CN104470962A - Alkali development type resin, and photosensitive resin composition using same - Google Patents

Alkali development type resin, and photosensitive resin composition using same Download PDF

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Publication number
CN104470962A
CN104470962A CN201380037427.2A CN201380037427A CN104470962A CN 104470962 A CN104470962 A CN 104470962A CN 201380037427 A CN201380037427 A CN 201380037427A CN 104470962 A CN104470962 A CN 104470962A
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resin
alkali developable
phenol resins
developable resin
hydroxyl group
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CN104470962B (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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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
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  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Epoxy Resins (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)

Abstract

The present invention relates to an alkali development type resin which is obtained by reacting a compound (b) having an alcoholic hydroxyl group and one epoxy group in the molecule with the hydroxyl groups of a phenolic resin (a), and further reacting the hydroxyl groups in the obtained reaction product X with saturated and/or unsaturated polybasic acid anhydride (c); and relates to a photosensitive resin composition containing (A) said alkali development type resin, (B) an epoxy resin, (C) a photopolymerization initiator, and (D) a diluent. Said resin composition has excellent drying properties and alkali developability, and a coated film after curing is outstanding in various characteristics such as adhesion, solder heat resistance, electroless gold plating resistance, PCT resistance, flexibility, thermal shock resistance, and HAST characteristics, and is useful as a solder resist, etching resist, plating resist, or inter-layer insulating material used during manufacture of printed wiring boards.

Description

Alkali developable resin, use the photosensitive polymer combination of this resin
Technical field
The present invention relates to alkali developable resin and the photosensitive polymer combination containing this resin.In more detail, the alkali developable resin for field of electronic materials such as the solder resist of printed wiring board, high-density multi-layered plate interlayer dielectric, semiconductor-sealing-purpose solder resists and photosensitive polymer combination is related to.
Background technology
In the past, permanent mask resist during printed wiring board manufactures can pass through the method manufacture of silk screen printing thermohardening type or ultraviolet hardening resist ink, but at present from productivity aspect, gradually to the future development of the liquid photoresistance solder flux of alkali developable.
But, for the in the past commercially available printed wiring board being applied with alkali developable solder resist, PCT (Pressure Cooker Test (pressure furnace test)) patience as the long-term reliability test of encapsulation is poor, and the stripping of cured article occurs.
In addition, due to the moisture absorption of solder resist, in the Reflow Soldering when encapsulation is installed, in the moisture boiling of the inner moisture absorption of encapsulation, observe the problem of the solder resist epithelium encapsulating inside and the so-called puffed rice phenomenon cracked thereof around.Resistance to water absorbability like this, the problem of long-term reliability, be not limited in the situation of above-mentioned field engineering, the solder resist used in the manufacture of the solder resist of general printed wiring board, flexible printed circuit board, carrier package (Tape Carrier Package), increase the multiwiring boards such as layer (Build-up) substrate other purposes such as interlayer insulating film goods in, also undesirably there is so resistance to water absorbability and the problem of long-term reliability.
Visible, along with the development of nearest electrical industry, semiconductor industry, require that characteristic improves further, such as, require to improve thermotolerance, toughness, flexibility, water tolerance, chemical-resistant, developing the various novel photoresist that can meet these.
In the past, particularly, using phenolic resin varnish type epoxy resin as the photoresist of starting raw material, due to its excellent tackiness, thermotolerance, chemical-resistant, electrical insulating property etc., and be widely used in the multiple fields of the electronic material such as solder resist, resist.Especially as the photoresist containing carboxyl of excellent heat resistance, use: make the resin (patent documentation 1) that multi-anhydride and cresol novolak type epoxy resin and the monocarboxylic reaction product containing unsaturated group carry out reacting and obtain more.But although the excellent heat resistance of this resin, contraction during solidification is large, extend less, shortcoming toughness, the difficult problem therefore existed easily cracks because of thermal shocking.As solving the photoresist of this difficult problem, propose: the photosensitivity prepolymer (patent documentation 2) of the reaction product of the resin obtained as the pendant hydroxyl moieties epoxidation by bisphenol-type epoxy resin, (methyl) vinylformic acid and multi-anhydride, make the reaction of Tetra Hydro Phthalic Anhydride and cresol novolak type epoxy resin, vinylformic acid and p-hydroxyphenylethanol and the Polycarboxylic acid resin (patent documentation 3) etc. containing unsaturated group that obtains.But these resins are yet not enough to meet thermotolerance and toughness simultaneously.
