ionic liquid can be produced, for example, by the method disclosed in paragraph 0045 of International Publication No. 2014 / 178254. The ionic liquid may be used alone or in combination of two or more.

[0395] As the organic solvent (S2) having a boiling point of less than 210°C under atmospheric pressure, it is preferable to select an organic solvent having a boiling point of less than 210°C under atmospheric pressure from among the various solvents exemplified as the organic solvent (S).

[0396] In the photosensitive resin composition, the content of the organic solvent (S1) is preferably 0.1 part by mass or more and 20 parts by mass or less, more preferably 0.2 part by mass or more and 18 parts by mass or less, and still more preferably 0.5 part by mass or more and 15 parts by mass, based on 100 parts by mass of the resin (B).

[0397] The content of the organic solvent (S) is not particularly limited as long as it does not inhibit the object of the present invention. When the photosensitive resin composition is used in a thick film application such that the film thickness of the photosensitive layer obtained by the spin coating method or the like is 5 μm or more, it is preferable to use the organic solvent (S) within the range where the solid content concentration of the photosensitive resin composition is 20% by mass or more and 70% by mass or less.

[0398] <Other components> The photosensitive resin composition may further contain a polyvinyl resin in order to improve plasticity. Specific examples of the polyvinyl resin include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinyl benzoic acid, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl phenol, and copolymers thereof. The polyvinyl resin is preferably polyvinyl methyl ether from the viewpoint of its low glass transition point.

[0399] Further, the photosensitive resin composition may further contain an adhesion aid in order to improve the adhesion between the patterned resist film such as a mold formed using the photosensitive resin composition and the substrate.

[0400] Further, the photosensitive resin composition may further contain a surfactant in order to improve coatability, defoaming property, leveling property, etc. As the surfactant, for example, a fluorine-based surfactant or a silicone-based surfactant is preferably used. Specific examples of the fluorosurfactant include commercially available fluorosurfactants such as BM-1000, BM-1100 (both manufactured by BM Chemie), Megafac F142D, Megafac F172, Megafac F173, Megafac F183 (all manufactured by Dainippon Ink and Chemicals, Inc.), Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431 (all manufactured by Sumitomo 3M Limited), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145 (all manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (all manufactured by Toray Silicone Co., Ltd.), etc., but are not limited thereto. As the silicone surfactant, an unmodified silicone surfactant, a polyether-modified silicone surfactant, a polyester-modified silicone surfactant, an alkyl-modified silicone surfactant, an aralkyl-modified silicone surfactant, a reactive silicone surfactant, etc. can be preferably used. As the silicone surfactant, a commercially available silicone surfactant can be used. Specific examples of the commercially available silicone surfactant include Painted M (manufactured by Toray Dow Corning Co., Ltd.), Topica K1000, Topica K2000, Topica K5000 (all manufactured by Takachiho Sangyo Co., Ltd.), XL-121 (a polyether-modified silicone surfactant, manufactured by Clariant), BYK-310 (a polyester-modified silicone surfactant, manufactured by BYK-Chemie), etc.

[0401] In addition, the photosensitive resin composition may further contain an acid or an acid anhydride in order to finely adjust the solubility in the developer.

[0402] Specific examples of the acid and acid anhydride include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid, cinnamic acid; hydroxy monocarboxylic acids such as 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; polycarboxylic acids such as 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; acid anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymic anhydride, 1,2,3,4-butanetetracarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol bisanhydromellitate, glycerin trisanhydromellitate; and the like.

[0403] In addition, the photosensitive resin composition may further contain a sensitizer in order to improve the sensitivity. In addition, the photosensitive resin composition may further contain a dye or a pigment.

[0404] <Method for preparing a chemically amplified positive photosensitive resin composition> The chemically amplified positive photosensitive resin composition is prepared by mixing and stirring the above components in a conventional manner. Examples of the apparatus that can be used for mixing and stirring the above components include a dissolver, a homogenizer, a three-roll mill, etc. After uniformly mixing the above components, the obtained mixture may be further filtered using a mesh, a membrane filter, etc. In a chemically amplified positive photosensitive resin composition, since the decomposition of the nonionic acid generator that generates sulfonic acid is suppressed, the function of the nonionic acid generator that generates sulfonic acid is less likely to deteriorate even after a long time has passed since the preparation of the chemically amplified positive photosensitive resin composition.

