Photosensitive resin composition, dry film, photosensitive dry film, resist film, substrate with mold, and method for producing plated molded article

Abstract

Provided are: a chemically amplified positive photosensitive resin composition which is used for exposure using an h-line and has excellent plating solution resistance and crack resistance; a photosensitive dry film provided with a photosensitive resin layer comprising a chemically amplified positive photosensitive resin composition; and a photosensitive dry film, a patterned resist film using the chemically amplified positive photosensitive resin composition, a tape mold substrate using the chemically amplified positive photosensitive resin composition, and a method for producing a plated molded article using the tape mold substrate. A chemically amplified positive photosensitive resin composition for use in the production of a mold for forming a plated molded article on a substrate having a metal surface, the chemically amplified positive photosensitive resin composition containing an acid generator (A) containing an acid generator having a specific naphthalimide skeleton, and a resin (B) having an increased solubility to an alkali due to the action of an acid, the acid generator (A) containing an acid generator having a specific naphthalimide skeleton, and the resin (B) containing an acid generator having a specific naphthalimide skeleton. The ratio of the acrylic resin to the total of the resin (B) and the resin other than the resin (B) is 70% by mass or more.

Description

[0001] This invention application is a divisional application filed based on the Chinese invention application that entered the Chinese national phase of an international application with PCT application number PCT / JP2019 / 051011 and a subject titled “Photosensitive resin composition and dry film, photosensitive dry film, resist film, substrate with mold and method for manufacturing plated molded object”. The application number of the Chinese invention application is 201980084592.0 and the application date is December 25, 2019. Technical Field

[0002] The present invention relates to a chemically amplified positive photosensitive resin composition, a photosensitive dry film having a photosensitive resin layer composed of the chemically amplified positive photosensitive resin composition, a method for producing the photosensitive dry film, a method for producing a patterned resist film using the chemically amplified positive photosensitive resin composition, a method for producing a molded substrate using the chemically amplified positive photosensitive resin composition, and a method for producing a plated molded object using the molded substrate. Background Art

[0003] At present, photofabrication has become the mainstream of precision microfabrication technology. Photofabrication refers to the general term for the technology of coating a photoresist composition on the surface of the workpiece to form a photoresist layer, patterning the photoresist layer using photolithography technology, and using the patterned photoresist layer (photoresist pattern) as a mask to perform chemical etching, electrolytic etching, or electroforming with electroplating as the main body, etc., to manufacture various precision parts such as semiconductor packaging.

[0004] In addition, in recent years, with the miniaturization of electronic devices, high-density mounting technology for semiconductor packaging has been continuously promoted, and multi-pin thin film mounting based on packaging, miniaturization of package size, and improvement of mounting density of 2D mounting technology and 3D mounting technology of flip chip method are being sought. In such high-density mounting technology, for example, protruding electrodes (mounting terminals) such as bumps protruding from the package or metal pillars connected to the mounting terminals by redistribution wiring (RDL) extending from the peripheral terminals on the wafer are arranged on the substrate with high precision as connection terminals.

[0005] In the above-mentioned photoelectric processing, a photoresist composition is used. As such a photoresist composition, a chemically amplified photoresist composition containing an acid generator is known. A chemically amplified photoresist composition is a composition in which an acid is generated from an acid generator by irradiation with radiation (exposure), and diffusion of the acid is promoted by heat treatment, thereby causing an acid-catalyzed reaction with respect to a matrix resin in the composition, etc., and changing its alkali solubility.

[0006] Such chemically amplified positive photoresist compositions are often used to prepare etching masks when processing substrates by etching (Patent Documents 1 and 2). Specifically, a photoresist layer of a desired film thickness is formed on a substrate using a chemically amplified photoresist composition, and then only a portion of the photoresist layer corresponding to the etching target site is exposed through a predetermined mask pattern, and then the exposed photoresist layer is developed to form a photoresist pattern used as an etching mask.

[0007] In addition, chemically amplified positive photoresist compositions are also used, for example, to form molds used in the manufacture of plated structures such as bumps, metal columns, and Cu rewiring. Specifically, a chemically amplified photoresist composition is used to form a photoresist layer of a desired film thickness on a support such as a metal substrate, and exposure and development are performed via a predetermined mask pattern to form a photoresist pattern used as a mold that selectively removes (peels off) the portion that forms the plated structure. Then, after a conductor such as copper is buried in the removed portion (non-resist portion) by plating, the photoresist pattern around it is removed, thereby forming bumps, metal columns, and Cu rewiring.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Publication No. 2018-169543

[0011] Patent Document 2: International Publication No. 2018 / 179641

[0012] Patent Document 3: Japanese Patent Application No. 2017-535595

[0013] Patent Document 4: Japanese Patent Application No. 2018-513113

[0014] Patent Document 5: Japanese Patent Application No. 2018-523640

[0015] Patent Document 6: Japanese Patent Application Publication No. 2018-087970

[0016] Patent Document 7: Japanese Patent Application Publication No. 2015-087759

[0017] Patent Document 8: Japanese Patent Application Publication No. 2017-107211

[0018] Patent Document 9: Japanese Patent Application Publication No. 2018-018087 Summary of the invention

[0019] Technical problem to be solved by the invention

[0020] In panel-level packaging with a larger area than wafer-level packaging, it is considered to use h-line as exposure light, and therefore it is expected that the photoresist composition can be applied to exposure using h-line.

[0021] For example, Patent Documents 3 to 5 disclose chemically amplified negative-type photoresist compositions or positive-type photoresist compositions for g-line, h-line, and i-line exposure.

[0022] However, when the photosensitive resin compositions described in Patent Documents 3 to 5 are used, there is a problem that the resistance to plating solution is poor and the shape of the resist pattern changes due to the plating process.

[0023] Patent Documents 4 to 9 disclose chemically amplified positive photoresist compositions for preparing molds for forming plated structures. However, when the chemically amplified positive photoresist compositions described in these documents are used, when a plating process is performed to embed a conductor such as copper by plating, the shape of the resist pattern often changes due to contact with a plating treatment solution, making it difficult to form plated structures such as bumps, metal pillars, and Cu rewiring having a desired shape.

[0024] Therefore, chemically amplified positive photoresist compositions used to prepare molds for forming plated objects are required to suppress changes in the shape of the resist pattern caused by plating treatment, that is, to have excellent resistance to plating solutions.

[0025] Furthermore, if cracks are formed in the resist pattern as a mold for forming a plated object, it is difficult to form a plated object of a desired shape. Therefore, the chemically amplified positive photoresist composition used to prepare a mold for forming a plated object is also required to suppress the occurrence of cracks, that is, to have excellent crack resistance.

[0026] The present invention has been made in view of the above technical problems, and its purpose is to provide a chemically amplified positive photosensitive resin composition that can be applied to exposure using h-line and easily forms a resist pattern with excellent plating solution resistance and crack resistance, a photosensitive dry film having a photosensitive resin layer composed of the chemically amplified positive photosensitive resin composition, a method for producing the photosensitive dry film, a method for producing a patterned resist film using the chemically amplified positive photosensitive resin composition, a method for producing a molded substrate using the chemically amplified positive photosensitive resin composition, and a method for producing a plated molded object using the molded substrate.

[0027] Solutions for solving the above technical problems

[0028] The present inventors have made intensive studies to achieve the above-mentioned object, and as a result, have found that in a chemically amplified positive photosensitive resin composition comprising an acid generator (A) that generates an acid by irradiation with active light or radiation, and a resin (B) whose solubility in alkali increases due to the action of the acid, at least one selected from a compound represented by the following formula (a1-i) or (a1-ii), a compound represented by the following formula (a2-i) or (a2-ii), and a compound represented by the following formula (a3-i) or (a3-ii) as the acid generator (A), and an acrylic resin containing 70 mol % or more of a structural unit derived from (meth)acrylic acid or a (meth)acrylic acid derivative, i.e., an acrylic structural unit, is blended with the composition, based on the total of the resin (B) and the resin other than the resin (B), thereby solving the above-mentioned technical problems and completing the present invention. Specifically, the present invention provides the following technical solutions.

[0029] The first embodiment of the present invention is a chemically amplified positive photosensitive resin composition for use in preparing a mold for forming a plated object by embedding a metal in a substrate having a metal surface by plating treatment, comprising: an acid generator (A) that generates an acid by irradiation with active light or radiation, and a resin (B) whose solubility in alkali increases due to the action of the acid.

[0030] The acid generator (A) contains at least one compound selected from the following compounds: a compound represented by the following formula (a1-i) or the following formula (a1-ii), a compound represented by the following formula (a2-i) or the following formula (a2-ii), a compound represented by the following formula (a3-i) or the following formula (a3-ii),

[0031] Formula (a1-i) or formula (a1-ii):

[0032]

Chemistry 1

[0033]

[0034] (In formula (a1-i) and (a1-ii), X 1a is an oxygen atom or a sulfur atom,

[0035] R 1a Select from the following groups:

[0036] an aliphatic group having 1 to 18 carbon atoms which may be substituted with one or more halogen atoms;

[0037] Containing -S-, -C(=O)-S-, -OS(=O)2-, -OC(=O)-O-, -C(=O)-NH-, -C(=O)-NR 10a- and -C(=O)-NR 10a R 11a At least one part of which is selected from the group consisting of an aliphatic group having 2 to 18 carbon atoms and which may be substituted with one or more halogen atoms;

[0038] A group represented by the following formula (a11);

[0039]

Chemistry 2

[0040] -R 3a -Ar (a11)

[0041] A group represented by the following formula (a12);

[0042]

Chemistry 3

[0043]

[0044] and a group represented by the following formula (a13),

[0045]

Chemistry 4

[0046]

[0047] In formula (a11), R 3a is a single bond or may contain -O-, -S-, -C(=O)-O-, -C(=O)-S-, -OS(=O)2-, -OC(=O)-O-, -C(=O)-NH-, -OC(=O)-NH-, -C(=O)-NR 10a - and -C(=O)-NR 10a - at least one part of which is an aliphatic group having 1 to 20 carbon atoms selected from the group consisting of

[0048] Ar is an aromatic group which may have one or more substituents selected from the group consisting of a halogen atom, an aliphatic group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a dialkylamino group, an acyloxy group, an acylthio group, an acylamino group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an alkylaryl group, a cyano group, and a nitro group,

[0049] In formula (a12), R 4a and R 5a are each independently an aliphatic group having 1 to 5 carbon atoms,

[0050] Y 1a is an oxygen atom,

[0051] R 6a is an aliphatic group having 1 to 10 carbon atoms,

[0052] R7a It is composed of -O-, -S-, -C(=O)-S-, -OS(=O)2-, -OC(=O)-O-, -C(=O)-NH-, -OC(=O)-NH-, -C(=O)-NR 10a -、-OC(=O)-NR 10a - and -C(=O)-NR 10a R 11a At least one part of the group consisting of is an aliphatic group having 1 to 18 carbon atoms,

[0053] In formula (a13), R 8a It may include -O-, -S-, -C(=O)-S-, -OS(=O)2-, -OC(=O)-O-, -C(=O)-NH-, -OC(=O)-NH-, -C(=O)-NR 10a - and -OC(=O)-NR 10a - at least one part of which is an aliphatic group having 2 to 18 carbon atoms, selected from the group consisting of

[0054] Y 2a is an oxygen atom,

[0055] R 9a The compound is selected from -O-, -S-, -C(=O)-O-, -C(=O)-S-, -OS(=O)2-, -OC(=O)-O-, -C(=O)-NH-, -OC(=O)-NH-, -C(=O)-NR 10a -、-OC(=O)-NR 10a - and -C(=O)-NR 10a R 11a At least one part of the group consisting of is an aliphatic group having 1 to 18 carbon atoms,

[0056] R 10a and R 11a are aliphatic groups having 1 to 10 carbon atoms, in -C(=O)-NR 10a R 11a In, R 10a and R 11a may be the same as or different from each other, and may be bonded to each other to form an alicyclic group.

[0057] R 2a Select from the following groups:

[0058] an aliphatic group having 1 to 18 carbon atoms which may be substituted with one or more halogen atoms;

[0059] Containing -O-, -S-, -C(=O)-O-, -C(=O)-S-, -OS(=O)2-, -OC(=O)-O-, -C(=O)-NH-, -OC(=O)-NH-, -C(=O)-NR 10a -、-OC(=O)-NR 10a - and -C(=O)-NR 10a R 11a At least one part of which is selected from the group consisting of an aliphatic group having 3 to 18 carbon atoms and which may be substituted with one or more halogen atoms;

[0060] an aromatic group having 4 to 18 carbon atoms, which may have one or more substituents selected from the group consisting of a halogen atom, an aliphatic group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a dialkylamino group, an acyloxy group, an acylthio group, an acylamino group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an alkylaryl group, a cyano group, and a nitro group; and

[0061] An alkyl group substituted with an aromatic group having 4 to 18 carbon atoms, which may have one or more substituents selected from the group consisting of a halogen atom, an aliphatic group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a dialkylamino group, an acyloxy group, an acylthio group, an acylamino group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an alkylaryl group, a cyano group, and a nitro group.

[0062] Formula (a2-i) or formula (a2-ii):

[0063]

Chemistry 5

[0064]

[0065] (In formulas (a2-i) to (a2-ii), R 21a for

[0066] Hydrogen atom;

[0067] an aliphatic group having 1 to 18 carbon atoms which may be substituted with one or more halogen atoms; or

[0068] It may include -O-, -S-, -C(=O)-, -C(=O)-O-, -C(=O)-S-, -OC(=O)-O-, -C(=O)-NH-, -OC(=O)-NH-, -C(=O)-NR 10a -、-OC(=O)-NR 10a - and -C(=O)-NR 10a R 11aAt least one part of which is selected from the group consisting of an aliphatic group having 2 to 18 carbon atoms and which may be substituted with one or more halogen atoms,

[0069] R 22a is a group selected from the group consisting of:

[0070] -CH3, -CH2F, -CHF2, -CF3, or an aliphatic group having 2 to 18 carbon atoms which may be substituted with one or more halogen atoms;

[0071] Containing -O-, -S-, -C(=O)-, -C(=O)-O-, -C(=O)-S-, -OC(=O)-O-, -C(=O)-NH-, -OC(=O)-NH-, -C(=O)-NR 10a -、-OC(=O)-NR 10a - and -C(=O)-NR 10a R 11a At least one part of which is selected from the group consisting of an aliphatic group having 2 to 18 carbon atoms and which may be substituted with one or more halogen atoms;

[0072] an aromatic group having 4 to 18 carbon atoms, which may have one or more substituents selected from the group consisting of a halogen atom, an aliphatic group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a dialkylamino group, an acyloxy group, an acylthio group, an acylamino group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an alkylaryl group, a cyano group, and a nitro group; and

[0073] an alkyl group substituted with an aromatic group having 4 to 18 carbon atoms, which may have at least one substituent selected from the group consisting of a halogen atom, an aliphatic group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a dialkylamino group, an acyloxy group, an acylthio group, an acylamino group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an alkylaryl group, a cyano group and a nitro group,

[0074] Among them, in R 22a In the case of -CF3, R 21a is a group selected from the group consisting of:

[0075] Hydrogen atom;

[0076] It may include -O-, -S-, -C(=O)-, -C(=O)-O-, -C(=O)-S-, -OC(=O)-O-, -C(=O)-NH-, -OC(=O)-NH-, -C(=O)-NR 10a -、-OC(=O)-NR 10a- and -C(=O)-NR 10a R 11a At least one part of which is selected from the group consisting of an aliphatic group having 2 to 18 carbon atoms and which may be substituted with one or more halogen atoms;

[0077] -CH2CH(CH3)2, -CH2CH=CHCH3 or -CH2CH2CH=CH2;

[0078] A group represented by the following formula (a21);

[0079]

Chemistry 6

[0080] -CH2-R 23a (a21)

[0081] and a group represented by the following formula (a22),

[0082]

Chemistry 7

[0083]

[0084] R 10a and R 11a are aliphatic groups having 1 to 10 carbon atoms, in -C(=O)-NR 10a R 11a In, R 10a and R 11a may be the same as or different from each other, and may be bonded to each other to form an alicyclic group.

[0085] In formula (a21), R 23a is an aliphatic group having 4 to 18 carbon atoms,

[0086] In formula (a22), R 24a is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, n a is an integer from 1 to 5.)

[0087] Formula (a3-i) or formula (a3-ii):

[0088]

Chemistry 8

[0089]

[0090] (In formulas (a3-i) to (a3-ii), R 31a and R 32a are independently selected from the group consisting of the following groups:

[0091] Hydrogen atom;

[0092] Cyano;

[0093] an aliphatic group having 1 to 18 carbon atoms which may be substituted with one or more halogen atoms;

[0094] It includes -O-, -S-, -C(=O)-, -C(=O)-O-, -C(=O)-S-, -OC(=O)-O-, -CN, -C(=O)-NH-, -C(=O)-NR 10a - and -C(=O)-NR 10a R 11a At least one part of which is selected from the group consisting of an aliphatic group having 1 to 18 carbon atoms and which may be substituted with one or more halogen atoms; and

[0095] an aromatic group having 4 to 18 carbon atoms, which may have one or more substituents selected from the group consisting of a halogen atom, an aliphatic group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a dialkylamino group, an acyloxy group, an acylthio group, an acylamino group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an alkylaryl group, a cyano group, and a nitro group,

[0096] R 31a and R 32a may be the same as or different from each other, and may be bonded to each other to form an alicyclic group or a heterocyclic group.

[0097] R 33a Select from the following groups:

[0098] an aliphatic group having 1 to 18 carbon atoms which may be substituted with one or more halogen atoms;

[0099] Containing -O-, -S-, -C(=O)-, -C(=O)-O-, -C(=O)-S-, -OC(=O)-O-, -CN, -C(=O)-NH-, -OC(=O)-NH-, -C(=O)-NR 10a -、-OC(=O)-NR 10a - and -C(=O)-NR 10a R 11a At least one part of which is selected from the group consisting of an aliphatic group having 1 to 18 carbon atoms and which may be substituted with one or more halogen atoms; and

[0100] an aromatic group having 4 to 18 carbon atoms, which may have one or more substituents selected from the group consisting of a halogen atom, an aliphatic group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a dialkylamino group, an acyloxy group, an acylthio group, an acylamino group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an alkylaryl group, a cyano group, and a nitro group,

[0101] R 10a and R 11a are aliphatic groups having 1 to 10 carbon atoms, in -C(=O)-NR 10a R 11a In, R 10a and R 11a They may be the same or different from each other, and may be bonded to each other to form an alicyclic group.)

[0102] The chemically amplified positive photosensitive resin composition contains an acrylic resin, wherein the acrylic resin is a resin containing 70 mol % or more of a structural unit derived from (meth)acrylic acid or a (meth)acrylic acid derivative, namely, an acrylic structural unit.

[0103] The ratio of the acrylic resin to the total of the resin (B) and the resin other than the resin (B) is 70% by mass or more.

[0104] A second aspect of the present invention is a photosensitive dry film comprising a base film and a photosensitive resin layer formed on a surface of the base film, wherein the photosensitive resin layer is composed of the chemically amplified positive photosensitive resin composition of the first aspect.

[0105] A third aspect of the present invention is a method for producing a photosensitive dry film, comprising coating the chemically amplified positive photosensitive resin composition of the first aspect on a substrate film to form a photosensitive resin layer.

[0106] A fourth aspect of the present invention is a method for producing a patterned resist film, comprising:

[0107] A lamination step of laminating a photosensitive resin layer composed of the chemically amplified positive photosensitive resin composition of the first embodiment on the substrate;

[0108] An exposure step of selectively irradiating the photosensitive resin layer with active light or radiation to perform exposure;

[0109] In the development step, the exposed photosensitive resin layer is developed.

[0110] A fifth aspect of the present invention is a method for manufacturing a substrate with a mold, comprising:

[0111] A lamination step of laminating a photosensitive resin layer composed of the chemically amplified positive photosensitive resin composition of the first embodiment on a substrate having a metal surface;

[0112] An exposure step of selectively irradiating the photosensitive resin layer with active light or radiation to perform exposure;

[0113] In the development step, the exposed photosensitive resin layer is developed to prepare a mold for forming a plated object.

[0114] A sixth aspect of the present invention is a method for producing a plated shaped object, comprising the step of plating the substrate with a mold produced by the method of the fifth aspect to form the plated shaped object in the mold.

[0115] Effects of the Invention

[0116] According to the present invention, there can be provided a chemically amplified positive photosensitive resin composition which is suitable for exposure using h-line and which easily forms a resist pattern having excellent plating solution resistance and crack resistance, a photosensitive dry film having a photosensitive resin layer composed of the chemically amplified positive photosensitive resin composition, a method for producing the photosensitive dry film, a method for producing a patterned resist film using the chemically amplified positive photosensitive resin composition, a method for producing a molded substrate using the chemically amplified positive photosensitive resin composition, and a method for producing a plated molded object using the molded substrate. DETAILED DESCRIPTION

[0117] Chemically amplified positive photosensitive resin composition

[0118] A chemically amplified positive photosensitive resin composition (hereinafter also referred to as a photosensitive resin composition) is used to prepare a mold for forming a plated object by embedding a metal on a substrate having a metal surface by plating. The photosensitive resin composition contains: an acid generator (A) (hereinafter also referred to as an acid generator (A)) that generates an acid by irradiation with active light or radiation; and a resin (B) (hereinafter also referred to as a resin (B)) whose solubility in alkali increases due to the action of the acid. In addition, in the present invention, the acid generator (A) contains at least one selected from a compound represented by the following formula (a1-i) or the following formula (a1-ii), a compound represented by the following formula (a2-i) or the following formula (a2-ii), and a compound represented by the following formula (a3-i) or the following formula (a3-ii). The photosensitive resin composition contains an acrylic resin, which is a resin containing 70 mol% or more of a structural unit derived from (meth)acrylic acid or a (meth)acrylic acid derivative, i.e., an acrylic structural unit. The ratio of the acrylic resin to the total of the resin (B) and the resin other than the resin (B) is 70% by mass or more.

