CN104470962B - Alkali developable resin, the photosensitive polymer combination using the resin - Google Patents

Alkali developable resin, the photosensitive polymer combination using the resin Download PDF

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Publication number
CN104470962B
CN104470962B CN201380037427.2A CN201380037427A CN104470962B CN 104470962 B CN104470962 B CN 104470962B CN 201380037427 A CN201380037427 A CN 201380037427A CN 104470962 B CN104470962 B CN 104470962B
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resin
alkali developable
phenol
hydroxyl group
photosensitive polymer
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CN104470962A (en
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山本和义
关根健二
堀口尚文
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • C08G8/32—Chemically modified polycondensates by organic acids or derivatives thereof, e.g. fatty oils
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/12—Chemically modified polycondensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/20—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with polyhydric phenols
    • C08G8/22—Resorcinol
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C09D161/04, C09D161/18 and C09D161/20
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—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
    • 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
    • H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces
    • H05K3/0076—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces characterised by the composition of the mask
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Materials For Photolithography (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Epoxy Resins (AREA)

Abstract

A kind of photosensitive polymer combination the present invention relates to alkali developable resin and containing (A) the alkali developable resin, (B) epoxy resin, (C) Photoepolymerizationinitiater initiater and (D) diluent, the alkali developable resin is further reacted with the hydroxyl in reaction product X obtained from the hydroxyl reaction of phenol resin (a) by the compound (b) for making to have alcoholic extract hydroxyl group and 1 epoxy radicals in molecule and obtained with saturation and/or unsaturated multi-anhydride (c)；The drying property and alkali-developable of the resin combination are excellent, and, the various characteristic goods such as adhesiveness, welding heat resistance, the gold-plated property of chemically-resistant, resistance to PCT, flexibility, cold-resistant thermal impact, the HAST characteristics of the film after solidification, available for solder resist, resist, plating resist application, interlayer dielectic used when manufacturing printed wiring board etc..

Description

Alkali developable resin, the photosensitive polymer combination using the resin
Technical field
Photosensitive polymer combination the present invention relates to alkali developable resin and containing the resin.In more detail, it is related to The electronic materials such as solder resist, high-density multi-layered plate interlayer dielectric, semiconductor-sealing-purpose solder resist for printed wiring board are led The alkali developable resin and photosensitive polymer combination in domain.
Background technology
In the past, the permanent mask resist in printed wiring board manufacture can be solid by silk-screen printing thermohardening type or ultraviolet The method manufacture of change type resist ink, but at present from productivity ratio aspect, gradually to the liquid photoresistance of alkali developable The direction of solder flux is developed.
However, for it is in the past commercially available be applied with the printed wiring board of alkali developable solder resist for, be used as the length of encapsulation PCT (Pressure Cooker Test (pressure furnace test)) patience of phase reliability test is poor, the stripping for occurring solidfied material.
Further, since the moisture absorption of solder resist, in Reflow Soldering when installing is encapsulated, in the moisture boiling of the internal moisture absorption of encapsulation Rise, it was observed that the internal solder resist epithelium of encapsulation and its around crack so-called puffed rice phenomenon the problem of.It is such The problem of resistance to hygroscopicity, long-term reliability, it is not limited in the situation of above-mentioned mounting technique, in the resistance of general printed wiring board Solder flux, flexible printed circuit board, the solder resist used in the manufacture of carrier package (Tape Carrier Package), increasing layer (Build-up) in the product of other purposes such as interlayer insulating film of the multiwiring board such as substrate, do not expect that appearance is such resistance to yet The problem of hygroscopicity and long-term reliability.
It can be seen that, with the development of nearest electrical industry, semiconductor industry, it is desirable to which characteristic is further improved, such as is required Heat resistance, toughness, flexibility, water resistance, chemical-resistant are improved, these various new photonasty trees can be met by developing Fat.
In the past, specifically, using phenolic resin varnish type epoxy resin as the photoresist of initiation material, because its is excellent Adhesivity, heat resistance, chemical-resistant, electrical insulating property etc., and it is widely used in a variety of of the electronic materials such as solder resist, resist In field.Especially as the photoresist containing carboxyl of excellent heat resistance, use more：Make multi-anhydride and cresol novolac (the patent text of resin obtained from type epoxy resin and monocarboxylic reaction product containing unsaturated group are reacted Offer 1).But, although the excellent heat resistance of the resin, but contraction during solidification is big, extend less, shortcoming toughness, therefore exist Problem be easily to be cracked because of thermal shock.It is used as the photoresist for solving the problem, it is proposed that：As by bisphenol type The sense of the reaction product of resin, (methyl) acrylic acid and multi-anhydride obtained from the pendant hydroxyl moieties epoxidation of epoxy resin Photosensitiveness prepolymer (patent document 2), make tetrabydrophthalic anhydride and cresol novolak type epoxy resin, acrylic acid and to hydroxyl Polycarboxylic acid resin (patent document 3) containing unsaturated group etc. obtained from the reaction product reaction of base benzyl carbinol.However, These resins are yet not enough to while meeting heat resistance and toughness.
In addition, being used as the resin with excellent long-term reliability, it is proposed that：Novolac resin is modified with alkylene oxide Afterwards, addition (methyl) acrylic acid, then the photoresist (patent document 4) obtained from addition multi-anhydride containing carboxyl.So And, there is the leeway of improvement in terms of the drying property after ink coating.That is, these compositions with dilute alkaline aqueous solution in order to be shown Shadow is, it is necessary to improve acid number.Therefore, must in the solvent seasoning process after the material for being combined with ink is coated on substrate Drying time must be shortened, by drying into a succession of process for exposing and developing, in the case of needing after the drying for a long time, deposited The problems such as can not promptly remove the unexposed part of film.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 1-54390 publications
Patent document 2：Japanese Unexamined Patent Publication 9-54434 publications
Patent document 3：Japanese Unexamined Patent Publication 11-288091 publications
Patent document 4：No. 3964326 publications of Japanese Patent No.
The content of the invention
Invent problem to be solved
The present invention makes in view of the above problems, it is therefore an objective to provide a kind of resin containing carboxyl, and it has good The various physical property such as developability, heat resistance, moisture-proof, adhesivity, and the excellent ink composite of drying property can be obtained.
It is a further object to provide a kind of liquid curing resin combination, it has the property that：Can be with The cured film of every characteristic good required by following various uses is formed, and the densification of printed wiring board can be tackled With surface installationization, it can be developed with dilute alkaline aqueous solution.That is, solder resist in general printed wiring board, for manufacturing In interlayer insulating films of multiwiring board such as flexible printed circuit board, the solder resist of carrier package, increasing layer substrate etc., it is desirable to have The cured film of every characteristics such as excellent developability, adhesiveness, welding heat resistance, resistance to hygroscopicity, PCT patience, electrical insulating property, especially It is in IC package, it is desirable to the cured film of the characteristic good such as resistance to hygroscopicity and PCT (pressure furnace test) patience.The mesh of the present invention Be to provide a kind of hardening resin composition, it can form the solidification of every characteristic good required by these various uses Film, and with above-mentioned characteristic.
The means used to solve the problem
The present inventor etc. are in order to solve the technical problem that these are conventional, it was found that one kind is using phenol resin as skeleton, wherein Introduce primary hydroxyl and reactive functional groups and obtain reaction product, then introduce in the reaction product carboxyl as functional group and Obtained alkali developable resin, i.e. make the hydroxyl of the compound (b) with phenol resin (a) in molecule with alcoholic extract hydroxyl group and 1 epoxy radicals Hydroxyl obtained from base reaction in reaction product X (resin) further with saturation and/or unsaturated multi-anhydride (c) reaction and The obtained resin containing carboxyl, i.e. alkali developable resin can reach above-mentioned purpose, so as to complete the present invention.
In addition, term " alkali developable resin " in this specification is can assign the resin of resin combination alkali-developable Implication, i.e. the implication that can assign the resin of alkali-developable is used.Therefore, alkali developable resin of the invention is best suitable for being used for Alkali development photosensitive polymer combination, it can also be used to the purposes beyond this purposes.