[0405] ≪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 resin composition.

[0406] The base film preferably has light transmissivity. Specifically, examples include polyethylene terephthalate (PET) film, polypropylene (PP) film, polyethylene (PE) film, etc. Among them, polyethylene terephthalate (PET) film is preferred in terms of excellent balance between light transmissivity and breaking strength.

[0407] The photosensitive dry film is manufactured by applying the above-mentioned photosensitive resin composition on the base film to form a photosensitive layer. When forming the photosensitive layer on the base film, an applicator, a bar coater, a wire bar coater, a roll coater, a curtain flow coater, etc. are used to apply the photosensitive resin composition on the base film 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, and then dried.

[0408] The photosensitive dry film may further have a protective film on the photosensitive layer. Examples of this protective film include polyethylene terephthalate (PET) film, polypropylene (PP) film, polyethylene (PE) film, etc.

[0409] ≪Method for manufacturing a patterned resist film, method for manufacturing a substrate with a mold, and method for manufacturing a substrate with a mask for plasma etching≫ A method for forming a patterned resist film on a substrate using the photosensitive resin composition described above is not particularly limited. Such a patterned resist film is suitably used as a mold for forming an electroformed article, an etching mask when processing the substrate by etching, and the like. As a preferred method, a laminating step of laminating a photosensitive layer made of the photosensitive resin composition on the substrate; an exposure step of selectively irradiating and exposing the photosensitive layer with actinic rays or radiation; a developing step of developing the exposed photosensitive layer; and a method for manufacturing a patterned resist film including the above steps can be mentioned. A method for manufacturing a substrate with a mold having a mold for forming an electroformed article includes a step of laminating a photosensitive layer on the metal surface of a substrate having a metal surface, and in the developing step, in addition to producing a mold for forming an electroformed article by development, it is the same as the method for manufacturing a patterned resist film.

[0410] The substrate on which the photosensitive layer is laminated is not particularly limited, and conventionally known substrates can be used. For example, substrates for electronic components, those having a predetermined wiring pattern formed thereon, and the like can be exemplified. As the substrate, a silicon substrate, a glass substrate, or the like can also be used. When manufacturing a substrate with a mold having a mold for forming an electroformed article, a substrate having a metal surface is used as the substrate. As the metal species constituting the metal surface, copper, gold, and aluminum are preferable, and copper is more preferable.

[0411] The photosensitive layer is laminated on a substrate as follows, for example. That is, a liquid photosensitive resin composition is applied onto the substrate, and the solvent is removed by heating to form a photosensitive layer with a desired film thickness. The thickness of the photosensitive layer is not particularly limited as long as a patterned resist film serving as a mold can be formed with a desired film thickness. Although the film thickness of the photosensitive layer is not particularly limited, it is preferably 0.5 μm or more, more preferably 0.5 μm or more and 300 μm or less, particularly preferably 1 μm or more and 150 μm or less, and most preferably 3 μm or more and 100 μm or less.

[0412] As a method for applying the photosensitive resin composition onto the substrate, methods such as a spin coating method, a slit coating method, a roll coating method, a screen printing method, an applicator method, etc. can be adopted. It is preferable to perform pre-baking on the photosensitive layer. The pre-baking conditions vary depending on the types of each component in the photosensitive resin composition, the blending ratio, the coating film thickness, etc., but are usually 70°C or higher and 200°C or lower, preferably 80°C or higher and 150°C or lower, and about 2 minutes or more and 120 minutes or less.

[0413] The photosensitive layer formed as described above is selectively irradiated (exposed) with actinic rays or radiation, for example, ultraviolet rays or visible light having a wavelength of 300 nm or more and 500 nm or less, such as g-line (wavelength 436 nm), h-line (wavelength 405 nm), and i-line (wavelength 365 nm) through a mask with a predetermined pattern.

