CN109426078A - 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
CN109426078A
CN109426078A CN201810722338.6A CN201810722338A CN109426078A CN 109426078 A CN109426078 A CN 109426078A CN 201810722338 A CN201810722338 A CN 201810722338A CN 109426078 A CN109426078 A CN 109426078A
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CN
China
Prior art keywords
resin composition
inorganic filler
methyl
hardening resin
resin
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Pending
Application number
CN201810722338.6A
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Chinese (zh)
Inventor
高桥元范
加藤文崇
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 CN109426078A publication Critical patent/CN109426078A/en
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    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/014—Stabilisers against oxidation, heat, light or ozone
    • 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
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general

Abstract

The present invention relates to hardening resin composition, dry film, solidfied material and printed circuit boards.It provides: the use of average grain diameter being 300nm inorganic filler below and the hardening resin composition for capableing of the cured product pattern easy to form with opening portion；Dry film with the resin layer obtained by the composition；The solidfied material of the resin layer of the composition or the dry film；With the printed circuit board with the solidfied material.The hardening resin composition contains: (A) photo-curable ingredient, (B) Photoepolymerizationinitiater initiater, the inorganic filler that (C) average grain diameter is 1~300nm and (D) ultraviolet absorbing agent.

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
Such as in the manufacture of printed circuit board, combined in the formation of the permanent overlay film such as general solder mask using curable resin Object develops composition (such as the patent document of the composition of dry-film type, liquid as such hardening resin composition 1)。
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.Follow the tendency, the miniaturization of semiconductor packages, slimming, more pinizations put into practical.It is specific and Speech, being referred to as QFP using the IC package replacement of referred to as BGA (ball grid array), CSP (wafer-level package) etc., (four sides are flat Flat package), the IC package of SOP (small outline packages) etc..In addition, in recent years, as the IC package of further densification, FC- BGA (flip-chip ball grid array) is also practical.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Application 61-243869 bulletin (claims)
Summary of the invention
Problems to be solved by the invention
It is permanent to solder mask formed on printed circuit board used in above-mentioned IC package (also referred to as package substrate) etc. Overlay film requires further filming.However, such as having following problem if carrying out filming: storage modulus is lower, breaks The solidification such as resistance to spalling film strength becomes inadequate.For such problems, it is contemplated that increase the compounding ratio of inorganic filler.So And using average grain diameter is 300nm inorganic filler below as in the hardening resin composition of inorganic filler, when exposure The influence of halation is big, and opening shape is unstable or path Kekelé structure count is insufficient, it is difficult to form opening portion.Therefore, in order to be easy shape At opening portion, it is contemplated that change compounding amount, the type of Photoepolymerizationinitiater initiater, but be only still difficult to shape by these changes, adjustment At opening portion.
Therefore, the object of the present invention is to provide: the use of average grain diameter is that 300nm inorganic filler below and can be easy Form the hardening resin composition with the cured product pattern of opening portion；With the tree obtained by the hardening resin composition The dry film of rouge layer；The solidfied material of the resin layer of the hardening resin composition or the dry film；With the printing electricity with the solidfied material Road plate.
The solution to the problem
The inventors of the present invention have made intensive studies, as a result, it has been found that: by including (A) photo-curable ingredient, (B) photopolymerization It is compounded ultraviolet absorbing agent in the hardening resin composition for the inorganic filler that initiator and (C) average grain diameter are 1~300nm, Foregoing problems are able to solve, the present invention is so far completed.
That is, hardening resin composition of the invention is characterized in that, draw containing (A) photo-curable ingredient, (B) photopolymerization Send out the inorganic filler and (D) ultraviolet absorbing agent of agent, (C) average grain diameter for 1~300nm.
Hardening resin composition of the invention is preferably, and contains carbon black as aforementioned (D) ultraviolet absorbing agent.
Hardening resin composition of the invention is preferably, the solid component containing said curing property resin combination Aforementioned (D) ultraviolet absorbing agent of 0.01~10 mass % of gross mass.
Hardening resin composition of the invention is preferably, and is more than also that the inorganic of 300nm is filled out containing (C1) average grain diameter Material, inorganic filler and aforementioned (C1) average grain diameter that aforementioned (C) average grain diameter is 1~300nm are more than the inorganic filler of 300nm Amount to the 45 mass % or more of the gross mass for the solid component that compounding amount is said curing property resin combination.
Dry film of the invention is characterized in that thering is the resin layer obtained by said curing property resin combination.
Solidfied material of the invention is characterized in that, is to consolidate the resin of said curing property resin combination or aforementioned dry film Obtained from change.
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: the use of average grain diameter being 300nm inorganic filler below and energy tool easy to form There is the hardening resin composition of the cured product pattern of opening portion；With the resin layer obtained by the hardening resin composition Dry film；The solidfied material of the resin layer of the hardening resin composition or the dry film；With the printed circuit board with the solidfied material.
Detailed description of the invention
It is 300nm inorganic filler below and the curability tree for being free of ultraviolet absorbing agent that Fig. 1, which is to average grain diameter is used, Oil/fat composition irradiates schematic diagram when ultraviolet light.
It is 300nm inorganic filler below and containing the of the invention of ultraviolet absorbing agent that Fig. 2, which is to average grain diameter is used, Hardening resin composition irradiates schematic diagram when ultraviolet light.
Fig. 3 is the microscope photo that the opening portion of the solidfied material of embodiment 1 is amplified to 1000 times.
Fig. 4 is the microscope photo that the opening portion of the solidfied material of comparative example 1 is amplified to 1000 times.
Description of symbols
1 solidfied material
2 hardening resin compositions
3 masks
4 ultraviolet lights
5 inorganic fillers
6 ultraviolet absorbing agents
Specific embodiment
Hardening resin composition of the invention contains: (A) photo-curable ingredient, (B) Photoepolymerizationinitiater initiater, (C) are average Partial size is the inorganic filler of 1~300nm, (D) ultraviolet absorbing agent.
It is in the hardening resin composition of 300nm inorganic filler below, when exposure, to exposure portion using average grain diameter The ultraviolet light of irradiation is reflected by inorganic filler and keeps the influence for solidifying the halation carried out in unexposed portion big, and opening shape is unstable Fixed or path Kekelé structure count is insufficient, and the formation of opening portion is difficult.Being shown in Fig. 1 to average grain diameter is used is 300nm nothing below Machine filler and the hardening resin composition for being free of ultraviolet absorbing agent irradiate schematic diagram when ultraviolet light.In Fig. 1, (A) is indicated In exposure, after (B) indicates exposure.As shown in Figure 1, in (A) exposure, although not combined to the curable resin covered by mask 3 Unexposed portion's direct irradiation ultraviolet light 4 of object 2, but ultraviolet light due to exposure portion inorganic filler 5 and 4 scattering, to solidify It promotes.
