CN106918993B

CN106918993B - Photosensitive resin composition, photosensitive resin laminate, and method for forming protective pattern

Info

Publication number: CN106918993B
Application number: CN201610936578.7A
Authority: CN
Inventors: 筒井大和
Original assignee: Asahi Kasei Corp
Current assignee: Asahi Kasei Corp
Priority date: 2015-10-26
Filing date: 2016-10-24
Publication date: 2020-03-10
Anticipated expiration: 2036-10-24
Also published as: JP6567952B2; CN106918993A; JP2017083553A

Abstract

[ problem ] to]Provided is a photosensitive resin composition having good plating resistance. [ solving means ]]Provided is a photosensitive resin composition comprising: (a) an alkali-soluble polymer; (b) an addition polymerizable monomer having an ethylenically unsaturated bond; (c) a photopolymerization initiator containing a 2,4, 5-triarylimidazole dimer; and (d) a compound represented by the following general formula (I) { formula (I) }, wherein R₁～R₄Each independently hydrogen or alkyl, and R₅Is a group defined in the specification of the application }.

Description

Photosensitive resin composition, photosensitive resin laminate, and method for forming protective pattern

Technical Field

The present invention relates to a photosensitive resin composition and the like.

Background

In the past, printed wiring boards have been generally manufactured by photolithography. The photolithography method refers to a method in which: the method for forming a conductive pattern on a substrate includes the steps of applying a photosensitive resin composition onto a substrate, pattern-exposing the composition to cure the exposed portion of the photosensitive resin composition by polymerization (negative type) or to dissolve the exposed portion in a developer (positive type), removing the unexposed portion (negative type) or the exposed portion (positive type) with the developer to form a protective pattern on the substrate, etching or plating the protective pattern to form a conductive pattern, and removing the protective pattern from the substrate to form the conductive pattern on the substrate.

For the photolithography, any of the following methods is generally used: a method in which, when a photosensitive resin composition is applied to a substrate such as a copper-clad laminate, a solution of the photosensitive resin composition is applied to the substrate and dried; or a method in which a support, a layer formed of a photosensitive resin composition (hereinafter also referred to as a "photosensitive resin layer"), and, if necessary, a protective layer are sequentially laminated to form a photosensitive resin laminate (hereinafter also referred to as a "dry film protective layer"). For the manufacture of printed circuit boards, the latter dry film resist is mostly used.

The dry film resist is an important element for coping with the increase in density and demand for printed circuit boards, and various characteristics are required to be improved as compared with conventional dry films. In order to improve the characteristics of the protective layer, various photosensitive resin compositions have been proposed (patent documents 1 to 3).

Documents of the prior art

Patent document

Patent document 1 International publication No. 2008/015754

Japanese patent laid-open publication No. 2015-152854 of patent document 2

Japanese patent laid-open No. 2012-203165 of patent document 3

Disclosure of Invention

Problems to be solved by the invention

In patent document 1, from the viewpoint of adhesion between a protective pattern and a copper surface of a substrate and prevention of discoloration of the copper surface after the protective pattern is formed on the substrate, a photosensitive resin composition containing a carboxylic acid compound (other than carboxybenzotriazole) and a heterocyclic compound such as carboxybenzotriazole in addition to a thermoplastic polymer, a photopolymerizable monomer having an ethylenically unsaturated bond, an amine, and a photopolymerization initiator such as 2,4, 5-triazole dimer has been studied as an example.

In recent years, there are cases where: as the cooling step after laminating the photosensitive resin layer on the substrate is simplified, the substrate is maintained at a high temperature for a long time, a thermal load is applied to the photosensitive resin composition, and an unexpected curing reaction proceeds, resulting in etching residue and poor platability. In connection with this, patent document 2 has studied the heating time required for development residue of the photosensitive resin composition to appear in order to suppress the progress of the curing reaction even after the heat storage of the photosensitive resin composition and thereby suppress etching residue and poor platability. Patent document 2 describes that, in addition to the alkali-soluble polymer, the addition polymerizable monomer having an ethylenically unsaturated bond, and the photopolymerization initiator, the photosensitive resin composition may contain a specific benzotriazole compound from the viewpoint of extending the time required for development residue to appear, and may contain a specific epoxy compound from the viewpoint of resolution.

Patent document 3 proposes a photosensitive resin composition containing an alkali-soluble polymer, an addition polymerizable monomer having an ethylenically unsaturated bond, a photopolymerization initiator such as a triazole dimer, and an alkylene oxide compound having 2 glycidyl groups, from the viewpoint of the color stability of a dry film resist.

When the dry film resist is used for plating, the resist pattern is peeled off and removed after the plating process. In the plating step, or after the plating step and before the protective pattern stripping step, a phenomenon (also referred to as "copper penetration") in which copper in the plating solution penetrates into the protective pattern may occur. Therefore, it is required for the protective pattern to improve plating resistance.

However, none of patent documents 1 to 3 have examined plating resistance of the protective pattern. Further, from the viewpoint of satisfying both plating resistance and color stability at a high level, the photosensitive resin compositions described in patent documents 1 and 3 still have room for improvement.

Accordingly, an object to be solved by the present invention is to provide a photosensitive resin composition having good plating resistance.

Means for solving the problems

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by the following technical means.

Namely, the present invention is as follows:

[1]

a photosensitive resin composition comprising:

(a) an alkali-soluble polymer;

(b) an addition polymerizable monomer having an ethylenically unsaturated bond;

(c)2,4, 5-triarylimidazole dimer;

(d) a compound represented by the following general formula (I); and

(e) an epoxy compound, which is a compound of the formula,

{ in formula (I), R₁～R₄Each independently is hydrogen or alkylAnd R is₅Is a group represented by the following general formula (II):

(in the formula (II), R₆And R₇Each independently selected from hydrogen, linear or branched alkyl optionally having substituents, or linear or branched hydroxyalkyl optionally having substituents, R₆And R₇One or both of which are not hydrogen, and n is an integer of 1 to 4) }.

[2]

The photosensitive resin composition according to [1], wherein the epoxy compound comprises a compound represented by the following general formula (III):

{ formula (III) wherein X is an oxygen atom or a group of formula-O-X₁-O- (formula-O-X)₁in-O-X₁A 2-valent group containing at least 1 hydrocarbon group selected from the group consisting of a linear or branched alkylene group having 1 to 100 carbon atoms, an alicyclic alkylene group having 3 to 10 carbon atoms, and an arylene group having 5 to 20 carbon atoms, and the hydrocarbon group is optionally substituted with at least 1 atom selected from the group consisting of a halogen atom, an oxygen atom, and a nitrogen atom); r₈And R₉Each independently is a 2-valent group containing at least 1 hydrocarbon group selected from the group consisting of a linear or branched alkylene group having 1 to 100 carbon atoms, an alicyclic alkylene group having 3 to 10 carbon atoms, and an arylene group having 5 to 20 carbon atoms, and the hydrocarbon group is optionally substituted with at least 1 atom selected from the group consisting of a halogen atom, an oxygen atom, and a nitrogen atom, and R is₈And R₉When they coexist, R₈And R₉Identical or different, R₈And R₉Not simultaneously, - (R)₈-O) -and- (R)₉-O) -is arranged as a block or random; and l and m are each independently an integer of 0 to 50, and l + m is an integer of 1 to 50 }.

[3]

The photosensitive resin composition according to [1] or [2], wherein the content of the epoxy compound is 0.001% by mass or more and less than 0.1% by mass relative to the total solid content of the photosensitive resin composition.

[4]

The photosensitive resin composition according to any one of [1] to [3], wherein the 2,4, 5-triarylimidazole dimer contains a compound represented by the following general formula (IV):

{ in formula (IV), Y¹、Y²And Y³Each independently represents one group selected from the group consisting of hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen, and p, q, and r are each independently an integer of 1 to 5 }.

[5]

The photosensitive resin composition according to any one of [1] to [4], wherein the photosensitive resin composition further contains an N-aryl amino acid.

[6]

The photosensitive resin composition according to any one of [1] to [5], wherein the photosensitive resin composition further comprises a compound represented by the following general formula (V):

{ formula (V), Z is hydrogen or C1-4 alkyl }.

