CN106054522A - Curable resin composition, dry film, cured product and printed circuit board - Google Patents

Curable resin composition, dry film, cured product and printed circuit board Download PDF

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Publication number
CN106054522A
CN106054522A CN201610237701.6A CN201610237701A CN106054522A CN 106054522 A CN106054522 A CN 106054522A CN 201610237701 A CN201610237701 A CN 201610237701A CN 106054522 A CN106054522 A CN 106054522A
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Prior art keywords
resin composition
coupling agent
methyl
resin
hardening resin
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Granted
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CN201610237701.6A
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CN106054522B (en
Inventor
高桥元范
二田完
米元护
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Taiyo Holdings Co Ltd
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Taiyo Ink Mfg Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/282—Applying non-metallic protective coatings for inhibiting the corrosion of the circuit, e.g. for preserving the solderability
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions
    • 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
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials For Photolithography (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)

Abstract

The invention provides a curable resin composition, a dry film, a cured product and a printed circuit board. The curable resin composition can overcome the defects of decreased sensitivity and resolution ratio due to long term saving even if including an oxime ether photo-polymerization initiator. The curable resin composition includes: (A) alkali-soluble resin, (B) an oxime ether photo-polymerization initiator, (C) a coupling agent and (D) solvent.

Description

Hardening resin composition, dry film, solidfied material and printed circuit board (PCB)
Technical field
The present invention relates to hardening resin composition, dry film, solidfied material and printed circuit board (PCB).
Background technology
As the material of the solder mask etc. for forming printed circuit board (PCB), utilize hardening resin composition.As this One of composition of hardening resin composition, uses oxime ester system's Photoepolymerizationinitiater initiater (such as patent documentation 1) all the time.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2011-022328 publication
Summary of the invention
The problem that invention is to be solved
Known: oxime ester system Photoepolymerizationinitiater initiater is by the curable resin requiring that highly sensitive fine material is used Compositions also is able to the composition (such as patent documentation 1) used, on the other hand, comprises the solidification of oxime ester system Photoepolymerizationinitiater initiater The property resin combination light characteristic such as sensitivity, resolution when stored can slowly reduce.Further, since this light characteristic through time Deterioration, it is provided that the hardening resin composition that after long-term preservation, light characteristic is also excellent is difficult.
Therefore, it is an object of the invention to, it is provided that be not easy to occur because of for a long time even if comprising oxime ester system Photoepolymerizationinitiater initiater Preserve and cause hardening resin composition that the light characteristic such as sensitivity, resolution reduces, there is the tree obtained by said composition The solidfied material of the resin bed of the dry film of lipid layer, said composition or this dry film and possess the printed circuit board (PCB) of this solidfied material.
For solving the scheme of problem
The present inventor etc. conduct in-depth research in view of the foregoing, found that: gather by being applied in combination oxime ester system light Close initiator and coupling agent, it is possible to solve the problems referred to above, thus complete the present invention.
That is, the hardening resin composition of the present invention is characterised by, it comprises (A) alkali soluble resins, (B) oxime ester system light Polymerization initiator, (C) coupling agent and (D) solvent.
The dry film of the present invention is characterised by, its have by said curing property resin combination on thin film coated and dried And the resin bed obtained.
The solidfied material of the present invention is characterised by, it is by said curing property resin combination or the resin bed of aforementioned dry film Solidify and obtain.
The printed circuit board (PCB) of the present invention is characterised by, it possesses said curing thing.
The store method of the present invention is characterised by, it is the guarantor of the compositions containing (B) oxime ester system Photoepolymerizationinitiater initiater Deposit method, compounded with (C) coupling agent in foregoing.
The effect of invention
Even if comprise oxime ester system Photoepolymerizationinitiater initiater be not easy to occur leading because of long-term preservation in accordance with the invention it is possible to provide Cause hardening resin composition that the light characteristic such as sensitivity, resolution reduces, there is the dry of the resin bed that obtained by said composition The solidfied material of the resin bed of film, said composition or this dry film and possess the printed circuit board (PCB) of this solidfied material.
Detailed description of the invention
The hardening resin composition of the present invention is characterised by, it comprises: (A) alkali soluble resins, (B) oxime ester system light gather Close initiator, (C) coupling agent and (D) solvent.
About (D) solvent, it is known that: for the resin combination used in the solder mask that printed circuit board (PCB) is used etc., one For as, compounding solvent is as diluent, and especially extensively application has the compound of ester bond as solvent.The present inventor etc. send out Now: especially in the presence of this esters solvent, oxime ester system Photoepolymerizationinitiater initiater gradually inactivates, after significantly causing long-term preservation Sensitivity, the reduction of the light characteristic such as resolution.According to the present invention, by compounding (C) coupling agent, become to be difficult to that light characteristic occurs Reduction, and all can obtain the hardening resin composition that light characteristic is excellent in the case of no matter using which kind of solvent species.
It addition, as (D) solvent, in the case of using ether solvent, be less susceptible to appearance and cause light because of long-term preservation The reduction of characteristic, therefore preferably.
Mix as epoxy resin and the esters solvent of Thermocurable composition or the mixed solvent that comprises esters solvent and send out The product of raw liquefaction is sold in a large number, but according to the present invention, even if in the case of containing this epoxy resin, it is also possible to obtain It is difficult to the hardening resin composition occurring causing light characteristic to reduce because of long-term preservation.
By the hardening resin composition of the present invention is solidified, it is also possible to obtain resistance to gold-plated property, acid resistance and alkali resistance Excellent solidfied material.
The hardening resin composition of the present invention can preserve with one-pack type form, it is also possible to the above shape of two-component-type Formula preserves.In the case of preserving with the above form of two-component-type, for the separation method of each composition, there is no particular limitation, oxime It is any that ester system Photoepolymerizationinitiater initiater can be contained in the 1st composition solution (host), the 2nd composition solution (firming agent) Person.For example, it is possible to be divided into the 1st composition solution (host) comprising alkali soluble resins and comprise oxime ester system Photoepolymerizationinitiater initiater 2nd composition solution (firming agent).In the case of preserving for a long time with the above form of two-component-type, preferably oxime ester system light gathers Close initiator and coupling agent preserves in the same solution.With one-pack type form preserve in the case of, preferably with The mode that will not carry out curing reaction etc. preserves at low temperatures.
Hereinafter, the composition contained for the hardening resin composition of the present invention is described in detail.
[(A) alkali soluble resins]
As (A) alkali soluble resins, it is preferably used containing carboxy resin or the resin Han phenolic hydroxyl group.Especially from developability side Face considers, more preferably uses containing carboxy resin.
As containing carboxy resin, especially as carrying out the photosensitive composite of alkali development, from photo-curable, resistance to developability From the standpoint of, more preferably molecule has ethylenical unsaturated double bonds containing carboxyl photoresist.And, this unsaturated double-bond Preferably originate from acrylic or methacrylic acid or their derivant.
As the concrete example containing carboxy resin, preferably enumerate the compound (oligomer and polymer) being exemplified below.
(1) by the unsaturated carboxylic acids such as (methyl) acrylic acid and styrene, α-methyl styrene, (methyl) acrylic acid lower The compound copolymerization containing unsaturated group such as Arrcostab, isobutene. and obtain containing carboxy resin.
(2) by aliphatic diisocyanate, Branched fatty (cyclo) aliphatic diisocyanates, ester ring type diisocyanate, aromatic series The diisocyanate such as diisocyanate and the carboxylic diol compound such as dihydromethyl propionic acid, dimethylolpropionic acid and poly-carbonic acid Ester system polyhydric alcohol, polyethers system polyhydric alcohol, polyester-based polyols, polyolefin polyhydric alcohol, acrylic polyol, bisphenol-A system ring Diatomic alcohol compounds such as oxygen alkane addition product dihydroxylic alcohols, the compound with phenolic hydroxyl group and alcohol hydroxyl group and having as required The sudden reaction of the compound of 1 alcohol hydroxyl group and obtain containing carboxyl polyurethane resin.
(3) by 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 fat, bisphenol-s epoxy resin, di-toluene phenol-type epoxy resin, united phenol-type epoxy resin Base) acrylate or the anhydride modified thing of its part, carboxylic diol compound and the sudden reaction of diatomic alcohol compounds and obtain Arrive containing carboxyl photonasty polyurethane resin.
(4) in the synthesis of aforementioned (2) or (3) resin, add in (methyl) acrylic acid hydroxy alkyl ester equimolecular and there is 1 Hydroxyl and the compound of more than 1 (methyl) acryloyl group and carried out end (methyl) acrylated and obtained containing carboxyl sense Photosensitiveness polyurethane resin.
