CN108885400A - Hardening resin composition, dry film, solidfied material and printed circuit board - Google Patents

Hardening resin composition, dry film, solidfied material and printed circuit board Download PDF

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Publication number
CN108885400A
CN108885400A CN201780018516.0A CN201780018516A CN108885400A CN 108885400 A CN108885400 A CN 108885400A CN 201780018516 A CN201780018516 A CN 201780018516A CN 108885400 A CN108885400 A CN 108885400A
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Prior art keywords
resin
group
resin composition
carboxylic
methyl
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Inventor
冈田和也
植田千穗
依田健志
伊藤信人
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Taiyo Holdings Co Ltd
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Taiyo Ink Mfg Co Ltd
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Publication of CN108885400A publication Critical patent/CN108885400A/en
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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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
    • C08G59/3281—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • C08G8/30—Chemically modified polycondensates by unsaturated compounds, e.g. terpenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/14—Copolymers of styrene with unsaturated esters
    • 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
    • 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
    • G03F7/075—Silicon-containing compounds
    • 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

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  • Chemical & Material Sciences (AREA)
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  • Spectroscopy & Molecular Physics (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials For Photolithography (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Epoxy Resins (AREA)

Abstract

The present invention provides：It can obtain the solidfied material of the resin layer of resistance to anti-thread breakage and the excellent solidfied material of insulating reliability hardening resin composition, the dry film with the resin layer obtained by the composition, the composition or the dry film and the printed circuit board with the solidfied material.The present invention is hardening resin composition etc., and the hardening resin composition is characterized in that, is contained：(A) carboxylic resin；With the epoxy resin of (B) with silsesquioxane skeleton.

Description

Hardening resin composition, dry film, solidfied material and printed circuit board
Technical field
The present invention relates to hardening resin composition, dry film, solidfied material and printed circuit boards.
Background technique
In the past, the material as the permanent overlay film such as solder mask, interlayer insulating film, coating for forming printed circuit board, example As disclosed in patent document 1 comprising active energy ray-curable resin, Photoepolymerizationinitiater initiater, photopolymerization monomer and epoxy The composition of resin, the active energy ray-curable resin is novolak type epoxy compounds and unsaturated monocarboxylic Reactant, with multi-anhydride reaction obtained from.
In recent years, due to the progress rapidly of semiconductor component and electronic equipment is in light and shortization, high performance, more The tendency of functionalization.The tendency is followed, the miniaturization of semiconductor packages, more pinizations put into practical.
Specifically, replacing being claimed using the IC package for being referred to as BGA (ball array encapsulation), CSP (wafer-level package) etc. For the IC package of QFP (QFP type), SOP (small outline packages) etc..In addition, in recent years, as further densification IC package, FC-BGA (encapsulation of flip-chip ball array) is also practical.
In printed circuit board used in such IC package (also referred to as package substrate), SRO (solder resist opening (Solder Resist Opening)) spacing is narrow and adjacent to each other and is formed, therefore, short circuit, interference are generated between SRO The worry of (cross talk noise) is got higher.In addition, the solder mask between being formed in SRO attenuates and thin, therefore, production is become easy Raw crackle.Therefore, the permanent overlay film such as solder mask used in package substrate is required after long-term high reliability, specifically For high resistance to anti-thread breakage and high insulating reliability.It is especially considering that, with the densification of package substrate from now on, reliability It is required that further increasing.
In the past, it is disclosed as the resist composition for the solder mask that can serve as package substrate, such as in patent document 2 A kind of photosensitive polymer combination, contains：Organopolysiloxane with the organic group containing epoxy group；With acryloyl group Phenol novolacs；Include the polyfunctional monomer with light functional group and/or more officials with light functional group Yu hot functional group The diluent of energy monomer；With Photoepolymerizationinitiater initiater.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Application 61-243869 bulletin
Patent document 2：Japanese Unexamined Patent Publication 2001-209183 bulletin
Summary of the invention
Problems to be solved by the invention
However, the resistance to anti-thread breakage and height for being unable to get height is exhausted in the hardening resin composition recorded in patent document 1 Edge reliability.
On the other hand, in the photosensitive polymer combination recorded in patent document 2, due to using the benzene with acryloyl group Phenol novolaks are lower therefore, it is necessary to improve solidification temperature with the adaptation of printed circuit board.Therefore it is difficult to obtain resistance to crackle Property.
That is, in the permanent overlay film such as solder mask used in previous package substrate, in resistance to anti-thread breakage and insulating reliability side There are rooms for improvement in face.
Therefore, the object of the present invention is to provide：It can obtain resistance to anti-thread breakage and the excellent solidfied material of insulating reliability consolidate The property changed resin combination, the dry film with the resin layer obtained by the composition, the composition or the dry film resin layer consolidate Compound and printed circuit board with the solidfied material.
The solution to the problem
The inventors of the present invention have made intensive studies in view of above-mentioned, as a result, it has been found that：By being compounded carboxylic resin and having The epoxy resin of silsesquioxane skeleton so far completes the present invention so as to solve aforementioned problems.In addition it finds：As Carboxylic resin, using the carboxylic resin having the following structure to which heat resistance and insulating reliability further increase, The structure is obtained from keeping the compound progress alkylene oxide with 2 or more phenolic hydroxyl group in 1 molecule modified.
That is, hardening resin composition of the invention is characterized in that, contain：(A) carboxylic resin；With (B) has The epoxy resin of silsesquioxane skeleton.
Hardening resin composition of the invention is preferably, and also contains (C) surface treated inorganic filler.
Hardening resin composition of the invention is preferably, and aforementioned (A) carboxylic resin has the following general formula (1) institute The structure shown.
(in formula, R1~R4Hydrogen atom or alkyl are each independently represented, k indicates any value in 0.3~10.)
Hardening resin composition of the invention is preferably, and aforementioned (A) carboxylic resin has the following general formula (2) institute The structure shown.
(in formula, R5~R7Hydrogen atom or alkyl are each independently represented, Z indicates that anhydride residue, m indicate in 0.3~10 Any value.)
Hardening resin composition of the invention is preferably, and aforementioned (B) has the epoxy resin of silsesquioxane skeleton With structure shown in the following general formula (3).
(in formula, R8~R11It is each independently group or organic group with SiO key, R8~R11At least one of For the group with epoxy group.)
Dry film of the invention is characterized in that thering is resin layer, the resin layer is by said curing property resin combination Obtained from being coated on film and drying.
Solidfied material of the invention is characterized in that, is the resin by said curing property resin combination or aforementioned dry film Obtained from layer solidification.
Printed circuit board of the invention is characterized in that thering is said curing object.
The effect of invention
According to the present invention it is possible to provide：It can obtain resistance to anti-thread breakage and the excellent solidfied material of insulating reliability curability tree Oil/fat composition, the dry film with the resin layer obtained by the composition, the composition or the dry film resin layer solidfied material and Printed circuit board with the solidfied material.
Specific embodiment
Hardening resin composition of the invention is characterized in that, is contained：(A) carboxylic resin；With, (B) have times The epoxy resin of half siloxane backbone.
Hardening resin composition of the invention contains carboxylic resin and the asphalt mixtures modified by epoxy resin with silsesquioxane skeleton Rouge, therefore, the glass transition temperature (Tg) of gained solidfied material is high, linear expansion coefficient (CTE α 1, α 2) is low, elasticity when high temperature Modulus (E) is high.Therefore, the mobility of solidfied material is suppressed at high temperature, is reduced and is generated stress, excellent heat resistance.In other words, may be used Crosslink density to say solidfied material of the invention is high, does not cause physical property to change substantially under high temperature.
In addition, hardening resin composition through the invention contains the epoxy resin with silsesquioxane skeleton, it can To inhibit warpage when solidifying, inhibit the generation stress of printed circuit intralamellar part.
In turn, hardening resin composition of the invention contains carboxylic resin and the ring with silsesquioxane skeleton Oxygen resin, therefore, the curability (reactivity) under low temperature improve, and can inhibit the oxidation of copper circuit caused by high-temperature process, Maintain the adaptation of solidfied material and printed circuit board.
In turn, it is believed that the elasticity modulus at a high temperature of solidfied material of the invention is high, therefore crosslink density is high, water absorption rate is low.
Detailed mechanism is unclear, but thinks based on such heat resistance, low warpage properties, curability at low temperatures, low water suction Property, the resistance to anti-thread breakage and insulating reliability of the solidfied material of hardening resin composition of the invention is excellent.It is additionally contemplated that as after It states, the maximum value of the Tan δ within the temperature range of 25~300 DEG C of solidfied material is small, therefore, available stable resistance to anti-thread breakage.
In addition, hardening resin composition according to the present invention, the also solidfied material of available excellent in resolution.
Hereinafter, each ingredient to hardening resin composition of the invention is illustrated.It should be noted that this specification In, (methyl) acrylate refers to, is referred to as the term of acrylate, methacrylate and their mixture, for other Similar performance is also the same.
[(A) carboxylic resin]
(A) carboxylic resin is polymerization or with (B) cross linking of epoxy resin and cured ingredient can by the inclusion of carboxyl To form alkali-soluble.In addition, in addition to carboxyl, preferably intramolecular has alkene from the viewpoint of photo-curable, resistance to developability Belong to unsaturated group, the carboxylic resin without ethylenically unsaturated group can be used only.As ethylenically unsaturated group, Preferably originate from the group of acrylic or methacrylic acid or their derivative.In carboxylic resin, preferably there is copolymerization knot The carboxylic resin of structure, the carboxylic resin with carbamate structures contain carboxylic using epoxy resin as starting material The resin of base, using phenolic compounds as the carboxylic resin of starting material.As the concrete example of carboxylic resin, can enumerate The compound (can for oligomer or polymer) being exemplified below.
(1) 2 functions or the polyfunctional epoxy resin more than it are reacted with (methyl) acrylic acid, in the hydroxyl for being present in side chain Contain carboxylic on base obtained from the dibasic acid anhydrides such as addition phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride The photoresist of base.Herein, 2 functions or the polyfunctional epoxy resin more than it are preferably solid.
(2) make 2 functional epoxy resins hydroxyl so that the polyfunctional epoxy resin made of epichlorohydrin epoxy with The reaction of (methyl) acrylic acid, the carboxylic photoresist obtained from addition dibasic acid anhydride on the hydroxyl of generation.Herein, 2 Functional epoxy resins are preferably solid.
(3) make that there is at least one alcohol hydroxyl group in the epoxide and 1 molecule with 2 or more epoxy groups in 1 molecule With the monocarboxylic acid reaction containing unsaturated group such as the compound of 1 phenolic hydroxyl group and (methyl) acrylic acid, reaction product is obtained, For the alcohol hydroxyl group of gained reaction product, make maleic anhydride, tetrabydrophthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, Carboxylic photoresist obtained from the reaction of the multi-anhydrides such as adipic anhydride.
(4) make bisphenol-A, Bisphenol F, bisphenol S, novolak phenolics, poly(4-hydroxystyrene), naphthols and aldehydes In 1 molecule such as condensation product of condensation product, dihydroxy naphthlene and aldehydes with 2 or more phenolic hydroxyl group compound, with ethylene oxide, The reaction of the alkylene oxides such as propylene oxide obtains reaction product, makes gained reaction product and (methyl) acrylic acid etc. containing unsaturated group Monocarboxylic acid reaction, make gained reaction product reacted with multi-anhydride obtained from carboxylic photoresist.
(5) make have the compound of 2 or more phenolic hydroxyl group and ethylene carbonate, propylene carbonate etc. cyclic annular in 1 molecule Carbonate products reaction obtains reaction product, reacts gained reaction product with the monocarboxylic acid containing unsaturated group, makes institute Obtain carboxylic photoresist obtained from reaction product is reacted with multi-anhydride.