[0119] In a photosensitive resin composition comprising an acid generator (A) that generates an acid by irradiation with active light or radiation and a resin (B) whose solubility in alkali increases due to the action of the acid, by containing a specific acid generator and setting the ratio of the content of the acrylic resin to the total of the resin (B) and the resin other than the resin (B) within a specific range, the photosensitive resin composition can be made suitable for exposure using h-rays as shown in the Examples described below, and a resist pattern excellent in plating solution resistance and crack resistance can be easily formed using the photosensitive resin composition.

[0120] The photosensitive resin composition may contain components such as a phenolic hydroxyl group-containing low molecular weight compound (C), an alkali-soluble resin (D), a sulfur-containing compound (E), an acid diffusion inhibitor (F), and an organic solvent (S), as necessary.

[0121] Hereinafter, essential or optional components contained in the photosensitive resin composition and a method for producing the photosensitive resin composition will be described.

[0122] <Acid Generator (A)>

[0123] The acid generator (A) is a compound that generates an acid by irradiation with active light or radiation, and is a compound that generates an acid directly or indirectly by light. The acid generator (A) includes at least one selected from a compound represented by the following formula (a1-i) or the following formula (a1-ii), a compound represented by the following formula (a2-i) or the following formula (a2-ii), and a compound represented by the following formula (a3-i) or the following formula (a3-ii).

[0124]

Chemistry 9

[0125]

[0126] (In formula (a1-i) and (a1-ii), X 1a is an oxygen atom or a sulfur atom,

[0127] R 1a Selected from the group consisting of: an aliphatic group having 1 to 18 carbon atoms which may be substituted with one or more halogen atoms;

[0128] Containing -S-, -C(=O)-S-, -OS(=O)2-, -OC(=O)-O-, -C(=O)-NH-, -C(=O)-NR 10a - and -C(=O)-NR 10a R 11a At least one part of which is selected from the group consisting of an aliphatic group having 2 to 18 carbon atoms and which may be substituted with one or more halogen atoms;

[0129] A group represented by the following formula (a11);

[0130]

Chemistry 10

[0131] -R 3a -Ar (a11)

[0132] A group represented by the following formula (a12);

[0133]

Chemistry 11

[0134]

[0135] as well as

[0136] A group represented by the following formula (a13),

[0137]

Chemistry 12

[0138]

[0139] In formula (a11), R 3a is a single bond or may contain -O-, -S-, -C(=O)-O-, -C(=O)-S-, -OS(=O)2-, -OC(=O)-O-, -C(=O)-NH-, -OC(=O)-NH-, -C(=O)-NR 10a - and -C(=O)-NR 10a - at least one part of which is an aliphatic group having 1 to 20 carbon atoms selected from the group consisting of

[0140] Ar is an aromatic group which may have one or more substituents selected from the group consisting of a halogen atom, an aliphatic group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a dialkylamino group, an acyloxy group, an acylthio group, an acylamino group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an alkylaryl group, a cyano group, and a nitro group,

[0141] In formula (a12), R 4a and R 5a are each independently an aliphatic group having 1 to 5 carbon atoms,

[0142] Y 1a is an oxygen atom,

[0143] R 6a is an aliphatic group having 1 to 10 carbon atoms,

[0144] R 7a It is composed of -O-, -S-, -C(=O)-S-, -OS(=O)2-, -OC(=O)-O-, -C(=O)-NH-, -OC(=O)-NH-, -C(=O)-NR 10a -、-OC(=O)-NR 10a - and -C(=O)-NR 10a R 11a At least one part of the group consisting of is an aliphatic group having 1 to 18 carbon atoms,

[0145] In formula (a13), R 8aIt may include -O-, -S-, -C(=O)-S-, -OS(=O)2-, -OC(=O)-O-, -C(=O)-NH-, -OC(=O)-NH-, -C(=O)-NR 10a - and -OC(=O)-NR 10a - at least one part of which is an aliphatic group having 2 to 18 carbon atoms, selected from the group consisting of

[0146] Y 2a is an oxygen atom,

[0147] R 9a The compound is selected from -O-, -S-, -C(=O)-O-, -C(=O)-S-, -OS(=O)2-, -OC(=O)-O-, -C(=O)-NH-, -OC(=O)-NH-, -C(=O)-NR 10a -、-OC(=O)-NR 10a - and -C(=O)-NR 10a R 11a At least one part of the group consisting of is an aliphatic group having 1 to 18 carbon atoms,

[0148] R 10a and R 11a are aliphatic groups having 1 to 10 carbon atoms, in -C(=O)-NR 10a R 11a In, R 10a and R 11a may be the same as or different from each other, and may be bonded to each other to form an alicyclic group.

[0149] R 2a Selected from the group consisting of: an aliphatic group having 1 to 18 carbon atoms which may be substituted with one or more halogen atoms;

[0150] Containing -O-, -S-, -C(=O)-O-, -C(=O)-S-, -OS(=O)2-, -OC(=O)-O-, -C(=O)-NH-, -OC(=O)-NH-, -C(=O)-NR 10a -、-OC(=O)-NR 10a - and -C(=O)-NR 10a R 11a At least one part of which is selected from the group consisting of an aliphatic group having 3 to 18 carbon atoms and which may be substituted with one or more halogen atoms;

[0151] an aromatic group having 4 to 18 carbon atoms, which may have one or more substituents selected from the group consisting of a halogen atom, an aliphatic group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a dialkylamino group, an acyloxy group, an acylthio group, an acylamino group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an alkylaryl group, a cyano group, and a nitro group; and

[0152] An alkyl group substituted with an aromatic group having 4 to 18 carbon atoms, which may have one or more substituents selected from the group consisting of a halogen atom, an aliphatic group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a dialkylamino group, an acyloxy group, an acylthio group, an acylamino group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an alkylaryl group, a cyano group, and a nitro group.

[0153]

Chemistry 13

[0154]

[0155] (In formulas (a2-i) to (a2-ii), R 21a is a hydrogen atom;

[0156] an aliphatic group having 1 to 18 carbon atoms which may be substituted with one or more halogen atoms; or

[0157] It may include -O-, -S-, -C(=O)-, -C(=O)-O-, -C(=O)-S-, -OC(=O)-O-, -C(=O)-NH-, -OC(=O)-NH-, -C(=O)-NR 10a -、-OC(=O)-NR 10a - and -C(=O)-NR 10a R 11a At least one part of which is selected from the group consisting of an aliphatic group having 2 to 18 carbon atoms and which may be substituted with one or more halogen atoms,

[0158] R 22a A group selected from the group consisting of -CH3, -CH2F, -CHF2, -CF3, or an aliphatic group having 2 to 18 carbon atoms which may be substituted with one or more halogen atoms;

[0159] Containing -O-, -S-, -C(=O)-, -C(=O)-O-, -C(=O)-S-, -OC(=O)-O-, -C(=O)-NH-, -OC(=O)-NH-, -C(=O)-NR 10a -、-OC(=O)-NR 10a - and -C(=O)-NR 10a R11a At least one part of which is selected from the group consisting of an aliphatic group having 2 to 18 carbon atoms and which may be substituted with one or more halogen atoms;

[0160] an aromatic group having 4 to 18 carbon atoms, which may have one or more substituents selected from the group consisting of a halogen atom, an aliphatic group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a dialkylamino group, an acyloxy group, an acylthio group, an acylamino group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an alkylaryl group, a cyano group, and a nitro group; and

[0161] an alkyl group substituted with an aromatic group having 4 to 18 carbon atoms, which may have at least one substituent selected from the group consisting of a halogen atom, an aliphatic group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a dialkylamino group, an acyloxy group, an acylthio group, an acylamino group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an alkylaryl group, a cyano group and a nitro group,

[0162] Among them, in R 22a In the case of -CF3, R 21a is a group selected from the group consisting of: a hydrogen atom;

[0163] It may include -O-, -S-, -C(=O)-, -C(=O)-O-, -C(=O)-S-, -OC(=O)-O-, -C(=O)-NH-, -OC(=O)-NH-, -C(=O)-NR 10a -、-OC(=O)-NR 10a - and -C(=O)-NR 10a R 11a At least one part of which is selected from the group consisting of an aliphatic group having 2 to 18 carbon atoms and which may be substituted with one or more halogen atoms;

[0164] -CH2CH(CH3)2, -CH2CH=CHCH3 or -CH2CH2CH=CH2;

[0165] A group represented by the following formula (a21);

[0166]

Chemistry 14

[0167] -CH2-R 23a (a21)

[0168] as well as

[0169] A group represented by the following formula (a22),

[0170]

Chemistry 15

[0171]

[0172] R 10a and R 11a are aliphatic groups having 1 to 10 carbon atoms, in -C(=O)-NR 10a R 11a In, R 10a and R 11a may be the same as or different from each other, and may be bonded to each other to form an alicyclic group.

[0173] In formula (a21), R 23a is an aliphatic group having 4 to 18 carbon atoms,

[0174] In formula (a22), R 24a is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, n a is an integer from 1 to 5.)

[0175]

Chemistry 16

[0176]

[0177] (In formulas (a3-i) to (a3-ii), R 31a and R 32a are each independently a group selected from the group consisting of: a hydrogen atom;

[0178] Cyano;

[0179] an aliphatic group having 1 to 18 carbon atoms which may be substituted with one or more halogen atoms;

[0180] It includes -O-, -S-, -C(=O)-, -C(=O)-O-, -C(=O)-S-, -OC(=O)-O-, -CN, -C(=O)-NH-, -C(=O)-NR 10a - and -C(=O)-NR 10a R 11a At least one part of which is selected from the group consisting of an aliphatic group having 1 to 18 carbon atoms and which may be substituted with one or more halogen atoms; and

[0181] an aromatic group having 4 to 18 carbon atoms, which may have one or more substituents selected from the group consisting of a halogen atom, an aliphatic group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a dialkylamino group, an acyloxy group, an acylthio group, an acylamino group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an alkylaryl group, a cyano group, and a nitro group,

[0182] R 31aand R 32a may be the same as or different from each other, and may be bonded to each other to form an alicyclic group or a heterocyclic group.

[0183] R 33a Selected from the group consisting of: an aliphatic group having 1 to 18 carbon atoms which may be substituted with one or more halogen atoms;

[0184] Containing -O-, -S-, -C(=O)-, -C(=O)-O-, -C(=O)-S-, -OC(=O)-O-, -CN, -C(=O)-NH-, -OC(=O)-NH-, -C(=O)-NR 10a -、-OC(=O)-NR 10a - and -C(=O)-NR 10a R 11a At least one part of which is selected from the group consisting of an aliphatic group having 1 to 18 carbon atoms and which may be substituted with one or more halogen atoms; and

[0185] an aromatic group having 4 to 18 carbon atoms, which may have one or more substituents selected from the group consisting of a halogen atom, an aliphatic group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a dialkylamino group, an acyloxy group, an acylthio group, an acylamino group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an alkylaryl group, a cyano group, and a nitro group,

[0186] R 10a and R 11a are aliphatic groups having 1 to 10 carbon atoms, in -C(=O)-NR 10a R 11a In, R 10a and R 11a They may be the same or different from each other, and may be bonded to each other to form an alicyclic group.)

[0187] The aliphatic groups in formula (a1-i), formula (a1-ii), formula (a2-i), formula (a2-ii), formula (a3-i), formula (a3-ii), formulas (a11) to (a13), formula (a21), and formula (a22) may be chain-shaped or cyclic, or may contain a chain structure and a cyclic structure. The aliphatic group may contain a heteroatom, a chain-shaped aliphatic group containing a heteroatom such as a nitrogen atom or a sulfur atom, or a heterocyclic aliphatic group.

[0188] The chain aliphatic group may be straight-chain or branched. As the chain aliphatic group, alkyl, alkenyl, and alkynyl may be exemplified. As the alkyl, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl and other straight-chain alkyl groups may be exemplified, and isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl and 1,1,3,3-tetramethylbutyl and other branched alkyl groups may be exemplified. As the alkenyl, 3-butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl and the like may be exemplified. As the alkynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decenyl and the like may be exemplified. In the alkyl, alkenyl and alkynyl, the hydrogen atoms bonded to these groups may also be substituted by one or more substituents. The substituent may, for example, be a halogen atom, a cyano group, an oxoalkoxy group, a hydroxyl group, an amino group, a nitro group, an aryl group or an alkyl group substituted with a halogen atom.

[0189] Examples of the cyclic aliphatic group include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornenyl, cubicyl, octahydro-indenyl, decahydro-naphthyl, bicyclo[3.2.1]octyl, bicyclo[2.2.2]octyl, bicyclo[3.3.1]nonyl, bicyclo[3.3.2]decyl, bicyclo[2.2.2]octyl, azacycloalkyl, and ((aminocarbonyl)cycloalkyl)cycloalkyl.

[0190] The aromatic group in the above formula may be an aromatic hydrocarbon group or an aromatic heterocyclic group containing a hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom.

[0191] Examples of the aromatic hydrocarbon group include aryl groups such as monocyclic groups (phenyl group, etc.), bicyclic groups (naphthyl group, biphenyl group, etc.), tricyclic groups (fluorenyl group, etc.), and aralkyl groups such as benzyl group, phenethyl group, etc.

[0192] Examples of the aromatic heterocyclic group include heteroaryl groups such as furyl and thienyl.

[0193] These aromatic hydrocarbon groups or aromatic heterocyclic groups may have an alkyl group as a substituent. The alkyl group is the same as described above.

[0194] In the above, as the aliphatic group or the aromatic group, a monovalent group is exemplified, and in the case of a divalent group, it is a group obtained by removing one hydrogen atom from the above monovalent group.

[0195] Examples of the halogen atom in the above formula include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0196] For the alkoxy (alkyl-O-), alkylthio (alkyl-S-), dialkylamino ((alkyl)2N-), acyloxy (alkyl-carbonyl-O-), acylthio (alkyl-carbonyl-S-), acylamino (alkyl-carbonyl-NH-), alkoxycarbonyl, alkylsulfonyl, alkylsulfinyl, aryl, alkyl or aryl of alkylaryl in the above formula, they are the same as those above.

[0197] The haloalkyl in the above formula is an alkyl substituted with one or more halogen atoms up to the maximum number of replaceable ones. The alkyl or halogen atom is the same as those above.

[0198] The haloalkoxy in the above formula is an alkoxy substituted with one or more halogen atoms up to the maximum number of replaceable ones. The alkyl or halogen atom is the same as those above.

[0199] As specific examples of the compound represented by formula (a1-i) or the following formula (a1-ii), the following structures can be cited, for example.

[0200]

Chemical 17

[0201]

[0202]

Chemical 18

[0203]

[0204]

Chemical 19

[0205]

[0206]

Chemical 20

[0207]

[0208] The compound represented by formula (a1-i) or formula (a1-ii) is preferably such that X 1a is a sulfur atom, and R 1a is a linear or branched alkyl having 1 to 3 carbon atoms, and R 2a is a chain aliphatic group having 1 to 18 carbon atoms substituted with one or more fluorine atoms.

[0209] As specific examples of the compound represented by formula (a2-i) or formula (a2-ii), the following structures can be cited, for example.

[0210]

Chemical 21

[0211]

[0212]

Chemical 22

[0213]

[0214]

Chemistry 23

[0215]

[0216]

Chemistry 24

[0217]

[0218]

Chemistry 25

[0219]

[0220] The compound represented by formula (a2-i) or formula (a2-ii) is preferably: 21a is a chain aliphatic group having 1 to 18 carbon atoms, R 22a It is a chain aliphatic group having 1 to 18 carbon atoms and substituted with one or more fluorine atoms.

[0221] Specific examples of the compound represented by formula (a3-i) or formula (a3-ii) include the following structures.

[0222]

Chemistry 26

[0223]

[0224]

Chemistry 27

[0225]

[0226]

Chemistry 28

[0227]

[0228] The compound represented by formula (a3-i) or formula (a3-ii) is preferably: 31a is a hydrogen atom, R 32a is a chain aliphatic group having 1 to 18 carbon atoms, R 33a It is a chain aliphatic group having 1 to 18 carbon atoms and substituted with one or more fluorine atoms.

[0229] The production method of the compound represented by formula (a1-i) or (a1-ii), the compound represented by formula (a2-i) or (a2-ii), and the compound represented by formula (a3-i) or (a3-ii) is not particularly limited, and can be produced, for example, by the production methods described in Patent Documents 3 to 5.

[0230] The acid generator (A) may also contain other acid generators (hereinafter also referred to as other acid generators) other than the compounds represented by the above formula (a1-i) or formula (a1-ii), the compounds represented by formula (a2-i) or formula (a2-ii), and the compounds represented by formula (a3-i) or formula (a3-ii). The other acid generator 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 other acid generator that can be contained in the acid generator (A), the acid generators of the first to fifth embodiments described below are preferred.

[0231] As the first embodiment of the other acid generator in the acid generator (A), a compound represented by the following formula (a101) can be exemplified.

[0232]

Chemical 29

[0233]

[0234] In the above formula (a101), X 101a represents a sulfur atom or an iodine atom having a valence of g, and g is 1 or 2. h represents the number of repeating units of the structure in parentheses. R 101a is an organic group bonded to X 101a and represents an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an alkynyl group having 2 to 30 carbon atoms. R 101a can be substituted with at least one selected from the group consisting of alkyl, hydroxyl, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro groups, and halogen. The number of R 101a is g + h(g - 1) + 1, and R 101a can be the same as or different from each other. In addition, two or more R 101a can be directly bonded to each other or bonded via -O-, -S-, -SO-, -SO2-, -NH-, -NR 102a -, -CO-, -COO-, -CONH-, an alkylene group having 1 to 3 carbon atoms, or a phenylene group to form a ring structure containing X 101a . R 102a is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

[0235] X 102a is a structure represented by the following formula (a102).

[0236]

Chemistry 30

[0237]

[0238] In the above formula (a102), X 104a represents an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a divalent group of a heterocyclic compound having 8 to 20 carbon atoms, and X 104a It may be substituted by at least one selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, a hydroxyl group, a cyano group, a nitro group, and a halogen. 105a Indicates -O-, -S-, -SO-, -SO2-, -NH-, -NR 102a -, -CO-, -COO-, -CONH-, an alkylene group or a phenylene group having 1 to 3 carbon atoms. h represents the number of repeating units of the structure in parentheses. h+1 X 104a and h X 105a They may be the same or different. 102a Same definition as above.

[0239] X 103a- The counter ion of onium may be a fluoroalkyl fluorophosphate anion represented by the following formula (a117) or a borate anion represented by the following formula (a118).

[0240]

Chemistry 31

[0241]

[0242] In the above formula (a117), R 103a represents an alkyl group in which 80% or more of hydrogen atoms are replaced by fluorine atoms. j represents R 103a The number of R is an integer from 1 to 5. 103a They may be the same or different.

[0243]

Chemistry 32

[0244]

[0245] In the above formula (a118), R 104a ~R 107a Each independently represents a fluorine atom or a phenyl group, and a part or all of the hydrogen atoms of the phenyl group may be substituted with at least one selected from the group consisting of a fluorine atom and a trifluoromethyl group.

[0246] Examples of the onium ion in the compound represented by the above formula (a101) include triphenylsulfonium, tri-p-tolylsulfonium, 4-(phenylthio)phenyl diphenylsulfonium, bis[4-(diphenylsulfonio)phenyl] sulfide, bis{4-[bis[4-(2-hydroxyethoxy)phenyl]sulfonio]phenyl} sulfide, bis{4-[bis(4-fluorophenyl)sulfonio]phenyl} sulfide, 4-(4-benzoyl-2-chlorophenylthio)phenyl bis(4-fluorophenyl)sulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yl di-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yl diphenylsulfonium, 2-[(diphenyl)sulfonio]xanthone, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyl di-p-tolylsulfonium, 4-(4-benzoylphenylthio)phenyl diphenylsulfonium, diphenylbenzoylmethylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl (1-ethoxycarbonyl)ethylsulfonium, 4-hydroxyphenylmethylbenzoylmethylsulfonium, phenyl[4-(4-biphenylthio)phenyl] 4-biphenylsulfonium, phenyl[4-(4-biphenylthio)phenyl] 3-biphenylsulfonium, [4-(4-acetylphenylthio)phenyl] diphenylsulfonium, octadecylmethylbenzoylmethylsulfonium, diphenyliodonium, di-p-tolyliodonium, bis(4-dodecylphenyl)iodonium, bis(4-methoxyphenyl)iodonium, (4-octyloxyphenyl)phenyl iodonium, bis(4-decyloxyphenyl)iodonium, 4-(2-hydroxytetradecyloxy)phenylphenyl iodonium, 4-isopropylphenyl (p-tolyl)iodonium, 4-isobutylphenyl (p-tolyl)iodonium, etc.

[0247] Among the onium ions in the compound represented by the above formula (a101), preferred onium ions include sulfonium ions represented by the following formula (a119).

[0248]

Chemical Formula 33

[0249]

[0250] In the above formula (a119), R 108a each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyl group, a halogen atom, an aryl group which may have a substituent, and an arylcarbonyl group. X 102a represents the same meaning as X in the above formula (a101). 102a

[0251] Specific examples of the sulfonium ion represented by the above formula (a119) include 4-(phenylthio)phenyldiphenylsulfonium, 4-(4-benzoyl-2-chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, phenyl[4-(4-biphenylthio)phenyl]4-biphenylsulfonium, phenyl[4-(4-biphenylthio)phenyl]3-biphenylsulfonium, [4-(4-acetylphenylthio)phenyl]diphenylsulfonium, and diphenyl[4-(p-terphenylthio)phenyl]diphenylsulfonium.

