CN110320747A - Hardening resin composition, dry film, solidfied material and printed circuit board - Google Patents

Abstract

The present invention provides hardening resin composition, dry film, solidfied material and printed circuit board.[project] provides: suitable for printed circuit board etc., reliability and excellent adhesion hardening resin composition.A kind of [solution] hardening resin composition, contains: (A) carboxylic resin, (B-1) Photoepolymerizationinitiater initiater, (C) have the following structure the inorganic filler of the surface treatment of epoxy resin and (D-1) through photoreactivity of formula.

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, specially A kind of hot curing resin composition is disclosed in sharp document 1, is contained: carboxylic polyurethane；It is lower than 0.7 with, total chlorine amount The multifunctional aliphatic glycidyl ether compound of quality %.

In recent years, due to the progress rapidly of semiconductor component, and electronic equipment be in light and shortization, high performance, The tendency of multifunction.The tendency is followed, the miniaturization of semiconductor packages, more pinizations have been practical.

Specifically, replacing quilt using the IC package for being referred to as BGA (ball array encapsulation), CSP (wafer-level package) etc. The IC package of referred to as QFP (QFP type), SOP (small outline packages) etc..In addition, in recent years, as further high density The IC package of change, FC-BGA (encapsulation of flip-chip ball array) have also been practical.

In printed circuit board used in such IC package (also referred to as package substrate), SRO (welding resistance opening (Solder Resist Opening)) spacing is narrow, and it is close to each other and formed, therefore, short circuit is generated between SRO, the worry of cross-talk noise becomes It is high.In addition, the solder mask between being formed in SRO attenuates and thin, therefore, becomes easy and crack.Therefore, in package substrate The permanent overlay film requirement such as solder mask used after long-term high reliability, specifically high insulating reliability.Especially Think, with the densification of package substrate from now on, the requirement of reliability is further increased.

Existing technical literature

Patent document

Patent document 1: No. 5167113 specifications of Japanese Patent No.

Patent document 2: Japanese Unexamined Patent Publication 2010-54912 bulletin

Summary of the invention

Problems to be solved by the invention

However, the hot curing resin composition recorded in above patent document 1 gradually becomes in recent years for the reliability It must can not be said to be sufficient.

In addition, in recent years, with the increase of the pin number of IC, the pin (drawing I ま わ) of wiring is apart from abruptly increase, therefore, In order to improve dielectric property, exist makes the not roughened tendency of wiring as far as possible.For it is such it is low roughening or it is not roughened Wiring, it is desirable that the previous above adaptation.

For the adaptation, the hot curing resin composition recorded in above patent document 1 also gradually becomes in recent years It can not be said to be sufficient.

In addition, sometimes including following compound: its heat resistance and solvent resistant characteristic about photosensitive composition It is excellent and indicate (patent document 2) with defined chemical formula.However, the photosensitive polymer combination recorded in patent document 2 is The photosensitive polymer combination of colour filter when being used for printed circuit board, is unable to get under the conditions of harsh high-temperature humidifying The characteristic of adaptation can sufficiently be maintained.

Therefore, the object of the present invention is to provide: suitable for printed circuit board etc., reliability and excellent adhesion Hardening resin composition；Dry film with the resin layer obtained by the composition；The resin layer of the composition or the dry film Solidfied material；With the printed circuit board with the solidfied material.

The solution to the problem

The inventors of the present invention further investigate exploitation to adaptation and hardening resin composition excellent in reliability repeatedly, as a result It was found that: by by specific epoxy resin, combined with specific inorganic filler and use, to obtain adaptation and high reliablity Solidfied material, so far complete the present invention.

Hardening resin composition of the invention is characterized in that, is contained: (A) carboxylic resin, (B-1) photopolymerization are drawn Hair agent, (C) have the following structure formula epoxy resin and

(D-1) inorganic filler of the surface treatment through photoreactivity.

In addition, hardening resin composition of the invention is characterized in that, contain: (A) carboxylic resin, (B-2) light Generated base alkaline agent, (C) have the following structure formula epoxy resin and

(D-2) inorganic filler of the surface treatment through heat reactivity.

Hardening resin composition of the invention is preferably, and the surface treated of above-mentioned (D-1) or (D-2) inorganic is filled out The average grain diameter of material is 1.0 μm hereinafter, and maximum particle diameter is 4.0 μm hereinafter, it is preferred that the compounding ratio of above-mentioned (D) inorganic filler is 25~80 mass %.

Dry film of the invention is characterized in that thering is resin layer, the resin layer is by above-mentioned hardening resin composition Obtained from being coated on film and drying.

In addition, solidfied material of the invention is characterized in that, it is by above-mentioned hardening resin composition or aforementioned dry film Obtained from resin layer solidification.

In turn, printed circuit board of the invention is characterized in that, has above-mentioned solidfied material.

The effect of invention

According to the present invention it is possible to obtain adaptation and solidfied material excellent in reliability.

Specific embodiment

Hardening resin composition of the invention contains (A) carboxylic resin and (C) has the following structure the epoxy of formula Resin,

And include at least one of (B-1) Photoepolymerizationinitiater initiater and (B-2) Photobase generator, and respectively, comprising should (B- 1) when Photoepolymerizationinitiater initiater, contain the inorganic filler of the surface treatment through photoreactivity as inorganic filler, comprising being somebody's turn to do (B-2) light When generated base alkaline agent, contain the inorganic filler of surface treatment of the heat through photoreactivity as inorganic filler.

Hardening resin composition of the invention contains the epoxy resin with above-mentioned specific structural formula.The epoxy resin Gardner Color is low, i.e. light transmittance is high, therefore, light is coated with the deep of the overlay film of hardening resin composition to reaching.Cause This can be with the depth that is present in the overlay film in the case where composition of inorganic filler comprising the surface treatment through photoreactivity The surface treating agent of the inorganic filler of the surface treatment through photoreactivity in portion reacts.In addition, comprising through heat reactivity In the case where the composition of the inorganic filler of surface treatment, by being present in the Photobase generator in its deep, can with through thermal response The surface treating agent of the inorganic filler of the surface treatment of property reacts.Accordingly it is also possible to solidify solidfied material sufficiently in deep, Moisture-proof improves, the solidfied material of available reliability, excellent adhesion.

It, therefore, can be in addition, the epoxy resin with above-mentioned specific structural formula has the skeleton of hydrophobicity and heat resistance Obtain the solidfied material of excellent moisture-proof, reliability, excellent adhesion.

In turn, the epoxy resin with above-mentioned specific structural formula has the skeleton of hydrophobicity and heat resistance, therefore, glass It is high to change transition temperature (Tg), it is therefore, low mutually auxiliary with linear expansion coefficient in addition, contain inorganic filler, there is excellent resistance to crackle Property, and there are low warpage properties.

In addition, the Gardner Color of the epoxy resin with above-mentioned specific structural formula is low, therefore, light reaction is not interfered Property, so that resin combination of the invention has high-resolution.

Based on such characteristic, it is believed that the solidfied material of hardening resin composition of the invention is adaptation and high reliablity Person.