[7]

A photosensitive resin laminate comprising: a photosensitive resin layer formed from the photosensitive resin composition according to any one of [1] to [6], and a support for supporting the photosensitive resin layer.

[8]

A method of forming a protective pattern, comprising:

a laminating step of laminating the photosensitive resin laminate according to [7] on a substrate;

an exposure step of exposing the photosensitive resin layer contained in the photosensitive resin laminate; and

and a developing step of removing the unexposed portion of the exposed photosensitive resin layer with a developing solution to form a protective pattern.

[9]

The method of forming a protective pattern according to [8], wherein the exposure step is a step of performing exposure by direct writing of a writing pattern.

[10]

A method of forming a conductor pattern, comprising:

a laminating step of laminating the photosensitive resin laminate according to [7] on a metal plate or a metal-coated insulating plate;

an exposure step of exposing the photosensitive resin layer contained in the photosensitive resin laminate;

a developing step of removing the unexposed portion of the exposed photosensitive resin layer with a developing solution to form a protective pattern; and the number of the first and second groups,

and a conductor pattern forming step of etching or plating a portion of the surface of the metal plate or the metal-coated insulating plate not covered with the protective pattern.

[11]

A method of manufacturing a printed circuit board, comprising:

a laminating step of laminating the photosensitive resin laminate according to [7] on a copper-clad laminate or a flexible substrate;

a developing step of removing the unexposed portion of the exposed photosensitive resin layer with a developing solution to form a protective pattern;

a conductor pattern forming step of etching or plating a portion of the surface of the copper-clad laminate or flexible substrate not covered with the protective pattern; and

and a peeling step of peeling the protective pattern from the copper-clad laminate or the flexible substrate.

[12]

A method of manufacturing a lead frame, comprising:

a laminating step of laminating the photosensitive resin laminate according to [7] on a metal plate;

an etching step of etching a portion of the surface of the metal plate not covered with the protective pattern; and

and a peeling step of peeling the protective pattern from the metal plate.

[13]

A method of manufacturing a semiconductor package, comprising:

a laminating step of laminating the photosensitive resin laminate of [7] on a wafer on which an LSI that is a large scale integrated circuit is formed;

a plating step of plating a portion of the wafer surface not covered with the protective pattern; and

and a peeling step of peeling the protective pattern from the wafer.

ADVANTAGEOUS EFFECTS OF INVENTION

The invention can provide a photosensitive resin composition with good plating resistance.

Detailed Description

The best mode for carrying out the present invention (hereinafter, simply referred to as "embodiment") will be described in detail below. The present invention is not limited to the following embodiments, and can be implemented by being variously modified within the scope of the gist thereof.

< photosensitive resin composition >

In an embodiment, the photosensitive resin composition comprises the following components (a) to (e):

(a) an alkali-soluble polymer;

(b) an addition polymerizable monomer having an ethylenically unsaturated bond;

(c)2,4, 5-triarylimidazole dimer;

(d) a compound represented by the following general formula (I); and

(e) an epoxy compound, which is a compound of the formula,

{ in formula (I), R₁～R₄Each independently hydrogen or alkyl, and R₅Is a group represented by the following general formula (II):

The photosensitive resin composition may contain a photopolymerization initiator (other than the component (c)), a coloring material, an additive, and the like as necessary. The components contained in the photosensitive resin composition will be described below.

[ (a) alkali-soluble Polymer ]

The alkali-soluble polymer is typically a thermoplastic copolymer having a weight average molecular weight of 5,000 to 500,000, which contains a carboxyl group-containing monomer as a copolymerization component.

The weight average molecular weight of the thermoplastic copolymer is preferably 5,000 to 500,000. The weight average molecular weight of the thermoplastic copolymer is preferably 5,000 or more from the viewpoint of uniformly maintaining the thickness of the dry film protective layer and obtaining resistance to a developing solution, and is preferably 500,000 or less from the viewpoint of maintaining developability. The lower limit of the weight average molecular weight of the thermoplastic copolymer is more preferably 20,000 and the upper limit is more preferably 300,000. The molecular weight distribution is preferably 1.5 to 7, and the lower limit is more preferably 2 and the upper limit is 5.

The thermoplastic copolymer is preferably obtained by copolymerizing copolymerization components containing 1 or more kinds of first monomers described later and 1 or more kinds of second monomers described later.

The first monomer is a monomer having a carboxyl group in the molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. Among them, (meth) acrylic acid is particularly preferable. Here, (meth) acrylic acid means acrylic acid or methacrylic acid. The same applies hereinafter.

The second monomer is non-acidic and is a monomer having at least 1 polymerizable unsaturated group in the molecule. Examples of the second monomer include vinyl alcohol esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, and vinyl acetate; (meth) acrylonitrile, styrene-based monomers (styrene, and polymerizable styrene derivatives), and the like. Among them, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, and benzyl (meth) acrylate are preferable.

The alkali-soluble polymer is preferably synthesized as follows: in a solution in which the above monomers are mixed and diluted with a solvent such as acetone, methyl ethyl ketone, methanol, ethanol, n-propanol or isopropanol, a radical polymerization initiator such as benzoyl peroxide, azobisisobutyronitrile is added in an appropriate amount and heated with stirring. Sometimes, the synthesis is carried out while a part of the mixture is added dropwise to the reaction solution. After the reaction, a solvent may be further added to adjust the concentration to a desired level. As the synthesis method, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

The alkali-soluble polymer is preferably 10 to 60% by mass of the first monomer, 40 to 90% by mass of the second monomer, more preferably 15 to 35% by mass of the first monomer, and 65 to 85% by mass of the second monomer, in terms of the copolymerization ratio of the first monomer and the second monomer.

Specific examples of the alkali-soluble polymer include polymers containing methyl methacrylate, methacrylic acid, and styrene as copolymerization components; a polymer containing methyl methacrylate, methacrylic acid, and n-butyl acrylate as copolymerization components; and polymers containing benzyl methacrylate, methyl methacrylate, and 2-ethylhexyl acrylate as copolymerization components.

In the embodiment, the content of the alkali-soluble polymer in the photosensitive resin composition (which is the same for each content component unless otherwise specified) is in the range of 20 to 90% by mass, with a preferred lower limit of 25% by mass, a preferred upper limit of 75% by mass, a more preferred lower limit of 40% by mass, and a more preferred upper limit of 65% by mass. The content is preferably 20 mass% or more from the viewpoint of maintaining the alkali developability, and is preferably 90 mass% or less from the viewpoint of sufficiently exhibiting the performance as a protective film of a protective pattern formed by exposure.

[ (b) addition-polymerizable monomers having ethylenically unsaturated bonds ]

The addition polymerizable monomer having an ethylenically unsaturated bond is a compound having addition polymerizability having at least 1 ethylenically unsaturated group in the molecule. The ethylenically unsaturated bond is preferably a terminal ethylenically unsaturated group.

The photosensitive resin composition comprises (b) a compound selected from the group consisting of₁）～（b₃) At least 1 of the group consisting of as component (b):

(b1) an addition polymerizable monomer represented by the following general formula (VI):

{ in formula (VI), m₁Is a number satisfying 2 to 40. };

（b₂) An addition polymerizable monomer represented by the following general formula (VII):

{ in formula (VII), R₁₁And R₁₂Each independently represents a hydrogen atom or a methyl group, A is C₂H₄B is C₃H₆，n₁、n₂、n₃And n₄Is satisfying n₁+n₂+n₃+n₄An integer having a relationship of =2 to 40, an arrangement of repeating units of- (a-O) -and- (B-O) -may be random or block, and in the case of a block, either of- (a-O) -and- (B-O) -may be on the biphenyl side }; and

（b₃) In addition to the above (b)₁) And (b)₂) Addition polymerizable monomers other than the component (A).

From the viewpoint of adjusting the size of the release sheet of the protective pattern, the photosensitive resin composition preferably contains at least 1 type of addition polymerizable monomer represented by the general formula (VI) as (b)₁) And (3) components.

In the general formula (VI), m is m from the viewpoint of the size of the release sheet₁Preferably 2 or more, m is m from the viewpoint of resolution and plating resistance₁Preferably 40 or less.