[0252] In the fluoroalkyl fluorophosphate anion represented by the above formula (a117), R 103a represents an alkyl group substituted with a fluorine atom, preferably having 1 to 8 carbon atoms, and more preferably having 1 to 4 carbon atoms. Specific examples of the alkyl group include: straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and octyl; branched-chain alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The proportion of hydrogen atoms of the alkyl group substituted with fluorine atoms is usually 80% or more, preferably 90% or more, and more preferably 100%. When the substitution rate of fluorine atoms is less than 80%, the acid strength of the fluoroalkyl fluorophosphate represented by the above formula (a101) is reduced.

[0253] Particularly preferred R 103a It is a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms and a fluorine atom substitution rate of 100%. Specific examples thereof include CF3, CF3CF2, (CF3)2CF, CF3CF2CF2, CF3CF2CF2CF2, (CF3)2CFCF2, CF3CF2(CF3)CF, and (CF3)3C. 103a The number j is an integer of 1 to 5, preferably 2 to 4, and particularly preferably 2 or 3.

[0254] Specific examples of preferred fluoroalkyl fluorophosphate anions include [(CF3CF2)2PF4] - 、[(CF3CF2)3PF3] - 、[((CF3)2CF)2PF4] - 、[((CF3)2CF)3PF3] - 、[(CF3CF2CF2)2PF4] - 、[(CF3CF2CF2)3PF3] - 、[((CF3)2CFCF2)2PF4] - 、[((CF3)2CFCF2)3PF3] - 、[(CF3CF2CF2CF2)2PF4]- or [(CF3CF2CF2)3PF3] - Among them, [(CF3CF2)3PF3] is particularly preferred. - 、[(CF3CF2CF2)3PF3] - 、[((CF3)2CF)3PF3] - 、[((CF3)2CF)2PF4] - 、[((CF3)2CFCF2)3PF3] - or [((CF3)2CFCF2)2PF4] - .

[0255] Preferred specific examples of the borate anion represented by the above formula (a118) include tetrakis(pentafluorophenyl)borate ([B(C6F5)4] - ), tetrakis(trifluoromethyl)phenyl)borate ([B(C6H4CF3)4] - ), difluorobis(pentafluorophenyl)borate ([(C6F5)2BF2] - ), trifluoro(pentafluorophenyl)borate ([(C6F5)BF3] - ), tetrakis(difluorophenyl)borate ([B(C6H3F2)4] - Among them, tetrakis(pentafluorophenyl)borate ([B(C6F5)4] - ).

[0256] As the second embodiment of other acid generators (A), examples include 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(2-furyl)vinyl]s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methyl-2-furyl)vinyl]s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-ethyl-2-furyl)vinyl]s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-propyl-2-furyl)vinyl]s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-dimethoxyphenyl)vinyl]s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-diethoxyphenyl)vinyl]s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-dipropoxyphenyl)vinyl]s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3-methoxy-5-ethoxyphenyl)vinyl]s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3-methoxy-5-propoxyphenyl)vinyl]s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-methylenedioxyphenyl)vinyl]s-triazine, 2,4-bis(trichloromethyl)-6-(3,4-methylenedioxyphenyl)s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyls-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyls-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxystyryl)phenyls-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxystyryl)phenyls-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(2-furyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(5-methyl-2-furyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(3,5-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-methylenedioxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, tris(1,3-dibromopropyl)-1,3,5-triazine, tris(2,3-dibromopropyl)-1,3,5-triazine and other halogen-containing triazine compounds such as tris(2,3-dibromopropyl)isocyanurate and halogen-containing triazine compounds represented by the following formula (a103).

[0257]

Chemical 34

[0258]

[0259] In the above formula (a103), R 109a , R 110a , R 111a Each independently represents a halogenated alkyl group.

[0260] In addition, as a third embodiment of other acid generators in the acid generator (A), α-(p-toluenesulfonyloxyimino)-phenylacetonitrile, α-(benzenesulfonyloxyimino)-2,4-dichlorophenylacetonitrile, α-(benzenesulfonyloxyimino)-2,6-dichlorophenylacetonitrile, α-(2-chlorobenzenesulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile and a compound represented by the following formula (a104) containing an oxime sulfonate group can be mentioned.

[0261]

Chemistry 35

[0262]

[0263] In the above formula (a104), R 112a represents a monovalent, divalent or trivalent organic group, R 113a represents a substituted or unsubstituted saturated hydrocarbon group, an unsaturated hydrocarbon group or an aromatic group, and n represents the number of repeating units of the structure in the brackets.

[0264] In the above formula (a104), the aromatic group may be, for example, an aryl group such as phenyl or naphthyl, or a heteroaryl group such as furyl or thienyl. 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. 113a Particularly preferred are alkyl groups having 1 to 6 carbon atoms, and examples thereof include methyl, ethyl, propyl and butyl. 112a is an aromatic group, R 113a A compound which is an alkyl group having 1 to 4 carbon atoms.

[0265] As the acid generator represented by the above formula (a104), when n=1, R 112a is any one of phenyl, methylphenyl and methoxyphenyl and R 113a The compound with a methyl group specifically includes α-(methylsulfonyloxyimino)-1-phenylacetonitrile, α-(methylsulfonyloxyimino)-1-(p-methylphenyl)acetonitrile, α-(methylsulfonyloxyimino)-1-(p-methoxyphenyl)acetonitrile, [2-(propylsulfonyloxyimino)-2,3-dihydroxythiophen-3-ylidene](o-tolyl)acetonitrile, etc. When n=2, the acid generator represented by the above formula (a104) specifically includes an acid generator represented by the following formula.

[0266] [Chemical 36]

[0267]

[0268] In addition, as a fourth embodiment of other acid generators in the acid generator (A), an onium salt having a naphthalene ring in the cationic part can be exemplified. The "having a naphthalene ring" means having a structure derived from naphthalene, means a structure having at least two rings, and their aromaticity is maintained. The naphthalene ring may have a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or the like as a substituent. Although the structure derived from the naphthalene ring may be a monovalent group (free valence is 1) or a divalent group (free valence is 2) or more, a monovalent group is desirable (however, in this case, the part bonded to the above substituent is removed to count the free valence). The number of naphthalene rings is preferably 1 or more and 3 or less.

[0269] As the cationic part of such an onium salt having a naphthalene ring in the cationic part, a structure represented by the following formula (a105) is preferable.

[0270] [Chemical 37]

[0271]

[0272] In the above formula (a105), R 114a , R 115a , R 116a At least one of them represents a group represented by the following formula (a106), and the rest represent a linear or branched alkyl group having 1 to 6 carbon atoms, a phenyl group which may have a substituent, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Or, one of R 114a , R 115a , R 116a is a group represented by the following formula (a106), and the remaining two are each independently a linear or branched alkylene group having 1 to 6 carbon atoms, and their ends may be bonded to form a ring.

[0273] [Chemical 38]

[0274]

[0275] In the above formula (a106), R 117a , R 118a each independently represents a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a linear or branched alkyl group having 1 to 6 carbon atoms, R 119arepresents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms which may have substituents. l and m each independently represent an integer of 0 to 2, and l + m is 3 or less. However, in the case where there are multiple R 117a s, they may be the same as or different from each other. Further, in the case where there are multiple R 118a s, they may be the same as or different from each other.

[0276] From the viewpoint of the stability of the compound, the number of the groups represented by the above formula (a106) among the above R 114a s, R 115a s, and R 116a s is preferably 1, and the rest are linear or branched alkylene groups having 1 to 6 carbon atoms, and their ends may be bonded to form a ring. In this case, the above two alkylene groups contain a sulfur atom to form a 3- to 9-membered ring. The number of atoms (including sulfur atoms) constituting the ring is preferably 5 or more and 6 or less.

[0277] In addition, examples of the substituents 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.

[0278] In addition, examples of the substituents 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.

[0279] As suitable structures for these cation moieties, structures represented by the following formulae (a107) and (a108) can be exemplified, and a structure represented by the following formula (a108) is particularly preferred.

[0280] [Chemical 39]

[0281]

[0282] As such a cation moiety, it may be an iodonium salt or a sulfonium salt, and from the viewpoints of acid generation efficiency and the like, a sulfonium salt is desired.

[0283] Therefore, as an anion suitable as the anion moiety of the onium salt having a naphthalene ring in the cation moiety, an anion capable of forming a sulfonium salt is desired.

[0284] As the anion moiety of such an acid generator, it is a fluoroalkylsulfonate ion or an arylsulfonate ion in which part or all of the hydrogen atoms are fluorinated.

[0285] The alkyl group in the fluoroalkylsulfonic acid ion may be a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and preferably has 1 to 10 carbon atoms from the perspective of the volume of the generated acid and its diffusion distance. In particular, branched or cyclic alkyl groups are preferred because they have a short diffusion distance. In addition, from the perspective of being inexpensive to synthesize, methyl, ethyl, propyl, butyl, octyl, etc. can be cited as preferred groups.

[0286] The aryl group in the arylsulfonate ion is an aryl group having 6 to 20 carbon atoms, and examples thereof include phenyl and naphthyl groups which may be substituted or unsubstituted with an alkyl group or a halogen atom. In particular, from the viewpoint of being inexpensive to synthesize, an aryl group having 6 to 10 carbon atoms is preferred. Specific examples of preferred aryl groups include phenyl, toluenesulfonyl, ethylphenyl, naphthyl, methylnaphthyl, and the like.

[0287] In the above-mentioned fluoroalkylsulfonate ions or arylsulfonate ions, the fluorination rate when part or all of the hydrogen atoms are fluorinated is preferably 10% to 100%, more preferably 50% to 100%, and in particular, the substance in which all the hydrogen atoms are replaced by fluorine atoms is preferred because the acid strength becomes stronger. As such examples, specifically, trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctanesulfonate, perfluorobenzenesulfonate, etc. can be cited.

[0288] Among them, as the preferred anionic portion, anionic portion represented by the following formula (a109) can be exemplified.

[0289]

Chemistry 40

[0290]

[0291] In the above formula (a109), R 120a It is a group represented by the following formulas (a110), (a111) and (a112).

[0292]

Chemistry 41

[0293]

[0294] In the above formula (a110), x represents an integer of 1 or more and 4 or less. In addition, in the above formula (a111), R 121a represents 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 them, trifluoromethanesulfonate and perfluorobutanesulfonate are preferred from the viewpoint of safety.

[0295] In addition, as the anion portion, the nitrogen-containing anion portion represented by the following formulas (a113) and (a114) can also be used.

[0296]

Chemistry 42

[0297]

[0298] In the above formulas (a113) and (a114), X a represents a linear or branched alkylene group in which at least one hydrogen atom is substituted by a fluorine atom, and the number of carbon atoms of the alkylene group is 2 to 6, preferably 3 to 5, and most preferably 3. a , Z a Each independently represents a linear or branched alkyl group in which at least one hydrogen atom is substituted by a fluorine atom, and the number of carbon atoms in the alkyl group is 1 to 10, preferably 1 to 7, and more preferably 1 to 3.

[0299] X a The number of carbon atoms in the alkylene group or Y a , Z a The smaller the number of carbon atoms of the alkyl group, the better the solubility in the organic solvent, so it is preferred.

[0300] In addition, in X a Alkylene or Y a , Z a The more hydrogen atoms are replaced by fluorine atoms in the alkyl group, the stronger the acid strength is, so it is preferred. The ratio of fluorine atoms in the alkylene or alkyl group, i.e., the fluorination rate, is preferably 70% to 100%, more preferably 90% to 100%, and most preferably a perfluoroalkylene or perfluoroalkyl group in which all hydrogen atoms are replaced by fluorine atoms.

[0301] Such compounds that have naphthalene rings in the cationic portion are preferred compounds represented by the following formulas (a115) and (a116).

[0302]

Chemistry 43

[0303]

[0304] In addition, as a fifth embodiment of the other acid generator in the acid generator (A), there can be mentioned: bis(p-toluenesulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane and other bissulfonyldiazomethane; 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, nitrobenzyl toluenesulfonate, dinitrobenzyl toluenesulfonate; , nitrobenzyl derivatives such as nitrobenzyl sulfonate, nitrobenzyl carbonate, and dinitrobenzyl carbonate; sulfonates such as pyrogallol trimesylate, pyrogallol trimesylate, benzyl toluenesulfonate, benzyl sulfonate, N-methylsulfonyloxysuccinimide, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyloxymaleimide, and N-methylsulfonyloxyphthalimide; sulfonates such as N-(trifluoromethylsulfonyloxy)phthalimide, N- Trifluoromethanesulfonates such as (trifluoromethylsulfonyloxy)-1,8-naphthalene dicarboximide and N-(trifluoromethylsulfonyloxy)-4-butyl-1,8-naphthalene dicarboximide (excluding compounds represented by formula (a1-i) or (a1-ii), compounds represented by formula (a2-i) or (a2-ii), and compounds represented by formula (a3-i) or (a3-ii)); diphenyliodonium hexafluorophosphate , (4-methoxyphenyl)phenyliodonium trifluoromethanesulfonate, bis(p-tert-butylphenyl)iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, (p-tert-butylphenyl)diphenylsulfonium trifluoromethanesulfonate and the like; benzoin toluenesulfonate esters such as benzoin toluenesulfonate and α-methylbenzoin toluenesulfonate; other diphenyliodonium salts, triphenylsulfonium salts, phenyldiazonium salts, benzyl carbonate and the like.

[0305] The total content of the acid generator (A) is preferably 0.01% by mass to 10% by mass, more preferably 0.03% by mass to 8% by mass, and particularly preferably 0.05% by mass to 5% by mass, based on the total solid content of the photosensitive resin composition.

[0306] In addition, the total amount of the compound represented by the above-mentioned formula (a1-i) or formula (a1-ii), the compound represented by formula (a2-i) or formula (a2-ii), and the compound represented by formula (a3-i) or formula (a3-ii) is preferably 0.01 mass % to 10 mass %, more preferably 0.03 mass % to 8 mass %, and particularly preferably 0.05 mass % to 5 mass %, relative to the total solid content of the photosensitive resin composition.

[0307] By making the amount of the acid generator (A) within the above range, a photosensitive resin composition with excellent storage stability is easy to prepare.

[0308] <Resin (B)>

[0309] The resin (B) whose solubility in alkali increases due to the action of an acid is not particularly limited, and any resin whose solubility in alkali increases due to the action of an acid can be used. Examples of the resin (B) whose solubility in alkali increases due to the action of an acid include novolac resin (B1), polyhydroxystyrene resin (B2), and acrylic resin (B3).

[0310] The resin (B) preferably comprises an acrylic resin (B3). The ratio of the acrylic resin contained in the resin (B) to the resin (B), that is, the ratio of the acrylic resin (B3) to the resin (B) is preferably 70 mass% or more.

[0311] [Novolac resin (B1)]

[0312] The novolac resin (B1) is a novolac resin having an acid dissociability dissolution inhibiting group.

[0313] As the novolac resin (B1), a resin containing a structural unit represented by the following formula (b1) can be used.

[0314]

Chemistry 44

[0315]

[0316] In the above formula (b1), R 1b represents an acid dissociative dissolution inhibitory group, R 2b , R 3b Each independently represents a hydrogen atom or an alkyl group having 1 or more carbon atoms or less.

[0317] As the above R 1b The acid dissociative dissolution inhibiting group represented is preferably a group represented by the following formula (b2) or (b3), 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.

[0318]

Chemistry 45

[0319]

[0320] In the above formulas (b2) and (b3), R 4b , R 5b It independently represents a linear or branched alkyl group having a hydrogen atom or carbon atom number of 1 or less, R 6b Represents a linear, branched or cyclic alkyl group having a carbon atom number of 1 or less, R 7bA linear, branched or cyclic alkyl group with a carbon atom number of 1 or less is represented by 6 or less, and o represents 0 or 1.

[0321] Examples of the linear or branched alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl. Examples of the cyclic alkyl group include cyclopentyl and cyclohexyl.

[0322] Here, as the acid dissociative dissolution inhibiting group represented by the above formula (b2), specifically, methoxyethyl, ethoxyethyl, n-propoxyethyl, isopropoxyethyl, n-butoxyethyl, isobutoxyethyl, tert-butoxyethyl, cyclohexyloxyethyl, methoxypropyl, ethoxypropyl, 1-methoxy-1-methyl-ethyl, 1-ethoxy-1-methylethyl, etc. can be mentioned. In addition, as the acid dissociative dissolution inhibiting group represented by the above formula (b3), specifically, tert-butoxycarbonyl, tert-butoxycarbonylmethyl, etc. can be mentioned. In addition, as the above trialkylsilyl group, groups in which the carbon number of each alkyl group such as trimethylsilyl and tri-tert-butyldimethylsilyl is 1 or more and 6 or less can be mentioned.

[0323] [Polyhydroxystyrene resin (B2)]

[0324] The polyhydroxystyrene resin (B2) is a polyhydroxystyrene resin having an acid dissociability dissolution inhibiting group.

[0325] In this specification, "polyhydroxystyrene resin" is not particularly limited as long as it is a resin that is considered to be a polyhydroxystyrene resin by a person skilled in the art in the art in the field of photosensitive resin composition. A typical polyhydroxystyrene resin is a resin in which the total amount of structural units derived from hydroxystyrene or hydroxystyrene derivatives, i.e., hydroxystyrene structural units and structural units derived from styrene is 70 mol% or more, and the total amount of hydroxystyrene structural units is 50 mol% or more. "Hydroxystyrene derivative" refers to a compound in which a hydrogen atom of a hydroxyl group of hydroxystyrene or a hydrogen atom bonded to a carbon atom at the α position of hydroxystyrene is substituted by a hydrocarbon group that may have an oxygen atom.

[0326] As the acid dissociable dissolution inhibiting group, an acid dissociable dissolution inhibiting group that is the same as the acid dissociable dissolution inhibiting group exemplified in the above formulae (b2) and (b3) may be mentioned.

[0327] As the polyhydroxystyrene resin (B2), resin containing structural units represented by the following formula (b4) can be used.

[0328]

Chemistry 46

[0329]

[0330] In the above formula (b4), R 8b Represents a hydrogen atom or an alkyl group having 1 or more carbon atoms or less, R 9b represents an acid-dissociative dissolution-inhibiting group.

[0331] 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 methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl and neopentyl, and examples of the cyclic alkyl group include cyclopentyl and cyclohexyl.

[0332] As mentioned above, R 9b The acid dissociable dissociable inhibiting group represented by the acid dissociable dissociable inhibiting group can be used, which is the same as the acid dissociable dissociable inhibiting group exemplified in formulas (b2) and (b3).

[0333] In addition, for the purpose of appropriately controlling physical and chemical properties, the resin containing the structural unit represented by the above formula (b4) as the polyhydroxystyrene resin (B2) can also contain other polymerizable compounds as structural units. As such polymerizable compounds, known free radical polymerizable compounds and anionic polymerizable compounds can be mentioned. In addition, as such polymerizable compounds, for example, 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 carboxyl group and an ester bond such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid; (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate; (meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; (Meth)acrylate aryl esters such as phenyl (meth)acrylate and benzyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; aromatic compounds containing vinyl groups such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene; aliphatic compounds containing vinyl groups such as vinyl acetate; conjugated dienes such as butadiene and isoprene; polymerizable compounds containing nitrile groups such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; polymerizable compounds containing amide bonds such as acrylamide and methacrylamide, etc.

[0334] When the polyhydroxystyrene resin (B2) contains other polymerizable compounds as structural units other than the structural unit represented by the above formula (b4), the structural unit derived from the other polymerizable compound may have an acid-dissociable dissolution inhibitory group.

[0335] [Acrylic resin (B3)]

[0336] The acrylic resin (B3) is an acrylic resin having an acid dissociability dissolution inhibiting group.

[0337] The acrylic resin (B3) is not particularly limited as long as it is an acrylic resin whose solubility in alkali increases due to the action of an acid and is an acrylic resin conventionally blended in various photosensitive resin compositions.

[0338] In this specification, "acrylic resin" refers to a resin containing 70 mol% or more of a structural unit derived from (meth)acrylic acid or (meth)acrylic acid derivative, i.e. a structural unit.

[0339] In addition, in this specification, "(meth)acrylic acid derivative" refers to (meth)acrylate, (meth)acrylamide, (meth)acrylonitrile, which may be an N-substituted body.

[0340] In addition, in this specification, "(meth)acrylic acid" means both "acrylic acid" and "methacrylic acid". "(meth)acrylate" means both "acrylate" and "methacrylate".

[0341] In the "acrylic resin", the (meth)acrylic resin may also contain structural units of 30 mol% or less from monomers other than (meth)acrylic acid and (meth)acrylic acid derivatives.

[0342] For example, the acrylic resin (B3) preferably contains a structural unit (b-3) derived from an acrylate containing a -SO2- cyclic group or a lactone cyclic group. In this case, when forming a resist pattern, a resist pattern having a preferred cross-sectional shape can be easily formed.

[0343] (Containing -SO2- cyclic group)

[0344] Here, "-SO2-containing cyclic group" means a cyclic group containing a ring containing -SO2- in its ring skeleton, specifically, a cyclic group in which the sulfur atom (S) in -SO2- forms a part of the ring skeleton of the cyclic group. In the ring skeleton, the ring containing -SO2- is counted as the first ring, and when there is only this ring, it is called a monocyclic group, and when there are other ring structures, it is called a polycyclic group regardless of its structure. The -SO2-containing cyclic group can be a monocyclic group or a polycyclic group.

[0345] The -SO2-ring group is particularly preferably a cyclic group containing -O-SO2- in its ring skeleton, that is, a cyclic group containing -OS- in -O-SO2-formed as part of the ring skeleton.