On the other hand, in the case where being 300nm inorganic filler below using average grain diameter, ultraviolet radiation absorption is added together In the hardening resin composition of the invention of agent, even if being reflected by inorganic filler when exposure the ultraviolet light of exposure portion irradiation, Ultraviolet absorbing agent is also absorbed, and therefore, can inhibit the solidification in unexposed portion.Therefore, it is possible to reduce halation when exposure Influence, can the cured film easy to form with opening portion pattern.Shown in Fig. 2 to use average grain diameter be 300nm with Under signal when irradiating ultraviolet light of inorganic filler and hardening resin composition of the invention containing ultraviolet absorbing agent Figure.In the schematic diagram of Fig. 2, also in the same manner as Fig. 1, (A) is indicated in exposure, after (B) indicates exposure.As shown in Fig. 2, of the invention In hardening resin composition 2, in (A) exposure, the ultraviolet light 4 of the reflection of inorganic filler 5 in portion is exposed by ultraviolet absorbing agent 6 It absorbs, therefore, the unexposed portion of the hardening resin composition 2 covered as mask 3 is not easily susceptible to produced by the scattering of ultraviolet light 4 Influence, can be with opening portion easy to form.
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) photo-curable ingredient]
(A) photo-curable ingredient contains photo-curable reactive group, can also contain photo-curable reactive group and thermosetting Both the property changed reactive groups.That is, (A) photo-curable ingredient can be to be conducive to both photocuring reaction and heat cure reaction Light and heat curability composition.
As (A) photo-curable ingredient, for the compound with ethylenically unsaturated group, polymer, oligomeric can be enumerated Object, monomer etc., or their mixture.By containing (A) photo-curable ingredient, pass through hardening resin composition It exposes and solidifies, and solidification film strength can be improved.
(A) photo-curable ingredient can be used alone or combine two or more use.
As the compound with ethylenically unsaturated group, the known common i.e. photopolymerization of photo-curable monomer can be used Property oligomer, optical polymerism vinyl monomer etc..
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..
(A) photo-curable ingredient can be used alone or combine two or more use.(A) compounding of photo-curable ingredient Ratio in the solid component in addition to the solvents of all compositions, be, for example, 0.1~55 mass %, preferably 0.2~50 matter Measure %.
[(B) Photoepolymerizationinitiater initiater]
Hardening resin composition of the invention contains (B) Photoepolymerizationinitiater initiater as essential component.As (B) photopolymerization Initiator can be used as long as the well known Photoepolymerizationinitiater initiater as Photoepolymerizationinitiater initiater, optical free radical producing agent.
As (B) Photoepolymerizationinitiater initiater, for example, double-(2,6- dichloro-benzoyl base) phenyl phosphine oxide, it is double- (2,6- dichloro-benzoyl base) -2,5- 3,5-dimethylphenyl phosphine oxide, double-(2,6- dichloro-benzoyl base) -4- propyl phenyl oxidation Phosphine, double-(2,6- dichloro-benzoyl base) -1- naphthalene phosphine oxide, double-(2,6- Dimethoxybenzoyl) phenyl phosphine oxide, it is double - (2,6- Dimethoxybenzoyl) -2,4,4- trimethylpentylphosphine oxide, double-(2,6- Dimethoxybenzoyl) -2,5- The bisacylphosphines phosphines such as 3,5-dimethylphenyl phosphine oxide, double-(2,4,6- trimethylbenzoyl)-phenyl phosphine oxide；2,6- bis- Methoxybenzoyl base diphenyl phosphine oxide, 2,6- dichloro-benzoyl base diphenyl phosphine oxide, 2,4,6- trimethylbenzoyl Phenyl-phosphonic acid methyl esters, 2- methyl benzoyl diphenyl phosphine oxide, valeryl phenyl-phosphonic acid isopropyl ester, 2,4,6- trimethylbenzene The monoacylphosphine oxides phosphines such as formoxyl diphenyl phosphine oxide (IGM corporation OmniradTPO)；1- hydroxy-cyciohexyl phenyl ketone, 1- [4- (2- hydroxyl-oxethyl)-phenyl] -2- hydroxy-2-methyl -1- propane -1- ketone, 2- hydroxyl -1- { 4- [4- (2- hydroxyl -2- Methyl-propanoyl)-benzyl] phenyl } hydroxyls such as -2- methyl-propan -1- ketone, 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone Acetophenones；Benzoin, benzyl, benzoin methylether, benzoin ethyl ether, benzoin positive propyl ether, benzoin iso-propylether, benzoin are just The benzoin class such as butyl ether；Benzoin alkyl ethers；Benzophenone, to methyl benzophenone, Michler's keton, methyl benzophenone, 4, The benzophenones such as 4 '-dichloro benzophenones, 4,4 '-bis- diethylamino benzophenone；Acetophenone, 2,2- dimethoxy -2- Phenyl acetophenone, 2,2- diethoxy -2- phenyl acetophenone, 1,1- dichloroacetophenone, 1- hydroxycyclohexylphenylketone, 2- first Base -1- [4- (methyl mercapto) phenyl] -2- morpholinyl -1- acetone, 2- benzyl -2- dimethylamino -1- (4- morpholino phenyl)-fourth Ketone -1,2- (dimethylamino) -2- [(4- aminomethyl phenyl) methyl) -1- [4- (4- morpholinyl) phenyl] -1- butanone, N, N- diformazan The acetophenones such as base aminoacetophenone；Thioxanthones, 2- ethyl thioxanthones, 2-isopropylthioxanthone, 2,4- dimethyl thioxanthone, 2, The thioxanthene ketone class such as 4- diethyl thioxanthone, 2-chlorothioxanthone, 2,4- diisopropylthioxanthone；Anthraquinone, chloroanthraquinone, 2- methyl anthracene The Anthraquinones such as quinone, 2- ethyl hydrazine, 2- tert-butyl anthraquinone, 1- chloroanthraquinone, 2- amyl anthraquinone, 2- amino anthraquinones；Acetophenone diformazan The ketals class such as base ketal, benzil dimethyl ketal；Ethyl -4- dimethyl aminobenzoate, 2- (dimethylamino) ethyl Benzoic ether, to benzoates such as mesitylenic acid ethyl esters；1- [4- (thiophenyl)-phenyl] -1,2- octanedione -2- The oximes such as (O- benzoyl oxime), 1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base]-ethyl ketone, 1- (O- acetyl oxime) Esters；Bis- (η 5-2,4- cyclopentadiene -1- bases)-bis- (the fluoro- 3- of 2,6- bis- (1H- pyrroles -1- base) phenyl) titaniums, bis- (cyclopentadiene Base) the titanocenes class such as-bis- [the fluoro- 3- of 2,6- bis- (2- (1- pyrroles -1- base) ethyl) phenyl] titaniums；Phenyl disulfide 2- nitrofluorene, Butyroin, anisoin ethyl ether, azobis isobutyronitrile, tetra methylthiuram disulfide etc..(B) Photoepolymerizationinitiater initiater can be independent Two or more use can also be combined using a kind.Wherein, preferably monoacylphosphine oxide phosphine, oxime esters are (hereinafter, also referred to as single respectively Acylphosphine oxide system Photoepolymerizationinitiater initiater, oxime ester system Photoepolymerizationinitiater initiater), more preferable 2,4,6- trimethyl benzoyl diphenyl bases Phosphine oxide, 1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base]-ethyl ketone 1- (O- acetyl oxime).