In addition, as the resin with excellent long-term reliability, propose: by modified for novolac resin oxirane, addition (methyl) vinylformic acid, then addition multi-anhydride and obtain containing the photoresist (patent documentation 4) of carboxyl.But, also have the leeway of improvement in the drying property after Ink Application.That is, these compositions are in order to develop with dilute alkaline aqueous solution, need to improve acid number.Therefore, in solvent seasoning operation after being coated on substrate by the material being combined with ink, must time of drying being shortened, to expose and in a succession of operation of developing by being dried to, under needing long situation after the drying, exist and cannot promptly remove the problems such as the unexposed part of film.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 1-54390 publication
Patent documentation 2: Japanese Unexamined Patent Publication 9-54434 publication
Patent documentation 3: Japanese Unexamined Patent Publication 11-288091 publication
Patent documentation 4: Japanese Patent No. 3964326 publication
Summary of the invention
Invent problem to be solved
The present invention makes in view of the above problems, and object is to provide a kind of resin containing carboxyl, and it has the various physical property such as good developability, thermotolerance, wet fastness, tackiness, and can obtain the excellent ink composite of drying property.
Another object of the present invention is to provide a kind of liquid curing resin combination, it has following characteristic: the cured film that can form the every characteristic good required by following various uses, and densification and the surface mounting of printed wiring board can be tackled, can develop with dilute alkaline aqueous solution.Namely, in the interlayer insulating film of the multiwiring boards such as the solder resist at general printed wiring board, the solder resist for the manufacture of flexible printed circuit board, carrier package, increasing laminar substrate etc., require the cured film with every characteristics such as excellent developability, adhesivity, welding thermotolerance, resistance to water absorbability, PCT patience, electrical insulating properties, especially, in IC encapsulation, the cured film of the characteristic good such as resistance to water absorbability and PCT (pressure furnace test) patience is required.The object of this invention is to provide a kind of curable resin composition, it can form the cured film of the every characteristic good required by these various uses, and has above-mentioned characteristic.
For the means of dealing with problems
The present inventor etc. are in order to solve these technical problems in the past, find that one is skeleton with phenol resins, introduce primary hydroxyl and reactive functional groups wherein and obtain reaction product, the carboxyl of functional group is introduced as again and the alkali developable resin obtained in this reaction product, namely, make to have in molecule the compound (b) of alcoholic extract hydroxyl group and 1 epoxy group(ing) and the hydroxyl reaction of phenol resins (a) and hydroxyl in the reaction product X (resin) that obtains react with saturated and/or unsaturated multi-anhydride (c) further and the resin containing carboxyl that obtains, namely, alkali developable resin can reach above-mentioned purpose, thus complete the present invention.
In addition, the term " alkali developable resin " in this specification sheets is can give the implication of the resin of resin combination alkali-developable, that is, the implication can giving the resin of alkali-developable uses.Therefore, alkali developable resin of the present invention is suitable for alkali development photosensitive polymer combination most, also can be used for the purposes beyond this purposes.