(6) pass through aliphatic diisocyanate, Branched fatty (cyclo) aliphatic diisocyanates, ester ring type diisocyanate, aromatic series The diisocyanate cpds such as diisocyanate and polycarbonate-based polyalcohol, polyester-based polyols, gather polyether system polyalcohol Olefin-based polyalcohol, acrylic polyol, bisphenol-A system alkylene oxide addition product glycol, with phenolic hydroxyl group and alcohol hydroxyl group The sudden reaction of the diol compounds such as compound and obtain carbamate resins, the end of the carbamate resins made With made of anhydride reaction containing the carbamate resins of terminal carboxyl group.
(7) by diisocyanate, with the carboxylic diatomic alcohol compounds such as dihydromethyl propionic acid, dimethylolpropionic acid, In the synthesis for the carboxylic carbamate resins that sudden reaction with diol compound obtains, (methyl) acrylic acid hydroxyl is added There is 1 hydroxyl and 1 or more the compound of (methyl) acryloyl group in the molecules such as base Arrcostab and carry out end (methyl) third Carboxylic carbamate resins obtained from alkene is acylated.
(8) it is obtained by diisocyanate, with carboxylic diatomic alcohol compounds, with the sudden reaction of diol compound In the synthesis of carboxylic carbamate resins, be added isophorone diisocyanate and pentaerythritol triacrylate etc. There is 1 isocyanate group and 1 or more the compound of (methyl) acryloyl group in the molecules such as moore reactant and carry out end Carboxylic carbamate resins obtained from (methyl) is acrylated.
(9) by unsaturated carboxylic acids such as (methyl) acrylic acid, low with styrene, α-methylstyrene, (methyl) acrylic acid Carboxylic photoresist obtained from the copolymerization of compound containing unsaturated group such as grade Arrcostab, isobutene.
(10) make the dicarboxyls such as multifunctional oxetane resin and adipic acid, phthalic acid, hexahydrophthalic acid Carboxylic polyester resin obtained from addition dibasic acid anhydride on the sour primary hydroxyl for reacting and generating.
(11) there is in 1 molecule of addition cyclic ether group and (first on any carboxylic resin in above-mentioned (1)~(10) Base) acryloyl group compound obtained from carboxylic photoresist.
As carboxylic resin, the carboxylic resin of preferably above-mentioned (1), (4), (5) and (9), from the resistance to of solidfied material From the perspective of hot (glass transition temperature) improves, the preferred carboxylic resin of (1), (4), (5).Wherein, from insulation From the perspective of reliability, the carboxylic resin of more preferable above-mentioned (4), (5).In turn, can be suitble to using such as above-mentioned (4), (5) the carboxylic resin with structure shown in the following general formula (1).
(in formula, R1~R4Hydrogen atom or alkyl are each independently represented, k indicates any value in 0.3~10.)
As R1~R4The alkyl that can be taken, the preferably alkyl of carbon number 1~20.
Furthermore it is possible to be suitble to contain carboxyl using as above-mentioned (4), (5), with structure shown in the following general formula (2) Resin.
(in formula, R5~R7Hydrogen atom or alkyl are each independently represented, Z indicates that anhydride residue, m indicate in 0.3~10 Any value.)
As R5~R7The alkyl that can be taken, the preferably alkyl of carbon number 1~20.
As the anhydride residue that Z can take, for the anhydride residue from carboxylic acid anhydrides shown in following, for example, tetrahydro The anhydride residue of phthalic anhydride, maleic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic dianhydride etc..
As the carboxylic resin with structure shown in structure shown in aforementioned formula (1) and aforementioned formula (2), Ke Yiju Out：Aforementioned (4) or (5) such, the compound in 1 molecule with 2 or more phenolic hydroxyl group and alkylene oxide or cyclic carbonate The reaction product of compound, with the reactant of carboxylic acid and multi-anhydride with ethylenically unsaturated group, that is, carboxylic tree Rouge.It should be noted that can not only make the compound and alkylene oxide or ring in aforementioned 1 molecule with 2 or more phenolic hydroxyl group The reaction product of shape carbonate products can also make to have in aforementioned 1 molecule with the carboxylic acid reaction with ethylenically unsaturated group There are the compound of 2 or more phenolic hydroxyl group and the reaction product of alkylene oxide or cyclic carbonate compound, with representative examples of saturated aliphatic list After at least either reaction in carboxylic acid and aromatic monocarboxylate, keep the carboxylic acid with ethylenically unsaturated group and multi-anhydride anti- It answers.
As the compound in aforementioned 1 molecule with 2 or more phenolic hydroxyl group, can enumerate：Catechol, isophthalic two Phenol, hydroquinone, dihydroxytoluene, naphthalene glycol, tert-butyl catechol, tert-butyl hydroquinone, pyrogallol, isophthalic three Phenol, bisphenol-A, Bisphenol F, bisphenol S, 4,4 '-dihydroxy benaophenonels, 4,4 '-dihydroxydiphenyl ethers, phenolphthalein, phenolic varnish type Phenolic resin, phenols with phenolic hydroxyl group aromatic aldehyde condensation product, poly(4-hydroxystyrene), 1- naphthols or beta naphthal with Condensation product (that is, naphthol type novolac resin), 1,2-, 1,3-, Isosorbide-5-Nitrae-, 1,5-, 1,6-, 2, the 3-, 2,6-, 2,7- of aldehydes etc. Condensation product, monohydroxy naphthalene or the dihydroxy naphthlene of the condensation product of dihydroxy naphthlene and aldehydes, single naphthols and above-mentioned dihydroxy naphthlene and aldehydes With the condensation product, monohydroxy naphthalene or dihydroxy naphthlene and the addition product of diolefin compound etc. of benzene dimethanol class, but it is not limited to these. These compounds with phenolic hydroxyl group can be used alone or mix two or more use.
Include in the above-mentioned compound with phenolic hydroxyl group：On phenol ring or it is bonded in the hydrocarbon skeleton of phenol ring and has Functional group comprising halogen atom, oxygen, nitrogen, sulphur etc., such as halogen radical, ether, ester group, carbonyl, hydroxyl, aldehyde radical, amino, amide The heteroaromatic groups such as base, itrile group, nitro, sulfydryl, thioether group and pyridyl group, imidazole radicals.
In these compounds with phenolic hydroxyl group, it is preferred that with the chemical combination of 3 or more phenolic hydroxyl group in 1 molecule Object can more preferably enumerate the condensation product of novolak phenolics, phenols and the aromatic aldehyde with phenolic hydroxyl group.
Addition ratio about alkylene oxide relative to the above-mentioned compound with phenolic hydroxyl group, relative to phenolic hydroxyl group Compound every 1 equivalent of phenolic hydroxyl group, preferably 0.3~10.0 mole.In the case where 0.3 mole or more, gained is photosensitive Containing in carboxy resin, photo-curable becomes good.In addition, photo-curable and Thermocurable become in 10.0 moles of situations below It obtains well.
Alkylene oxide preferably carries out the addition reaction of the aforementioned compound with phenolic hydroxyl group at room temperature~250 DEG C.Make For reaction dissolvent, can be suitble to use：Benzene,toluene,xylene, durol, n-hexane, hexamethylene, hexahydrotoluene, ethyl Hexamethylene, octane, methyl iso-butyl ketone (MIBK), Di Iso Propyl Ether etc..These organic solvents, which can be used alone or mix two or more, to be made With.
As catalysts, can be suitble to use：Potassium carbonate, sodium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, hydrogen The phosphorus such as the imidazolium compounds such as the tertiary amines such as the alkali metal compounds such as barium monoxide, triethylamine, 2-ethyl-4-methylimidazole, triphenylphosphine Compound, tetramethyl ammonium chloride, tetrabutylammonium bromide, trimethyl benzyl ammonium halide, durol ammonium formate, tetramethyl hydroxide It is the quaternary bases salt compounds such as ammonium, tetraethyl ammonium hydroxide, four methyl phosphonium hydroxides, aphthenic acids, lauric acid, stearic acid, oleic acid, pungent The metal salt etc. of the organic acids such as lithium, chromium, zirconium, potassium, the sodium of acid.These catalyst can be used alone or mix two or more use.
As alkylene oxide, ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, oxinane can be enumerated Deng.As cyclic carbonate compound, known common carbonate products can be used, for example, carbonic acid Asia second Ester, propylene carbonate, butylene carbonate, 2,3- carbonic ester propyl methacrylate etc., it is preferred that in terms of reactive It sets out, preferably pentacyclic ethylene carbonate, propylene carbonate.These alkylene oxides and cyclic carbonate compound can be single respectively Solely two or more is used or mixes to use.
It reacts the above-mentioned compound with phenolic hydroxyl group with alkylene oxide or cyclic carbonate compound and obtains reaction production Object reacts gained reaction product with the monocarboxylic acid containing unsaturated group, available reaction product, in esterification at this time Preferably 50~120 DEG C of reaction temperature, under reduced pressure, under normal pressure, pressurization under can be reacted.In the esterification, contain The double bond equivalent that the monocarboxylic acid expectation of unsaturated group is set as the photosensitive carboxylic resin of gained becomes 300~800g/eq. Addition amount.
As reaction dissolvent, can be suitble to using benzene,toluene,xylene, durol, n-hexane, hexamethylene, methyl ring Hexane, ethyl cyclohexane, octane, methyl iso-butyl ketone (MIBK), Di Iso Propyl Ether etc..These organic solvents can be used alone or mix Two or more is used.
As esterification catalyst, can be suitable for using sulfuric acid, hydrochloric acid, phosphoric acid, boron fluoride, methanesulfonic acid, benzene sulfonic acid, to toluene Sulfonic acid, cation exchange resin etc..Esterification preferably carries out in the presence of polymerization inhibitor, as polymerization inhibitor, can be suitble to make With quinhydrones, methylnaphthohydroquinone, Hydroquinone monomethylether, catechol, pyrogallol etc..
As the typical example of the aforementioned monocarboxylic acid containing unsaturated group, acrylic acid, methacrylic acid, crotons can be enumerated Acid, cinnamic acid, alpha-cyano cinnamic acid, β-styrene acrylic, β-furfuryl acrylic acid etc..It is particularly preferably acrylic acid herein And methacrylic acid.These monocarboxylic acids containing unsaturated group can be used alone or mix two or more use.
React previous reaction product and the reaction product of the monocarboxylic acid containing unsaturated group with multi-anhydride, it is available Carboxylic photoresist (photonasty prepolymer), in the reaction, the dosage of multi-anhydride be generate it is carboxylic photosensitive Property resin acid value preferably become 20~200mgKOH/g, more preferably become 50~120mgKOH/g addition amount.Reaction is rear In the presence of the organic solvent stated or in the presence of non-, in quinhydrones, methylnaphthohydroquinone, Hydroquinone monomethylether, catechol, pyrogallol It is carried out in the presence of equal polymerization inhibitors, usually with about 50~150 DEG C.The tertiary amines such as triethylamine, three second can be added as needed at this time The phosphorus compounds such as the imidazolium compounds such as the quaternary ammonium salts such as base benzyl ammonium chloride, 2-ethyl-4-methylimidazole, triphenylphosphine, aphthenic acids, Metal salts of organic acids such as lauric acid, stearic acid, oleic acid, the lithium of octanoic acid, chromium, zirconium, potassium, sodium etc. are used as catalyst.These catalysis Agent can be used alone or mix two or more use.