As specific examples of the addition polymerizable monomer represented by the general formula (VI), m is preferable₁Tetraethylene glycol diacrylate (tetraethylene glycol diacrylate) = 4) and (m)₁Nonaethylene glycol diacrylate of =9, or m₁Polyethylene glycol diacrylate of = 14.

From the viewpoint of resolution and plating resistance, the photosensitive resin composition preferably contains at least 1 addition polymerizable monomer represented by the general formula (VII) as the (b)₂) And (3) components.

In the general formula (VII), B may be-CH₂CH₂CH₂-or-CH (CH)₃)CH₂-, n represents the number of repetitions₁、n₂、n₃And n₄Each independently may be an integer of 0 to 20 inclusive, and preferably n is satisfied from the viewpoint of masking property₁+n₂+n₃+n₄More preferably, n is satisfied₁+n₂+n₃+n₄A relationship of ≧ 4, and from the viewpoint of resolution, it is preferable that n be satisfied₁+n₂+n₃+n₄A relation of ≦ 40, more preferably, n is satisfied₁+n₂+n₃+n₄The relation of less than or equal to 35.

Preferable specific examples of the addition polymerizable monomer represented by the general formula (VII) include di (meth) acrylate of polyethylene glycol in which ethylene oxide of an average number 1 unit is added to each of both ends of bisphenol A, di (meth) acrylate of polyethylene glycol in which ethylene oxide of an average number 2 unit is added to each of both ends of bisphenol A, di (meth) acrylate of polyethylene glycol in which ethylene oxide of an average number 5 unit is added to each of both ends of bisphenol A, di (meth) acrylate of polyethylene glycol having an average of 7 units of ethylene oxide added to each end of bisphenol a, di (meth) acrylate of polyalkylene glycol having an average of 6 units of ethylene oxide and an average of 2 units of propylene oxide added to each end of bisphenol a, di (meth) acrylate of polyalkylene glycol having an average of 15 units of ethylene oxide and an average of 2 units of propylene oxide added to each end of bisphenol a, and the like.

For as a division (b)₁) And (b)₂) Of monomers other than component (b)₃) As the component (B), for example, a known compound having at least 1 terminal ethylenically unsaturated group can be mentioned.

As (b)₃) Specific examples of the component (B) include 4-nonylphenylheptaethyleneglycol dipropylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, phenoxyhexaethyleneglycol acrylate, phthalic anhydride and 2-hydroxy acrylateA reaction product of a half ester compound of propyl ester and propylene oxide, and polyoxyalkylene glycol di (meth) acrylates such as 1, 6-hexanediol di (meth) acrylate, 1, 4-cyclohexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and polyoxyethylene polyoxypropylene glycol di (meth) acrylate; 2-bis (p-hydroxyphenyl) propane di (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, 2-bis (4-methacryloxypentaethoxyphenyl) propane, glycerol triacrylate, triacrylate acrylated on trimethylolpropane, triacrylate of ethylene oxide having an average of 3 units added to trimethylolpropane, tetraacrylate of diol having an average of 4 units added to pentaerythritol, polyfunctional (meth) acrylate containing urethane groups (for example, urethane compounds of hexamethylene diisocyanate and pentamethylene glycol monomethacrylate, more specifically, urethane compounds of hexamethylene diisocyanate and pentamethylene glycol monomethacrylate), polyfunctional (meth) acrylates of trimerized isocyanate compounds, and the like. These may be used alone or in combination of 2 or more.

The content of the addition polymerizable monomer having an ethylenically unsaturated bond (b) in the photosensitive resin composition is preferably in the range of 5 to 75% by mass. The content is preferably 5% by mass or more from the viewpoint of suppressing curing failure and delay in development time, and is preferably 75% by mass or less from the viewpoint of suppressing cold flow and delay in peeling of the cured protective film. The lower limit of the content is more preferably 15% by mass and the upper limit is preferably 60% by mass. The lower limit of the content is more preferably 30% by mass and the upper limit is more preferably 50% by mass.

[ (c)2,4, 5-triarylimidazole dimer ]

From the viewpoint of achieving both plating resistance and color stability, the photosensitive resin composition preferably contains a 2,4, 5-triarylimidazole dimer as a photopolymerization initiator. The photopolymerization initiator is a compound that polymerizes monomers by light.

The 2,4, 5-triarylimidazole dimer is preferably a compound represented by the following general formula (IV):

For compounds of formula (IV), the covalent bond to 2 triphenylimidazolyl is attached at the 1,1 ' -, 1,2 ' -, 1,4 ' -, 2 ' -, 2,4 ' -or 4,4 ' -position, but compounds attached at the 1,2 ' -position are preferred. Examples of the 2,4, 5-triarylimidazole dimer include 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4, 5-bis- (m-methoxyphenyl) imidazole dimer, and 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer, with 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer being particularly preferred.

The content of the 2,4, 5-triarylimidazole dimer in the photosensitive resin composition is preferably 0.1 to 20% by mass. The content is 0.1% by mass or more from the viewpoint of resolution, adhesion, and plating resistance, and is 20% by mass or less from the viewpoint of color stability and development aggregation. The content is more preferably in a range of 0.5 to 15% by mass, and still more preferably in a range of 1 to 10% by mass.

[ photopolymerization initiator (except 2,4, 5-triarylimidazole dimer) ]

In order to increase the sensitivity in the exposure step, the photosensitive resin composition preferably contains a photopolymerization initiator other than the 2,4, 5-triarylimidazole dimer.

As the photopolymerization initiator (except for 2,4, 5-triarylimidazole dimer), acridine compounds, pyrazoline compounds, N-aryl amino acids, quinones, aromatic ketones, benzoin ethers, and the like can be used.

Examples of the acridine compound include acridine, 9-phenylacridine, 9- (4-tolyl) acridine, 9- (4-methoxyphenyl) acridine, 9- (4-hydroxyphenyl) acridine, 9-ethylacridine, 9-chloroethylacridine, 9-methoxyacridine, 9-ethoxyacridine, 9- (4-methylphenyl) acridine, 9- (4-ethylphenyl) acridine, 9- (4-n-propylphenyl) acridine, 9- (4-n-butylphenyl) acridine, 9- (4-tert-butylphenyl) acridine, 9- (4-ethoxyphenyl) acridine, 9- (4-acetylphenyl) acridine, 9- (4-dimethylaminophenyl) acridine, 9- (4-ethylphenyl) acridine, 9-n-butylacridine, 9-ethoxyphenyl) acridine, and, 9- (4-chlorophenyl) acridine, 9- (4-bromophenyl) acridine, 9- (3-methylphenyl) acridine, 9- (3-tert-butylphenyl) acridine, 9- (3-acetylphenyl) acridine, 9- (3-dimethylaminophenyl) acridine, 9- (3-diethylaminophenyl) acridine, 9- (3-chlorophenyl) acridine, 9- (3-bromophenyl) acridine, 9- (2-pyridyl) acridine, 9- (3-pyridyl) acridine, 9- (4-pyridyl) acridine and the like.

Examples of the pyrazoline compound include 1-phenyl-3- (4-tert-butylstyrene) -5- (4-tert-butylphenyl) pyrazoline, 1- (4- (benzoxazol-2-yl) phenyl) -3- (4-tert-butylstyrene) -5- (4-tert-butylphenyl) pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butylphenyl) pyrazoline, and 1-phenyl-3- (4-biphenyl) -5- (4-tert-octylphenyl) pyrazoline.

Examples of the N-arylamino acid include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like.

Examples of the quinones include 2-ethylanthraquinone, octaethylanthraquinone, 1, 2-benzoanthraquinone, 2, 3-benzoanthraquinone, 2-phenylanthraquinone, 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, 1, 4-naphthoquinone, 9, 10-phenanthrenequinone, 2-methyl-1, 4-naphthoquinone, 2, 3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.

Examples of the aromatic ketone include benzophenone, michler's ketone [4,4 ' -bis (dimethylamino) benzophenone ], and 4,4 ' -bis (diethylamino) benzophenone. Among these, 4' -bis (diethylamino) benzophenone is preferable from the viewpoint that when it is used in combination with a 2,4, 5-triarylimidazole dimer, the sensitivity of the photosensitive resin composition can be improved.