[0346] The number of carbon atoms in the -SO2- containing cyclic group is preferably 3 to 30, more preferably 4 to 20, further preferably 4 to 15, particularly preferably 4 to 12. 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.

[0347] The -SO2-containing cyclic group may be an aliphatic cyclic group containing -SO2- or an aromatic cyclic group containing -SO2-. Preferred is an aliphatic cyclic group containing -SO2-.

[0348] As the aliphatic cyclic group containing -SO2-, there can be exemplified a group obtained by removing at least one hydrogen atom from an aliphatic hydrocarbon ring after a part of the carbon atoms constituting the ring skeleton is replaced by -SO2- or -O-SO2-. More specifically, there can be exemplified a group obtained by removing at least one hydrogen atom from an aliphatic hydrocarbon ring after -CH2- constituting the ring skeleton is replaced by -SO2-, a group obtained by removing at least one hydrogen atom from an aliphatic hydrocarbon ring after -CH2-CH2- constituting the ring is replaced by -O-SO2-, etc.

[0349] The carbon number 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 a polycyclic group or a monocyclic group. As a monocyclic alicyclic hydrocarbon ring, it is preferably a group obtained by removing two hydrogen atoms from a monocyclic alkane having a carbon number of 3 or more and 6 or less. As the monocyclic alkane, cyclopentane, cyclohexane, etc. can be exemplified. As a polycyclic alicyclic hydrocarbon ring, it is preferably a group obtained by removing two hydrogen atoms from a polycyclic alkane having a carbon number of 7 or more and 12 or less, and as the polycyclic alkane, specifically, adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. can be exemplified.

[0350] The -SO2-containing cyclic group may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, an oxygen atom (=O), -COOR", -OC(=O)R", a hydroxyalkyl group, and a cyano group.

[0351] The alkyl group as the substituent is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably linear or branched. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, etc. may be mentioned. Among these, methyl or ethyl is preferred, and methyl is particularly preferred.

[0352] The alkoxy group as the substituent is preferably an alkoxy group having a carbon number of 1 to 6. The alkoxy group is preferably linear or branched. Specifically, a group in which the alkyl group exemplified as the alkyl group as the substituent is bonded to an oxygen atom (-O-) can be mentioned.

[0353] Examples of the halogen atom of the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, and a fluorine atom is preferred.

[0354] As the halogenated alkyl group of the substituent, a group obtained by substituting part or all of the hydrogen atoms of the above-mentioned alkyl group with the above-mentioned halogen atoms can be exemplified.

[0355] The halogenated alkyl group as the substituent may be a group in which a part or all of the hydrogen atoms of the alkyl group exemplified as the above-mentioned alkyl group as the substituent are substituted with the above-mentioned halogen atoms. The halogenated alkyl group is preferably a fluoroalkyl group, and particularly preferably a perfluoroalkyl group.

[0356] R in -COOR" and -OC(=O)R" are both hydrogen atoms or linear, branched or cyclic alkyl groups having 1 or less carbon atoms.

[0357] When R< / or branched alkyl group, the number of carbon atoms of the chain alkyl group is preferably 1 to 10 or less, more preferably 1 to 5 or less, and particularly preferably 1 or 2.

[0358] When R" is a cyclic alkyl group, the number of carbon atoms of the cyclic alkyl group is preferably 3 to 15, more preferably 4 to 12, and particularly preferably 5 to 10. Specifically, examples include groups obtained by removing one or more hydrogen atoms from a monocycloalkane which may be substituted with or unsubstituted by a fluorine atom or a fluoroalkyl group, or from a polycycloalkane such as a bicycloalkane, a tricycloalkane or a tetracycloalkane. More specifically, examples include groups obtained by removing one or more hydrogen atoms from a monocycloalkane such as cyclopentane or cyclohexane, or a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane.

[0359] The hydroxyalkyl group as the substituent is preferably a hydroxyalkyl group having a carbon number of 1 to 6. Specifically, it may be a group in which at least one hydrogen atom of the alkyl group exemplified as the alkyl group as the substituent is substituted with a hydroxy group.

[0360] More specifically, the group represented by the following formula (3-1) to (3-4) can be exemplified as the -SO2-ring group.

[0361]

Chemistry 47

[0362]

[0363] (In the formula, A' is an alkylene group, an oxygen atom or sulfur atom that may contain an oxygen atom or sulfur atom, an oxygen atom or sulfur atom, and z is an integer of 0 or less, and R 10b It is an alkyl group, an alkoxy group, a halogenated alkyl group, a hydroxy group, -COOR", -OC(=O)R", hydroxyalkyl or cyano group, and R" is a hydrogen atom or alkyl group.)

[0364] In the above formulae (3-1) to (3-4), A' is an alkylene group having 1 to 5 carbon atoms, an oxygen atom or a sulfur atom, which may contain an oxygen atom (-O-) or a sulfur atom (-S-). The alkylene group having 1 to 5 carbon atoms in A' is preferably a linear or branched alkylene group, and examples thereof include a methylene group, an ethylene group, a n-propylene group, an isopropylene group and the like.

[0365] When the alkylene group contains an oxygen atom or a sulfur atom, specific examples thereof include groups having -O- or -S- at the end of the alkylene group or between carbon atoms, such as -O-CH2-, -CH2-O-CH2-, -S-CH2-, -CH2-S-CH2-, etc. As A', an alkylene group having 1 to 5 carbon atoms or -O- is preferred, an alkylene group having 1 to 5 carbon atoms is more preferred, and a methylene group is most preferred.

[0366] z may be any one of 0, 1 and 2, most preferably 0. When z is 2, multiple R 10b They may be the same or different.

[0367] As R 10b The alkyl, alkoxy, haloalkyl, -COOR", -OC(=O)R", and hydroxyalkyl in the above-mentioned examples can be the same groups as the alkyl, alkoxy, haloalkyl, -COOR", -OC(=O)R", and hydroxyalkyl groups mentioned as substituents that the -SO2- containing cyclic group may have.

[0368] Hereinafter, a specific ring formula represented by the above formulas (3-1) to (3-4) will be exemplified. In addition, "Ac" in the formula represents an acetyl group.

[0369]

Chemistry 48

[0370]

[0371]

Chemistry 49

[0372]

[0373] As the -SO2- containing cyclic group, it is preferably a group represented by the above formula (3-1), more preferably at least one selected from the group consisting of groups represented by any one of the chemical formulas (3-1-1), (3-1-18), (3-3-1) and (3-4-1), and most preferably a group represented by the chemical formula (3-1-1).

[0374] (Contains lactone ring group)

[0375] "Lactone-containing cyclic group" means a cyclic group containing a ring (lactone ring) containing -OC(=O)- in its ring skeleton. The lactone ring is recorded as the first ring. When there is only a lactone ring, it is called a monocyclic group. When there are other ring structures, it is called a polycyclic group regardless of the structure. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group.

[0376] The lactone-containing cyclic group in the structural unit (b-3) is not particularly limited, and any lactone-containing cyclic group can be used. Specifically, as the lactone-containing monocyclic group, there can be mentioned a group obtained by removing one hydrogen atom from a 4- to 6-membered ring lactone, for example, a group obtained by removing one hydrogen atom from β-propiolactone, a group obtained by removing one hydrogen atom from γ-butyrolactone, a group obtained by removing one hydrogen atom from δ-valerolactone, etc. In addition, as the lactone-containing polycyclic group, there can be mentioned a group obtained by removing one hydrogen atom from a bicycloalkane, a tricycloalkane, or a tetracycloalkane having a lactone ring.

[0377] As the structural unit (b-3), as long as it is a structural unit containing a -SO2-cyclic group or a lactone cyclic group, the structure of the other parts is not particularly limited. It is preferably at least one structural unit selected from the group consisting of a structural unit (b-3-S) derived from an acrylate in which a hydrogen atom bonded to a carbon atom at the α-position may be substituted with a substituent and containing a -SO2-cyclic group, and a structural unit (b-3-L) derived from an acrylate in which a hydrogen atom bonded to a carbon atom at the α-position may be substituted with a substituent and containing a lactone cyclic group.

[0378] [Structural unit (b-3-S)]

[0379] As an example of the structural unit (b-3-S), more specifically, the structural unit represented by the following formula (b-S1) can be exemplified.

[0380]

Chemistry 50

[0381]

[0382] (In the formula, R is a hydrogen atom, an alkyl group having 1 or less carbon atoms or less, or a halogenated alkyl group having 1 or less carbon atoms or less, R11b is a -SO2- cyclic group, R 12b is a single bond or a divalent linking group. )

[0383] In the formula (b-S1), R is the same as described above.

[0384] R 11b The same as the above-mentioned -SO2-containing cyclic group.

[0385] R 12b It can be either a single bond or a divalent linking group.

[0386] As R 12b The divalent linking group in the divalent linking group is not particularly limited, and as preferred examples, divalent hydrocarbon groups that may have substituents, divalent linking groups that contain heteroatoms, etc. can be mentioned.

[0387] · A divalent hydrocarbon group which may have a substituent

[0388] The hydrocarbon group as the divalent linking group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group refers to a hydrocarbon group that does not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated. Generally, a saturated hydrocarbon group is preferred. More specifically, the aliphatic hydrocarbon group may be a straight-chain or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, and the like.

[0389] The linear or branched aliphatic hydrocarbon group has a carbon number of preferably 1 to 10 or less, more preferably 1 to 8 or less, and more preferably 1 to 5 or less.

[0390] As the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred, and specific examples thereof include methylene [-CH2-], ethylene [-(CH2)2-], propylene [-(CH2)3-], butylene [-(CH2)4-], pentylene [-(CH2)5-], and the like.

[0391] The branched aliphatic hydrocarbon group is preferably a branched alkylene group. Specifically, examples thereof include alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkylpropylene groups such as -CH(CH3)CH2CH2-, and -CH2CH(CH3)CH2-; and alkylalkylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0392] The above-mentioned straight-chain or branched aliphatic hydrocarbon group may have a substituent (a group or atom other than a hydrogen atom) to replace a hydrogen atom, or may have no substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted by a fluorine atom, and an oxo group (=O).

[0393] Examples of the aliphatic hydrocarbon group containing a ring in the above structure include a cyclic aliphatic hydrocarbon group containing a heteroatom in the ring structure and optionally containing a substituent (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), a group obtained by bonding the cyclic aliphatic hydrocarbon group to the terminal of a linear or branched aliphatic hydrocarbon group, a group in which the cyclic aliphatic hydrocarbon group is interposed between linear or branched aliphatic hydrocarbon groups, etc. Examples of the linear or branched aliphatic hydrocarbon group include the same groups as described above.

[0394] The number of carbon atoms in the cyclic aliphatic hydrocarbon group is preferably 3 or more and 20 or less, more preferably 3 or more and 12 or less.

[0395] The cyclic aliphatic hydrocarbon group may be a polycyclic or a monocyclic group. As a monocyclic aliphatic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocyclic alkane is preferred. The number of carbon atoms of the monocyclic alkane is preferably 3 or more and 6 or less. Specifically, cyclopentane, cyclohexane, etc. may be mentioned. As a polycyclic aliphatic hydrocarbon group, a group obtained by removing two hydrogen atoms from a polycyclic alkane is preferred. The number of carbon atoms of the polycyclic alkane is preferably 7 or more and 12 or less. Specifically, adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. may be mentioned.

[0396] The cyclic aliphatic hydrocarbon group may or may not have a substituent (a group or atom other than a hydrogen atom) replacing a hydrogen atom. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, and an oxo group (═O).

[0397] The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group.

[0398] The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, preferably a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group and a tert-butoxy group, and particularly preferably a methoxy group and an ethoxy group.

[0399] Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferred.

[0400] Examples of the halogenated alkyl group as the substituent include groups in which a part or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms described above.

[0401] In the cyclic aliphatic hydrocarbon group, a part of the carbon atoms constituting the ring structure may be substituted by -O- or -S-. As the heteroatom-containing substituent, -O-, -C(=O)-O-, -S-, -S(=O)2-, -S(=O)2-O- are preferred.

[0402] The aromatic hydrocarbon group as a divalent hydrocarbon group is a divalent hydrocarbon group having at least one aromatic ring, which 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 a monocyclic or polycyclic ring. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, further preferably 6 to 15, and particularly preferably 6 to 12. However, the number of carbon atoms does not include the number of carbon atoms in the substituent.

[0403] As the aromatic ring, specifically, there can be mentioned aromatic hydrocarbon rings such as benzene, naphthalene, anthracene and phenanthrene; aromatic heterocyclic rings obtained by replacing a part of carbon atoms constituting the aromatic hydrocarbon rings with heteroatoms, etc. As heteroatoms in the aromatic heterocyclic ring, there can be mentioned oxygen atoms, sulfur atoms, nitrogen atoms, etc. As the aromatic heterocyclic ring, specifically, there can be mentioned pyridine rings, thiophene rings, etc.

[0404] Specifically, the aromatic hydrocarbon group as the divalent hydrocarbon group may be a group obtained by removing two hydrogen atoms from the above-mentioned aromatic hydrocarbon ring or aromatic heterocyclic ring (arylene group or heteroarylene group); a group obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (for example, biphenyl, fluorene, etc.); a group obtained by removing one hydrogen atom from the above-mentioned aromatic hydrocarbon ring or aromatic heterocyclic ring (aryl group or heteroaryl group) in which one hydrogen atom is substituted by an alkylene group (for example, a group obtained by further removing one hydrogen atom from the aryl group in an arylalkyl group such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.); and the like.

[0405] The number of carbon atoms of the alkylene group bonded to the 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 or more.

[0406] In the above-mentioned aromatic hydrocarbon group, the hydrogen atom possessed by the aromatic hydrocarbon group may be substituted by a substituent. For example, the hydrogen atom bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted by a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, an oxo group (=O), and the like.

[0407] The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and a tert-butyl group.

[0408] The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, and is preferably a methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, and tert-butoxy group, and more preferably a methoxy group and ethoxy group.

[0409] The halogen atom as a substituent may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a fluorine atom is preferred.

[0410] Examples of the halogenoalkyl group as the substituent include groups in which a part or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms.

[0411] ·Divalent connecting group containing heteroatom

[0412] The hetero atom in the hetero atom-containing divalent linking group refers to an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom and a halogen atom.

[0413] Specific examples of the heteroatom-containing divalent linking group include -O-, -C(=O)-, -C(=O)-O-, -OC(=O)-O-, -S-, -S(=O)2-, -S(=O)2-O-, -NH-, -NH-C(=O)-, -NH-C(=NH)-, =N- and other non-hydrocarbon linking groups, and combinations of at least one of these non-hydrocarbon linking groups with a divalent hydrocarbon group. Examples of the divalent hydrocarbon group include the same groups as the divalent hydrocarbon groups which may have substituents, and preferably a linear or branched aliphatic hydrocarbon group.

[0414] In the above, H in -NH-, -NH-, and -NH-C(=NH)- in -C(=O)-NH- may be substituted by a substituent such as an alkyl group or an acyl group. The number of carbon atoms in the substituent is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5.

[0415] As R 12b The divalent linking group in is particularly preferably a linear or branched alkylene group, a cyclic aliphatic hydrocarbon group or a heteroatom-containing divalent linking group.

[0416] In 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 to 10, more preferably 1 to 6, particularly preferably 1 to 4, and most preferably 1 to 3. Specifically, the same linear alkylene group and branched alkylene group as those exemplified as the linear or branched aliphatic hydrocarbon group in the description of the "divalent hydrocarbon group which may have a substituent" as the divalent linking group can be mentioned.

[0417] In R 12b In the case where the divalent connecting group in is a cyclic aliphatic hydrocarbon group, the cyclic aliphatic hydrocarbon group may be the same as the cyclic aliphatic hydrocarbon group exemplified 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 connecting group.

[0418] The cyclic aliphatic hydrocarbon group is particularly preferably a group obtained by removing two or more hydrogen atoms from cyclopentane, cyclohexane, norbornane, isobornane, adamantane, tricyclodecane or tetracyclododecane.

[0419] In R 12bIn the case where the divalent linking group in is a divalent linking group containing a heteroatom, preferred examples of the linking group include -O-, -C(=O)-O-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH- (H may be substituted by an alkyl group, an acyl group or the like), -S-, -S(=O)2-, -S(=O)2-O-, and the general formula -Y 1b -OY 2b -、-[Y 1b -C(=O)-O] m’ -Y 2b -or-Y 1b -OC(=O)-Y 2b -represented by a group [wherein, Y 1b and Y 2b Each independently represents a divalent hydrocarbon group which may have a substituent, O represents an oxygen atom, and m' represents an integer of 0 to 3].

[0420] In R 12b When the divalent linking group in -NH- is -NH-, the hydrogen atom in -NH- may be substituted by 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 to 10, more preferably 1 to 8, and particularly preferably 1 to 5.

[0421] Formula-Y 1b -OY 2b -、-[Y 1b -C(=O)-O] m’ -Y 2b -or-Y 1b -OC(=O)-Y 2b -Medium,Y 1b and Y 2b Each independently represents a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include the same groups as those exemplified as the "divalent hydrocarbon group which may have a substituent" in the description of the divalent linking group.

[0422] As Y 1b , preferably a straight-chain aliphatic hydrocarbon group, more preferably a straight-chain alkylene group, more preferably a straight-chain alkylene group having 1 to 5 carbon atoms, particularly preferably a methylene group and an ethylene group.

[0423] As Y 2b , preferably a straight-chain 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 straight-chain alkyl group having 1 to 5 carbon atoms, more preferably a straight-chain alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.

[0424] In the form -[Y 1b -C(=O)-O] m’ -Y 2b -, m' is an integer from 0 to 3, preferably an integer from 0 to 2, more preferably 0 or 1, and particularly preferably 1. 1b -C(=O)-O] m’ -Y 2b -, particularly preferably a group represented by the formula -Y 1b -C(=O)-OY 2b - represented by a group. Among them, preferably a group represented by the formula -(CH2) a’ -C(=O)-O-(CH2) b’ -represented by a group. In the formula, a' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, further preferably 1 or 2, and most preferably 1. b' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, further preferably 1 or 2, and most preferably 1.

[0425] For R 12b The divalent connecting group in the formula -Y is preferably an organic group composed of a combination of at least one non-hydrocarbon group and a divalent hydrocarbon group. Among them, a linear group having an oxygen atom as a heteroatom, such as a group containing an ether bond or an ester bond, is preferred. 1b -OY 2b -、-[Y 1b -C(=O)-O] m’ -Y 2b -or-Y 1b -OC(=O)-Y 2b -represented by the group, particularly preferably the group represented by the formula -[Y 1b -C(=O)-O] m’ -Y 2b -or-Y 1b -OC(=O)-Y 2b -represented group.

[0426] As R 12b The divalent linking group in is preferably an alkylene group or a divalent linking group containing an ester bond (—C(═O)—O—).

[0427] The alkylene group is preferably a straight-chain or branched alkylene group. Preferred examples of the straight-chain aliphatic hydrocarbon group include methylene [-CH2-], ethylene [-(CH2)2-], propylene [-(CH2)3-], butylene [-(CH2)4-], and pentylene [-(CH2)5-]. Preferred 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-; alkylpropylene groups such as -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-; alkylbutylene groups such as -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2-, and the like.

[0428] As the divalent linking group containing an ester bond, a group having the formula: -R 13b -C(=O)-O-[wherein, R 13b is a divalent linking group]. That is, the structural unit (b-3-S) is preferably a structural unit represented by the following formula (b-S1-1).

[0429]

Chemistry 51

[0430]

[0431] (In the formula, R and R 11b The same as above, R 13b It is a divalent linking group. )

[0432] As R 13b , is not particularly limited, for example, the same R as described above can be cited 12b The same group as the divalent connecting group in .

[0433] As R 13b The divalent linking group is preferably a linear or branched alkylene group, an aliphatic hydrocarbon group containing a ring in the structure, or a divalent linking group containing a heteroatom, and is more preferably a linear or branched alkylene group or a divalent linking group containing an oxygen atom as a heteroatom.

[0434] As a straight-chain alkylene group, methylene or ethylene is preferred, and methylene is particularly preferred. As a branched-chain alkylene group, alkylmethylene or alkylethylene is preferred, and -CH(CH3)-, -C(CH3)2- or -C(CH3)2CH2- is particularly preferred.

[0435] As the divalent linking group containing an oxygen atom, a divalent linking group containing an ether bond or an ester bond is preferred, and the above-mentioned -Y is more preferred. 1b -OY 2b -、-[Y 1b -C(=O)-O] m’ -Y 2b -or-Y 1b -OC(=O)-Y 2b -.Y 1b and Y 2b Each of them is independently a divalent hydrocarbon group which may have a substituent, and m' is an integer from 0 to 3. 1b -OC(=O)-Y 2b -, particularly preferably -(CH2) c -OC(=O)-(CH2) d -. c is an integer from 1 to 5, preferably 1 or 2. d is an integer from 1 to 5, preferably 1 or 2.

[0436] As the structural unit (b-3-S), a structural unit represented by the following formula (b-S1-11) or (b-S1-12) is particularly preferred, and a structural unit represented by the formula (b-S1-12) is more preferred.

[0437]

Chemistry 52

[0438]

[0439] (In the formula, R, A', R 10b , z and R 13b Same as above.)

[0440] In the formula (b-S1-11), A' is preferably a methylene group, an oxygen atom (-O-) or a sulfur atom (-S-).

[0441] As R 13b , preferably a linear or branched alkylene group or a divalent linking group containing an oxygen atom. 13b The linear or branched alkylene group and the divalent linking group containing an oxygen atom in the above-mentioned linear or branched alkylene group and the divalent linking group containing an oxygen atom may be the same as those mentioned above, respectively.

[0442] As the structural unit represented by the formula (b-S1-12), particularly preferably, it is a structural unit represented by the following formula (b-S1-12a) or (b-S1-12b).