(5) in the synthesis of aforementioned (2) or (3) resin, isophorone diisocyanate and tetramethylolmethane three propylene are added The reaction with same mole thing equimolecular of acid esters has 1 NCO and the compound of more than 1 (methyl) acryloyl group and Carried out end (methyl) acrylated and obtain containing carboxyl photonasty polyurethane resin.
(6) by make 2 officials can or 2 officials can react with (methyl) acrylic acid by polyfunctional epoxy resin above, make side chain deposit Hydroxyl and dibasic acid anhydride addition and obtain containing carboxyl photoresist.Herein, epoxy resin is preferably solid-state.Hereinafter, It is referred to as carboxyl acid modified epoxy acrylate.It should be noted that as the concrete example of polyfunctional epoxy resin, such as can lift Go out the 0039th section of shown content of Japanese Unexamined Patent Publication 2011-213828 publication.
(7) make, with epoxychloropropane, the polyfunctional epoxy resin that the further epoxidation of hydroxyl of 2 functional epoxy resins obtains React with (methyl) acrylic acid, and make the hydroxyl of generation and dibasic acid anhydride addition and obtain containing carboxyl photoresist.Herein, Epoxy resin is preferably solid-state.
(8) make 2 officials can the dicarboxylic acids such as oxetane resins and adipic acid, phthalic acid, hexahydrophthalic acid anti- Should, and make the dibasic acid anhydrides such as the primary hydroxyl of generation and phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride Addition and obtain containing carboxyl polyester resin.
(9) bisphenol-A, Bisphenol F, bisphenol S, novolak phenolics, poly(4-hydroxystyrene), naphthols and aldehydes are made 1 molecules such as the condensation substance of condensation substance, dihydroxy naphthlene and aldehydes have compound and oxirane, the epoxy of multiple phenolic hydroxyl group The product that the alkylene oxides such as propane react and obtain and the monocarboxylic acid containing unsaturated group react, and the reaction of gained are produced Thing react with multi-anhydride and obtain containing carboxyl photoresist.
(10) by making the compound in 1 molecule with multiple phenolic hydroxyl group and the ring such as ethylene carbonate, propylene carbonate The product that shape carbonate products reacts and obtains and the monocarboxylic acid containing unsaturated group react, and by the reaction of gained Product react with multi-anhydride and obtain containing carboxyl photoresist.
(11) have by making 1 molecule has in 1 molecules such as the epoxide of multiple epoxy radicals and p-hydroxyphenylethanol There is the monocarboxylic acid containing unsaturated group such as the compound of at least 1 alcohol hydroxyl group and 1 phenolic hydroxyl group and (methyl) acrylic acid anti- Should, and make alcohol hydroxyl group and maleic anhydride, tetrabydrophthalic anhydride, trimellitic anhydride, the PMA of gained product The multi-anhydride such as acid anhydride, adipic anhydride reaction and obtain containing carboxyl photoresist.
(12) make the resin of above-mentioned (1)～(11) further with (methyl) glycidyl acrylate, (methyl) acrylic acid Alpha-Methyl ethylene oxidic ester equimolecular has 1 epoxy radicals and the compound addition of more than 1 (methyl) acryloyl group and obtains Arrive containing carboxyl photoresist.
It should be noted that in this specification, (methyl) acrylate refer to be referred to as acrylate, methacrylate and The term of their mixture, the statement similar for other is also same.
In the hardening resin composition of the present invention, the resin combined containing carboxy resin the most above-mentioned (6) and (12), Specifically, the most carboxyl acid modified epoxy acrylate with there is epoxy radicals and the chemical combination of free-radical polymerised unsaturated group Thing reacts and obtains (A1) photoresist Han carboxyl.
As described above containing carboxy resin, there is on the side chain of trunk polymer multiple carboxyl, therefore, it is possible to utilize dilute Aqueous alkali develops.
It addition, the above-mentioned acid number containing carboxy resin be preferably 20～200mgKOH/g scope, more preferably 40～ The scope of 150mgKOH/g.When acid number containing carboxy resin is more than 20mgKOH/g, the adaptation of film becomes good, and alkali shows Shadow becomes good.On the other hand, when acid number is below 200mgKOH/g, it is possible to exposure portion molten that suppression is caused by developer solution Solve, therefore, it is possible to suppression line will not carefully to more than necessity, or according to circumstances exposure portion as broad as longly with unexposed portion by developing Liquid dissolves to be peeled off, it is possible to the protective layer of depicting pattern shape well.
It addition, the above-mentioned weight average molecular weight containing carboxy resin is different because of resin matrix, preferably 2000～150000, enter One step is preferably the scope of 5000～100000.When weight average molecular weight is more than 2000, non-adhesion behavior is good, the film after exposure Moisture-proof good, and film minimizing when can suppress development, suppress the reduction of resolution.On the other hand, weight average molecular weight is When less than 150000, developability is good, and storage-stable is the most excellent.
Can be used alone a kind containing carboxy resin or combine two or more use.The hardening resin composition of the present invention contains When having two or more to contain carboxy resin, such as, preferably comprise above-mentioned (A1) photoresist Han carboxyl.
It addition, for the hardening resin composition of the present invention, in other embodiments, as containing carboxy resin, also Can containing above-mentioned (A1) containing carboxyl photoresist and do not have alicyclic skeleton containing carboxy acrylic analog copolymer.As Do not have alicyclic skeleton containing carboxy acrylic analog copolymer, can enumerate: lifted as the above-mentioned concrete example containing carboxy resin (1) the styrene copolymerized type gone out containing carboxy resin.As compounding do not have alicyclic skeleton containing carboxy acrylic class copolymerization Compounding rate during thing, will contain carboxy resin entirety when being set to 100 mass parts, for example, 10～95 mass parts, be preferably 10～80 Mass parts.
As containing phenolic hydroxyl group resin, as long as main chain or side chain have phenolic hydroxyl group, the hydroxyl that is i.e. bonded with phenyl ring just It is not particularly limited.It is preferably the compound in 1 molecule with more than 2 phenolic hydroxyl group.As 1 molecule has more than 2 The compound of phenolic hydroxyl group, can enumerate: catechol, resorcinol, hydroquinone, orcin, naphthalene glycol, tert-butyl o benzene two Phenol, tertiary butylated hydroquinone, pyrogallol, phloroglucinol, bisphenol-A, Bisphenol F, bisphenol S, xenol, di-cresols, novolaks Type phenolic resin, phenolic varnish type alkyl phenolic resin, bisphenol A novolac resin, dicyclopentadiene type phenolic resin, new phenol (Xylok) type phenolic resin, terpene modified phenolic resin, polystyrene phenols, phenols and the aromatic aldehyde with phenolic hydroxyl group The condensation substance of class, 1-naphthols or beta naphthal and the condensation substance etc. of aromatic series aldehydes, but it is not limited to these.Containing phenolic hydroxyl group Compound can be used alone a kind or combines two or more use.
(A) the compounding amount of alkali soluble resins is relative to hardening resin composition, in terms of solid constituent conversion, for example, 10 ～95 mass %.It is preferably 10～80 mass %.
[(B) oxime ester system Photoepolymerizationinitiater initiater]
As (B) oxime ester system Photoepolymerizationinitiater initiater, preferably comprise the oxime of structure division shown in described below, logical formula (I) Ester system Photoepolymerizationinitiater initiater and then more preferably there is the oxime ester system Photoepolymerizationinitiater initiater of carbazole structure.As aforementioned, there is carbazole The oxime ester system Photoepolymerizationinitiater initiater of structure, it is possible to use dimeric oxime ester system Photoepolymerizationinitiater initiater.
In logical formula (I), R1Represent hydrogen atom, phenyl, alkyl, cycloalkyl, alkanoyl or benzoyl.R2Represent phenyl, alkane Base, cycloalkyl, alkanoyl or benzoyl.
R1And R2Shown phenyl can have substituent group, as this substituent group, such as, can enumerate: carbon number 1～6 Alkyl, phenyl, halogen atom etc..
As R1And R2Shown alkyl, the preferably alkyl of carbon number 1～20, can comprise more than 1 oxygen in alkyl chain Atom.Alternatively, it is also possible to replace with more than 1 hydroxyl.
As R1And R2Shown cycloalkyl, the preferably cycloalkyl of carbon number 5～8.
As R1And R2Shown alkanoyl, the preferably alkanoyl of carbon number 2～20.