In addition, term " (methyl) vinylformic acid " uses with at least any one the implication of acrylic or methacrylic acid, and (methyl) acrylate (acrylate or methacrylic ester at least any one) etc. is also use 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 " resin Y of the present invention " or referred to as " resin Y "), the hydroxyl in its reaction product X (hereinafter also referred to as " intermediate X ") obtained by making to have in molecule the compound (b) (hereinafter also referred to as " compound b ") of alcoholic extract hydroxyl group and 1 epoxy group(ing) and the hydroxyl reaction of phenol resins (a) reacts with above-mentioned multi-anhydride (c) (hereinafter also referred to as " multi-anhydride (c) ") and obtains further.
(2) the alkali developable resin as described in above-mentioned (1), is characterized in that, makes above-claimed cpd (b) with the ratio reaction relative to phenolic hydroxyl group 1 equivalent of phenol resins (a) being 0.1 ~ 0.9 mole.
(3) the alkali developable resin as described in above-mentioned (1) or (2), is characterized in that, makes above-mentioned multi-anhydride (c) with the ratio reaction relative to hydroxyl 1 equivalent of reaction product X being 0.05 ~ 0.9 mole.
(4) the alkali developable resin according to any one of above-mentioned (1) ~ (3), wherein, relative to the total phenolic hydroxyl group number in phenol resins (a), the ratio of phenolic hydroxyl group residual in alkali developable resin is 10 ~ 90%.
(5) the alkali developable resin according to any one of above-mentioned (1) ~ (4), wherein, phenol resins (a) is the phenol resins (a) containing biphenyl backbone.
(6) the alkali developable resin according to any one of above-mentioned (1) ~ (5), wherein, phenol resins (a) is the phenol resins (a1) shown in following general formula (1):
In formula, m1, m2 and m3 are the integer of 1 or 2 independently of one another, and n represents the integer of 0 ~ 10.
(7) the alkali developable resin as described in above-mentioned (6), wherein, phenol resins (a1) is the phenol resins wherein containing Resorcinol structure.
(8) the alkali developable resin as described in above-mentioned (7), wherein, the hydroxyl equivalent of the phenol resins containing Resorcinol structure is 70 ~ 170g/ equivalent.
(9) the alkali developable resin according to any one of above-mentioned (1) ~ (8), wherein, compound (b) is Racemic glycidol.
(10) the alkali developable resin according to any one of above-mentioned (1) ~ (9), wherein, above-mentioned multi-anhydride (c) is for having the acid anhydrides of the polyprotonic acid of 2 or 3 carboxyls.
(11) photosensitive polymer combination, is characterized in that, contains:
Alkali developable resin (A) according to any one of above-mentioned (1) ~ (10),
(B) epoxy resin,
(C) Photoepolymerizationinitiater initiater and
(D) thinner.
(12) photosensitive polymer combination as described in above-mentioned (11), is characterized in that, thinner is polymerizable unsaturated compound and/or solvent.
(13) photosensitive polymer combination as described in above-mentioned (11) or (12), is characterized in that,
(A) alkali developable resin-phase is 10 ~ 80 % by weight for the total amount of composition;
(B) epoxy resin is 1 ~ 50 % by weight relative to the total amount of composition;
(C) Photoepolymerizationinitiater initiater is 0.5 ~ 20 % by weight relative to the total amount of composition; And
(D) thinner is 10 ~ 200 weight parts relative to alkali developable resin 100 weight part.
(14) photosensitive polymer combination according to any one of above-mentioned (11) ~ (13), wherein, relative to alkali developable resin 100 weight part, the scope using 5 ~ 200 % by weight contains polymerizable unsaturated compound as thinner.
(15) photosensitive polymer combination as described in above-mentioned (14), wherein, polymerizable unsaturated compound is (methyl) acrylic compound.
(16) cured article of the photosensitive polymer combination according to any one of above-mentioned (11) ~ (15).
(17) cured article of the photosensitive polymer combination as described in above-mentioned (16), it carries out patterning and the cured article that obtains for using the photolithography that light can be utilized to carry out superstructure technologies.
(18) base material, it has the layer of above-mentioned (16) or the cured article described in (17).