(B) Photoepolymerizationinitiater initiater can be used alone or combine two or more use.(B) compounding of Photoepolymerizationinitiater initiater Ratio is, for example, 0.01~30 mass parts relative to 100 mass parts of (A) photo-curable ingredient.
[inorganic filler that (C) average grain diameter is 1~300nm]
Hardening resin composition of the invention contains inorganic filler that (C) average grain diameter is 1~300nm as must be at Point, the inorganic filler is preferably applied in combination and (C1) average grain diameter is more than the inorganic filler of 300nm.In turn, from raising intensity, storage From the perspective of hiding stability, reducing linear expansion coefficient (CTE), the gross mass of the solid component containing composition is preferably amounted to (C) inorganic filler and (C1) inorganic filler of 45 mass % or more.The ratio is 60 mass % or more, 70 mass % or more, 80 It is more effective when quality % or more, it is especially effective when being 83 mass % or more.Similarly, in order to improve the solidfied materials such as storage modulus Intensity, (C) average grain diameter for preferably comprising the 5 mass % or more of the gross mass of the solid component of composition is the nothing of 1~300nm Machine filler, it is more effective when being 10 mass % or more, it is especially effective when being 15 mass % or more.
Herein, in this specification, the average grain diameter of (C) inorganic filler and (C1) inorganic filler is not only including primary particle Partial size average grain diameter and also the average grain diameter (D50) including the partial size of second particle (aggregation), be by swash The value of the D50 of optical diffraction method measurement.As the measurement device based on laser diffractometry, Nikkiso Company Limited can be enumerated Microtrac MT3300EXII.It should be noted that also utilizing above-mentioned dress for maximum particle diameter (D100) and partial size (D10) It sets and is carried out similarly measurement.
By containing 2 kinds of different (C) inorganic fillers of average grain diameter and (C1) inorganic filler and (C) inorganic filler being filled out It is charged to the gap of (C1) inorganic filler, it is possible to reduce remaining gap, available resin content is few, filling out i.e., in gross mass The high hardening resin composition of the ratio of the quality of material.In the same product of common commercially available product, partial size also has 2 originally~ 3 times of fluctuation, but for its ratio, does not enter gap aspect effectively from thin particle, preferably (C) inorganic filler with (C1) average grain diameter of inorganic filler has 5 times or more of difference.(C) the average grain diameter ratio of inorganic filler and (C1) inorganic filler is got over Greatly, the better.(C1) average grain diameter of inorganic filler be more preferably 8 times or more of average grain diameter of (C) inorganic filler, it is further More preferable 10 times or more.
(C1) preferably 5 μm or less of the average grain diameter of inorganic filler.(C1) average grain diameter of inorganic filler is according to curability tree The purposes of oil/fat composition and it is different, such as the use of cured film is formed on IC package substrate on the way, preferably 5 μm hereinafter, motherboard On printed circuit board formed cured film use on the way, preferably 30 μm hereinafter, mould (sealing) use on the way, preferably 40 μm or less.In turn, (C1) partial size (D10) of inorganic filler is preferably 5 times or more of the average grain diameter (D50) of (C) inorganic filler.The ratio is 5 times When above, (C) inorganic filler improves the charging efficiency in the gap of (C1) inorganic filler, the intensity of solidfied material and the lamination of dry film Property harmony it is excellent.
(C), the mix ratio of (C1) two inorganic filler with volume basis, preferably (C): (C1)=5:5~1:9, further it is excellent Select 4:6~2:8.When in aforementioned range, the plyability of the further intensity for realizing solidfied material and dry film is taken into account.
(C) material of inorganic filler and (C1) inorganic filler is not particularly limited, for example, silica, sulfuric acid Barium, barium titanate, Nuo Yibao tripoli, talcum, clay, magnesium carbonate, calcium carbonate, aluminium oxide, titanium oxide, aluminium hydroxide, silicon nitride, nitrogen Change aluminium etc..Wherein, preferred silica, inhibits the cure shrinkage of the solidfied material of hardening resin composition, becomes lower CTE, In addition, improving the characteristics such as storage modulus, adaptation, hardness.As silica, fused silica, spherical two can be enumerated Silica, amorphous silica, crystallinity silica etc..
(C) the presence or absence of the surface treatment of inorganic filler and (C1) inorganic filler is not particularly limited.However, it has been observed that originally The resin content of the hardening resin composition of invention is few, and therefore, (C) inorganic filler and (C1) inorganic filler are preferably used for Improve the surface treatment of dispersibility.By using the filler being surface-treated, it is also possible to prevent to assemble.
(C) surface treatment method of inorganic filler and (C1) inorganic filler is not particularly limited, and uses known common side Method preferably uses surface treating agent with curability reactive group, for example with curability reactive group as organic group The coupling agent etc. of group handles the surface of inorganic filler.
As coupling agent, the coupling agents such as silane system, titanate esters system, aluminate-series and zircoaluminate system can be used.Wherein, It is preferred that silane series coupling agent.As the example of above-mentioned silane series coupling agent, vinyltrimethoxysilane, vinyl can be enumerated Triethoxysilane, N- (2- amino methyl) -3- aminopropylmethyldimethoxysilane, N- (2- amino-ethyl) -3- amino Propyl trimethoxy silicane, 3-aminopropyltriethoxysilane, 3- anilino- propyl trimethoxy silicane, 3- glycidoxy Propyl trimethoxy silicane, 3- epoxy propoxy propyl methyl dimethoxysilane, 2- (3,4- epoxycyclohexyl) ethyl front three Oxysilane, 3- methacryloxypropyl trimethoxy silane, 3-mercaptopropyi trimethoxy silane etc., they can be single Solely uses or be applied in combination and use.These silane series coupling agents preferably first pass through absorption in advance or reaction is immobilized onto inorganic fill out The surface of material.Herein, treating capacity preferably 0.5~10 mass parts of the coupling agent relative to 100 mass parts of inorganic filler.It needs to illustrate , the present invention in, to inorganic filler apply coupling agent be not included in the compound with ethylenically unsaturated group.
As photo-curable reactive group, vinyl, styryl, methylacryloyl, acryloyl group etc. can be enumerated Ethylenically unsaturated group.Wherein, at least wantonly a kind in preferred vinyl and (methyl) acryloyl group.
As Thermocurable reactive group, can enumerate hydroxyl, carboxyl, isocyanate group, amino, imino group, epoxy group, Oxetanylmethoxy, sulfydryl, methoxy, methoxy ethyl, ethoxyl methyl, ethoxyethyl group, oxazoline group etc..Wherein, It is preferred that at least wantonly a kind in amino and epoxy group.
It should be noted that (C) inorganic filler is with (C1) as long as the surface treated inorganic filler of inorganic filler is to pass through The state of surface treatment is contained in hardening resin composition of the invention, can be by the untreated inorganic filler in surface It is compounded with surface treating agent and inorganic filler is surface-treated respectively in the composition, be preferably compounded preparatory surface treated Inorganic filler.By being compounded surface treated inorganic filler in advance, can prevent may residual in the case where being compounded respectively Surface treatment in resistance to anti-thread breakage equal reduction caused by the surface treating agent that is not consumed.When being surface-treated in advance, It is preferred that with the pre-dispersed pre-dispersed liquid for having inorganic filler in miscible agent, curability composition, it is even more preferred that by surface treated Inorganic filler is pre-dispersed in a solvent, which is matched and is mixed in composition, or the untreated inorganic filler in surface is pre- It is sufficiently surface-treated when being scattered in solvent, then the pre-dispersed liquid is matched and is mixed in composition.