[0443]

Chemical Formula 53

[0444]

[0445] (In the formula, R and A' are the same as above respectively, and c to e are each independently an integer of 1 or more and 3 or less.)

[0446] 〔Structural unit (b-3-L)〕

[0447] As an example of the structural unit (b-3-L), for example, a structural unit obtained by substituting R in the above formula (b-S1) 11b with a lactone ring-containing group can be cited. More specifically, structural units represented by the following formulas (b-L1) to (b-L5) can be cited.

[0448]

Chemical Formula 54

[0449]

[0450] (In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms; R' are each independently a hydrogen atom, an alkyl group, an alkoxy group, a haloalkyl 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.)

[0451] R in the formulas (b-L1) to (b-L5) is the same as above.

[0452] As the alkyl group, alkoxy group, haloalkyl group, -COOR", -OC(=O)R", and hydroxyalkyl group in R', groups similar to those described above for the substituents that the -SO2-ring-containing group may have can be cited respectively.

[0453] Considering industrial availability and the like, R' is preferably a hydrogen atom.

[0454] The alkyl group in R" can be any of linear, branched, and cyclic.

[0455] When R" is a linear or branched alkyl group, the number of carbon atoms is preferably 1 to 10, and more preferably 1 to 5.

[0456] When R" is a cyclic alkyl group, the number of carbon atoms is preferably 3 to 15, more preferably 4 to 12, and most preferably 5 to 10. Specifically, there can be exemplified groups obtained by removing one or more hydrogen atoms from a monocycloalkane which may be substituted with or unsubstituted by a fluorine atom or a fluoroalkyl group, or from a polycycloalkane such as a bicycloalkane, a tricycloalkane, or a tetracycloalkane. Specifically, there can be exemplified groups obtained by removing one or more hydrogen atoms from a monocycloalkane such as cyclopentane or cyclohexane, or from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane.

[0457] As A", the same groups as A' in the above formula (3-1) can be mentioned. A" is preferably an alkylene group having 1 to 5 carbon atoms, an oxygen atom (-O-) or a sulfur atom (-S-), and more preferably an alkylene group having 1 to 5 carbon atoms or -O-. As the alkylene group having 1 to 5 carbon atoms, methylene or dimethylmethylene is more preferred, and methylene is most preferred.

[0458] R 12b and R in the formula (b-S1) 12b same.

[0459] In formula (b-L1), s" is preferably 1 or 2.

[0460] Specific examples of the structural units represented by the formulae (b-L1) to (b-L3) are shown below. α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

[0461]

Chemistry 55

[0462]

[0463]

Chemistry 56

[0464]

[0465]

Chemistry 57

[0466]

[0467] As the structural unit (b-3-L), it is preferred to select at least one kind from the group consisting of structural units represented by the above-mentioned formulas (b-L1) to (b-L5), more preferably at least one kind selected from the group consisting of structural units represented by the above-mentioned formulas (b-L1) to (b-L3), and particularly preferably at least one kind selected from the group consisting of structural units represented by the above-mentioned formulas (b-L1) or (b-L3).

[0468] Among them, it is preferred to select at least one from the group consisting of structural units represented by the formulae (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).

[0469] Furthermore, as the structural unit (b-3-L), structural units represented by the following formulae (b-L6) to (b-L7) are also preferred.

[0470]

Chemistry 58

[0471]

[0472] In formula (b-L6) and (b-L7), R and R 12b Same as above.

[0473] The acrylic resin (B3) includes structural units represented by the following formulae (b5) to (b7) having an acid-dissociable group as structural units that improve the solubility of the acrylic resin (B3) in alkalis due to the action of an acid.

[0474]

Chemistry 59

[0475]

[0476] In the above formulas (b5) to (b7), R 14b and R 18b ~R 23b each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom, or a linear or branched fluoroalkyl group having 1 to 6 carbon atoms, and R 15b ~R 17b each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched fluoroalkyl group having 1 to 6 carbon atoms, or an aliphatic cyclic group having 5 to 20 carbon atoms, each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched fluoroalkyl group having 1 to 6 carbon atoms, R 16b and R 17bThey may bond to each other to form a hydrocarbon ring having 5 to 20 carbon atoms together with the carbon atoms to which they are bonded, Yb represents an aliphatic cyclic group or an alkyl group which may have a substituent, p represents an integer of 0 to 4, and q represents 0 or 1.

[0477] In addition, examples of the linear or branched alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. In addition, the fluoroalkyl group refers to a group in which a part or all of the hydrogen atoms of the alkyl group are substituted by fluorine atoms.

[0478] As a specific example of an aliphatic cyclic group, a group obtained by removing one or more hydrogen atoms from a monocycloalkane or from a polycycloalkane such as a bicycloalkane, a tricycloalkane, or a tetracycloalkane. Specifically, a group obtained by removing one hydrogen atom from a monocycloalkane such as cyclopentane, cyclohexane, cycloheptane, or a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane can be cited. In particular, a group obtained by removing one hydrogen atom from cyclohexane or adamantane (which may also have a substituent).

[0479] In the above R 16b and R 17b When the hydrocarbon rings are not bonded to each other, the above R 15b , R 16b and R 17b , preferably a linear or branched alkyl group having 2 or more and 4 or less carbon atoms. 19b , R 20b , R 22b , R 23b , preferably a hydrogen atom or a methyl group.

[0480] The above R 16b and R 17b It is also possible to form an aliphatic cyclic group having a carbon number of 5 or more and 20 or less together with the carbon atoms to which the two are bonded. As a specific example of such an aliphatic cyclic group, a group obtained by removing one or more hydrogen atoms from a monocycloalkane or from a polycycloalkane such as a bicycloalkane, a tricycloalkane, a tetracycloalkane, etc. can be cited. Specifically, a group obtained by removing one or more hydrogen atoms from a monocycloalkane such as cyclopentane, cyclohexane, cycloheptane, cyclooctane, or a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane can be cited. In particular, it is preferably a group obtained by removing one or more hydrogen atoms from cyclohexane and adamantane (which may also have a substituent).

[0481] Furthermore, in the above R 16b and R 17bWhen the formed aliphatic cyclic group has a substituent on its ring skeleton, examples of the substituent include polar groups such as hydroxyl, carboxyl, cyano, oxygen atom (=O), or linear or branched alkyl groups having a carbon number of 1 to 4. As the polar group, oxygen atom (=O) is particularly preferred.

[0482] The above Y b It is an aliphatic cyclic group or an alkyl group, and examples thereof include groups obtained by removing one or more hydrogen atoms from a monocycloalkane or from a polycycloalkane such as a bicycloalkane, a tricycloalkane, or a tetracycloalkane. Specifically, examples thereof include groups obtained by removing one or more hydrogen atoms from a monocycloalkane such as cyclopentane, cyclohexane, cycloheptane, or cyclooctane, or from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane. In particular, groups obtained by removing one or more hydrogen atoms from adamantane (which may further have a substituent) are preferred.

[0483] Furthermore, in the above Y b When the aliphatic cyclic group has a substituent on its ring skeleton, examples of the substituent include polar groups such as hydroxyl, carboxyl, cyano, oxygen atom (=O), or linear or branched alkyl groups having 1 to 4 carbon atoms. As the polar group, oxygen atom (=O) is particularly preferred.

[0484] In addition, in Y b In the case of an alkyl group, a linear or branched alkyl group having a carbon number of 1 to 20, preferably 6 to 15, is preferred. Such an alkyl group is particularly preferably an alkoxyalkyl group, and examples of such an alkoxyalkyl group include 1-methoxyethyl, 1-ethoxyethyl, 1-n-propoxyethyl, 1-isopropoxyethyl, 1-n-butoxyethyl, 1-isobutoxyethyl, 1-tert-butoxyethyl, 1-methoxypropyl, 1-ethoxypropyl, 1-methoxy-1-methyl-ethyl, and 1-ethoxy-1-methylethyl.

[0485] Preferred specific examples of the structural unit represented by the above formula (b5) include structural units represented by the following formulae (b5-1) to (b5-33).

[0486]

Chemistry 60

[0487]

[0488] In the above formulas (b5-1) to (b5-33), R 24b represents a hydrogen atom or a methyl group.

[0489] Preferred specific examples of the structural unit represented by the above formula (b6) include structural units represented by the following formulae (b6-1) to (b6-26).

[0490]

Chemistry 61

[0491]

[0492] In the above formulas (b6-1) to (b6-26), R 24b represents a hydrogen atom or a methyl group.

[0493] Preferred specific examples of the structural unit represented by the above formula (b7) include structural units represented by the following formulae (b7-1) to (b7-15).

[0494]

Chemistry 62

[0495]

[0496] In the above formulas (b7-1) to (b7-15), R 24b represents a hydrogen atom or a methyl group.

[0497] Among the structural units represented by formulae (b5) to (b7) described above, the structural unit represented by formula (b6) is preferred from the viewpoint of easy synthesis and relatively easy high sensitivity. b is a structural unit of an alkyl group, and preferably R 19b and R 20b One or both of them are structural units of alkyl groups.

[0498] Furthermore, the acrylic resin (B3) is preferably a resin composed of a copolymer containing structural units represented by the above formulae (b5) to (b7) and structural units derived from a polymerizable compound having an ether bond.

[0499] As the above-mentioned polymerizable compound having an ether bond, free radical polymerizable compounds such as (meth)acrylic acid derivatives having an ether bond and an ester bond can be exemplified, and as specific examples, 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, etc. can be cited. In addition, the above-mentioned polymerizable compound having an ether bond is preferably 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and methoxytriethylene glycol (meth)acrylate. These polymerizable compounds can be used alone or in combination of two or more.

[0500] Furthermore, in order to appropriately control physical and chemical properties, the acrylic resin (B3) may contain other polymerizable compounds as structural units. Such polymerizable compounds may, for example, be known radical polymerizable compounds or anionic polymerizable compounds.

[0501] Examples of such polymerizable compounds include the following compounds: 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 carboxyl group and an ester bond such as 2-methacryloyloxyethylsuccinic acid, 2-methacryloyloxyethylmaleic acid, 2-methacryloyloxyethylphthalic acid, and 2-methacryloyloxyethylhexahydrophthalic acid; alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and cyclohexyl (meth)acrylate; and (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. Hydroxyalkyl esters; (meth)acrylate aryl esters such as phenyl (meth)acrylate and benzyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; aromatic compounds containing vinyl groups such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene; aliphatic compounds containing vinyl groups such as vinyl acetate; conjugated dienes such as butadiene and isoprene; polymerizable compounds containing nitrile groups such as acrylonitrile and methacrylonitrile; polymerizable compounds containing chlorine such as vinyl chloride and vinylidene chloride; polymerizable compounds containing amide bonds such as acrylamide and methacrylamide.

[0502] As described above, the acrylic resin (B3) may also contain a structural unit derived from a polymerizable compound having a carboxyl group such as the above-mentioned monocarboxylic acid or dicarboxylic acid. However, from the viewpoint of easily forming a resist pattern including a non-resist portion with a rectangular shape having a good cross-sectional shape, the acrylic resin (B3) is preferably substantially free of structural units derived from a polymerizable compound having a carboxyl group. Specifically, the ratio of structural units derived from a polymerizable compound having a carboxyl 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.

[0503] Among acrylic resins (B3), it is preferred to use in combination an acrylic resin containing a relatively large amount of a structural unit derived from a polymerizable compound having a carboxyl group and an acrylic resin containing only a small amount or no structural unit derived from a polymerizable compound having a carboxyl group.

[0504] In addition, as polymerizable compounds, (meth)acrylates and vinyl-containing aromatic compounds having an acid-non-dissociating aliphatic polycyclic group can be exemplified. From the viewpoint of industrial availability, the acid-non-dissociating aliphatic polycyclic group is particularly preferably a tricyclodecanyl group, adamantyl group, tetracyclododecyl group, isobornyl group, norbornyl group, etc. These aliphatic polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.

[0505] Specific examples of the (meth)acrylates having an acid-non-dissociable aliphatic polycyclic group include compounds having structures represented by the following formulae (b8-1) to (b8-5).

[0506]

Chemistry 63

[0507]

[0508] In the above formulas (b8-1) to (b8-5), R 25b represents a hydrogen atom or a methyl group.

[0509] When the acrylic resin (B3) contains a structural unit (b-3) containing a -SO2- cyclic group or a lactone 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 an amount within the above range, it is easy to achieve both good developability and good pattern shape.

[0510] The acrylic resin (B3) preferably contains 5% by mass or more of the structural units represented by the above formulae (b5) to (b7), more preferably 10% by mass or more, and particularly preferably 10% by mass or more and 50% by mass or less.

[0511] The acrylic resin (B3) preferably contains a structural unit derived from the above-mentioned polymerizable compound having an ether bond. The content of the structural unit derived from the polymerizable compound having an ether bond in the acrylic resin (B3) is preferably 0% by mass to 50% by mass, more preferably 5% by mass to 30% by mass.

[0512] The acrylic resin (B3) preferably contains a structural unit derived from the above-mentioned (meth)acrylate having an acid-non-dissociable aliphatic polycyclic group. The content of the structural unit derived from the (meth)acrylate having an acid-non-dissociable aliphatic polycyclic group in the acrylic resin (B3) is preferably 0% by mass to 50% by mass, and more preferably 5% by mass to 30% by mass.

[0513] The polystyrene-equivalent mass average molecular weight (hereinafter also referred to as "mass average molecular weight") of the resin (B) described above is preferably 10,000 to 600,000, more preferably 20,000 to 400,000, further preferably 30,000 to 300,000, and particularly preferably 40,000 to 300,000. By setting the mass average molecular weight in this way, the peelability of the photosensitive resin layer from the substrate can be kept from being reduced, and the sufficient strength of the photosensitive resin layer can be maintained, and the expansion of the profile or the generation of cracks during plating can be further prevented.

[0514] In addition, the molecular weight distribution coefficient of resin (B) is preferably 1.05 or more. Here, the molecular weight distribution coefficient refers to the value obtained by dividing the mass average molecular weight by the number average molecular weight. By setting such a molecular weight distribution coefficient, the desired stress resistance relative to plating can be obtained or the problem that the metal layer obtained by the plating process becomes easy to expand can be further avoided.

[0515] The content of the resin (B) is preferably 5% by mass or more and 98% by mass or less, and more preferably 5% by mass or more and 85% by mass or less, based on the total solid content of the photosensitive resin composition.

[0516] <Phenolic hydroxyl group-containing low molecular weight compound (C)>

[0517] The photosensitive resin composition preferably contains a phenolic hydroxyl group-containing low-molecular compound (C).

[0518] The phenolic hydroxyl group refers to a hydroxyl group (OH) directly bonded to a benzene ring. Since the phenolic hydroxyl group-containing low molecular compound (C) has a phenolic hydroxyl group, it is an alkali-soluble compound. The alkali-soluble compound refers to a substance that dissolves in a 2.38 mass % TMAH aqueous solution.

[0519] The low molecular weight compound refers to a non-polymer compound, for example, a compound having a molecular weight of 1500 or less.

[0520] The low molecular weight compound (C) containing a phenolic hydroxyl group can increase the dissolution rate of the exposed part and improve the sensitivity.

[0521] The type of the low molecular weight compound (C) containing a phenolic hydroxyl group is not particularly limited within the scope of not hindering the purpose of the present invention. As the low molecular weight compound (C) containing a phenolic hydroxyl group, a compound having two or more phenolic hydroxyl groups is preferred. As specific examples of the low molecular weight compound (C) containing a phenolic hydroxyl group, the following compounds can be cited.

[0522]

Chemistry 64

[0523]

[0524] In addition, the following compounds can be cited as the low molecular weight compound (C) containing a phenolic hydroxyl group: polyhydroxybenzophenones such as 2,3,4-trihydroxybenzophenone and 2,3,4,4'-tetrahydroxybenzophenone; tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,3,5-trimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane; , bis(4-hydroxy-3,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenyl bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2,4-dihydroxyphenylmethane, bis(4-hydroxyphenyl)-3-methoxy-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)- triphenolic compounds such as bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3,4-dihydroxyphenylmethane, 4,4'-[(3,4-dihydroxyphenyl)methylene]bis(2-cyclohexyl-5-methylphenol); linear tri-nuclear phenolic compounds such as 2,4-bis(3,5-dimethyl-4-hydroxybenzyl)-5-hydroxyphenol and 2,6-bis(2,5-dimethyl-4-hydroxybenzyl)-4-methylphenol;1,1-bis[3-(2-hydroxy-5-methylbenzyl)-4-hydroxy-5-cyclohexylphenyl]isopropane, bis[2,5-dimethyl-3-(4-hydroxy-5-methylbenzyl)-4-hydroxyphenyl]methane, bis[2,5-dimethyl-3-(4-hydroxybenzyl)-4-hydroxyphenyl]methane, bis[3-(3,5-dimethyl-4-hydroxybenzyl)-4-hydroxy-5-methylphenyl]methane, bis[3-(3,5-dimethyl-4-hydroxybenzyl)-4-hydroxy-5-ethylphenyl]methane, bis[3-(3,5-dimethyl-4-hydroxybenzyl)-4-hydroxy-5-ethylphenyl]methane, bis[3-(3,5-diethyl-4-hydroxybenzyl)-4-hydroxy-5-methylphenyl]methane, bis[3-(3,5-diethyl-4-hydroxybenzyl)-4-hydroxy-5-methylphenyl]methane, Linear tetranuclear phenol compounds such as bis[2-hydroxy-3-(3,5-dimethyl-4-hydroxybenzyl)-5-methylphenyl]methane, bis[2-hydroxy-3-(2-hydroxy-5-methylbenzyl)-5-methylphenyl]methane, bis[4-hydroxy-3-(2-hydroxy-5-methylbenzyl)-5-methylphenyl]methane, bis[2,5-dimethyl-3-(2-hydroxy-5-methylbenzyl)-4-hydroxyphenyl]methane; 2,4-bis[2-hydroxy-3-(4-hydroxybenzyl)-5-methylbenzyl]-6-cyclohexylphenol, 2,4-bis[4-hydroxy-3-(4-hydroxybenzyl)-5-methylbenzyl]- linear polyphenol compounds such as linear pentapeptide phenol compounds such as 6-cyclohexylphenol, 2,6-bis[2,5-dimethyl-3-(2-hydroxy-5-methylbenzyl)-4-hydroxybenzyl]-4-methylphenol; bis(2,3,4-trihydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)methane, 2,3,4-trihydroxyphenyl-4'-hydroxyphenylmethane, 2-(2,3,4-trihydroxyphenyl)-2-(2',3',4'-trihydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(3-fluoro-4-hydroxyphenyl)- Bisphenol compounds such as 2-(3'-fluoro-4'-hydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2-(4'-hydroxy-3',5'-dimethylphenyl)propane; polynuclear branched compounds such as 1-[1-(3-methyl-4-hydroxyphenyl)isopropyl]-4-[1,1-bis(3-methyl-4-hydroxyphenyl)ethyl]benzene; condensed phenol compounds such as 1,1-bis(4-hydroxyphenyl)cyclohexane, or bisphenol A, pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, etc. These can be used alone or in combination of two or more. ;

[0525] When the photosensitive resin composition contains a phenolic hydroxyl group-containing low molecular weight compound (C), the content of the phenolic hydroxyl group-containing low molecular weight compound (C) is preferably 1 mass part to 20 mass parts, and more preferably 3 mass parts to 15 mass parts, when the total amount of the resin contained in the photosensitive resin composition is 100 mass parts.

[0526] <Alkali-soluble resin (D)>

[0527] In order to improve alkali solubility, the photosensitive resin composition preferably further contains an alkali-soluble resin (D). Here, the alkali-soluble resin refers to a resin film having a film thickness of 1 μm formed on a substrate using a resin solution having a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate), and a resin that dissolves 0.01 μm or more when immersed in a 2.38% by mass TMAH (tetramethylammonium hydroxide) aqueous solution for 1 minute, and refers to a resin that does not belong to the above-mentioned (B) component (typically, 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 novolac resin (D1), a polyhydroxystyrene resin (D2) and an acrylic resin (D3).

[0528] [Novolac resin (D1)]

[0529] Novolac resins are obtained, for example, by addition polymerization of aromatic compounds having a phenolic hydroxyl group (hereinafter, simply referred to as "phenols") and aldehydes in the presence of an acid catalyst.

[0530] 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, hydroxybiphenyl, bisphenol A, gallic acid, gallic acid esters, α-naphthol, β-naphthol and the like.

[0531] Examples of the aldehydes include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde and acetaldehyde.

[0532] The catalyst for the addition polymerization reaction is not particularly limited, and, for example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, etc. among acid catalysts can be used.

[0533] In addition, the flexibility of the novolac resin can be further improved by using o-cresol, substituting the hydrogen atoms of the hydroxyl groups in the resin with other substituents, or using bulky aldehydes.

[0534] The mass average molecular weight of the novolac resin (D1) is not particularly limited as long as it is within a range that does not hinder the purpose of the present invention, but is preferably 1,500 or more and 50,000 or less.

[0535] [Polyhydroxystyrene resin (D2)]

[0536] Examples of the hydroxystyrene compounds (hydroxystyrene, hydroxystyrene derivatives) constituting the polyhydroxystyrene resin (D2) include p-hydroxystyrene, α-methylhydroxystyrene and α-ethylhydroxystyrene.

[0537] Furthermore, the polyhydroxystyrene resin (D2) is preferably a copolymer with a styrene resin. Examples of the styrene-based compound constituting the styrene resin include styrene, chlorostyrene, chloromethylstyrene, vinyltoluene and α-methylstyrene.

[0538] 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 1,500 or more and 50,000 or less.

