CN112445068A - Photosensitive resin composition - Google Patents

Photosensitive resin composition Download PDF

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Publication number
CN112445068A
CN112445068A CN202010895678.6A CN202010895678A CN112445068A CN 112445068 A CN112445068 A CN 112445068A CN 202010895678 A CN202010895678 A CN 202010895678A CN 112445068 A CN112445068 A CN 112445068A
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resin composition
photosensitive resin
meth
component
acrylate
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唐川成弘
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Ajinomoto Co Inc
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Ajinomoto Co Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/144—Polymers containing more than one epoxy group per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/282—Applying non-metallic protective coatings for inhibiting the corrosion of the circuit, e.g. for preserving the solderability
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/3452—Solder masks

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Architecture (AREA)
  • Materials For Photolithography (AREA)
  • Polymerisation Methods In General (AREA)
  • Epoxy Resins (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The invention provides a photosensitive resin composition which can obtain a cured product with excellent bending property and insulating property and has excellent resolution. The photosensitive resin composition comprises (A) a resin containing an ethylenically unsaturated group and a carboxyl group, (B) an epoxy resin, (C) a photopolymerizable monomer and (D) a photopolymerization initiator, wherein any one of the component (A), the component (B) and the component (C) contains an oxyalkylene chain, and is a reference material represented by the following formula (1)The number X is 4 or more and 25 or less.

Description

Photosensitive resin composition
Technical Field
The present invention relates to a photosensitive resin composition. The invention also relates to a photosensitive film obtained by using the photosensitive resin composition, a photosensitive film with a support, a printed wiring board and a semiconductor device.
Background
In a printed wiring board, a solder resist layer may be provided as a permanent protective film for suppressing adhesion of solder to a portion where solder is not required and for suppressing corrosion of a circuit board. As the solder resist layer, for example, a photosensitive resin composition as described in patent document 1 is generally used.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2014-115672.
Disclosure of Invention
Technical problem to be solved by the invention
In general, a photosensitive resin composition for a solder resist layer is required to have resolution (resolution), insulation properties, and the like. In recent years, with the miniaturization of electronic devices and the like, further space saving is required, and hence bendability (bendability) is required for printed wiring boards. The solder resist layer used for the printed wiring board is also required to have flexibility.
However, the present inventors have conducted extensive studies and as a result, have found that if the flexibility is improved, the insulation property of the solder resist layer may be deteriorated, and that there is a trade-off relationship between the flexibility and the insulation property in the photosensitive resin composition for the solder resist layer.
The subject of the invention is to provide: a photosensitive resin composition which can give a cured product having excellent flexibility and insulation properties and having excellent resolution, a photosensitive film obtained from the photosensitive resin composition, a photosensitive film with a support, a printed wiring board, and a semiconductor device are provided.
Technical scheme for solving technical problem
The present inventors have conducted extensive studies and, as a result, have found that flexibility and insulation properties are improved by including an oxyalkylene chain in any of an ethylenically unsaturated group-and carboxyl group-containing resin, an epoxy resin and a photopolymerizable monomer contained in a photosensitive resin composition and by allowing the oxyalkylene chain to satisfy a predetermined relationship, and have completed the present invention.
That is, the present invention includes the following items,
[1] a photosensitive resin composition comprising the following components (A) to (D),
(A) a resin containing an ethylenically unsaturated group and a carboxyl group,
(B) Epoxy resin,
(C) Photopolymerizable monomer, and
(D) a photopolymerization initiator,
wherein any of the component (A), the component (B) and the component (C) contains an oxyalkylene chain, and a parameter X represented by the following formula (1) is 4 to 25 inclusive;
[ mathematical formula 1]
Figure BDA0002658381230000021
In the formula (1), the reaction mixture is,
MAOthe value represented by the following formula (2) is shown in the case where the component containing an oxyalkylene chain is a copolymer, or the molecular weight of the oxyalkylene chain of each compound contained in the (A) to (C)/((the molecular weight of each compound contained in the (A) to (C)) is shown in the case where the component containing an oxyalkylene chain is not a copolymer,
n represents the solid content (parts by mass) of all the compounds contained in the components (A) to (C),
n represents the solid content (parts by mass) of each compound contained in components (A) to (C);
[ mathematical formula 2]
Figure BDA0002658381230000022
In the formula (2), the reaction mixture is,
AAOrepresents the molecular weight of the oxyalkylene chain of each monomer comprising an oxyalkylene chain,
a represents the molecular weight of each monomer containing an oxyalkylene chain,
BAOrepresents the number of moles of each monomer containing an oxyalkylene chain,
b represents the total mole number of all monomers contained in the copolymer;
[2] the photosensitive resin composition according to [1], further comprising (E) an inorganic filler;
[3] the photosensitive resin composition according to [1] or [2], wherein an oxyalkylene chain is contained in any one of the component (B) and the component (C);
[4] the photosensitive resin composition according to any one of [1] to [3], wherein the component (A) comprises an acid-modified unsaturated epoxy ester resin;
[5] the photosensitive resin composition according to any one of [1] to [4], wherein the component (A) comprises an acid-modified epoxy (meth) acrylate;
[6] the photosensitive resin composition according to any one of [1] to [5], wherein the component (A) comprises: any one of acid-modified epoxy (meth) acrylate containing a naphthalene skeleton and acid-modified epoxy (meth) acrylate containing a bisphenol skeleton;
[7] the photosensitive resin composition according to [6], wherein the acid-modified epoxy (meth) acrylate having a bisphenol skeleton has one of a bisphenol A skeleton and a bisphenol F skeleton;
[8] the photosensitive resin composition according to any one of [1] to [7], wherein the component (B) has a biphenyl skeleton;
[9] the photosensitive resin composition according to any one of [1] to [8], wherein the component (D) comprises an oxime ester photopolymerization initiator;
[10] a photosensitive film comprising the photosensitive resin composition according to any one of [1] to [9 ];
[11] a photosensitive film with a support, comprising: a support, and a photosensitive resin composition layer provided on the support and containing the photosensitive resin composition according to any one of [1] to [9 ];
[12] a printed wiring board comprising an insulating layer formed by using a cured product of the photosensitive resin composition according to any one of [1] to [9 ];
[13] the printed wiring board according to [12], wherein the insulating layer is a solder resist layer;
[14] a semiconductor device comprising the printed wiring board of [12] or [13 ].
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention, if adopted, can provide: a photosensitive resin composition which can give a cured product having excellent flexibility and insulation properties and having excellent resolution, a photosensitive film obtained from the photosensitive resin composition, a photosensitive film with a support, a printed wiring board, and a semiconductor device are provided.
Detailed Description
The photosensitive resin composition, photosensitive film with a support, printed wiring board, and semiconductor device of the present invention will be described in detail below.
[ photosensitive resin composition ]
The photosensitive resin composition of the present invention comprises (A) a resin containing an ethylenically unsaturated group and a carboxyl group, (B) an epoxy resin, (C) a photopolymerizable monomer, and (D) a photopolymerization initiator, wherein any one of the components (A), (B), and (C) contains an oxyalkylene chain, and the parameter X represented by the following formula (1) is 4 to 25;
[ mathematical formula 3]
Figure BDA0002658381230000031
In the formula (1), MAOThe value represented by the following formula (2) is shown in the case where the component containing an oxyalkylene chain is a copolymer, or the value represented by ((molecular weight of oxyalkylene chain of each compound contained in components a) to C)/((molecular weight of each compound contained in components (a) to C)) is shown in the case where the component containing an oxyalkylene chain is not a copolymer. N represents the solid content (parts by mass) of all the compounds contained in components (A) to (C). n represents the solid content (parts by mass) of each compound contained in components (A) to (C);
[ mathematical formula 4]
Figure BDA0002658381230000041
In the formula (2), AAODenotes the molecular weight of the oxyalkylene chain of each monomer containing an oxyalkylene chain, A denotes the molecular weight of each monomer containing an oxyalkylene chain, BAORepresents the moles of each monomer containing an oxyalkylene chainThe number of moles, B, represents the total number of moles of all monomers contained in the copolymer.
In the present invention, by adjusting the content of the oxyalkylene chain contained in any of the components (a), (B) and (C) relative to the whole of the components (a) to (C) as the curable resin, it is possible to provide a photosensitive resin composition which can obtain a cured product having excellent flexibility and insulation properties and also has excellent resolution. In addition, a cured product having excellent adhesion can be obtained. The present inventors have found that if a photosensitive resin composition is hydrophilic, the flexibility is excellent, but the insulation is poor. Therefore, the content of oxyalkylene chains having a hydrophobic structure participating in polymerization in the components (A) to (C) is focused. As a result, if the content of the oxyalkylene chain contained in any of the components (a), (B) and (C) is adjusted to satisfy the above formula (1) with respect to the whole of the components (a) to (C), the flexibility of the photosensitive resin composition is increased, and both the flexibility and the insulating property can be improved. Further, it is considered that the adhesiveness is also improved by the hydrophobic structure of the oxyalkylene chain.
The oxyalkylene chain is a structure represented by the following formula (a);
[ chemical formula 1]
Figure BDA0002658381230000042
In the formula (a), R independently represents an alkylene group optionally having a substituent, and q represents an integer of 1 to 100.
R represents an alkylene group optionally having a substituent. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably an alkylene group having 1 to 5, 1 to 4, or 1 to 3 carbon atoms. Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, an isopropylene group, an n-butylene group, a pentylene group, and a hexylene group.
The alkylene group may have a substituent. Examples of the substituent include an alkyl group having 1 to 3 carbon atoms, a halogen atom and the like. The substituents may be contained singly or in combination of 2 or more.
q represents an integer of 1 to 100, preferably an integer of 1 to 50, more preferably an integer of 1 to 10, and further preferably an integer of 1 to 5.
Examples of the oxyalkylene chain include a methylene oxide, an Ethylene Oxide (EO), a Propylene Oxide (PO), an isopropylene oxide, and a Butylene Oxide (BO).
The oxyalkylene chain is preferably contained in the component (A), preferably in the component (B), and preferably in the component (C). The oxyalkylene chain is preferably contained in the components (a) and (B), preferably in the components (a) and (C), preferably in the components (B) and (C), preferably in the components (a) to (C). Among these, the oxyalkylene chain is more preferably contained in the component (B) and the component (C).
(A) The components (A) to (C) may have 1 oxyalkylene chain or a plurality of oxyalkylene chains in 1 molecule.
The photosensitive resin composition may further contain an optional component in combination with the components (a) to (D). Examples of the optional components include (E) an inorganic filler, (F) a solvent, and (G) other additives. Hereinafter, each component contained in the photosensitive resin composition will be described in detail.