As R1And R2Shown benzoyl, can have substituent group, as this substituent group, such as, can enumerate: carbon atom Number is alkyl, the phenyl etc. of 1～6.
As comprising the oxime ester system Photoepolymerizationinitiater initiater of structure division shown in logical formula (I), can enumerate: { 1-[4-(benzene sulfur Base)-2-(O-benzoyl oxime)] 1,2-acetyl caproyl, the compound shown in following formula (I-1), 2-(Acetyloxyimino methyl) Thioxanthene-9-one and 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-1-(O-acetyl oxime) ethyl ketone and under State the compound etc. shown in formula (I-2) and there is the oxime ester based compound etc. of carbazole skelton.
In formula (I-2), R11With the R in logical formula (I)1Synonym, R12And R14Separately with the R in logical formula (I)2With Justice.R13Represent hydrogen atom, halogen atom, the alkyl of carbon number 1～12, cyclopenta, cyclohexyl, phenyl, benzyl, benzoyl Base, the alkanoyl of carbon number 2～12, the alkoxy carbonyl of carbon number 2～12 (constitute the carbon number of the alkyl of alkoxyl When being more than 2, alkyl can replace with more than 1 hydroxyl, it is also possible to has more than 1 oxygen atom at alkyl middle-of-chain) or Phenoxy group carboxyl.
This oxime ester system Photoepolymerizationinitiater initiater can improve the present invention's due to such as exposure relative to direct imaging The sensitivity of hardening resin composition, excellent in resolution, therefore preferably.It addition, oxime ester system Photoepolymerizationinitiater initiater can also be two Aggressiveness.
As dimeric oxime ester system Photoepolymerizationinitiater initiater, the compound shown in the most following formula (I-3).
In formula (I-3), R23Represent hydrogen atom, alkyl, alkoxyl, phenyl, naphthyl.R21、R22Represent hydrogen independently of one another Atom, alkyl, alkoxyl, halogen group, phenyl, naphthyl, anthryl, pyridine radicals, benzofuranyl, benzothienyl.
Ar represents singly-bound or the alkylidene of carbon number 1～10, ethenylidene, phenylene, biphenylene, pyridylidene (pyridylene group), naphthylene, anthrylene, sub-thienyl, furylidene (furylene group), 2,5-pyrroles- Diyl, 4,4 '-stilbene-diyl, 4,2 '-styrene-diyl.
N represents the integer of 0～1.
As R23Shown alkyl, the preferably alkyl of carbon number 1～17.
As R23Shown alkoxyl, the preferably alkoxyl of carbon number 1～8.
R23Shown phenyl can have substituent group, as this substituent group, such as, can enumerate: alkyl (preferably carbon number Be 1～17), alkoxyl (preferably carbon number is 1～8), amino, alkyl amino (the preferably carbon number of alkyl is 1～8) or Dialkyl amido (the preferably carbon number of alkyl is 1～8) etc..
R23Shown naphthyl can have substituent group, as this substituent group, can enumerate: with R23Shown phenyl can have The group that the above-mentioned substituent group that has is identical.
As R21And R22Shown alkyl, the preferably alkyl of carbon number 1～17.
As R21And R22Shown alkoxyl, the preferably alkoxyl of carbon number 1～8.
R21And R22Shown phenyl can have substituent group, as this substituent group, such as, can enumerate: (preferably carbon is former for alkyl Subnumber is 1～17), alkoxyl (preferably carbon number is 1～8), amino, alkyl amino (preferably the carbon number of alkyl be 1～ 8) or dialkyl amido (the preferably carbon number of alkyl is 1～8) etc..
R21And R22Shown naphthyl can have substituent group, as this substituent group, can enumerate: with R21And R22Shown benzene The group that above-mentioned substituent group that base can have is identical.
And then, in formula (I-3), R21、R23It is each independently methyl or ethyl, R22For methyl or phenyl, Ar is single Key, phenylene, naphthylene or sub-thienyl, n is preferably 0.
As the compound shown in formula (I-3), the most following compound.
For (B) oxime ester system Photoepolymerizationinitiater initiater, as commercially available product, can enumerate: the CGI-of BASF JAPAN LTD. 325, IRGACURE OXE01 (1-[4-(thiophenyl)-2-(O-benzoyl oxime)] 1,2-acetyl caproyl), IRGACURE OXE02 (1- [9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-1-(O-acetyl oxime) ethyl ketone)；ADEKA CORPORATION N-1919, NCI-831 of system；The TR-PBG-304 of Changzhou Tronly New Electronic Materials Co., Ltd.；Japan of Co., Ltd. chemistry The TOE-04-A3 etc. that industry is made.
(B) oxime ester system Photoepolymerizationinitiater initiater can be used alone a kind or combines two or more use.(B) oxime ester system photopolymerization The compounding amount of initiator is relative to (A) alkali soluble resins 100 mass parts, preferably 0.01～20 mass parts, more preferably 0.01 ～the ratio of 10 mass parts, more preferably 0.1～5.0.(B) the compounding amount of Photoepolymerizationinitiater initiater is more than 0.01 mass parts Time, the photo-curable on copper becomes good, and the coating characteristics such as film is not easily stripped, chemical proofing become good.Another Aspect, when the compounding amount of (B) Photoepolymerizationinitiater initiater is below 20 mass parts, the light of (B) Photoepolymerizationinitiater initiater absorbs and becomes good, Deep curable improves.
The hardening resin composition of the present invention can contain other Photoepolymerizationinitiater initiater.Cause as other photopolymerization Agent, such as, can enumerate: benzophenone series, 1-Phenylethanone. system, aminoacetophenone system, benzoin ether system, benzil ketals system, acyl group oxygen Change the known usual compounds such as phosphine system, oxime ether system, titanocenes system.
In order to improve the sensitivity to exposure, preferred compositions uses the alpha-amido benzene comprising structure division shown in logical formula (II) Ethyl ketone system Photoepolymerizationinitiater initiater etc..
In logical formula (II), R3And R4Separately represent the alkyl or aryl alkyl of carbon number 1～12, R5And R6Point Represent hydrogen atom or the alkyl of carbon number 1～6 the most independently, or both can also combine formation cyclic alkyl ether.
As comprising the alpha-aminoacetophenone system Photoepolymerizationinitiater initiater of structure division shown in logical formula (II), can enumerate: 2-first Base-1-[4-(methyl sulfur) phenyl]-2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-fourth Alkane-1-ketone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone, N, N- Dimethylamino benzoylformaldoxime etc..
[(C) coupling agent]
As (C) coupling agent, it is possible to use silane series coupling agent, titanium system coupling agent, zirconium system coupling agent, aluminum system coupling agent Deng.Wherein, preferred silane series coupling agent.The organic reaction group being had as coupling agent, can enumerate: vinyl, acryloyl The ethylenically unsaturated groups such as base (unsaturated alkyl), alkoxyl, epoxy radicals, amino, sulfydryl, NCO, imidazole radicals, thiazole Base, triazolyl etc., wherein, be preferably selected from ethylenically unsaturated group (unsaturated alkyl), epoxy radicals, alkoxyl and sulfydryl extremely Few a kind.
As silane series coupling agent, can enumerate: trimethoxy silane, triethoxysilane, tetramethoxy-silicane, four ethoxies Base silane, tetrapropoxysilane, MTMS, ethyl trimethoxy silane, MTES, ethyl three Methoxy silane, dimethyldimethoxysil,ne, diethyldiethoxysilane, vinyltrimethoxy silane, vinyl three Ethoxysilane, vinyl three ('beta '-methoxy ethyoxyl) silane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, Gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, phenyltrimethoxysila,e, phenyl triethoxy Silane, phenyl tripropoxy silane, dimethoxydiphenylsilane, diphenyl diethoxy silane, γ-glycidoxypropyl group Trimethoxy silane, γ-glycidoxypropyl diethoxy silane, γ-glycidoxypropyl group triethoxysilane, γ-methacryloyloxypropyl methyl dimethoxysilane, γ-methacryloxypropyl trimethoxy silane, γ-first Base acryloxypropyl diethoxy silane, γ-methacryloxypropyl, N-β-(amino Ethyl) gamma-amino hydroxypropyl methyl dimethoxysilane, N-β-(amino-ethyl) gamma-amino propyl trimethoxy silicane, N-β- (amino-ethyl) γ aminopropyltriethoxy silane, N-phenyl-gamma-amino propyl trimethoxy silicane etc..