As above-mentioned multi-anhydride, it is adjacent that methyl tetrahydrophthalic anhydride, tetrabydrophthalic anhydride, hexahydro can be enumerated Phthalate anhydride, methylhexahydrophthalic anhydride, carbic anhydride, 3,6 endomethylene tetrahydrophthalic anhydride, methyl The ester ring types dibasic acid anhydride such as Nadic anhydride, tetrabromophthalic anhydride；Succinic anhydride, maleic anhydride, Aliphatic or the virtues such as itaconic anhydride, octenyl succinic acid anhydride, five decenyl succinic acid anhydrides, phthalic anhydride, trimellitic anhydride Binary or ternary acid anhydrides or biphenyltetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butane tetracarboxylic acid dianhydride, the ring penta of fragrant race The aliphatic such as alkane tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride or aromatic series quaternary acid dianhydride, can be used It is one kind or two or more in them.Wherein, particularly preferred ester ring type dibasic acid anhydride.
(A) acid value of carboxylic resin preferably 20~200mgKOH/g.(A) acid value of carboxylic resin be 20~ When 200mgKOH/g, the formation of the pattern of solidfied material is become easy.More preferable 50~130mgKOH/g.
(A) compounding amount of carboxylic resin in terms of hardening resin composition total amount benchmark in addition to the solvents, for example For 15~60 mass %, preferably 20~60 mass %.By being set as 15 mass % or more, preferably 20 mass % or more, Ke Yiti High coating strength.And by being set as 60 mass % hereinafter, viscosity becomes suitably, processability is improved.More preferable 30~50 matter Measure %.(A) carboxylic resin can be used alone or combine two or more use.
[epoxy resin that (B) has silsesquioxane skeleton]
There is the epoxy resin (hereinafter, also referred to as " (B) epoxy resin ") of silsesquioxane skeleton as (B), as long as For silsesquioxane, i.e., will 3 functional silanes hydrolysis obtained from have (RSiO1.5)nStructure network-type polymer or It polyhedron cluster and is just not particularly limited with the compound of the group comprising epoxy group.Each silicon of silsesquioxane it is average with 1.5 oxygen atoms and 1 alkyl bonding.
Herein, (B) epoxy resin is preferably halogen-free the epoxy resin of atom.
As (B) epoxy resin, preferably there is silsesquioxane skeleton shown in the following general formula (3).
(in formula, R8~R11It is each independently group or organic group with SiO key, R8~R11At least one of For the group with epoxy group.) herein, organic group refer to, the group comprising carbon atom.
The structure of aforementioned silsesquioxane is not particularly limited, and disordered structure, trapezium structure, complete cage modle knot can be used The silsesquioxane of common structure known in structure, incomplete cagelike structure etc..
As R8~R11The group with SiO key that can be taken, is not particularly limited, can enumerate：With SiO key and fat The group of race's skeleton, has SiO key and heteroatomic group etc. at the group with SiO key and aromatic backbone, under preferably becoming State person in the range of epoxide equivalent.
As R8~R11The organic group that can be taken, is not particularly limited, and can enumerate the aliphatic groups such as methyl, phenyl etc. Aromatic group has heteroatomic group etc..It is preferred that the organic group of carbon atom number 1~30, preferably becomes following epoxies and works as Person in the range of amount.
R8~R11At least one of be the group with epoxy group, herein as the group with epoxy group, without special It does not limit, as long as group or organic group with SiO key have epoxy group.
(B) epoxide equivalent of epoxy resin preferably 100~400g/eq., more preferable 150~250g/eq..100g/eq. with In the case where upper, storage stability becomes good.In 400g/eq. situation below, the CTE (α 1, α of solidfied material can be reduced 2)。
(B) compounding amount of epoxy resin is relative to (A) carboxylic 100 mass parts of resin, for example, 1~100 mass parts, It is preferred that 5~80 mass parts, more preferable 10~80 mass parts, and then preferably 10~60 mass parts, particularly preferred 20~60 mass parts, Most preferably 25~60 mass parts.(B) when the compounding amount of epoxy resin is 1 mass parts or more, resistance to anti-thread breakage and insulating reliability into One step improve, be 100 below the mass when, storage stability improve.
((C) surface treated inorganic filler)
Hardening resin composition of the invention preferably comprises inorganic filler, in addition, inorganic filler more preferably (C) is through surface The inorganic filler of processing (hereinafter, also referred to as " (C) inorganic filler ").By the inclusion of (C) inorganic filler, the resistance to crackle of solidfied material Property further increases.
Herein, the surface treatment of (C) inorganic filler refers to, for improving and (A) carboxylic resin or (B) epoxy resin Compatibility processing.
(C) surface treatment of inorganic filler is not particularly limited, and it is anti-preferably to import curability on the surface of inorganic filler Answer the surface treatment of group.
It as inorganic filler, is not particularly limited, known common filler, such as silica, crystallization can be used Property silica, Nuo Yibao tripoli, aluminium hydroxide, glass powder, talcum, clay, magnesium carbonate, calcium carbonate, natural mica, synthesis Mica, aluminium hydroxide, barium sulfate, barium titanate, iron oxide, Non-fibrous glass, hydrotalcite, mineral wool, alumina silicate, calcium silicates, zinc The inorganic fillers such as China.Wherein, preferably silica, stress small from surface area disperse in entirety and are not easy becoming crackle The aspect of point is set out, in addition, from excellent in resolution aspect, more preferable spherical silicon dioxide.
(C) inorganic filler preferably has and at least either in (A) carboxylic resin and (B) epoxy resin on surface The curability reactive group of reaction.Curability reactive group can may be photo-curable reaction for Thermocurable reactive group Group.As Thermocurable reactive group, hydroxyl, carboxyl, isocyanate group, amino, imino group, epoxy group, oxygen can be enumerated Heterocycle butyl, sulfydryl, methoxy, methoxy ethyl, ethoxyl methyl, ethoxyethyl group, oxazolinyl etc..It is solid as light The property changed reactive group, can enumerate vinyl, styryl, methylacryloyl, acryloyl group etc..Wherein, as photocuring Property reactive group, preferably methylacryloyl, acryloyl group, vinyl, as Thermocurable reactive group, preferably epoxy group. In addition, (C) inorganic filler can have curability reactive group of more than two kinds.As (C) inorganic filler, preferably through surface at The silica of reason.By the inclusion of surface treated silica, glass transition temperature can be improved.
The method for importing curability reactive group to the surface of (C) inorganic filler is not particularly limited, as long as known in Common method imports, can with curability reactive group surface treating agent, for example with curability reactive group The coupling agent etc. of group handles the surface of inorganic filler.
As the surface treatment of (C) inorganic filler, preferably by the surface treatment of coupling agent.As coupling agent, can make With silane coupling agent, titanium coupling agent, zirconium coupling agent, aluminum coupling agent etc..Wherein, preferred silane coupling agent.
As silane coupling agent, the silane coupling agent of solidification reactivity group can be preferably imported to (C) inorganic filler.As The silane coupling agent of heat cure reactive group can be imported, can be enumerated：Silane coupling agent with epoxy group, with amino Silane coupling agent, the silane coupling agent with sulfydryl, the silane coupling agent with isocyanate group, wherein more preferably there is ring The silane coupling agent of oxygroup.As the silane coupling agent that can import photocuring reaction group, preferably with the silane of vinyl Coupling agent, the silane coupling agent with styryl, the silane coupling agent with methylacryloyl, the silicon with acryloyl group Alkane coupling agent, wherein more preferably with the silane coupling agent of methylacryloyl.
In addition, as (C) inorganic filler for not having curability reactive group, for example, at through oxidation aluminium surface The inorganic filler etc. of reason.
(C) as long as inorganic filler is matched with surface treated state is mixed in hardening resin composition of the invention, Table will can also be carried out to inorganic filler in the composition after the untreated inorganic filler in surface and surface treating agent compounding respectively Surface treatment is preferably compounded surface treated inorganic filler in advance.It, can be with by being compounded surface treated inorganic filler in advance Resistance to anti-thread breakage equal drop caused by the surface treating agent not being consumed in possible remaining surface treatment when preventing from being compounded respectively It is low.In the case where being surface-treated in advance, preferably it is compounded in solvent, pre-dispersed in resin component has the pre- of (C) inorganic filler Dispersion liquid, it is further preferred that keeping surface treated inorganic filler pre-dispersed in solvent, be in the composition compounded that this is pre-dispersed Liquid, or after making the untreated inorganic filler in surface is pre-dispersed to be sufficiently surface-treated when solvent, compounding should in the composition Pre-dispersed liquid.
It is resistance to anti-thread breakage more excellent when the average grain diameter of inorganic filler is 2 μm or less in hardening resin composition of the invention It is different, therefore it is preferred that.More preferable 1 μm or less.It should be noted that average grain diameter refers in this specification, Nikkiso Company Limited is used The value of the D50 of Microtrac grain size analysis meter measurement processed.
Total amount of the compounding amount of inorganic filler relative to the solid component of hardening resin composition, preferably 20~80 matter Measure %, more preferable 30~80 mass % and then preferably 35~80 mass %.
Hardening resin composition of the invention can combine (C) inorganic filler with not surface treated inorganic filler It uses.Under above situation, total amount of (C) inorganic filler relative to (C) inorganic filler and not surface treated inorganic filler is excellent Select 30 mass % or more, more preferable 50 mass % or more and then preferably 70 mass % or more.In addition, not surface treated nothing The preferred spherical silicon dioxide of machine filler.
(in Photoepolymerizationinitiater initiater and Photobase generator at least any one)
, it is preferable to use Photoepolymerizationinitiater initiater and light in the case where making hardening resin composition photo-curable of the invention At least any one in generated base alkaline agent.As Photoepolymerizationinitiater initiater, as long as being as Photoepolymerizationinitiater initiater, optical free radical producing agent Well known Photoepolymerizationinitiater initiater just can be used.