(19) article, it has the base material described in above-mentioned (18).
(20) a kind of formation method of cured coating film, it is characterized in that, photosensitive polymer combination according to any one of above-mentioned (11) ~ (15) is coated on printed wiring board and forms film, carry out exposing, developing, then make it solidify by irradiation ultraviolet radiation and/or heating.
(21) have the purposes for the manufacture of the alkali developable resin described in above-mentioned (1) of the reaction product X of phenolic hydroxyl group and alcoholic extract hydroxyl group, this reaction product X obtains by making to have in molecule the compound (b) of alcoholic extract hydroxyl group and 1 epoxy group(ing) and the hydroxyl reaction of phenol resins (a).
Invention effect
Drying property, the alkali-developable of photosensitive polymer combination of the present invention are excellent, and adhesivity, every characteristic good such as welding thermotolerance, the gold-plated property of chemically-resistant, resistance to PCT, flexibility, cold-hot impact, HAST characteristic etc. of film after solidification.Can low cost and productivity forms cured film well, therefore, except may be used for using the ultraviolet hardening printing-ink purposes that is cured of active energy beam etc., be also useful in the solder resist, resist, plating resist application, interlayer dielectic etc. that use when manufacturing printed wiring board.
Embodiment
Below, the present invention is illustrated in greater detail.
First, in resin Y of the present invention, use phenol resins (a) as skeleton resin.Phenol resins (a) in the present invention refers to sensu lato phenol resins, refers to " resin in a part with at least 2 phenolic hydroxyl groups ".Therefore, as phenol resins (a), be used in a part the phenol resins with more than at least 2 phenolic hydroxyl groups.The phenol resins that this phenol resins (a) can use soluble type, phenolic varnish type, cresols type etc. whole.In addition, also can use: the epoxide modified type obtained with the multifunctional phenolic compound of epoxy compounds modification, make phenols and divinyl (being total to) polymkeric substance addition and the polymer resin etc. of the polymer resin of phenols addition divinyl (being total to) polymkeric substance, phenols and the dicyclopentadiene that obtain, phenols and biphenyl.
Specifically, can illustrate: the novolak type phenol resin such as phenol resol resins, cresol novolac resin, biphenyl phenolic varnish type resorcinol resin; To the novolak type phenol resin of xylylene modified novolac resin, a modification such as xylylene modified novolac resin, adjacent xylylene modified novolac resin; The bisphenol cpd such as dihydroxyphenyl propane, Bisphenol F; Biphenyl type phenol resin; Soluble type phenol resins; The aralkyl type phenol resin such as phenol aralkyl resin, biphenyl aralkyl type phenol resin; The alkane type phenol resins such as trisphenol alkane type resin and polymkeric substance thereof; Phenol resins containing naphthalene nucleus, dicyclopentadiene modified phenolic resin, ester ring type phenol resins, heterocyclic type phenol resins etc.These phenol resins can use a kind or and use two or more.
As the molecular weight of this phenol resins (a), use molecular weight to be about 300 ~ about 30, the phenol resins of 000, preferred molecular weight is about 400 ~ about 15,000.As the molecular weight of resin, use number-average molecular weight or weight-average molecular weight, as long as any one is in above-mentioned scope.
As the preferred resin of above-mentioned phenol resins (a), can enumerate: novolak type phenol resin, more preferably can enumerate: the phenol resins in its structure with cresols skeleton or biphenyl backbone, further preferably can enumerate: the phenol resins with biphenyl backbone.Specifically, as the novolak type phenol resin with cresols skeleton, cresols type novolac resin can be enumerated; As the phenol resins with biphenyl backbone, biphenyl aralkyl type phenol resin, biphenyl novolak type phenol resin etc. can be enumerated.
Be more preferably the novolak type phenol resin containing biphenyl backbone, the phenol resins (a1) more preferably shown in following general formula (1);
In formula, m1, m2 and m3 are the integer of 1 or 2 independently of one another, and n represents the integer of 0 ~ 10.