In addition, term " (methyl) acrylic acid " is used with least implication of any one of acrylic or methacrylic acid, (methyl) acrylate (acrylate or methacrylate at least any one) etc. is also to be used with same implication.
In more detail, the present invention relates to the invention described in following (1)~(21).
(1) a kind of alkali developable resin (hereinafter also referred to " and resin Y " of the invention or referred to as " resin Y "), it passes through Compound (b) (hereinafter also referred to as " compound b ") and the phenol resin (a) for making there is alcoholic extract hydroxyl group and 1 epoxy radicals in molecule Hydroxyl in reaction product X obtained from hydroxyl reaction (hereinafter also referred to as " intermediate X ") further with above-mentioned multi-anhydride (c) (hereinafter also referred to as " multi-anhydride (c) ") reacts and obtained.
(2) alkali developable resin as described above described in (1), it is characterised in that make above-claimed cpd (b) with relative to phenol tree The equivalent of phenolic hydroxyl group 1 of fat (a) reacts for 0.1~0.9 mole of ratio.
(3) alkali developable resin as described above described in (1) or (2), it is characterised in that make above-mentioned multi-anhydride (c) with phase Reacted for the reaction product X equivalent of hydroxyl 1 for 0.05~0.9 mole of ratio.
(4) alkali developable resin as described above any one of (1)~(3), wherein, relative in phenol resin (a) The ratio of the phenolic hydroxyl group remained in total phenolic hydroxyl group number, alkali developable resin is 10~90%.
(5) alkali developable resin as described above any one of (1)~(4), wherein, phenol resin (a) is to contain biphenyl The phenol resin (a) of skeleton.
(6) alkali developable resin as described above any one of (1)~(5), wherein, phenol resin (a) is following formulas (1) phenol resin (a1) shown in：
M1, m2 and m3 are each independently 1 or 2 integer in formula, and n represents 0~10 integer.
(7) alkali developable resin as described above described in (6), wherein, phenol resin (a1) is wherein to contain resorcinol structure Phenol resin.
(8) alkali developable resin as described above described in (7), wherein, the hydroxyl of the phenol resin containing resorcinol structure is worked as Measure as 70~170g/ equivalents.
(9) alkali developable resin as described above any one of (1)~(8), wherein, compound (b) is glycidol.
(10) alkali developable resin as described above any one of (1)~(9), wherein, above-mentioned multi-anhydride (c) is tool There is the acid anhydrides of the polyacid of 2 or 3 carboxyls.
(11) a kind of photosensitive polymer combination, it is characterised in that contain：
Alkali developable resin any one of (A) above-mentioned (1)~(10),
(B) epoxy resin,
(C) Photoepolymerizationinitiater initiater and
(D) diluent.
(12) photosensitive polymer combination as described above described in (11), it is characterised in that diluent is polymerizable unsaturation Compound and/or solvent.
(13) photosensitive polymer combination as described above described in (11) or (12), it is characterised in that
(A) alkali developable resin is 10~80 weight % relative to the total amount of composition；
(B) epoxy resin is 1~50 weight % relative to the total amount of composition；
(C) Photoepolymerizationinitiater initiater is 0.5~20 weight % relative to the total amount of composition；And
(D) diluent is 10~200 parts by weight relative to the parts by weight of alkali developable resin 100.
(14) photosensitive polymer combination as described above any one of (11)~(13), wherein, relative to alkali development The parts by weight of type resin 100, contain polymerizable unsaturated compound using 5~200 weight % scope and are used as diluent.
(15) photosensitive polymer combination as described above described in (14), wherein, polymerizable unsaturated compound is (methyl) Acrylate compounds.
(16) solidfied material of the photosensitive polymer combination any one of above-mentioned (11)~(15).
(17) solidfied material of photosensitive polymer combination as described above described in (16), it is that use can be surpassed using light Solidfied material obtained from the photoetching process of microfabrication is patterned.
(18) a kind of base material, it has the layer of the solidfied material described in above-mentioned (16) or (17).
(19) a kind of article, it has the base material described in above-mentioned (18).
(20) a kind of forming method of cured coating film, it is characterised in that by any one of above-mentioned (11)~(15) Photosensitive polymer combination is coated on printed wiring board and forms film, is exposed, develops, then passes through irradiation ultraviolet radiation And/or heating solidifies it.
(21) the reaction product X with both phenolic hydroxyl group and alcoholic extract hydroxyl group be used for manufacture alkali developable described in above-mentioned (1) The purposes of resin, reaction product X is by making the compound (b) with alcoholic extract hydroxyl group and 1 epoxy radicals in molecule and phenol resin (a) Hydroxyl reaction and obtain.
Invention effect
The drying property of the photosensitive polymer combination of the present invention, alkali-developable are excellent, and the adhesion of the film after solidification Property, welding heat resistance, the gold-plated property of chemically-resistant, resistance to PCT, flexibility, cold-resistant thermal impact, every characteristic good such as HAST characteristics. Can low cost and productivity ratio forms cured film well, therefore, solidified except being used for active energy beam Ultraviolet hardening printing-ink purposes etc. beyond, the solder resist that is used when manufacturing printed wiring board, resist, plating resist are applied It is also useful in terms of agent, interlayer dielectic.
Embodiment
Hereinafter, the present invention is described in more detail.
First, in resin Y of the invention, skeleton resin is used as using phenol resin (a).Phenol resin (a) in the present invention is Refer to sensu lato phenol resin, refer to " resin in a molecule with least two phenolic hydroxyl group ".Therefore, as phenol resin (a), Use the phenol resin in a molecule with least two above phenolic hydroxyl group.The phenol resin (a) can use soluble type, phenolic aldehyde clear Whole phenol resin such as paint shaped, cresols type.Alternatively, it is also possible to use：Multifunctional phenolic compounds is modified with epoxide and is obtained To epoxide modified type, make phenols and butadiene (co) polymer addition obtained from phenols addition butadiene (co) polymer, Polymer resin of the polymer resin of phenols and dicyclopentadiene, phenols and biphenyl etc..
Specifically, it can illustrate：Between phenol resol resins, cresol novolac resin, biphenyl phenolic varnish type The novolak type phenol resins such as benzenediol resin；Phenol is modified to xylylene modified novolac resin, an xylylene The modified novolak type phenol resins such as Novolac resin, adjacent xylylene modified novolac resin；Bisphenol-A, Bisphenol F etc. Bisphenol compound；Biphenyl type phenol resin；Soluble type phenol resin；The aralkyls such as phenol aralkyl resin, biphenyl aralkyl type phenol resin Fundamental mode phenol resin；The alkane type phenol resin such as trisphenol alkane type resin and its polymer；Phenol resin containing naphthalene nucleus, two polycyclics penta Diene modified phenol resin, ester ring type phenol resin, heterocyclic type phenol resin etc..These phenol resin can use a kind or and with 2 kinds with On.
The use of molecular weight is about 300~about 30 as the molecular weight of the phenol resin (a), 000 phenol resin, preferably molecule Amount is about 400~about 15,000.As the molecular weight of resin, using number-average molecular weight or weight average molecular weight, as long as any one In above range.
As the preferred resin of above-mentioned phenol resin (a), it can enumerate：Novolak type phenol resin, more preferably can be with Enumerate：There is cresols skeleton or the phenol resin of biphenyl backbone in its structure, can further preferably enumerate：With biphenyl bone The phenol resin of frame.Specifically, as the novolak type phenol resin with cresols skeleton, cresols type novolaks can be enumerated Resin；As the phenol resin with biphenyl backbone, biphenyl aralkyl type phenol resin, biphenyl novolak type phenol resin can be enumerated Deng.
The more preferably novolak type phenol resin containing biphenyl backbone, shown in more preferably following formulas (1) Phenol resin (a1)；
M1, m2 and m3 are each independently 1 or 2 integer in formula, and n represents 0~10 integer.