As Photoepolymerizationinitiater initiater, for example, double-(2,6- dichloro-benzoyl base) phenyl phosphine oxide, double-(2,6- Dichloro-benzoyl base) -2,5- 3,5-dimethylphenyl phosphine oxide, double-(2,6- dichloro-benzoyl base) -4- propylphenylphosphine oxide, it is double - (2,6- dichloro-benzoyl base) -1- naphthalene phosphine oxide, double-(2,6- Dimethoxybenzoyl) phenyl phosphine oxide, double-(2,6- Dimethoxybenzoyl) -2,4,4- trimethylpentylphosphine oxide, double-(2,6- Dimethoxybenzoyl) -2,5- dimethyl Phenyl phosphine oxide, double-(2,4,6- trimethylbenzoyl)-phenyl phosphine oxide (BASF JAPAN corporation IRGACURE819) Equal bisacylphosphines phosphine；2,6- Dimethoxybenzoyl diphenyl phosphine oxide, the oxidation of 2,6- dichloro-benzoyl base diphenyl Phosphine, 2,4,6- trimethylbenzoyl phenyl methyl-phosphonate, 2- methyl benzoyl diphenyl phosphine oxide, valeryl Phenylphosphine The list acyl such as isopropyl propionate, 2,4,6- trimethyl benzoyl diphenyl base phosphine oxide (BASF JAPAN corporation IRGACURE TPO) Base phosphinoxides；1- hydroxy-cyciohexyl phenyl ketone, 1- [4- (2- hydroxyl-oxethyl)-phenyl] -2- hydroxy-2-methyl -1- third Alkane -1- ketone, 2- hydroxyl -1- { 4- [4- (2- hydroxy-2-methyl-propiono)-benzyl] phenyl } -2- methyl-propan -1- ketone, 2- The hydroxy acetophenones classes such as hydroxy-2-methyl -1- phenyl-propane -1- ketone；Benzoin, dibenzoyl, benzoin methylether, benzoin second The benzoin class such as ether, benzoin positive propyl ether, benzoin iso-propylether, benzoin n-butylether；Benzoin alkyl ethers；Benzophenone, To methyl benzophenone, Michler's keton, methyl benzophenone, 4,4 '-dichloro benzophenones, 4,4 '-bis- diethylamino hexichol first The benzophenones such as ketone；Acetophenone, 2,2- dimethoxy -2- phenyl acetophenone, 2,2- diethoxy -2- phenyl acetophenone, 1, 1- dichloroacetophenone, 1- hydroxycyclohexylphenylketone, 2- methyl-1-[4- (methyl mercapto) phenyl]-2- morpholinyl-1- acetone, 2- Benzyl -2- dimethylamino -1- (4- morpholino phenyl) -1- butanone, 2- (dimethylamino) -2- [(4- aminomethyl phenyl) first Base) -1- [4- (4- morpholinyl) phenyl] -1- butanone, N, the acetophenones such as N- dimethylamino benzoylformaldoxime；Thioxanthones, 2- ethyl Thioxanthones, 2-isopropylthioxanthone, 2,4- dimethyl thioxanthone, 2,4- diethyl thioxanthone, 2-chlorothioxanthone, 2,4- diisopropyl The thioxanthene ketone class such as base thioxanthones；Anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2- ethyl hydrazine, 2- tert-butyl anthraquinone, 1- chloroanthraquinone, 2- The Anthraquinones such as amyl anthraquinone, 2- amino anthraquinones；The ketals class such as acetophenone dimethyl ketal, benzil dimethyl ketal；Ethyl -4- Dimethyl aminobenzoate, 2- (dimethylamino) ethylamino benzonitrile acid esters, to benzoates such as mesitylenic acid ethyl esters； 1- [4- (thiophenyl)-phenyl] -1,2- octanedione -2- (O- benzoyl oxime), 1- [9- ethyl -6- (2- methyl benzoyl) - 9H- carbazole -3- base] the oximes esters such as-ethyl ketone 1- (O- acetyl oxime)；Bis- (η 5-2,4- cyclopentadiene -1- bases)-bis- (2,6- bis- is fluoro- 3- (1H- pyrroles -1- base) phenyl) titanium, bis- (cyclopentadienyl groups)-bis- [the fluoro- 3- of 2,6- bis- (2- (1- pyrroles -1- base) ethyl) benzene Base] the titanocenes class such as titanium；Phenyl disulfide 2- nitrofluorene, butyroin, anisoin ethyl ether, azobis isobutyronitrile, tetramethyl autumn Blue nurse disulfide etc..Photoepolymerizationinitiater initiater can be used alone or combine two or more use.Wherein, preferred monoacylphosphine oxide Phosphine, oxime esters, more preferable 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1- [9- ethyl -6- (2- toluyl Base) -9H- carbazole -3- base]-ethyl ketone 1- (O- acetyl oxime).
The compounding amount of Photoepolymerizationinitiater initiater is relative to (A) carboxylic 100 mass parts of resin, preferably 0.5~20 mass parts. In the case where more than 0.5 mass parts, surface cure becomes well, 20 below the mass in the case where, be not likely to produce halation, can To obtain good resolution ratio.
Photobase generator be irradiated by the light of ultraviolet light, visible light etc. molecular structure change or molecular cleavage and The compound for a kind or more the alkaline matter that the catalyst reacted as heat cure functions can be generated.As alkaline matter, example Secondary amine, tertiary amine can such as be enumerated.
As Photobase generator, for example, alpha-aminoacetophenone compound, oxime ester compound, N- formylated aromatic series Amino-compound, N- acylated aromatic race amino-compound, nitrobenzylamino formic acid ester compound, alkoxybenzyl carbamic acid Ester compounds etc..Wherein, preferably oxime ester compound, alpha-aminoacetophenone compound, more preferable oxime ester compound, more preferable 1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base]-ethyl ketone 1- (O- acetyl oxime).As alpha-aminoacetophenone Object is closed, particularly preferably with the substance of 2 or more nitrogen-atoms.Photobase generator, which can be used alone, can also combine two or more It uses.
In addition, quaternary ammonium salt etc. can be enumerated as Photobase generator.
As other Photobase generators, WPBG-018 (trade name also can be used：9-anthrylmethyl N, N '- Diethylcarbamate), WPBG-027 (trade name：(E)-1-[3-(2-hydroxyphenyl)-2-propenoyl] Piperidine), WPBG-082 (trade name：guanidinium2-(3-benzoylphenyl)propionate),WPBG- 140 (trade names：1- (anthraquinon-2-yl) ethyl imidazolecarboxylate) etc..
In turn, a part of substance of foregoing photo-polymerization initiator is also functioned as Photobase generator.For being also used as light The Photoepolymerizationinitiater initiater that generated base alkaline agent functions, preferably oxime ester system Photoepolymerizationinitiater initiater and the photopolymerization of alpha-aminoacetophenone system cause Agent.
The compounding amount of Photobase generator is relative to (A) carboxylic 100 mass parts of resin preferably 0.1~20 mass parts.0.1 matter Measure part more than in the case where, surface cure becomes well, 20 below the mass in the case where, be not likely to produce halation, can obtain To good resolution ratio.
(compound with ethylenically unsaturated group)
In the case where making hardening resin composition photo-curable of the invention, it is preferable to use in molecule have 1 with The compound of upper ethylenically unsaturated group.As the compound with ethylenically unsaturated group, can be used as known common Optical polymerism oligomer, the optical polymerism vinyl monomer of photo-sensitive monomer etc..It should be noted that so-called herein have alkene Belong to do not include in the compound of unsaturated group have ethylenically unsaturated group ((A) carboxylic resin and (E) through surface at The inorganic filler of reason.
As optical polymerism oligomer, unsaturated polyester system oligomer, (methyl) acrylic ester oligomer can be enumerated Deng.As (methyl) acrylic ester oligomer, phenol Novolac epoxy (methyl) acrylate, cresol novolac can be enumerated Epoxies (methyl) acrylate, carbamic acid such as novalac epoxy (methyl) acrylate, biphenol type epoxy (methyl) acrylate Ester (methyl) acrylate, epoxy amino formic acid esters (methyl) acrylate, polyester (methyl) acrylate, polyethers (methyl) third Olefin(e) acid ester, polybutadiene-modified (methyl) acrylate etc..
As optical polymerism vinyl monomer, known common substance, such as styrene, chlorostyrene, α-can be enumerated The styrene derivatives such as methyl styrene；The vinyl esters such as vinyl acetate, vinyl butyrate or vinyl benzoate；Vinyl Isobutyl ether, vinyl-n-butyl ether, the tertiary butyl ether of vinyl-, vinyl-n-amylether, vinyl isoamyl ether, vinyl-n-octadecane The vinyl ethers such as ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ethers, triethylene glycol monomethyl vinyl ethers；Propylene Amide, Methacrylamide, N- hydroxymethylacrylamide, N- hydroxymethyl Methacrylamide, N- methoxy propylene Amide, N- ethoxymethyl acrylamide, N- butoxy methyl acrylamide etc. (methyl) acrylic amide；Triallyl isocyanide The allyl compounds such as urea acid esters, diallyl phthalate, diallyl isophthalate；(methyl) acrylic acid 2- ethyl Own ester, (methyl) lauryl acrylate, (methyl) acrylic acid tetrahydrofuran ester, (methyl) isobornyl acrylate, (methyl) third The esters of (methyl) acrylic acid such as olefin(e) acid phenyl ester, (methyl) phenoxyethyl acrylate；(methyl) Hydroxyethyl Acrylate, (first Base) (methyl) the hydroxyalkyl acrylates class such as hydroxypropyl acrylate, pentaerythrite three (methyl) acrylate；(methyl) third Olefin(e) acid methoxy acrylate, (methyl) ethoxyethyl acrylate etc. alkoxyalkylenes glycol list (methyl) esters of acrylic acid；Second Glycol two (methyl) acrylate, butanediol two (methyl) esters of acrylic acid, neopentyl glycol two (methyl) acrylate, 1.6- oneself Glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate, two Poly- (methyl) acrylate of the alkylidene polyols such as pentaerythrite six (methyl) acrylate；Diethylene glycol two (methyl) acrylic acid Ester, triethylene glycol two (methyl) acrylate, ethoxylated trimethylolpropane triacrylate, propoxylation trihydroxy methyl third Poly- (methyl) esters of acrylic acid of the polyether polyols such as alkane three (methyl) acrylate；Hydroxy new pentane acid neopentyl glycol ester two Poly- (methyl) esters of acrylic acid such as (methyl) acrylate；The isocyanides ureas such as three [(methyl) acryloyl-oxyethyl] isocyanuric acid esters Poly- (methyl) esters of acrylic acid of acid esters type etc..They can be used alone or in combination of two or more kinds according to characteristic is required.
The compounding amount of compound with ethylenic unsaturated bond relative to (A) carboxylic 100 mass parts of resin preferably 3~ 40 mass parts.In the case where more than 3 mass parts, surface cure improve, 40 below the mass in the case where, halation be suppressed. More preferable 5~30 mass parts.
(thermal curing catalyst)
Hardening resin composition of the invention preferably comprises thermal curing catalyst.As such thermal curing catalyst, For example, imidazoles, 2-methylimidazole, 2- ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2- phenylimidazole, 4- phenyl miaow The imdazole derivatives such as azoles, 1- cyano ethyl -2- phenylimidazole, 1- (2- cyano ethyl) -2-ethyl-4-methylimidazole；Dicyandiamide, Benzyldimethylamine, 2,4,4- (dimethylamino)-N, N- dimethyl benzyl amine, 4- methoxyl group-N, N- dimethyl benzyl amine, 4- first The hydrazine compounds such as amine compounds, adipic dihydrazide, the sebacic dihydrazides such as base-N, N- dimethyl benzyl amine；Triphenylphosphine etc. Phosphorus compound etc..Alternatively, it is also possible to use guanamines, acetylguanamine, benzoguanamine, melamine, 2,4- diamino -6- methyl-prop Alkene trimethylammonium-s-triazine, 2- vinyl -2,4- diamino-s-triazine, 2- vinyl -4,6- diamino-s-triazine are different The s-triazine such as cyanurate addition product, 2,4- diamino -6- methacryloxyethyl-s-triazine isocyanuric acid adduct spread out Biology, the compound for being preferably also used as adaptation imparting agent to function these are applied in combination with thermal curing catalyst.
The compounding amount of thermal curing catalyst relative to 100 mass parts of (B) epoxy resin, for example, 0.05~80 mass parts, It is preferred that 0.05~50 mass parts, more preferable 0.05~40 mass parts and then preferably 0.1~30 mass parts.
(curing agent)
Hardening resin composition of the invention can contain curing agent.As curing agent, phenolic resin can be enumerated, gathered Carboxylic acid and its acid anhydrides, cyanate ester resin, active ester resin, maleimide compound, ester ring type olefin polymer etc..Curing agent It can be used alone or combine two or more use.
Curing agent can be carried out the official of heat cure reaction preferably with the epoxy group etc. in the heat-curing resins such as (B) epoxy resin Can group, with the functional group in the curing agent of the functional group reactions ratio become curing agent functional group/can be carried out heat cure The ratio of functional group's (equivalent proportion)=0.2~3 of reaction is compounded.By being set as above range, storage stability and solidification Property harmony it is excellent.
(colorant)
It may include colorant in hardening resin composition of the invention.As colorant, can be used it is red, blue, green, Colorant well known to yellow, black, white etc., can be pigment, dyestuff, pigment,.But from reduction carrying capacity of environment and to people From the perspective of the influence of body, halogen is not preferably contained.