As titanium system coupling agent, can enumerate: tetraethoxy titanate esters, tetra isopropyl titanate, tetra-n-butyl titanate esters etc. Titanium alkoxides class, butyl titanium dimer, four (2-ethylhexyl) titanate esters, multi-hydroxy stearic acid titanium, four titanium acetylacetones, poly-acetyl Acetone titanium, ethohexadiol titanium, titanium ethyl acetoacetic ester, lactic acid titanium, triethanolamine titanium etc..
As zirconium system and aluminum system coupling agent, it is possible to use the compound corresponding with titanium sub-group compound.
(C) coupling agent can be used alone a kind or combines two or more use.(C) the compounding amount of coupling agent is relative to solidification Property resin combination total amount (comprising solvent), preferably 0.02～2.5 mass %, more preferably 0.06～1.3 mass %.(C) When the compounding of coupling agent is more than 0.02 mass %, excellent storage stability, when being below 2.5 mass %, developability is stable, therefore Preferably.
[(D) solvent]
As (D) solvent, organic solvent is preferably used, such as, can enumerate: butanone, Ketohexamethylene, methyl butyl ketone, methyl tert-butyl The ketones solvents such as ketone；The aromatic hydrocarbon solvents such as toluene, dimethylbenzene, durol；The molten fibre of cellosolve, methyl cellosolve, butyl Agent, carbitol, methyl carbitol, butyl carbitol, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol The ether solvents such as monomethyl ether, dipropylene glycol monomethyl ether (DPM), dipropylene glycol diethyl ether, Tripropylene glycol monomethyl Ether；Ethyl acetate, Butyl acetate, isobutyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl Carbitol acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetas, dipropyl two The esters solvents such as alcohol methyl ether acetate, propylene carbonate；Ethanol, propanol, 2-methoxypropanol, n-butyl alcohol, isobutanol, isoamyl The alcohols solvents such as alcohol, ethylene glycol, propylene glycol；The Aliphatic hydrocarbon solvents such as octane, decane；Petroleum ether, Petroleum, hydrogenation stone brain The petroleum solvents such as oil, solvent naphtha etc. and N,N-dimethylformamide (DMF), tetrachloroethylene, Oleum Terebinthinae etc..It addition, The SWASOL 1000 of Maruzen Petrochemical Co., Ltd., SWASOL 1500 can be used；Standard Sekiyu Osaka Solvesso100, Solvesso 150 of Hatsubaisho CO., LTD.；Three Solvent# being total to KCC 100、Solvent#150；SHELLSOL A100, the SHELLSOL A150 of Shell Chemicals Japan Ltd.；Go out The organic solvents such as the Ipzole of Guang Xingchan Co., Ltd. 100, Ipzole 150.(D) solvent can be used alone a kind Or combine two or more use.There is no particular limitation in the combination of solvent during for combining two or more, such as, can enumerate: comprise Ether solvent and the solvent of esters solvent, comprise the solvent etc. of aromatic hydrocarbon solvent and esters solvent.
In the present invention, (D) solvent is as described above, it is preferred to ether solvent, even if it addition, in the case of using esters solvent, It also is able to the hardening resin composition obtaining being difficult to occur causing light characteristic to reduce because of long-term preservation.
The application target of solvent is, is dissolved by aforementioned (A) alkali soluble resins, dilutes, thus makes liquid and be coated, Then it is made temporarily to be dried and make film, so that contact exposure is possibly realized.The consumption of solvent be not limited to specifically than Example, can be appropriately configured according to the coating process etc. selected.
(curable composition)
For the hardening resin composition of the present invention, can be solid containing Thermocurable composition and light as curable composition The property changed composition.
Thermocurable composition contains to give thermostability to compositions, particularly preferably uses in molecule and has 2 Individual above cyclic ether group becomes with at least any of Thermocurable in cyclic thioether base (the most ring-type (sulfur) ether) Point.When using Thermocurable composition, not only confirm thermostability and improve, further acknowledge that the adaptation with substrate improves.
This molecule has 2 Thermocurable compositions with upper annular (sulfur) ether as molecule in there are more than 23 yuan Any one in ring, 4 rings or the cyclic ether group of 5 rings or cyclic thioether base or the compound of any two groups, such as may be used Enumerate: intramolecular at least has the compound of more than 2 epoxy radicals, i.e. multi-functional epoxy compound；Intramolecular at least has 2 The compound of above oxetanyl, the most multifunctional oxetane compound；Intramolecular has the change of more than 2 thioether groups Compound, the most multifunctional episulfide resin etc..
As multi-functional epoxy compound, such as, can enumerate: the Epikote828 of Mitsubishi chemical Co., Ltd, Epikote 834, Epikote 1001, Epikote 1004, EPICLON840, EPICLON 850 of Dainippon Ink Chemicals, EPICLON 1050, EPICLON 2055, the EPOTOHTO YD-011 of Toto Kasei KK, YD-013, YD-127, D.E.R.317, D.E.R.331, D.E.R.661, D.E.R.664 of YD-128, Dow Chemical Company, Sumiepoxy ESA-011, ESA-014, ELA-115, ELA-128 of Sumitomo Chemical Co., Ltd., Asahi A.E.R.330, A.E.R.331, A.E.R.661, A.E.R.664 etc. (being trade name) of Kasei Corporation are double Phenol A type epoxy resin；The Epikote YL903 of Mitsubishi chemical Co., Ltd, the EPICLON 152 of Dainippon Ink Chemicals, EPICLON 165, EPOTOHTO YDB-400, YDB-500 of Toto Kasei KK, Dow Chemical Company SumiepoxyESB-400, ESB-700 of D.E.R.542, the Sumitomo Chemical Co., Ltd. of system, Asahi A.E.R.711, A.E.R.714 etc. (the being trade name) brominated epoxy resin of Kasei Corporation；Mitsubishi Chemical's strain The Epikote 152 of formula commercial firm, Epikote 154, the D.E.N.431 of Dow Chemical Company, D.E.N.438, the EPICLON N-730 of Dainippon Ink Chemicals, EPICLON N-770, EPICLON N-865, Dongdu chemical conversion strain EPPN-201, EOCN-of EPOTOHTO YDCN-701, YDCN-704 of formula commercial firm, Nippon Kayaku Co., Ltd. The SumiepoxyESCN-of 1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Chemical Co., Ltd. 195X, ESCN-220, A.E.R.ECN-235, ECN-299 etc. (being trade name) of Asahi Kasei Corporation Phenolic resin varnish type epoxy resin；The EPICLON 830 of Dainippon Ink Chemicals, the Epikote of Mitsubishi chemical Co., Ltd 807, (the being trade name) Bisphenol F such as EPOTOHTO YDF-170, YDF-175, YDF-2004 of Toto Kasei KK Type epoxy resin；EPOTOHTO ST-2004, ST-2007, ST-3000 (trade name) of Toto Kasei KK etc. hydrogenate Bisphenol A type epoxy resin；The Epikote 604 of Mitsubishi chemical Co., Ltd, the EPOTOHTO of Toto Kasei KK (the being trade name) glycidyl amines such as the SumiepoxyELM-120 of YH-434, Sumitomo Chemical Co., Ltd. Type epoxy resin；Hydantoin type epoxy resin；DAICEL CHEMICAL INDUSTRIES, the CELLOXIDE of LTD. 2021 grade (being trade name) alicyclic epoxy resins；The YL-933 of Mitsubishi chemical Co., Ltd, Dow Chemical T.E.N., EPPN-501, EPPN-502 etc. (being trade name) the trihydroxy benzene methylmethane type epoxy resin of Company；Three Di-toluene phenolic or the xenols such as YL-6056, YX-4000, YL-6121 (being trade name) of Pedicellus et Pericarpium Trapae KCC Type epoxy resin or their mixture；EBPS-200, the ADEKA CORPORATION of Nippon Kayaku Co., Ltd. The bisphenol-s epoxy resins such as the EPX-30, the EXA-1514 (trade name) of Dainippon Ink Chemicals of system；Mitsubishi chemical Co., Ltd The bisphenol A novolac type epoxy resin such as the Epikote157S (trade name) of system；The Epikote of Mitsubishi chemical Co., Ltd YL-931 etc. (being trade name) four hydroxy phenyl ethane type epoxy resin；NISSAN CHEMICAL INDUSTRIES, LTD. system (being trade name) the hetero ring type epoxy resin such as TEPIC；The O-phthalics such as the BLEMMER DGT of NOF CORPORATION Acid 2-glycidyl ester resin；The four glycidyl group xylenol ethane resin such as the ZX-1063 of Toto Kasei KK； ESN-190, ESN-360 of Nippon Steel Chemical Co., Ltd., HP-4032, EXA-of Dainippon Ink Chemicals 4750, EXA-4700 etc. are containing Naphthol-based Epoxy Resin；HP-7200, HP-7200H etc. of Dainippon Ink Chemicals have dicyclopentadiene The epoxy resin of skeleton；The glycidyl methacrylate such as CP-50S, CP-50M of NOF CORPORATION copolymerization system ring Epoxy resins；N-cyclohexylmaleimide and the copolymerization epoxy resin of glycidyl methacrylate further；Epoxide modified Polybutadiene rubber derivant (such as DAICEL CHEMICAL INDUSTRIES, the PB-3600 etc. of LTD.), CTBN is modified Epoxy resin (YR-102, YR-450 etc. of such as Toto Kasei KK) etc., but it is not limited to these.