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]

As carboxylic resin, the known various carboxylic resins in molecule with carboxyl can be used. It is carboxylic photosensitive with ethylenical unsaturated double bonds from photo-curable, resistance to developability aspect, particularly preferred molecule Property resin.Ethylenical unsaturated double bonds preferably originate from acrylic or methacrylic acid or their derivative.Using only without alkene In the case where the carboxylic resin for belonging to unsaturated double-bond, in order to make composition photo-curable, it is necessary to will be in aftermentioned molecule Compound, i.e. photoreactivity monomer with multiple ethylenically unsaturated groups are applied in combination.

As the concrete example of carboxylic resin, compound below (oligomer and polymer) can be enumerated.

(1) pass through the unsaturated carboxylic acids such as (methyl) acrylic acid and styrene, α-methylstyrene, low alkyl group (methyl) Carboxylic resin obtained from the copolymerization of the compound containing unsaturated group such as acrylate, isobutene.

(2) pass through aliphatic diisocyanate, Branched fatty (cyclo) aliphatic diisocyanates, ester ring type diisocyanate, aromatic series The carboxylic diol compound such as the diisocyanate such as diisocyanate and dihydromethyl propionic acid, dimethylolpropionic acid and poly- carbon Acid esters system polyalcohol, polyether system polyalcohol, polyester-based polyols, polyolefin polyalcohol, acrylic polyol, bisphenol-A system The sudden reactions of diatomic alcohol compounds such as alkylene oxide addition product dihydric alcohol, compound with phenolic hydroxyl group and alcohol hydroxyl group and obtain The carboxylic polyurethane resin arrived.

(3) 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) the anhydride modified object of acrylate or part thereof, carboxylic diol compound and diatomic alcohol compounds sudden reaction and obtain The carboxylic photonasty polyurethane resin arrived.

(4) in the synthesis of the resin of aforementioned (2) or (3), the intramoleculars such as (methyl) hydroxyalkyl acrylates tool is added There is the compound of 1 hydroxyl and 1 or more (methyl) acryloyl group, through end (methyl) acrylated carboxylic photonasty Polyurethane resin.

(5) in the synthesis of the resin of aforementioned (2) or (3), isophorone diisocyanate and pentaerythrite 3 third is added The intramoleculars such as the reaction with same mole object of olefin(e) acid ester have the compound of 1 isocyanate group and 1 or more (methyl) acryloyl group, Through end (methyl) acrylated carboxylic photonasty polyurethane resin.

(6) it reacts 2 functions or multifunctional (solid) epoxy resin more than it with (methyl) acrylic acid, is being present in side Carboxylic photoresist obtained from addition dibasic acid anhydride on the hydroxyl of chain.

(7) make the hydroxyl of 2 functions (solid) epoxy resin and then obtain multi-functional epoxy with epichlorohydrin epoxy Resin, the polyfunctional epoxy resin made are reacted with (methyl) acrylic acid, the addition dibasic acid anhydride on the hydroxyl of generation and obtain The carboxylic photoresist arrived.

(8) make the dicarboxylic acids such as 2 function oxetane resins and adipic acid, phthalic acid, hexahydrophthalic acid anti- It answers, the binary acid such as addition phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride on the primary hydroxyl of generation Carboxylic polyester resin obtained from acid anhydride.

(9) make to have at least in 1 molecules such as epoxide and the p-hydroxyphenylethanol with multiple epoxy groups in 1 molecule The monocarboxylic acid reaction containing unsaturated group such as compound and (methyl) acrylic acid of 1 alcohol hydroxyl group and 1 phenolic hydroxyl group, obtains To reaction product, make the alcohol hydroxyl group and maleic anhydride, tetrabydrophthalic anhydride, trimellitic anhydride, of gained reaction product Carboxylic resin obtained from the multi-anhydride reaction of pyromellitic anhydride, adipic acid etc..

(10) make the compound in 1 molecule with multiple phenolic hydroxyl group, reacted with alkylene oxides such as ethylene oxide, propylene oxide And obtain reaction product, make gained reaction product reacted with the monocarboxylic acid containing unsaturated group, make obtained by reaction product with it is polynary Carboxylic photoresist obtained from anhydride reaction.

(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 obtains reaction product, reacts gained reaction product with the monocarboxylic acid containing unsaturated group, makes gained Reaction product carboxylic photoresist obtained from being reacted with multi-anhydride.

(12) 1 intramolecular of addition has 1 epoxy group and 1 or more (first in turn on the resin of aforementioned (1)~(11) Base) acryloyl group compound made of carboxylic photoresist.

It should be noted that (methyl) acrylate refers in this specification, it is referred to as acrylate, methacrylate It is also the same for other similar performance with the term of their mixture.

(A) acid value of carboxylic resin preferably 20~200mgKOH/g.(A) acid value of carboxylic resin is if it is 20 ~200mgKOH/g, then the pattern formation of solidfied material becomes easy.More preferable 50~130mgKOH/g.

In addition, the weight average molecular weight of aforementioned carboxylic resin is different according to resin matrix, it is however generally that, it is preferably in 2000~150000 range, the range for being in 5000~100000 in turn.Weight average molecular weight is exposed if it is 2000 or more The resistance to developability of the overlay film in portion improves, excellent in resolution.On the other hand, weight average molecular weight is if it is 150000 hereinafter, not exposing then The favorable solubility in light portion, excellent in resolution, and also improved sometimes on storage-stable.Weight average molecular weight can pass through gel Permeation chromatography and measure.

(A) compounding amount of carboxylic resin in terms of hardening resin composition total amount benchmark in addition to the solvents, for example For 10~60 mass %, preferably 20~60 mass %.By being set as 10 mass % or more, preferably 20 mass % or more, Ke Yiti High coating strength.Moreover, by being set as 60 mass % hereinafter, processability improves to which viscosity becomes appropriate.

These carboxylic resins can be not limited to the resin of aforementioned list and use, and can be used alone, can also A variety of mixing to be used.It wherein, the use of phenolic compounds is starting material as aforementioned carboxylic resin (10), (11) And the HAST under the high voltage of the carboxylic resin synthesized is tested, i.e. B-HAST patience, PCT patience is excellent, therefore can be fitted It closes and uses.