< (A) resin having ethylenically unsaturated group and carboxyl group
The photosensitive resin composition contains a resin containing an ethylenically unsaturated group and a carboxyl group as the component (A). By adding the component (A) to the photosensitive resin composition, the developability can be improved.
Examples of ethylenically unsaturated groups include: vinyl group, allyl group, propargyl group, butenyl group, ethynyl group, phenylethynyl group, maleimide group, nadimido group (nadiimide), and (meth) acryloyl group is preferable from the viewpoint of reactivity in photo radical polymerization. "(meth) acryloyl" means methacryloyl and acryloyl.
(A) The component (A) has an ethylenically unsaturated group and a carboxyl group. With this structure, the component (a) can realize not only photoradical polymerization but also alkaline development. The component (a) is preferably a resin having both a carboxyl group and 2 or more ethylenically unsaturated groups in 1 molecule.
As one form of the resin containing an ethylenically unsaturated group and a carboxyl group, an acid-modified unsaturated epoxy ester resin obtained by reacting an unsaturated carboxylic acid with an epoxy compound and further with an acid anhydride, and the like can be cited. Specifically, an unsaturated epoxy ester resin is obtained by reacting an unsaturated carboxylic acid with an epoxy compound, and an acid-modified unsaturated epoxy ester resin is obtained by reacting an unsaturated epoxy ester resin with an acid anhydride. Any of the epoxy compound, the unsaturated carboxylic acid and the acid anhydride may have an oxyalkylene chain.
The epoxy compound may be any compound having an epoxy group in the molecule, and examples thereof include: bisphenol epoxy resins such as epoxy group-containing copolymers, bisphenol a epoxy resins, hydrogenated bisphenol a epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, bisphenol S epoxy resins, and modified bisphenol F epoxy resins modified by reacting epichlorohydrin with bisphenol F epoxy resins to have 3 or more functions; biphenol-type epoxy resins such as biphenol-type epoxy resins and tetramethylbiphenol-type epoxy resins; novolac (novolac) type epoxy resins such as phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol a novolac type epoxy resins, and alkylphenol novolac type epoxy resins; fluorine-containing epoxy resins such as bisphenol AF type epoxy resins and perfluoroalkyl type epoxy resins; naphthalene-skeleton-containing epoxy resins (naphthalene-skeleton-containing epoxy resins) such as naphthalene-type epoxy resins, dihydroxynaphthalene-type epoxy resins, polyhydroxynaphthalene-type epoxy resins, naphthol-type epoxy resins, binaphthol-type epoxy resins, naphthylene ether-type epoxy resins, naphthol novolac-type epoxy resins, and naphthalene-type epoxy resins obtained by a condensation reaction of polyhydroxynaphthalene and aldehydes; a biphenol-type epoxy resin; dicyclopentadiene type epoxy resins; a trisphenol type epoxy resin; tertiary butyl catechol-type epoxy resins; epoxy resins having a condensed ring skeleton such as anthracene-type epoxy resins; glycidyl amine type epoxy resins; glycidyl ester type epoxy resins; biphenyl type epoxy resin; a linear aliphatic epoxy resin; an epoxy resin having a butadiene structure; a cycloaliphatic epoxy resin; heterocyclic epoxy resins; epoxy resins containing spiro rings; cyclohexane dimethanol type epoxy resins; a trimethylol type epoxy resin; tetraphenylethane type epoxy resins; glycidyl group-containing acrylic resins such as polyglycidyl (meth) acrylate and copolymers of glycidyl methacrylate and acrylic acid esters; a fluorene-type epoxy resin; halogenated epoxy resins, and the like.
The epoxy compound is preferably an epoxy group-containing copolymer or an aromatic skeleton-containing epoxy resin from the viewpoint of reducing the average linear thermal expansion coefficient. Here, the aromatic skeleton refers to a concept that also includes polycyclic aromatic and aromatic heterocycles. The epoxy compound is preferably an epoxy resin containing a naphthalene skeleton; an epoxy resin containing a condensed ring skeleton; biphenyl type epoxy resin; bisphenol epoxy resins such as bisphenol F epoxy resin and bisphenol a epoxy resin; cresol novolac type epoxy resins; glycidyl ester type epoxy resin.
The epoxy group-containing copolymer can be obtained by polymerizing an epoxy group-containing monomer and an optional monomer used as necessary. Examples of the epoxy group-containing monomer include: epoxy group-containing (meth) acrylate monomers such as glycidyl (meth) acrylate, 3, 4-epoxybutyl (meth) acrylate, 2-methyl-3, 4-epoxycyclohexyl (meth) acrylate, and allyl glycidyl ether, and glycidyl (meth) acrylate is preferred. The epoxy group-containing monomers may be used alone in 1 kind or in combination of 2 or more kinds.
Examples of the optional monomer include: styrene, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, docosyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, acrylamide, N-dimethyl (meth) acrylamide, (meth) acrylonitrile, 3- (meth) acryloylpropyltrimethoxysilane, N-dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, styrene, alpha-methylstyrene, p-methoxystyrene, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, benzyl (meth, 1, 4-cyclohexanedimethanol mono (meth) acrylate, glycerol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, lactone-modified (meth) acrylate having a hydroxyl group at the terminal, 1-adamantyl (meth) acrylate, and the like, with n-butyl (meth) acrylate being preferred. Any of the monomers may be used alone in 1 kind, or 2 or more kinds may be used in combination. "(meth) acrylic acid" means acrylic acid and methacrylic acid. "(meth) acrylate" means acrylate and methacrylate.
As the naphthalene skeleton-containing epoxy resin, a dihydroxynaphthalene-type epoxy resin, a polyhydroxynaphthalene-type epoxy resin, and a naphthalene-type epoxy resin obtained by a condensation reaction of polyhydroxynaphthalene and aldehydes are preferable. Examples of the dihydroxynaphthalene-type epoxy resin include: 1, 3-diepoxyloxynaphthalene (diglycidyl naphthalene), 1, 4-diepoxyloxynaphthalene, 1, 5-diepoxyloxynaphthalene, 1, 6-diepoxyloxynaphthalene, 2, 3-diepoxyloxynaphthalene, 2, 6-diepoxyloxynaphthalene, 2, 7-diepoxyloxynaphthalene, and the like. As the polyhydroxynaphthalene type epoxy resin, for example, there can be mentioned: 1,1 '-bis (2-glycidoxy) naphthalene, 1- (2, 7-diepoxoxy) -1' - (2 '-glycidoxy) binaphthyl, 1' -bis (2, 7-diepoxoxy) naphthalene, and the like. Examples of the naphthalene-type epoxy resin obtained by the condensation reaction of a polyhydroxynaphthalene and an aldehyde include 1,1 '-bis (2, 7-diepoxygonaphthalenyl) methane, 1- (2, 7-diepoxygonaphthalenyl) -1' - (2 '-glycidyloxynaphthyl) methane, and 1,1' -bis (2-glycidyloxynaphthyl) methane.
Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, glycidyl methacrylate, and glycidyl acrylate, and 1 kind of these carboxylic acids may be used alone, or 2 or more kinds may be used in combination. Among them, acrylic acid and methacrylic acid are preferable from the viewpoint of improving the photocurability of the photosensitive resin composition. In the present specification, the epoxy ester resin which is a reaction product of the epoxy compound and (meth) acrylic acid may be referred to as "epoxy (meth) acrylate", and herein, the epoxy group of the epoxy compound is substantially eliminated by the reaction with (meth) acrylic acid.
Examples of the acid anhydride include: maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, and the like, and 1 kind of these acid anhydrides may be used alone, or 2 or more kinds may be used in combination. Among them, succinic anhydride and tetrahydrophthalic anhydride are preferable from the viewpoint of improving the resolution and insulation reliability of the cured product.
When the acid-modified unsaturated epoxy ester resin is obtained, a catalyst, a solvent, a polymerization inhibitor and the like may be used as required.
The acid-modified unsaturated epoxy ester resin is preferably an acid-modified epoxy (meth) acrylate, and more preferably any of an acid-modified epoxy (meth) acrylate having a naphthalene skeleton and an acid-modified epoxy (meth) acrylate having a bisphenol skeleton. The "epoxy" in the acid-modified unsaturated epoxy ester resin means a structure derived from the above-mentioned epoxy compound. For example, the term "bisphenol-type acid-modified epoxy (meth) acrylate" refers to an acid-modified unsaturated epoxy ester resin obtained by using a bisphenol-type epoxy resin as an epoxy compound and (meth) acrylic acid as an unsaturated carboxylic acid.
The acid-modified unsaturated epoxy ester resin is preferably a (meth) acrylic polymer having a glass transition temperature of-20 ℃ or lower. The (meth) acrylic polymer is a polymer containing a structural unit having a structure formed by polymerizing a (meth) acrylic monomer. Examples of such a (meth) acrylic polymer include a polymer obtained by polymerizing a (meth) acrylic monomer, and a polymer obtained by copolymerizing a (meth) acrylic monomer and a monomer copolymerizable with the (meth) acrylic monomer.
Examples of the (meth) acrylic polymer having a glass transition temperature of-20 ℃ or lower include acid-modified unsaturated epoxy (meth) acrylic copolymers obtained by reacting an epoxy group-containing copolymer with (meth) acrylic acid and further reacting the epoxy group-containing copolymer with an acid anhydride. Specifically, an unsaturated epoxy (meth) acrylic copolymer is obtained by reacting an epoxy group-containing copolymer with (meth) acrylic acid, and an acid-modified unsaturated epoxy (meth) acrylic copolymer is obtained by reacting an acid anhydride with the unsaturated epoxy (meth) acrylic copolymer.
A preferred embodiment of the (meth) acrylic polymer having a glass transition temperature of-20 ℃ or lower is a compound obtained by reacting an epoxy group-containing copolymer obtained by polymerizing an epoxy group-containing monomer and an optional monomer, a (meth) acrylic acid, and an acid anhydride, wherein the epoxy group-containing monomer is glycidyl methacrylate, the optional monomer is butyl acrylate, and the acid anhydride is tetrahydrophthalic anhydride.
Commercially available products can be used as the acid-modified unsaturated epoxy ester resin, and specific examples thereof include: "ZAR-2000" (a reaction product of bisphenol A epoxy resin, acrylic acid and succinic anhydride) manufactured by Nippon Kagaku K.K., "ZFR-1491H", "ZFR-1533H" (a reaction product of bisphenol F epoxy resin, acrylic acid and tetrahydrophthalic anhydride (acid-modified epoxy acrylate containing a bisphenol F skeleton)), and "PR-300 CP" (a reaction product of cresol novolak epoxy resin, acrylic acid and acid anhydride) manufactured by Showa Denko K.K., and the like. These resins may be used alone in 1 kind, or 2 or more kinds may be used in combination.