(C) usage mode of inorganic filler and (C1) inorganic filler hardening resin composition according to the present invention can be with Powder or the compounding such as solid state and (A) ingredient can also form after slurry with solvent, dispersant and match with (A) ingredient etc. It is mixed.
[(D) ultraviolet absorbing agent]
As above-mentioned, from the viewpoint of improving intensity, storage modulus, reducing linear expansion coefficient (CTE), combination is preferably comprised (C) inorganic filler and (C1) inorganic filler of the 45 mass % or more of the gross mass of the solid component of object, particularly preferably contains 83 Quality % or more, when improving compounding ratio, the formation of opening portion is more difficult from.However, curable resin of the invention combines In object, by containing (D) ultraviolet absorbing agent as essential component, the compounding ratio of (C) inorganic filler and (C1) inorganic filler It, can also be with opening portion easy to form in the case where height.
(D) ultraviolet absorbing agent of the invention can be used as long as the light of absorbing wavelength 300nm~450nm.
As (D) ultraviolet absorbing agent, inorganic system's ultraviolet lights such as carbon black, black oxidation titanium (also referred to as titanium is black) can be enumerated Absorbent, organic system ultraviolet absorbing agent etc..Wherein, among them, from the viewpoint of the resolution ratio of solidfied material, most preferably charcoal It is black.
As organic system ultraviolet absorbing agent, benzophenone derivates, benzoate derivatives, benzotriazole can be enumerated Derivative, pyrrolotriazine derivatives, benzothiazole derivant, cinnamate derivates, anthranilate derivatives, dibenzoyl Methylmethane derivative etc..As the concrete example of benzophenone derivates, ESCALOL 567,2- can be enumerated Hydroxyl -4- oxy-octyl benzophenone, 2,2 '-dihydroxy -4- methoxy benzophenones and 2,4 dihydroxyl benzophenone etc..Make For the concrete example of benzoate derivatives, 2-ethylhexyl salicylate, phenyl salicylate, salicylic acid can be enumerated to tert-butyl benzene Ester, 2,4- di-tert-butyl-phenyl -3,5- di-tert-butyl-4-hydroxybenzoic acid ester and cetyl -3,5- di-t-butyl -4- hydroxyl Benzoic ether etc..As the concrete example of benzotriazole derivatives, 2- (2 '-hydroxyls -5 '-tert-butyl-phenyl) benzo three can be enumerated Azoles, 2- (2 '-hydroxyls -5 '-aminomethyl phenyl) benzotriazole, -5- chlorobenzene is simultaneously by 2- (2 '-hydroxyls -3 '-tert-butyl -5 '-aminomethyl phenyl) Triazole, 2- (2 '-hydroxyls -3 ', 5 '-di-tert-butyl-phenyls) -5- chlorobenzotriazole, 2- (2 '-hydroxyls -5 '-aminomethyl phenyl) benzo Triazole and 2- (2 '-hydroxyls -3 ', 5 '-di-tert-pentyl-phenyls) benzotriazole etc..As the concrete example of pyrrolotriazine derivatives, Ke Yiju Hydroxyphenyltriazinuv, double ethylhexyl oxygroup phenol methoxyphenyl triazines etc. out.
Can be commercially available product as ultraviolet absorbing agent, for example, TINUVIN PS, TINUVIN 99-2, TINUVIN 109、TINUVIN 384-2、TINUVIN 900、TINUVIN 928、TINUVIN 1130、TINUVIN 400、 TINUVIN 405, TINUVIN 460, TINUVIN 479 (more than, BASF Japan Co. Ltd. system, trade name) etc..
Above-mentioned organic system ultraviolet absorbing agent is preferably applied in combination with carbon black.By being applied in combination with carbon black, resolution ratio is more Stablize.
(D) ultraviolet absorbing agent, which can be used alone, can also combine two or more use.(D) ultraviolet absorbing agent with It is a small amount of just effective, 0.01~10 mass % of the gross mass of the solid component of composition is preferably comprised, is divided to solidfied material From the perspective of the deep curability that resolution impacts, more preferable 0.02~7 mass %.Contain carbon black and is used as (D) ultraviolet light In the case where absorbent, from the viewpoint of the resolution ratio of solidfied material, the gross mass of the solid component of composition is preferably comprised 0.01~1 mass %, further preferably 0.02~0.5 mass % of the gross mass of the solid component of composition, particularly preferably contain There is 0.05~0.30 mass % of the gross mass of the solid component of composition.
((E) Thermocurable ingredient)
Hardening resin composition of the invention further preferably (E) Thermocurable ingredient.In addition, curability of the invention Resin combination, which is further preferably used as in (E) Thermocurable ingredient, alkali soluble resins and molecule, has multiple ring-types The compound of ether or cyclic thioether base.By containing (E) Thermocurable ingredient, solidification film strength can be improved.(E) thermosetting The property changed ingredient can be used alone or combine two or more use.
As (E) Thermocurable ingredient, well known substance be can be used.Melamine resin, benzene can be used for example And the amino resins such as guanamine resin, melamine derivative, benzoguanamine derivative, isocyanate compound, sealing end isocyanic acid Ester compounds, cyclic carbonate compound, epoxide, oxetane compound, epithio ether resin, bismaleimide, Thermocurable ingredient well known to carbodiimide resin, alkali soluble resins etc..It is particularly preferred that having multiple cyclic ethers in molecule The compound and alkali soluble resins of base or cyclic thioether base (hereinafter, brief note makees cyclic annular (sulphur) ether).
Compound with multiple cyclic annular (sulphur) ethers in above-mentioned molecule is preferably to have multiple three-membered rings, quaternary in molecule The compound of ring or pentacyclic cyclic annular (sulphur) ether, for example: intramolecular has the compound, i.e. of multiple epoxy groups Multi-functional epoxy compound；Intramolecular has compound, the i.e. multifunctional oxetane compound of multiple oxetanylmethoxies；Point With compound, i.e. epithio ether resin etc. of multiple thioether groups in sub.
As multi-functional epoxy compound, epoxidized vegetable oil can be enumerated；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；Union II toluene phenolic or biphenyl phenolic Epoxy resin or their mixture；Bisphenol-s epoxy resin；Phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin；Four hydroxy phenyl ethane types Epoxy resin；Hetero ring type epoxy resin；O-phthalic acid diglycidyl ester resin；Four glycidol dimethlbenzene ethane trees Rouge；Epoxy resin containing naphthalene；Epoxy resin with bicyclopentadiene skeleton；Glycidyl methacrylate copolymerization is ring Oxygen resin；The copolymerization epoxy resin of N-cyclohexylmaleimide and glycidyl methacrylate；Epoxy-modified polybutadiene Alkene rubber derivative；CTBN modified epoxy etc., but it is not limited to these.These epoxy resin can be used alone or Combine two or more use.Wherein, particularly preferred phenolic resin varnish type epoxy resin, bisphenol-type epoxy resin, union II cresols type ring Oxygen resin, united phenol-type epoxy resin, xenol phenolic resin varnish type epoxy resin, naphthalene type epoxy resin or their mixture.