In addition, in the phenol resins (a1) (hereinafter also referred to as " phenol resins (a1) ") of above-mentioned general formula (1), the phenol resins of the phenyl ring (preferred Resorcinol structure) at least partially with 2 hydroxyls in the skeleton of more preferably phenol resins (a1).
Relative to the total phenolic hydroxyl group number in phenol resins (a1), there is the ratio of the hydroxyl value in the phenyl ring (preferred Resorcinol structure) of 2 hydroxyls, be preferably the ratio of 5 ~ 100%.This ratio is: the ratio calculated by the phenol of use during synthesis phenol resins (a1) and the molar ratio of dihydroxy-benzene (preferred Resorcinol), used phenol mole number is set to d1, when the mole number of dihydroxy-benzene (preferred Resorcinol) is set to d2, calculated by following formula.
{(d2×2)/(d1+d2×2)}×100
As phenol resins (a1), preferably molecular-weight average is used to be about 500 ~ about 15, the phenol resins of 000.
In addition, the phenol resins (a1) of these general formulas (1) can obtain according to the method manufacture recorded in known document; Such as, according to the record of Japanese Unexamined Patent Publication 8-143648 publication, Japanese Unexamined Patent Publication 7-292066 publication etc., or according to this record, can easily obtain.That is, can by making two (methoxymethyl) biphenyl or two (chloromethyl) biphenyl etc. with phenol or/and resorcin reaction and obtaining.
The preferable range of the hydroxyl equivalent of phenol resins (a1) is about 70 ~ about 170g/ equivalent, can be according to circumstances about 102 ~ about 140g/ equivalent.The mensuration of the hydroxyl equivalent of phenol resins can be undertaken by ordinary method.
As react with above-mentioned phenol resins (a), the compound (b) in the molecule with alcoholic extract hydroxyl group and 1 epoxy group(ing), as long as have the compound of alcoholic extract hydroxyl group and 1 epoxy group(ing) in the molecule, just can use known various compound, can enumerate such as: Racemic glycidol, or the monoglycidyl ether etc. of the glycol of the carbonatoms 2 ~ 4 such as ethylene glycol monoglycidyl ether.In the present invention, particularly preferably Racemic glycidol.
In the reaction of phenol resins (a) with compound (b), compound (b) is preferably made to be 0.1 ~ 0.9 mole with phenolic hydroxyl group 1 equivalent relative to phenol resins (a), more preferably 0.1 ~ 0.8 mole, preferably the ratio of 0.2 ~ 0.8 mole is reacted further.In addition, according to circumstances, make compound (b) to be the ratio of 0.1 ~ 0.7 mole or the ratio of 0.1 ~ 0.6 mole relative to phenolic hydroxyl group 1 equivalent of phenol resins (a), it is very preferred for reacting with the ratio of 0.2 ~ 0.6 mole further.
When the amount of compound (b) is too much, follow-up reaction with multi-anhydride (c) and obtain the water-soluble of resin X of the present invention and become too high, thus the water tolerance being sometimes combined with the cured article of the resin combination of resin X declines.
In the reaction, the epoxy group(ing) of compound (b) and the phenolic hydroxyl group open loop addition of phenol resins (a), thus form ehter bond, and form secondary hydroxyl group.
In the reaction of phenol resins (a) with compound (b), preferably, phenol resins (a) is not that whole phenolic hydroxyl groups and compound (b) react (hereinafter also referred to alcohol modification), but reacts in the mode of the unreacted phenolic hydroxyl group of a residual part.Consequently, preferred intermediate X contains unreacted phenolic hydroxyl group and alcoholic extract hydroxyl group.By the total amount of the phenolic hydroxyl group of the phenol resins (a) of initial substance (in intermediate X, the phenolic hydroxyl group of alcohol modification and the total amount of residual phenolic hydroxyl group) when being set to 1, relative to this, the ratio of phenolic hydroxyl group residual in intermediate X is the ratio of about 0.1 ~ about 0.9, be preferably the ratio of about 0.2 ~ about 0.9, be more preferably the ratio of about 0.3 ~ about 0.9.