Multi-functional epoxy compound can be appointing in solid epoxy resin, semisolid epoxy resin, liquid-state epoxy resin One.Solid epoxy resin and semisolid epoxy resin need to be diluted with solvent, as this solvent use esters solvent or The situation of the mixed solvent comprising esters solvent is more, and oxime ester system Photoepolymerizationinitiater initiater significantly inactivates, but according to the present invention, even if Being at least not easy in the case of any one in using solid epoxy resin and semisolid epoxy resin occurs because of long-term preservation And the reduction of the light characteristic caused.In this specification, solid epoxy resin refers to the epoxy resin at 40 DEG C for solid, shaped, and half is solid State epoxy resin refer at 20 DEG C for solid, shaped and at 40 DEG C for the epoxy resin of liquid, liquid-state epoxy resin refers at 20 DEG C It is down the epoxy resin of liquid.The judgement of liquid makes (autonomous portion order in 1989 according to the test of dangerous materials and the dependent part of character No. 1) adnexa the 2nd article " confirmation method of liquid " carry out.
As multifunctional oxetane compound, can enumerate: double [(3-methyl-3-oxetanylmethoxy) first Base] ether, double [(3-ethyl-3-oxetanylmethoxy) methyl] ether, the double [(3-methyl-3-oxetanyl first of 1,4- Epoxide) methyl] benzene, 1,4-double [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, acrylic acid (3-methyl-3-oxa- Tetramethylene. base) methyl ester, acrylic acid (3-ethyl-3-oxetanyl) methyl ester, methacrylic acid (3-methyl-3-oxa-ring fourth Alkyl) methyl ester, methacrylic acid (3-ethyl-3-oxetanyl) methyl ester, their oligomer or copolymer etc. be multifunctional Oxetanes class and oxetanes alcohol and novolac resin, poly-(4-Vinyl phenol), cardo type bisphenols, cup Aromatic hydrocarbons, resorcinol calixarenes (calixresorcinarene) class or silsesquioxane (silsesquioxane) etc. have The etherate etc. of the resin of hydroxyl.Additionally, also can enumerate: have unsaturated monomer and (methyl) acrylic acid of oxetanes ring The copolymer etc. of Arrcostab.
As molecule has the compound of more than 2 cyclic thioether bases, such as, can enumerate: Mitsubishi chemical Co., Ltd's system Bisphenol A-type episulfide resin YL7000 etc..Utilize same synthetic method by nobolak type epoxy tree alternatively, it is also possible to use The oxygen atom of the epoxy radicals of fat replaces with the episulfide resin etc. of sulphur atom.
Thermocurable composition can be used alone a kind or combines two or more use.Molecule has 2 with upper annular The compounding amount of the Thermocurable composition of (sulfur) ether, relative to alkali solubility group 1 equivalent of (A) alkali soluble resins, is preferably set to 0.6～2.8 equivalents, more preferably it is set to the scope of 0.8～2.5 equivalents.By compounding amount is set to above-mentioned scope, it is possible to solidification Thing gives good thermostability.
As photo-curable composition, photopolymerization monomer can be contained.For dividing of being used as photopolymerization monomer Son has the compound of more than 1 ethylenically unsaturated group, such as, can enumerate: (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) Acrylic acid 2-hydroxypropyl acrylate, NVP, acryloyl morpholine (Acryloylmorpholine), methoxyl group TEG (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, Polyethylene Glycol two (methyl) acrylate, N, N-diformazan Base (methyl) acrylamide, N-methylol (methyl) acrylamide, N, N-dimethylaminopropyl (methyl) acrylamide, (first Base) acrylic acid N, N-dimethylamino ethyl ester, (methyl) acrylic acid N, N-dimethylamino propyl ester, tripolycyanamide (methyl) propylene Acid esters, two (methyl) acrylic acid binaryglycol ester, two (methyl) acrylic acid triglycol ester, two (methyl) acrylic acid propylene glycol Ester, two (methyl) acrylic acid dipropylene glycol ester, two (methyl) acrylic acid tripropylene glycol ester, two (methyl) acrylic acid polypropylene glycol Ester, (methyl) acrylate, (methyl) tetrahydrofurfuryl acrylate, (methyl) cyclohexyl acrylate, two (methyl) third Olefin(e) acid glycerin diglycidyl ether ester, three (methyl) acrylic acid T 55 ester, (methyl) isobornyl acrylate, Single (methyl) acrylic acid cyclopentadiene ester or two (methyl) acrylic acid cyclopentadiene ester；Hexanediol, trimethylolpropane, Ji Wusi Polynary (methyl) acrylate of the polyhydric alcohol such as alcohol, double trimethylolpropane, dipentaerythritol, tris(2-hydroxy ethyl)isocyanurate Class；Polyprotic acid and the monoesters of (methyl) hydroxyalkyl acrylates, diester, three esters or its above polyester etc..These photopolymerization Property monomer can be used alone a kind or combine two or more use.
The compounding amount of photopolymerization monomer relative to (A) alkali soluble resins 100 mass parts, the scope of 5～40 mass parts is Suitable.When the compounding amount of photopolymerization monomer is more than 5 mass parts, photo-curable gives effect and becomes better.The opposing party Face, when being below 40 mass parts, the dry to touch of film becomes good.
(inorganic filler)
For the hardening resin composition of the present invention, in order to make the fall of the light characteristic caused because of long-term preservation further Low becoming is difficult to appearance, preferably comprises inorganic filler.It addition, in order to improve the adaptation of solidfied material, mechanical strength, line expand system The characteristics such as number, can be compounded inorganic filler.As this filler, such as, can use: barium sulfate, Barium metatitanate., silica powder, micro- Powdery silicon oxide, silicon dioxide, Talcum, clay, magnesium carbonate, calcium carbonate, aluminium oxide, aluminium hydroxide, mica powder etc. are known usual Filler.Wherein, preferably barium sulfate and silicon dioxide.Inorganic filler can be used alone a kind or combines two or more use.
The compounding amount of inorganic filler is relative to (A) alkali soluble resins 100 mass parts, preferably 10～500 mass parts, more excellent Electing 20～200 mass parts as, the compounding ratio of inorganic filler is 10～during 500 mass parts, and the viscosity of compositions will not become Height, coating is good, it is possible to obtain as solder mask, the solidfied material with excellent specific property, therefore preferably.
(coloring agent)
The hardening resin composition of the present invention can contain coloring agent.As coloring agent, such as can use red, blue, The usual known coloring agent such as green, yellow, white, black, can be any person in pigment, dyestuff, pigment.But, from carrying capacity of environment Reduce and on the impact of human body from the viewpoint of, preferably do not contain halogen.Coloring agent can be used alone a kind or combination 2 kinds Used above.
(other any composition)
In the hardening resin composition of the present invention, hydroquinone, hydroquinone monomethyl ether, tertiary fourth can be compounded the most as required Base catechol, the known usual polymerization inhibitor such as pyrogallol, phenothiazine, fine particle silica, organobentonite, montmorillonite etc. At least any of, imidazoles system in the defoamer such as known usual thickening agent, silicone-based, fluorine system, macromolecular and levelling agent, thiophene Silane coupler, antioxidant, organic filler, photopolymerization sensitizer, light stabilizer, dispersant, the heat cures such as azoles system, triazole system Such known usual additive kind such as catalyst, curing accelerator, fire retardant, flame retardant.
The hardening resin composition of the present invention be suitable to printed circuit board (PCB), the solder mask of flexible printed circuit board, cover layer, The permanent formation of film, the formation of etchant resist such as interlayer insulating films, from the standpoint of light characteristic excellence, be particularly suitable for densification Formation with the printed circuit board (PCB) of high graph thinning.It addition, for patterning method there is no particular limitation, the solidification of the present invention Property resin combination is also suitably for being patterned by laser direct imagings such as h line direct imaging (HDI).The curable of the present invention Resin combination can be also used for printer's ink, ink-jet, photomask make material, printing pull (proof) make material, etc. from The partition wall of daughter display panel (PDP), dielectric pattern, electrode (conductor circuit) pattern, the wiring pattern of electronic unit, conduction The making of the occlusion image etc. such as paste, conducting film, black matrix.