As multifunctional oxetane compound, for example, bis- [(3- methyl -3- oxetanylmethoxy methoxyl groups) Methyl] ether, bis- [(3- ethyl -3- oxetanylmethoxy methoxyl group) methyl] ethers, the bis- [(3- methyl -3- oxetanylmethoxy methoxies of Isosorbide-5-Nitrae - Base) methyl] benzene, bis- [(3- ethyl -3- oxetanylmethoxy methoxyl group) methyl] benzene of Isosorbide-5-Nitrae -, acrylic acid (3- methyl -3- oxa- ring fourth Base) methyl esters, acrylic acid (3- ethyl -3- oxetanylmethoxy) methyl esters, methacrylic acid (3- methyl -3- oxetanylmethoxy) methyl esters, The multifunctional oxetanes classes such as methacrylic acid (3- ethyl -3- oxetanylmethoxy) methyl esters, their oligomer or copolymer, And oxetanes alcohol and novolac resin, poly- (4-Vinyl phenol), Cardo type bisphenols, calixarene kind, cup isophthalic Diphenol aromatic hydrocarbons or half siloxanes etc. have the etherate etc. of the resin of hydroxyl.Further, it is also possible to enumerate with oxetanes The copolymer etc. of the unsaturated monomer of ring and (methyl) alkyl acrylate.
As the compound in molecule with multiple cyclic thioether bases, bisphenol A-type epithio ether resin etc. can be enumerated.Separately Outside, it can also use and be substituted by sulphur using same synthetic method, by the oxygen atom of the epoxy group of phenolic resin varnish type epoxy resin Epithio ether resin of atom etc..
As amino resins such as melamine derivative, benzoguanamine derivatives, melamine methylol can be enumerated Close object, methylolbenzoguanamine compound, methylol glycoluril compound and methylol urea compounds etc..
As isocyanate compound, polyisocyanate compound can be compounded.It, can be with as polyisocyanate compound Enumerate 4,4 '-methyl diphenylene diisocyanates, 2,4 toluene diisocyanate, 2,6- toluene di-isocyanate(TDI), naphthalene -1,5- two Isocyanates, O-phthalic group diisocyanate, xylylene diisocyanate and 2,4- toluene diisocyanate dimer etc. Aromatic polyisocyanate；Tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, front three The aliphatic such as base hexamethylene diisocyanate, 4,4- di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate) and isophorone diisocyanate Polyisocyanates；The ester ring types polyisocyanates such as norbornane triisocyanate；And the above-mentioned isocyanate compound enumerated Adduct, biuret body and isocyanuric acid ester body etc..
As blocked isocyanate compounds, the addition that isocyanate compound can be used with isocyanate-terminated dose is anti- Answer product.As the isocyanate compound that can be reacted with isocyanate-terminated dose, for example, above-mentioned polyisocyanates Compound etc..As isocyanate-terminated dose, for example, phenol system end-capping reagent；Lactams system end-capping reagent；Active methylene Base system end-capping reagent；Alcohol system end-capping reagent；Oxime system end-capping reagent；Mercaptan system end-capping reagent；Amide system end-capping reagent；Imide series end-capping reagent；Amine It is end-capping reagent；Imidazoles system end-capping reagent；Imines system end-capping reagent etc..
In addition, preferably comprising the alkali soluble resins with alkali solubility group as (E) Thermocurable ingredient.As alkali soluble Property resin, for example: compound with 2 or more phenolic hydroxyl group, containing carboxy resin, there is phenolic hydroxyl group and carboxyl Compound, the compound with 2 or more sulfydryls.Wherein, alkali soluble resins is containing carboxy resin or when phenolic resin, with base The adaptation at bottom improves, therefore it is preferred that.Especially since developability is excellent, therefore, alkali soluble resins more preferably contains carboxyl tree Rouge.It is preferably the photoresist containing carboxyl with ethylenically unsaturated group containing carboxy resin, or do not have olefinic not Saturated group contains carboxy resin.When alkali soluble resins has ethylenically unsaturated group, also played as (A) photo-curable ingredient Function.It should be noted that can be not only used in the case that hardening resin composition of the invention includes alkali soluble resins The purposes for carrying out alkali development, can be also used for the purposes without alkali development.
As the concrete example containing carboxy resin, the compound (oligomer and polymer) being exemplified below can be enumerated.
(1) pass through the unsaturated carboxylic acids such as (methyl) acrylic acid and styrene, α-methylstyrene, (methyl) acrylic acid lower Contain carboxy resin obtained from the copolymerization of the compound containing unsaturated group such as Arrcostab, isobutene.
(2) pass through aliphatic diisocyanate, Branched fatty (cyclo) aliphatic diisocyanates, ester ring type diisocyanate, aromatic series The compound containing carboxylic diol such as the diisocyanate such as diisocyanate and dihydromethyl propionic acid, dimethylolpropionic acid and polycarbonate It is polyalcohol, polyether system polyalcohol, polyester-based polyols, polyolefin polyalcohol, acrylic polyol, bisphenol-A system epoxy Contain carboxylic obtained from the sudden reactions of diol compounds such as alkane addition product glycol, compound with phenolic hydroxyl group and alcohol hydroxyl group Based polyurethanes resin.
(3) 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, polyether system polyalcohol, polyester-based polyols, polyene Hydrocarbon system polyalcohol, acrylic polyol, bisphenol-A system alkylene oxide addition product glycol, the change with phenolic hydroxyl group and alcohol hydroxyl group Close carboxylic containing end made of the end for making polyurethane resin obtained from the sudden reactions of diol compounds such as object and anhydride reaction The polyurethane resin of base.
(4) pass through diisocyanate and bisphenol A type epoxy resin, bisphenol-A epoxy resin, bisphenol F type epoxy tree (the first of 2 functional epoxy resins such as rouge, bisphenol-s epoxy resin, union II toluene phenol-type epoxy resin, united phenol-type epoxy resin Base) obtained from acrylate or part thereof the sudden reaction of anhydride modified object, compound containing carboxylic diol and diol compound Polyurethane resin containing carboxyl.
(5) it in the synthesis of the resin of above-mentioned (2) or (4), is added in the molecules such as (methyl) hydroxyalkyl acrylates and has There is the compound of 1 hydroxyl and 1 or more (methyl) acryloyl group, carries out containing carboxyl obtained from end (methyl) is acrylated Polyurethane resin.
(6) isophorone diisocyanate and three propylene of pentaerythrite are added in the synthesis of the resin of above-mentioned (2) or (4) Compound with 1 isocyanate group and 1 or more (methyl) acryloyl group in the molecules such as the reaction with same mole object of acid esters, into Polyurethane resin containing carboxyl obtained from row end (methyl) is acrylated.
(7) react polyfunctional epoxy resin with (methyl) acrylic acid, to the hydroxyl addition O-phthalic for being present in side chain Contain carboxy resin obtained from the dibasic acid anhydrides such as acid anhydrides, tetrabydrophthalic anhydride, hexahydrophthalic anhydride.