In addition, in the phenol resin (a1) (hereinafter also referred to as " phenol resin (a1) ") of above-mentioned formula (1), more preferably phenol tree The phenol resin of phenyl ring (preferably resorcinol structure) of at least a portion with 2 hydroxyls in the skeleton of fat (a1).
Relative to total phenolic hydroxyl group number in phenol resin (a1), in the phenyl ring (preferably resorcinol structure) with 2 hydroxyls Hydroxyl value ratio, preferably 5~100% ratio.The ratio is：The phenol and dihydroxy used during by synthesizing phenol resin (a1) The ratio that the molar ratio of base benzene (preferably resorcinol) is calculated, is set to d1, dihydroxy benzenes is (excellent by used phenol molal quantity Select resorcinol) molal quantity when being set to d2, calculated by following formula.
{(d2×2)/(d1+d2×2)}×100
As phenol resin (a1), it is about 500~about 15 to preferably use mean molecule quantity, 000 phenol resin.
In addition, the phenol resin (a1) of these formulas (1) can be manufactured and obtained according to the method described in known document；Example Such as, according to the record of Japanese Unexamined Patent Publication 8-143648 publications, Japanese Unexamined Patent Publication 7-292066 publications etc., or according to the note Carry, can be readily derived.I.e., it is possible to by make double (methoxy) biphenyl or double (chloromethyl) biphenyl etc. and phenol or/ Obtained with resorcin reaction.
The preferred scope of the hydroxyl equivalent of phenol resin (a1) is about 70~about 170g/ equivalents, according to circumstances can be about 102 ~about 140g/ equivalents.The measure of the hydroxyl equivalent of phenol resin may be carried out by conventional means.
As compound (b) reacted with above-mentioned phenol resin (a), in the molecule with alcoholic extract hydroxyl group and 1 epoxy radicals, As long as there is the compound of alcoholic extract hydroxyl group and 1 epoxy radicals in the molecule, it is possible to use known various compounds, Ke Yilie Citing is such as：Glycidol, or the monoglycidyl ether of the glycol of carbon number 2~4 such as ethylene glycol monoglycidyl ether etc..At this In invention, particularly preferred glycidol.
In the reaction of phenol resin (a) and compound (b), preferably make compound (b) with the phenol relative to phenol resin (a) The equivalent of hydroxyl 1 reacts for 0.1~0.9 mole, more preferably 0.1~0.8 mole, further preferred 0.2~0.8 mole of ratio. In addition, according to circumstances, make compound (b) using the equivalent of phenolic hydroxyl group 1 relative to phenol resin (a) as 0.1~0.7 mole ratio or 0.1~0.6 mole of ratio, is further highly preferred with 0.2~0.6 mole of ratio reaction.
When the amount of compound (b) is excessive, follow-up reacts with multi-anhydride (c) and obtains the water-soluble of resin X of the invention Property become too high so that be combined with sometimes the solidfied material of resin X resin combination water resistance decline.
In the reaction, the epoxy radicals of compound (b) and the phenolic hydroxyl group open loop addition of phenol resin (a), so that ehter bond is formed, And form secondary hydroxyl group.
In the reaction of phenol resin (a) and compound (b), it is preferable that phenolic hydroxyl group and chemical combination that phenol resin (a) is not all of Thing (b) reacts (hereinafter also referred to alcohol modification), but is reacted in the way of remaining a part of unreacted phenolic hydroxyl group.It is tied Fruit is that intermediate X preferably contains both unreacted phenolic hydroxyl group and alcoholic extract hydroxyl group.By the phenol hydroxyl of the phenol resin (a) of initial substance When the total amount (in intermediate X, the total amount of the phenolic hydroxyl group that alcohol is modified and residual phenolic hydroxyl group) of base is set to 1, in contrast, intermediate The ratio of the phenolic hydroxyl group remained in X is about 0.1~about 0.9 ratio, and preferably from about 0.2~about 0.9 ratio is even more preferably about 0.3~about 0.9 ratio.
In addition, the residual phenolic hydroxyl group of intermediate X is kept intact in resin Y.Because：In the intermediate X and subsequently In the reaction of the multi-anhydride (c) reacted, the alcoholic extract hydroxyl group in multi-anhydride (c) and the intermediate X reacts, without with phenol hydroxyl Base reacts.
In the mill during mesosome X, solvent can be used in the reaction of phenol resin (a) and compound (b).As being used Solvent, known solvent can be used, can be enumerated for example：The ketones such as methyl ethyl ketone, cyclohexanone；Toluene, dimethylbenzene, four The arenes such as methylbenzene；Dipropylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol dimethyl ether, DPG The ethers of the glycol such as Anaesthetie Ether；Ethyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetic acid esters, diethyl Glycol list monoethyl ether acetate, diethylene glycol monobutyl ether acetic acid esters, propylene glycol monomethyl ether, DPG monomethyl The esters such as ether acetic acid ester, butyl cellosolve acetate, carbitol acetate；The aliphatic hydrocarbons such as octane, decane；Petroleum ether, naphtha, The organic solvent classes such as the oil series solvent such as hydrogenated naphtha, solvent naphtha.
Alternatively, it is also possible to use carbitol (methyl) acrylate, pentaerythrite four (methyl) acrylate, trihydroxy methyl Propane (methyl) acrylate, three (ethoxy) isocyanuric acid ester three (methyl) acrylate, dipentaerythritol six (methyl) third Olefin(e) acid ester isoreactivity monomer class.
In addition, the reaction in order to promote phenol resin (a) and compound (b), preferably uses catalyst, as in this case Epoxy radicals and phenolic hydroxyl group catalysts, known catalyst can be used.As such catalyst, example can be enumerated Such as：Triethylamine, benzyldimethylamine, 2,4, methyl triethyl ammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, three Phenylphosphine, antimony triphenyl, sad chromium, zirconium caprylate etc..The usage amount of such catalyst is preferred relative to reacting material mixture For 0.01~1 weight %.Reaction temperature is preferably 60~150 DEG C.In addition, the reaction time is preferably 5~24 hours.So can be with Obtain intermediate X.
Resin Y enters one by the hydroxyl (alcoholic extract hydroxyl group) for the intermediate X for making above-mentioned multi-anhydride (c) and obtaining in the above described manner Step is reacted and obtained.As the multi-anhydride (c), it can enumerate：Maleic anhydride, succinic anhydride, itaconic anhydride, phthalic acid The adjacent benzene two of acid anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, Nadic anhydride, methyl tetrahydrochysene The dibasic acid anhydrides such as formic anhydride, chlorendic anhydride；Trimellitic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic acid anhydride, biphenyltetracarboxyacid acid acid anhydride Deng multi-anhydride.Generally preferably single acid anhydride, in particular it is preferred that trimellitic anhydride, tetrahydrochysene phthalate anhydride, succinic anhydride, hexahydrobenzene Dicarboxylic acid anhydride etc. has the acid anhydrides of the polyacid of 2 or 3 carboxyls, more preferably has 2 on the hydrocarbon of carbon number 2~6 Or single acid anhydride of the polyacid of 3 carboxyls, more preferably there is the list of the polyacid of 2 or 3 carboxyls in the yuan of rings of carbon 6 Acid anhydride.The yuan of rings of carbon 6 can be aromatic rings or aliphatic ring.Most preferably trimellitic anhydride or tetrahydrophthalic acid Acid anhydride.
When manufacturing resin Y, generally make saturation or unsaturated multi-anhydride (c) with relative to the hydroxyl in above-mentioned intermediate X The equivalent of base (alcoholic extract hydroxyl group) 1 reacts for 0.05~0.9 mole of ratio.
Preferably, above-mentioned saturation or unsaturated multi-anhydride (c) are made with relative to the hydroxyl (alcoholic extract hydroxyl group) 1 in intermediate X Equivalent reacts for 0.1~0.8 mole of ratio, more preferably 0.1~0.7 mole of ratio reaction.The multi-anhydride (c) of reaction When amount (addition) is very few, because the ratio of acidic-group is few, the dissolubility in alkali is deteriorated, and cannot get sufficient alkali sometimes and shows Shadow；When excessive, the electrical characteristics of cured coating film decline sometimes.