The hardening resin composition of the present invention can become and is coated with on thin film, is dried and the form of dry film that obtains. Even the form of dry film, in the case of solvent also can remain, it is possible to produce the photopolymerization of oxime ester system according to solvent species and cause The inactivation of agent, but according to the present invention, as set forth above, it is possible to obtain being difficult to that the dry film that light characteristic reduces occurs.During dry film, incite somebody to action this The hardening resin composition of invention to adjust to suitable viscosity, passes through comma coater with above-mentioned organic solvent diluting (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), delivery roll coating machine (transfer roll Cater), gravure coater (gravure coater), flush coater etc. in carrier film (supporter), be coated into uniform thickness, Generally it is dried 1～30 minute at a temperature of 50～130 DEG C such that it is able to form dry coating.Spy is not had for coating film thickness Other restriction, generally, with dried film thickness gauge, in 0.1～100 μm, preferably suitably selects in the range of 0.5～50 μm.
As carrier film, it is possible to use plastic sheeting, the mylars such as polyethylene terephthalate is preferably used, gathers The plastic sheetings such as imide membrane, polyamidoimide thin film, polypropylene film, polystyrene film.Thickness for carrier film Degree has no particular limits, and generally suitably selects in the range of 0.1～150 μm.
Now, after forming film on a carrier film, in order to prevent the surface attachment dust etc. of film, further preferably it is being coated with The strippable coverlay of surface stacking of film.As strippable coverlay, such as, can use polyethylene film, polytetrafluoroethyl-ne Alkene thin film, polypropylene film, surface treated paper etc., as long as film is less than with the bonding force of coverlay when peeling off coverlay The coverlay of the bonding force of film and carrier film.
It addition, use above-mentioned solvent to be adjusted to be suitable to the viscosity of coating process by the hardening resin composition of the present invention After, utilize the methods such as dip coating, flow coat method, rolling method, stick coating method, silk screen print method, curtain coating, die coating method to be applied to base material On, at a temperature of about 50～90 DEG C, make organic solvent volatile dry (being temporarily dried) contained in compositions, such that it is able to shape Become not viscous dry coating.For the ratio of the residual content of the compounding amount of dried solvent, i.e. solvent, solvent-laden to wrap The resin bed total amount benchmark meter of dry film, preferably 0.1～4 mass %, more preferably 0.3～3 mass %.It addition, by the present invention Hardening resin composition be applied in carrier film, be dried and form thin film, batched and in the case of the dry film that obtains, will It utilizes laminating machine etc. to fit on base material in the way of the film of compositions contacts with base material, then peels off carrier film, thus The layer of film can be formed on base material.
Such as these films are irradiated by active energy beam and make its photocuring or be heated to the temperature of 100～250 DEG C Spend and make its heat cure, thus can obtain solidfied material.
As above-mentioned base material, in addition to being pre-formed with the printed circuit board (PCB) of circuit, flexible printed circuit board, it is also possible to Enumerate: use employ paper phenolic resin, paper epoxy resin, glass cloth epoxy resin, glass polyimide resin, glass cloth/ Non-woven fabrics epoxy resin, glass cloth/paper epoxy resin, synthetic fibers epoxy resin, fluorine polyethylene polyphenylene oxide resin (polyphenyl Support oxygen) all grades (FR-4 etc.) copper-clad laminated of the material such as high-frequency circuit copper-clad laminated board of cyanate ester resin etc. Plate and Kapton, PET film, glass substrate, ceramic substrate, wafer board etc..
After the hardening resin composition of the coating present invention volatile dry that carries out can use heated air circulation type drying oven, IR stove, hot plate, convection oven etc. are carried out, i.e. use the device of the thermal source with the air mode of heating utilizing steam to make In drying machine hot air convection contact method and blow the method to supporter by nozzle.
As the exposure machine irradiated for active energy beam, as long as being equipped with high voltage mercury lamp, ultrahigh pressure mercury lamp, metal Halide lamp, mercury short arc lamp etc. and irradiate 350～450nm the device of ultraviolet of scope, further, it is also possible to use Directly drawing apparatus (such as by from the cad data of computer utilize direct irradiation active energy beam and depiction as Direct imaging device).As directly retouching the light source of machine, as long as using maximum wavelength to be in the light of the light in the range of 350～410nm Source.For formed the light exposure of image according to thickness etc. and different, generally can be 20～800mJ/cm2, preferably It is 20～600mJ/cm2In the range of.
It addition, as developing method, it is possible to use infusion process, elution method, nebulization, spread coating etc., as developer solution, can To use the aqueous alkali of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amine etc..
The store method of the present invention is characterised by, it is the guarantor of the compositions containing (B) oxime ester system Photoepolymerizationinitiater initiater Deposit method, compounded with (C) coupling agent in foregoing.Foregoing can also draw containing except the photopolymerization of (B) oxime ester system Send out the composition beyond agent and (C) coupling agent, such as mentioned component.In the presence of (C) coupling agent, as long as preserving containing (B) oxime The compositions of ester system Photoepolymerizationinitiater initiater, for compounding (C) coupling agent in the composition, can be by (B) oxime ester system light Before polymerization initiator is compounded in compositions, it is also possible to after which.
Embodiment
Hereinafter, use embodiment that the present invention is described in more detail, but the present invention is not limited to following embodiment.Need Being noted that following, " part " and " % " is quality criteria in case of no particular description.
[synthesis of alkali soluble resins and preparation]
(containing the synthesis of carboxy resin A-1)
In TC acetas 600g, put into o-cresol phenolic epoxy varnish (big Japan oil Ink chemical industry Co., Ltd. system, EPICLON N-695, softening point 95 DEG C, epoxide equivalent are 214, average functional group number is 7.6) 1070g ((+)-2,3-Epoxy-1-propanol radix (aromatic rings sum): 5.0 moles), acrylic acid 360g (5.0 moles) and hydroquinone 1.5g, add Heat is stirred to 100 DEG C, uniform dissolution.
Then, put into triphenylphosphine 4.3g, after being heated to 110 DEG C of reactions 2 hours, be warming up to 120 DEG C and carry out again 12 hours Reaction.Fragrance family hydrocarbon (Solvesso 150) 415g, tetrabydrophthalic anhydride 456.0g is put in the reactant liquor obtained (3.0 moles), carry out the reaction of 4 hours with 110 DEG C, cool down, obtain photosensitive containing carboxy resin solution (referred to as varnish A-1)。
The solid constituent of so obtained resin solution (varnish A-1) is 65%, the acid number of solid constituent is 89mgKOH/ g。
(embodiment 1～12, comparative example 1；Permanent film hardening resin composition)
According to the formula shown in following table, it is compounded each composition, after utilizing blender to carry out premixing, makes it with triple-roller mill Disperse and carry out mixing, preparation the 1st composition solution (host) and the 2nd composition solution (firming agent).Compounding scale in table Show mass parts.
[table 1]
[table 2]
A-1: above-mentioned synthesis obtain containing carboxy resin solution A-1
B-1:IRGACURE OXE02 (oxime ester system Photoepolymerizationinitiater initiater, BASF JAPAN LTD. system)
B-2:TOE-04-A3 (oxime ester system Photoepolymerizationinitiater initiater, Nippon Chemical Works Co. Ltd.'s system)
C-1:KBM-5103 is (containing acryloyl group as the silane coupler of organic reaction group, Shin-Etsu Chemical Co., Ltd. system)
C-2:KBM-3033 is (containing alkoxyl as the silane coupler of organic reaction group, Shin-Etsu Chemical Co., Ltd. system)
C-3:KBM-403 is (containing epoxy radicals as the silane coupler of organic reaction group, Shin-Etsu Chemical Co., Ltd. system)
C-4:KBM-803 is (containing sulfydryl as the silane coupler of organic reaction group, Shin-Etsu Chemical Co., Ltd. system)
D-1: carbitol acetate
D-3:DPM (dipropylene glycol methyl ether)
* 1:DPHA (dipentaerythritol acrylate, Nippon Kayaku Co., Ltd. system)
* 3:KS-66 (Shin-Etsu Chemical Co., Ltd. system)
* 4: dicyandiamide (DICY)
* 5:FASTGEN BLUE 5380 (Dainippon Ink Chemicals's system)
* 6:B-30 (barium sulfate, KCC's system)
* 7:jER828 (there is the epoxy resin of carboxyl, Mitsubishi chemical Co., Ltd's system)
* 8: tripolycyanamide (Misao Kusano's system)
According to herein below, for the 1st composition solution (host) obtained, the 2nd composition solution (firming agent) and The embodiment 1 mixing them and obtain～12 and the hardening resin composition of comparative example 1 be evaluated.The results are shown in down State in table.