In addition, the residual phenolic hydroxyl group of intermediate X is kept intact in resin Y.This is because: in this intermediate X and follow-up with the reaction of the multi-anhydride (c) of its reaction, multi-anhydride (c) reacts with the alcoholic extract hydroxyl group in this intermediate X, and does not react with phenolic hydroxyl group.
In the mill during mesosome X, solvent can be used in the reaction of phenol resins (a) with compound (b).As used solvent, known solvent can be used, can enumerate such as: the ketone such as methyl ethyl ketone, pimelinketone; The arenes such as toluene, dimethylbenzene, tetramethyl-benzene; The ethers of the glycol such as dipropylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether; The ester classes such as ethyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetic ester, TC acetic ester, diethylene glycol monobutyl ether acetic ester, propylene glycol monomethyl ether, DPGME acetic ester, butyl cellosolve acetate, carbitol acetate; The aliphatic hydrocarbon such as octane, decane; The organic solvent classes such as petroleum solvent such as sherwood oil, petroleum naphtha, hydrogenated naphtha, solvent naphtha.
In addition, Trivalin SF (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, TriMethylolPropane(TMP) (methyl) acrylate, three (hydroxyethyl) isocyanuric acid ester three (methyl) acrylate, Dipentaerythritol six (methyl) acrylate isoreactivity monomer class can also be used.
In addition, in order to promote the reaction of phenol resins (a) and compound (b), preferably using catalyzer, as the catalysts of epoxy group(ing) in this case and phenolic hydroxyl group, known catalyzer can be used.As such catalyzer, can enumerate such as: triethylamine, benzyl dimethyl amine, methyl triethyl ammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, antimony triphenyl, sad chromium, zirconium caprylate etc.The usage quantity of such catalyzer is preferably 0.01 ~ 1 % by weight relative to reacting material mixture.Temperature of reaction is preferably 60 ~ 150 DEG C.In addition, the reaction times is preferably 5 ~ 24 hours.So intermediate X can be obtained.
Resin Y obtains by making above-mentioned multi-anhydride (c) react further with the hydroxyl (alcoholic extract hydroxyl group) of the intermediate X obtained in the above described manner.As this multi-anhydride (c), can enumerate: the dibasic acid anhydrides such as maleic anhydride, succinyl oxide, itaconic anhydride, Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, Nadic anhydride, methyl tetrahydrophthalic anhydride, hexachloroendomethylene-tetrahvdrophthalic anhydride; The multi-anhydrides such as trimellitic acid 1,2-anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic acid anhydride, biphenyltetracarboxyacid acid acid anhydride.Usual preferred single acid anhydride, particularly, preferred trimellitic acid 1,2-anhydride, tetrahydrochysene phthalate anhydride, succinyl oxide, hexahydrophthalic acid anhydride etc. have the acid anhydrides of the polyprotonic acid of 2 or 3 carboxyls, be more preferably single acid anhydride of the polyprotonic acid on the hydrocarbon of carbonatoms 2 ~ 6 with 2 or 3 carboxyls, more preferably there is single acid anhydride of the polyprotonic acid of 2 or 3 carboxyls in carbon 6 ring.This carbon 6 ring can be aromatic nucleus, also can be aliphatics ring.Most preferably be trimellitic acid 1,2-anhydride or Tetra Hydro Phthalic Anhydride.
When manufacturing resin Y, usually make saturated or unsaturated multi-anhydride (c) with the ratio reaction relative to hydroxyl (alcoholic extract hydroxyl group) 1 equivalent in above-mentioned intermediate X being 0.05 ~ 0.9 mole.