In addition, in resulting resin Y, generally, the phenolic hydroxyl group remained in intermediate X is remained as former state.It is residual in resin Y The phenolic hydroxyl group number stayed relative to the phenolic hydroxyl group number (total phenolic hydroxyl group number) of raw material phenol resin (a) ratio, typically about 10~about 90%, preferably 20~90%, more preferably 30~80%.
In addition, phenolic hydroxyl group number (total phenol of the phenolic hydroxyl group number remained in above-mentioned resin Y relative to raw material phenol resin (a) Hydroxyl value) ratio, carried out due to reacting in substantially quantitative mode, therefore can be calculated from the input amount of raw material.
In the case where resin Y is used for into photosensitive polymer combination, judge that the resin Y more than the phenolic hydroxyl group of residual is conducive to Improve the heat resistance of solidfied material.
In addition, in resin Y, existing by reacting the carboxyl introduced with above-mentioned multi-anhydride (c).As a result, of the invention Preferred resin Y be the phenolic hydroxyl group containing above-mentioned residual, carboxyl and with multi-anhydride (c) do not react the alcohol that remains The resin of this three of hydroxyl.
The preferred resin Y of the present invention is illustrated, as described below.
I. a kind of alkali developable resin, it is by making saturation and/or unsaturated multi-anhydride (c) with relative to reaction product The equivalent of hydroxyl (alcoholic extract hydroxyl group) 1 in X is further for the hydroxyl (alcoholic extract hydroxyl group) in 0.05~0.9 mole of ratio and reaction product X React and obtain, reaction product X is by making to have the compound (b) of alcoholic extract hydroxyl group and 1 epoxy radicals in molecule with relative to phenol The equivalent of hydroxyl 1 of resin (a) obtains for 0.1~0.9 mole of ratio with the hydroxyl reaction of phenol resin (a).
II. the alkali developable resin as described in above-mentioned I, wherein, there is the compound of alcoholic extract hydroxyl group and 1 epoxy radicals in molecule (b) it is glycidol or the monoglycidyl ether of the glycol of carbon number 2~4.
III. the alkali developable resin as described in above-mentioned II, wherein, above-claimed cpd (b) is glycidol.
IV. the alkali developable resin as any one of above-mentioned I~III, wherein, phenol resin (a) is contains cresols bone The phenol resin of frame or biphenyl backbone.
V. the alkali developable resin as described in above-mentioned IV, wherein, the phenol resin containing biphenyl backbone is above-mentioned formula (1) institute The phenol resin (a1) shown.
VI. the alkali developable resin as described in above-mentioned V, wherein, above-mentioned phenol resin (a1) contains resorcinol structure, and Hydroxyl equivalent is 70~140g/ equivalents.
VII. the alkali developable resin as any one of above-mentioned I~VI, wherein, above-mentioned multi-anhydride (c) is with 2 The acid anhydrides of individual or 3 carboxyls polyacid.
VIII. the alkali developable resin as described in above-mentioned VII, wherein, the acid anhydrides of the polyacid with 2 or 3 carboxyls For in the group being made up of trimellitic anhydride, tetrabydrophthalic anhydride, succinic anhydride and hexahydrophthalic anhydride extremely Few one kind.
IX. the alkali developable resin as described in above-mentioned VIII, wherein, the acid anhydrides of the polyacid with 2 or 3 carboxyls is There is the acid anhydrides of the polyacid of 2 or 3 carboxyls in the yuan of rings of carbon 6.
X. the alkali developable resin as described in above-mentioned IX, wherein, there is the polyacid of 2 or 3 carboxyls in the yuan of rings of carbon 6 Acid anhydrides be trimellitic anhydride or tetrabydrophthalic anhydride.
The invention further relates to a kind of photosensitive polymer combination, it is characterised in that resin Y, (B) containing (A) present invention Epoxy resin, (C) Photoepolymerizationinitiater initiater and (D) diluent.As diluent, particularly preferably containing polymerizable unsaturated chemical combination The mode of thing, such as (methyl) acrylate compounds.
Contained resin Y amount, total relative to photosensitive polymer combination in the photosensitive polymer combination of the present invention Amount, more preferably preferably from about 10~about 80 weight %, even more preferably about 15~about 60 weight %, 30~60 weight %.
As the epoxy resin (B) of the photosensitive polymer combination for the present invention, being generally used in 1 molecule has 2 The epoxy resin of individual above epoxy radicals.
It can enumerate for example：Biphenyl phenolic resin varnish type epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, Bisphenol-A epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, phenol aralkyl Type epoxy resin, dicyclopentadiene-phenol novolak type epoxy resin, phenol-cresol novolaks cocondensation mould assembly epoxy Resin, phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F phenolic type epoxy resin or their halogenated epoxide, Three oxybenzene methylmethane type epoxy resin, alkyl replace three oxybenzene methylmethane type epoxy resin, four hydroxy phenyl ethane type epoxy resin Obtained etc. multifunctional phenol and epoxy resin, multifunctional hydroxyl naphthalenes and epichlorohydrin reaction obtained from epichlorohydrin reaction The epoxy resin that arrives, polysiloxane modified epoxy resin, 6-caprolactone modified epoxy, by epoxychloropropane and primary amine or Hetero ring type epoxy resin such as glycidyl amine type epoxy resin, isocyanic acid three-glycidyl ester etc. obtained from the reaction of secondary amine. These epoxy resin can use a kind or and use two or more.In addition, on the basis for ensuring glass transition temperature Tg The upper purpose for improving toughness, using isocyanate modified epoxy resin, or from the viewpoint of anti-flammability is assigned, using phosphorous Epoxy resin etc., is all effective.
In order to improve adhesiveness, heat resistance, resistance to plating etc. as every characteristic of solder resist, in the composition with closing Epoxy resin (B) is stated as heat curable component, when manufacturing printed wiring board etc., after being developed with dilute alkaline aqueous solution, by adding Heat makes resin solidification, assigns wiring plate more excellent adhesiveness, heat resistance, resistance to plating etc..
Epoxy resin (B) can be used alone or be used in the form of mixture of more than two kinds, photonasty of the invention The amount of the epoxy resin contained in resin combination, relative to the total amount of composition, typically about 1~about 50 weight %, preferably It is about 3~about 45 weight %, even more preferably about 5~about 45 weight %.
During using epoxy resin (B) as above-mentioned heat curable component, in order to further improve adhesiveness, chemicals-resistant The characteristics such as property, heat resistance, preferably and use epoxy curing agent.As such epoxy curing agent, it can enumerate：Imidazoles Derivative, amphyl, dicyandiamide, cyanoguanidine derivative, hydrazide derivatives, amine, acid anhydrides etc..These curing agent can be used 1 kind or it is mixed with two or more.For the usage amount of curing agent, relative to the equivalent of epoxy radicals 1 of the epoxy resin, The amount of the reactive hydrogen of curing agent is preferably the ratio of 0.5~1.2 equivalent.
As the concrete example of the Photoepolymerizationinitiater initiater (C) of the photosensitive polymer combination for the present invention, it can enumerate：Benzene Acyloin class, acetophenones, Anthraquinones, thioxanthene ketone class, benzophenone etc., for example：There are benzoin, benzoin in benzoin class The derivatives such as methyl ether, benzoin iso-propylether；There are acetophenone, 2,2- dimethoxy -2- phenyl acetophenones, 2,2- in acetophenones Diethoxy -2- phenyl acetophenones, 1,1- dichloroacetophenones, 1- hydroxycyclohexylphenylketones, 2- methyl isophthalic acids-[4- (methyl mercapto) Phenyl] -2- morpholinopropane -1- ketone, N, the derivative such as N- dimethylamino benzoylformaldoximes；Have in Anthraquinones 2-methylanthraquinone, The derivatives such as 2- chloroanthraquinones, 2- EAQs, 2- tert-butyl groups anthraquinone, 2- amyl anthraquinones, 2- amino anthraquinones；Have in thioxanthene ketone class Thioxanthones, 2,4- dimethyl thioxanthones, 2,4- diethyl thioxanthones, CTX, ITX, 2,4- diisopropyls The derivatives such as base thioxanthones；There are benzophenone, 4- benzoyl -4'- dimethyl diphenyl sulfides, 4,4'- in benzophenone Dichloro benzophenone, N, double (diethylamino) benzophenone of N- dimethylamino benzophenones, methyl benzophenone, 4,4'-, The derivatives such as Michler's keton, 4- benzoyl -4'- dimethyl diphenyl sulfides；2,4,6- trimethylbenzoyldiphenyls are aoxidized Thing etc., can be used alone or two or more is applied in combination.