[0539] [Acrylic resin (D3)]

[0540] The acrylic resin (D3) preferably includes a structural unit derived from a polymerizable compound having an ether bond and a structural unit derived from a polymerizable compound having a carboxyl group.

[0541] 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.

[0542] Examples of the polymerizable compound having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; compounds having a carboxyl group and an ester bond such as 2-methacryloyloxyethylsuccinic acid, 2-methacryloyloxyethylmaleic acid, 2-methacryloyloxyethylphthalic acid, and 2-methacryloyloxyethylhexahydrophthalic acid. The polymerizable compound having a carboxyl group is preferably acrylic acid or methacrylic acid. These polymerizable compounds may be used alone or in combination of two or more.

[0543] The mass average molecular weight of the acrylic resin (D3) is not particularly limited within a range not hindering the purpose of the present invention, but is preferably 50,000 to 800,000.

[0544] When the total solid content of the photosensitive resin composition is 100 parts by mass, the content of the alkali-soluble resin (D) is preferably 3 parts by mass or more and 70 parts by mass or less, and more preferably 5 parts by mass or more and 50 parts by mass or less. By setting the content of the alkali-soluble resin (D) to the above range, alkali solubility can be easily improved.

[0545] <Sulfur-containing compounds (E)>

[0546] Since the photosensitive resin composition is used to form a pattern on a metal substrate, the photosensitive resin composition preferably contains a sulfur-containing compound (E). The sulfur-containing compound (E) is a compound containing a sulfur atom that can coordinate with a metal. In addition, with respect to a compound that can generate two or more tautomers, when at least one tautomer contains a sulfur atom that coordinates with a metal constituting the surface of the metal substrate, the compound belongs to the sulfur-containing compound.

[0547] When a resist pattern used as a mold for plating is formed on a surface composed of metal such as Cu, it is easy to produce defects in cross-sectional shapes such as footing. However, when the photosensitive resin composition contains a sulfur-containing compound (E), even when a resist pattern is formed on a surface composed of metal of a substrate, it is easy to suppress the occurrence of defects in cross-sectional shapes such as footing. In addition, "footing" refers to a phenomenon in which the width of the bottom of the non-resist portion is narrower than the width of the top in the non-resist portion because the resist portion extends toward the non-resist portion near the contact surface between the substrate surface and the resist pattern.

[0548] The sulfur atom capable of coordinating with a metal is included in the sulfur-containing compound in the form of, for example, a mercapto group (—SH), a thiocarboxyl group (—CO-SH), a dithiocarboxyl group (—CS-SH), and a thiocarbonyl group (—CS-).

[0549] The sulfur-containing compound preferably has a mercapto group, since it is easy to coordinate with a metal and has an excellent effect of suppressing footing.

[0550] Preferred examples of the sulfur-containing compound having a mercapto group include compounds represented by the following formula (e1).

[0551]

Chemistry 65

[0552]

[0553] (Where R e1 and R e2Each independently represents a hydrogen atom or an alkyl group, R e3 represents a single bond or an alkylene group, R e4 represents a u-valent aliphatic group which may contain atoms other than carbon, and u represents an integer of 2 to 4. )

[0554] In R e1 and R e2 When it is an alkyl group, the alkyl group may be linear or branched, and is preferably linear. e1 and R e2 In the case of an alkyl group, the number of carbon atoms of the alkyl group is not particularly limited as long as it does not hinder the purpose 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. e1 With R e2 In the combination of , it is preferred that one is a hydrogen atom and the other is an alkyl group, and it is particularly preferred that one is a hydrogen atom and the other is a methyl group.

[0555] In R e3 In the case of an alkylene group, the alkylene group may be linear or branched, and is preferably linear. e3 In the case of an alkylene group, the number of carbon atoms of the alkylene group is not particularly limited as long as it does not hinder the purpose of the present invention. The number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 or 2, and most preferably 1.

[0556] R e4 It is a divalent or higher and tetravalent aliphatic group which may contain atoms other than carbon. e4 Atoms other than carbon that may be contained include nitrogen atom, oxygen atom, sulfur atom, fluorine atom, chlorine atom, bromine atom and iodine atom. e4 The structure of the aliphatic group may be linear, branched, or cyclic, or a combination of these structures.

[0557] Among the compounds represented by the formula (e1), the compounds represented by the following formula (e2) are more preferred.

[0558]

Chemistry 66

[0559]

[0560] (In formula (e2), R e4 and u has the same meaning as in formula (e1).

[0561] Among the compounds represented by the above formula (e2), the following compounds are preferred.

[0562]

Chemistry 67

[0563]

[0564] Compounds represented by the following formulas (e3-L1) to (e3-L7) are also exemplified as preferred examples of sulfur-containing compounds having a mercapto group.

[0565]

Chemical Formula 68

[0566]

[0567] (In the formulas (e3-L1) to (e3-L7), R’, s”, A” and r are the same as those in the formulas (b-L1) to (b-L7) described for the acrylic resin (B3).)

[0568] As specific preferred examples of the mercapto compounds represented by the above formulas (e3-L1) to (e3-L7), the following compounds can be exemplified.

[0569]

Chemical Formula 69

[0570]

[0571] Compounds represented by the following formulas (e3-1) to (e3-4) are also exemplified as preferred examples of sulfur-containing compounds having a mercapto group.

[0572]

Chemical Formula 70

[0573]

[0574] (Regarding the definitions of the abbreviated symbols in the formulas (e3-1) to (e3-4), they are the same as those described for the formulas (3-1) to (3-4) for the acrylic resin (B3).)

[0575] As specific preferred examples of the mercapto compounds represented by the above formulas (e3-1) to (e3-4), the following compounds can be exemplified.

[0576]

Chemical Formula 71

[0577]

[0578] In addition, as a preferred example of a compound having a mercapto group, a compound represented by the following formula (e4) can be exemplified.

[0579]

Chemical Formula 72

[0580]

[0581] (In the formula (e4), R e5is a group selected from the group consisting of a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, a mercaptoalkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, and a halogen atom, n1 is an integer of 0 to 3, n0 is an integer of 0 to 3, and when n1 is 2 or 3, R e5 Can be the same or different.)

[0582] As R e5 Specific examples of the alkyl group having 1 to 4 carbon atoms and optionally having a hydroxyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl. Among these alkyl groups, methyl, hydroxymethyl and ethyl are preferred.

[0583] As R e5 Specific examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy. Among these alkoxy groups, methoxy and ethoxy are preferred, and methoxy is more preferred.

[0584] As R e5 Specific examples of the alkylthio group having 1 to 4 carbon atoms include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio and tert-butylthio. Among these alkylthio groups, methylthio and ethylthio are preferred, and methylthio is more preferred.

[0585] As R e5 Specific examples of the hydroxyalkyl group having 1 to 4 carbon atoms include hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 3-hydroxy-n-propyl, and 4-hydroxy-n-butyl. Among these hydroxyalkyl groups, hydroxymethyl, 2-hydroxyethyl, and 1-hydroxyethyl are preferred, and hydroxymethyl is more preferred.

[0586] As R e5 Specific examples of the mercaptoalkyl group having 1 to 4 carbon atoms include mercaptomethyl, 2-mercaptoethyl, 1-mercaptoethyl, 3-mercapto-n-propyl, and 4-mercapto-n-butyl. Among these mercaptoalkyl groups, mercaptomethyl, 2-mercaptoethyl, and 1-mercaptoethyl are preferred, and mercaptomethyl is more preferred.

[0587] In R e5 In the case of a halogenated alkyl group having 1 to 4 carbon atoms, examples of the halogen atom contained in the halogenated alkyl group include fluorine, chlorine, bromine and iodine. e5Specific examples of the halogenated alkyl group having 1 to 4 carbon atoms include chloromethyl, bromomethyl, iodomethyl, fluoromethyl, dichloromethyl, dibromomethyl, difluoromethyl, trichloromethyl, tribromomethyl, trifluoromethyl, 2-chloroethyl, 2-bromoethyl, 2-fluoroethyl, 1,2-dichloroethyl, 2,2-difluoroethyl, 1-chloro-2-fluoroethyl, 3-chloro-n-propyl, 3-bromo-n-propyl, 3-fluoro-n-propyl, and 4-chloro-n-butyl. Among these halogenated alkyl groups, chloromethyl, bromomethyl, iodomethyl, fluoromethyl, dichloromethyl, dibromomethyl, difluoromethyl, trichloromethyl, tribromomethyl, and trifluoromethyl are preferred, and chloromethyl, dichloromethyl, trichloromethyl, and trifluoromethyl are more preferred.

[0588] As R e5 Specific examples of the halogen atom include fluorine, chlorine, bromine and iodine.

[0589] In formula (e4), n1 is an integer from 0 to 3, and more preferably 1. When n1 is 2 or 3, a plurality of R e5 Can be the same or different.

[0590] In the compound represented by formula (e4), R on the benzene ring e5 The substitution position of is not particularly limited. e5 The substitution position is preferably relative to -(CH2) n0 The bonding position of -SH is meta or para.

[0591] The compound represented by formula (e4) preferably has at least one group selected from the group consisting of an alkyl group, a hydroxyalkyl group, and a mercaptoalkyl group as R. e5 The compound preferably has one group selected from the group consisting of an alkyl group, a hydroxyalkyl group and a mercaptoalkyl group as R e5 The compound represented by formula (e4) has one group selected from the group consisting of alkyl, hydroxyalkyl and mercaptoalkyl as R e5 In the case of alkyl, hydroxyalkyl or mercaptoalkyl, the substitution position on the benzene ring is preferably relative to -(CH2) n0 The bonding position of -SH is the meta position or the para position, and more preferably the para position.

[0592] In formula (e4), n0 is an integer of 0 to 3. From the viewpoint of easy preparation and availability of the compound, n0 is preferably 0 or 1, and more preferably 0.

[0593] As specific examples of the compound represented by the formula (e4), examples include p-mercaptophenol, p-thiocresol, m-thiocresol, 4-(methylthio)benzenethiol, 4-methoxybenzenethiol, 3-methoxybenzenethiol, 4-ethoxybenzenethiol, 4-isopropoxybenzenethiol, 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-bis(mercaptomethyl)phenol, 1,3-bis(mercaptomethyl)phenol, 4-fluorobenzenethiol, 3-fluorobenzenethiol, 4-chlorobenzenethiol, 3-chlorobenzenethiol, 4-bromobenzenethiol, 4-iodobenzenethiol, 3-bromobenzenethiol, 3,4-dichlorobenzenethiol, 3,5-dichlorobenzenethiol, 3,4-difluorobenzenethiol, 3,5-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.

[0594] In addition, as sulfur-containing compounds having a mercapto group, examples include compounds containing a nitrogen-containing aromatic heterocycle substituted with a mercapto group and tautomers of compounds containing a nitrogen-containing aromatic heterocycle substituted with a mercapto group.

[0595] As preferred specific examples of the nitrogen-containing aromatic heterocycle, examples 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.

[0596] As preferred specific examples of nitrogen-containing heterocyclic compounds and tautomers of nitrogen-containing heterocyclic compounds that are suitably sulfur-containing compounds, the following compounds can be cited.

[0597]

Chemical formula 73

[0598]

[0599] When the photosensitive resin composition contains a sulfur-containing compound (E), the amount used 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, relative to 100 parts by mass of the total mass of the resin (B) and the alkali-soluble resin (D).

[0600] <Acid Diffusion Inhibitor (F)>

[0601] In order to improve the shape of the resist pattern used as a casting mold, or the static stability of the photosensitive resin film, the photosensitive resin composition preferably further contains an acid diffusion inhibitor (F). As the acid diffusion inhibitor (F), a nitrogen-containing compound (F1) is preferred, and an organic carboxylic acid, or an oxyacid of phosphorus or a derivative thereof (F2) can be further contained as needed.

[0602] [Nitrogen-containing compounds (F1)]

[0603] 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'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N 1,1-dimethylacetamide, 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-tris(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.

[0604] In addition, commercially available hindered amine compounds such as ADK STAB LA-52, ADK STAB LA-57, ADK STAB LA-63P, ADK STAB LA-68, ADK STAB LA-72, ADK STAB LA-77Y, ADK STAB LA-77G, ADK STAB LA-81, ADK STAB LA-82 and ADK STAB LA-87 (all manufactured by ADEKA Corporation) or 4-hydroxy-1,2,2,6,6-pentamethylpiperidine derivatives, or pyridines obtained by replacing the 2,6-positions 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).

[0605] The nitrogen-containing compound (F1) is usually used in an amount of 0 to 5 parts by mass, particularly preferably 0 to 3 parts by mass, based on 100 parts by mass of the total mass of the resin (B) and the alkali-soluble resin (D).

[0606] [Organic carboxylic acid, or phosphorus oxoacid or its derivative (F2)]

[0607] Among the organic carboxylic acids, or phosphorus oxyacids or derivatives thereof (F2), the organic carboxylic acid is preferably malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, etc., and particularly preferably salicylic acid.

[0608] As the oxyacid of phosphorus or its derivative, phosphoric acid, di-n-butyl phosphate, diphenyl phosphate and other phosphoric acid and their ester derivatives; phosphonic acid, dimethyl phosphonate, di-n-butyl phosphonate, phenylphosphonic acid, diphenyl phosphonate, dibenzyl phosphonate and other phosphonic acid and their ester derivatives; phosphinic acid, phenylphosphinic acid and other phosphinic acid and their ester derivatives, etc. can be cited. Among these, phosphonic acid is particularly preferred. They can be used alone or in combination of two or more.

[0609] The organic carboxylic acid, or phosphorus oxyacid or its derivative (F2) is usually used in a range of 0 to 5 parts by mass, and particularly preferably in a range of 0 to 3 parts by mass, based on 100 parts by mass of the total mass of the resin (B) and the alkali-soluble resin (D).

[0610] In order to form a salt and stabilize it, the organic carboxylic acid, or phosphorus oxoacid or its derivative (F2) is preferably used in an amount equivalent to that of the nitrogen-containing compound (F1).

[0611] <Organic Solvent (S)>

[0612] The photosensitive resin composition preferably contains an organic solvent (S). The type of the organic solvent (S) is not particularly limited within the range not hindering the purpose of the present invention, and an organic solvent (S) can be appropriately selected and used from organic solvents conventionally used for positive photosensitive resin compositions.

[0613] Specific examples of the organic solvent (S) include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; polyols such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, and monophenyl ether of ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, and dipropylene glycol monoacetate, and their derivatives; cyclic ethers such as dioxane; ethyl formate, methyl lactate, ethyl lactate, acetic acid Esters such as methyl ester, ethyl acetate, butyl acetate, 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-methylbutyrate, 3-methoxybutyl acetate, and 3-methyl-3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene, etc. These may be used alone or in combination of two or more.

[0614] The content of the organic solvent (S) is not particularly limited within the scope of not hindering the purpose of the present invention. When the photosensitive resin composition is used for thick film applications such as making the film thickness of the photosensitive resin layer obtained by spin coating method reach 5 μm or more, it is preferred to use the organic solvent (S) so that the solid content concentration of the photosensitive resin composition is within the range of 30 mass % to 70 mass %.

[0615] <Other ingredients>

[0616] In order to improve plasticity, the photosensitive resin composition may also contain a polyethylene resin. Specific examples of the polyethylene resin include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinyl benzoic acid, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl phenol and copolymers thereof. From the viewpoint of a lower glass transition point, the polyethylene resin is preferably polyvinyl methyl ether.

[0617] Furthermore, in order to improve the adhesion between the mold formed using the photosensitive resin composition and the metal substrate, the photosensitive resin composition may further contain an adhesion aid.

[0618] The photosensitive resin composition may further contain a surfactant in order to improve coating properties, defoaming properties, leveling properties, etc. As the surfactant, for example, a fluorine-based surfactant or a silicone-based surfactant is preferably used.

[0619] Specific examples of the fluorine-based surfactant include commercially available fluorine-based surfactants such as BM-1000, BM-1100 (all manufactured by BM Chemical Co., Ltd.), MEGAFAC F142D, MEGAFAC F172, MEGAFAC F173, MEGAFAC F183 (all manufactured by Dainippon Ink & Chemicals Co., Ltd.), Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431 (all manufactured by Sumitomo 3M Co., Ltd.), 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, and SF-8428 (all manufactured by Toray Silicone Co., Ltd.), but are not limited to these.

[0620] As the silicone-based surfactant, unmodified silicone-based surfactants, polyether-modified silicone-based surfactants, polyester-modified silicone-based surfactants, alkyl-modified silicone-based surfactants, aralkyl-modified silicone-based surfactants, reactive silicone-based surfactants, and the like can be preferably used.

[0621] As the silicone surfactant, a commercially available silicone surfactant can be used. Specific examples of commercially available silicone surfactants include PAINTADD M (manufactured by Toray Dow Corning Co., Ltd.), Topica K1000, Topica K2000, Topica K5000 (all manufactured by Takachiho Sangyo Co., Ltd.), XL-121 (polyether-modified silicone surfactant, manufactured by Clariant), BYK-310 (polyester-modified silicone surfactant, manufactured by BYK Chemical Co., Ltd.), etc.

[0622] Furthermore, in order to finely adjust the solubility in a developer, the photosensitive resin composition may further contain an acid, an acid anhydride, or a high-boiling-point solvent.

[0623] Specific examples of the acid and the acid anhydride include: monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid, and cinnamic acid; hydroxymonocarboxylic 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, and syringic acid; 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, Polycarboxylic acids such as 2,4-cyclohexanetricarboxylic acid, butanetetracarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid; anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenylsuccinic anhydride, tricarboxylic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, 1,2,3,4-butanetetracarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol ditrimellitic anhydride, glycerol trimellitic anhydride, etc.

[0624] In addition, specific examples of high boiling point solvents include N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonylacetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol phenyl ether acetate.

[0625] Furthermore, the photosensitive resin composition may further contain a sensitizer in order to improve sensitivity. In the present specification, the sensitizer is defined as a compound other than the phenolic hydroxyl group-containing low molecular compound (C).

[0626] In the photosensitive resin composition, as a resin, a resin (B) is included as an essential component, and a resin other than the resin (B) such as an alkali-soluble resin (D) is also included as needed. In addition, in the specification and claims of the present application, "resin" refers to a polymer compound having a mass average molecular weight exceeding 1500, and is a polymer obtained by polymerizing a monomer compound. The mass average molecular weight is a mass average molecular weight based on polystyrene conversion by GPC (gel permeation chromatography).

[0627] Furthermore, in the photosensitive resin composition, the ratio of the acrylic resin to the total of the resin (B) and the resins other than the resin (B) is 70% by mass or more. The ratio of the acrylic resin to the total of the resin (B) and the resins other than the resin (B) is preferably 80% by mass or more, and more preferably 90% by mass or more.

[0628] The acrylic resin may be either resin (B) or a resin other than resin (B), but preferably resin (B) contains an acrylic resin. The ratio of the acrylic resin contained in resin (B) to resin (B) is preferably 70% by mass or more.

[0629] The “resin other than the resin (B)” is a resin other than the resin (B) contained in the photosensitive resin composition. For example, the alkali-soluble resin (D) and the polyethylene resin as a plasticizer belong to the “resin other than the resin (B)”.

[0630] “The total of resin (B) and resins other than resin (B)” refers to the total of resins contained in the photosensitive resin composition. For example, when the resin contained in the photosensitive resin composition is only resin (B), “the total of resin (B) and resins other than resin (B)” is only “resin (B)”. In addition, when the resins contained in the photosensitive resin composition are resin (B) and the alkali-soluble resin (D), “the total of resin (B) and resins other than resin (B)” is “the total of resin (B) and alkali-soluble resin (D)”. In addition, when the resins contained in the photosensitive resin composition are resin (B), the alkali-soluble resin (D), and resins other than resin (B) and alkali-soluble resin (D), “the total of resin (B) and resins other than resin (B)” is the total of resin (B), alkali-soluble resin (D), and resins other than resin (B) and alkali-soluble resin (D).

[0631] Thus, in a chemically amplified positive photosensitive resin composition comprising an acid generator (A) that generates an acid by irradiation with active light or radiation and a resin (B) whose solubility in alkali increases due to the action of the acid, by containing a specific acid generator and setting the content of the acrylic resin relative to the total of the resin (B) and the resin other than the resin (B) within a specific range, as shown in the Examples described below, a chemically amplified positive photosensitive resin composition that is suitable for exposure using h-lines and that easily forms a resist pattern that is excellent in plating solution resistance and crack resistance can be obtained. In addition, the cross-sectional shape of the resist pattern is also good.

[0632] The photosensitive resin composition of the present invention, which is suitable for exposure using h-line and easily forms a resist pattern having excellent plating solution resistance and crack resistance, is used to prepare a mold for forming a plated object by embedding metal in a substrate having a metal surface by plating.

[0633] Since the photosensitive resin composition has the above-mentioned specific composition, it is applicable to exposure using h-line. Therefore, the photosensitive resin composition can be preferably used to prepare a mold for forming a plated pattern on a panel-level substrate that is generally larger in area than a wafer.

[0634] When the area of ​​the substrate is large, the plating conditions sometimes become too harsh compared to the case where the area of ​​the substrate is small. If the area of ​​the substrate is large, there is a tendency for the stress applied to the substrate, the mold, the plated molded object, etc. to increase. For panel-level substrates, the shape of the main surface to which the photosensitive resin composition is applied is mostly rectangular. When the shape of the panel is rectangular, the stress is prone to deviation compared to the circular shape. Therefore, in the case of a substrate with a large applicable area or a rectangular substrate, the photosensitive resin composition is further required to have plating solution resistance and crack resistance.

[0635] Since the photosensitive resin composition is suitable for exposure using h-lines and has excellent resistance to plating solutions and cracks, it can be particularly preferably used as a chemically amplified positive photosensitive resin composition as follows: a chemically amplified positive photosensitive resin composition used to form a mold for a plated object by embedding metal by plating on a substrate having a large area or a rectangular substrate and having a metal surface.