Examples of the benzoin ethers include benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, and ethylbenzoin.

Examples of the oxime esters include 1-phenyl-1, 2-propanedione-2-O-benzoinoxime and 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime.

Examples of the combination of the thioxanthone and the alkylaminobenzoic acid include a combination of ethylthioxanthone and ethyl dimethylaminobenzoate, a combination of 2-chlorothioxanthone and ethyl dimethylaminobenzoate, and a combination of isopropylthioxanthone and ethyl dimethylaminobenzoate.

Among the above-listed photopolymerization initiators, N-aryl amino acids are preferable, and N-phenylglycine is more preferable, from the viewpoint that when it is used in combination with 2,4, 5-triarylimidazole dimer, the sensitivity of the photosensitive resin composition can be improved.

The content of the photopolymerization initiator (except for the 2,4, 5-triarylimidazole dimer) in the photosensitive resin composition is preferably 0.01 to 20% by mass. The content is 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity in photopolymerization by exposure, and is 20% by mass or less from the viewpoint of sufficiently transmitting light to the bottom surface (i.e., a portion away from the light source) of the photosensitive resin composition in photopolymerization to obtain good resolution and adhesion. The content is preferably 0.05% by mass at the lower limit, more preferably 0.1% by mass at the lower limit, more preferably 15% by mass at the upper limit, and more preferably 10% by mass at the upper limit.

[ (d) Compounds represented by the general formula (I) ]

From the viewpoint of achieving both plating resistance and color stability, the photosensitive resin composition preferably contains a compound represented by the following general formula (I):

The mechanism of the photosensitive resin composition containing the component (c), the component (d), and the component (e) to exhibit good plating resistance is not clear, but is considered as follows. The reason for the decrease in plating resistance is considered to be that when copper ions contained in the plating solution are coordinated to carboxyl groups contained in the component (a) and pseudo-crosslinking occurs, the entire cured protective pattern shrinks, and the cured protective pattern is easily peeled off from the substrate. Here, the polymerization reaction of the component (c) and the component (b) proceeds efficiently in the presence of the component (d) and the dispersibility in the composition is improved, so that the crosslinked structure becomes compact and the migration of copper ions to the curing protective pattern can be reduced. It is also presumed that the interaction between the unpaired electrons on the nitrogen atom in the component (d) or the unpaired electrons on the oxygen atom in the component (e) with the copper ions in the coexistence environment of the components (d) and (e) suppresses the reduction in plating resistance.

The hydrogen on the aromatic ring of the compound of formula (I) is not substituted by a polar group, but the group R₅Containing a group having a tertiary or secondary amino group. The radical R in the general formula (II)₆And R₇More preferably, each independently is a linear or branched alkyl group having 1 to 30 carbon atoms, which may have a substituent, and further preferably a branched alkyl group having 1 to 30 carbon atoms, which may have a substituent, and the substituent may be an aromatic group, an alicyclic group, or the like, but preferably does not have a carboxyl group. In particular, the radical R₆And R₇May each independently be propyl, isopropyl, butyl, isobutyl, sec-butyl, or,T-butyl, pentyl, sec-pentyl, t-pentyl, isopentyl, hexyl, heptyl, 1-ethylpentyl, octyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, isostearyl, 2-heptylundecyl, eicosyl, heneicosyl, and the like.

As the radical R in the formula (I)₅Examples thereof include N, N-bis (2-ethylhexyl) aminomethyl and 1-N-dibutylaminomethyl. Among them, N-bis (2-ethylhexyl) aminomethyl is preferable.

Examples of the compound represented by the general formula (I) include 1- [ N, N-bis (2-ethylhexyl) aminomethyl ] benzotriazole, 1- [ N, N-bis (2-ethylhexyl) aminomethyl ] methylbenzotriazole, N- (N, N-bis-2-hydroxyethyl) aminomethylene benzotriazole, 1-N-dipropylaminomethylbenzotriazole, and 1-N-dibutylaminomethylbenzotriazole. Among them, 1- [ N, N-bis (2-ethylhexyl) aminomethyl ] benzotriazole is preferable from the viewpoint of compatibility between plating resistance and color stability.

The content of the compound represented by the general formula (I) in the photosensitive resin composition is in the range of 0.05 to 10% by mass, preferably in the range of 0.10 to 8% by mass, and more preferably in the range of 0.15 to 7% by mass. The content is 0.05 mass% or more from the viewpoint of the stability of the retention time after lamination and exposure, and 10 mass% or less from the viewpoint of resolution.

[ (e) epoxy Compound ]

The photosensitive resin composition preferably contains an epoxy compound from the viewpoint of compatibility between plating resistance and color stability. The epoxy compound is a compound having an epoxy group. In the present embodiment, coloring during storage of the dry film protective layer can be effectively prevented by utilizing the acid trapping effect of the epoxy compound, and thus good storage stability of hue and good resolution can be obtained.

Examples of the epoxy compound include alkylene oxide compounds and the like. The alkylene oxide compound preferably contains at least 2 glycidyl groups in the molecule.

Examples of the alkylene oxide compound include compounds represented by the following general formula (III):

As X in the above general formula (III), from the viewpoint of resolution, an oxygen atom, a 2-valent group (hereinafter, also referred to as a bisphenol a-type group) in which hydrogen is removed from a hydroxyl group of bisphenol a, and a 2-valent group (hereinafter, also referred to as a hydrogenated bisphenol a-type group) in which hydrogen is removed from a hydroxyl group of hydrogenated bisphenol a are preferable, and a bisphenol a-type group and a hydrogenated bisphenol a-type group are more preferable.