In addition, Photoepolymerizationinitiater initiater (C) can also and with sensitising agent known to tertiary amines etc..It can specifically enumerate：Three second Hydramine, tripropanol amine, triethylamine, N, N- dimethylaminos ethyl benzoate, N, N- dimethylamino benzoic acids isopentyl ester, 4- dimethylaminobenzoic acid pentyl esters etc..
Above-mentioned Photoepolymerizationinitiater initiater (C) can use a kind or be mixed with two or more, and can also further be used in combination Known sensitising agent.In the total amount of photosensitive polymer combination, the use ratio of Photoepolymerizationinitiater initiater (C) is about 0.5~about 20 weight %, preferably from about 1.0~about 15 weight %.
In the photosensitive polymer combination of the present invention, dilution is used as using polymerizable unsaturated compound and/or solvent Agent (D).The polymerizable unsaturated compound and/or solvent used as diluent (D) is to improve will be for active energy Amount light is coating when curability and/or photosensitive polymer combination are used as resist ink and used.
As such polymerizable unsaturated compound, the monomer class of preferably active energy light curability can be with Enumerate：Acrylic acid 2- hydroxy methacrylates, acrylic acid 2- hydroxy propyl esters, N- pyrrolidones, N- acryloyl morpholines, N, N- dimethyl propylenes Acrylamide, N, N- acrylamides, acrylic acid N, N- dimethylamino ethyl ester, acrylic acid N, N- dimethylamino propyl ester, Methoxy polyethylene glycol acrylate, ethyoxyl polyethylene glycol acrylate, melamine acrylate, acrylic acid phenoxy group second Ester, acrylic acid phenoxy-propyl, glycol diacrylate, propylene glycol diacrylate, poly- (propane diols) diacrylate, Trimethylolpropane trimethacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, the propylene of dipentaerythritol six Acid esters, glycerol diacrylate, isobornyl acrylate, propylene acid dihydride dicyclopentadiene base epoxide ethyl ester and and these Corresponding various methacrylates etc. (methyl) acrylate compounds.These polymerizable unsaturated compounds can use 1 Plant or and use two or more.
Generally preferable above-mentioned (methyl) acrylate compounds, in (methyl) acrylate compounds, preferably many officials (methyl) acrylate compounds of energy (methyl) acrylate compounds, generally more preferably 2~6 functions.
In the present invention, in order to form photosensitive polymer combination, the mode of polymerizable unsaturated compound is preferably comprised.
The use level of the polymerizable unsaturated compound, the parts by weight of total amount 100 relative to resin Y, usually 3~200 Parts by weight, preferably 5~200 parts by weight, more preferably even more preferably about 5~about 100 parts by weight, 7~50 parts by weight.
On the other hand, as solvent, it can enumerate：The ketones such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone；Toluene, The aromatic hydrocarbon such as dimethylbenzene；The carbitol class such as ethyl cellosolve, butyl cellosolve, carbitol, butyl carbitol；Ethyl acetate, second Acid butyl ester, cellosolve acetate, butyl cellosolve acetate, ethylcarbitol acetate, ethylene glycol monomethyl ether acetate, second Glycol monobutyl ether acetate, TC acetic acid esters, diethylene glycol monobutyl ether acetic acid esters, propylene glycol monomethyl Ether acetic acid ester (PGMEA), DPGME acetic acid esters etc..These solvents can use a kind or and use two or more.
The polymerizable unsaturated compound or solvent used as diluent (D) can be used alone or with 2 kinds with On the form of mixture be used in combination.Moreover, the usage amount of polymerizable unsaturated compound and/or solvent, relative to above-mentioned resin Y 100 parts by weight, the total amount of polymerizable unsaturated compound and/or solvent is about 10~about 200 parts by weight, preferably from about 20~about 150 parts by weight.Wherein, polymerizable unsaturated compound is also chemical combination of the imparting resin for the curability of active-energy light Thing, its usage amount is relative to the above-mentioned parts by weight of resin Y 100, usually more than 3 parts by weight, more than preferably 5 parts by weight, more excellent Elect as more than 7 parts by weight, more than most preferably 10 parts by weight, when very few, light sensitivity becomes too low sometimes, on the other hand, exceed During 200 parts by weight, in the case where photosensitive polymer combination is used as resist ink, viscosity becomes too low, makees sometimes Become insufficient for the characteristic of cured coating film.Therefore, in the present invention, it is preferred to and with appropriate polymerizable unsaturated compound with Solvent, and be prepared as fluid composition to obtain for example good coating and cured coating film characteristic.
In addition, in the photosensitive polymer combination of the present invention, in order to improve the characteristics such as adhesiveness, hardness, as needed, also It can use amorphous silica, calcium carbonate, magnesium carbonate, barium sulfate, clay, talcum, silica powder, mica powder etc. are inorganic to fill out Fill agent：The coloring pigments such as phthalocyanine green, phthalocyanine blue, titanium oxide, carbon black；The various additives such as defoamer, levelling agent, and quinhydrones, The polymerization inhibitors such as resorcinol, catechol, 1,2,3,-thrihydroxy-benzene, Hydroquinone monomethylether, tert-butyl catechol, phenthazine.
The photosensitive polymer combination of the present invention is by the way that above-mentioned each gradation composition is preferably coordinated with aforementioned proportion, and profit It is obtained by uniformly mixingg with three-roll mill etc..
As the preferred photosensitive polymer combination of the present invention, following resin combinations can be enumerated.
I. a kind of photosensitive polymer combination, wherein：
(A) alkali developable resin any one of (1) in the means used to solve the problem~(9) or as upper State the alkali developable resin any one of I~X that preferred resin Y of the invention is recorded is relative to the total amount of composition 10~80 weight %,
(B) epoxy resin is 1~50 weight % relative to the total amount of composition,
(C) Photoepolymerizationinitiater initiater is 0.5~20 weight % relative to the total amount of composition, and
(D) diluent is 10~200 parts by weight relative to the parts by weight of alkali developable resin 100.
II. the photosensitive polymer combination as described in above-mentioned I, wherein, epoxy resin be phenolic resin varnish type epoxy resin or Aralkyl-type epoxy resin.
III. the photosensitive polymer combination as described in above-mentioned I or II, wherein, epoxy resin is the ring containing biphenyl backbone Oxygen tree fat.
IV. the photosensitive polymer combination as any one of above-mentioned I~III, wherein, relative to alkali developable resin 100 parts by weight, contain the polymerizable unsaturated compound of 3~200 parts by weight as diluent.
V. the photosensitive polymer combination as described in above-mentioned IV, wherein, can relative to the parts by weight of alkali developable resin 100 The content for polymerizeing unsaturated compound is 5~100 parts by weight.
VI. the photosensitive polymer combination as described in above-mentioned IV or V, wherein, polymerizable unsaturated compound is (methyl) Acrylate compounds.
VII. the photosensitive polymer combination as any one of above-mentioned IV~VI, wherein, contain solvent as dilution Agent, the total amount of polymerizable unsaturated compound and solvent, relative to the parts by weight of alkali developable resin 100, is 10~200 weight Part.
VIII. the photosensitive polymer combination as any one of above-mentioned I~VII, wherein, relative to alkali developable tree The parts by weight of fat 100, the inorganic filler of the scope also containing 1~100 parts by weight.