Another embodiment of the resin containing an ethylenically unsaturated group and a carboxyl group includes: an unsaturated modified (meth) acrylic resin obtained by introducing an ethylenically unsaturated group by reacting an epoxy compound having an ethylenically unsaturated group with a (meth) acrylic resin having a structural unit obtained by polymerizing (meth) acrylic acid. Examples of the epoxy compound having an ethylenically unsaturated group include: glycidyl methacrylate, 4-hydroxybutyl ester glycidyl ether (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, and the like. Further, an acid anhydride may be reacted with a hydroxyl group generated when an unsaturated group is introduced. The acid anhydride may be the same as the acid anhydride described above, and the preferable range is the same.
Commercially available products can be used as such unsaturated modified (meth) acrylic resins, and specific examples thereof include: "SPC-1000" and "SPC-3000" available from Showa Denko K.K., "CYCLOMER P (ACA) Z-250", "CYCLOMER P (ACA) Z-251", "CYCLOMER P (ACA) Z-254", "CYCLOMER P (ACA) Z-300" and "CYCLOMER P (ACA) Z-320" available from Daicel-ALLNEX K.K.
The weight average molecular weight of the component (a) is preferably 1000 or more, more preferably 1500 or more, and further preferably 2000 or more, from the viewpoint of film-forming properties. The upper limit is preferably 50000 or less, more preferably 30000 or less, and further preferably 25000 or less, from the viewpoint of developability. The weight average molecular weight is a weight average molecular weight in terms of polystyrene measured by Gel Permeation Chromatography (GPC).
The acid value of the component (A) is preferably 0.1mgKOH/g or more, more preferably 0.5mgKOH/g or more, and still more preferably 1mgKOH/g or more, from the viewpoint of improving the alkali developability of the photosensitive resin composition. On the other hand, from the viewpoint of suppressing elution of a fine pattern of a cured product by development and improving insulation reliability, the acid value is preferably 150mgKOH/g or less, more preferably 120mgKOH/g or less, and still more preferably 100mgKOH/g or less. The acid value herein refers to the residual acid value of the carboxyl group present in the component (a), and the acid value can be measured by the following method. First, about 1g of a measurement resin solution was precisely weighed, and 30g of acetone was added to the resin solution to uniformly dissolve the resin solution. Then, phenolphthalein as an indicator was added to the solution in an appropriate amount, and titration was performed with a 0.1N KOH aqueous solution. Then, the acid value was calculated by the following formula.
Formula (II): a (b) ═ 10 × Vf × 56.1/(Wp × I)
In the above formula, A (b) represents an acid value (mgKOH/g), Vf represents a titration amount (mL) of KOH, Wp represents a measurement resin solution mass (g), and I represents a ratio (% by mass) of nonvolatile components in the measurement resin solution.
(A) In the production of the component (b), the ratio of the "number of moles of epoxy groups in the epoxy resin" to the "total number of moles of carboxyl groups in the unsaturated carboxylic acid and the acid anhydride" is preferably in the range of 1:0.8 to 1.3, more preferably in the range of 1:0.9 to 1.2, from the viewpoint of improving the storage stability.
The glass transition temperature (Tg) of the component (A) is preferably-300 ℃ or higher, more preferably-200 ℃ or higher, still more preferably-80 ℃ or higher, preferably-20 ℃ or lower, more preferably-23 ℃ or lower, and still more preferably-25 ℃ or lower, from the viewpoint of improving flexibility. Here, the glass transition temperature of the component (a) is a theoretical glass transition temperature of the main chain of the component (a), and the theoretical glass transition temperature can be calculated by the FOX equation shown below. Since the glass transition temperature obtained by the FOX formula substantially coincides with the glass transition temperature measured by differential scanning calorimetry (TMA, DSC, DTA), the glass transition temperature of the main chain of component (a) can also be measured by differential scanning calorimetry; 1/Tg ═ W1/Tg1) + (W2/Tg2) + … + (Wm/Tgm)
W1+W2+…+Wm＝1
Wm denotes the content (mass%) of each monomer constituting the component (a), and Tgm denotes the glass transition temperature (K) of each monomer constituting the component (a).
From the viewpoint of improving the alkali developability, the content of the component (a) is preferably 3 mass% or more, more preferably 5 mass% or more, and still more preferably 10 mass% or more, assuming that the nonvolatile component in the photosensitive resin composition is 100 mass%. From the viewpoint of improvement in heat resistance and average linear expansion coefficient, the upper limit is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less. In the present invention, unless otherwise stated, the content of each component in the photosensitive resin composition is a value when the nonvolatile component in the photosensitive resin composition is 100 mass%.
(B) epoxy resin
The photosensitive resin composition contains an epoxy resin as the component (B). By containing the component (B), insulation reliability can be improved. However, the component (B) mentioned here does not include epoxy resins containing an ethylenically unsaturated group and a carboxyl group.
Examples of the component (B) include: bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, t-butyl catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, aliphatic epoxy resin containing an oxidized olefinic chain, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic type epoxy resin, epoxy resin containing a spiro ring, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, naphthylene ether type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, t-butyl catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, cresol novolac type epoxy resin, cresol, Trimethylol type epoxy resins, tetraphenylethane type epoxy resins, and the like. Among them, the epoxy resin (B) is preferably a biphenyl type epoxy resin or a linear aliphatic epoxy resin, and more preferably a biphenyl type epoxy resin. (B) The epoxy resin can be used alone in 1 kind, also can be used in more than 2 kinds combination. Examples of the oxyalkylene-chain-containing aliphatic epoxy resin include oxyalkylene-chain-containing linear aliphatic epoxy resins, oxyalkylene-chain-containing branched aliphatic epoxy resins, oxyalkylene-chain-containing cyclic aliphatic epoxy resins, and the like.
The photosensitive resin composition preferably contains an epoxy resin having 2 or more epoxy groups in 1 molecule as the component (B). From the viewpoint of remarkably obtaining the desired effect of the present invention, the proportion of the epoxy resin having 2 or more epoxy groups in 1 molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more, relative to 100% by mass of the nonvolatile component of the component (B).
(B) The component (C) includes an epoxy resin which is liquid at a temperature of 20 ℃ (hereinafter sometimes referred to as "liquid epoxy resin") and an epoxy resin which is solid at a temperature of 20 ℃ (hereinafter sometimes referred to as "solid epoxy resin"). In the resin composition, the component (B) may contain only a liquid epoxy resin, may contain only a solid epoxy resin, or may contain both a liquid epoxy resin and a solid epoxy resin.
The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in 1 molecule, and more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in 1 molecule.
The solid epoxy resin is preferably a biphenol-type epoxy resin, a naphthalene-type tetrafunctional epoxy resin, a cresol novolak-type epoxy resin, a dicyclopentadiene-type epoxy resin, a trisphenol-type epoxy resin, a naphthol-type epoxy resin, a biphenyl-type epoxy resin, a naphthylene ether-type epoxy resin, an anthracene-type epoxy resin, a bisphenol a-type epoxy resin, a bisphenol AF-type epoxy resin, or a tetraphenylethane-type epoxy resin, and more preferably a naphthalene-type epoxy resin.
Specific examples of the solid epoxy resin include: "HP 4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC; "N-690" (cresol novolac type epoxy resin) manufactured by DIC; "N-695" (cresol novolac type epoxy resin) available from DIC; "HP-7200", "HP-7200 HH" and "HP-7200H" (dicyclopentadiene type epoxy resins) manufactured by DIC; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S" and "HP 6000" (naphthylene ether type epoxy resins) available from DIC; "EPPN-502H" (a trisphenol type epoxy resin) manufactured by Nippon chemical Co., Ltd.; "NC 7000L" (naphthol novolac type epoxy resin) manufactured by japan chemical corporation; "NC 3000H", "NC 3000L" and "NC 3100" (biphenyl type epoxy resins) manufactured by japan chemical corporation; "ESN 475V" (naphthol type epoxy resin) manufactured by Nippon iron Japan chemical Co., Ltd; "ESN 485" (naphthol novolac type epoxy resin) manufactured by Nippon iron Japan chemical Co., Ltd.; "YX 4000H", "YX 4000" and "YL 6121" (biphenyl type epoxy resin) manufactured by mitsubishi chemical corporation; "YX 4000 HK" (a biphenol-type epoxy resin) manufactured by mitsubishi chemical corporation; "YX 8800" (anthracene-based epoxy resin) available from Mitsubishi chemical; PG-100 and CG-500 produced by Osaka gas chemical Co., Ltd; "YL 7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi chemical corporation; "YL 7800" (fluorene-based epoxy resin) manufactured by Mitsubishi chemical corporation; "jER 1010" (solid bisphenol a type epoxy resin) manufactured by mitsubishi chemical corporation; "jER 1031S" (Tetrahydroxyphenylethane-type epoxy resin) manufactured by Mitsubishi chemical corporation, and the like. These can be used alone in 1, can also be more than 2 combination use.
The liquid epoxy resin is preferably a liquid epoxy resin having 2 or more epoxy groups in 1 molecule.
The liquid epoxy resin is preferably a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, a naphthalene type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, a phenol novolac type epoxy resin, an alicyclic epoxy resin having an ester skeleton, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, a glycidyl amine type epoxy resin, or an epoxy resin having a butadiene structure, and more preferably a bisphenol a type epoxy resin or a bisphenol F type epoxy resin.
Specific examples of the liquid epoxy resin include: "HP 4032", "HP 4032D" and "HP 4032 SS" (naphthalene epoxy resins) manufactured by DIC; "828 US", "jER 828 EL", "825", "EPIKOTE 828 EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi chemical corporation; "jER 807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi chemical corporation; "jER 152" (phenol novolac type epoxy resin) manufactured by mitsubishi chemical corporation; "630" and "630 LSD" (glycidyl amine type epoxy resins) manufactured by mitsubishi chemical corporation; "ZX 1059" (a mixture of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin) manufactured by Nissian Ciki Kaisha; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX; "EX-821" and "EX-920" (linear aliphatic epoxy resin having an oxyalkylene chain) manufactured by Nagase ChemteX; "CELLOXIDE 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by cellosolve corporation; "PB-3600" (epoxy resin having a butadiene structure) manufactured by Dailuo corporation; "ZX 1658" and "ZX 1658 GS" (liquid 1, 4-glycidylcyclohexane-type epoxy resins) available from Nippon iron Japan chemical Co., Ltd. These can be used alone in 1, can also be more than 2 combination use.