(8) make further with epoxychloropropane by the epoxidised polyfunctional epoxy resin of the hydroxyl of 2 functional epoxy resins with (methyl) acrylic acid reacts, and carboxy resin is contained obtained from the hydroxyl addition dibasic acid anhydride to generation.
(9) it reacts multifunctional oxetane resin with dicarboxylic acids, the primary hydroxyl addition dibasic acid anhydride of generation is obtained That arrives contains carboxyl polyester resin.
(10) compound in 1 molecule with multiple phenolic hydroxyl group is reacted with alkylene oxides such as ethylene oxide, propylene oxide Obtained from reaction product reacted with the monocarboxylic acid containing unsaturated group, so that gained reaction product is reacted and is obtained with multi-anhydride Contain carboxy resin.
(11) make the cyclic annular carbon such as compound and ethylene carbonate, propylene carbonate in 1 molecule with multiple phenolic hydroxyl group Ester compound reaction obtained from reaction product reacted with the monocarboxylic acid containing unsaturated group, make obtained by reaction product with it is polynary Contain carboxy resin obtained from anhydride reaction.
(12) make to have extremely in 1 molecules such as epoxide and the p-hydroxyphenylethanol with multiple epoxy groups in 1 molecule The monocarboxylic acid reactions containing unsaturated group such as the compound and (methyl) acrylic acid of few 1 alcohol hydroxyl group and 1 phenolic hydroxyl group, Make gained reaction product alcohol hydroxyl group and maleic anhydride, tetrabydrophthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, Contain carboxy resin obtained from the reaction of the multi-anhydrides such as adipic anhydride.
(13) to the further addition containing carboxy resin (methyl) glycidyl recorded in above-mentioned (1)~(12) etc. With 1 epoxy group and 1 or more (methyl) acryloyl group in the molecules such as ester, (methyl) acrylic acid Alpha-Methyl ethylene oxidic ester Contain carboxy resin made of compound.
It is above-mentioned containing in carboxy resin, preferably (1), (7), (8), record in (10)~(13) contain carboxy resin.
As the compound with phenolic hydroxyl group, for example, using have biphenyl backbone or phenylene skeleton or its Compound, phenol, o-cresol, paracresol, metacresol, 2,3- xylenol, 2,4- xylenol, the 2,5- diformazan of the skeleton of the two Phenol, 2,6- xylenol, 3,4- xylenol, 3,5- xylenol, catechol, resorcinol, quinhydrones, methylnaphthohydroquinone, 2,6- diformazan Base quinhydrones, trimethylhydroquinone, pyrogallol, phloroglucin etc. and synthesize, phenolic resin with various skeletons.
In addition, as the compound with phenolic hydroxyl group, for example, phenol resol resins, alkylphenol phenol Novolac resin, bisphenol A novolac resin, dicyclopentadiene type phenol resin, Xylok type phenolic resin, terpene modified phenol The condensation of urea formaldehyde, polyvinylphenol class, Bisphenol F, bisphenol S type phenolic resin, poly(4-hydroxystyrene), naphthols and aldehydes Common phenolic resin known in condensation product of object, dihydroxy naphthlene and aldehydes etc..
As the commercially available product of phenolic resin, for example, HF1H60 (bright and chemical conversion Co. Ltd. system), PHENOLITE TD-2090, PHENOLITE TD-2131 (Janpanese Printing Co., Ltd's system), Besmol CZ-256-A (Dainippon Ink Chemicals System), Shonol BRG-555, Shonol BRG-556 (Showa Denko K. K's system), (ball is apt to petroleum strain formula meeting to CGR-951 Society's system), CST70, CST90, S-1P, S-2P of polyvinylphenol (ball is apt to petroleum Co. Ltd. system).
The acid value of alkali soluble resins is desired for the range of 20~200mgKOhg, the range of more preferable 40~150mgKOhg. (A) when the acid value of alkali soluble resins is 20mgKOhg or more, the adaptation of film is good, and alkali development becomes good.On the other hand, sour When value is 200mgKOhg or less, the dissolution of exposure portion caused by developer solution can be inhibited, therefore, make line taper to it is necessary with On, or according to circumstances, can inhibit the phenomenon that dissolve removing in developer solution in the case where not distinguishing exposure portion and unexposed portion, Corrosion-resisting pattern can be drawn well.
The weight average molecular weight of alkali soluble resins is different according to resin matrix, and preferably 1500~50000 and then preferably 1500 ~30000 range.When weight average molecular weight is 1500 or more, tack-free functional, the moisture-proof of the film after exposure is good, Film when development can be inhibited to reduce, inhibit the reduction of resolution ratio.On the other hand, when weight average molecular weight is 50000 or less, development Property is good, and storage-stable is also excellent.
Alkali soluble resins can be used alone or combine two or more use.The compounding ratio of alkali soluble resins is in whole It is, for example, 0~55 mass %, preferably 3~50 mass % in the solid component in addition to the solvents of composition.
(E) Thermocurable ingredient can be used alone or combine two or more use.(E) compounding of Thermocurable ingredient Ratio is, for example, 0~55 mass %, preferably 1~50 mass % in the solid component in addition to the solvents of all compositions.
(thermal curing catalyst)
When hardening resin composition of the invention contains (E) Thermocurable ingredient, preferably along with heat cure catalyst Agent.As thermal curing catalyst, for example, imidazoles, 2-methylimidazole, 2- ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2- phenylimidazole, 4- phenylimidazole, 1- cyano ethyl -2- phenylimidazole, 1- (2- cyano ethyl) -2-ethyl-4-methylimidazole Equal imdazole derivatives；Dicyandiamide, benzyldimethylamine, 2,4,4- (dimethylamino)-N, N- dimethyl benzyl amine, 4- methoxyl group-N, Amine compounds, adipic dihydrazide, the sebacic dihydrazides such as N- dimethyl benzyl amine, 4- methyl-N, N- dimethyl benzyl amine etc. Hydrazine compound；Phosphorus compounds such as triphenylphosphine etc..Alternatively, it is also possible to use guanamines, acetylguanamine, benzoguanamine, melamine, 2,4- diamino -6- methacryloxyethyl-s-triazine, 2- vinyl -2,4- diamino-s-triazine, vinyl -4 2-, 6- diamino-s-triazine isocyanuric acid adduct, 2,4- diamino -6- methacryloxyethyl-s-triazine isocyanide The Striazine derivatives such as urea acid addition product, the compound for being preferably also used as adaptation imparting agent to function these and heat cure Catalyst combination uses.
Thermal curing catalyst can be used alone or combine two or more use.The compounding ratio phase of thermal curing catalyst It is preferably 0.1~20 mass parts for 100 mass parts of (E) Thermocurable ingredient.
(organic solvent)
Hardening resin composition of the invention for prepare composition, adjustment be coated on substrate, carrier film when viscosity The purpose of can contain organic solvent.It as organic solvent, can be used: the ketones such as methyl ethyl ketone, cyclohexanone；Toluene, dimethylbenzene, Durene etc. is aromatic hydrocarbon；Cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, Propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetic acid esters, tripropylene glycol list first The glycol ethers such as ether；Ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol Acetic acid esters, 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；Known in petroleum series solvent such as petroleum ether, naphtha, solvent naphtha etc. there are commonly Solvent.These organic solvents can be used alone or combine two or more use.