[(B-1) Photoepolymerizationinitiater initiater or (B-2) Photobase generator]

As Photoepolymerizationinitiater initiater, as long as Photoepolymerizationinitiater initiater, optical free radical producing agent and well known photopolymerization Initiator 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, 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- diformazan Base phenyl phosphine oxide, double-(2,4,6- trimethylbenzoyl)-phenyl phosphine oxide (IGM Resins corporation Omnirad (Omnirad) the bisacylphosphines phosphine such as 819)；2,6- Dimethoxybenzoyl diphenyl phosphine oxide, 2,6- dichloro-benzoyl It is base diphenyl phosphine oxide, 2,4,6- trimethylbenzoyl phenyl methyl-phosphonate, 2- methyl benzoyl diphenyl phosphine oxide, new Valeryl phenyl-phosphonic acid isopropyl ester, 2,4,6- trimethyl benzoyl diphenyl base phosphine oxide (IGM Resins corporation Omnirad (Omnirad) TPO) etc. monoacylphosphine oxides phosphine；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- hydroxy-2-methyl-propiono)-benzyl] phenyl } -2- The hydroxy acetophenones classes such as methyl-propan -1- ketone, 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone；Benzoin, dibenzoyl, benzene are even The benzoin class such as relation by marriage methyl ether, benzoin ethyl 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- two The benzophenones such as ethylamino benzophenone；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- morpholine Base -1- acetone, 2- benzyl -2- dimethylamino -1- (4- morpholino phenyl) -1- butanone, 2- (dimethylamino) -2- [(4- first Base phenyl) methyl) -1- [4- (4- morpholinyl) phenyl] -1- butanone, N, the acetophenones such as N- dimethylamino benzoylformaldoxime；Thioxanthene Ketone, 2- ethyl thioxanthones, 2-isopropylthioxanthone, 2,4- dimethyl thioxanthone, 2,4- diethyl thioxanthone, 2-chlorothioxanthone, The thioxanthene ketone class such as 2,4- diisopropylthioxanthone；Anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2- ethyl hydrazine, 2- tert-butyl anthraquinone, The Anthraquinones such as 1- chloroanthraquinone, 2- amyl anthraquinone, 2- amino anthraquinones；The contracting such as acetophenone dimethyl ketal, benzil dimethyl ketal Ketone；Ethyl -4- dimethyl aminobenzoate, 2- (dimethylamino) ethylamino benzonitrile acid esters, to mesitylenic acid ethyl ester Equal benzoates；{ 1- [4- (thiophenyl) -2- (O- benzoyl oxime)] } 1,2- acetyl caproyl, 1- [9- ethyl -6- (2- methylbenzene Formoxyl) -9H- carbazole -3- base] the oximes esters such as -1- (O- acetyl oxime) ethyl ketone；Bis- (η 5-2,4- cyclopentadiene -1- bases)-it is bis- (2, The fluoro- 3- of 6- bis- (1H- pyrroles -1- base) phenyl) titanium, bis- (cyclopentadienyl groups)-bis- [the fluoro- 3- of 2,6- bis- (2- (1- pyrroles -1- base) Ethyl) phenyl] the titanocenes class such as titanium；Phenyl disulfide 2- nitrofluorene, butyroin, anisoin ethyl ether, azobis isobutyronitrile, four Methyl thiuram disulfide etc..Photoepolymerizationinitiater initiater can be used alone, and can also combine two or more use.Wherein, excellent Menu acylphosphine oxide class, oxime esters, more preferable 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base] -1- (O- acetyl oxime) ethyl ketone.

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 good, 20 below the mass in the case where, be not likely to produce halation, can be with Obtain good resolution ratio.

Photobase generator is following compound: by the light of ultraviolet light, visible light etc. irradiate molecular structure change or Molecular cleavage, to generate a kind or more of the alkaline matter that the catalyst that can be reacted as heat cure functions.As alkalinity Substance, for example, secondary amine, tertiary amine.

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] -1- (O- acetyl oxime) ethyl ketone.As alpha-aminoacetophenone Object is closed, particularly preferably there are 2 or more nitrogen-atoms.Photobase generator can be used alone, and can also combine two or more use.

In addition, quaternary ammonium salt etc. can be enumerated as Photobase generator.

As other Photobase generators, WPBG-018 (trade name: 9-anthrylmethyl N, N '-also can be used 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 In the case where more than mass parts, surface cure becomes good, 20 below the mass in the case where, be not likely to produce halation, can obtain To good resolution ratio.

[epoxy resin that (C) has specific structure formula]

Hardening resin composition of the invention includes the epoxy resin for the formula that has the following structure.

By the inclusion of the low above-mentioned epoxy resin of Gardner Color, so as to so that light to the deep for reaching overlay film, can be with Obtain adaptation, solidfied material excellent in reliability.Therefore, hardening resin composition of the invention is high suitable for gradually requiring Layer used in the printed circuit board of reliability under warm, how wet environment, especially detector insulating materials, semiconductor device Stack etc., suitable for semiconductor packages, vehicle-mounted.

It should be noted that hardening resin composition contains above-mentioned epoxide and aftermentioned through specific surface The inorganic filler of processing has resistance to anti-thread breakage, excellent adaptation under hot and humid environment etc. as essential component as a result,.

In hardening resin composition of the invention, together with the epoxy resin that above-mentioned (C) has specific structure formula, not In the range of damaging the distinctive effect of the present invention, it may include in addition to the epoxy resin that above-mentioned (C) has specific structure formula Epoxy resin.Above-mentioned (C) there is the epoxy resin other than the epoxy resin of specific structure formula can enumerate: epoxidised 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 resin varnish type epoxy resin；Bisphenol f type epoxy resin；Hydrogenated bisphenol A type Epoxy resin；Glycidyl amine type epoxy resin；Hydantoins type epoxy resin；Alicyclic epoxy resin；Trihydroxy phenyl first Alkane type epoxy resin；Union II toluene phenolic or united phenol-type epoxy resin or their mixture；Bisphenol-s epoxy resin；It is double Phenol A phenolic resin varnish type epoxy resin；Four hydroxy phenyl ethane type epoxy resin；Hetero ring type epoxy resin；2-glycidyl neighbour benzene two Formate resin；Four glycidol dimethylbenzene acyl group ethane resins；Epoxy resin containing naphthalene；With bicyclopentadiene skeleton Epoxy resin；Glycidyl methacrylate copolymerization is epoxy resin；N-cyclohexylmaleimide and Glycidyl methacrylate The copolymerization epoxy resin of glyceride；Epoxy-modified polybutadiene rubber derivative；CTBN modified epoxy etc., but be not limited to These.

(C) compounding amount of the epoxy resin with specific structure formula is relative to (A) carboxylic 100 mass parts of resin, example For example 1~100 mass parts, preferably 10~80 mass parts, more preferable 20~60 mass parts.(C) with the epoxy of specific structure formula The compounding amount of resin if it is 10 mass parts more than, resistance to anti-thread breakage and insulating reliability further increases, if it is 100 mass Part is hereinafter, then storage stability improves.

[surface treatment of inorganic filler or (D-2) through heat reactivity of the surface treatment of (D-1) through photoreactivity it is inorganic Filler]

Hardening resin composition of the invention contains the inorganic filler or (D- of the surface treatment of (D-1) through photoreactivity 2) inorganic filler of the surface treatment through heat reactivity.By the inclusion of inorganic filler, so that solidfied material is resistance to anti-thread breakage further It improves.

Herein, by for surface treated inorganic filler, so as to improve and (A) carboxylic resin or (C) ring The compatibility of oxygen resin.

In addition, the curable resin combination of the invention of the inorganic filler of the surface treatment comprising (D-1) through photoreactivity In object, (B-1) Photoepolymerizationinitiater initiater is cracked by the light transmitted, anti-with the inorganic filler of the surface treatment through photoreactivity It answers, it is thus possible to improve the curability in the deep of overlay film.

In addition, the curable resin combination of the invention of the inorganic filler of the surface treatment comprising (D-2) through heat reactivity In object, (B-2) Photobase generator generates alkali by the light transmitted, reacts with the inorganic filler of the surface treatment through heat reactivity, It is thus possible to improve the curability in the deep of overlay film.