The additive amount of colorant is not particularly limited, relative to (A) carboxylic 100 mass parts of resin preferably 10 mass Part or less, the ratios of particularly preferred 0.1~7 mass parts be sufficient.
(organic solvent)
It is viscous when being coated on substrate, carrier film for preparing composition, adjusting in hardening resin composition of the invention The purpose of spending can contain organic solvent.As organic solvent, can be used：The ketones such as methyl ethyl ketone, cyclohexanone；Toluene, diformazan Benzene, durene etc. are aromatic hydrocarbon；Cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl card must Alcohol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetic acid esters, tripropylene glycol list The glycol ethers such as methyl ether；Ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, card must Alcohol acetic ester, acetate of butyl carbitol, propylene glycol methyl ether acetate, dipropylene glycol monomethyl ether acetic acid esters, propylene carbonate Etc. esters；The aliphatic hydrocarbons such as octane, decane；It is common known in petroleum series solvent such as petroleum ether, naphtha, solvent naphtha etc. Organic solvent.These organic solvents can be used alone or in combination of two or more kinds.
(any other ingredient)
In turn, in hardening resin composition of the invention, can be compounded in the field of electronic material it is known it is common its His additive.As other additives, hot polymerization inhibitor, ultraviolet absorbing agent, silane coupling agent, plasticizer, fire-retardant can be enumerated Agent, antistatic agent, anti-aging agent, antibacterial mildew inhibitor, defoaming agent, levelling agent, thickener, adaptation imparting agent, thixotropy assign Agent, light-initiated auxiliary agent, sensitizer, thermoplastic resin, organic filler, release agent, surface treating agent, dispersing agent, dispersing aid, table Face modifying agent, stabilizer, fluorophor etc..
Hardening resin composition of the invention can be containing except (B) epoxy in the range of not impairing the effect of the present invention Heat-curing resin other than resin.As heat-curing resin, as long as showing electrical insulating property to solidify by heating Resin, for example,：Epoxide, oxetane compound, melamine in addition to (B) epoxy resin Resin, organic siliconresin etc., they can also be applied in combination.
There are multiple cyclic annular (sulphur) ethers as the heat-curing resin in addition to aforementioned (B) epoxy resin, preferably in molecule The compound of base.Compound with multiple cyclic annular (sulphur) ethers in above-mentioned molecule is to have multiple 3 member rings, 4 member rings in molecule Or 5 member ring ring-type (sulphur) ether compound, for example,：Intramolecular have multiple epoxy groups compound, i.e., it is more Functional epoxide compound, intramolecular have multiple oxetanylmethoxies compound, i.e., multifunctional oxetane compound, divide Compound in sub with multiple thioether groups, i.e., multifunctional episulfide resin etc..
As multi-functional epoxy compound, can enumerate：Epoxidized vegetable oil；Bisphenol A type epoxy resin；Hydroquinone type epoxy Resin；Bisphenol-type epoxy resin；Thioether-type epoxy resin；Brominated epoxy resin；Phenolic resin varnish type epoxy resin；Xenol phenolic aldehyde Type epoxy resin；Bisphenol f type epoxy resin；Bisphenol-A epoxy resin；Glycidyl amine type epoxy resin；In second Uride type epoxy resin；Alicyclic epoxy resin；Trihydroxy benzene methylmethane type epoxy resin；Alkylbenzene phenol-type epoxy resin (example Such as union II toluene phenol-type epoxy resin)；United phenol-type epoxy resin；Bisphenol-s epoxy resin；Bisphenol A novolac type ring oxygen Resin；Four hydroxy phenyl ethane type epoxy resin；Hetero ring type epoxy resin；O-phthalic acid diglycidyl ester resin；Four shrink Glyceryl xylenol ethane resin；Epoxy resin containing naphthalene；Epoxy resin with bicyclopentadiene skeleton；Triphenyl methane Type epoxy resin；Epoxy resin with silsesquioxane skeleton；Glycidyl methacrylate copolymerization is epoxy resin；Ring The copolymerization epoxy resin of hexyl maleimide and glycidyl methacrylate；Epoxy-modified polybutadiene rubber is derivative Object；CTBN modified epoxy etc., but it is not limited to these.These epoxy resin can be used alone or combine two or more It uses.Wherein, particularly preferred triphenylmethane type epoxy resin, phenolic resin varnish type epoxy resin, bisphenol-type epoxy resin, union II Toluene phenol-type epoxy resin, united phenol-type epoxy resin, xenol phenolic resin varnish type epoxy resin, naphthalene type epoxy resin or it Mixture.By (B) being had the epoxy resin of silsesquioxane skeleton and other epoxy composites use, Ke Yiti The glass transition temperature of high solidification object.
Hardening resin composition of the invention is preferably, Tan δ of the solidfied material in 25~300 DEG C of temperature range Maximum value be lower than 0.25.If it is such physical property, though the temperature of cured film become Tg nearby, Tg or more, can also be with It obtains stable resistance to anti-thread breakage.
It should be noted that in this specification, Tan δ just refers to as long as no being particularly limited to, for the dry of resin combination Resin layer after dry is with about 500mJ/cm2After irradiating ultraviolet light, and then to have the UV furnace conveyor of high-pressure sodium lamp with 1J/cm2Exposure After light quantity irradiation, heated 60 minutes with 160 DEG C, the physical property of 40 μm of thickness of solidfied material obtained from resin layer is fully cured. In addition, ultraviolet light refers to, wavelength is the electromagnetic wave of 10~400nm.Tan δ is the loss modulus measured in Measurement of Dynamic Viscoelasticity Divided by value obtained from storage modulus, that is, loss angle tangent (=loss modulus/storage modulus), Tan δ is base in this specification In under conditions of frequency 1Hz, 5 DEG C/min of heating rate measurement from 25 DEG C to 300 DEG C obtained from chart figure.
Tan δ (=loss modulus/storage modulus) lesser solidfied material in order to obtain, can reduce loss modulus (viscosity at Both point) or increase storage modulus (elastic component) or carry out, it is more than elastic component as far as possible viscous Property ingredient.
For scheme of the maximum value of Tan δ lower than 0.25 to be not particularly limited.
The maximum value of Tan δ lower than 0.20, preferably 0.15 hereinafter, when especially 0.13 or less, it is resistance to anti-thread breakage further to mention Height, therefore it is preferred that.
In addition, by the equivalent for reducing the epoxy groups of heat curable components such as (B) epoxy resin, in addition, compounding has olefinic Make compounding amount a small amount of in the case where the compound of unsaturated group, also can reduce the Tan δ of solidfied material.(B) epoxy resin The preferred 400g/eq. or less of the equivalent of epoxy group.
In the biggish situation of maximum value of the Tan δ of solidfied material, viscosity when solidfied material is exposed to high temperature, in solidfied material Ingredient is easy movement, and physical property has large change, but if being lower than 0.25 solidfied material for the maximum value of Tan δ, then becomes and connects The condition of high temperature of the Tg of nearly solidfied material, viscosity component also do not move substantially, and physical property variation is also small, can further suppress crackle Occur.
Hardening resin composition of the invention can carry out dry film and use, and can also form liquid and use.With The form of liquid is in use, can may be bi-component or more for one pack system.
Then, dry film of the invention has resin layer, and the resin layer is to apply hardening resin composition of the invention It is distributed in carrier film and obtained from drying.When forming dry film, firstly, hardening resin composition of the invention is had with above-mentioned Solvent dilution after being adjusted to viscosity appropriate, is applied by comma coater (comma coater), knife type coater, lip Cloth machine (lip coater), bar coater (rod coater), extrusion coating machine (squeeze coater), inverse formula coating machine (reverse coater), transmitting roll-coater (transfer roll cater), gravure coater (gravure Coater), flush coater etc. is coated into uniform thickness on a carrier film.Later, by the composition of coating usually 40~130 Drying in 1~30 minute is carried out at a temperature of DEG C, so as to form resin layer.Coating film thickness is not particularly limited, generally With the film thickness gauge after drying, suitable selection in the range of 3~150 μm, preferably 5~60 μm.
As carrier film, plastic film can be used, it is poly- that polyethylene terephthalate (PET) etc. can be used for example Ester film, Kapton, polyamidoimide film, polypropylene film, polystyrene film etc..For the thickness of carrier film Degree is not particularly limited, and is usually suitably selected in the range of 10~150 μm, in the range of more preferable 15~130 μm.
After forming the resin layer comprising hardening resin composition of the invention on a carrier film, for preventing dust from adhering to In the surface of resin layer the purpose of, strippable cover film further preferably is laminated on the surface of resin layer.As strippable Polyethylene film, polytetrafluoroethylene film, polypropylene film, surface treated paper etc. can be used for example in cover film.As Cover film, as long as when removing cover film less than the bonding force of resin layer and carrier film.
It should be noted that hardening resin composition of the invention can be coated on above-mentioned cover film in the present invention And it makes it dry to form resin layer, and laminated carrier film on the surface thereof.That is, in the present invention, when manufacturing dry film, as painting The film of cloth hardening resin composition of the invention, can be used carrier film and cover film.
Printed circuit board of the invention has to be obtained by the resin layer of hardening resin composition or dry film of the invention Solidfied material.As the manufacturing method of printed circuit board of the invention, for example, using above-mentioned organic solvent by curability of the invention Resin combination is adjusted to the viscosity suitable for coating method, utilizes dip coating, flow coat method, rolling method, stick coating method, silk-screen printing The methods of method, curtain coating are applied on substrate, then 60~100 DEG C at a temperature of wave organic solvent contained in composition It is dry dry (temporarily dry), to form not viscous resin layer.In addition, for dry film, using laminating machine etc. to set The mode that rouge layer is contacted with substrate fits on substrate, then removes carrier film, thus forms resin layer on substrate.
As above-mentioned base material, in addition to first pass through in advance copper etc. be formed with the printed circuit board of circuit, flexible printed circuit board with Outside, it can also enumerate and use paper-phenolic resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimides, glass Cloth/non-woven fabrics-epoxy resin, glass cloth/paper-epoxy resin, synthetic fibers-epoxy resin, fluororesin polyethylene polyphenyl All grades (FR-4 etc.) of the materials such as the high-frequency circuit copper-clad laminated board of ether (polyphenylene oxide) cyanate etc. Copper-clad laminated board and metal substrate, Kapton, PET film, polyethylene naphthalate (PEN) film, glass Substrate, ceramic substrate, wafer board etc..
Be coated with the volatile dry carried out after hardening resin composition of the invention can be used heated air circulation type drying oven, IR furnace, hot plate, convection oven etc. (using the device of the heat source with the air heating method using steam, make in drying machine The method of hot air convection contact and blowed nozzle to supporter) carry out.
In the case that hardening resin composition of the invention is Thermocurable, such as it is heated to 100~220 DEG C of temperature And make its heat cure, it is excellent so as to form each characteristics such as heat resistance, chemical resistance, resistance to hygroscopicity, adaptation, electrical characteristics Different curing overlay film (solidfied material).
In the case that hardening resin composition of the invention is photo-curable, resin layer is formed on a printed circuit Afterwards, by being formed with the photomask of predetermined pattern, being selectively exposed using active energy beam, pass through dilute alkaline aqueous solution (for example, 0.3~3 mass % aqueous sodium carbonate) develops unexposed portion, to form the pattern of solidfied material.In turn, to solid It is heating and curing (for example, 100~220 DEG C) after compound irradiation active energy beam or irradiates active-energy after being heating and curing Ray is only heating and curing and it is made to be finally completed solidification (being fully cured), and each characteristic such as adaptation, hardness is consequently formed Excellent cured film.