In addition, the photosensitive polymer combination of the present invention is usually fluid composition, for example, solidified by following modes And obtain solidfied material.That is, by methods such as screen painting method, spraying process, rolling method, electrostatic coating processes, curtain coating methods, in printing cloth The composition of the present invention is coated with line plate with 10~160 μm of thickness, by film in 60~110 DEG C of dryings, then, makes negative film straight The film (or being placed on discontiguous state on film) is contacted, then irradiation ultraviolet radiation exposes composition, with dilute Aqueous alkali dissolving removes unexposed part and developed, and then in order to further improve every physical property, and passes through irradiation Ultraviolet and/or heating (for example being heated 0.5~1.0 hour at 100~200 DEG C) are sufficiently solidified, so as to be solidified Film.
The photosensitive polymer combination of the present invention, can also be with addition to the method being coated directly onto with liquid on base material The form of dry film is used, and the dry film is to be coated with solder resist and drying on the films such as polyethylene terephthalate in advance and formed The film with solder mask layer.Dry film have be sequentially laminated with carrier film, solder mask layer and use as needed it is peelable Cover layer structure.
In order that making diaphragm on printed wiring board of dry film, cover layer is peeled off, by solder mask layer with being formed with electricity The base material on road is overlapping, is fitted using laminating machine etc., so as to form solder mask layer on the base material for be formed with circuit.As long as right The solder mask layer that is formed similar to the above expose, develop, being heating and curing, it is possible to form cured coating film.
Embodiment
Hereinafter, the present invention is explained by embodiment and comparative example, but the present invention is not limited only to these embodiments. In addition, " part " and " % " in each example, if not otherwise specified, represents " parts by weight " and " weight % " respectively.
Synthesis example 1 (resin Y-1 synthesis example)
Input cresol novolac resin [Shonol CRG-951, Showa Highpolymer Co., Ltd's system, hydroxyl equivalent 118, 96 DEG C of softening point, number-average molecular weight 750] 118 parts of (1.0 equivalent) and 124.71 parts of propylene glycol monomethyl ethers, it is heated to 80 DEG C, by said mixture uniform dissolution.Confirm after dissolving, 37.04 parts of glycidol (0.5 mole) and triphen are added wherein 0.47 part of base phosphine, is heated to 120 DEG C and reacts about 8 hours, so as to obtain reaction product X (resins：Intermediate X).Pass through GPC (gel permeation chromatography) determines reactivity, and as a result the reactivity of glycidol is 98%.Then, reaction product X is being contained Reaction solution in, add 32.03 parts of trimellitic anhydride (0.17 mole), 100 DEG C react about 6 hours, so as to obtain the present invention Curable resin (Y-1) (solid content acid number 100mgKOH/g, solid concentration 60%).Resin Y-1 mean molecule quantity Mw is 3,200.
Synthesis example 2 (resin Y-2 synthesis example)
Put into biphenyl aralkyl type phenol resin [GPH-103, Nippon Kayaku K. K's system, hydroxyl equivalent 239, softening point 103 DEG C, all resorcinol hydroxyls of phenolic hydroxyl group (resorcinol hydroxyl 100%), weight average molecular weight 3220] 239 parts (1.0 work as Amount) and 222.04 parts of propylene glycol monomethyl ether, 80 DEG C are heated to, by said mixture uniform dissolution.Confirm after dissolving, 0.83 part of 37.04 parts of glycidol (0.5 mole) and triphenylphosphine are added wherein, are heated to 120 DEG C and are reacted about 8 hours, So as to obtain reaction product X (resins：Intermediate X).Determined by GPC and obtain reactivity, as a result the reactivity of glycidol is 98%.Then, in the reaction solution containing reaction product X, 57.02 parts of trimellitic anhydride (0.3 mole) is added, at 100 DEG C Reaction about 6 hours, so as to obtain curable resin (Y-2) (the solid content acid number 100mgKOH/g, solid concentration of the present invention 60%).Resin Y-2 average molecular weight Mw is 15,000.
Compare synthesis example 1 (curable resin Z synthesis example)
Input cresol novolak type epoxy resin [EOCN-104s, Nippon Kayaku K. K's system, epoxide equivalent 219, 90 DEG C of softening point] 219 parts of (1.0 equivalent), 72 parts of acrylic acid (1.0 moles), the 2,6- di-t-butyls as heat polymerization inhibitors 216.65 parts of 1.3 parts of paracresol and propylene glycol monomethyl ether, are heated to 95 DEG C, by said mixture uniform dissolution.Really Recognize after dissolving, 1.3 parts of triphenylphosphine is put into wherein, be heated to 100 DEG C and react about 24 hours, so as to obtain reaction product (below solid content acid number 3.0mgKOH/g).109.10 parts of tetrabydrophthalic anhydride (0.72 mole), heating are added wherein To 98 DEG C and react about 6 hours, so as to obtain the curable resin Z that compares, (solid content acid number 100mgKOH/g, solid content is dense Degree is 65%).Curable resin Z average molecular weight Mw is 6,500.
Embodiment 1~3 and comparative example 1：
Using by above-mentioned synthesis example 1 and 2 and photoresist and polymer that synthesis example 1 is obtained is compared, according to the institute of table 1 The compounding ratio shown, is kneaded using three-roll mill, so as to prepare the photosensitive resin composition of examples and comparative examples of the present invention Thing.Each composition of the embodiment 1~3 prepared with mixing ratio shown in table 1 and comparative example 1 is diluted with methyl ethyl ketone, applied Cloth is on a pet film and dry 30 minutes at 80 DEG C, so as to make the dry film shape photosensitive polymer combination layer of 20 μm of thickness.Exist again 80 DEG C predrying 30 minutes, is subsequently cooled to room temperature and obtains dry coating.The negative film with resist pattern is set to adhere to the painting On film, using ultraviolet exposure apparatus according with 350mJ/cm2Exposure, is removed after negative film, using 1% aqueous sodium carbonate, with 2.0kgf/cm2Atomisation pressure develop 60 seconds, be partly dissolved removing by unexposed.Afterwards, using air drier, 150 DEG C it is heating and curing 60 minutes, so as to prepare the solidfied material overlay film with resist pattern.
The photosensitive polymer combination of table 1.
*1NC-3000H CA75：Biphenyl phenolic resin varnish type epoxy resin [Nippon Kayaku K. K's system]
*2Irg.907：2- methyl isophthalic acids-[4- (methyl mercapto) phenyl] -2- morpholinopropanones -1 [Irgacure907, vapour Ba Our company's system]
*3DETEX-S：2,4- diethyl thioxanthones [KAYACURE DETEX-S, Nippon Kayaku K. K's system]
*4TMPTA：Trimethylolpropane trimethacrylate [ラ イ ト ア Network リ レ ー ト TMP-A, the chemistry strain formula meeting of common prosperity society Society's system]
Using the present invention and each test film for comparing product with curing overlay film obtained in the above described manner, according to following institutes The test method shown, carries out developability, adhesiveness, welding heat resistance, the gold-plated property of chemically-resistant, resistance to PCT, flexure test, cold-resistant Thermal impact experiment, HAST attribute testings, carry out the various evaluation of physical property of film.The evaluation result of these experiments is shown in table 2 With table 3.Wherein, developability is that film obtained from 80 DEG C of pre-drying-time is changed into the various times beyond 30 minutes is made Evaluated for sample.
＜ developability ＞
Each dry coating to pre-drying-time to be set as to 20 minutes, 40 minutes, 60 minutes, 80 minutes, 100 minutes, Using 1% aqueous sodium carbonate with 2.0kgf/cm2Atomisation pressure develop 60 seconds, the presence or absence of film after observation development, and pressing Evaluated according to following benchmark.
○：Film is completely removed after development, can be developed completely.
×：There is a small amount of film residual not being removed after development, development is incomplete.
＜ adhesivenesses ＞
According to JIS D 0202 test method, by the cured film cross-cut of each test film into chessboard trellis, Ran Houli Disbonded test is carried out with adhesive tape (セ ロ Ha ン テ ー プ), the exfoliated state after experiment is visually confirmed.According to following base Standard is evaluated.