(other optional members)
It can according to need compounding light-initiated auxiliary agent, cyanate esters, bullet in hardening resin composition of the invention Property body, sulfhydryl compound, thermal curing catalyst, urethanation catalyst, thixotroping agent, closely sealed promotor, block copolymerization Object, chain-transferring agent, polymerization inhibitor, copper deactivator, antioxidant, antirust agent, fine particle silica, organobentonite, montmorillonite etc. The silane such as the defoaming agents such as thickener, organic silicon-type, fluorine system, macromolecular and/or levelling agent, imidazoles system, thiazole system, triazole system are even Join the ingredients such as fire retardants, the colorants such as the phosphorus compounds such as agent, phosphinates, phosphate derivative, phosphazene compound.They are in electricity Well known substance can be used in the field of sub- material.
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.
Hardening resin composition of the invention can be used to form the print as solder mask, coating, interlayer insulating film etc. The pattern layer of the permanent overlay film of printed circuit board, it is especially useful to solder mask is formed.In addition, in addition, even if can also be with for film The excellent solidfied material of coating strength is formed, therefore, hardening resin composition of the invention can also be suitable for requiring film The formation of pattern layer in the printed circuit board of change, such as IC package substrate (printed circuit board used in IC package).In turn, The solidfied material obtained by hardening resin composition of the invention, can also be with for high elastic modulus and in terms of becoming low CTE Suitable for the pattern layer formed the thin rigid insufficient IC package substrate of overall thickness.
The form of dry film can also be made in hardening resin composition of the invention, which has: carrier film (support Body) and the resin layer formed by above-mentioned hardening resin composition that is formed in the carrier film.When carrying out dry film, it incite somebody to action this The hardening resin composition of invention is adjusted to viscosity appropriate with above-mentioned organic solvent diluting, passes through comma coater (comma coater), knife type coater, lip coating machine (lip coater), bar coater (rod coater), extrusion coated Machine (squeeze coater), inverse formula coating machine (reverse coater), transmitting roll-coater (transfer roll Cater), gravure coater (gravure coater), flush coater etc. are coated into uniform thickness on a carrier film, usually 50 It is dried 1~30 minute at a temperature of~130 DEG C and obtains film.Coating film thickness is not particularly limited, in general, after with drying Film thickness gauge, suitably selected in the range of 1~150 μm, preferably 10~60 μm.
As carrier film, plastic film can be used, it is preferable to use the polyester films such as polyethylene terephthalate, poly- The plastic films such as imide membrane, polyamidoimide film, polypropylene film, polystyrene film.For the thickness of carrier film Degree is not particularly limited, and is usually suitably selected in the range of 10~150 μm.
After forming the resin layer of hardening resin composition of the invention on a carrier film, the surface of resin layer in order to prevent Further preferably strippable cover film is laminated on the surface of resin layer in adhesive dust etc..As strippable cover film, such as Polyethylene film, polytetrafluoroethylene film, polypropylene film, surface treated paper etc. can be used, as long as covering in removing The bonding force of resin layer and cover film is less than the bonding force of resin layer and carrier film when 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 and blowed nozzle to supporter that hot air convection contacts) Lai Jinhang.
After forming resin layer on substrate, by being formed with the photomask of predetermined pattern, being selected using active energy beam It is exposed to property, unexposed portion is developed by dilute alkaline aqueous solution (for example, 0.3~3 mass % aqueous sodium carbonate), thus Form the pattern of solidfied material.In turn, it is heating and curing after irradiating active energy beam to solidfied material (for example, 100~220 DEG C) or irradiate active energy beam after being heating and curing or be only heating and curing and so that it is finally completed solidification (completely solid Change), the cured film of each excellent such as adaptation, hardness is consequently formed.
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 can be not only used for the pattern that cured film is formed by above-mentioned developer solution Purposes, can be also used for not forming the purposes of pattern, such as mould purposes (seal applications).
Embodiment
Hereinafter, showing embodiment and the present invention is specifically described in comparative example, but the present invention is not by following embodiments Limitation.It should be noted that hereinafter, " part " and " % " all quality criterias in case of no particular description.
(Examples 1 to 6 and comparative example 1)
(synthesis of alkali soluble resins)
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 (trade name " Shonol CRG951 ", Showa Denko K. K's system, OH equivalent: 119.4) 119.4 parts of 119.4 parts, 1.19 parts of potassium hydroxide and toluene simultaneously stir, and on one side to nitrogen displacement is carried out in system, carry out heating and rise Temperature.Then, 63.8 parts of propylene oxide are slowly added dropwise, in 125~132 DEG C, 0~4.8kg/cm2Under make its react 16 hours.So Afterwards, be cooled to room temperature, in the reaction solution addition mixing .56 part of 89% phosphatase 11 in and potassium hydroxide, to not waved Send out ingredient 62.1%, the propylene oxide reaction for the phenolic varnish type cresol resin that hydroxyl value is 182.2mgKOhg (307.9g/eq.) Solution.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 solid component 65%, the photosensitive solution containing carboxy resin of the acid value 87.7mgKOH/g of solid component.Hereinafter, should Photoresist containing carboxyl is known as the alkali soluble resins of (E) synthesis example 1.
(preparation of (C1) inorganic filler (silica))
By Admatech corporation spherical silicon dioxide (Adamfine SO-E2) 700g, as the PMA (propylene glycol of solvent Methyl ether acetate) 300g carries out decentralized processing with 0.5 μm of zirconium oxide bead in ball mill.It is repeated 3 times, with 3 μm of mistakes Filter filtering, preparation average grain diameter become the silica slurry of 500nm.It should be noted that being somebody's turn to do the grain of (C1) inorganic filler 1 Diameter D10 is 250nm, maximum particle diameter D100 is 3 μm.
(preparation of (C) inorganic filler (silica))
Use silica slurry (YA050C, PMA of the average grain diameter 50nm with vinyl of Admatech company (propylene glycol methyl ether acetate) solvent).It should be noted that the partial size D10 for being somebody's turn to do (C) inorganic filler is 20nm, maximum particle diameter D100 is 0.2 μm.
(preparation of (C1) inorganic filler (aluminium oxide))
As 4 μm of alumina slurry of average grain diameter, electrochemically Co. Ltd. system spherical alumina (DAW-03) is used.
(preparation of (C) inorganic filler (aluminium oxide))
As the alumina slurry of average grain diameter 300nm, the spherical alumina (ASFP- of electrochemically Co., Ltd. is used 20)。
Various composition shown in following tables is compounded with the ratio of solid component shown in table, is premixed with blender It after conjunction, is kneaded with ball mill, prepares hardening resin composition.Gained hardening resin composition is used into applicator respectively It is coated on 38 μm of polyester film, it is 20 minutes dry with 80 DEG C, make the dry film of the resin layer with 20 μm of thickness.