[0636] <Method for preparing chemically amplified positive photosensitive resin composition>

[0637] The chemically amplified positive photosensitive resin composition is prepared by mixing and stirring the above components in a common manner. As an apparatus that can be used when mixing and stirring the above components, a dissolver, a homogenizer, a three-roll mill, etc. can be mentioned. After the above components are uniformly mixed, the obtained mixture can be further filtered using a sieve, a membrane filter, etc.

[0638] 《Photosensitive dry film》

[0639] The photosensitive dry film comprises a base film and a photosensitive resin layer formed on the surface of the base film, and the photosensitive resin layer is composed of the above-mentioned photosensitive resin composition.

[0640] The substrate film preferably has light transmittance. Specifically, polyethylene terephthalate (PET) film, polypropylene (PP) film, polyethylene (PE) film, etc. can be cited. From the perspective of achieving an excellent balance between light transmittance and breaking strength, polyethylene terephthalate (PET) film is preferred.

[0641] The photosensitive resin composition is applied onto a substrate film to form a photosensitive resin layer, thereby manufacturing a photosensitive dry film.

[0642] When forming a photosensitive resin layer on a substrate film, a photosensitive resin composition is applied and dried using a coater, a rod coater, a wire bar coater, a roll coater, a curtain coater, etc., so that the film thickness after drying on the substrate film is preferably from 0.5 μm to 300 μm, more preferably from 1 μm to 300 μm, and particularly preferably from 3 μm to 100 μm.

[0643] The photosensitive dry film may further have a protective film on the photosensitive resin layer. Examples of the protective film include polyethylene terephthalate (PET) film, polypropylene (PP) film, polyethylene (PE) film and the like.

[0644] "Method for producing patterned resist film and substrate with mold"

[0645] The method for forming a patterned resist film on a substrate using the photosensitive resin composition described above is not particularly limited. The patterned resist film is used as a mold for forming a plated object.

[0646] As a suitable method, a method for producing a patterned resist film including the following steps can be mentioned:

[0647] A lamination step of laminating a photosensitive resin layer composed of a photosensitive resin composition on the substrate;

[0648] An exposure step of selectively irradiating the photosensitive resin layer with active light or radiation to perform exposure;

[0649] In the development step, the exposed photosensitive resin layer is developed.

[0650] The method for manufacturing a molded substrate having a mold for forming a plated object is the same as the method for manufacturing a patterned resist film, except that it includes a step of stacking a photosensitive resin layer on the metal surface of a substrate having a metal surface, and using development in a development step to produce the mold for forming the plated object.

[0651] As the substrate on which the photosensitive resin layer is laminated, a substrate having a metal surface can be used. The metal species constituting the metal surface is preferably copper, gold, or aluminum, and more preferably copper.

[0652] For example, a photosensitive resin layer is stacked on a substrate in the following manner. That is, a liquid photosensitive resin composition is applied to the substrate, and the solvent is removed by heating to form a photosensitive resin layer of a desired film thickness. As long as a resist pattern as a mold can be formed with a desired film thickness, the thickness of the photosensitive resin layer is not particularly limited. The film thickness of the photosensitive resin layer is not particularly limited, and 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.

[0653] As a coating method for coating the photosensitive resin composition on the substrate, a spin coating method, a slit coating method, a roll coating method, a screen printing method, an applicator method, etc. can be used. Preferably, the photosensitive resin layer is pre-baked. The pre-baking conditions vary depending on the type of each component in the photosensitive resin composition, the blending ratio, the coating film thickness, etc., but are generally performed at 70°C to 200°C, preferably 80°C to 150°C, for about 2 minutes to 120 minutes.

[0654] The photosensitive resin layer formed as described above is selectively irradiated (exposed) with active light or radiation, such as ultraviolet light or visible light with a wavelength of 300 nm to 500 nm, through a mask of a predetermined pattern. The active light or radiation irradiated preferably includes light (h-line) with a wavelength of 405 nm, for example, broadband light of a mercury lamp including h-line, bandpass h-line single light, and gh-line.

[0655] By using the above-mentioned chemically amplified positive photosensitive resin composition, it is possible to form a resist pattern with excellent plating solution resistance and crack resistance using an h-line that can be applied to large-area panel-level packaging. The above-mentioned chemically amplified positive photosensitive resin composition contains at least one selected from the compound represented by formula (a1-i) or formula (a1-ii), the compound represented by formula (a2-i) or formula (a2-ii), and the compound represented by formula (a3-i) or formula (a3-ii) as an acid generator (A) and a resin (B) whose solubility in alkali is increased by the action of an acid, and the ratio of the acrylic resin to the total of the resin (B) and the resin other than the resin (B) is 70% by mass or more.

[0656] As the radiation source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon laser, etc. can be used. In addition, the radiation includes microwaves, infrared rays, visible rays, ultraviolet rays, X-rays, gamma rays, electron rays, proton rays, neutron rays, ion rays, etc. The radiation exposure amount varies depending on the composition of the photosensitive resin composition, the film thickness of the photosensitive resin layer, etc. For example, when an ultra-high-pressure mercury lamp is used, it is 100 mJ / cm 2 Above 10000mJ / cm2 Hereinafter, in order to generate an acid, the radiation includes light that activates the acid generator (A).

[0657] After the exposure, the photosensitive resin layer is heated by a known method to promote the diffusion of the acid, thereby changing the alkali solubility of the photosensitive resin layer in the exposed portion of the photosensitive resin film.

[0658] Next, the exposed photosensitive resin layer is developed according to a conventionally known method to dissolve and remove unnecessary portions, thereby forming a mold for forming a predetermined resist pattern or a plated object. At this time, an alkaline aqueous solution can be used as a developer.

[0659] As the developer, for example, aqueous solutions of alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, 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, etc. can be used. In addition, aqueous solutions prepared by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the above-mentioned aqueous alkali solution can also be used as the developer.

[0660] The development time varies depending on the composition of the photosensitive resin composition, the thickness of the photosensitive resin layer, etc., but is usually between 1 minute and 30 minutes. The development method may be any of a liquid development method, an immersion method, a static (puddle) development method, and a spray development method.

[0661] After development, washing with running water for 30 to 90 seconds is performed, and drying is performed using an air gun, an oven, etc. In this way, a resist pattern patterned into a desired shape is formed on the metal surface of the substrate having a metal surface. In addition, in this way, a molded substrate having a resist pattern as a mold can be produced on the metal surface of the substrate having a metal surface.

[0662] The film thickness of the resist pattern (patterned resist film) formed using the photosensitive resin composition is not particularly limited, and both thick films and thin films can be applied. The photosensitive resin composition is preferably used to form a thick film resist pattern. The film thickness of the resist pattern formed using the photosensitive resin composition is preferably 0.5 μm or more, more preferably 0.5 μm or more and 300 μm or less, further preferably 0.5 μm or more and 200 μm or less, and particularly preferably 0.5 μm or more and 150 μm or less.

[0663] The upper limit of the film thickness may be, for example, 100 μm or less, and the lower limit of the film thickness may be, for example, 1 μm or more, or 3 μm or more.

[0664] 《Method for manufacturing plated shaped objects》

[0665] In the non-resist part (the part removed by the developer) in the casting mold of the casting mold substrate formed by the above method, a conductor such as a metal is embedded in the casting mold by plating, so that a connection terminal such as a bump and a metal column or a plated molding such as a Cu rewiring can be formed. In addition, the plating treatment method is not particularly limited, and various methods known in the past can be adopted. As the plating solution, it is particularly suitable to use a solder plating solution, a copper plating solution, a gold plating solution, and a nickel plating solution. The remaining casting mold is removed at the end using a stripping solution according to the usual method. The resist pattern obtained by the above method can suppress the change of the shape of the resist pattern before and after the plating treatment because the plating solution has excellent resistance. Therefore, a plated molding of a desired shape can be obtained.

[0666] When manufacturing a plated shaped object, it is sometimes preferable to perform an ashing treatment on the metal surface exposed in the non-pattern portion of the resist pattern of the mold for forming the plated shaped object.

[0667] Specifically, for example, a pattern formed using a photosensitive resin composition containing a sulfur-containing compound (E) is used as a mold to form a plated object. In this case, the adhesion of the plated object to the metal surface is sometimes easily impaired. This disadvantage is more significant when using the sulfur-containing compound (E) represented by the formula (e1) or the sulfur-containing compound (E) represented by the formula (e4).

[0668] However, if the above-mentioned ashing treatment is performed, even if a pattern formed using a photosensitive resin composition containing a sulfur-containing compound (E) is used as a mold, a plated molded product that adheres well to a metal surface can be easily formed.

[0669] In addition, when a compound containing a nitrogen-containing aromatic heterocycle substituted with a mercapto group is used as the sulfur-containing compound (E), the above-mentioned problem related to the adhesion of the plated shaped object hardly occurs or is mild. Therefore, when a compound containing a nitrogen-containing aromatic heterocycle substituted with a mercapto group is used as the sulfur-containing compound (E), a plated shaped object with good adhesion to the metal surface can be easily formed even without ashing treatment.

[0670] The ashing treatment is not particularly limited as long as it is a method that does not cause damage to the extent that a plated object of a desired shape cannot be formed on a resist pattern serving as a mold for forming a plated object.

[0671] As a preferable ashing method, a method using oxygen plasma can be cited. In order to ash the metal surface on the substrate using oxygen plasma, it is only necessary to generate oxygen plasma using a known oxygen plasma generation device and irradiate the oxygen plasma onto the metal surface on the substrate.

[0672] In the gas used for generating oxygen plasma, various gases that have been conventionally used together with oxygen for plasma processing can be mixed within a range that does not hinder the object of the present invention. As such gases, for example, nitrogen gas, hydrogen gas, and CF4 gas can be cited.

[0673] The ashing conditions using oxygen plasma are not particularly limited as long as they are within a range that does not hinder the object of the present invention. 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.

[0674] By setting the processing time using oxygen plasma within the above range, it is easy to exhibit the effect of improving the adhesion of the plating molded object without changing the shape of the resist pattern.

[0675] According to the above method, since the h-line applicable to panel-level packaging for a large area can be used and a resist pattern excellent in plating solution resistance and crack resistance can be used as a mold for forming a plating molded object, not only on the wafer level but also on the large-area panel level, or not only for a substrate having a circular main surface but also for a substrate having a shape other than a circular shape, such as a rectangular main surface, a plating molded object having a desired shape can be manufactured.

[0676] Examples

[0677] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

[0678] [Preparation Example 1]

[0679] (Synthesis of mercapto compound T2)

[0680] In Preparation Example 1, a mercapto compound T2 having the following structure was synthesized as the sulfur-containing compound (E).

[0681] [Chemical Formula 74]

[0682]

[0683] 15.00 g of 7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride and 150.00 g of tetrahydrofuran were added to a flask and stirred. Then, 7.64 g of thioacetic acid (AcSH) was added to the flask, and the mixture was stirred at room temperature for 3.5 hours. Then, the reaction solution was concentrated to obtain 22.11 g of 5-acetylthio-7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride.

[0684] After adding 22.11 g of 5-acetylthio-7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride and 30.11 g of a 10% by mass aqueous sodium hydroxide solution to the flask, the contents of the flask were stirred at room temperature for 2 hours. Then, 20% by mass hydrochloric acid (80.00 g) was added to the flask to make the reaction solution acidic. Then, extraction was performed 4 times with 200 g of ethyl acetate to obtain an extract containing the mercapto compound T2. For the residue recovered by concentrating the extract, 25.11 g of tetrahydrofuran (THF) was added to dissolve it. Heptane was added dropwise to the obtained THF solution to precipitate the mercapto compound T2, and the precipitated mercapto compound T2 was recovered by filtration. The 1 The measurement results of 1H-NMR of the mercapto compound T2 are described below.

[0685] 1 1H-NMR (DMSO-d6): δ 12.10 (s, 2H), 4.72 (d, 1H), 4.43 (s, 1H), 3.10 (t, 1H), 3.01 (d, 1H), 2.85 (d, 1H), 2.75 (d, 1H), 2.10 (t, 1H), 1.40 (m, 1H)

[0686]

Chemical formula 75

[0687]

[0688] 〔Examples 1 to 19 and Comparative Examples 1 to 5〕

[0689] In Examples 1 to 19 and Comparative Examples 1 to 5, the compounds PAG1 and PAG2 of the following formula were used as the acid generator (A).

[0690]

Chemical formula 76

[0691]

[0692] In Examples 1 to 19 and Comparative Examples 1 to 5, the following Acryl-1 to Acryl-11, PHS-1, and PHS-2 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 formula represent the content (mol%) of the structural unit in each resin. Since Acryl-1 to Acryl-11 contain 70 mol% or more of structural units derived from (meth)acrylic acid or (meth)acrylic acid derivatives, that is, acrylic structural units, they are acrylic resins (B3). In addition, PHS-1 and PHS-2 are polyhydroxystyrene resins (B2).

[0693] The weight-average molecular weight Mw of Acryl-1 to Acryl-7 is 40,000. Acryl-8 to Acryl-11 are resins having the same structural unit and composition ratio as Acryl-1 but different weight-average molecular weights. The weight-average molecular weight of Acryl-8 is 10,000, the weight-average molecular weight of Acryl-9 is 20,000, the weight-average molecular weight of Acryl-10 is 80,000, and the weight-average molecular weight of Acryl-11 is 120,000. In addition, the molecular weight distribution coefficient (Mw / Mn) of Acryl-1 to Acryl-11 is 2.6 for all of them.

[0694] In addition, the weight-average molecular weight Mw of PHS-1 is 10,000, and the molecular weight distribution coefficient (Mw / Mn) is 2.1. The weight-average molecular weight Mw of PHS-2 is 11,500, and the molecular weight distribution coefficient (Mw / Mn) is 1.08.

[0695]

Chemical formula 77

[0696]

[0697]

Chemical formula 78

[0698]

[0699]

Chemical formula 79

[0700]

[0701] As the low-molecular compound (C) containing a phenolic hydroxyl group, the following compound C1 was used.

[0702]

Chemical formula 80

[0703]

[0704] As the alkali-soluble resin (D), the following PHS-3 (polyhydroxystyrene resin) and Novolak-1 (phenolic varnish resin (meta-cresol monocondensate)) were used. The numbers on the lower right of the brackets in each structural unit in the following structural formula represent the content (mol %) of the structural unit in each resin. The mass average molecular weight (Mw) of PHS-3 is 2500, and the molecular weight distribution coefficient (Mw / Mn) is 2.4. The mass average molecular weight (Mw) of Novolak-1 is 8000.

[0705]

Chemistry 81

[0706]

[0707]

Chemistry 82

[0708]

[0709] As the sulfur-containing compound (E), the following sulfur-containing compounds T1 to T3 were used.

[0710]

Chemistry 83

[0711]

[0712] As the acid diffusion inhibitor (F), the following Amine-1 to Amine-3 were used.

[0713] Amine-1: ADK STAB LA-63P (made by ADEKA)

[0714] Amine-2: Diphenylpyridine

[0715] Amine-3: Triphenylpyridine

[0716] The types and amounts of the acid generator (A), resin (B), low molecular weight compound containing phenolic hydroxyl group (C), alkali soluble resin (D), sulfur compound (E), acid diffusion inhibitor (F) and surfactant (BYK310, manufactured by BYK Chemie) described in Tables 1 and 2 were dissolved in 3-methoxybutyl acetate (MA) to obtain the photosensitive resin compositions of each example and comparative example. In addition, the surfactant (BYK310, manufactured by BYK Chemie) was added in an amount of 0.05 parts by mass relative to the total amount of the resin (B) and the alkali soluble resin (D). The photosensitive resin compositions of Examples 1 to 18 and Comparative Examples 1 to 5 were prepared in a solid content concentration of 40% by mass. In addition, the photosensitive resin composition of Example 19 was prepared in a solid content concentration of 53% by mass. In addition, the ratio of the acrylic resin to the total of the resin (B) and the resin other than the resin (B) is described in the "Ratio of acrylic resin (% by mass)" column of Tables 1 and 2.

[0717] The photosensitive resin composition obtained was used to evaluate the formation of a resist pattern, the shape and crack resistance of the resist pattern, and the shape after immersion in a copper sulfate plating solution according to the following method. In addition, for Examples 1 to 18 and Comparative Examples 1 to 5, the evaluation was performed at a film thickness of 7 μm. On the other hand, for Example 19, the evaluation was performed at a film thickness of 55 μm. These evaluation results are recorded in Tables 1 and 2.

[0718] (Formation of a resist pattern for evaluation with a film thickness of 7 μm)

[0719] A substrate having a sputtered copper layer on the surface of a glass substrate having a diameter of 500 mm was prepared, and the photosensitive resin compositions of Examples 1 to 18 and Comparative Examples 1 to 5 were coated on the copper layer of the substrate to form a photosensitive resin layer having a film thickness of 7 μm. Next, the photosensitive resin layer was pre-baked at 130°C for 5 minutes. After pre-baking, a mask having a line and space pattern with a line width of 2 μm and a spacing width of 2 μm and an exposure device Prisma GHI5452 (manufactured by Ultratech) equipped with an i-line filter were used to expose the pattern using gh lines at an exposure amount of 1.2 times the minimum exposure amount that can form a pattern of a specified size until a spacing of 2.5 μm was formed. Next, the substrate was placed on a hot plate and subjected to post-exposure heating (PEB) at 90°C for 1.5 minutes. Then, the following operation was repeated twice in total: a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (developer, NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was dropped onto the exposed photosensitive resin layer and then allowed to stand at 23° C. for 30 seconds. Thereafter, the surface of the resist pattern was cleaned (rinsed) with running water and nitrogen gas was blown to obtain a resist pattern.

[0720] (Formation of a resist pattern for evaluation with a film thickness of 55 μm)

[0721] A substrate having a sputtered copper layer on the surface of a glass substrate having a diameter of 500 mm was prepared, and the photosensitive resin composition of Example 19 was coated on the copper layer of the substrate to form a photosensitive resin layer having a film thickness of 55 μm. Next, the photosensitive resin layer was pre-baked at 100°C for 5 minutes. After pre-baking, a mask capable of forming a square pattern of a rectangular opening of 30 μm×30 μm and an exposure device Prisma GHI5452 (manufactured by Ultratech) equipped with an i-line filter were used to expose the pattern by gh lines at an exposure amount of 1.2 times the minimum exposure amount that can form a pattern of a specified size until a rectangular opening with one side of 35 μm was formed. Next, the substrate was placed on a hot plate and subjected to post-exposure heating (PEB) at 100°C for 3 minutes. Then, the following operation was repeated 4 times in total: a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (developer, NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was dropped onto the exposed photosensitive resin layer and then allowed to stand at 23° C. for 60 seconds. Thereafter, the surface of the resist pattern was cleaned (rinsed) with running water and nitrogen gas was blown to obtain a resist pattern.

[0722] [Evaluation of Resist Pattern Shape]

[0723] The cross-sectional shape of the resist pattern was observed using a scanning electron microscope, and the cross-sectional shape of the pattern was evaluated. Specifically, when the width of the opposite surface (top surface) of the surface of the resist pattern in contact with the substrate was set to Wt, and the pattern width in the middle part of the thickness direction of the cross section of the resist pattern was set to Wm, the case where Wm was within ±10% of Wt was evaluated as ○, and the case where Wm was outside the range of ±10% of Wt was evaluated as ×. In addition, in all embodiments, the pattern width in the middle part of the thickness direction of the cross section of the resist pattern was almost the same as the width of the surface (bottom surface) of the cross section of the resist pattern in contact with the substrate.

[0724] [Evaluation of Crack Resistance of Resist Pattern]

[0725] For the substrate formed with the resist pattern, a hot and cold shock test was carried out with a hot and cold shock device (TSA-103EL from Espec Corporation) with 60°C for 5 minutes and -5°C for 5 minutes as one cycle. The resist pattern was observed at 10 locations with an optical microscope at a magnification of 10 times. The case where cracks were observed in the first cycle was evaluated as ×, the case where cracks were first observed in the second cycle was evaluated as △, the case where cracks were first observed in the third cycle was evaluated as ○, and the case where no cracks were observed until the fourth cycle was evaluated as ◎.

[0726] [Evaluation of the Plating Solution Resistance of the Resist Pattern]

[0727] The resist pattern was immersed in a copper sulfate plating solution (UTB-W30 manufactured by Ishihara Chemical Co., Ltd.) at 28° C. together with the substrate. The cross-sectional shape of the resist pattern after immersion was observed with a scanning electron microscope, and the cross-sectional shape of the pattern was evaluated.

[0728] Specifically, the case where no shape change of the resist pattern was observed before and after the immersion for 30 minutes was evaluated as ◎, the case where no shape change of the resist pattern was observed during the immersion for 15 minutes but the resist pattern was dissolved in the plating solution during the immersion for 30 minutes was evaluated as ○, and the case where the resist pattern was dissolved in the plating solution during the immersion for 15 minutes was evaluated as ×.

[0729]

Table 1

[0730]

[0731]

Table 2

[0732]

[0733] According to Examples 1 to 19, it can be seen that a positive photosensitive resin composition containing at least one selected from a compound represented by formula (a1-i) or (a1-ii), a compound represented by formula (a2-i) or (a2-ii), and a compound represented by formula (a3-i) or (a3-ii) as an acid generator (A) that generates an acid by irradiation with active light or radiation, and a resin (B) whose solubility in alkali increases due to the action of the acid, and an acrylic resin with a ratio of 70% by mass or more relative to the total of the resin (B) and the resin other than the resin (B), can form a resist pattern by h-line exposure, and the formed resist pattern has excellent plating solution resistance and crack resistance. In addition, it can be seen that the cross-sectional shape of the resist pattern is good.