○：Do not peel off completely.
△：There is a little stripping in cross-cut portion.
×：Film has stripping.
＜ welding heat resistances ＞
According to JIS C 6481 test method, each test film is impregnated 10 seconds in 280 DEG C of solder bath, carried out 3 times Dipping, after taking-up, observes the change of outward appearance.Evaluated according to following benchmark.
○：The outward appearance of cured film is unchanged.
△：Confirm cured film discoloration.
×：Cured film has tilting, stripping, solder intrusion (dive り in half field).
The gold-plated property ＞ of ＜ chemically-resistants
As the pre-treatment of test film, each test film is carried out in 30 DEG C of acidic degreasing liquid dipping → dipping washing → Soft etching process → dipping is washed → assigns catalyst (being impregnated 7 minutes in 30 DEG C of plating Raney nickel liquid) → dipping washing Process.Then, as chemical nickel plating process, dipping is carried out in the nickel-plating liquid (85 DEG C, pH 4.6) to each test film 20 minutes → Acid dip (10 volume % aqueous sulfuric acids at room temperature) 1 minute → dipping washing, finally, as chemical gilding process, to each examination Test piece and pass through dipping 10 minutes in gold plating liquid (95 DEG C, pH6, the volume % aqueous solution of potassium auricyanide 3) → dipping washing → and use 60 DEG C warm water immersion cleaning → fully washing after → remove the process of water → dryings completely and carry out chemical gilding, tested for these The change of piece observation outward appearance simultaneously carries out disbonded test using adhesive tape, evaluates film.Evaluated according to following benchmark.
○：Outward appearance is unchanged, completely the stripping without resist.
△：Although outward appearance is unchanged, the stripping of resist is somewhat observed.
×：It was observed that the tilting of resist, plating intrusion (メ ッ キ dive り), the stripping of resist is obvious in disbonded test.
＜ PCT tests ＞
Visually judge each test film at 121 DEG C, 2 atmospheric pressure, the film under saturated vapor atmosphere after placement 100 hours Outward appearance.Evaluated according to following benchmark.
○：Film is without expansion, stripping.
×：There are expansion, stripping.
＜ flexure tests ＞
According to JIS K5400, using Erichsen testing machines specified in JIS B7729A methods, by above-mentioned each photonasty Resin combination is coated on the steel plate of phosphatization processing → and dryings → exposure → development → heating is so as to prepare test film.It is right In resulting each test film, steel ball is released from the back side, and determine when deforming test film until the rupture that produces film and Release distance untill stripping.Evaluate and carried out according to following benchmark.
○：The distance for releasing steel ball is more than 4mm, and does not produce the rupture and stripping of film.
△：It is 2mm less than 4mm to release the distance of steel ball, and does not produce the rupture and stripping of film.
×：The distance for releasing steel ball is less than 2mm, and produces the rupture and stripping of film.
The cold-resistant thermal impact experiment ＞ of ＜
Make to have and be formed with pierced patterns, the evaluation substrate of the solder resist cured coating film of zero pierced pattern.For institute Obtained evaluation substrate, using cold shock testing device (Etac company systems), will make for -55 DEG C/30 minutes~150 DEG C/30 minutes For 1 circulation, the resistance test of 1000 circulations is carried out, after experiment, the cured film after observation processing, and under by visual observation The benchmark stated judges the production of crackle.
○：The generation rate of crackle is less than 30%
△：The generation rate of crackle is 30%~50%
×：The generation rate of crackle is more than 50%
＜ HAST characteristics ＞
It is being formed with the BT substrates of comb-type electrode (line width/line-spacing=30 μm/30 μm), is forming solder resist cured coating film, So as to be made evaluation substrate.The evaluation substrate is put into 130 DEG C, in the hot and humid groove in the environment of humidity 85%, applies electricity 5.5V is pressed, HAST experiments (insulating properties experiment) in the groove of various times are carried out.According to following judgment standards, evaluate by various The groove interior insulation resistance value of time.
○：After 240 hours, in 108 more than Ω
×：After 240 hours, in 108 below Ω
The developability evaluation result of table 2
80 DEG C of drying times (minute) Embodiment 1 Embodiment 2 Embodiment 3 Comparative example 1
20 ○ ○ ○ ○
40 ○ ○ ○ ○
60 ○ ○ ○ ×
80 ○ ○ ○ ×
100 ○ ○ ○ ×
120 ○ ○ ○ ×
The various evaluation results of table 3
Pilot project Embodiment 1 Embodiment 2 Embodiment 3 Comparative example 1
Adhesiveness ○ ○ ○ ○
Weld heat resistance ○ ○ ○ ×
The gold-plated property of chemically-resistant ○ ○ ○ △
Resistance to PCT ○ ○ ○ ×
It is flexible ○ ○ ○ △
Cold-resistant thermal impact ○ ○ ○ ×
HAST characteristics ○ ○ ○ ×
From the evaluation result of table 2 and table 3, alkali developable resin of the invention and known epoxies photonasty Resin is compared, and drying property, alkali-developable are excellent, the adhesiveness of its solidfied material, welding heat resistance, the gold-plated property of chemically-resistant, resistance to PCT Property, flexibility, cold-resistant thermal impact, HAST characteristics etc. are excellent.
Synthesis example 3 (resin Y-3 synthesis example)
The record according to Japanese Unexamined Patent Publication 8-143648 is put into, with generally relative to 9 moles of phenol, 1 mole of resorcinol Ratio use as both phenol and resorcinol of phenolic compounds manufacture biphenyl phenolic varnish type contain resorcinol Phenol resin [hydroxyl equivalent 134g/ equivalents, 93.4 DEG C of softening point, ratio { (the resorcinol hydroxyl value/phenol tree of resorcinol hydroxyl Total phenolic hydroxyl group number in fat (a1)) × 100=about 20%] 134 parts of (hydroxyl equivalents：1.0 equivalents), propylene glycol monomethyl ether second 179.56 parts of acid esters, is heated to 80 DEG C, the above-mentioned mixture of uniform dissolution.Confirm after dissolving, glycidol is put into wherein 14.82 parts (0.2 mole), 0.45 part of triphenylphosphine, are heated to 120 DEG C and react about 8 hours, so as to obtain reaction product X (trees Fat：Intermediate X).Determined by GPC and obtain reactivity, as a result the reactivity of glycidol is 98%.Then, anti-containing this In the reaction solution for answering product X, 30.74 parts of trimellitic anhydride (0.16 mole) is added, is reacted about 6 hours at 100 DEG C, so as to obtain The curable resin (Y-3) (solid concentration 50%, solid content acid number 100mgKOH/g) of the present invention.Resin Y-3's is averaged Molecular weight Mw is 1,900.
Synthesis example 4 (resin Y-4 synthesis example)
Put into the biphenyl phenolic varnish type resorcinol resin synthesized according to the embodiment 1 of Japanese Unexamined Patent Publication 7-292066 [hydroxyl equivalent 102,85.2 DEG C of softening point] 102 parts of (1.0 equivalent) and 192.09 parts of propylene glycol monomethyl ethers, are heated to 80 DEG C, by said mixture uniform dissolution.Confirm after dissolving, 37.04 parts of glycidol (0.5 mole), triphen are added wherein 0.42 part of base phosphine, is heated to 120 DEG C and reacts about 8 hours, so as to obtain reaction product X (resins：Intermediate X).Surveyed by GPC Surely reactivity is obtained, as a result the reactivity of glycidol is 98%.Then, in the reaction solution containing reaction product X, add 51.05 parts of tetrabydrophthalic anhydride (0.34 mole), reacts about 6 hours at 100 DEG C, so as to obtain the curability tree of the present invention Fat (Y-4) (solid concentration 50%, solid content acid number 100mgKOH/g).Resin Y-4 average molecular weight Mw is 1,200.