Preferable examples of the alkylene oxide compound in the general formula (III) include ethylene glycol diglycidyl ether (for example, Eplight 40E manufactured by Co., Ltd.), diethylene glycol diglycidyl ether (for example, Eplight 100E manufactured by Co., Ltd.), triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether (for example, Eplight 200E manufactured by Co., Ltd.), pentaethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, heptaethylene glycol diglycidyl ether, octaethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether (for example, Eplight 400E manufactured by Co., Ltd.), decaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether (for example, Eplight 70P manufactured by Co., Ltd.), dipropylene glycol diglycidyl ether, and tripropylene glycol diglycidyl ether (for example, Eplight 200P manufactured by Co., Ltd.), and, Tetrapropylene glycol diglycidyl ether, pentapropylene glycol diglycidyl ether, hexapropylene glycol diglycidyl ether, heptapropylene glycol diglycidyl ether (for example, Eplight 400P manufactured by Kyoeisha chemical Co., Ltd.), octapropylene glycol diglycidyl ether, nonapropylene glycol diglycidyl ether, decapropylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, ditetramethylene glycol diglycidyl ether, tritetramethylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, pentatetramethylene glycol diglycidyl ether, hexatetramethylene glycol diglycidyl ether, heptatetramethylene glycol diglycidyl ether, octatetramethylene glycol diglycidyl ether, nonatetramethylene glycol diglycidyl ether, diglycidyl ethers containing 1 mole and 2 moles of ethylene glycol and propylene glycol, diglycidyl ethers containing 1 mole and 3 moles of ethylene glycol and propylene glycol, respectively, Diglycidyl ethers containing 1 mole and 4 moles of ethylene glycol and propylene glycol, respectively, diglycidyl ethers containing 1 mole and 5 moles of ethylene glycol and propylene glycol, respectively, diglycidyl ethers containing 1 mole and 9 moles of ethylene glycol and propylene glycol, respectively, diglycidyl ethers containing 2 moles and 1 mole of ethylene glycol and propylene glycol, respectively, diglycidyl ethers containing 2 moles and 2 moles of ethylene glycol and propylene glycol, respectively, diglycidyl ethers containing 2 moles and 3 moles of ethylene glycol and propylene glycol, respectively, diglycidyl ethers containing 2 moles and 4 moles of ethylene glycol and propylene glycol, respectively, diglycidyl ethers containing 2 moles and 5 moles of ethylene glycol and propylene glycol, respectively, diglycidyl ethers containing 2 moles and 8 moles of ethylene glycol and propylene glycol, respectively, diglycidyl ethers containing 3 moles and 1 mole of ethylene glycol and propylene glycol, respectively, Diglycidyl ethers containing 3 moles and 2 moles of ethylene glycol and propylene glycol, respectively, diglycidyl ethers containing 3 moles and 3 moles of ethylene glycol and propylene glycol, respectively, diglycidyl ethers containing 3 moles and 4 moles of ethylene glycol and propylene glycol, respectively, diglycidyl ethers containing 3 moles and 5 moles of ethylene glycol and propylene glycol, respectively, diglycidyl ethers containing 3 moles and 7 moles of ethylene glycol and propylene glycol, respectively, diglycidyl ethers containing 5 moles and 1 mole of ethylene glycol and propylene glycol, respectively, diglycidyl ethers containing 5 moles and 2 moles of ethylene glycol and propylene glycol, respectively, diglycidyl ethers containing 5 moles and 3 moles of ethylene glycol and propylene glycol, respectively, diglycidyl ethers containing 5 moles and 4 moles of ethylene glycol and propylene glycol, respectively, diglycidyl ethers containing 5 moles and 5 moles of ethylene glycol and propylene glycol, respectively, Diglycidyl ethers containing 6 moles and 1 mole of ethylene glycol and propylene glycol, respectively, diglycidyl ethers containing 6 moles and 2 moles of ethylene glycol and propylene glycol, respectively, diglycidyl ethers containing 6 moles and 3 moles of ethylene glycol and propylene glycol, respectively, diglycidyl ethers containing 6 moles and 4 moles of ethylene glycol and propylene glycol, respectively, diglycidyl ethers containing 7 moles and 1 mole of ethylene glycol and propylene glycol, respectively, diglycidyl ethers containing 7 moles and 2 moles of ethylene glycol and propylene glycol, respectively, diglycidyl ethers containing 7 moles and 3 moles of ethylene glycol and propylene glycol, respectively, diglycidyl ethers containing 8 moles and 1 mole of ethylene glycol and propylene glycol, respectively, diglycidyl ethers containing 8 moles and 2 moles of ethylene glycol and propylene glycol, respectively, 9 moles and 1 mole of ethylene glycol and propylene glycol, respectively, Neopentyl glycol diglycidyl ether (for example, Eplight 1500NP manufactured by Kyowa Kagaku Co., Ltd.), 1, 6-hexanediol diglycidyl ether (for example, Eplight 1600 manufactured by Kyowa Kagaku Co., Ltd.), hydrogenated bisphenol A diglycidyl ether (for example, Eplight 4000 manufactured by Kyowa Kagaku Co., Ltd.), and the like. Among them, hydrogenated bisphenol A diglycidyl ether is preferable.

In addition, in the case where X in the above general formula (III) is a bisphenol A-type group, preferable examples of the alkylene oxide compound include bisphenol A-propylene oxide 2 mol adduct diglycidyl ether (for example, Eplight 3002 manufactured by Kyowa chemical Co., Ltd.), bisphenol A-propylene oxide 4 mol adduct diglycidyl ether, bisphenol A-propylene oxide 6 mol adduct diglycidyl ether, bisphenol A-propylene oxide 8 mol adduct diglycidyl ether, bisphenol A-propylene oxide 10 mol adduct diglycidyl ether, bisphenol A-ethylene oxide 2 mol adduct diglycidyl ether, bisphenol A-ethylene oxide 4 mol adduct diglycidyl ether, bisphenol A-ethylene oxide 6 mol adduct diglycidyl ether, bisphenol A-ethylene oxide 8 mol adduct diglycidyl ether, Bisphenol a-ethylene oxide 10 mole adduct diglycidyl ether, and the like. Among them, diglycidyl ether which is a 2-mole adduct of bisphenol A-propylene oxide is preferable.

In addition, in the case where X in the above general formula (III) is a hydrogenated bisphenol A-type group, preferable examples of the alkylene oxide compound include a hydrogenated bisphenol A-ethylene oxide 2 mol adduct diglycidyl ether, a hydrogenated bisphenol A-ethylene oxide 4 mol adduct diglycidyl ether, a hydrogenated bisphenol A-ethylene oxide 6 mol adduct diglycidyl ether, a hydrogenated bisphenol A-ethylene oxide 8 mol adduct diglycidyl ether, a hydrogenated bisphenol A-ethylene oxide 10 mol adduct diglycidyl ether, a hydrogenated bisphenol A-propylene oxide 2 mol adduct diglycidyl ether, a hydrogenated bisphenol A-propylene oxide 4 mol adduct diglycidyl ether, a hydrogenated bisphenol A-propylene oxide 6 mol adduct diglycidyl ether, a hydrogenated bisphenol A-propylene oxide 8 mol adduct diglycidyl ether, Hydrogenated bisphenol A-propylene oxide 10 mole adduct diglycidyl ether, and the like.

The epoxy compounds described above may be used alone or in combination of two or more.

The content of the epoxy compound in the photosensitive resin composition is preferably 0.001 mass% or more and 0.2 mass% or less, more preferably 0.001 mass% or more and 0.15 mass% or less, and particularly preferably 0.001 mass% or more and less than 0.1 mass%, from the viewpoint of maintaining an optimum balance between plating resistance and color stability.

[ coloring matter ]

From the viewpoint of sensitivity, the photosensitive resin composition preferably contains a coloring material such as a dye or a pigment. As the dye, a basic dye is preferable.

From the viewpoint of sensitivity, the photosensitive resin composition preferably further contains a compound represented by the following general formula (V) as a basic dye:

{ formula (V), Z is hydrogen or C1-4 alkyl }.

Specific examples of the compound represented by the above general formula (V) include basic blue 7[ CAS No.: 2390-60-5].

Examples of the coloring substance that can be used in addition to the compound represented by the general formula (V) include basic green 1[ CAS number (the same applies hereinafter): 633-03-4, malachite green oxalate [2437-29-8], brilliant green [633-03-4], fuchsin [632-99-5], methyl violet [603-47-4], methyl violet 2B [8004-87-3], crystal violet [548-62-9], methyl green [82-94-0], Victoria blue B [2580-56-5], rhodamine B [81-88-9], rhodamine 6G [989-38-8], basic yellow 2[2465-27-2] and other alkali dyes.

The content of the coloring material in the photosensitive resin composition is preferably 0.001 to 1% by mass. When the amount of the coloring material added is 0.001% by mass or more, the effect of improving the handling property is obtained, and when the amount is 1% by mass or less, the effect of maintaining the storage stability is obtained.

In addition, a developer may be contained in the photosensitive resin composition to impart a visible image by exposure. Examples of such a color-developing dye include a leuco dye, and a combination of a fluorane dye and a halogen compound.

Examples of the leuco dye include tris (4-dimethylamino-2-methylphenyl) methane [ leuco crystal violet ], tris (4-dimethylamino-2-methylphenyl) methane [ leuco malachite green ], and fluoran dyes. Among them, when leuco crystal violet is used, the contrast is good and preferable.

Examples of the halogen compound include bromopentane, bromoisopentane, brominated isobutylene, brominated ethylene, diphenylbromomethane, dibromotoluene, dibromomethane, tribromomethylphenylsulfone, carbon tetrabromide, tris (2, 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, iodoisobutane, 1,1, 1-trichloro-2, 2-bis (p-chlorophenyl) ethane, hexachloroethane, and chlorinated triazine compounds.

When the photosensitive resin composition contains these dyes, the content of the dyes in the photosensitive resin composition is preferably 0.1 to 10% by mass, respectively.

[ additives ]

The photosensitive resin composition may contain various additives in addition to the components (a) to (e), the photopolymerization initiator (other than 2,4, 5-triarylimidazole dimer), and the coloring matter.

In order to improve the thermal stability and storage stability of the photosensitive resin composition, it is preferable to contain a radical polymerization inhibitor or a benzotriazole (except for the component (d)) in the photosensitive resin composition.

Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, t-butylcatechol, cuprous chloride, 2, 6-di-t-butyl-p-cresol, 2 '-methylenebis (4-methyl-6-t-butylphenol), 2' -methylenebis (4-ethyl-6-t-butylphenol), nitrosophenylhydroxylamine aluminum salt, and diphenylnitrosamine.

Examples of benzotriazoles (other than component (d)) include 1,2, 3-benzotriazole, 1-chloro-1, 2, 3-benzotriazole, 4-carboxy-1, 2, 3-benzotriazole, 5-carboxy-1, 2, 3-benzotriazole, (N, N-dibutylamino) carboxybenzotriazole, N- (N, N-di-2-ethylhexyl) aminomethylene carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylene carboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) aminoethylidenecarboxybenzotriazole.

The total amount of the radical polymerization inhibitor and the benzotriazole (excluding the component (d)) is preferably 0.001 to 3% by mass based on the total solid content of the photosensitive resin composition, with a more preferred lower limit of 0.05% by mass and a more preferred upper limit of 1% by mass. The total amount added is preferably 0.001 mass% or more from the viewpoint of imparting storage stability to the photosensitive resin composition, and is preferably 3 mass% or less from the viewpoint of maintaining sensitivity.

The photosensitive resin composition may contain other plasticizers as necessary. Examples of the plasticizer include glycol esters such as polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxypropylene monoethyl ether, and polyoxyethylene polyoxypropylene monoethyl ether; sorbitan derivatives such as polyoxyethylene sorbitan laurate and polyoxyethylene sorbitan oleate; phthalic acid esters such as diethyl phthalate; o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl acetylcitrate, tri-n-propyl acetylcitrate, tri-n-butyl acetylcitrate, propylene glycol obtained by adding propylene oxide to both sides of bisphenol A, and ethylene glycol, polyoxyethylene glyceryl ether and polyoxypropylene glyceryl ether obtained by adding ethylene oxide to both sides of bisphenol A. Among them, from the viewpoint of suppressing the delay of the peeling time, polypropylene glycol in which propylene oxide having an average of 3 units is added to both ends of p-toluenesulfonamide and bisphenol a, and polyoxypropylene glyceryl ether having a weight average molecular weight of 3000 are preferable.

The content of the plasticizer in the photosensitive resin composition is preferably 0.1 to 50% by mass, and a more preferable lower limit is 1% by mass, and a more preferable upper limit is 30% by mass. The content is preferably 0.1% by mass or more from the viewpoint of suppressing the delay of the development time and imparting flexibility to the cured film, and is preferably 50% by mass or less from the viewpoint of suppressing insufficient curing and cold flow.

The photosensitive resin composition may contain other antioxidants as needed. Examples of the antioxidant include triphenyl phosphite, tris (2, 4-di-t-butylphenyl) phosphite, tris (monononylphenyl) phosphite, and bis (monononylphenyl) -dinonylphenyl phosphite.

The content of the antioxidant in the photosensitive resin composition is preferably in the range of 0.01 to 0.8 mass%, with a more preferred lower limit of 0.01 mass% and a more preferred upper limit of 0.3 mass%. When the content is 0.01% by mass or more, the effect of excellent hue stability of the photosensitive resin composition is exhibited well, and the sensitivity of the photosensitive resin composition at the time of exposure becomes good. On the other hand, when the content is 0.8% by mass or less, since color development can be suppressed, color stability is good and adhesion is also good.

< photosensitive resin composition preparation liquid >

The photosensitive resin composition may be used in the form of a photosensitive resin composition mixed liquid in which a solvent is added. Preferred examples of the solvent include ketones typified by Methyl Ethyl Ketone (MEK) and alcohols such as methanol, ethanol, and isopropanol. The solvent is preferably added to the photosensitive resin composition so that the viscosity of the photosensitive resin composition mixture liquid becomes 500 to 4000mPa · s at 25 ℃.

< photosensitive resin laminate >

In an embodiment, the photosensitive resin laminate includes a photosensitive resin layer formed of the photosensitive resin composition and a support for supporting the photosensitive resin layer. If necessary, the photosensitive resin layer may have a protective layer on the support formation side and on the opposite side.

As the support, a transparent support which transmits light irradiated by the exposure light source is preferable. Examples of such a support include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. As these films, stretched films may be used as needed.

The haze of the support is preferably 0.01% to 5.0%, more preferably 0.01% to 2.5%, and still more preferably 0.01% to 1.0%. When the thickness of the film is small, it is advantageous in terms of image formability and economy, but since it is necessary to maintain strength, a film of 10 μm to 30 μm is preferably used.

In addition, an important characteristic of the protective layer used in the photosensitive resin laminate is that the protective layer is sufficiently smaller than the support in terms of adhesion force with the photosensitive resin layer and can be easily peeled off. For example, a polyethylene film, a polypropylene film, or the like can be preferably used as the protective layer. Further, for example, a film excellent in releasability as disclosed in Japanese patent application laid-open No. 59-202457 can be used. The thickness of the protective layer is preferably 10 μm to 100 μm, and more preferably 10 μm to 50 μm.

The thickness of the photosensitive resin layer of the photosensitive resin laminate is preferably 5 μm to 100 μm, and more preferably 7 μm to 60 μm. The thickness of the photosensitive resin layer is appropriately selected according to the application because the resolution is improved as the thickness is smaller, and the film strength is improved as the thickness is thicker.

As a method for producing a photosensitive resin laminate by laminating the support, the photosensitive resin layer, and the protective layer as needed, a conventionally known method can be employed.

For example, a photosensitive resin composition for forming a photosensitive resin layer is first prepared as a photosensitive resin composition blend liquid, and is first applied to a support using a bar coater or a roll coater and dried, and a photosensitive resin layer formed from the photosensitive resin composition is laminated on the support. Next, a protective layer is laminated on the photosensitive resin layer as necessary, whereby a photosensitive resin laminate can be produced.

< method for Forming protective Pattern >

In an embodiment, the method of forming a protective pattern includes, for example, the following steps in order: a laminating step of forming a photosensitive resin layer on a substrate using the photosensitive resin laminate; an exposure step of exposing the photosensitive resin layer; and a developing step of removing the unexposed portion of the exposed photosensitive resin layer with a developing solution to form a protective pattern.

More specifically, for example, first, in the laminating step, a photosensitive resin layer is formed on a substrate using a laminator. Specifically, in the case where the photosensitive resin laminate has a protective layer, the photosensitive resin layer is thermally pressed and bonded to the surface of the substrate by a laminator after the protective layer is peeled off, and the laminate is laminated. Examples of the material of the substrate include copper, stainless steel (SUS), glass, and Indium Tin Oxide (ITO). In this case, the photosensitive resin layer may be laminated only on one surface of the substrate surface, or may be laminated on both surfaces as necessary. The heating temperature for the lamination is usually 40 to 160 ℃. In addition, the heating and pressure welding is performed for 2 times or more, thereby improving the adhesion between the obtained protective pattern and the substrate. In this case, a two-stage laminator provided with two pairs of rollers may be used for pressure bonding, or a laminate of the substrate and the photosensitive resin layer may be repeatedly passed through the rollers and pressure bonded.

Next, in the exposure step, the photosensitive resin composition is exposed to active light using an exposure machine. The exposure may be carried out after the support is peeled off, if necessary. In the case of exposure through a photomask, the exposure amount is determined by the illuminance of the light source and the exposure time, and may be measured using a light meter.

The exposure process may use a maskless exposure method. For maskless exposure, exposure is performed on a substrate by a direct writing apparatus without using a photomask. As the light source, a semiconductor laser having a wavelength of 350nm to 410nm, an ultrahigh pressure mercury lamp, or the like can be used. The trace pattern is computer-controlled, and the exposure amount in this case is determined by the illuminance of the exposure light source and the moving speed of the substrate.

Next, in the developing step, an unexposed portion of the exposed photosensitive resin layer is removed by a developing solution using a developing device. After exposure, when the support is present on the photosensitive resin layer, it is removed. Next, the unexposed portion is removed by development using a developer containing an aqueous alkaline solution, thereby obtaining a protective image. As the alkaline aqueous solution, Na is preferred₂CO₃Or K₂CO₃Etc. are water-solubleAnd (4) liquid. These may be selected according to the characteristics of the photosensitive resin layer, and are usually Na in a concentration of 0.2 to 2 mass%₂CO₃An aqueous solution. The alkaline aqueous solution may contain a surfactant, a defoaming agent, a small amount of an organic solvent for promoting development, and the like. The temperature of the developing solution in the developing step is preferably kept constant within a range of 20 to 40 ℃.