[0734] On the other hand, according to Comparative Examples 1 to 5, although the positive photosensitive resin composition contains formula (a1-i) or formula (a2-i) as the acid generator (A), when the proportion of the acrylic resin is less than 70% by mass, the plating solution resistance and crack resistance of the resist pattern are inferior to those of Examples 1 to 19.

[0735] [Reference Example (Example)]

[0736] In Examples 1 to 21, compounds PAG1 and PAG2 represented by the following formulae were used as the acid generator (A).

[0737]

Chemistry 84

[0738]

[0739] In Reference Examples 1 to 21, the following Resin-A1 to Resin-A4 are used as resins (resins (B)) whose solubility in alkali increases due to the action of acid. The numbers on the lower right of the brackets in each structural unit in the following structural formula represent the content (mass %) of the structural unit in each resin. The mass average molecular weight Mw of resin Resin-A1 is 80,000, and the molecular weight distribution coefficient (Mw / Mn) is 2.6. The mass average molecular weight Mw of resin Resin-A2 is 80,000, and the molecular weight distribution coefficient (Mw / Mn) is 2.6. The mass average molecular weight Mw of resin Resin-A3 is 98,000. The mass average molecular weight Mw of resin Resin-A4 is 11,500, and the molecular weight distribution coefficient (Mw / Mn) is 1.08.

[0740]

Chemistry 85

[0741]

[0742] As the phenolic hydroxyl group-containing low-molecular compound (C), the following compound C1 was used.

[0743]

Chemistry 86

[0744]

[0745] As the alkali-soluble resin (D), the following Resin-B (polyhydroxystyrene resin) and Resin-C (phenolic varnish resin (meta-cresol monocondensate)) are used. The numbers on the lower right of the brackets in each structural unit in the following structural formula represent the content (mass %) of the structural unit in each resin. The mass average molecular weight (Mw) of the resin Resin-B is 2500, and the molecular weight distribution coefficient (Mw / Mn) is 2.4. The mass average molecular weight (Mw) of the resin Resin-C is 8000.

[0746]

Chemistry 87

[0747]

[0748]

Chemistry 88

[0749]

[0750] As the sulfur-containing compound (E), the following sulfur-containing compounds T1 to T3 were used.

[0751]

Chemistry 89

[0752]

[0753] As the acid diffusion inhibitor (F), the following Amine-1 to Amine-3 were used.

[0754] Amine-1: ADK STAB LA-63P (made by ADEKA)

[0755] Amine-2: Diphenylpyridine

[0756] Amine-3: Triphenylpyridine

[0757] The types and amounts of the acid generator (A), resin (B), phenolic hydroxyl group-containing low molecular weight compound (C), alkali-soluble resin (D), sulfur-containing compound (E), acid diffusion inhibitor (F) and surfactant (BYK310, manufactured by BYK Chemie) described in Tables 3 and 4 were dissolved in a mixed solvent of 3-methoxybutyl acetate (MA) and propylene glycol monomethyl ether acetate (PM) (MA / PM=6 / 4 (mass ratio)) to obtain the photosensitive resin composition of each reference example. In addition, the surfactant (BYK310, manufactured by BYK Chemie) was added so as to be 0.05 parts by mass relative to the total amount of the resin (B) and the phenolic hydroxyl group-containing low molecular weight compound (C).

[0758] The photosensitive resin compositions of Reference Examples 1 to 9 used in the evaluation at a film thickness of 55 μm described below were prepared to have a solid content concentration of 50 mass %. The photosensitive resin compositions of Reference Examples 10 to 21 used in the evaluation at a film thickness of 7 μm were prepared to have a solid content concentration of 40 mass %.

[0759] The obtained photosensitive resin composition was used to evaluate the shape after immersion in a copper sulfate plating solution according to the following method. In addition, for reference examples 1 to 9, the evaluation was performed at a film thickness of 55 μm. On the other hand, for reference examples 10 to 21, the evaluation was performed at a film thickness of 7 μm. These evaluation results are recorded in Tables 3 and 4.

[0760] [Evaluation of shape]

[0761] (Evaluation at a film thickness of 55 μm)

[0762] A substrate having a sputtered copper layer on the surface of a glass substrate with a diameter of 500 mm was prepared, and the photosensitive resin composition of the reference example was coated on the copper layer of the substrate to form a photosensitive resin layer with a film thickness of 55 μm. Next, the photosensitive resin layer was pre-baked at 100°C for 5 minutes. After pre-baking, a mask capable of forming a square pattern of a rectangular opening of 30 μm × 30 μm and an exposure device Prisma GHI5452 (manufactured by Ultratech) equipped with an i-line filter were used to expose the pattern by gh lines at an exposure amount of 1.2 times the minimum exposure amount that can form a pattern of a specified size until a rectangular opening with one side of 35 μm was formed. Next, the substrate was placed on a hot plate and subjected to post-exposure heating (PEB) at 100°C for 3 minutes. Then, the following operation was repeated 4 times in total: a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (developer, NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was dropped onto the exposed photosensitive resin layer and then allowed to stand at 23° C. for 60 seconds. Thereafter, the surface of the resist pattern was cleaned (rinsed) with running water and nitrogen gas was blown to obtain a resist pattern.

[0763] The obtained resist pattern and the substrate were immersed in a 28° C. copper sulfate plating solution (UTB-W30 manufactured by Ishihara Chemical Co., Ltd.) for 10 minutes. The cross-sectional shape of the resist pattern after immersion was observed with a scanning electron microscope, and the cross-sectional shape of the pattern was evaluated.

[0764] Specifically, the case where no change was observed in the resist pattern before and after the immersion was evaluated as "○", and the case where the resist pattern was dissolved in the plating solution and corrosion was observed in the resist pattern was evaluated as "×".

[0765] (Evaluation at a film thickness of 7 μm)

[0766] A substrate having a sputtered copper layer on the surface of a glass substrate with a diameter of 500 mm was prepared, and the photosensitive resin composition of the reference example was coated on the copper layer of the substrate to form a photosensitive resin layer with a film thickness of 7 μm. Next, the photosensitive resin layer was pre-baked at 130°C for 5 minutes. After pre-baking, a mask with a line and space pattern with a line width of 2 μm and a spacing width of 2 μm and an exposure device Prisma GHI5452 (manufactured by Ultratech) equipped with an i-line filter were used to expose the pattern using gh lines at an exposure amount of 1.2 times the minimum exposure amount that can form a pattern of a specified size until a spacing of 2.2 μm is formed. Next, the substrate was placed on a hot plate and subjected to post-exposure heating (PEB) at 90°C for 1.5 minutes. Then, the following operation was repeated twice in total: a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (developer, NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was dropped onto the exposed photosensitive resin layer and then allowed to stand at 23° C. for 30 seconds. Thereafter, the surface of the resist pattern was cleaned (rinsed) with running water and nitrogen gas was blown to obtain a resist pattern.

[0767] The obtained resist pattern and the substrate were immersed in a 28° C. copper sulfate plating solution (UTB-W30 manufactured by Ishihara Chemical Co., Ltd.) for 10 minutes. The cross-sectional shape of the resist pattern after immersion was observed with a scanning electron microscope, and the cross-sectional shape of the pattern was evaluated.

[0768] Specifically, the case where no change was observed in the resist pattern before and after the immersion was evaluated as "○", and the case where the resist pattern was dissolved in the plating solution and corrosion was observed in the resist pattern was evaluated as "×".

[0769]

Table 3

[0770]

[0771]

Table 4

[0772]

[0773] According to reference examples 1 to 21, it can be seen that a positive photosensitive resin composition containing at least one selected from a compound represented by formula (a1-i) or formula (a1-ii), a compound represented by formula (a2-i) or formula (a2-ii), and a compound represented by formula (a3-i) or formula (a3-ii) as an acid generator (A) that generates an acid by irradiation with active light or radiation, and an acrylic resin as a resin (B) whose solubility in alkali increases due to the action of the acid, can form a resist pattern by h-line exposure, and the formed resist pattern has excellent plating solution resistance. In addition, it can be predicted that the crack resistance is excellent as in the above-mentioned embodiment. In addition, it can be predicted that the cross-sectional shape of the resist pattern is good as in the above-mentioned embodiment.

Claims

1. A chemically amplified positive photosensitive resin composition for use in producing a mold for a plated object formed by embedding a metal in a substrate having a metal surface by plating, comprising: an acid generator (A) that generates an acid by irradiation with active light or radiation, and a resin (B) whose solubility in alkali increases due to the action of the acid, characterized in that: The acid generator (A) comprises at least one compound selected from the following compounds: a compound represented by the following formula (a1-i) or the following formula (a1-ii), a compound represented by the following formula (a2-i) or the following formula (a2-ii), a compound represented by the following formula (a3-i) or the following formula (a3-ii), Formula (a1-i) or formula (a1-ii): 【Chemistry 1】 In formula (a1-i) and formula (a1-ii), X 1a is an oxygen atom or a sulfur atom, R 1a Select from the following groups: an aliphatic group having 1 to 18 carbon atoms which may be substituted with one or more halogen atoms; Containing -S-, -C(=O)-S-, -OS(=O)2-, -OC(=O)-O-, -C(=O)-NH-, -C(=O)-NR 10a - and -C(=O)-NR 10a R 11a At least one part of which is selected from the group consisting of an aliphatic group having 2 to 18 carbon atoms and which may be substituted with one or more halogen atoms; A group represented by the following formula (a11); 【Chemistry 2】 —R 3a —Ar (a11) A group represented by the following formula (a12); 【Chemistry 3】 and a group represented by the following formula (a13), 【Chemistry 4】 In the formula (a11), R 3a is a single bond or may contain -O-, -S-, -C(=O)-O-, -C(=O)-S-, -OS(=O)2-, -OC(=O)-O-, -C(=O)-NH-, -OC(=O)-NH-, -C(=O)-NR 10a - and -C(=O)-NR 10a - at least one part of which is an aliphatic group having 1 to 20 carbon atoms selected from the group consisting of Ar is an aromatic group which may have one or more substituents selected from the group consisting of a halogen atom, an aliphatic group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a dialkylamino group, an acyloxy group, an acylthio group, an acylamino group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an alkylaryl group, a cyano group, and a nitro group, In the formula (a12), R 4a and R 5a are each independently an aliphatic group having 1 to 5 carbon atoms, Y 1a is an oxygen atom, R 6a is an aliphatic group having 1 to 10 carbon atoms, R 7a It is composed of -O-, -S-, -C(=O)-S-, -OS(=O)2-, -OC(=O)-O-, -C(=O)-NH-, -OC(=O)-NH-, -C(=O)-NR 10a -、-OC(=O)-NR 10a - and -C(=O)-NR 10a R 11a At least one part of the group consisting of is an aliphatic group having 1 to 18 carbon atoms, In the formula (a13), R 8a It may include -O-, -S-, -C(=O)-S-, -OS(=O)2-, -OC(=O)-O-, -C(=O)-NH-, -OC(=O)-NH-, -C(=O)-NR 10a - and -OC(=O)-NR 10a - at least one part of which is an aliphatic group having 2 to 18 carbon atoms, selected from the group consisting of Y 2a is an oxygen atom, R 9a The compound includes -O-, -S-, -C(=O)-O-, -C(=O)-S-, -OS(=O)2-, -OC(=O)-O-, -C(=O)-NH-, -OC(=O)-NH-, -C(=O)-NR 10a -、-OC(=O)-NR 10a - and -C(=O)-NR 10a R 11a At least one part of the group consisting of is an aliphatic group having 1 to 18 carbon atoms, R 10a and R 11a are aliphatic groups having 1 to 10 carbon atoms, in -C(=O)-NR 10a R 11a In, R 10a and R 11a may be the same as or different from each other, and may be bonded to each other to form an alicyclic group. R 2a Select from the following groups: an aliphatic group having 1 to 18 carbon atoms which may be substituted with one or more halogen atoms; Containing -O-, -S-, -C(=O)-O-, -C(=O)-S-, -OS(=O)2-, -OC(=O)-O-, -C(=O)-NH-, -OC(=O)-NH-, -C(=O)-NR 10a -、-OC(=O)-NR 10a - and -C(=O)-NR 10a R 11a At least one part of which is selected from the group consisting of an aliphatic group having 3 to 18 carbon atoms and which may be substituted with one or more halogen atoms; an aromatic group having 4 to 18 carbon atoms, which may have one or more substituents selected from the group consisting of a halogen atom, an aliphatic group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a dialkylamino group, an acyloxy group, an acylthio group, an acylamino group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an alkylaryl group, a cyano group, and a nitro group; and an alkyl group substituted with an aromatic group having 4 to 18 carbon atoms, which may have at least one substituent selected from the group consisting of a halogen atom, an aliphatic group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a dialkylamino group, an acyloxy group, an acylthio group, an acylamino group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an alkylaryl group, a cyano group and a nitro group, Formula (a2-i) or formula (a2-ii): 【Chemistry 5】 In formulas (a2-i) to (a2-ii), R 21a for Hydrogen atom; an aliphatic group having 1 to 18 carbon atoms which may be substituted with one or more halogen atoms; or It may include -O-, -S-, -C(=O)-, -C(=O)-O-, -C(=O)-S-, -OC(=O)-O-, -C(=O)-NH-, -OC(=O)-NH-, -C(=O)-NR 10a -、-OC(=O)-NR 10a - and -C(=O)-NR 10a R 11a At least one part of which is selected from the group consisting of an aliphatic group having 2 to 18 carbon atoms and which may be substituted with one or more halogen atoms, R 22a is a group selected from the group consisting of: -CH3, -CH2F, -CHF2, -CF3, or an aliphatic group having 2 to 18 carbon atoms which may be substituted with one or more halogen atoms; Containing -O-, -S-, -C(=O)-, -C(=O)-O-, -C(=O)-S-, -OC(=O)-O-, -C(=O)-NH-, -OC(=O)-NH-, -C(=O)-NR 10a -、-OC(=O)-NR 10a - and -C(=O)-NR 10a R 11a At least one part of which is selected from the group consisting of an aliphatic group having 2 to 18 carbon atoms and which may be substituted with one or more halogen atoms; an aromatic group having 4 to 18 carbon atoms, which may have one or more substituents selected from the group consisting of a halogen atom, an aliphatic group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a dialkylamino group, an acyloxy group, an acylthio group, an acylamino group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an alkylaryl group, a cyano group, and a nitro group; and an alkyl group substituted with an aromatic group having 4 to 18 carbon atoms, which may have at least one substituent selected from the group consisting of a halogen atom, an aliphatic group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a dialkylamino group, an acyloxy group, an acylthio group, an acylamino group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an alkylaryl group, a cyano group and a nitro group, Among them, in R 22a In the case of -CF3, R 21a is a group selected from the group consisting of: Hydrogen atom; It may include -O-, -S-, -C(=O)-, -C(=O)-O-, -C(=O)-S-, -OC(=O)-O-, -C(=O)-NH-, -OC(=O)-NH-, -C(=O)-NR 10a -、-OC(=O)-NR 10a - and -C(=O)-NR 10a R 11a At least one part of which is selected from the group consisting of an aliphatic group having 2 to 18 carbon atoms and which may be substituted with one or more halogen atoms; -CH2CH(CH3)2, -CH2CH=CHCH3 or -CH2CH2CH=CH2; A group represented by the following formula (a21); 【Chemistry 6】 —CH2—R 23a (s21) and a group represented by the following formula (a22), 【Chemistry 7】 R 10a and R 11a are aliphatic groups having 1 to 10 carbon atoms, in -C(=O)-NR 10a R 11a In, R 10a and R 11a may be the same as or different from each other, and may be bonded to each other to form an alicyclic group. In the formula (a21), R 23a is an aliphatic group having 4 to 18 carbon atoms, In the formula (a22), R 24a is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, na is an integer from 1 to 5, Formula (a3-i) or formula (a3-ii): 【Chemistry 8】 In formulas (a3-i) to (a3-ii), R 31a and R 32a are independently selected from the group consisting of the following groups: Hydrogen atom; Cyano; an aliphatic group having 1 to 18 carbon atoms which may be substituted with one or more halogen atoms; It includes -O-, -S-, -C(=O)-, -C(=O)-O-, -C(=O)-S-, -OC(=O)-O-, -CN, -C(=O)-NH-, -C(=O)-NR 10a - and -C(=O)-NR 10a R 11a At least one part of which is selected from the group consisting of an aliphatic group having 1 to 18 carbon atoms and which may be substituted with one or more halogen atoms; and an aromatic group having 4 to 18 carbon atoms, which may have one or more substituents selected from the group consisting of a halogen atom, an aliphatic group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a dialkylamino group, an acyloxy group, an acylthio group, an acylamino group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an alkylaryl group, a cyano group, and a nitro group, R 31a and R 32a may be the same as or different from each other, and may be bonded to each other to form an alicyclic group or a heterocyclic group. R 33a Select from the following groups: an aliphatic group having 1 to 18 carbon atoms which may be substituted with one or more halogen atoms; Containing -O-, -S-, -C(=O)-, -C(=O)-O-, -C(=O)-S-, -OC(=O)-O-, -CN, -C(=O)-NH-, -OC(=O)-NH-, -C(=O)-NR 10a -、-OC(=O)-NR 10a - and -C(=O)-NR 10a R 11a At least one part of which is selected from the group consisting of an aliphatic group having 1 to 18 carbon atoms and which may be substituted with one or more halogen atoms; and an aromatic group having 4 to 18 carbon atoms, which may have one or more substituents selected from the group consisting of a halogen atom, an aliphatic group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a dialkylamino group, an acyloxy group, an acylthio group, an acylamino group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an alkylaryl group, a cyano group, and a nitro group, R 10a and R 11a are aliphatic groups having 1 to 10 carbon atoms, in -C(=O)-NR 10a R 11a In, R 10a and R 11a may be the same as or different from each other, and may be bonded to each other to form an alicyclic group. The resin (B) contains an acrylic resin (B3), wherein the acrylic resin (B3) is a resin containing 70 mol % or more of a structural unit derived from (meth)acrylic acid or a (meth)acrylic acid derivative, that is, a propylene structural unit, The acrylic resin (B3) comprises a structural unit derived from a polymerizable compound having a carboxyl group, The ratio of the acrylic resin (B3) to the total of the resin (B) and the resin other than the resin (B) is 70% by mass or more, The chemically amplified positive photosensitive resin composition further contains a low molecular weight compound (C) containing a phenolic hydroxyl group having a molecular weight of 1500 or less, wherein the content of the low molecular weight compound (C) containing a phenolic hydroxyl group is 1 to 20 parts by weight when the total amount of the resin (B) and the resin other than the resin (B) is 100 parts by weight, and the low molecular weight compound (C) containing a phenolic hydroxyl group is a non-polymer compound. The chemically amplified positive photosensitive resin composition further contains a compound including a nitrogen-containing aromatic heterocyclic ring substituted with a mercapto group and a tautomer thereof.

2. The chemically amplified positive photosensitive resin composition according to claim 1, characterized in that: The acid generator (A) includes a compound represented by the formula (a1-i), the formula (a1-ii), the formula (a2-i) or the formula (a2-ii).

3. The chemically amplified positive photosensitive resin composition according to claim 1, characterized in that: It also contains an alkali-soluble resin (D).

4. The chemically amplified positive photosensitive resin composition according to claim 3, characterized in that: The alkali-soluble resin (D) includes a novolac resin (D1).

5. The chemically amplified positive photosensitive resin composition according to claim 3, characterized in that: The alkali-soluble resin (D) includes a polyhydroxystyrene resin (D2).

6. The chemically amplified positive photosensitive resin composition according to claim 1, characterized in that: For h-line exposure.

7. The chemically amplified positive photosensitive resin composition according to claim 1, characterized in that: The main surface of the substrate having the metal surface is rectangular.

8. A photosensitive dry film, characterized in that: A photosensitive resin layer comprising a substrate film and formed on a surface of the substrate film, wherein the photosensitive resin layer is composed of the chemically amplified positive photosensitive resin composition according to any one of claims 1 to 7.

9. A method for producing a photosensitive dry film, characterized in that: The method comprises coating the chemically amplified positive photosensitive resin composition according to any one of claims 1 to 7 on a substrate film to form a photosensitive resin layer.

10. A method for producing a patterned resist film, characterized in that: include: A lamination step of laminating a photosensitive resin layer composed of the chemically amplified positive photosensitive resin composition according to any one of claims 1 to 7 on a substrate; An exposure step of selectively irradiating the photosensitive resin layer with active light or radiation to perform exposure; The developing step is to develop the photosensitive resin layer after exposure.

11. The method for producing a patterned resist film according to claim 10, wherein: The active light or the radiation is an h-ray.

12. The method for producing a patterned resist film according to claim 10 or 11, wherein: The thickness of the resist film after patterning is 1 μm or more.

13. A method for manufacturing a substrate with a casting mold, characterized in that: include: A lamination step of laminating a photosensitive resin layer composed of the chemically amplified positive photosensitive resin composition according to any one of claims 1 to 7 on a substrate having a metal surface; An exposure step of selectively irradiating the photosensitive resin layer with active light or radiation to perform exposure; The developing step is to develop the exposed photosensitive resin layer to prepare a mold for forming a plated object.

14. The method for manufacturing a substrate with a mold according to claim 13, wherein: The active light or the radiation is an h-ray.

15. The method for manufacturing a substrate with a mold according to claim 13, wherein: The thickness of the mold is 1 μm or more.

16. The method for producing a substrate with a mold according to any one of claims 13 to 15, wherein: The main surface of the substrate having the metal surface is rectangular.

17. A method for manufacturing a plated shaped object, characterized in that: include: The plating step is to plate the substrate with a casting mold manufactured by the method for manufacturing a substrate with a casting mold according to any one of claims 13 to 16 to form a plated molded object in the casting mold.

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