It should be noted that preferably being exposed in the case that hardening resin composition of the invention includes Photobase generator It is heated afterwards and before developing, as the heating condition after exposure and before developing, such as preferably with 60~150 DEG C, heating 1~60 Minute.
As the exposure machine irradiated for above-mentioned active energy beam, if for equipped with high-pressure sodium lamp, ultrahigh pressure mercury lamp, The device of the ultraviolet light of metal halide lamp, mercury short arc lamp etc. and irradiation 350~450nm range, further, it is also possible to make (such as directly describe the laser direct imaging of image by CAD data from computer, using laser with direct drawing apparatus Device).As the lamp source or laser source for directly retouching machine, as long as maximum wavelength is in the range of 350~410nm.For The light exposure for forming image is different according to film thickness etc., can usually make its 10~1000mJ/cm2, preferably 20~800mJ/ cm2In the range of.
As above-mentioned developing method, infusion process, elution method, spray-on process, spread coating etc. can be used, it, can as developer solution To use the aqueous alkali of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium metasilicate, ammonia, amine etc..
Hardening resin composition of the invention suitable for cured film is formed on a printed circuit, more suitably, It is used to form permanent overlay film, and then is suitble to, solder mask, interlayer insulating film, coating are used to form.In addition, utilizing this hair Therefore bright hardening resin composition, the available resistance to anti-thread breakage and excellent solidfied material of insulating reliability can be suitble to use In forming the printed circuit board of the wiring pattern for having fine spacing for requiring high reliability, such as package substrate, especially It is the permanent overlay film (especially solder mask) of FC-BGA
Embodiment
Hereinafter, being illustrated in more details using embodiment to the present invention, but the present invention is not limited to the following examples.It needs It is noted that hereinafter, " part " and " % " all quality criterias in case of no particular description.
[synthesis of carboxylic Resin A -1]
In the autoclave for having thermometer, nitrogen gatherer and alkylene oxide gatherer and agitating device, lead on one side Enter phenolic varnish type cresol resin (Showa Denko K. K Shownor CRG95, OH equivalent：119.4) 119.4 parts, hydrogen 119.4 parts of 1.19 parts of potassium oxide and toluene simultaneously stir, and on one side to nitrogen displacement is carried out in system, carry out heat temperature raising.Then, delay It is slow to be added dropwise 63.8 parts of propylene oxide, in 125~132 DEG C, 0~4.8kg/cm2Under make its react 16 hours.It is then cooled to room Temperature, in the reaction solution addition mixing .56 part of 89% phosphatase 11 in and potassium hydroxide, to obtain nonvolatile component 62.1%, hydroxyl value is the propylene oxide reaction solution of the phenolic varnish type cresol resin of 182.2mgKOH/g (307.9g/eq.). It is averaged made of 1.08 moles of addition of propylene oxide for every 1 equivalent phenolic hydroxyl group.
In having the reactor that blender, thermometer and air are blown into pipe, gained phenolic varnish type cresol resin is imported 293.0 parts of propylene oxide reaction solution, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 part of methylnaphthohydroquinone and toluene 252.9 parts, air was blown into 10ml/ minutes speed, with while stirring 110 DEG C make its react 12 hours.Pass through reaction And the water generated distills the water of 12.6 parts of removal in the form of the azeotropic mixture with toluene.It is then cooled to room temperature, by institute It obtains reaction solution to be neutralized for 35.35 parts with 15% sodium hydrate aqueous solution, then be washed.Thereafter, it using evaporator, uses 118.1 parts of displacement toluene of diethylene glycol monoethyl ether acetic acid esters simultaneously carry out distillation removal, to obtain phenolic varnish type acrylic acid Ester resin solution.Then, in having the reactor that blender, thermometer and air are blown into pipe, gained phenolic varnish type is imported 332.5 parts and 1.22 parts of triphenylphosphine of acrylic ester resin solution, air was blown into 10ml/ minutes speed, stirs one on one side While being slowly added 60.8 parts of tetrabydrophthalic anhydride, it is reacted 6 hours with 95~101 DEG C, is taken out after cooling.In this way, To the solution of the photosensitive carboxylic Resin A -1 of solid component 65%, the acid value 87.7mgKOH/g of solid component.Hereinafter, The solution of the carboxylic photoresist is known as resin solution A-1.
[synthesis of carboxylic Resin A -2]
In the flask for having condenser pipe, blender, 456 parts of bisphenol-A, 228 parts of water, 649 parts of 37% formaldehyde are put into, is protected 40 DEG C of temperature below are held, 228 parts of 25% sodium hydrate aqueous solution is added, are reacted 10 hours after addition with 50 DEG C.Reaction After be cooled to 40 DEG C, while remain 40 DEG C with below with 37.5% phosphate aqueous solution be neutralized to pH be 4.It stands later, it will Water layer separation.300 parts of methyl iso-butyl ketone (MIBK) are added after separation, are carried out after equably dissolving, are cleaned 3 times with 500 parts of distilled water, with 50 DEG C of temperature below, under reduced pressure, water, solvent etc. are removed.The poly- methylol compound of gained is dissolved in 550 parts of methanol, Obtain 1230 parts of methanol solution of poly- methylol compound.
It is at room temperature that a part of the methanol solution of the poly- methylol compound of gained is dry in vacuum drier, as a result Solid component is 55.2%.
In the flask for having condenser pipe, blender, 500 parts of the methanol solution of the poly- methylol compound of investment gained, 2, It 440 parts of 6- dimethlbenzene, is equably dissolved with 50 DEG C.Equably dissolve after at 50 DEG C of temperature below, under reduced pressure, Methanol is removed.8 parts of oxalic acid are added later, is reacted 10 hours with 100 DEG C.After reaction, in 180 DEG C, the decompression of 50mmHg Under will distillate ingredient removal, obtain 550 parts of novolac resin A.
In the autoclave for having thermometer, nitrogen gatherer and alkylene oxide gatherer and agitating device, phenol is put into 130 parts of Novolac Resin A, 2.6 parts of 50% sodium hydrate aqueous solution, toluene/methyl iso-butyl ketone (MIBK) (mass ratio=2/1) 100 Part, nitrogen displacement, then, heat temperature raising, in 150 DEG C, 8kg/cm will be carried out while stirring in system2Under, slowly import ring 60 parts of Ethylene Oxide simultaneously reacts.Reaction is for about 4 hours until gauge pressure becomes 0.0kg/cm2Afterwards, it is cooled to room temperature.It is molten in the reaction Addition mixes 3.3 parts of 36% aqueous hydrochloric acid solution in liquid, and sodium hydroxide is neutralized.By the neutralization reaction product dilution with toluene, 3 washings are carried out, carry out desolventizing with evaporimeter, the propylene oxide for obtaining the novolac resin A that hydroxyl value is 189g/eq. adds At object.It is averaged made of 1 mole of addition of propylene oxide for every 1 equivalent phenolic hydroxyl group.
In having the reactor that blender, thermometer, air are blown into pipe, the epoxy of investment gained novolac resin A 189 parts of propane addition product, 36 parts of acrylic acid, 3.0 parts of p-methyl benzenesulfonic acid, 0.1 part of Hydroquinone monomethylether, 140 parts of toluene, while being blown into Air side is stirred, and is warming up to 115 DEG C, and the water and toluene that are generated by reaction are distilled in the form of azeotropic mixture and gone on one side It except one side and then reacts 4 hours, then cools to room temperature.Gained reaction solution is washed with 5%NaCl aqueous solution, is passed through Vacuum distillation is added after toluene removal diethylene glycol monoethyl ether acetic acid esters, obtains the acrylate tree of solid component 67% Lipoprotein solution.
Then, in the four-hole boiling flask of belt stirrer and reflux condenser, investment gained acrylic ester resin solution 322 The mixture is heated to 110 DEG C, tetrabydrophthalic anhydride is added by part, 0.1 part of Hydroquinone monomethylether, 0.3 part of triphenylphosphine It 60 parts, reacts it 4 hours, is taken out after cooling.The solid component of the obtained photosensitive carboxylic resin solution is 70%, solid component acid value is 81mgKOH/g.Hereinafter, the solution of the carboxylic photoresist is known as resin solution A- 2。
[synthesis of carboxylic Resin A -3]
In diethylene glycol monoethyl ether acetic acid esters 600g, o-cresol phenolic epoxy varnish (DIC plants of formula meetings are put into Society EPICLON N-695,95 DEG C of softening point, epoxide equivalent 214, average functional group number 7.6) 1070g (glycidol radix (aromatic rings sum)：5.0 moles), acrylic acid 360g (5.0 moles) and quinhydrones 1.5g, be heated to 100 DEG C and stir, carry out equal Even dissolution.
Then, triphenylphosphine 4.3g is put into, is heated to 110 DEG C, after carrying out reaction in 2 hours, is warming up to 120 DEG C, Jin Erjin It reacts within row 12 hours.In gained reaction solution, aromatic hydrocarbon (Solvesso 150) 415g, tetrabydrophthalic anhydride are put into 456.0g (3.0 moles) react within 4 hours with 110 DEG C, cooling, obtains photosensitive carboxylic resin solution.Such To resin solution solid component be 65%, the acid value of solid component is 89mgKOH/g.Hereinafter, this is carboxylic photosensitive The solution of property resin is known as resin solution A-3.
[synthesis of carboxylic Resin A -4]
In the flask for having thermometer, blender, dropping funel and reflux condenser, by the dipropylene glycol as solvent 325.0 parts of monomethyl ether were heated to 110 DEG C, with 3 hours 174.0 parts of dropwise addition methacrylic acids, 6-caprolactone modified methyl propylene 174.0 parts of sour (average molecular weight 314), 77.0 parts of methyl methacrylate, 222.0 parts of dipropylene glycol monomethyl ether and as poly- The mixture for closing 12.0 parts of t-butyl peroxy -2 ethyl hexanoic acid ester (Japan Oil Co Perbutyl O) of catalyst, into And stirred 3 hours with 110 DEG C, polymerization catalyst is inactivated, resin solution is obtained.
After resin solution cooling, A200289.0 parts of Daicel chemical industry Co. Ltd. system Cyclomer of addition, 3.0 parts of triphenylphosphine, 1.3 parts of Hydroquinone monomethylether, are warming up to 100 DEG C and stir, so that the open loop addition for carrying out epoxy group is anti- It answers, obtains photosensitive carboxylic resin solution.
The weight average molecular weight (Mw) of the obtained resin solution be 15000 and solid component be 57%, the acid of solids Value is 79.8mgKOH/g.Hereinafter, the solution of the carboxylic photoresist is known as resin solution A-4.
[synthesis of the epoxy resin B-1 with silsesquioxane skeleton]
90.0 parts of γ-glycidoxypropyltrime,hoxysilane, 93 parts of methyl iso-butyl ketone (MIBK) are put into the reaction vessel, It is warming up to 80 DEG C.After heating, with 30 minutes 0.1 21.6 parts of weight % potassium hydroxide aqueous solutions of continuous dropwise addition.After completion of dropwise addition, side Flash trimming is gone to react 5 hours with 80 DEG C the methanol of generation.After reaction, washing is repeated until cleaning solution becomes neutrality.Then, Solvent is removed under reduced pressure, to obtain 69 parts of epoxy resin with silsesquioxane skeleton.The ring of gained epoxy resin Oxygen equivalent is 165g/eq., weight average molecular weight 2000.