When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (B), the amount ratio thereof (liquid epoxy resin: solid epoxy resin) is preferably 1:1 to 1:20, more preferably 1:1.5 to 1:15, and particularly preferably 1:2 to 1:10 in terms of mass ratio. By making the amount ratio of the liquid epoxy resin to the solid epoxy resin within the range, the desired effects of the present invention can be remarkably obtained.
(B) The epoxy equivalent of the component is preferably 50g/eq to 5000g/eq, more preferably 50g/eq to 3000g/eq, even more preferably 80g/eq to 2000g/eq, and even more preferably 110g/eq to 1000g/eq. When the amount is within this range, the crosslinking density of the cured product of the resin composition layer becomes sufficient, and an insulating layer having a small surface roughness can be provided. The epoxy equivalent is the mass of an epoxy resin containing 1 equivalent of an epoxy group. The epoxy equivalent can be measured according to JIS K7236.
The weight average molecular weight (Mw) of the component (B) is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 1500, from the viewpoint of remarkably obtaining the desired effect of the present invention. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by Gel Permeation Chromatography (GPC).
From the viewpoint of obtaining an insulating layer exhibiting good tensile mechanical strength and insulation reliability, the content of the component (B) is preferably 1 mass% or more, more preferably 2 mass% or more, and still more preferably 3 mass% or more, assuming that the nonvolatile component in the resin composition is 100 mass%. The upper limit of the content of the component (B) is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass or less, from the viewpoint of remarkably obtaining the desired effect of the present invention.
[ C ] photopolymerizable monomer
The photosensitive resin composition contains a photopolymerizable monomer as the component (C). However, the component (C) does not include the component (A) and the component (B). When the photosensitive resin composition contains (C) a photopolymerizable monomer, the photoreactivity can be improved. As the component (C), for example, a photosensitive (meth) acrylate compound having 1 or more (meth) acryloyl groups in a molecule, which is liquid, solid, or semi-solid at room temperature, can be used. The room temperature means about 25 ℃.
Examples of the photosensitive (meth) acrylate compound include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate; mono-or di (meth) acrylates of glycols such as ethylene glycol, methoxyethylene glycol, polyethylene glycol, and propylene glycol; acrylamides such as N, N-dimethylacrylamide and N-methylolacrylamide; aminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl acrylate; polyhydric (meth) acrylates such as polyhydric alcohols such as trimethylolpropane, pentaerythritol and dipentaerythritol, and adducts of these polyhydric alcohols with ethylene oxide, propylene oxide and epsilon-caprolactone; phenols such as phenoxy acrylate and phenoxy ethyl acrylate, and (meth) acrylates such as ethylene oxide and propylene oxide adducts thereof; epoxy acrylates derived from glycidyl ethers such as trimethylolpropane triglycidyl ether, modified epoxy acrylates, melamine acrylates, and/or methacrylates corresponding to the above-mentioned acrylic acid. The (meth) acrylate refers to acrylate and methacrylate.
Among these, mono-or di- (meth) acrylates of glycols, phenols such as phenoxy acrylate and phenoxy ethyl acrylate, or (meth) acrylates and poly (meth) acrylates such as ethylene oxide or propylene oxide adducts thereof are preferable.
Examples of the mono-or di- (meth) acrylates of diols include polytetramethylene glycol diacrylate and the like.
Examples of the phenol such as phenoxy acrylate and phenoxy ethyl acrylate, and the (meth) acrylate such as an ethylene oxide or propylene oxide adduct thereof include EO-modified bisphenol A type acrylate.
The poly (meth) acrylate is preferably a ternary acrylate or methacrylate, and examples of the ternary acrylate or methacrylate include 1, 9-nonanediol diacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane EO addition tri (meth) acrylate, glycerol PO addition tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tetrahydrofurfuryl alcohol oligo (meth) acrylate, ethyl carbitol oligo (meth) acrylate, 1, 4-butanediol oligo (meth) acrylate, 1, 6-hexanediol oligo (meth) acrylate, trimethylolpropane oligo (meth) acrylate, pentaerythritol oligo (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, trimethylolpropane oligo (meth) acrylate, pentaerythritol oligo (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, trimethylolpropane tetra (meth) acrylate, and the like, Dipentaerythritol hexa (meth) acrylate, (meth) acrylate of N, N' -tetrakis (. beta. -hydroxyethyl) ethylenediamine, etc., as ternary or higher acrylates or methacrylates, examples thereof include phosphoric acid triester (meth) acrylates such as tris (2- (meth) acryloyloxyethyl) phosphate, tris (2- (meth) acryloyloxypropyl) phosphate, tris (3- (meth) acryloyl-2-hydroxypropyloxy) phosphate, bis (3- (meth) acryloyl-2-hydroxypropyloxy) (2- (meth) acryloyloxyethyl) phosphate, and (3- (meth) acryloyl-2-hydroxypropyloxy) bis (2- (meth) acryloyloxyethyl) phosphate. These photosensitive (meth) acrylate compounds may be used alone in 1 kind, or 2 or more kinds may be used in combination.
(C) Commercially available photopolymerizable monomers can be used. Examples of commercially available products include "DPHA" manufactured by Nippon Kagaku K.K., "EBECRYL 3708" manufactured by Zyowa Katsuku K.K., "R-551" manufactured by Nippon Kagaku K.K., "A-PTMG-65" manufactured by Nippon Kagaku K.K., and "1.9 ND" manufactured by Kyowa Kagaku K.K.
The content of the photopolymerizable monomer (C) is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 1.5% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less, based on 100% by mass of the total solid content of the photosensitive resin composition, from the viewpoint of promoting photocuring.
[ D ] photopolymerization initiator
The photosensitive resin composition contains a photopolymerization initiator as the component (D). By adding (D) a photopolymerization initiator to the photosensitive resin composition, the photosensitive resin composition can be efficiently photocured. These can be used alone in 1, also can be used in 2 or more combinations.
(D) Any compound can be used as the photopolymerization initiator, and examples thereof include: acylphosphine oxide photopolymerization initiators such as bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide) and 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide; oxime ester photopolymerization initiators such as 1- [4- (phenylthio) -1, 2-octanedione 2- (O-benzoyloxime) and 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethanone 1- (O-acetyloxime); α -aminoalkylphenone type photopolymerization initiators such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] - [4- (4-morpholino) phenyl ] -1-butanone, and 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone; benzophenone, methylbenzophenone, o-benzoylbenzoic acid, benzoylethyl ether, 2-diethoxyacetophenone, 2, 4-diethylthioxanthone, diphenyl- (2,4, 6-trimethylbenzoyl) phosphine oxide, ethyl (2,4, 6-trimethylbenzoyl) phenylphosphonate, 4' -bis (diethylamino) benzophenone, 1-hydroxy-cyclohexyl-phenyl ketone, 2-dimethoxy-1, 2-diphenylethan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide; sulfonium salt type photopolymerization initiators, and the like. These photopolymerization initiators may be used alone in 1 kind, or 2 or more kinds may be used in combination. Among these, from the viewpoint of more effectively photocuring the photosensitive resin composition, any of an acylphosphine oxide-based photopolymerization initiator and an oxime ester-based photopolymerization initiator is preferable, and an oxime ester-based photopolymerization initiator is more preferable.
Specific examples of the photopolymerization initiator (D) include "Omnirad 907", "Omnirad 369", "Omnirad 379", "Omnirad 819" and "Omnirad TPO" available from IGM, and "Irgacure OXE-01", "Irgacure OXE-02", "Irgacure TPO" and "Irgacure 819" available from Pasteur, and "N-1919" and "NCI-831" available from ADEKA.
The photosensitive resin composition may further contain, in combination with (D) a photopolymerization initiator, a tertiary amine such as ethyl N, N-dimethylaminobenzoate, isoamyl N, N-dimethylaminobenzoate, amyl-4-dimethylaminobenzoate, triethylamine, or triethanolamine, and may further contain a photosensitizer such as pyrazolines, anthracenes, coumarins, xanthenes, or thioxanthones. These compounds may be used alone in 1 kind, or in combination of 2 or more kinds.
The content of the photopolymerization initiator (D) is preferably 0.001 mass% or more, more preferably 0.005 mass% or more, and further preferably 0.01 mass% or more, when the nonvolatile content of the photosensitive resin composition is 100 mass%, from the viewpoint of sufficiently photocuring the photosensitive resin composition and improving the insulation reliability. On the other hand, from the viewpoint of suppressing the decrease in resolution due to hypersensitivity, the upper limit is preferably 3% by mass or less, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less. When the photosensitive resin composition contains a photopolymerization initiation aid, the total content of the photopolymerization initiator (D) and the photopolymerization initiation aid is preferably within the above range.
(E) inorganic filler
In addition to the above components, as an optional component, the photosensitive resin composition may further contain an inorganic filler as the component (E).
As the material of the inorganic filler (E), an inorganic compound is used. Examples of the material of the inorganic filler include: silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, zirconium phosphate, zirconium phosphotungstate, and the like. Among them, silica and magnesium hydroxide are preferable, and magnesium hydroxide is particularly preferable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Further, the silica is preferably spherical silica. (F) The inorganic filler may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
Examples of commercially available products of the component (E) include: UFP-20 and UFP-30 manufactured by DENKA K.K.; "SP 60-05" and "SP 507-05" manufactured by Nissi iron alloy materials Kabushiki Kaisha; "SC 2050", "YC 100C", "YA 050C", "YA 050C-MJE", "YA 010C", "SC 2500 SQ", "SO-C4", "SO-C2", "SO-C1", manufactured by Yadama (Admatechs) of Kabushiki Kaisha; "SILFIL NSS-3N", "SILFIL NSS-4N", "SILFILNSS-5N" manufactured by Kyuyama, Inc.; "EP 4-A" manufactured by Shendao chemical Co., Ltd.
The specific surface area of the component (E) is preferably 1m2A value of at least g, more preferably 2m2A total of 3m or more, particularly 3m2More than g. The upper limit is not particularly limited, but is preferably 60m2Less than 50 m/g2Less than or equal to 40 m/g2The ratio of the carbon atoms to the carbon atoms is less than g. Specific surface area measurement device (MOUNTECH strain) can be used according to the BET methodMacsorb HM-1210, manufactured by kosha corporation) was obtained by adsorbing nitrogen gas onto the surface of a sample and calculating the specific surface area by the BET multipoint method.
The average particle diameter of the component (E) is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, preferably 5 μm or less, more preferably 2 μm or less, and further preferably 1 μm or less, from the viewpoint of remarkably obtaining the desired effect of the present invention.