Embodiment 4~7 and comparative example 2：
Use respectively by above-mentioned synthesis example 2,3,4 and above-mentioned compare resin Y-2, Y-3, Y-4 and the solidification that synthesis example 1 is obtained Property resin Z, according to the allotment ratio shown in table 4 utilize three-roll mill knead, prepare examples and comparative examples of the present invention sense Photosensitive resin composition.By the embodiment 4~7 and each composition methyl of comparative example 2 that are prepared with the mixing ratio shown in table 4 Ethyl ketone dilutes, and coating is on a pet film and dry 30 minutes at 80 DEG C, so as to make the photonasty tree of the dry film shape of 20 μm of thickness Oil/fat composition layer.Then, at 80 DEG C after predrying 30 minutes, it is cooled to room temperature to obtain dry coating.Make with resist figure The negative film of case is adhered on the film, using ultraviolet exposure apparatus according, with 350mJ/cm2Exposure, removes after negative film, uses 1% Aqueous sodium carbonate, with 2.0kgf/cm2Atomisation pressure develop 60 seconds, be partly dissolved removing by unexposed.Afterwards, use Air drier, is heating and curing 60 minutes at 150 DEG C, so as to make the solidfied material overlay film (examination of the invention with resist pattern Test piece and compare and use test film).
The photoresist of table 4 is constituted
*1NC-3000H CA75：Biphenyl phenolic resin varnish type epoxy resin [Nippon Kayaku K. K's system]
*2Irg.907：2- methyl isophthalic acids-[4- (methyl mercapto) phenyl] -2- morpholinopropanones -1 [Irgacure907, vapour Ba Our company's system]
*3DETEX-S：2,4- diethyl thioxanthones [KAYACURE DETEX-S, Nippon Kayaku K. K's system]
*4DPTA：Dipentaerythritol acrylate [KAYARAD DPHA, Nippon Kayaku K. K's system]
Using the present invention with the curing overlay film obtained in the above described manner and each test film compared, according to above-mentioned Test method, carries out developability, adhesiveness, welding heat resistance, the gold-plated property of chemically-resistant, resistance to PCT, flexure test, carries out film Various evaluation of physical property.The evaluation result of these experiments is shown in table 5 and table 6.Wherein, developability is predrying by 80 DEG C Film obtained from time changes into the various times beyond 30 minutes is evaluated as sample.Metewand and table 2 Situation is identical.
The developability evaluation result of table 5
80 DEG C of drying times (minute) Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Comparative example 2
20 ○ ○ ○ ○ ○
40 ○ ○ ○ ○ ○
60 ○ ○ ○ ○ ×
80 ○ ○ ○ ○ ×
100 ○ ○ ○ × ×
120 ○ ○ ○ × ×
The various evaluation results of table 6
Pilot project Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Comparative example 2
Adhesiveness ○ ○ ○ ○ ○
Weld heat resistance ○ ○ ○ ○ ×
The gold-plated property of chemically-resistant ○ ○ ○ ○ △
Resistance to PCT ○ ○ ○ ○ ×
It is flexible ○ ○ ○ ○ △
Cold-resistant thermal impact ○ ○ ○ ○ ×
HAST characteristics ○ ○ ○ ○ ×
From the evaluation result of table 5 and table 6, alkali developable resin of the invention and known epoxies photonasty Resin is compared, and drying property, alkali-developable are excellent, the adhesiveness of its solidfied material, welding heat resistance, the gold-plated property of chemically-resistant, resistance to PCT Property, flexibility, cold-resistant thermal impact, HAST characteristics etc. are excellent.
Particularly, the alkali developable resin of the invention of the phenol resin of resorcinol is contained comprising biphenyl phenolic varnish type, It is more excellent than other in terms of drying property and alkali-developable in the alkali developable resin of the present invention.
Industrial applicability
The drying property of the photosensitive polymer combination of the present invention, alkali-developable are excellent, and the adhesion of the film after solidification Property, welding heat resistance, the gold-plated property of chemically-resistant, resistance to PCT, flexibility, cold-resistant thermal impact, each characteristic good such as HAST characteristics.Can With with low cost and productivity ratio forms cured film well, therefore, the purple except being used for active energy ray-curable Outside purposes of outside line curing type printing-ink etc., manufacture printed wiring board when use solder resist, resist, plating resist apply It is also useful in terms of agent, interlayer dielectic.

Claims (16)

1. a kind of alkali developable resin, it is by making to have in molecule the compound (b) and phenol resin of alcoholic extract hydroxyl group and 1 epoxy radicals (a) hydroxyl in reaction product X obtained from hydroxyl reaction further reacts with saturation and/or unsaturated multi-anhydride (c) And obtain, wherein,
The compound (b) is set to be reacted by 0.1~0.9 mole of ratio of the equivalent of phenolic hydroxyl group 1 relative to phenol resin (a),
The multi-anhydride (c) is set to be reacted by 0.05~0.9 mole of ratio of the equivalent of alcoholic extract hydroxyl group 1 relative to reaction product X,
Relative to total phenolic hydroxyl group number in phenol resin (a), the ratio of the phenolic hydroxyl group remained in alkali developable resin is 30~80%,
Phenol resin (a) is the phenol resin (a1) shown in following formulas (1)：
M1, m2 and m3 are each independently 1 or 2 integer in formula, and n represents 0~10 integer.
2. alkali developable resin as claimed in claim 1, wherein, phenol resin (a1) is the phenol wherein containing resorcinol structure Resin.
3. alkali developable resin as claimed in claim 2, wherein, the hydroxyl equivalent of the phenol resin containing resorcinol structure is 70~170g/ equivalents.
4. alkali developable resin as claimed in claim 1 or 2, wherein, compound (b) is glycidol.
5. alkali developable resin as claimed in claim 1 or 2, wherein, the multi-anhydride (c) is with 2 or 3 carboxyls Polyacid acid anhydrides.
6. a kind of photosensitive polymer combination, it is characterised in that contain：
(A) alkali developable resin according to any one of claims 1 to 5,
(B) epoxy resin,
(C) Photoepolymerizationinitiater initiater and
(D) diluent.
7. photosensitive polymer combination as claimed in claim 6, it is characterised in that diluent is polymerizable unsaturated compound And/or solvent.
8. photosensitive polymer combination as claimed in claims 6 or 7, it is characterised in that
(A) alkali developable resin is 10~80 weight % relative to the total amount of composition；
(B) epoxy resin is 1~50 weight % relative to the total amount of composition；
(C) Photoepolymerizationinitiater initiater is 0.5~20 weight % relative to the total amount of composition；And
(D) diluent is 10~200 parts by weight relative to the parts by weight of alkali developable resin 100.
9. photosensitive polymer combination as claimed in claims 6 or 7, wherein, relative to the parts by weight of alkali developable resin 100, Polymerizable unsaturated compound is contained using 5~200 weight % scope and is used as diluent.
10. photosensitive polymer combination as claimed in claim 9, wherein, polymerizable unsaturated compound is (methyl) propylene Ester compound.
11. the solidfied material of the photosensitive polymer combination any one of claim 6~10.
12. the solidfied material of photosensitive polymer combination as claimed in claim 11, it is that use can carry out ultra micro using light Solidfied material obtained from the photoetching process of fining-off is patterned.
13. a kind of base material, it has the layer of claim 11 or the solidfied material described in claim 12.
14. a kind of article, it has the base material described in claim 13.
15. a kind of forming method of cured coating film, it is characterised in that by the photonasty any one of claim 6~10 Resin combination is coated on printed wiring board and forms film, is exposed, develops, then by irradiation ultraviolet radiation and/or Heating solidifies it.
16. the reaction product X's with both phenolic hydroxyl group and alcoholic extract hydroxyl group is used for the alkali developable resin described in manufacturing claims 1 Purposes, the reaction product X is by making to have the compound (b) of alcoholic extract hydroxyl group and 1 epoxy radicals in molecule with relative to phenol tree The equivalent of hydroxyl 1 of fat (a) obtains for 0.1~0.9 mole of ratio with the hydroxyl reaction of phenol resin (a).
CN201380037427.2A 2012-07-13 2013-07-03 Alkali developable resin, the photosensitive polymer combination using the resin Expired - Fee Related CN104470962B (en)

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