[0414] As a radiation source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon gas laser, etc. can be used. Also, radiation includes microwaves, infrared rays, visible light, ultraviolet rays, X-rays, γ-rays, electron beams, proton beams, neutron beams, ion beams, etc. The radiation dose also varies depending on the composition of the photosensitive resin composition, the film thickness of the photosensitive layer, etc. For example, it is 100 J / m 2 or more and 10000 J / m 2 or less. Also, radiation includes light rays that activate the acid generator (A) to generate an acid.

[0415] After exposure, the photosensitive layer is heated by a known method to promote the diffusion of the acid, and in the exposed portion of the photosensitive layer, the alkali solubility of the photosensitive layer is changed.

[0416] Next, the exposed photosensitive layer is developed according to a conventionally known method, and unnecessary portions are dissolved and removed to form a predetermined patterned resist film, a mold for forming an electroformed article, or a mask for plasma etching. At this time, an alkaline aqueous solution is used as the developer.

[0417] As the developer, for example, aqueous solutions of alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (tetramethylammonium hydroxide), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene, 1,5-diazabicyclo[4,3,0]-5-nonane can be used. Also, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the above aqueous solution of alkalis can be used as the developer.

[0418] The development time varies depending on the composition of the photosensitive resin composition, the film thickness of the photosensitive layer, etc., but is usually between 1 minute and 30 minutes. The development method may be any of a puddle method, a dipping method, a paddle method, a spray development method, etc.

[0419] After development, perform running water washing for 30 seconds or more and 90 seconds or less, and dry using an air gun, an oven, or the like. In this way, a resist film patterned into a desired shape is formed on the surface of the substrate. Also, in this way, a substrate with a patterned resist film serving as a mold is provided on the metal surface of a substrate having a metal surface, and a substrate provided with a patterned resist film as a mask for plasma etching on the etching surface of the substrate can be manufactured.

[0420] The film thickness (patterned resist film) of the patterned resist film formed using the photosensitive resin composition is not particularly limited, and it can be applied to both thick films and thin films. The photosensitive resin composition is preferably used for forming a thick-film patterned resist film. Specifically, the film thickness of the patterned resist film formed using the photosensitive resin composition is preferably 0.5 μm or more, more preferably 0.5 μm or more and 300 μm or less, still more preferably 0.5 μm or more and 200 μm or less, and particularly preferably 0.5 μm or more and 150 μm or less. The upper limit value of the film thickness may be, for example, 100 μm or less. The lower limit value of the film thickness may be, for example, 1 μm or more, or may be 3 μm or more.

[0421] ≪Method for manufacturing electroformed article≫ By embedding a conductor such as a metal by plating in the non-resist portion (the portion removed by the developer) in the mold of the substrate with a mold formed by the above method, for example, connection terminals such as bumps and metal posts, and electroformed articles such as Cu rewiring can be formed. Note that the plating treatment method is not particularly limited, and various conventionally known methods can be adopted. As the plating solution, solder plating, copper plating, gold plating, and nickel plating solutions are particularly preferably used. The remaining mold is finally removed using a stripping solution or the like according to a conventional method.

[0422] When manufacturing an electroformed article, it may be preferable to perform an ashing treatment on the metal surface exposed in the non-patterned portion of the patterned resist film serving as a mold for forming the electroformed article. Specifically, for example, when a plating formed object is formed using, as a mold, a pattern formed using a photosensitive resin composition containing a sulfur-containing compound (E), the adhesion of the plating formed object to the metal surface may be easily impaired. This problem is prominent when using the sulfur-containing compound (E) represented by the aforementioned formula (e1) or the sulfur-containing compound (E) represented by formula (e4). However, when the above-mentioned ashing treatment is performed, even when using, as a mold, a pattern formed using a photosensitive resin composition containing a sulfur-containing compound (E), it is easy to form a plating formed object that adheres well to the metal surface. When a compound containing a nitrogen-containing aromatic heterocyclic ring substituted with a mercapto group is used as the sulfur-containing compound (E), the above-mentioned problem regarding the adhesion of the plating formed object is hardly present or is mild. Therefore, when a compound containing a nitrogen-containing aromatic heterocyclic ring substituted with a mercapto group is used as the sulfur-containing compound (E), it is easy to form a plating formed object with good adhesion to the metal surface without performing the ashing treatment.