(E) The average particle diameter of the component can be measured by a laser diffraction scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be measured on a volume basis by a laser diffraction scattering particle size distribution measuring apparatus, and the median particle size is measured as an average particle size. As the measurement sample, a sample obtained by weighing 100mg of the inorganic filler and 10g of methyl ethyl ketone in a vial and dispersing them by ultrasonic waves for 10 minutes can be used. For the measurement sample, the volume-based particle size distribution of the component (E) was measured in a flow cell system using a laser diffraction type particle size distribution measuring apparatus with the wavelengths of the light source used being blue and red, and the average particle size was calculated from the obtained particle size distribution as the median particle size. Examples of the laser diffraction type particle size distribution measuring apparatus include "LA-960" manufactured by horiba, Ltd.
From the viewpoint of improving moisture resistance and dispersibility, the (E) component is preferably treated with a surface treatment agent. Examples of the surface treatment agent include vinyl silane coupling agents, (meth) acrylic coupling agents, fluorine-containing silane coupling agents, amino silane coupling agents, epoxy silane coupling agents, mercapto silane coupling agents, alkoxysilanes, organosilicon nitrogen compounds, titanate coupling agents, and the like. Among these, vinyl silane coupling agents, (meth) acrylic coupling agents, and amino silane coupling agents are preferable from the viewpoint of remarkably obtaining the effects of the present invention. Further, the surface treatment agent may be used alone in 1 kind, or may be used in any combination of 2 or more kinds.
Examples of commercially available surface treatment agents include: "KBM 1003" (vinyltriethoxysilane) manufactured by shin-Etsu chemical industries, the "KBM 503" (3-methacryloxypropyltriethoxysilane) manufactured by shin-Etsu chemical industries, the "KBM 403" (3-glycidoxypropyltrimethoxysilane) manufactured by shin-Etsu chemical industries, the "KBM 803" (3-mercaptopropyltrimethoxysilane) manufactured by shin-Etsu chemical industries, the "KBE 903" (3-aminopropyltriethoxysilane) manufactured by shin-Etsu chemical industries, the "KBM 573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by shin-Etsu chemical industries, the "SZ-31" (hexamethyldisilazane) manufactured by shin-Etsu chemical industries, the "KBM 103" (phenyltrimethoxysilane) manufactured by shin-Etsu chemical industries, the "KBM-4803" (long-chain silane coupling agent) manufactured by shin-Etsu chemical industries, "KBM-7103" (3,3, 3-trifluoropropyltrimethoxysilane) manufactured by shin-Etsu chemical Co., Ltd.
From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment by the surface treatment agent is preferably controlled within a predetermined range. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2 to 5 parts by mass of a surface treatment agent, more preferably 0.2 to 3 parts by mass of a surface treatment agent, and still more preferably 0.3 to 2 parts by mass of a surface treatment agent.
The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02mg/m from the viewpoint of improving the dispersibility of the inorganic filler2Above, more preferably 0.1mg/m2Above, more preferably 0.2mg/m2The above. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in the form of a film, 1mg/m is preferable2The concentration is more preferably 0.8mg/m or less2The concentration is more preferably 0.5mg/m or less2The following.
The amount of carbon per unit surface area of the inorganic filler material can be measured after subjecting the surface-treated inorganic filler material to a cleaning treatment with a solvent such as Methyl Ethyl Ketone (MEK). Specifically, MEK was added in a sufficient amount as a solvent to the inorganic filler surface-treated by the surface treatment agent, and ultrasonic cleaning was performed at 25 ℃ for 5 minutes. After removing the supernatant liquid and drying the solid components, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by horiba, Ltd., can be used.
From the viewpoint of remarkably obtaining the effect of the present invention, the content of the component (E) is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less, 60% by mass or less, 50% by mass or less, and 40% by mass or less, when the nonvolatile component in the photosensitive resin composition is taken as 100% by mass.
(F) solvent
The photosensitive resin composition may further contain (F) a solvent as an optional component in addition to the above components. By adding the (F) solvent, the varnish viscosity can be adjusted. The solvent (F) may be an organic solvent.
Examples of the solvent (F) include: ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl cellosolve acetate, carbitol acetate, and diethylene glycol monoethyl ether acetate; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, solvent naphtha, and the like. These solvents may be used alone in 1 kind, or in combination of 2 or more kinds. The content of the solvent used may be appropriately adjusted from the viewpoint of coatability of the resin composition.
< (G) other additives
The photosensitive resin composition may further contain (G) other additives to such an extent that the object of the present invention is not impaired. As (G) other additives, for example: thermoplastic resins, organic fillers, fine particles of melamine, organobentonite, etc., phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, colorants such as naphthalene black, polymerization inhibitors such as hydroquinone, phenothiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, etc., thickeners such as bentonite (Benton), montmorillonite, etc., flame retardants such as silicones, fluorines, vinyl resin-based antifoaming agents, brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphorus compounds, aromatic condensed phosphates, halogen-containing condensed phosphates, etc., and various additives such as thermosetting resins such as phenol curing agents, cyanate curing agents, etc.
The photosensitive resin composition can be prepared by mixing the above-mentioned components (a) to (D) as essential components, appropriately mixing the above-mentioned components (E) to (G) as optional components, and if necessary, kneading (kneading) or stirring with a kneading apparatus such as a three-roll mill, a ball mill, a bead mill, or a sand mill, or a stirring apparatus such as a super mixer or a planetary mixer.
< Properties and applications of photosensitive resin composition >
The photosensitive resin composition contains an oxyalkylene chain in any of the component (A), the component (B) and the component (C). In this case, the parameter X represented by the following formula (1) is 4 or more and 25 or less. By satisfying the formula (1), a cured product having excellent bendability and insulating properties can be obtained;
[ math figure 5]
Figure BDA0002658381230000181
In the formula (1), MAOWhen the component containing an oxyalkylene chain is a copolymer, the following formula (2) represents a value. Furthermore, MAOWhen the component containing an oxyalkylene chain is not a copolymer, it represents ((molecular weight of oxyalkylene chain of each compound contained in components (a) to (C))/((molecular weight of each compound contained in components (a) to (C)). Thus, including oxidationWhen the constituent of the olefinic chain is not a copolymer, MAORepresents the mass ratio of the oxyalkylene chain in each of these components. N represents the solid content (parts by mass) of all the compounds contained in components (A) to (C), and N represents the solid content (parts by mass) of each compound contained in components (A) to (C). Therefore, X is the calculation of M for all the components (A) to (C) in the resin compositionAOThe product with N, summing all the products thus obtained, dividing the sum by N and expressing the value in percentage;
[ mathematical formula 6]
Figure BDA0002658381230000182
In the formula (2), AAODenotes the molecular weight of the oxyalkylene chain of each monomer containing an oxyalkylene chain, A denotes the molecular weight of each monomer containing an oxyalkylene chain, BAORepresents the number of moles of each monomer containing an oxyalkylene chain, and B represents the total number of moles of all monomers contained in the copolymer.
The term "copolymer" refers to a polymer obtained by polymerization with 2 or more monomers, and is a polymer having a weight average molecular weight of 10000 or more. The copolymer may be any of random copolymerization, block copolymerization, alternating copolymerization, and graft copolymerization.
The copolymer may be randomly copolymerized as described above, and it may be difficult to calculate M from the molecular weightAOThe value of (c). Since the addition usually holds for the copolymer, it is difficult to calculate M from the molecular weightAOIn the case of the value of (3), M can be calculated by the formula (2)AO. By A in formula (2)AOA, the average molecular weight per unit of oxyalkylene chain is determined and multiplied by B in formula (2)AOThe molar ratio of the oxyalkylene chain-containing monomer represented by/B, whereby M in the copolymer can be calculatedAOThe value of (c). The "monomer" described in the definition of the formula (2) represents a compound corresponding to a monomer unit contained in the copolymer. "monomer unit" refers to a partial structure in a copolymer formed by polymerizing a certain compound.
From the viewpoint of obtaining a cured product having excellent bendability and insulating properties and improving the resolution, X in formula (1) is 25 or less, preferably 23 or less, more preferably 20 or less, and even more preferably 18 or less. From the viewpoint of remarkably obtaining the effect of the present invention, the lower limit of X in formula (1) is 4 or more, preferably 5 or more, and more preferably 6 or more.
The cured product obtained by photocuring the photosensitive resin composition of the present invention exhibits excellent resolution. Therefore, when a circular hole (through hole) having an opening diameter of 100 μm is formed by the cured product, the formation of residue at the bottom of the circular hole can be suppressed. Evaluation of the residue at the bottom of the via hole can be carried out by the method described in < evaluation of residue at the bottom of the via hole > described later.
The cured product obtained by photocuring the photosensitive resin composition of the present invention exhibits excellent flexibility. As a specific example of the measurement of the flexibility, a photosensitive film obtained by subjecting a photosensitive resin composition layer to whole surface exposure, development and heat treatment was used, and the flexibility was evaluated by an MIT bending fatigue tester in accordance with JIS P8115. In this case, the number of bending is usually 100 or more, preferably 300 or more on average. The flexural properties can be evaluated specifically by the methods described in the examples described below.
The cured product obtained by photocuring the photosensitive resin composition of the present invention has excellent insulating properties. As a specific example of the insulation evaluation, a photosensitive resin film is exposed from above the comb-shaped wiring pattern, developed, and heat-treated. Copper wires were welded as electrodes on both sides of the comb-shaped pattern, a predetermined voltage was applied, and the resistance value at 7 points after 500 hours was measured. In this case, the resistance value is preferably 108Omega or more. The insulation property can be measured specifically by the method described in the examples described later.
The cured product obtained by photocuring the photosensitive resin composition of the present invention generally exhibits excellent adhesion strength to a copper foil. As a specific example of evaluation of adhesion strength, a photosensitive resin composition layer to which a glass epoxy substrate is bonded to a rolled copper foil, and whole surface exposure, development, and heat treatment are performed. For the copper peeling, a tensile tester (manufactured by TSE, "AC-50C-SL") based on Japanese Industrial Standard (JIS C6481) was used to peel the copper foil. In this case, the adhesion strength to the copper foil is usually 0.5kgf or more. The adhesion strength can be measured by the method described in the examples described later.
The photosensitive resin composition of the present invention can be used in a wide variety of applications requiring a photosensitive resin composition, such as photosensitive films, photosensitive films with supports, insulating resin films such as prepregs, circuit boards (for laminate boards, multilayer printed wiring boards, and the like), solder resists (solder resists), underfill materials, die bonding materials, semiconductor sealing materials, hole filling resins, and component embedding resins. Among them, it can be suitably used as: the photosensitive resin composition for an insulating layer of a printed wiring board (a printed wiring board having a cured product of the photosensitive resin composition as an insulating layer), the photosensitive resin composition for an interlayer insulating layer (a printed wiring board having a cured product of the photosensitive resin composition as an interlayer insulating layer), the photosensitive resin composition for plating (a printed wiring board having a plating layer formed on a cured product of the photosensitive resin composition), and the photosensitive resin composition for a solder resist (a printed wiring board having a cured product of the photosensitive resin composition as a solder resist).