Preferably, make above-mentioned saturated or unsaturated multi-anhydride (c) with the ratio reaction relative to hydroxyl (alcoholic extract hydroxyl group) 1 equivalent in intermediate X being 0.1 ~ 0.8 mole, more preferably the ratio reaction of 0.1 ~ 0.7 mole.When the amount (addition) of the multi-anhydride (c) of reaction is very few, because the ratio of acidic-group is few, the solvability in alkali is deteriorated, and sometimes can not get sufficient alkali-developable; Time too much, the electrical characteristic of cured coating film decline sometimes.
In addition, in obtained resin Y, usually, residual in intermediate X phenolic hydroxyl group former state remains.Phenolic hydroxyl group number residual in this resin Y, relative to the ratio of the phenolic hydroxyl group number (total phenolic hydroxyl group number) of raw material phenol resins (a), is generally about 10 ~ about 90%, is preferably 20 ~ 90%, is more preferably 30 ~ 80%.
In addition, phenolic hydroxyl group number residual in above-mentioned this resin Y, relative to the ratio of the phenolic hydroxyl group number (total phenolic hydroxyl group number) of raw material phenol resins (a), because reaction is carried out in roughly quantitative mode, therefore can calculate from the input amount of raw material.
When resin Y is used for photosensitive polymer combination, the resin Y that the phenolic hydroxyl group that judgement remains is many is conducive to the thermotolerance improving cured article.
In addition, in resin Y, exist by the carboxyl introduced with the reaction of above-mentioned multi-anhydride (c).Consequently, preferred resin Y of the present invention is containing the above-mentioned phenolic hydroxyl group remained, carboxyl and the resin not reacting this three of alcoholic extract hydroxyl group remained with multi-anhydride (c).
Illustrate preferred resin Y of the present invention, as described below.
I. an alkali developable resin, it is by making saturated and/or unsaturated multi-anhydride (c) being that hydroxyl (alcoholic extract hydroxyl group) in the ratio of 0.05 ~ 0.9 mole and reaction product X reacts further and obtains relative to hydroxyl (alcoholic extract hydroxyl group) 1 equivalent in reaction product X, this reaction product X by the compound (b) that makes to have in molecule alcoholic extract hydroxyl group and 1 epoxy group(ing) being that the ratio of 0.1 ~ 0.9 mole and the hydroxyl reaction of phenol resins (a) obtain relative to hydroxyl 1 equivalent of phenol resins (a).
II. the alkali developable resin as described in above-mentioned I, wherein, the monoglycidyl ether of the glycol that the compound (b) in molecule with alcoholic extract hydroxyl group and 1 epoxy group(ing) is Racemic glycidol or carbonatoms 2 ~ 4.
III. the alkali developable resin as described in above-mentioned II, wherein, above-claimed cpd (b) is Racemic glycidol.
IV. as the alkali developable resin according to any one of above-mentioned I ~ III, wherein, phenol resins (a) is the phenol resins containing cresols skeleton or biphenyl backbone.
V. the alkali developable resin as described in above-mentioned IV, wherein, the phenol resins containing biphenyl backbone is the phenol resins (a1) shown in above-mentioned general formula (1).
VI. the alkali developable resin as described in above-mentioned V, wherein, above-mentioned phenol resins (a1) is containing Resorcinol structure, and hydroxyl equivalent is 70 ~ 140g/ equivalent.
VII. as the alkali developable resin according to any one of above-mentioned I ~ VI, wherein, above-mentioned multi-anhydride (c) is for having the acid anhydrides of the polyprotonic acid of 2 or 3 carboxyls.
VIII. the alkali developable resin as described in above-mentioned VII, wherein, the acid anhydrides with the polyprotonic acid of 2 or 3 carboxyls is be selected from least one in the group that is made up of trimellitic acid 1,2-anhydride, Tetra Hydro Phthalic Anhydride, succinyl oxide and hexahydrophthalic anhydride.