[0423] The ashing treatment is not particularly limited as long as it does not damage the patterned resist film serving as a mold for forming the plating formed object to such an extent that the plating formed object with the desired shape cannot be formed. A preferred ashing treatment method is a method using oxygen plasma. To perform ashing on the metal surface on the substrate using oxygen plasma, oxygen plasma may be generated using a known oxygen plasma generator and irradiated onto the metal surface on the substrate.

[0424] In the gas used for generating oxygen plasma, various gases conventionally used for plasma treatment together with oxygen can be mixed as long as the object of the present invention is not inhibited. Examples of such gases include nitrogen gas, hydrogen gas, and CF4 gas. The ashing conditions using oxygen plasma are not particularly limited as long as they do not inhibit the object of the present invention. However, the processing time is, for example, in the range of 10 seconds or more and 20 minutes or less, preferably in the range of 20 seconds or more and 18 minutes or less, and more preferably in the range of 30 seconds or more and 15 minutes or less. By setting the processing time by oxygen plasma within the above range, the effect of improving the adhesion of the electroformed product can be easily achieved without causing a change in the shape of the patterned resist film.

[0425] ≪Method for etching substrate≫ By performing plasma etching on the substrate with a mask for plasma etching manufactured by the manufacturing method of the substrate with a mask for plasma etching manufactured as described above, the substrate is etched. As described above, the patterned resist film as a mask for plasma etching is formed on the etching surface. Examples of the material of the etching surface include titanium, titanium nitride, aluminum, molybdenum, tantalum, tungsten, silicon, silicon dioxide, and silicon nitride. Examples of the plasma as an etchant include plasmas such as CF4, Cl2, CCl4, SiCl4, BCl3, SF6, NF3, and CCl2F2. The conditions for plasma etching are appropriately set within the range of the conditions of conventional loop plasma etching in consideration of the material of the etching surface, the type of plasma as an etchant, the depth of the recess formed by etching, and the like.

[0426] As described above, the present inventors provide the following (1) to (14). (1) An acid generator (A) that generates an acid by irradiation with actinic rays or radiation, a resin (B) whose solubility in alkali increases by the action of an acid, and an organic solvent (S), The organic solvent (S) includes an organic solvent (S1) having a boiling point of 210 °C or higher under atmospheric pressure or an organic solvent having no boiling point under atmospheric pressure, and an organic solvent (S2) having a boiling point of less than 210 °C under atmospheric pressure, a chemically amplified positive photosensitive composition. (2) The chemically amplified positive photosensitive composition according to (1), wherein the content of the organic solvent (S1) is 0.1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the resin (B). (3) The chemically amplified positive photosensitive composition according to (1) or (2), wherein the boiling point of the organic solvent (S1) under atmospheric pressure is 240°C or higher and 300°C or lower. (4) The chemically amplified positive photosensitive composition according to any one of (1) to (3), wherein the boiling point of the organic solvent (S2) under atmospheric pressure is 80°C or higher and 180°C or lower. (5) The chemically amplified positive photosensitive composition according to any one of (1) to (4), wherein the resin (B) is a novolak resin (B1) in which at least a part of phenolic hydroxyl groups are protected by acid-dissociable dissolution inhibiting groups, or a polyhydroxystyrene resin (B2) in which at least a part of phenolic hydroxyl groups are protected by acid-dissociable dissolution inhibiting groups. (6) The chemically amplified positive photosensitive composition according to (5), wherein the resin (B) is a polyhydroxystyrene resin (B2) in which at least a part of phenolic hydroxyl groups are protected by acid-dissociable dissolution inhibiting groups. (7) The chemically amplified positive photosensitive composition according to (5) or (6), wherein the acid-dissociable dissolution inhibiting group is an acetal-type protecting group. (8) The chemically amplified positive photosensitive composition according to any one of (1) to (7), which is used for forming a mold for forming a plating molded article or a mask for plasma etching. (9) A photosensitive dry film having 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 photosensitive composition according to any one of (1) to (8). (10) A lamination step of laminating a photosensitive layer composed of the chemically amplified positive photosensitive composition according to any one of (1) to (8) on a substrate; An exposure step of selectively irradiating the photosensitive layer with actinic rays or radiation; And a developing step of developing the photosensitive layer after exposure, which is a method for manufacturing a patterned resist film. (11) A lamination step of laminating a photosensitive layer made of the chemically amplified positive photosensitive composition according to any one of (1) to (8) on a substrate, An exposure step of selectively irradiating the photosensitive layer with actinic rays or radiation, A development step of developing the exposed photosensitive layer to create a mold for forming a plated molded article, The manufacturing method of the substrate with a mold including this. (12) A method for manufacturing a plated molded article, including a step of plating the mold-attached substrate manufactured by the method for manufacturing a mold-attached substrate according to (11) to form a plated molded article in the mold. (13) A lamination step of laminating a photosensitive layer made of the chemically amplified positive photosensitive composition according to any one of (1) to (8) on a substrate, An exposure step of selectively irradiating the photosensitive layer with actinic rays or radiation, A development step of developing the exposed photosensitive layer to create a mask for plasma etching, The manufacturing method of the substrate with a mask for plasma etching including this. (14) A method for etching a substrate, which performs plasma etching on the substrate with a mask for plasma etching manufactured by the method for manufacturing a substrate with a mask for plasma etching according to (13).