(resolution ratio)
Hardening resin composition whole face is coated on copper foil, it is 30 minutes dry with 80 DEG C, on composition, exposed with 1 Light quantity becomes 50mJ/cm2Mode using direct imaging exposure device (light source is high-pressure sodium lamp) carry out light irradiation, at 30 DEG C Develop in 1wt% aqueous sodium carbonate, forms the pattern of solidfied material.After pattern is formed, evaluate whether that 80 μm can be formed Opening diameter and shape it is whether good.
◎: opening portion can be formed, the wall surface of opening portion is rectilinear form.
Zero: opening portion can be formed.
×: opening portion can not be formed.
(storage modulus)
Make the gloss surface side (copper foil) of GTS-MP foil (Furukawa Circuit Foil Co Ltd system) upward, it will be above-mentioned The embodiment of middle production and each dry film of comparative example in such a way that resin layer is contacted with copper foil, with vacuum laminator (CVP-300: Nikko Materials Corporation system), in 80 DEG C of the first Room vacuum press 30 seconds 3hPa, vacuum time items It is laminated, is then pressurizeed under conditions of moulding pressure 0.5MPa, pressing time 30 seconds, by carrier film stripping under part. By it in cumulative exposure amount 1000mJ/cm in UV furnace conveyor2Under conditions of carry out ultraviolet light irradiation after, with 170 DEG C heating 60 Minute is solidified.Later, by cured film from copper foil removing after, by sample be cut into measurement size (40mm × 10mm × 20 μm Size (length × width x thickness)).Sample is supplied to tensile test apparatus AG-X (Shimadzu Scisakusho Ltd's system), by tensile speed It is set as 1mm/ seconds, the storage modulus at 25 DEG C of measurement.
Storage modulus is 10GPa or more at ◎: 25 DEG C.
Storage modulus is 8GPa or more at zero: 25 DEG C.
×: storage modulus is lower than 8GPa at 25 DEG C.
(linear expansion coefficient (CTE))
Make the gloss surface side (copper foil) of GTS-MP foil (Furukawa Circuit Foil Co Ltd system) upward, it will be above-mentioned The embodiment of middle production and each dry film of comparative example use vacuum lamination in such a way that resin layer is contacted with copper foil as described above Machine is pasted, so that resin layer is formed on copper foil, by carrier film stripping.By it in UV furnace conveyor, in cumulative exposure amount 1000mJ/cm2Under conditions of carry out ultraviolet light irradiation after, heated and solidified with 170 DEG C for 60 minutes.Later, by cured film from After copper foil removing, sample is cut into measurement size (sizes (length × width x thickness) of 5mm × 50mm × 20 μm), is supplied to Seiko Instruments Inc. TMA6100.TMA measurement is following to be carried out: test aggravates 5g, by sample with 10 DEG C/min of heating Speed heats up from room temperature, and METHOD FOR CONTINUOUS DETERMINATION 2 times.Using the intersection point of 2 different tangent lines of the 2nd linear expansion coefficient as vitrifying Transition temperature (Tg) is evaluated as the linear expansion coefficient (CTE (α 1)) in the region below Tg.For example following institute of determinating reference It states.
◎: Tg temperature CTE below is 10ppm or less.
Zero: Tg temperature CTE below is 20ppm or less.
×: Tg temperature CTE below is more than 20ppm.
[table 1]
* 1:BASF Co. Ltd. system Laromer LR8863 (photo-curable ingredient)
* 2:IGM corporation OmniradTPO (2,4,6- trimethylbenzoy-dipheny-phosphine oxide) (draw by photopolymerization Send out agent)
* 3: (C1) inorganic filler for preparing among the above, silica
* 4: (C) inorganic filler for preparing among the above, silica
* 5: above-mentioned (C1) inorganic filler, aluminium oxide
* 6: above-mentioned (C) inorganic filler, aluminium oxide
* 7: Mitsubishi chemical Co., Ltd MA-100 (ultraviolet absorbing agent)
* 8:Mitsubishi Materials Corporation 13M-C (ultraviolet absorbing agent)
* 9:BASF corporation TINUVIN460 (ultraviolet absorbing agent)
* 10:DIC Co. Ltd. system Epiclon N-730A (Thermocurable ingredient)
* 11: the alkali soluble resins (65 mass % of solid component) (Thermocurable ingredient) of synthesis example 1
As shown in above-mentioned table, by comprising (A) photo-curable ingredient, (B) Photoepolymerizationinitiater initiater, (C) average grain diameter be 1~ The dry film of the Examples 1 to 6 of (D) ultraviolet absorbing agent of the inorganic filler of 300nm and carbon black, black oxidation titanium etc obtains The solidfied material arrived becomes following result: storage modulus is high, and linear expansion coefficient (CTE) is low, and resolution ratio is also high, can be easy shape At opening portion.On the other hand, in the comparative example 1 without (D) ultraviolet absorbing agent, the resolution ratio for becoming solidfied material is poor, opening portion The difficult result of formation.It is shown in Fig. 3 and the opening portion of the solidfied material of embodiment 1 is amplified to 1000 times of microscope photo, It is shown in Fig. 4 and the opening portion of the solidfied material of comparative example 1 is amplified to 1000 times of microscope photo.In embodiment 1, be open wall surface It is formed and is open with rectilinear form, and opening can not be formed in comparative example 1.
In addition, by Examples 1 to 6 it is found that as (D) ultraviolet absorbing agent, most preferably carbon black is a small amount of just effective, special When not being 0.02~0.5 mass % of the gross mass of the solid component containing composition, can opening portion easy to form, resolution ratio It is excellent.
In turn, by embodiment 1 and 5 it is found that being put down from the viewpoint of storage modulus, linear expansion coefficient (CTE) as (C) Inorganic filler and (C1) average grain diameter that equal partial size is 1~300nm are more than the inorganic filler of 1~300nm, preferably silica.

Claims (7)

1. a kind of hardening resin composition, which is characterized in that contain:
(A) photo-curable ingredient,
(B) Photoepolymerizationinitiater initiater,
(C) average grain diameter be 1~300nm inorganic filler and
(D) ultraviolet absorbing agent.
2. hardening resin composition according to claim 1, which is characterized in that it is ultraviolet to contain (D) described in carbon black conduct Light absorbers.
3. hardening resin composition according to claim 1, which is characterized in that contain the hardening resin composition Solid component gross mass 0.01~10 mass % (D) ultraviolet absorbing agent.
4. hardening resin composition according to claim 1, which is characterized in that be also more than containing (C1) average grain diameter The inorganic filler of 300nm, (C) average grain diameter is the inorganic filler of 1~300nm and (C1) average grain diameter is more than The total compounding amount of the inorganic filler of 300nm is 45 mass % of the gross mass of the solid component of the hardening resin composition More than.
5. a kind of dry film, which is characterized in that have and obtained by hardening resin composition according to any one of claims 1 to 4 The resin layer arrived.
6. a kind of solidfied material, which is characterized in that it is by hardening resin composition according to any one of claims 1 to 4 Or obtained from the resin layer solidification of dry film described in claim 5.
7. a kind of printed circuit board, which is characterized in that have solidfied material as claimed in claim 6.
CN201810722338.6A 2017-08-30 2018-06-29 Hardening resin composition, dry film, solidfied material and printed circuit board Pending CN109426078A (en)

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