Therefore, hardening resin composition of the invention includes the inorganic filler of the surface treatment of (D-1) through photoreactivity When, include (B-1) Photoepolymerizationinitiater initiater, when including the inorganic filler of (D-2) through the surface treatment of heat reactivity, includes (B-2) Photobase generator.It should be noted that it has been observed that a part of substance of Photoepolymerizationinitiater initiater is also functioned as Photobase generator, Therefore, Photoepolymerizationinitiater initiater is not distinguished strictly with Photobase generator.

It as surface treated inorganic filler, is not particularly limited, known common filler, such as two can be used Silica, crystallinity silica, Nuo Yibao tripoli, aluminium hydroxide, glass powder, talcum, clay, magnesium carbonate, calcium carbonate, day Right mica, synthetic mica, aluminium hydroxide, barium sulfate, barium titanate, iron oxide, Non-fibrous glass, hydrotalcite, mineral wool, silicic acid The inorganic fillers such as aluminium, calcium silicates, zinc white.Wherein, preferred silica, surface area is small, stress is scattered in entirety, and is not easy to become The starting point of crackle, therefore, more preferable spherical silicon dioxide.

Herein, for surface treated inorganic filler, in the inorganic filler of (D-1), cause as with (B-1) photopolymerization The curability reactive group of agent reaction, implementing can import at the surface of photo-curable reactive group to the surface of inorganic filler It manages, in the inorganic filler of (D-2), as the curability reactive group reacted with (B-2) Photobase generator, implementing can fill out to inorganic The surface of material imports the surface treatment of Thermocurable reactive group.The inorganic of surface treatment as (D-1) through photoreactivity is filled out The photo-curable reactive group of material can enumerate vinyl, styryl, methacrylic acid group (メ タ Network リ Le base), acrylic acid Base (ア Network リ Le base) etc..Wherein, as photo-curable reactive group, preferably methacrylic acid group, acrylic, vinyl.

The Thermocurable reactive group of the inorganic filler of surface treatment as (D-2) through heat reactivity, can enumerate hydroxyl Base, carboxyl, isocyanate group, amino, imino group, epoxy group, oxetanylmethoxy, sulfydryl, methoxy, methoxy ethyl, Ethoxyl methyl, ethoxyethyl group, oxazoline group etc..Wherein, preferably amino, epoxy group.

In addition, the inorganic filler of (D-1) or the inorganic filler of (D-2) can have curability reactive group of more than two kinds. As (D) inorganic filler, preferably surface treated silica.By the inclusion of surface treated silica, so as to To reduce CTE, improve glass transition temperature.

The method for importing curability reactive group to the surface of (D) inorganic filler is not particularly limited, as long as known in use 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 (D) 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 (D) inorganic filler.As The silane coupling agent of heat cure reactive group can be imported, silane coupling agent with epoxy group can be enumerated, with amino Silane coupling agent, the silane coupling agent with sulfydryl, the silane coupling agent with isocyanate group, wherein more preferably having epoxy The silane coupling agent of base.As the silane coupling agent that can import photocuring reaction group, preferably the silane with vinyl is even Join agent, the silane coupling agent with styryl, the silane coupling agent with methacrylic acid group, the silane with acrylic Coupling agent, wherein more preferably with the silane coupling agent of methacrylic acid group.

(D-1) or (D-2) if inorganic filler with surface treated state with being mixed in curable resin of the invention The untreated inorganic filler in surface and surface treating agent can also be compounded, in the composition to inorganic by composition respectively Filler is surface-treated, and surface treated inorganic filler in advance is preferably compounded.By being compounded surface treated nothing in advance Machine filler, so as to prevent the surface treating agent institute not being consumed in possible remaining surface treatment in the case where being compounded respectively Caused resistance to anti-thread breakage equal reduction.In the case where being surface-treated in advance, preferably with pre-dispersed in miscible agent, resin component There is the pre-dispersed liquid of (D) inorganic filler, it is more preferably that surface treated inorganic filler is pre-dispersed in solvent, by the pre-dispersed liquid With being mixed in composition, or by the untreated inorganic filler in surface is pre-dispersed be sufficiently surface-treated when the solvent after, by this Pre-dispersed liquid, which is matched, is mixed in composition.

In hardening resin composition of the invention, the average grain diameter of the inorganic filler of (D-1) or the inorganic filler of (D-2) It is resistance to anti-thread breakage more excellent when being 1 μm or less, therefore it is preferred that.More preferable 0.8 μm or less.It should be noted that being put down in this specification Equal partial size refers to, the value of D50, the value for example, measured using Nikkiso Company Limited Microtrac grain size analysis meter.

In addition, efficiency is good when the maximum particle diameter of the inorganic filler of (D-1) or the inorganic filler of (D-2) is 4.0 μm or less Ground is reacted, and it is resistance to it is anti-thread breakage, adaptation is more excellent, therefore it is preferred that.More preferable 3.0 μm or less.It should be noted that this theory In bright book, maximum particle diameter refers to, the value of D100, for example, using Nikkiso Company Limited Microtrac grain size analysis meter and The value of measurement.

Total amount of the compounding amount of inorganic filler relative to the solid component of hardening resin composition, preferably 25~85 matter Measure %, more preferable 30~75 mass % and then preferably 35~70 mass %.

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；Ethylene Base isobutyl ether, vinyl n-butyl ether, vinyl tertbutyl ether, vinyl n-pentyl ether, vinyl isoamyl ether, vinyl The ethylene such as n-octadecane base ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ethers, triethylene glycol monomethyl vinyl ethers Base ethers；Acrylamide, Methacrylamide, N- hydroxymethylacrylamide, N- hydroxymethyl Methacrylamide, N- methoxy Butylmethacrylamide, N- ethoxymethyl acrylamide, N- butoxy methyl acrylamide etc. (methyl) acrylic amide；It is different The allyl compounds such as triallyl cyanurate, diallyl phthalate, diallyl isophthalate；(methyl) propylene Sour 2- ethylhexyl, (methyl) lauryl acrylate, (methyl) tetrahydrofurfuryl acrylate, (methyl) isobornyl acrylate, (first Base) (methyl) acrylic acid such as phenyl acrylate, (methyl) phenoxyethyl acrylate esters；(methyl) dihydroxypropyl second (methyl) the hydroxyalkyl acrylates classes such as ester, (methyl) hydroxypropyl acrylate, pentaerythrite three (methyl) acrylate； (methyl) methoxyethyl acrylate, (methyl) ethoxyethyl acrylate etc. alkoxyalkylenes glycol list (methyl) acrylic acid Esters；Ethylene glycol two (methyl) acrylate, butanediol two (methyl) esters of acrylic acid, neopentyl glycol two (methyl) acrylic acid Ester, 1.6- hexylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) third Poly- (methyl) acrylate of the alkylidene polyols such as olefin(e) acid ester, dipentaerythritol six (methyl) acrylate；Two (first of diethylene glycol Base) acrylate, triethylene glycol two (methyl) acrylate, ethoxylated trimethylolpropane triacrylate, propoxylation Poly- (methyl) esters of acrylic acid of the polyether polyols such as trimethylolpropane tris (methyl) acrylate；Hydroxyl trimethylacetic acid new penta Poly- (methyl) esters of acrylic acid such as diol ester two (methyl) acrylate；Three [(methyl) acryloyl-oxyethyl] isocyanuric acid esters Equal poly- (methyl) esters of acrylic acid of isocyanurate types etc..They can according to require characteristic and be used alone or combine 2 kinds with Upper use.