[ photosensitive film ]
The photosensitive resin composition of the present invention can be applied to a support substrate in the form of a resin varnish and dried with an organic solvent to form a photosensitive resin composition layer, thereby forming a photosensitive film. Further, a photosensitive film formed on a support in advance may be laminated on the support substrate. The photosensitive film can be laminated on various support substrates. Examples of the support substrate include substrates such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate.
[ photosensitive film with support ]
The photosensitive resin composition of the present invention can be suitably used in the form of a photosensitive film with a support, in which the photosensitive resin composition layer is formed on the support. That is, the photosensitive film with a support comprises a support and a photosensitive resin composition layer formed from the photosensitive resin composition of the present invention provided on the support.
Examples of the support include a polyethylene terephthalate film, a polyethylene naphthalate film, a polypropylene film, a polyethylene film, a polyvinyl alcohol film, and a triacetyl acetate film, and a polyethylene terephthalate film is particularly preferable.
Examples of commercially available supports include, but are not limited to, polypropylene films such as "ALPHAN MA-410" and "E-200C" manufactured by Wangzi paper corporation, polyethylene terephthalate films such as PS series films such as "PS-25" manufactured by Kitty corporation, and the like. In order to facilitate removal of the photosensitive resin composition layer, a release agent such as a silicone coating agent may be applied to the surface of these supports. The thickness of the support is preferably in the range of 5 to 50 μm, more preferably in the range of 10 to 25 μm. By making the thickness of 5 μm or more, the cracking of the support can be suppressed at the time of peeling off the support before development; by making the thickness of 50 μm or less, the resolution at the time of exposure from the support can be improved. Further, a support with a low white point (fish eye) is preferable. Here, white spots refer to defects formed when a material is thermally melted and a film is produced by kneading, extrusion, biaxial stretching, casting, or the like, and foreign matter, undissolved matter, an oxidized degraded product, or the like of the material enters the film.
In addition, the support is preferably made of a material having excellent transparency in order to reduce light scattering when exposed to active energy rays such as ultraviolet rays. The support is particularly preferably a material having a haze (haze standardized in JIS-K6714) of 0.1 to 5 as an index of transparency. Further, the photosensitive resin composition layer may be protected by a protective film.
By protecting the photosensitive resin composition layer side of the photosensitive film of the support body with the protective film, adhesion of dust or the like to the surface of the photosensitive resin composition layer and formation of scratches can be prevented. As the protective film, a film made of the same material as the support can be used. The thickness of the protective film is not particularly limited, but is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, and still more preferably in the range of 10 μm to 30 μm. The handling property of the protective film can be improved by making the thickness of the protective film to be 1 μm or more; when the thickness is 40 μm or less, the economy (low cost) tends to be improved. In the protective film, it is preferable that the adhesive strength between the photosensitive resin composition layer and the protective film is smaller than the adhesive strength between the photosensitive resin composition layer and the support.
The photosensitive film with a support of the present invention can be produced by a method known to those skilled in the art, for example, a resin varnish obtained by dissolving the photosensitive resin composition of the present invention in an organic solvent is prepared, the resin varnish is applied to the support, and the organic solvent is dried by heating or blowing with hot air, to form a photosensitive resin composition layer. Specifically, the photosensitive film with a support can be produced by first completely removing bubbles in the photosensitive resin composition by a vacuum defoaming method or the like, then coating the photosensitive resin composition on the support, removing the solvent by a hot-air furnace or a far-infrared furnace, drying the solvent, and then, if necessary, laminating a protective film on the obtained photosensitive resin composition layer. The specific drying conditions vary depending on the curability of the photosensitive resin composition and the amount of organic solvent in the resin varnish, and the resin varnish containing 30 to 60 mass% of organic solvent may be dried at 80 to 120 ℃ for 3 to 13 minutes. The amount of the residual organic solvent in the photosensitive resin composition layer is preferably 5% by mass or less, more preferably 2% by mass or less, with respect to the total amount of the photosensitive resin composition layer, from the viewpoint of preventing the diffusion of the organic solvent in the subsequent step. The person skilled in the art can appropriately set suitable drying conditions by simple experiments. From the viewpoint of improving the handling property and suppressing the decrease in sensitivity and resolution inside the photosensitive resin composition layer, the thickness of the photosensitive resin composition layer is preferably in the range of 5 μm to 500 μm, more preferably in the range of 10 μm to 200 μm, further preferably in the range of 15 μm to 150 μm, further preferably in the range of 20 μm to 100 μm, and particularly preferably in the range of 20 μm to 60 μm.
Examples of the coating method of the photosensitive resin composition include: a gravure coating method, a micro gravure coating method, a reverse coating (reverse coating) method, a kiss reverse coating (kiss reverse coating) method, a die coating (die coating) method, a slot die (slot die) method, a lip coating (lip coating) method, a comma coating (comma coating) method, a blade coating (blade coating) method, a roll coating method, a knife coating (knife coating) method, a curtain coating (curve coating) method, a closed cavity (chamber) gravure coating method, a slot nozzle (slot orientation) method, a spray coating method, a dip coating method, and the like. The photosensitive resin composition may be applied in several portions, or may be applied in one portion, or may be applied in combination of a plurality of different manners. Among them, a die coating method having excellent coating uniformity is preferable. In order to avoid contamination with foreign matter, the coating step is preferably performed in an environment where foreign matter is less generated, such as a clean room.
[ printed Wiring Board ]
The printed wiring board of the present invention comprises an insulating layer formed using a cured product of the photosensitive resin composition of the present invention. The insulating layer is preferably used as a solder resist layer.
Specifically, the printed wiring board of the present invention can be produced using the photosensitive film or the photosensitive film with a support. Hereinafter, a case where the insulating layer is a solder resist layer will be described.
< coating and drying Process >
The photosensitive resin composition is directly applied to a circuit board in the form of a resin varnish, and the organic solvent is dried to form a photosensitive film on the circuit board.
Examples of the circuit board include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. Here, the circuit board refers to a board having a conductor layer (circuit) patterned on one or both surfaces of the board as described above. In a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, a substrate on which a conductor layer (circuit) is patterned on one surface or both surfaces of the outermost layer of the multilayer printed wiring board is also included in the circuit substrate described herein. The surface of the conductive layer may be roughened in advance by blackening treatment, copper etching, or the like.
As the coating method, full-page printing by a screen printing method is generally used in many cases, but any other means may be used as long as it is a coating method capable of uniform coating. For example, a spray coating method, a hot melt coating method, a bar coating method, a blade coating method, an air knife coating method, a curtain flow coating method, a roll coating method, a gravure coating method, an offset printing method, a dip coating method, a brush coating method, and other general coating methods can all be used. After coating, the coating is dried in a hot-air furnace, a far-infrared furnace, or the like as needed. The drying conditions are preferably such that the drying is carried out at 80 to 120 ℃ for 3 to 13 minutes. This operation forms a photosensitive film on the circuit board.
< lamination Process >
On the other hand, in the case of using a photosensitive film with a support, the photosensitive resin composition layer side is laminated on one surface or both surfaces of the circuit board using a vacuum laminator. In the laminating step, when the photosensitive film with a support has a protective film, the protective film is removed, and then the photosensitive film with a support and the circuit board are preheated as necessary, and the photosensitive resin composition layer is pressed and heated to be bonded to the circuit board. The photosensitive film with a support is preferably laminated on a circuit board under reduced pressure by a vacuum lamination method.
The conditions of the laminating step are not particularly limited, and for example, preferable conditions are: the pressure bonding temperature (lamination temperature) is preferably 70 to 140 ℃, and the pressure bonding pressure is preferably 1kgf/cm2～11kgf/cm2(9.8×104N/m2～107.9×104N/m2) The lamination is preferably performed under a reduced pressure with a pressure bonding time of 5 seconds to 300 seconds and an air pressure of 20mmHg (26.7hPa) or less. Further, the lamination process may be batch-wiseThe formula (I) may be a continuous type using a roll. The vacuum lamination process can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include: a vacuum applicator manufactured by Nikko-Materials, a vacuum pressure laminator manufactured by Kabushiki Kaisha, a roll-type dry coater manufactured by Hitachi Industries, a vacuum laminator manufactured by Hitachi AIC, and the like. In this way, a photosensitive film is formed on the circuit board.
< Exposure Process >
After a photosensitive film is provided on a circuit board by a coating and drying step or a laminating step, an exposure step is performed in which a predetermined portion of the photosensitive resin composition layer is irradiated with active light through a mask pattern to photocure the photosensitive resin composition layer in the irradiated portion. Examples of the active light include ultraviolet rays, visible light rays, electron beams, and X-rays, and ultraviolet rays are particularly preferable. The dose of ultraviolet irradiation was about 10mJ/cm2～1000mJ/cm2. The exposure method includes a contact exposure method in which a mask pattern is bonded to a printed wiring board, and a non-contact exposure method in which exposure is performed using parallel light rays in a state where the mask pattern is not bonded to the printed wiring board. When the support is present on the photosensitive resin composition layer, the support may be exposed to light from the support or may be exposed to light after being peeled off.
The photosensitive resin composition of the present invention is used for a solder resist layer, and therefore, the photosensitive resin composition has excellent resolution. Therefore, as the exposure pattern in the mask pattern, for example, a pattern in which the ratio (L/S) of the circuit width (line width, L) to the width between circuits (line pitch, S) is 100 μm/100 μm or less (that is, 200 μm or less in wiring pitch), L/S is 80 μm/80 μm or less (160 μm or less in wiring pitch), L/S is 70 μm/70 μm or less (140 μm or less in wiring pitch), and L/S is 60 μm/60 μm or less (120 μm or less in wiring pitch) can be used. Note that the pitch need not be the same throughout the circuit substrate.
< developing Process >
When a support is present on the photosensitive resin composition layer after the exposure step, the support is removed, and then a portion that has not been cured by light (unexposed portion) is removed by wet development or dry development, and developed, whereby a pattern can be formed.
In the case of the wet development, a safe and stable developer having good workability, such as an alkaline aqueous solution, an aqueous developer, or an organic solvent, can be used as the developer, and among them, a developing step using an alkaline aqueous solution is preferably employed. As the developing method, known methods such as spraying, dipping with shaking, brushing (brushing), and knife coating (scraping) can be suitably used.