The protective pattern can be obtained by the above-mentioned steps, but a heating step at 100 to 300 ℃ may be carried out as the case may be. By performing this heating step, chemical resistance can be further improved. For heating, a heating furnace of a hot air, infrared ray, far infrared ray or the like can be used.

By using such a method for forming a protective pattern, a conductor pattern, a printed circuit board, a lead frame, a base material having a concave-convex pattern, a semiconductor package, and the like can be manufactured.

< method for Forming conductor Pattern >

As a method for forming the conductor pattern, a method including, for example, the following steps in order is preferable: a laminating step of forming a photosensitive resin layer on a substrate, which is a metal plate or a metal-coated insulating plate, using the photosensitive resin laminate; an exposure step of exposing the photosensitive resin layer; a developing step of removing the unexposed portion of the exposed photosensitive resin layer with a developing solution to form a protective pattern; and an etching or plating step of etching or plating the substrate on which the protective pattern is formed.

< method for producing printed Circuit Board >

As a method for manufacturing a printed wiring board, for example, after the conductor pattern is manufactured, the protective pattern is peeled from the substrate with an aqueous solution having an alkali stronger than a developer, and a printed wiring board having a desired wiring pattern can be obtained. For the production of printed wiring boards, copper-clad laminates or flexible substrates are preferably used as substrates. The alkali aqueous solution for stripping (hereinafter also referred to as "stripping solution") is not particularly limited, and an aqueous solution of NaOH or KOH having a concentration of 2 to 5 mass% is generally used. A small amount of water-soluble solvent may be added to the stripping solution. The temperature of the stripping solution in the stripping step is preferably in the range of 40 to 70 ℃.

< method for manufacturing lead frame >

As a method for manufacturing a lead frame, a method including, for example, the following etching steps is preferable: a protective pattern is formed by the aforementioned protective pattern forming method using a metal plate of copper, a copper alloy, an iron-based alloy, or the like as a substrate, and the exposed substrate is etched by development. After the etching step, a peeling step of peeling the protective pattern by the same method as the method for manufacturing the printed wiring board is preferably performed to obtain a desired lead frame.

< method for producing substrate having uneven Pattern >

The protective pattern formed by the protective pattern forming method can be used as a protective mask member for processing a substrate by a sand blast method. In this case, examples of the substrate include glass, silicon wafer, amorphous silicon, polycrystalline silicon, ceramics, sapphire, and a metal material.

Examples of the method for producing a substrate having a concave-convex pattern include the following methods: a protective pattern is formed on these substrates by the same method as the protective pattern forming method described above. Thereafter, a base material having a fine uneven pattern on a substrate is produced through a blast treatment step of blasting an abrasive material from the formed protective pattern and cutting the protective pattern to a target depth, and a peeling step of removing the portion of the protective pattern remaining on the substrate from the substrate with an alkali peeling liquid or the like. As the abrasive used in the blasting step, a known abrasive can be used, and for example, SiC or SiO can be used₂、Al₂O₃、CaCO₃Fine particles of ZrO, glass, stainless steel, etc. The particle size of the fine particles is preferably about 2 μm to about 100. mu.m.

< method for manufacturing semiconductor Package >

As a method for manufacturing a semiconductor package, for example, a wafer on which a large scale integrated circuit (LSI) is formed as a substrate is used, and after a protective pattern is formed thereon by the above-described protective pattern forming method, a semiconductor package is manufactured through the following steps. First, a plating step of forming a conductor pattern by applying columnar plating of copper, solder, or the like to the opening exposed by development is performed. Thereafter, a peeling step of peeling off the protective pattern by the same method as the above-described method for manufacturing a printed wiring board is performed, and a step of removing the thin metal layer except for the columnar plating by etching is further performed, thereby obtaining a desired semiconductor package.

The photosensitive resin composition can be used for precision processing of metal foil, such as manufacturing of printed wiring boards, manufacturing of lead frames for mounting IC chips, and manufacturing of metal masks; the manufacture of packages such as Ball Grid Array (BGA) or Chip Scale Package (CSP); manufacturing a tape substrate such as a Chip On Film (COF) or Tape Automated Bonding (TAB); the manufacture of semiconductor bumps, the manufacture of ITO electrodes, address electrodes, and the manufacture of barrier ribs for flat panel displays such as electromagnetic wave shields.

It should be noted that the above-mentioned various parameters were measured according to the measurement methods of the examples described later unless otherwise specified.

Examples

The following are descriptions of methods for producing the evaluation samples of examples 1 to 6 and comparative examples 1 to 6, and methods and results of evaluation of the obtained samples.

1. Preparation of evaluation sample

The photosensitive resin laminates of examples 1 to 6 and comparative examples 1 to 6 were produced as follows.

< production of photosensitive resin laminate >

Compounds shown in table 1 below were compounded in the composition ratios (unit is part by mass) shown in table 2 or 3 below, and sufficiently stirred and mixed to prepare a photosensitive resin composition solution. The obtained photosensitive resin composition solution was uniformly applied to the surface of a 16 μm-thick polyethylene terephthalate film (manufactured by Takara デュポンフィルム, GR-16) as a support by using a bar coater, and dried in a dryer at 95 ℃ for 3 minutes to form a photosensitive resin layer. The thickness of the photosensitive resin layer was 38 μm.

In the compositions shown in tables 2 and 3 below, the mass parts of B-1 and B-2 were the solid content.

Subsequently, a 19 μm-thick polyethylene film (タマポリ (product of Ltd.), GF-18) was attached as a protective layer to the surface of the photosensitive resin layer on the side where the polyethylene terephthalate film was not laminated to obtain a photosensitive resin laminate sample for evaluation of hue stability.

< entire surface of substrate >

As a substrate for evaluation of overhang peeling resistance, plating resistance, release sheet size, resolution, and sensitivity, a 1.6mm thick copper-clad laminate in which a 35 μm rolled copper foil was laminated was used, and the surface was subjected to wet polishing roll polishing (manufactured by スリーエム corporation, スコッチブライト (registered trademark) HD #600, passes 2 times).

< lamination >

The polyethylene film of the photosensitive resin laminate was peeled off, and was laminated on the entire surface of a copper-clad laminate preheated to 60 ℃ at a roll temperature of 105 ℃ by a hot roll laminator (manufactured by Asahi Kasei corporation, AL-70). The air pressure was set to 0.35MPa, and the lamination speed was set to 1.5 m/min.

< Exposure >

A mask film required for evaluating the photosensitive resin layer was placed on a polyethylene terephthalate film as a support, and exposure was performed with an exposure amount of 8 steps by a 21-step exposure rule by a scholar system using an ultrahigh pressure mercury lamp (オーク charging system, HMW-201 KB).

< development >

After the polyethylene terephthalate film was peeled off, 1 mass% Na was extruded at 30 ℃ using an alkali developing apparatus (フジ, dry film developing apparatus)₂CO₃The aqueous solution was sprayed for a predetermined time to dissolve and remove the unexposed portion of the photosensitive resin layer in a time 2 times the minimum development time. Here, the "minimum development time" means the minimum time required for the photosensitive resin layer of the unexposed portion to be completely dissolved.

< peeling of protective film >

After the copper sulfate plating described later, a 4 mass% aqueous solution of sodium hydroxide at 50 ℃ was sprayed for 72 seconds using a small-sized peeling device (manufactured by an inhibitor ), and the cured protective film was peeled off.

2. Evaluation method

(1) Weight average molecular weight and molecular weight distribution

The measurement was carried out using a Gel Permeation Chromatograph (GPC) system manufactured by Japan Spectroscopy, Inc., and using a calibration curve of standard polystyrene (Shodex STANDARD SM-105 manufactured by Showa Denko K.K.). The details of the measurement conditions are as follows.