[synthesis of the epoxy resin B-2 with silsesquioxane skeleton]
90.0 parts of γ-glycidoxypropyltrime,hoxysilane, phenyltrimethoxysila,e are put into the reaction vessel 3.0 parts, 2.0 parts of methyltrimethoxysilane, 93 parts of methyl iso-butyl ketone (MIBK), are warming up to 80 DEG C.After heating, with 30 minutes continuous drops Add 0.1 21.6 parts of weight % potassium hydroxide aqueous solution.After completion of dropwise addition, while going flash trimming small with 80 DEG C of reactions 5 methanol of generation When.After reaction, washing is repeated until cleaning solution becomes neutrality.Then, solvent is removed under reduced pressure, to be had 69 parts of the epoxy resin of silsesquioxane skeleton.The epoxide equivalent of gained epoxy resin is 176g/eq., weight average molecular weight is 2200。
[synthesis of the epoxy resin B-3 with silsesquioxane skeleton]
65.0 parts of γ-glycidoxypropyltrime,hoxysilane, phenyltrimethoxysila,e are put into the reaction vessel 12.0 parts, 8.0 parts of methyltrimethoxysilane, 93 parts of methyl iso-butyl ketone (MIBK), are warming up to 80 DEG C.It is continuous with 30 minutes after heating 0.1 21.6 parts of weight % potassium hydroxide aqueous solution is added dropwise.After completion of dropwise addition, while going flash trimming with 80 DEG C of reactions 5 methanol of generation Hour.After reaction, washing is repeated until cleaning solution becomes neutrality.Then, solvent is removed under reduced pressure, to be had There are 69 parts of epoxy resin of silsesquioxane skeleton.The epoxide equivalent of gained epoxy resin is 236g/eq., weight average molecular weight is 2200。
[synthesis of the epoxy resin B-4 with silsesquioxane skeleton]
40.0 parts of γ-glycidoxypropyltrime,hoxysilane, phenyltrimethoxysila,e are put into the reaction vessel 25.0 parts, 15.0 parts of methyltrimethoxysilane, 93 parts of methyl iso-butyl ketone (MIBK), are warming up to 80 DEG C.It is continuous with 30 minutes after heating 0.1 21.6 parts of weight % potassium hydroxide aqueous solution is added dropwise.After completion of dropwise addition, while going flash trimming with 80 DEG C of reactions 5 methanol of generation Hour.After reaction, washing is repeated until cleaning solution becomes neutrality.Then, solvent is removed under reduced pressure, to be had There are 69 parts of epoxy resin of silsesquioxane skeleton.The epoxide equivalent of gained epoxy resin is 400g/eq., weight average molecular weight is 2200。
[adjustment of surface treated inorganic filler (silica) C-1]
Make spherical silicon dioxide (Denka corporation SFP-20M) 70g, PMA (the propylene glycol monomethyl ether second as solvent Acid esters) 28g and silane coupling agent (Shin-Etsu Chemial Co., Ltd KBM-503) 2g it is evenly dispersed, it is molten to obtain silica Agent disperses product D-1.
[adjustment of surface treated inorganic filler (barium sulfate) C-2]
Make barium sulfate (Sakai Chemical Industry Co., Ltd. B-30 (aluminium oxide surface treatment barium sulfate)) 70g, as solvent PMA (propylene glycol monomethyl ether) 28g and dispersing agent (BYK Co. Ltd. system BYK-111) 2g it is evenly dispersed, obtain sulphur Sour barium solvent disperses product D-2.
[adjustment of not surface treated silica]
Make spherical silicon dioxide (Denka corporation SFP-20M) 70g, PMA (the propylene glycol monomethyl ether second as solvent Acid esters) 28g and dispersing agent (BYK Co. Ltd. system BYK-111) 2g it is evenly dispersed, obtain silica solvent dispersion product.
[embodiment 1~16, the Comparative Examples 1 to 5]
By together with various composition shown in above-mentioned resin solution (varnish) and table 1 with ratio shown in table 1 (mass parts) into Row compounding, after being pre-mixed with blender, is kneaded with triple-roller mill, prepares hardening resin composition.
< glass transition temperature Tg and thermal expansion coefficient CTE >
(embodiment 1~15, the Comparative Examples 1 to 5)
Hardening resin composition whole face, which is coated on copper clad laminate, by silk-screen printing becomes dry film thickness about 40μm.By it with 80 DEG C of dryings, cooled to room temperature obtains to form the resin layer comprising hardening resin composition The evaluation substrate of each uncured sample with each embodiment and comparative example.For it, ORC A.B. HMW680GW (gold is utilized Belong to halide lamp, scattering light), with optimum exposure：800mJ is exposed by the negative mask of the strip of 50mm × 3mm.It Afterwards, develop in 30 DEG C of 1wt.% aqueous sodium carbonate, obtain the pattern of cured film.And then make cumulative exposure amount After 1000mJ irradiates ultraviolet light, being heated 1 hour with 160 DEG C makes its solidification.
It will be removed by the cured film of evaluation substrate obtained above from copper foil, implementation evaluation.Measurement uses TMA measurement device (Shimadzu Scisakusho Ltd's system, kinds of machine title：TMA6000 it) carries out, for Tg, CTE α 1 (0 DEG C -50 DEG C) and CTE α 2 (200 DEG C -250 DEG C) is evaluated.Evaluation criteria is as described below.
(embodiment 16)
Hardening resin composition whole face, which is coated on copper clad laminate, by silk-screen printing becomes dry film thickness about 40μm.By it with 80 DEG C of dryings, cooled to room temperature, to form the resin layer comprising hardening resin composition.By its Being heated 1 hour with 160 DEG C makes its solidification, obtains the evaluation substrate with cured film.
It will be removed by the cured film of evaluation substrate obtained above from copper foil, be cut into the strip of 50mm × 3mm, implement to comment Valence.Measurement uses TMA measurement device (Shimadzu Scisakusho Ltd's system, kinds of machine title：TMA6000 it) carries out, for Tg, CTE α 1 (0 DEG C -50 DEG C) and CTE α 2 (200 DEG C -250 DEG C) are evaluated.Evaluation criteria is as described below.
(Tg)
150 DEG C of ◎ ... or more
Zero ... 145 DEG C more than or lower than 150 DEG C
140 DEG C of △ ... more than or lower than 145 DEG C
× ... it is lower than 140 DEG C
(CTEα1)
◎ ... is lower than 40ppm
Zero ... 40ppm is more than or lower than 50ppm
△ ... 50ppm is more than or lower than 60ppm
× ... 60ppm or more
(CTEα2)
◎ ... is lower than 110ppm
Zero ... 110ppm is more than or lower than 120ppm
△ ... 120ppm is more than or lower than 130ppm
× ... 130ppm or more
< elastic modulus E and Tan δ >
(embodiment 1~15, the Comparative Examples 1 to 5)
Hardening resin composition whole face, which is coated on copper clad laminate, by silk-screen printing becomes dry film thickness about 40μm.By it with 80 DEG C of dryings, cooled to room temperature obtains to form the resin layer comprising hardening resin composition The evaluation substrate of each uncured sample with each embodiment and comparative example.For it, ORC A.B. HMW680GW (gold is utilized Belong to halide lamp, scattering light), it is exposed with 800mJ by the negative mask of the strip of 50mm × 5mm.Later, at 30 DEG C Develop in 1wt.% aqueous sodium carbonate, obtains the pattern of curing overlay film.And then irradiate cumulative exposure amount 1000mJ It after ultraviolet light, is heating and curing 1 hour with 160 DEG C, obtains the evaluation substrate with cured film.
It will be removed by the curing overlay film of evaluation substrate obtained above from copper foil, implementation evaluation.Measurement uses DMA measurement dress Set (Shimadzu Scisakusho Ltd's kinds of machine title：DMS6100 it) carries out, the E at 260 DEG C is evaluated.It closes In Tan δ, be warming up to 300 DEG C from 25 DEG C with Hitachi Hightech corporation DMS6100, with 5 DEG C/min, frequency 1Hz, stretch just String wave mode measures, and takes the maximum value in temperature measuring region.
(embodiment 16)
Hardening resin composition whole face, which is coated on copper clad laminate, by silk-screen printing becomes dry film thickness about 40μm.So that it is heating and curing 1 hour with 160 DEG C, obtains the evaluation substrate with cured film.
It will be removed by the curing overlay film of evaluation substrate obtained above from copper foil, implementation evaluation.Measurement uses DMA measurement dress Set (Shimadzu Scisakusho Ltd's kinds of machine title：DMS6100 it) carries out, the E at 260 DEG C is evaluated.It closes In Tan δ, be warming up to 300 DEG C from 25 DEG C with Hitachi Hightech corporation DMS6100, with 5 DEG C/min, frequency 1Hz, stretch just String wave mode measures, and takes the maximum value in temperature measuring region.
Evaluation criteria is as described below.
(elastic modulus E)
◎…1×109Pa or more
○…5×108Pa is more than or lower than 1 × 109Pa
△…1×108Pa is more than or lower than 5 × 108Pa
× ... it is lower than 1 × 108Pa
(Tanδ)
◎ ... is lower than 0.20
Zero ... 0.20 more than or lower than 0.25
△ ... 0.25 is more than or lower than 0.30
× ... 0.30 or more
< warpage >
(embodiment 1~15, the Comparative Examples 1 to 5)
Hardening resin composition whole face is coated on the 35 μm of copper clad laminates handled through CZ by silk-screen printing and is made Dry film thickness becomes 20 μm.By it with 80 DEG C of dryings, cooled to room temperature, to be formed comprising hardening resin composition Resin layer obtains the evaluation substrate with each uncured sample of each embodiment and comparative example.For it, ORC A.B.'s system is utilized HMW680GW (metal halide lamp, scattering light), with optimum exposure：800mJ carries out whole face exposure.Later, at 30 DEG C Development treatment is carried out in 1wt.% aqueous sodium carbonate, obtains the pattern of cured film.And then shine cumulative exposure amount 1000mJ After penetrating ultraviolet light, being heated 1 hour with 160 DEG C makes its solidification.
50mm × 50mm will be cut by the cured film of evaluation substrate obtained above, cured film is statically placed in water under Flat platform.After standing, for 4 jiaos of the cured film being cut into, the distance from horizontal platform to Cu foil is measured respectively, is found out average Value, is evaluated Ru following.
(embodiment 16)
Hardening resin composition whole face is coated on the 35 μm of copper clad laminates handled through CZ by silk-screen printing and is made Dry film thickness becomes 20 μm.By it with 80 DEG C of dryings, cooled to room temperature, to be formed comprising hardening resin composition Resin layer.To be heated 1 hour with 160 DEG C makes its solidification, obtains the evaluation substrate with cured film.
50mm × 50mm will be cut by the cured film of evaluation substrate obtained above, cured film is statically placed in water under Flat platform.After standing, for 4 jiaos of the cured film being cut into, the distance from horizontal platform to Cu foil is measured respectively, is found out average Value, is evaluated Ru following.
◎ ... is lower than 10mm
Zero ... 10mm is more than or lower than 15mm
△ ... 15mm is more than or lower than 20mm
× ... 20mm or more
< reactivity >
(embodiment 1~15, the Comparative Examples 1 to 5)
To plating copper base with CZ8101 with 1 μm/m of etch-rate2It is handled, by silk-screen printing by curable resin group Closing object whole face and being coated on the face makes dry film thickness become about 20 μm.By it with 80 DEG C of dryings, cooled to room temperature, thus The resin layer comprising hardening resin composition is formed, evaluation substrate α is obtained.For this, ORC A.B. HMW680GW is utilized (metal halide lamp, scattering light), with optimum exposure：800mJ carries out whole face exposure.Later, in 30 DEG C of 1wt.% carbonic acid It is handled in sodium water solution, obtains cured film.And then after so that cumulative exposure amount 1000mJ is irradiated ultraviolet light, in following conditions Under heat and solidify, obtain evaluation substrate β.