Example

[0427] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0428] In the examples and comparative examples, the following PAG1 to PAG3 were used as the acid generator (A).

Chemical formula

[0429] In the examples and comparative examples, the following Resins B1 to B5 were used as the resin (Resin (B)) whose solubility in alkali increases due to the action of an acid. The numbers in the lower right of the parentheses in each structural unit in the following structural formulas represent the content (mol%) of the structural unit in the resin. The weight average molecular weight Mw of Resin B1 is 20,000. The weight average molecular weight Mw of Resin B2 is 5,500. The weight average molecular weight of Resin B3 is 40,000. Resin B4 is a resin obtained by adding 4 mol% of 1,4-cyclohexanedimethanol divinyl ether to a novolak resin having a weight average molecular weight Mw of 10,000 and a m-cresol / p-cresol ratio of 40 / 60 with respect to the amount of hydroxyl groups in the novolak resin. Resin B5 is a resin obtained by adding 15 mol% of ethyl vinyl ether to a novolak resin having a weight average molecular weight Mw of 7,000 and a m-cresol / p-cresol ratio of 60 / 40 with respect to the amount of hydroxyl groups in the novolak resin.

[0430]

Chemical formula

[0431] In the examples and comparative examples, the following C1 was used as the radical generator (C). The value of the absorption attenuation amount of the following C1 determined by the aforementioned method is 0.14.

Chemical formula

[0432] In the examples and comparative examples, the following Sa to Sc were used as the organic solvent (S1), and the following S’a and and S’b were used as the organic solvent (S’1) for addition that does not correspond to the organic solvent (S1). Sa: Triacetin (boiling point at atmospheric pressure: 259 °C) Sb: Glycerin (boiling point at atmospheric pressure: 290 °C) Sc: Ionic liquid (a salt composed of a tributylmethylphosphonium cation and a bis(trifluoromethanesulfonyl)imide ion, boiling point at atmospheric pressure: none) S’a: Gamma-butyrolactone (boiling point at atmospheric pressure: 204 °C) S’b: 3-Methoxybutyl acetate (boiling point at atmospheric pressure: 146 °C)

[0433] In the examples and comparative examples, the following F1 to F4 were used as the acid diffusion controller (F). F1: Trioctylamine F2: Tripentylamine F3: Salicylic acid F4: 2,6-Diphenylpyridine

[0434] 〔Example 1, Example 2, Comparative Example 1, and Comparative Example 2〕 100 parts by mass of resin B1 as resin (B), 3 parts by mass of the organic solvent (S1) or organic solvent (S’1) of the type described in Table 1, 0.3 parts by mass of PAG1 as the photoacid generator (A), and 1 part by mass of PAG3, and the acid diffusion controller (F) of the type and amount described in Table 1, and 0.08 parts by mass of the surfactant (BYK310, manufactured by BYK Chemie) were dissolved in propylene glycol monomethyl ether acetate as the organic solvent (S2) so that the solid content concentration was 33% by mass to obtain the photosensitive resin compositions of Example 1, Example 2, Comparative Example 1, and Comparative Example 2. In Comparative Example 1, neither the organic solvent (S1) nor the organic solvent (S’1) was used.