The compounding amount of compound with ethylenic unsaturated bond is relative to (A) carboxylic 100 mass parts of resin, and 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 is pressed down System.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 is relative to 100 mass parts of (C) epoxy resin, preferably 0.05~40 mass parts, more It is preferred that 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 function of heat cure reaction preferably with the epoxy group etc. of the heat-curing resins such as (C) epoxy resin Group, with the ratio of the functional group in the curing agent with its functional group reactions as curing agent functional group/to can be carried out heat cure anti- The ratio for the functional group's (equivalent proportion)=0.2~3 answered is compounded.By being set as above range, thus storage stability and solid The harmony for the property changed 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, with preferably 10 matter Part is measured hereinafter, the ratio of particularly preferred 0.1~7 mass parts is sufficient.

(organic solvent)

In hardening resin composition of the invention, for prepare composition, adjustment be coated on substrate, carrier thin film when The purpose of viscosity, can contain organic solvent.It as organic solvent, can be used: the ketones such as methyl ethyl ketone, cyclohexanone；Toluene, two Toluene, durene etc. are aromatic hydrocarbon；Cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl card It must alcohol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetic acid esters, tripropylene glycol The glycol ethers such as monomethyl ether；Ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, card It must alcohol acetic ester, acetate of butyl carbitol, propylene glycol methyl ether acetate, dipropylene glycol monomethyl ether acetic acid esters, polypropylene carbonate The esters such as ester；The aliphatic hydrocarbons such as octane, decane；It is commonly used 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 contain (C) asphalt mixtures modified by epoxy resin in the range of not impairing the effect of the present invention Heat-curing resin other than rouge.As heat-curing resin, as long as to embody the resin of electrical insulating property and being heating and curing , for example, epoxide, oxetane compound other than (C) epoxy resin, melamine resin, having Machine silicone resin etc., they can be applied in combination.

Hardening resin composition of the invention can be used with dry film, can also be formed liquid and be used.Form liquid State and in the case where use, can for 1 fluidity may be 2 fluidities or more.

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 on carrier thin film and obtained from drying.When forming dry film, firstly, by hardening resin composition of the invention with above-mentioned After organic solvent diluting is adjusted to viscosity appropriate, applied using 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 carrier thin film.Later, by coated composition usually 40~ It is 1~30 minute dry at a temperature of 130 DEG C, so as to form resin layer.It for coating film thickness, is not particularly limited, generally For, with the film thickness gauge after drying, suitable selection in the range of 3~150 μm, preferably 5~60 μm.

As carrier thin film, plastic film can be used, polyethylene terephthalate (PET) etc. can be used for example Polyester film, Kapton, polyamidoimide film, polypropylene film, polystyrene film etc..For carrier thin film Thickness, be not particularly limited, it is however generally that, in the range of 10~150 μm be suitable for selection.More preferable 15~130 μm of model It encloses.

After forming the resin layer formed by hardening resin composition of the invention on carrier thin film, for preventing dust The covering film that can be removed is laminated preferably and then on the surface of resin layer in the purpose of being attached to the surface of resin layer.As can shell From covering film, polyethylene film, polytetrafluoroethylene film, polypropylene film, surface treated paper can be used for example Deng.As covering film, when by covering film removing, as long as being less than the bonding force of resin layer and carrier thin film.

It should be noted that curable resin combination of the invention can be coated on above-mentioned covering film in the present invention Object simultaneously makes it dry to form resin layer, and laminated carrier film on the surface thereof.That is, when manufacturing dry film, making in the present invention For the film for being coated with hardening resin composition of the invention, carrier thin film and covering film can be used,.

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 thin 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 a printed circuit, by being formed with the photomask of predetermined pattern, being penetrated using active-energy It is exposed to line options, is shown unexposed portion by dilute alkaline aqueous solution (for example, 0.3~3 mass % aqueous sodium carbonate) Shadow, to 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 (complete Solidification), the cured film of each excellent such as adaptation, hardness is consequently formed.

It should be noted that preferably being exposed in the case that hardening resin composition of the invention includes Photobase generator Heating before development afterwards is heated 1~60 minute as the heating condition before developing after exposure, such as preferably at 60~150 DEG C.

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 is particularly suited for shape suitable for cured film is formed on a printed circuit At permanent overlay film, and then it is suitable for forming solder mask, interlayer insulating film, coating.In addition, utilizing curability tree of the invention Therefore oil/fat composition, the available resistance to anti-thread breakage and excellent solidfied material of insulating reliability can be suitable for requiring height Printed circuit board, such as package substrate, particularly the FC-BGA's of the wiring pattern for having fine spacing of reliability is permanent The formation of overlay film (especially solder mask).

Embodiment

Hereinafter, being illustrated in more details according to embodiment to the present invention, but the present invention is not limited to the following examples.It needs It is noted that " portion " and " % " all quality criterias in case of no particular description in following.

By each ingredient shown in table 1~3 with the compounding of ratio shown in table 1~3, after being pre-mixed in blender, use Triple-roller mill is kneaded, the hardening resin composition of preparation Examples 1 to 20, the Comparative Examples 1 to 5.For gained curability group Object is closed, each characteristic is evaluated, its result is remembered together in table 1~3.

[table 1]

[table 2]

[table 3]

Alkali-developable resin in table 1~3 is prepared as follows.

[synthesis of (A-1) Alkali-developable resin]

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 CRG951, 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 (A-2) Alkali-developable resin]

O-cresol phenolic epoxy varnish (DIC plants of formula meetings are put into diethylene glycol monoethyl ether acetic acid esters 600g 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 hydroquinone 1.5g, be heated to 100 DEG C and stir, Even dissolution.

Then, triphenylphosphine 4.3g is put into, after being heated to 110 DEG C, reaction 2 hours, is warming up to 120 DEG C, and then carry out 12 Hour reaction.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-2.

[synthesis of (A-3) Alkali-developable resin]

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 conduct The mixture of 12.0 parts of the tert-butyl peroxide 2 ethyl hexanoic acid ester (Japan Oil Co Perbutyl O) of polymerization catalyst, And then with 110 stirring 3 hours, polymerization catalyst is inactivated, resin solution is obtained.

After resin solution cooling, Daicel Chemical Industries, Ltd. Cyclomer A200 is added 289.0 parts, 3.0 parts of triphenylphosphine, 1.3 parts of hydroquinone monomethyl ether, are warming up to 100 DEG C, are stirred, to carry out epoxy The opening of base obtains photosensitive carboxylic resin solution.

The obtained resin solution is as follows: weight average molecular weight (Mw) be 15000 and solid component be 57%, solids Acid value be 79.8mgKOH/g.Hereinafter, the solution of the carboxylic photoresist is known as resin solution A-3.

In table 1~3, Photoepolymerizationinitiater initiater is as follows.