Examples of the alkaline aqueous solution used as the developer include: an aqueous solution of an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide, or potassium hydroxide, a carbonate or bicarbonate such as sodium carbonate or sodium bicarbonate, an aqueous solution of an alkali metal phosphate such as sodium phosphate or potassium phosphate, an alkali metal pyrophosphate such as sodium pyrophosphate or potassium pyrophosphate, or an aqueous solution of an organic base not containing metal ions such as tetraalkylammonium hydroxide is preferably an aqueous solution of tetramethylammonium hydroxide (TMAH) from the viewpoint of not containing metal ions and not affecting the semiconductor chip.
In these alkaline aqueous solutions, a surfactant, an antifoaming agent, or the like may be added to the developer to improve the developing effect. The pH of the alkaline aqueous solution is, for example, preferably in the range of 8 to 12, more preferably in the range of 9 to 11. The alkali concentration of the alkaline aqueous solution is preferably 0.1 to 10% by mass. The temperature of the alkaline aqueous solution is appropriately selected depending on the developability of the photosensitive resin composition layer, and is preferably 20 to 50 ℃.
Examples of the organic solvent used as the developer include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethanol, isopropanol, butanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether.
The concentration of such an organic solvent is preferably 2 to 90% by mass based on the total amount of the developer. Further, the temperature of such an organic solvent can be adjusted according to the developability. Further, such organic solvents may be used alone or in combination of 2 or more. Examples of the organic solvent-based developer used alone include 1,1, 1-trichloroethane, N-methylpyrrolidone, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ -butyrolactone.
In the pattern formation, the above-mentioned 2 or more developing methods may be used in combination as necessary. The development method includes a dipping method, a spin-coating immersion method, a spraying method, a high-pressure spraying method, a brush coating method, a blade coating method, and the like, and the high-pressure spraying method is preferable because of the improvement in resolution. The spraying pressure in the case of the spraying method is preferably 0.05MPa to 0.3 MPa.
< Heat curing (post-baking) Process
After the development step is completed, a thermosetting (post-baking) step is performed to form a solder resist layer. Examples of the post-baking step include an ultraviolet irradiation step using a high-pressure mercury lamp and a heating step using a Clean Oven (Clean Oven). When ultraviolet rays are irradiated, the dose of the ultraviolet rays can be adjusted as necessary, and the dose can be set to 0.05J/cm, for example2～10J/cm2The irradiation is performed with right and left irradiation amounts. The heating conditions may be appropriately selected depending on the type, content, and the like of the resin component in the photosensitive resin composition, and are preferably selected in the range of 20 minutes to 180 minutes at 150 ℃ to 220 ℃, and more preferably in the range of 30 minutes to 120 minutes at 160 ℃ to 200 ℃.
< other working procedures >
The printed wiring board may further include a hole opening step and a desmear (desmear) step after the solder resist layer is formed. These steps can be performed by various methods known to those skilled in the art used in the production of printed wiring boards.
After the solder resist layer is formed, a via hole or a via hole is formed by performing a hole opening process on the solder resist layer formed on the circuit board as necessary. The hole forming step can be performed by a known method such as a drill, a laser, or plasma, and if necessary, by combining these methods, and is preferably performed by a hole forming step using a laser such as a carbon dioxide laser or a YAG laser.
The desmear process is a process for desmear treatment. Resin residue (scum) generally adheres to the inside of the opening formed in the hole forming step. Since the smear causes the electrical connection failure, a treatment for removing the smear (desmear treatment) is performed in this step.
The desmear treatment can be carried out by a dry desmear treatment, a wet desmear treatment or a combination thereof.
Examples of the dry desmear treatment include desmear treatment using plasma. The desmear treatment using plasma can be carried out using a commercially available plasma desmear treatment apparatus. Examples of commercially available plasma desmear treatment apparatuses suitable for use in the production of printed wiring boards include a microwave plasma apparatus manufactured by NISSIN corporation and an atmospheric pressure plasma etching apparatus manufactured by hydroprocess chemical industries.
Examples of the wet desmear treatment include desmear treatment using an oxidizing agent solution. When the desmear treatment is performed with the oxidant solution, it is preferable to perform the swelling treatment with the swelling solution, the oxidation treatment with the oxidant solution, and the neutralization treatment with the neutralizing solution in this order. Examples of the Swelling liquid include "spinning Dip securigrant P" and "spinning Dip securigrant SBU" manufactured by atmott JAPAN (ato ech JAPAN). The swelling treatment is preferably performed by immersing the substrate having the through-hole or the like formed therein in a swelling solution heated to 60 to 80 ℃ for 5 to 10 minutes. The oxidizing agent solution is preferably an alkaline aqueous solution of permanganic acid, and examples thereof include a solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The oxidation treatment with the oxidizing agent solution is preferably performed by immersing the swollen substrate in the oxidizing agent solution heated to 60 to 80 ℃ for 10 to 30 minutes. Examples of commercially available alkaline permanganic acid aqueous solutions include "Concentrate Compact CP" and "Dosing solution securigant P" manufactured by anmant japan ltd. The neutralization treatment with the neutralization solution is preferably carried out by immersing the substrate after the oxidation treatment in the neutralization solution at 30 to 50 ℃ for 3 to 10 minutes. The neutralizing solution is preferably an acidic aqueous solution, and examples of commercially available products include "Reduction solution securiganteh P" manufactured by anmant japan ltd.
When the dry-method desmearing treatment and the wet-method desmearing treatment are carried out in combination, the dry-method desmearing treatment can be carried out first, and the wet-method desmearing treatment can also be carried out first.
When the insulating layer is used as an interlayer insulating layer, the opening step, the desmear step, and the plating step may be performed after the thermosetting step, in the same manner as in the case of the solder resist layer.
The plating step is a step of forming a conductor layer on the insulating layer. The conductive layer may be formed by a combination of electroless plating and electrolytic plating, or may be formed by electroless plating alone, with a plating resist layer having a pattern opposite to that of the conductive layer. As a method of forming a pattern thereafter, for example, a subtractive method, a semi-additive method, or the like known to those skilled in the art can be used.
[ semiconductor device ]
The semiconductor device of the present invention includes a printed wiring board. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.
Examples of the semiconductor device include various semiconductor devices used in electric products (for example, a computer, a mobile phone, a digital camera, a television, and the like) and vehicles (for example, a motorcycle, an automobile, a train, a ship, an aircraft, and the like).
The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The "conductive portion" refers to a portion of the printed wiring board that conducts an electrical signal, and may be located on the surface or embedded in the printed wiring board. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.
The method of mounting the semiconductor chip in the production of the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip can effectively function, and specific examples thereof include a wire bonding mounting method, a flip chip mounting method, a mounting method using a build-up layer without solder (BBUL), a mounting method using an Anisotropic Conductive Film (ACF), a mounting method using a nonconductive film (NCF), and the like. Here, the "mounting method using a build-up layer without solder (BBUL)" refers to a "mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board and the semiconductor chip is connected to a wiring on the printed wiring board".
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the following description, "part" and "%" representing amounts refer to "part by mass" and "% by mass", respectively, unless otherwise explicitly indicated.
(Synthesis example 1: Synthesis of resin (A-1))
Into a four-necked flask, 60.8 parts (0.26mol) of bisphenol A, 43.4 parts (0.11mol) of a bisphenol A type epoxy compound (YD8125, manufactured by Nippon iron chemical Co., Ltd.), 145.8 parts (0.13mol) of polyethylene glycol diglycidyl ether (EX861, manufactured by Nagase ChemteX), 1.25 parts of triphenylphosphine as a catalyst, 1.25 parts of N, N-dimethylbenzylamine, and 250 parts of toluene as a solvent were charged, and the mixture was heated to 110 ℃ with stirring under a nitrogen stream to react for 8 hours, thereby obtaining a hydroxyl group-containing resin. Subsequently, 49.8 parts (0.48mol) of succinic anhydride (RIKACID SA, manufactured by Nippon chemical Co., Ltd.) as an acid anhydride was charged and reacted at 110 ℃ for 4 hours. After confirming the disappearance of the absorption of the acid anhydride group by the FT-IR measurement, the reaction mixture was cooled to room temperature. Then, 41.1 parts (0.29mol) of glycidyl methacrylate (GMA, manufactured by Nichikoku K.K.) and 0.17 part of hydroquinone as a polymerization inhibitor were charged while stirring, and reacted at 80 ℃ for 8 hours. After the reaction, 26.0 parts (0.25mol) of RIKACID SA (manufactured by Nippon chemical Co., Ltd.: succinic anhydride) as an acid anhydride was charged and the mixture was reacted at 80 ℃ for 4 hours. After confirming the disappearance of the absorption of the acid anhydride group by the FT-IR measurement, the reaction mixture was cooled to room temperature. To this solution was added methyl ethyl ketone to adjust the solid content to 50%. The weight-average molecular weight of the resin (A-1) thus obtained was 20000, and the acid value of the resin solid content was 70 mgKOH/g.
The resin (A-1) is a copolymer. Therefore, M in formula (1) is obtained from formula (2)AO. Specifically, the following is obtained; the monomer having an oxyalkylene chain is polyethylene glycol diglycidyl ether (EX 861). The molecular weight of EX861 is 1098, so A in formula (2) is 1098. Further, the molecular weight of the oxyalkylene chain is 968,therefore, A in the formula (2)AOIs 968;
the resin (A-1) is a copolymer of bisphenol A, a bisphenol A type epoxy compound, polyethylene glycol diglycidyl ether, succinic anhydride, and glycidyl methacrylate. The oxyalkylene chain-containing monomer is a polyethylene glycol diglycidyl ether, so that B in the formula (2)AOIs 0.13. Further, B in formula (2) is 0.26+0.11+0.13+0.48+0.29+0.25 — 1.52;
therefore, the formula (2) is (968/1098) × (0.13/1.52) ≈ 0.08.
Synthesis example 2 Synthesis of Polymer 1
Into a four-necked flask were charged 510g of propylene glycol monomethyl ether acetate, 50g of methyl methacrylate, 90g of butyl methacrylate, 60g of hydroxyethyl methacrylate and 2g of azobisisobutyronitrile, and the mixture was heated at 80 ℃ for 6 hours while introducing nitrogen gas. The weight average molecular weight of the resulting polymer 1 was 40000.
(preparation of resin varnish)
Resin materials were blended as shown in the following formulation table, and a resin varnish was obtained using a high-speed rotary mixer.