[0435] 〔Examples 3 to 8, and Comparative Examples 3 to 5〕 100 parts by mass of resin B2 as resin (B), 3 parts by mass of the organic solvent (S1) or organic solvent (S’1) of the type described in Table 1, 1.2 parts by mass of PAG1 as the photoacid generator (A), and the acid diffusion controller (F) of the type and amount described in Table 1, and 0.08 parts by mass of the surfactant (BYK310, manufactured by BYK Chemie) were dissolved in propylene glycol monomethyl ether acetate as the organic solvent (S2) so that the solid content concentration was 33% by mass to obtain the photosensitive resin compositions of Examples 3 to 8, and Comparative Examples 3 to 5. In Comparative Example 3, neither the organic solvent (S1) nor the organic solvent (S’1) was used.

[0436] 〔Example 9 and Comparative Example 6〕 100 parts by mass of Resin B3 as Resin (B), 3 parts by mass of the organic solvent (S1) or organic solvent (S'1) of the type described in Table 1, 0.5 parts by mass of PAG2 as photoacid generator (A), the acid diffusion control agent (F) of the type and amount described in Table 1, and 0.08 parts by mass of surfactant (BYK310, manufactured by BYK Chemie) were dissolved in propylene glycol monomethyl ether acetate as organic solvent (S2) so that the solid content concentration was 33% by mass, to obtain the photosensitive resin compositions of Example 9 and Comparative Example 6. In Comparative Example 6, neither the organic solvent (S1) nor the organic solvent (S'1) was used.

[0437] 〔Example 10, Example 11, Comparative Example 7, and Comparative Example 8〕 100 parts by mass of Resin B4 or Resin B5 as Resin (B), the organic solvent (S1) of the type described in Table 1, 1.8 parts by mass of PAG1 as photoacid generator (A), the acid diffusion control agent (F) of the type and amount described in Table 1, and 0.08 parts by mass of surfactant (BYK310, manufactured by BYK Chemie) were dissolved in propylene glycol monomethyl ether acetate as organic solvent (S2) so that the solid content concentration was 33% by mass, to obtain Example 10, Example 11, Comparative Example 7, and Comparative Example 8. In Comparative Example 7 and Comparative Example 8, neither the organic solvent (S1) nor the organic solvent (S'1) was used.

[0438] Using the photosensitive resin compositions obtained in each example and each comparative example, the sidewall roughness was evaluated by the following method. <Sidewall Roughness Evaluation> On the Ti thin film of a silicon substrate on which a 100 nm Ti thin film was sputtered, the photosensitive resin compositions of each example and each comparative example were applied. The photosensitive resin composition applied on the substrate was dried to obtain a coating film with a thickness of 3 μm. Next, the coating film was exposed with an i-line exposure machine through a photomask. The exposed coating film was heated on a hot plate at 100 °C for 90 seconds. After heating, paddle development was performed twice for 50 seconds on the exposed coating film using an aqueous solution of tetramethylammonium hydroxide with a concentration of 2.38% by mass as a developer. In this way, a resist film patterned in a line-and-space pattern with both the line width and the space width being 1.1 μm was obtained. Roughness appears on the sidewalls of the line portions of the obtained resist pattern due to the standing wave effect. This roughness was evaluated by the following method. Specifically, at an arbitrary location in the line-and-space pattern, the variation in the space width (CD) in the thickness direction of the line portion (perpendicular to the main surface of the substrate) was evaluated. First, the space width (CD) was measured by cross-sectional SEM at an arbitrary 20 heights within the range of 0.2 μm to 1.0 μm from the substrate. Based on the maximum value CDmax and the minimum value CDmin of the measured values of the space width at 20 points, the value of the sidewall roughness was calculated by the following formula. Sidewall roughness (nm) = (CDmax - CDmin) / 2 Based on the calculated value of the sidewall roughness, the degree of roughness on the pattern sidewall was determined according to the following criteria. In the case of A evaluation and B evaluation, the roughness of the sidewall is sufficiently small. A: The value of the sidewall roughness is 20 nm or less. B: The value of the sidewall roughness is more than 20 nm and 25 nm or less. C: The value of the sidewall roughness is more than 25 nm and 35 nm or less. D: The value of the sidewall roughness is more than 35 nm.