(B-1.1): IGM Resins corporation Omnirad (Omnirad) TPO (2,4,6- trimethylbenzoyl-hexichol Base phosphine oxide)

(B-1, B-2.1): (2- methyl-1-(the 4- methyl thio of IGM Resins corporation Omnirad (Omnirad) 907 Phenyl) -2- morpholinyl -1- acetone)

(B-1, B-2.1): BASF JAPAN corporation IRGACURE OXE02 (1- [9- ethyl -6- (2- toluyl Base) -9H- carbazole -3- base] -1- (O- acetyl oxime) ethyl ketone)

(B-2.1): Wako Pure Chemicals Co., Ltd. WPBG-082 (2- (3- benzoylphenyl) propionic acid guanidine)

In table 1~3, (C) of the invention has epoxy resin, that is, special epoxy resin of specific structure formula as follows.

(C-1): the epoxy resin (epoxide equivalent 210) with following skeletons

(C-2): the epoxy resin (epoxide equivalent 232) with above-mentioned skeleton

Moreover, the curable resin composition of table 1~3 may include following epoxy resin (C-3)~(C-6) as above-mentioned (C) epoxy resin other than the epoxy resin comprising specific structure formula.

(C-3) with the alicyclic epoxy resin (epoxide equivalent 96) of following skeletons

(C-4) Dow Chemical Company DEN431 (phenol novolac epoxy resins)

(C-5) Dainippon Ink Chemicals N-870 75EA (phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin)

(C-6) Dainippon Ink Chemicals HP-7241 (tris-phenol type epoxy resin)

[adjustment of (D-1.1) inorganic processing → methacryl silanes processing silica slurry]

By the water slurry of spherical silica particles (Admatechs Co., Ltd. SO-C2, average grain diameter: 500nm) 50g After material is warming up to 70 DEG C, for silica dioxide granule, addition is water-soluble with 10% sodium metasilicate that silica dioxide granule conversion is calculated as 1% Liquid.Hydrochloric acid is added in the slurry makes pH 4, cures 30 minutes, and in turn, pH is maintained 7 ± 1 with hydrochloric acid by lateral dominance, while for Silica dioxide granule is added with aluminium oxide (Al₂O₃) conversion be calculated as 5% 20% sodium aluminate (NaAlO₂) aqueous solution.Later, add Enter 20% sodium hydroxide water bath shampoo, pH is adjusted to 7, is cured 30 minutes.Later, slurry is filtered washing with filter press, Vacuum drying obtains the solids of the silica dioxide granule covered with the hydrous oxide of the hydrous oxide of silicon and aluminium.It obtains It is evenly dispersed to have the silica dioxide granule 50g covered using the hydrous oxide of silicon obtained as described above, as solvent The dioxy of PMA48g and silane coupling agent (Shin-Etsu Chemial Co., Ltd KBM-503) 2g with methacrylic acid group SiClx solvent disperses product.

[adjustment of (D-1.2) inorganic processing → methacryl silanes processing barium sulfate slurry]

After the water slurry of barium sulfate particle (Sakai Chemical Industry Co., Ltd.'s settleability barium 100) 50g is warming up to 70 DEG C, For silica dioxide granule, addition is calculated as 1% 10% sodium silicate aqueous solution with silica dioxide granule conversion.Add in the slurry Entering hydrochloric acid makes pH 4, cures 30 minutes, in turn, pH is maintained 7 ± 1 with hydrochloric acid by lateral dominance, while adding for silica dioxide granule It is subject to aluminium oxide (Al₂O₃) conversion be calculated as 5% 20% sodium aluminate (NaAlO₂) aqueous solution.Later, 20% sodium hydroxide water is added PH is adjusted to 7, cured 30 minutes by bath foam.Later, slurry is filtered washing with filter press, is dried in vacuo, obtains using silicon Hydrous oxide and aluminium hydrous oxide covering barium sulfate particle solids.It obtains evenly dispersed having as described above The barium sulfate particle 50g covered using the hydrous oxide of silicon that ground obtains, as solvent PMA48g and there is methacrylic acid The silica solvent of silane coupling agent (Shin-Etsu Chemial Co., Ltd KBM-503) 2g of base disperses product.

[adjustment of (D-1.3) methacryl silanes processing silica slurry]

Obtain it is evenly dispersed have spherical silica particles (Admatechs Co., Ltd. SO-C2, average grain diameter: 500nm) 50g, the PMA48g as solvent and (the SHIN-ETSU HANTOTAI's chemical industry strain formula meeting of the silane coupling agent with methacrylic acid group Society KBM-503) 2g silica solvent disperse product.

[adjustment of (D-1.4) acrylic silane processing silica slurry]

Obtain it is evenly dispersed have spherical silica particles (Admatechs Co., Ltd. SO-C2, average grain diameter: 500nm) 50g, the PMA48g as solvent and (the Shin-Etsu Chemial Co., Ltd's system of the silane coupling agent with acrylic KBM-5103) the silica solvent of 2g disperses product.

[adjustment of (D-1.5) vinyl silanes processing silica slurry]

Obtain it is evenly dispersed have spherical silica particles (Admatechs Co., Ltd. SO-C2, average grain diameter: 500nm) 50g, the PMA48g as solvent and (the Shin-Etsu Chemial Co., Ltd's system of the silane coupling agent with vinyl KBM-1003) the silica solvent of 2g disperses product.

[adjustment of (D-1.6) inorganic processing → methacryl silanes processing silica slurry]

By spherical silica particles (Denka Company Limited SFP-20M, average grain diameter: 400nm) 50g Water slurry be warming up to 70 DEG C after, for silica dioxide granule, addition is calculated as 1% 10% silicic acid with silica dioxide granule conversion Sodium water solution.Hydrochloric acid is added in the slurry makes pH 4, cures 30 minutes, and in turn, pH is maintained 7 ± 1 with hydrochloric acid by lateral dominance, While adding silica dioxide granule with aluminium oxide (Al₂O₃) conversion be calculated as 5% 20% sodium aluminate (NaAlO₂) aqueous solution.It Afterwards, 20% sodium hydroxide water bath shampoo is added, pH is adjusted to 7, is cured 30 minutes.Later, slurry is filtered with filter press Washing, vacuum drying obtain the solids of the silica dioxide granule covered with the hydrous oxide of the hydrous oxide of silicon and aluminium. Obtain evenly dispersed having the silica dioxide granule 50g covered using the hydrous oxide of silicon obtained as described above, as molten The PMA48g's of agent and silane coupling agent (Shin-Etsu Chemial Co., Ltd KBM-503) 2g with methacrylic acid group Silica solvent disperses product.