Differential refractometer: the RI-1530 of the first embodiment,

a pump: the components of the PU-1580,

a degassing device: the DG-980-50 is adopted,

column heating furnace: the reaction solution is prepared from the raw materials of CO-1560,

column: KF-8025, KF-806 MX 2 and KF-807 in sequence,

eluent: THF (tetrahydrofuran)

(2) Evaluation of plating resistance

Using a substrate after 15 minutes from the treatment described in the above < lamination >, a substrate was laminated such that the width of the exposed portion and the unexposed portion was 1: the line pattern of the ratio of 1 was exposed and developed. Regarding the exposure, exposure was performed by an exposure amount of 6 steps by using an ultra-high pressure mercury lamp (オーク, HMW-201 KB) and by stout of 21 steps of exposure scale.

Further, copper sulfate plating was performed according to the following plating conditions.

< plating conditions >

Pretreatment: the resultant was immersed in an acidic degreasing bath (LP-200, manufactured by ローム & アンド & ハース, 10% sulfuric acid, 10% aqueous solution) at 40 ℃ for 10 minutes. Thereafter, the resultant was washed with water, and immersed in an APS aqueous solution (ammonium persulfate aqueous solution, concentration 200 g/L) at room temperature for 1 minute, and then immersed in a 10% sulfuric acid aqueous solution for 2 minutes after washing with water.

Copper sulfate plating: 2.0A/dm of the plating bath composition²Current density of (2) for 50 minutes of plating. At this time, the plating height measured by using a micrometer depth height (thickness) measuring instrument (KY-90 model, manufactured by Nissan precision optics Co., Ltd.) was 20 μm.

The copper sulfate-plated line with L/S =125/125 μm after peeling of the cured protective film was observed by an optical microscope and classified as follows. The cured protective film was peeled off by immersing the developed evaluation substrate in a 4 mass% aqueous solution of sodium hydroxide heated to 50 ℃.

◎ (remarkably good) no penetration of the secondary copper plating was seen at all.

○ good penetration of the secondary copper plating can be seen, but the penetration range is less than 2 μm on one side of the line.

△ (permission) the penetration of the secondary copper plating was observed, but the penetration range was 2 μm or more and 5 μm or less on one side of the line.

X (bad): the penetration range of the secondary copper plating is greater than 5 μm on one side of the line.

(3) Evaluation of hue stability (difference in light transmittance at 600 nm)

The polyethylene film was peeled from the photosensitive resin laminate, and the light transmittance at a wavelength of 600nm was measured using a UV-vis spectrometer (UV-240, manufactured by Shimadzu corporation). At this time, a polyethylene terephthalate film similar to the film used in the photosensitive resin laminate was placed on the reference side of the spectrometer, and the light transmittance from the polyethylene terephthalate film was eliminated.

The light transmittance of a sample for evaluation of hue stability of a photosensitive resin laminate produced using a photosensitive resin composition solution stored at 40 ℃ for 3 days was compared with that of a photosensitive resin laminate produced using a photosensitive resin composition solution before storage, and the results were classified based on the difference between them as follows.

○ (good). The absolute value of the difference in light transmittance at 600nm is less than 1%.

△ (permission), wherein the absolute value of the difference in light transmittance at 600nm is 1% or more and less than 5%.

X (bad): the absolute value of the difference in light transmittance at 600nm is 5% or more.

(4) Evaluation of sensitivity

Use of the above<Lamination of>The substrate after 15 minutes of the treatment described in (1) was exposed to light at a rate of 45mJ/cm using a 21-stage exposure scale manufactured by Schwark²The exposure is carried out at the exposure amount of (1) and development is carried out. The highest residual film number of the obtained cured protective film was set to the sensitivity, and was classified as follows.

◎ (remarkably good). The value of the sensitivity is 8 or more.

○ (good), the value of the sensitivity is 7 or more and less than 8.

The evaluation results of examples 1 to 6 are shown in Table 2 below, and the evaluation results of comparative examples 1 to 6 are shown in Table 3 below.

[ Table 1]

[ Table 2]

TABLE 2

[ Table 3]

TABLE 3

Claims

1. A photosensitive resin composition comprising:

(a) an alkali-soluble polymer;

(b) an addition polymerizable monomer having an ethylenically unsaturated bond;

(c)2,4, 5-triarylimidazole dimer;

(d) a compound represented by the following general formula (I); and

(e) an epoxy compound, which is a compound of the formula,

in the formula (I), R₁～R₄Each independently hydrogen or alkyl, and R₅Is a group represented by the following general formula (II):

in the formula (II), R₆And R₇Each independently selected from hydrogen, linear or branched alkyl optionally having substituents, or linear or branched hydroxyalkyl optionally having substituents, R₆And R₇One or both of which are not hydrogen, and n is an integer of 1 to 4.

2. The photosensitive resin composition according to claim 1, wherein the epoxy compound comprises a compound represented by the following general formula (III):

in the formula (III), X is an oxygen atom or a group of the formula-O-X₁A group of formula-O-X₁in-O-X₁A 2-valent group containing at least 1 hydrocarbon group selected from the group consisting of a linear or branched alkylene group having 1 to 100 carbon atoms, an alicyclic alkylene group having 3 to 10 carbon atoms, and an arylene group having 5 to 20 carbon atoms, and the hydrocarbon group is optionally substituted with at least 1 atom selected from the group consisting of a halogen atom, an oxygen atom, and a nitrogen atom; r₈And R₉Each independently is a 2-valent group containing at least 1 hydrocarbon group selected from the group consisting of a linear or branched alkylene group having 1 to 100 carbon atoms, an alicyclic alkylene group having 3 to 10 carbon atoms, and an arylene group having 5 to 20 carbon atoms, and the hydrocarbon group is optionally substituted with at least 1 atom selected from the group consisting of a halogen atom, an oxygen atom, and a nitrogen atom, and R is₈And R₉When they coexist, R₈And R₉Identical or different, R₈And R₉Not simultaneously, - (R)₈-O) -and- (R)₉-O) -repeatsThe arrangement of the units is block or random; and l and m are each independently an integer of 0 to 50, and l + m is an integer of 1 to 50.

3. The photosensitive resin composition according to claim 1 or 2, wherein a content of the epoxy compound is 0.001% by mass or more and less than 0.1% by mass with respect to a total solid content of the photosensitive resin composition.

4. The photosensitive resin composition according to claim 1 or 2, wherein the 2,4, 5-triarylimidazole dimer comprises a compound represented by the following general formula (IV):

in the formula (IV), Y¹、Y²And Y³Each independently represents one group selected from the group consisting of hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen, and p, q, and r are each independently an integer of 1 to 5.

5. The photosensitive resin composition according to claim 1 or 2, wherein the photosensitive resin composition further comprises an N-aryl amino acid.

6. The photosensitive resin composition according to claim 1 or 2, further comprising a compound represented by the following general formula (V):

in the formula (V), Z is hydrogen or alkyl with 1-4 carbon atoms.

7. A photosensitive resin laminate comprising: a photosensitive resin layer comprising the photosensitive resin composition according to any one of claims 1 to 6, and a support for supporting the photosensitive resin layer.

8. A method of forming a protective pattern, comprising:

a laminating step of laminating the photosensitive resin laminate according to claim 7 on a substrate;

9. The method of forming a protective pattern according to claim 8, wherein the exposure step is a step of performing exposure by direct writing of a writing pattern.

10. A method of forming a conductor pattern, comprising:

a laminating step of laminating the photosensitive resin laminate according to claim 7 on a metal plate or a metal-coated insulating plate;

11. A method of manufacturing a printed circuit board, comprising:

a laminating step of laminating the photosensitive resin laminate according to claim 7 on a copper-clad laminate or a flexible substrate;

12. A method of manufacturing a lead frame, comprising:

a laminating step of laminating the photosensitive resin laminate according to claim 7 on a metal plate;

and a peeling step of peeling the protective pattern from the metal plate.

13. A method of manufacturing a semiconductor package, comprising:

a laminating step of laminating the photosensitive resin laminate according to claim 7 on a wafer on which an LSI, which is a large scale integrated circuit, is formed;

and a peeling step of peeling the protective pattern from the wafer.