(cohesiveness)
It is applied to be formed with figure by the most whole face of photosensitive polymer combination of embodiment and comparative example by silk screen printing On the copper clad laminate of case, utilize the heated air circulation type kiln dried 30 minutes of 80 DEG C, be cooled to room temperature.PET film is pressed On this substrate, the then sticking state of thin film during evaluation stripping negative film.Metewand is as described below.The result obtained is shown In Table 3 below, 4.
◎: entirely without viscosity.
Zero: inviscid.
△: slightly viscosity.
×: toughness.
(resistance to soldering heat performance)
By the way of the solidification compound of each embodiment and comparative example is become 20 μm with dry film thickness by silk screen printing Whole face is applied to be formed on figuratum copper clad laminate, is dried 30 minutes, is cooled to room temperature at 80 DEG C.To this substrate, use The exposure device being equipped with high voltage mercury lamp carries out pattern exposure with optimum exposure, then by the 1wt% sodium carbonate of 30 DEG C Solution carries out developing 60 seconds under conditions of spraying 0.2MPa, obtains pattern.60 points are solidified after being carried out at 150 DEG C by this substrate Clock, obtains being formed with the substrate of cured product pattern.Coating rosin series scaling powder on the substrate, as evaluating substrate.This is commented Valency substrate is immersed in the solder bath being redefined for 260 DEG C, after modified alcohol cleaning scaling powder, and visualization protective layer swollen Swollen, peeling, and be evaluated.Metewand is as described below.Show the result in Table 3 below, 4.
Zero: even if being repeated 3 times by the dipping of 10 seconds, also do not observe peeling.
△: slightly peel off when the dipping of 10 seconds is repeated 3 times above.
×: carry out there is the expansion of protective layer, peeling during within 3 times 10 seconds dippings.
(electrical insulation reliability)
By the way of the solidification compound of each embodiment and comparative example is become 20 μm with dry film thickness by silk screen printing Whole face is applied to be formed on the substrate of the comb-type electrode pattern of wired/spacing=50/50 μm, is dried 30 minutes at 80 DEG C, cold But to room temperature.To this substrate, the exposure device being equipped with high voltage mercury lamp is used to be exposed with optimum exposure, then by 30 DEG C 1wt% aqueous sodium carbonate carry out developing under conditions of spraying 0.2MPa 60 seconds, obtain pattern.By this substrate 150 Solidifying 60 minutes after carrying out at DEG C, obtain being formed with the evaluation substrate of cured product pattern, (electrode is rotten then to carry out insulating reliability Erosion property) evaluation.
Evaluation methodology be by this comb-type electrode 121 DEG C, apply the biasing of DC30V under the conditions of the heating and moistening of 97%R.H. Voltage, measures the time till insulation degradation.Wherein, at resistance less than 1 × 106The moment of Ω is judged to insulation degradation. Metewand is as described below.Show the result in Table 3 below, 4.
◎: the time till insulation degradation is more than 300 hours
Zero: the time till insulation degradation be 200 hours less than 300 hours
△: the time till insulation degradation be 100 hours less than 200 hours
×: the time till insulation degradation is less than 100 hours
(resistance to gold-plated property)
By the way of the solidification compound of each embodiment and comparative example is become 20 μm with dry film thickness by silk screen printing Whole face is applied to be formed on figuratum copper clad laminate, is dried 30 minutes, is cooled to room temperature at 80 DEG C.To this substrate, use The exposure device being equipped with high voltage mercury lamp carries out pattern exposure with optimum exposure, then by the 1wt% sodium carbonate of 30 DEG C Solution carries out developing 60 seconds under conditions of spraying 0.2MPa, obtains pattern.60 points are solidified after being carried out at 150 DEG C by this substrate Clock, obtains being formed with the evaluation substrate of cured product pattern.
Use the electroless nickel bath of commercially available product and chemical gilding bath, 80～90 DEG C, nickel 5 μm, under conditions of golden 0.05 μm Plating is carried out to evaluating substrate.For plated evaluation substrate, by the presence or absence of the infiltration of visual valuation plating, then pass through The presence or absence that (tape peeling) evaluates the peeling of protective layer peeled off by band.Determinating reference is as described below.The obtained results are shown in Table 3 below, 4.
◎: do not observe infiltration after plating completely, after band is peeled off, nothing is peeled off.
Zero: slightly observe infiltration after plating, but after band is peeled off, nothing is peeled off.
△: confirm a small amount of infiltration after plating, band slightly peels off after peeling off.
×: confirming infiltration after plating, band also observes peeling after peeling off.
(acid resistance)
By the way of the solidification compound of each embodiment and comparative example is become 20 μm with dry film thickness by silk screen printing Whole face is applied to be formed on figuratum copper clad laminate, is dried 30 minutes, is cooled to room temperature at 80 DEG C.To this substrate, use The exposure device being equipped with high voltage mercury lamp carries out pattern exposure with optimum exposure, then by the 1wt% sodium carbonate of 30 DEG C Solution carries out developing 60 seconds under conditions of spraying 0.2MPa, obtains pattern.60 points are solidified after being carried out at 150 DEG C by this substrate Clock, obtains being formed with the evaluation substrate of cured product pattern.
Use the electroless nickel bath of commercially available product and chemical gilding bath, 80～90 DEG C, nickel 5 μm, under conditions of golden 0.05 μm This evaluation substrate is carried out plating.
Above-mentioned gold-plated after, be impregnated into the 10vol%H of 30 DEG C2SО4In solution after 30 minutes, by visual valuation plating The presence or absence penetrated into, then peels off the presence or absence of the peeling evaluating protective layer by band.Metewand is as described below.The result that will obtain Be shown in Table 3 below, 4.
◎: do not observe infiltration completely, after band is peeled off, nothing is peeled off.
Zero: slightly observe infiltration, but after band is peeled off, nothing is peeled off.
△: confirm infiltration, band slightly peels off after peeling off.
×: confirming infiltration, band also observes peeling after peeling off.
(alkali resistance)
By the way of the solidification compound of each embodiment and comparative example is become 20 μm with dry film thickness by silk screen printing Whole face is applied to be formed on figuratum copper clad laminate, is dried 30 minutes, is cooled to room temperature at 80 DEG C.To this substrate, use The exposure device being equipped with high voltage mercury lamp carries out pattern exposure with optimum exposure, then by the 1wt% sodium carbonate of 30 DEG C Solution carries out developing 60 seconds under conditions of spraying 0.2MPa, obtains pattern.60 points are solidified after being carried out at 150 DEG C by this substrate Clock, obtains being formed with the evaluation substrate of cured product pattern.
Use the electroless nickel bath of commercially available product and chemical gilding bath, 80～90 DEG C, nickel 5 μm, under conditions of golden 0.05 μm This evaluation substrate is carried out plating.
By above-mentioned gold-plated after evaluate substrate be impregnated in the 10wt%Na О H solution of 30 DEG C after 30 minutes, by visually Evaluate the presence or absence of the infiltration of plating, then peeled off the presence or absence of the peeling evaluating protective layer by band.Metewand is as described below.Will The result obtained be shown in Table 3 below, 4.
◎: do not observe infiltration completely, after band is peeled off, nothing is peeled off.
Zero: slightly observe infiltration, but after band is peeled off, nothing is peeled off.
△: confirm infiltration, band slightly peels off after peeling off.
×: confirming infiltration, band also observes peeling after peeling off.
(developability)
By silk screen printing, the hardening resin composition of each embodiment and comparative example is become 20 μm with dry film thickness The whole face of mode is applied to be formed on figuratum copper clad laminate, is dried 30 minutes, is cooled to room temperature at 80 DEG C.To this substrate, Carry out developing under conditions of spraying 0.2MPa 60 seconds by the 1wt% aqueous sodium carbonates of 30 DEG C, obtain pattern.Use obtains Evaluation substrate, by being visually confirmed to be the situation of residue, and be evaluated.Metewand is as described below.The result obtained is shown In Table 3 below, 4.
Zero: without residue.