[0439] [Table 1]

[0440] According to the comparison between Example 1 and Example 2 with Comparative Example 1 and Comparative Example 2, the comparison between Examples 3 to 8 and Comparative Examples 3 to 5, the comparison between Example 9 and Comparative Example 6, the comparison between Example 10 and Comparative Example 7, and the comparison between Example 11 and Comparative Example 8, in the chemically amplified positive photosensitive composition containing the photoacid generator (A), the aforementioned resin (B), and the organic solvent (S), by using an organic solvent (S1) having a boiling point of 210°C or higher under atmospheric pressure as the organic solvent (S), it can be seen that the roughness of the side wall in the patterned resist film is suppressed.

Claims

1. A chemically amplified positive photosensitive composition comprising an acid generator (A) that generates an acid upon irradiation with actinic rays or radiation, a resin (B) whose solubility in an alkali increases by the action of an acid, and an organic solvent (S), wherein the organic solvent (S) includes an organic solvent (S1) having a boiling point of 210 °C or higher under atmospheric pressure or having no boiling point under atmospheric pressure, and an organic solvent (S2) having a boiling point of less than 210 °C under atmospheric pressure.

2. The chemically amplified positive photosensitive composition according to claim 1, wherein the content of the organic solvent (S1) is 0.1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the resin (B).

3. The chemically amplified positive photosensitive composition according to claim 1, wherein the boiling point of the organic solvent (S1) under atmospheric pressure is 240 °C or higher and 300 °C or lower.

4. The chemically amplified positive photosensitive composition according to claim 1, wherein the boiling point of the organic solvent (S2) under atmospheric pressure is 80 °C or higher and 180 °C or lower.

5. The chemically amplified positive photosensitive composition according to claim 1, wherein the resin (B) is a novolak resin (B1) in which at least some phenolic hydroxyl groups are protected with acid dissociable dissolution inhibiting groups, or a polyhydroxystyrene resin (B2) in which at least some phenolic hydroxyl groups are protected with acid dissociable dissolution inhibiting groups.

6. The chemically amplified positive photosensitive composition according to claim 5, wherein the resin (B) is a polyhydroxystyrene resin (B2) in which at least some phenolic hydroxyl groups are protected with acid dissociable dissolution inhibiting groups.

7. The chemically amplified positive photosensitive composition according to claim 5, wherein the acid dissociable dissolution inhibiting group is an acetal type protecting group.

8. The chemically amplified positive photosensitive composition according to claim 1, which is used for forming a mold for forming a plated object or forming a mask for plasma etching.

9. A photosensitive dry film having 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 photosensitive composition according to any one of claims 1 to 8.

10. A lamination step of laminating a photosensitive layer composed of the chemically amplified positive photosensitive composition according to any one of claims 1 to 8 on a substrate, An exposure step of selectively irradiating the photosensitive layer with actinic rays or radiation, A developing step of developing the exposed photosensitive layer, and a method for producing a patterned resist film.

11. A lamination step of laminating a photosensitive layer made of the chemically amplified positive photosensitive composition according to any one of claims 1 to 8 on a substrate; An exposure step of selectively irradiating the photosensitive layer with actinic rays or radiation; A development step of developing the photosensitive layer after exposure to create a mold for forming a plating molded article, the method for manufacturing a substrate with a mold.

12. A method for manufacturing a plating molded article, including a step of plating the substrate with a mold manufactured by the method for manufacturing a substrate with a mold according to claim 11 to form a plating molded article in the mold.

13. A lamination step of laminating a photosensitive layer made of the chemically amplified positive photosensitive composition according to any one of claims 1 to 8 on a substrate; An exposure step of selectively irradiating the photosensitive layer with actinic rays or radiation; A development step of developing the photosensitive layer after exposure to create a mask for plasma etching, the method for manufacturing a substrate with a mask for plasma etching.

14. A method for etching a substrate, comprising performing plasma etching on the substrate with a mask for plasma etching manufactured by the method for manufacturing a substrate with a mask for plasma etching according to claim 13.

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