It carries out measuring the reactivity of epoxy group by the FT-IR measurement of evaluation substrate α, β obtained above.
The reactivity of epoxy group is as follows：Use Microscope spotlight200 as measurement device, by as being originated from The 913cm of the vibration of epoxy group-1Neighbouring peak height and calculate.
(embodiment 16)
To plating copper base with CZ8101 with 1 μm/m of etch-rate2It is handled, by silk-screen printing by curable resin group Closing object whole face and being coated on the face makes dry film thickness become about 20 μm.By it with 80 DEG C of dryings, cooled to room temperature, thus The resin layer comprising hardening resin composition is formed, evaluation substrate α is obtained.It is heated and solidified under the following conditions, is obtained To evaluation substrate β.
It carries out measuring the reactivity of epoxy group by the FT-IR measurement of evaluation substrate α, β obtained above.
The reactivity of epoxy group is as follows：Use Microscope spotlight200 as measurement device, by as being originated from The 913cm of the vibration of epoxy group-1Neighbouring peak height and calculate.
◎ ... with 150 DEG C, solidification in 60 minutes and the reactivity of epoxy reaches 98% or more
Zero ... with 160 DEG C, solidification in 60 minutes and the reactivity of epoxy reaches 98% or more
△ ... with 170 DEG C, solidification in 60 minutes and the reactivity of epoxy reaches 98% or more
× ... it is lower than 98% with the reactivity of 170 DEG C, solidification in 60 minutes and epoxy
< resolution ratio evaluates >
(embodiment 1~15, the Comparative Examples 1 to 5)
To plating copper base with CZ8101 with 1 μm/m of etch-rate2It is handled, by silk-screen printing by curable resin group Closing object whole face and being coated on the face makes dry film thickness become about 20 μm.By it with 80 DEG C of dryings, cooled to room temperature, thus Form the resin layer comprising hardening resin composition.For it, using ORC A.B. HMW680GW, (metal halide lamp dissipates Penetrate light), with optimum exposure：800mJ carries out pattern exposure.Later, it is shown in 30 DEG C of 1wt.% aqueous sodium carbonate Shadow obtains the pattern of cured film.And then after so that cumulative exposure amount 1000mJ is irradiated ultraviolet light, being heated 1 hour with 160 DEG C makes it Solidification.
Observation is confirmed whether to generate halation, undercutting, be evaluated by the opening diameter of evaluation substrate obtained above.
◎ ... obtains good opening diameter under 50 μm
Zero ... obtains good opening diameter under 70 μm
△ ... obtains good opening diameter under 100 μm
× ... it is unable to get good opening diameter under 100 μm or can not develop
< insulating reliability (resistance to HAST) >
(embodiment 1~15, the Comparative Examples 1 to 5)
It is by silk-screen printing that hardening resin composition is whole using the substrate for the comb-like pattern for being formed with L/S=20/20 Face is coated with so that dry film thickness becomes about 20 μm.By it with 80 DEG C of dryings, cooled to room temperature, so that being formed includes curability The resin layer of resin combination obtains the evaluation substrate with each uncured sample of each embodiment and comparative example.It is sharp for it With ORC A.B. HMW680GW (metal halide lamp, scattering light), with optimum exposure：800mJ carries out whole face exposure.Later, Develop in 30 DEG C of 1wt.% aqueous sodium carbonate, obtains the pattern of cured film.And then make cumulative exposure amount After 1000mJ irradiates ultraviolet light, being heated 1 hour with 160 DEG C makes its solidification.
Gained evaluation substrate is connect with electrode later, is put into 130 DEG C, the hot and humid groove under the atmosphere of humidity 85%, Implement HAST test under conditions of voltage 5V, measurement electrical insulating property becomes 1 × 106Time when Ω or less.
(embodiment 16)
It is by silk-screen printing that hardening resin composition is whole using the substrate for the comb-like pattern for being formed with L/S=20/20 Face is coated with so that dry film thickness becomes about 20 μm.By it with 80 DEG C of dryings, cooled to room temperature, so that being formed includes curability The resin layer of resin combination.It is heated 1 hour with 160 DEG C makes its solidification, obtains the evaluation substrate with cured film.
Gained evaluation substrate is connect with electrode later, is put into 130 DEG C, the hot and humid groove under the atmosphere of humidity 85%, Implement HAST test under conditions of voltage 5V, measurement electrical insulating property becomes 1 × 106Time when Ω or less.
Pass through within ◎ ... 300 hours
Pass through within zero ... 200 hour
Pass through within △ ... 150 hours
× ... it is NG within 150 hours
Resistance to anti-thread breakage (resistance to TCT) > of <
(embodiment 1~15, the Comparative Examples 1 to 5)
It is that the FC-BGA that 250 μm of spacing are formed evaluates base that hardening resin composition whole face, which is coated on pad spacing, On plate.It is dried, cooled to room temperature, to form the resin layer comprising hardening resin composition.For it, with most Good light exposure：800mJ, on copper pad with 80 μm of SRO (Solder Resist Opening) of opening size carry out directly at As exposure.Later, 30 DEG C of 1wt% aqueous sodium carbonate is sprayed to develop, and obtains the pattern of cured film.And then make to tire out Product light exposure is after 1000mJ irradiates ultraviolet light, and being heated 1 hour with 160 DEG C makes its solidification.Later, plating Au processing, solder are carried out Convex block forms, installs Si chip, obtains evaluation substrate.
The cold-hot circulating machine that temperature cycles are carried out between -65 DEG C and 150 DEG C will be placed in by evaluation substrate obtained above, It carries out TCT (Thermal Cycle Test).Then, observe 600 circulation when, 800 circulation when and 1000 circulation when The surface of cured film.Determinating reference is as described below.
(embodiment 16)
It is that the FC-BGA that 250 μm of spacing are formed evaluates base that hardening resin composition whole face, which is coated on pad spacing, On plate.It is dried, cooled to room temperature, to form the resin layer comprising hardening resin composition.By it with 160 DEG C Heating makes its solidification in 1 hour, obtains the substrate with cured film.For it, CO is used2Laser machine (Hitachi Biomechanics corporation) formation through-hole makes top diameter become 80 μm in cured film.Later, carry out plating Au processing, Solder projection forms, installs Si chip, obtains evaluation substrate.
The cold-hot circulating machine that temperature cycles are carried out between -65 DEG C and 150 DEG C will be placed in by evaluation substrate obtained above, It carries out TCT (Thermal Cycle Test).Then, observe 600 circulation when, 800 circulation when and 1000 circulation when The surface of cured film.Determinating reference is as described below.
◎ ... is without exception in 1000 circulations
Zero ... 800 circulation in it is without exception, 1000 circulation in crack
△ ... 600 circulation in it is without exception, 800 circulation in crack
× ... it is cracked in 600 circulations
[table 1]
[table 2]
[table 3]
* 1：The carboxylic resin solution A-1 synthesized among the above
* 2：The carboxylic resin solution A-2 synthesized among the above
* 3：The carboxylic resin solution A-3 synthesized among the above
* 4：The carboxylic resin solution A-4 synthesized among the above
* 5：BASF JAPAN Co. Ltd. system Irgacure TPO (2,4,6- trimethylbenzoy-dipheny-oxidation Phosphine)
* 6：(2- methyl-1-(4- the methylthiophenyi)-2- morpholine of BASF JAPAN Co. Ltd. system Irgacure 907 Base propane -1- ketone)
* 7：BASF JAPAN Co. Ltd. system Irgacure OXE02 (1- [9- ethyl -6- (2- methyl benzoyl) - 9H- carbazole -3- base]-ethyl ketone 1- (O- acetyl oxime))
* 8：The epoxy resin B-1 with silsesquioxane skeleton synthesized among the above
* 9：The epoxy resin B-2 with silsesquioxane skeleton synthesized among the above
* 10：The epoxy resin B-3 with silsesquioxane skeleton synthesized among the above
* 11：The epoxy resin B-4 with silsesquioxane skeleton synthesized among the above
* 12：Mitsubishi chemical Co., Ltd jER828 (bisphenol A type epoxy resin)
* 13：Dow Chemical corporation DEN431 (phenol novolac epoxy resins)
* 14：Dainippon Ink Chemicals N-870 75EA (phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin)
* 15：Dainippon Ink Chemicals EXA-724 (triphenylmethane type epoxy resin))
* 16：The surface treated silica solvent dispersion product C-1 adjusted among the above is (uniform by spherical silicon dioxide It is scattered in PMA.Methacrylic acid surface treatment.Dioxide-containing silica 70wt% (solid component).Silica average grain diameter 0.8 μm)
* 17：Barium sulfate (is dispersed in by the surface treated barium sulfate solvent dispersion product C-2 adjusted among the above PMA.Aluminium oxide surface treatment.Barium sulfate content 70wt% (solid component).Barium sulfate average grain diameter (0.5 μm))
* 18：The not surface treated silica solvent dispersion product adjusted among the above are (uniform by spherical silicon dioxide It is scattered in PMA.Without surface treatment.Dioxide-containing silica 70wt% (solid component).0.8 μm of silica average grain diameter)
* 19：Settleability barium sulfate is dispersed in substance made of PMA.Barium sulfate content 70wt% (solid at Point).Non- surface treated.
* 20：Nippon Kayaku K. K DPHA (dipentaerythritol hexaacrylate)
* 21：Blue colorant, 12 mass % of colorant content
* 22：Yellow colorants, 10 mass % of colorant content
* 23：DICY (dicyandiamide)
* 24：It does not evaluate
The result as shown in above-mentioned table it is found that the hardening resin composition of the embodiment of the present invention 1~16 solidification The resistance to anti-thread breakage and insulating reliability of object is excellent.In contrast, if using the Comparative Examples 1 to 5 hardening resin composition, Especially high temperature when elasticity modulus (E) be lower, it is difficult to obtain the resistance to anti-thread breakage and insulating reliability of height.

Claims (8)

1. a kind of hardening resin composition, which is characterized in that contain：
(A) carboxylic resin；With the epoxy resin of (B) with silsesquioxane skeleton.
2. hardening resin composition according to claim 1, which is characterized in that also contain (C) surface treated nothing Machine filler.
3. hardening resin composition according to claim 1, which is characterized in that (A) the carboxylic resin has Structure shown in the following general formula (1),
In formula, R1~R4Hydrogen atom or alkyl are each independently represented, k indicates any value in 0.3~10.
4. hardening resin composition according to claim 1, which is characterized in that (A) the carboxylic resin has Structure shown in the following general formula (2),
In formula, R5~R7Hydrogen atom or alkyl are each independently represented, Z indicates that anhydride residue, m indicate any in 0.3~10 Value.
5. hardening resin composition according to claim 1, which is characterized in that (B) has silsesquioxane bone The epoxy resin of frame has structure shown in the following general formula (3),
In formula, R8~R11It is each independently group or organic group with SiO key, R8~R11At least one of for The group of epoxy group.
6. a kind of dry film, which is characterized in that there is resin layer, the resin layer is by curable resin described in claim 1 Obtained from composition is coated on film and dries.
7. a kind of solidfied material, which is characterized in that it is to combine curable resin described in any one of Claims 1 to 5 Obtained from the solidification of the resin layer of object or dry film as claimed in claim 6.
8. a kind of printed circuit board, which is characterized in that have solidfied material as claimed in claim 7.
CN201780018516.0A 2016-03-31 2017-03-30 Hardening resin composition, dry film, solidfied material and printed circuit board Pending CN108885400A (en)

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