△: have a little residue to remain (filler residual).
×: there is residue.
(resolution initial after manufacture)
By silk screen printing, the whole face of hardening resin composition of each embodiment and comparative example is applied on full copper base, And be dried 30 minutes at 80 DEG C.Use L/S=50/500 negative film be exposed with optimum exposure, by 30 DEG C 1% Na2CO3Aqueous solution is spraying 2kg/cm2Condition carry out 60 seconds development, obtain pattern.After development, float with observation by light microscope Carving shape, is carried out as follows evaluation.The obtained results are shown in Table 3 below, 4.
◎: the skew to pattern the most unconfirmed, broaden and undercut (difference in size of top and bottom).
Zero: the skew that slightly confirms pattern, any person broadening and undercuting in (difference in size of top and bottom).
×: the skew that substantially confirms pattern, any person broadening and undercuting in (difference in size of top and bottom).
(manufacturing the resolution of latter 6 months)
By the 1st composition solution (host) and the 2nd composition solution (firming agent) 20～25 DEG C (room temperature) after fabrication, wet Degree 60% mixes, by silk screen printing by each embodiment obtained and the solidification of comparative example after taking care of 6 months individually below Property the whole face of resin combination be applied on full copper base, at 80 DEG C be dried 30 minutes.Use the negative film of L/S=50/500 with Good light exposure is exposed, by the 1%Na of 30 DEG C2CO3Aqueous solution is spraying 2kg/cm2Under conditions of carry out 60 seconds development, To pattern.After development, use observation by light microscope relief shape, be carried out as follows evaluation.The obtained results are shown in Table 3 below, 4。
◎: the skew to pattern the most unconfirmed, broaden and undercut (difference in size of top and bottom).
Zero: the skew that slightly confirms pattern, any person broadening and undercuting in (difference in size of top and bottom).
×: the skew that substantially confirms pattern, any person broadening and undercuting in (difference in size of top and bottom).
(sensitivity initial after manufacture)
By silk screen printing by the solidification compound of each embodiment and comparative example with whole by the way of becoming 10 μm after drying Face is applied on cleaned full copper base, is dried 10 minutes at 80 DEG C with heated air circulation type drying oven.This film is put Put the stage actinometer (41 sections) of Stouffer Corporation, utilize and be equipped with ORC MANUFACTURING CO., The exposure machine of the metal halide lamp LTD. made is with 50mJ/cm2Light exposure be exposed, determine and pass through 1wt%Na2CO3Water-soluble Liquid carries out the residual hop count after development in 1 minute under spraying 0.1Mpa.Residual hop count is the most, and sensitivity is the best, thus preferably. The obtained results are shown in Table 3 below, 4.
(manufacturing the sensitivity of latter 6 months)
By the 1st composition solution (host) and the 2nd composition solution (firming agent) 20～25 DEG C (room temperature) after fabrication, wet Degree 60% mixes, by silk screen printing by each embodiment obtained and the solidification of comparative example after taking care of 6 months individually below Property resin combination whole face in the way of becoming 10 μm after drying be applied on cleaned full copper base, with heated air circulation type do Dry stove is dried 10 minutes at 80 DEG C.This film is placed the stage actinometer (41 of Stouffer Corporation Section), utilize and be equipped with ORC MANUFACTURING CO., the exposure machine of the metal halide lamp of LTD. is with 50mJ/cm2's Light exposure is exposed, and determines and passes through 1wt%Na2CO3Aqueous solution carries out the residual section after development in 1 minute under spraying 0.1Mpa Number.Residual hop count is the most, and sensitivity is the best, thus preferably.The obtained results are shown in Table 3 below, 4.
(storage stability (thickening property))
Viscosity after just being manufactured by the hardening resin composition of each embodiment and comparative example is set to initial value, for system The relation of the viscosity of the hardening resin composition after 20～25 DEG C (room temperature), humidity less than 60% are taken care of 6 months after making, passes through Following formula calculates thickening efficiency (%).It should be noted that viscosity is to take sample 0.2ml, use cone and plate viscometer (TOKI The TV-33 of SANGYO CO., LTD.), measure 25 DEG C, the viscosity being worth for 30 seconds of rotating speed 5rpm.
Thickening efficiency=(20～25 DEG C, humidity less than 60% keeping 6 months after viscosity/initial viscosity) × 100
According to the value of thickening efficiency, evaluate storage stability as follows.The obtained results are shown in Table 3 below, 4.
Zero: less than 10%
△: 10～30%
×: higher than 30%
[table 3]
[table 4]
Understand: even if the hardening resin composition of embodiment 1～12 6 months after fabrication, sensitivity and resolution are also Excellent.On the other hand, it is known that: the hardening resin composition of the comparative example 1 not containing coupling agent causes spirit because of long-term preservation Sensitivity and resolution significantly reduce.
(embodiment 13, comparative example 2；Resist hardening resin composition)
According to the formula shown in following table, it is compounded each composition, after utilizing blender to carry out premixing, makes it with triple-roller mill Disperse and carry out mixing, preparation the 1st composition solution (host) and the 2nd composition solution (firming agent).Compounding scale in table Show mass parts.
[table 5]
A-1: above-mentioned preparation containing carboxy resin solution A-1
B-2:TOE-04-A3 (oxime ester system Photoepolymerizationinitiater initiater, Co., Ltd.'s Japanization length of schooling are made made)
C-3:KBM-403 is (containing epoxy radicals as the silane coupler of organic reaction group, Shin-Etsu Chemical Co., Ltd. system)
D-1: carbitol acetate
D-2:PMA (propylene glycol methyl ether acetate)
* 1:DPHA (dipentaerythritol acrylate, Nippon Kayaku Co., Ltd. system)
* 3:KS-66 (Shin-Etsu Chemical Co., Ltd. system)
* 5:FASTGEN BLUE 5380 (Dainippon Ink Chemicals's system)
* 7: tripolycyanamide (Misao Kusano's system)
According to herein below, for the 1st composition solution (host) obtained, the 2nd composition solution (firming agent) and The embodiment 13 mixing them and obtain and the hardening resin composition of comparative example 2 are evaluated.The results are shown in following In table.
(developability)
By silk screen printing, the photosensitive polymer combination of each embodiment and comparative example is become 20 μm with dry film thickness The whole face of mode is applied to be formed on figuratum copper clad laminate, is dried 30 minutes, is cooled to room temperature at 80 DEG C.To this substrate, Carry out developing under conditions of spraying 0.2MPa 60 seconds by the 1wt% aqueous sodium carbonates of 30 DEG C, obtain pattern.Use obtains Evaluation substrate, by being visually confirmed to be the situation of residue, and be evaluated.Metewand is as described below.The result obtained is shown In table 6 below.
Zero: without residue.
△: have a little residue to remain (filler residual).
×: there is residue.
(resolution initial after manufacture, manufacture latter 6 months resolution, manufacture after initial sensitivity, manufacture latter 6 The sensitivity of the moon and storage stability (thickening property))
Method same as described above is utilized to be evaluated.The obtained results are shown in table 6 below.
[table 6]
Understand: even if the hardening resin composition of embodiment 13 6 months after fabrication, sensitivity and resolution are the most excellent Different.On the other hand, it is known that: the hardening resin composition of the comparative example 2 not containing coupling agent causes sensitive because of long-term preservation Degree and resolution significantly reduce.

Claims (7)

1. a hardening resin composition, it is characterised in that comprise:
(A) alkali soluble resins,
(B) oxime ester system Photoepolymerizationinitiater initiater,
(C) coupling agent and
(D) solvent.
Hardening resin composition the most according to claim 1, wherein, described (C) coupling agent is silane series coupling agent, titanium It is at least one in coupling agent, zirconium system coupling agent and aluminum system coupling agent.
Hardening resin composition the most according to claim 1, wherein, the compounding amount of described (C) coupling agent is relative to bag It is 0.02～2.5 mass % containing solvent in interior hardening resin composition total amount.
4. a dry film, it is characterised in that it has the hardening resin composition according to any one of claims 1 to 3 Coated and dried and the resin bed that obtains on thin film.
5. a solidfied material, it is characterised in that it is by the hardening resin composition according to any one of claims 1 to 3 Or the resin bed of the dry film described in claim 4 solidifies and obtains.
6. a printed circuit board (PCB), it is characterised in that it possesses the solidfied material described in claim 5.
7. a store method, it is characterised in that it is the preservation side of the compositions containing (B) oxime ester system Photoepolymerizationinitiater initiater Method, compounded with (C) coupling agent in described compositions.
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