[adjustment of (D-2.1) inorganic processing → epoxy silane processing silica slurry]

By the water slurry of spherical silica particles (Admatechs Co., Ltd. SO-C2, average grain diameter: 500nm) 50g After material is warming up to 70 DEG C, for silica dioxide granule, addition is water-soluble with 10% sodium metasilicate that silica dioxide granule conversion is calculated as 1% Liquid.Hydrochloric acid is added in the slurry makes pH 4, cures 30 minutes, and in turn, pH is maintained 7 ± 1 with hydrochloric acid by lateral dominance, while for Silica dioxide granule is added with aluminium oxide (A_l2O₃) conversion be calculated as 5% 20% sodium aluminate (NaAlO₂) aqueous solution.Later, add Enter 20% sodium hydroxide water bath shampoo, pH is adjusted to 7, is cured 30 minutes.Later, slurry is filtered washing with filter press, Vacuum drying obtains the solids of the silica dioxide granule covered with the hydrous oxide of the hydrous oxide of silicon and aluminium.It obtains It is evenly dispersed to have the silica dioxide granule 50g covered using the hydrous oxide of silicon obtained as described above, as solvent The silica of PMA48g and silane coupling agent (Shin-Etsu Chemial Co., Ltd KBM-403) 2g with epoxy group are molten Agent disperses product.

[adjustment of (D-2.2) inorganic processing → epoxy silane processing barium sulfate slurry]

After the water slurry of barium sulfate particle (Sakai Chemical Industry Co., Ltd.'s settleability barium 100) 50g is warming up to 70 DEG C, For silica dioxide granule, addition is calculated as 1% 10% sodium silicate aqueous solution with silica dioxide granule conversion.Add in the slurry Entering hydrochloric acid makes pH 4, cures 30 minutes, in turn, pH is maintained 7 ± 1 with hydrochloric acid by lateral dominance, while adding for silica dioxide granule It is subject to aluminium oxide (Al₂O₃) conversion be calculated as 5% 20% sodium aluminate (NaAlO₂) aqueous solution.Later, 20% sodium hydroxide water is added PH is adjusted to 7, cured 30 minutes by bath foam.Later, slurry is filtered washing with filter press, is dried in vacuo, obtains with silicon Hydrous oxide and aluminium hydrous oxide covering barium sulfate particle solids.It obtains evenly dispersed having as described above Barium sulfate particle 50g, the PMA48g as solvent and the silicon with epoxy group that the hydrous oxide using silicon that ground obtains covers The silica solvent of alkane coupling agent (Shin-Etsu Chemial Co., Ltd KBM-403) 2g disperses product.

[adjustment of (D-2.3) epoxy silane processing silica slurry]

Obtain it is evenly dispersed have to spherical silica particles (Admatechs Co., Ltd. SO-C2, average grain diameter: 500nm) 50g, the PMA48g as solvent and (the Shin-Etsu Chemial Co., Ltd's system of the silane coupling agent with epoxy group KBM-403) the silica solvent of 2g disperses product.

[adjustment of (D-2.4) amino processing silica slurry]

Obtain it is evenly dispersed have spherical silica particles (Admatechs Co., Ltd. SO-C2, average grain diameter: 500nm) 50g, the PMA48g as solvent and (the Shin-Etsu Chemial Co., Ltd's system of the silane coupling agent with acrylic KBM-573) the silica solvent of 2g disperses product.

[adjustment of (D-3) silica slurry]

Obtain it is evenly dispersed have spherical silica particles (Admatechs Co., Ltd. SO-C2, average grain diameter: 500nm) the silica solvent of 50g, the PMA48g as solvent and dispersing agent (BYK-111) 2g disperse product.

[adjustment of (D-4) inorganic processing barium sulfate slurry]

After the water slurry of barium sulfate particle (Sakai Chemical Industry Co., Ltd.'s settleability barium 100) 50g is warming up to 70 DEG C, For silica dioxide granule, addition is calculated as 1% 10% sodium silicate aqueous solution with silica dioxide granule conversion.Add in the slurry Entering hydrochloric acid makes pH 4, cures 30 minutes, in turn, pH is maintained 7 ± 1 with hydrochloric acid by lateral dominance, while adding for silica dioxide granule It is subject to aluminium oxide (Al₂O₃) conversion be calculated as 5% 20% sodium aluminate (NaAlO₂) aqueous solution.Later, 20% sodium hydroxide water is added PH is adjusted to 7, cured 30 minutes by bath foam.Later, slurry is filtered washing with filter press, is dried in vacuo, obtains with silicon Hydrous oxide and aluminium hydrous oxide covering barium sulfate particle solids.It obtains evenly dispersed having as described above The barium sulfate particle 50g covered using the hydrous oxide of silicon that ground obtains, as the PMA48g and dispersing agent (BYK- of solvent 111) the silica solvent of 2g disperses product.

[adjustment of (D-5) barium sulfate slurry]

Obtain evenly dispersed having barium sulfate particle (Sakai Chemical Industry Co., Ltd.'s settleability barium 100) 50g, as solvent PMA48g and dispersing agent (BYK-111) 2g barium sulfate solvent disperse product.

Moreover, the curable resin composition of table 1~3 includes ingredient below sometimes.

Nippon Kayaku K. K DPHA (dipentaerythritol hexaacrylate)

NIKKO BICS CO., LTD. CZ-601D (blue colorant)

NIKKO BICS CO., LTD. CZ-309D (yellow colorants)

DICY (dicyandiamide)

(production of dry film)

For the hardening resin composition of each embodiment, each comparative example shown in table 1~3, respectively for each implementation Example, comparative example make hardening resin composition pass through 60~120 DEG C of drying with 10m/ minutes on PET using die coating machine Furnace makes solvent volatilize, to obtain dry film.

(production of standard evaluation substrate)

Using vacuum laminator CVP-300 (Nikko Materials, Inc. system), the dry film that will in the above way obtain It is laminated to test substrate, obtains the laminated body of photosensitive polymer combination.For the laminated body, DXP-3580 (ORC A.B. is used System, ultrahigh pressure mercury lamp DI exposure machine), with Stouffer41 grades of stage exposure meters, in a manner of as 10 grades of solidification series, Implement pattern exposure according to assessment item.After exposure after ten minutes, remove PET film, in 30 DEG C of 1 mass % sodium carbonate Developed in solution with 2 times of developing time of the point that develops (Break Point, most short developing time).It is conveyed later with UV Machine (ORC A.B.'s system, metal halide lamp), with cumulative exposure amount 2000mJ/cm²Be exposed, in heat-circulation type Box furnace with 170 DEG C solidify within 60 minutes, to obtain evaluation substrate.

< glass transition temperature Tg >

On copper clad laminate, forms each hardening resin composition and film thickness is made to become about 40 μm, with the item of 50mm × 3mm The pattern of shape is exposed.Later, implement development, solidification under the same conditions in the production with above-mentioned standard evaluation substrate.

It will be removed by the curing overlay film of evaluation substrate obtained above from copper foil, implementation evaluation.Measurement uses TMA measurement dress It sets (Shimadzu Scisakusho Ltd's control equipment title: TMA6000) and carries out, carry out the evaluation of Tg.For example following institute of evaluation criteria It states.

180 DEG C of ◎ ... or more

Zero ... 170 DEG C more than or lower than 180 DEG C

160 DEG C of △ ... more than or lower than 170 DEG C

× ... it is lower than 160 DEG C

< obdurability evaluates (production for having the copper clad laminate of resin layer) >

Hardening resin composition is formed on copper clad laminate, so that film thickness becomes about 40 μm, with the item of 80mm × 10mm The pattern of shape is exposed.Later, implement development, solidification under the same conditions in the production with above-mentioned standard evaluation substrate.