[ Table 1]
Figure BDA0002658381230000271
Abbreviations in the table, etc., are as follows:
[ A-1 ]: resin (A-1) synthesized in Synthesis example 1, methyl Ethyl Ketone solution with 50% solid content, MAO×100＝8
ZFR-1491H: acid-modified epoxy acrylate having bisphenol F (bis-F) skeleton, manufactured by Nippon Chemicals K.K., EDGAc (diethylene glycol monoethyl ether acetate) blend (cut), solid content 70%, MAO×100＝0
ZAR-2000: acid-modified epoxy acrylate having bisphenol A (bis-A) skeleton, manufactured by Nippon Chemicals, Ltd., EDGAc blending, solid content 70%, MAO×100＝0
EX-821: polyethylene glycol diglycidyl ether, n4, epoxy equivalent 185g/eq, Nagase ChemteX strainManufactured by society, MAO×100＝58
EX-920: polypropylene glycol diglycidyl ether, n-3, epoxy equivalent 176g/eq, manufactured by Nagase ChemteX, MAO×100＝57
NC 3000H: biphenyl type epoxy resin (manufactured by Nippon chemical Co., Ltd., epoxy equivalent of about 272g/eq.), MAO×100＝0
R-551: EO-modified bisphenol A-type acrylate, manufactured by Nippon Kabushiki Kaisha, MAO×100＝34
A-PTMG-65: polytetramethylene glycol #650 diacrylate, produced by Mizhongcun chemical industries, LtdAO×100＝83
1.9 ND-A: 1, 9-nonanediol diacrylate, available from Kyoeisha chemical Co., Ltd., MAO×100＝0
NCI-831: oxime ester photopolymerization initiator available from ADEKA K.K
EP 4-A: magnesium hydroxide treated with aminosilane (available from Shendao chemical Co., Ltd.)
MEK: methyl Ethyl Ketone, pure chemical Co., Ltd
Polymer 1: polymer 1 synthesized in Synthesis example 2, propylene glycol monomethyl ether acetate solution with a solid content of 25%, MAO×100＝8。
"A-PTMG-65" manufactured by Xinzhongmura chemical industry Co., Ltd. has the following structural formula. Since A-PTMG-65 is not a copolymer, M is determined by the formula (1)AO；
[ chemical formula 2]
Figure BDA0002658381230000281
The molecular weight of A-PTMG-65 is 774. Further, the molecular weight of the oxyalkylene chain is 648(72 × 9 ═ 648). Thus, MAO648/774 ≈ 0.83.
X in formula (1) of example 1 is determined as follows;
X＝{(2.5÷55)×58}+{(7÷55)×34}+{(3÷55)×83}≈11.5。
(production of photosensitive film with support)
As the support, a PET film (LUMIRROR T6AM, 38 μm thick, 130 ℃ softening point, "PET for mold release") subjected to mold release treatment with an alkyd resin-based mold release agent ("AL-5", manufactured by Lindco corporation) was prepared. The resin varnish thus obtained was uniformly applied to the release PET by a die coater under the condition that the thickness of the dried photosensitive resin composition layer became 25 μm, and dried at 80 to 120 ℃.
(formation of laminate for evaluation)
The copper layer of a glass epoxy substrate (copper-clad laminate) on which a circuit was formed by patterning the copper layer having a thickness of 18 μm was roughened by treatment with a surface treatment agent containing an organic acid (CZ8100, manufactured by MEC corporation). Next, the photosensitive resin composition layer of the photosensitive film with a support obtained in examples and comparative examples was disposed so as to be in contact with the surface of the copper layer, and the resultant was laminated by a vacuum laminator (VP 160, manufactured by Nikko-Materials corporation), thereby forming a laminate in which the copper-clad laminate, the photosensitive resin composition layer, and the support were sequentially laminated. The pressure bonding conditions were vacuum evacuation time 30 seconds, pressure bonding temperature 80 ℃, pressure bonding pressure 0.7MPa, and pressure bonding time 30 seconds. The laminate was allowed to stand at room temperature for 30 minutes or longer, and exposed to ultraviolet light from the support of the laminate using a pattern forming apparatus using a circular hole pattern. As for the exposure pattern, the drawing opening: 50 μm/60 μm/70 μm/80 μm/90 μm/100 μm round hole (through hole), L/S (line width/line pitch): a square quartz glass mask of 50 μm/50 μm, 60 μm/60 μm, 70 μm/70 μm, 80 μm/80 μm, 90 μm/90 μm, 100 μm/100 μm in line width and line pitch, 1cm × 2 cm. After standing at room temperature for 30 minutes, the support was peeled off from the laminate. The entire surface of the insulating layer on the laminate was subjected to spray development using a 1 mass% sodium carbonate aqueous solution at 30 ℃ as a developer at a spray pressure of 0.2MPa for 2 minutes. After spray development, 1J/cm2Further subjected to a heat treatment at 180 ℃ for 30 minutes to form a layer on the laminateAn insulating layer having an opening. This was used as a laminate for evaluation.
< evaluation of residue at bottom of Via >
The round holes of 100 μm formed in the laminate for evaluation were evaluated according to the following criteria;
o: no residue is left;
x: residues were observed, either film peeling or partial resin dissolution.
< evaluation of bendability >
The photosensitive resin composition layer of the photosensitive film with a support obtained in examples and comparative examples was subjected to full-surface exposure, development, and heat treatment. The conditions of exposure, development, and heat treatment were the same as those for forming the laminate for evaluation. The support was peeled off to obtain a cured film. The cured film was cut into a size of 15mm × 110mm, and the flexibility was evaluated by an MIT bending fatigue tester (manufactured by Toyo Seiki Seisaku-Sho Ltd.). The test was carried out according to JIS P8115 under the conditions of tension: 500g, test speed: 175 times/min, bending angle: 135 °, R of the bending clip: 0.38 mm. The number of bending times until breakage was counted, and the average value of the number of bending times (number of bending times) counted 3 times was evaluated according to the following criteria;
very good: more than 300 times
O: more than 100 times and less than 300 times
X: less than 100 times.
< evaluation of copper adhesion force >
A rolled copper foil (BHY-22B-T, manufactured by JX Nissan metals Co., Ltd., thickness: 18 μm) was prepared, which was washed with 10% sulfuric acid and dried. The photosensitive film with a support was bonded to the glossy surface of the rolled copper foil, and subjected to full-surface exposure, development, and heat treatment to obtain a substrate. The conditions of exposure, development and heat treatment were the same as those for the evaluation of bendability. The insulating layer side of the obtained substrate was bonded to a glass epoxy substrate, and the peel strength of the copper foil was measured using a tensile tester (manufactured by TSE, inc. "AC-50C-SL") based on japanese industrial standards (JIS C6481), and evaluated according to the following criteria;
o: the adhesion strength is more than 0.5kgf
X: the adhesion strength is less than 0.5 kgf.
< evaluation of insulating Property (HHBT) >
From the support of the photosensitive film with a support, a comb-shaped wiring pattern having an L (wiring width)/S (space) of 20 μm/20 μm was used, and whole surface exposure, development, and heat treatment were performed by ultraviolet rays. The conditions of the entire surface exposure, development and heat treatment were the same as those for forming the laminate for evaluation. Copper wires as electrodes were welded to both sides of the comb-shaped wiring pattern, a voltage of 50V was applied at 85 ℃ and 85% RH, and the resistance value (Ω) was measured 500 hours later, and the average value was calculated from the resistance value at 7 points, and evaluated according to the following criteria;
o: the average value of the resistance values was 108Omega or more
X: average value of resistance value is less than 108Ω。
From the results of the above table, it is understood that the use of the photosensitive resin composition of the present invention provides excellent developability, flexibility, adhesion, and insulation properties. In comparative example 3, it is considered that although the acrylic polymer having an oxyalkylene chain (polymer 1) was used, the polymer 1 was a thermoplastic resin and was not incorporated into the curing system, and thus the desired effect could not be obtained.
In each example, it was confirmed that even when the components (E) and (F) were not contained, the results were similar to those in the above examples, although the differences were somewhat observed.

Claims (14)

1. A photosensitive resin composition comprising the following components (A) to (D),
(A) a resin containing an ethylenically unsaturated group and a carboxyl group,
(B) Epoxy resin,
(C) Photopolymerizable monomer, and
(D) a photopolymerization initiator,
wherein any of the component (A), the component (B) and the component (C) contains an oxyalkylene chain, and a parameter X represented by the following formula (1) is 4 to 25 inclusive;
Figure DEST_PATH_IMAGE002
in the formula (1), the reaction mixture is,
MAOthe value represented by the following formula (2) is shown in the case where the component containing an oxyalkylene chain is a copolymer, or the molecular weight of the oxyalkylene chain of each compound contained in the (A) to (C)/((the molecular weight of each compound contained in the (A) to (C)) is shown in the case where the component containing an oxyalkylene chain is not a copolymer,
n represents the solid content (parts by mass) of all the compounds contained in the components (A) to (C),
n represents the solid content (parts by mass) of each compound contained in components (A) to (C);
Figure DEST_PATH_IMAGE004
in the formula (2), the reaction mixture is,
AAOrepresents the molecular weight of the oxyalkylene chain of each monomer comprising an oxyalkylene chain,
a represents the molecular weight of each monomer containing an oxyalkylene chain,
BAOrepresents the number of moles of each monomer containing an oxyalkylene chain,
b represents the total mole number of all monomers contained in the copolymer.
2. The photosensitive resin composition according to claim 1, further comprising (E) an inorganic filler.
3. The photosensitive resin composition according to claim 1, wherein an oxyalkylene chain is contained in any of the components (B) and (C).
4. The photosensitive resin composition according to claim 1, wherein the component (A) comprises an acid-modified unsaturated epoxy ester resin.
5. The photosensitive resin composition according to claim 1, wherein the component (A) comprises an acid-modified epoxy (meth) acrylate.
6. The photosensitive resin composition according to claim 1, wherein the component (A) comprises any one of an acid-modified epoxy (meth) acrylate having a naphthalene skeleton and an acid-modified epoxy (meth) acrylate having a bisphenol skeleton.
7. The photosensitive resin composition according to claim 6, wherein the acid-modified epoxy (meth) acrylate having a bisphenol skeleton has one of a bisphenol A skeleton and a bisphenol F skeleton.
8. The photosensitive resin composition according to claim 1, wherein the component (B) has a biphenyl skeleton.
9. The photosensitive resin composition according to claim 1, wherein the component (D) comprises an oxime ester photopolymerization initiator.
10. A photosensitive film comprising the photosensitive resin composition according to any one of claims 1 to 9.
11. A photosensitive film with a support, comprising:
support body, and
a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 9 provided on the support.
12. A printed wiring board comprising an insulating layer formed by using a cured product of the photosensitive resin composition according to any one of claims 1 to 9.
13. The printed wiring board of claim 12, wherein the insulating layer is a solder resist layer.
14. A semiconductor device comprising the printed wiring board of claim 12.
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