It will be removed by the curing overlay film of evaluation substrate obtained above from copper foil, implementation evaluation.Measurement uses tension test Machine (Shimadzu Scisakusho Ltd's control equipment title: AGS-G 100N) and carry out, maximum point stress or breaking point are extended Rate is evaluated.Evaluation criteria is as described below.

◎ ... maximum point stress is 80MPa or more or breaking point elongation is 6% or more

Zero ... maximum point stress is 70MPa more than or lower than 80MPa or breaking point elongation is 4% more than or lower than 6%

It more than or lower than 70MPa, breaking point elongation is 2% more than or lower than 4% that △ ... maximum point stress, which is 50MPa,

× ... maximum point stress is lower than 2% lower than 50MPa or breaking point elongation

< warpage >

With CZ-8101B, with 1.0 μm/m of etch-rate²The processed 35 μm of copper clad laminates of condition on form each solidification Property resin combination so that film thickness become about 20 μm, carry out whole face exposure.Later, implementation develops, is solid under the conditions of known Change.

50mm × 50mm will be cut by the curing overlay film of evaluation substrate obtained above, makes curing overlay film under, and It is statically placed in horizontal platform.After standing, the distance from horizontal platform to Cu foil is measured, amount of warpage is measured.

◎ ... is lower than 10mm

Zero ... 10mm is more than or lower than 15mm

△ ... 15mm is more than or lower than 20mm

× ... it is lower than 20mm

The initial closely sealed > of < Low-Profile adaptation-

With CZ-8201B, with 0.5 μm/m of etch-rate²The processed copper foil of condition on formed curable resin combination Object carries out whole face exposure so that film thickness becomes about 20 μm.Later, identical as the evaluation production of substrate of known above-mentioned standard Under conditions of implement development, solidification.Later, Thermocurable adhesive A raldite is formed on hardening resin composition surface (NICHIBAN CO., LTD. system), makes it be adhered to FR-4 substrate, solidify within 6 hours with 80 DEG C.Later, substrate will be evaluated It is cut with the interval 20mm, removes both sides so that Cu foil is wide to become 10mm wide, production evaluation item.For the evaluation item, drawing is used It stretches testing machine (Shimadzu Scisakusho Ltd's control equipment title: AGS-G 100N) and carries out 90 ° of disbonded tests, carry out adaptation Evaluation.Evaluation criteria is as described below.

◎: 6.0N/cm or more

Zero: 5.0N/cm more than or lower than 6.0N/cm

△: 4.0N/cm more than or lower than 5.0N/cm

×: it is lower than 4.0N/cm

Closely sealed > after < Low-Profile adaptation-HAST50 hours

With CZ-8201B, with 0.5 μm/m of etch-rate²The processed copper foil of condition on formed curable resin combination Object carries out whole face exposure so that film thickness becomes about 20 μm.Later, in condition identical with the above-mentioned standard evaluation production of substrate Lower implementation development, solidification.Later, Thermocurable adhesive A raldite is formed on hardening resin composition surface (NICHIBAN CO., LTD. system), makes it be adhered to FR-4 substrate, solidify within 6 hours with 80 DEG C.Later, substrate will be evaluated It is cut with the interval 20mm, removes both sides so that Cu foil is wide to become 10mm wide, production evaluation item.For the evaluation item, with 130 DEG C, 85% carry out 50 hours handle, use cupping machine (Shimadzu Scisakusho Ltd's control equipment title: AGS-G 100N) 90 ° of disbonded tests are carried out, the evaluation of adaptation is carried out.Evaluation criteria is as described below.

◎: 5.0N/cm or more

Zero: 4.0N/cm more than or lower than 5.0N/cm

△: 3.0N/cm more than or lower than 4.0N/cm

×: it is lower than 3.0N/cm

< resolution ratio evaluates >

With CZ-8101B, with 1.0 μm/m of etch-rate²The processed plating copper base of condition on form curable resin Composition is exposed so that film thickness becomes about 20 μm with various patterns of openings.Later, substrate is being evaluated with above-mentioned standard Development is implemented in production under the same conditions, implements solidification under evaluation condition.

Observation is confirmed the generation without halation, lateral erosion, is evaluated by the opening diameter of evaluation substrate obtained above.

Good opening diameter under 60 μm of ◎ ...

Good opening diameter under zero ... 70 μm

Good opening diameter under 80 μm of △ ...

× ... it is unable to get good opening diameter under 80 μm, or can not develop

< HAST patience >

With CZ-8101B, with 1.0 μm/m of etch-rate²The processed comb shape for being formed with L/S=20/20 μm of condition Hardening resin composition is formed on the substrate of pattern, so that film thickness becomes about 20 μm, carries out whole face exposure.Later, with it is upper Development, solidification are implemented in the production for stating standard evaluation substrate under the same conditions.

Connection electrode later implements HAST test under conditions of 130 DEG C, 85%, 5V.

Pass through within ◎: 400 hours

Pass through within zero: 350 hour

Pass through within △: 300 hours

×: it can not pass through within 250 hours

< TCT patience >

With CZ-8101B, with 1.0 μm/m of etch-rate²The processed package substrate of condition on form curable resin Composition carries out SRO80 μm of exposure so that film thickness becomes about 18 μm on Cu on copper packing.Later, base is being evaluated with above-mentioned standard Development, solidification are implemented in the production of plate under the same conditions.Later, carry out plating Au processing, solder projection formed, install Si chip, Obtain 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 curing overlay film.Determinating reference is as described below.

It is without exception in ◎: 1000 circulations

It is cracked in without exception in zero: 800 circulation, 1000 circulations

It is cracked in without exception in △: 600 circulations, 800 circulations

×: it is cracked in 600 circulations

The result as shown in table 1~3 it is found that the hardening resin composition of the embodiment of the present invention 1~20 solidfied material Resistance to anti-thread breakage and insulating reliability, excellent adhesion.In contrast, if the curable resin using the Comparative Examples 1 to 5 combines Object, then adaptation is poor, it is difficult to obtain insulating reliability.

Claims (7)

1. a kind of hardening resin composition, which is characterized in that contain:

(A) carboxylic resin,

(B-1) Photoepolymerizationinitiater initiater,

(C) have the following structure formula epoxy resin and

(D-1) inorganic filler of the surface treatment through photoreactivity.

2. a kind of hardening resin composition, which is characterized in that contain:

(A) carboxylic resin,

(B-2) Photobase generator,

(C) have the following structure formula epoxy resin and

(D-2) inorganic filler of the surface treatment through heat reactivity.

3. hardening resin composition according to claim 1 or 2, wherein the surface treated inorganic filler Average grain diameter is 1.0 μm hereinafter, and maximum particle diameter is 4.0 μm or less.

4. hardening resin composition described in any one of claim 1 to 3, wherein the surface treated nothing The compounding ratio of machine filler is 25~80 mass %.

5. a kind of dry film, which is characterized in that there is resin layer, the resin layer is will be according to any one of claims 1 to 4 Obtained from hardening resin composition is coated on film and dries.

6. a kind of solidfied material, which is characterized in that its be 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.