IX. the alkali developable resin as described in above-mentioned VIII, wherein, the acid anhydrides with the polyprotonic acid of 2 or 3 carboxyls is the acid anhydrides in carbon 6 ring with the polyprotonic acid of 2 or 3 carboxyls.
X. the alkali developable resin as described in above-mentioned IX, wherein, the acid anhydrides that carbon 6 ring has the polyprotonic acid of 2 or 3 carboxyls is trimellitic acid 1,2-anhydride or Tetra Hydro Phthalic Anhydride.
The invention still further relates to a kind of photosensitive polymer combination, it is characterized in that, containing (A) resin Y of the present invention, (B) epoxy resin, (C) Photoepolymerizationinitiater initiater and (D) thinner.As thinner, the mode particularly preferably containing polymerizable unsaturated compound, such as (methyl) acrylic compound.
The amount of resin Y contained in photosensitive polymer combination of the present invention, relative to the total amount of photosensitive polymer combination, is preferably about 10 ~ about 80 % by weight, is more preferably about 15 ~ about 60 % by weight, and more preferably 30 ~ 60 % by weight.
As the epoxy resin (B) for photosensitive polymer combination of the present invention, be generally used in the epoxy resin in 1 molecule with more than 2 epoxy group(ing).
Can enumerate such as: 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 phenolic varnish cocondensation mould assembly epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F phenolic type epoxy resin, or their halogenated epoxide, three hydroxyphenyl methane type epoxy resin, alkyl replaces three hydroxyphenyl methane type epoxy resin, the multifunctional phenol such as four hydroxy phenyl ethane type epoxy resin and epichlorohydrin reaction and the epoxy resin obtained, multifunctional hydroxyl naphthalene class and epichlorohydrin reaction and the epoxy resin obtained, polysiloxane modified epoxy resin, 6-caprolactone modified epoxy, by the reaction of epoxy chloropropane and primary amine or secondary amine and the glycidyl amine type epoxy resin obtained, the hetero ring type epoxy resin etc. such as isocyanic acid three-glycidyl ester.These epoxy resin can use a kind or and use two or more.In addition, for the object improving toughness on the basis of guaranteeing glass transition temperature Tg, use isocyanate modified epoxy resin, or from the viewpoint of imparting flame retardant resistance, using phosphorous epoxy resin etc., is all effective.
In order to improve the every characteristic as solder resist such as adhesivity, thermotolerance, resistance to plating, coordinate above-mentioned epoxy resin (B) as heat curable component in the composition, when manufacture printed wiring board etc., after with dilute alkaline aqueous solution development, make resin solidification by heating, give adhesivity, thermotolerance, resistance to plating etc. that running board is more excellent.
Epoxy resin (B) can be used alone or uses with the form of mixture of more than two kinds, the amount of the epoxy resin contained in photosensitive polymer combination of the present invention, relative to the total amount of composition, be generally about 1 ~ about 50 % by weight, be preferably about 3 ~ about 45 % by weight, be more preferably about 5 ~ about 45 % by weight.
When using epoxy resin (B) as above-mentioned heat curable component, in order to further improve the characteristics such as adhesivity, chemical-resistant, thermotolerance, preferably and use epoxy curing agent.As such epoxy curing agent, can enumerate: imdazole derivatives, amphyl, Dyhard RU 100, cyanoguanidine derivative, hydrazide derivatives, amine, acid anhydrides etc.These solidifying agent can use a kind or be mixed with two or more.For the usage quantity of solidifying agent, relative to epoxy group(ing) 1 equivalent of this epoxy resin, the amount of the active hydrogen of solidifying agent is preferably the ratio of 0.5 ~ 1.2 equivalent.
As the concrete example of the Photoepolymerizationinitiater initiater (C) for photosensitive polymer combination of the present invention, can enumerate: bitter almond oil camphor class, acetophenones, Anthraquinones, thioxanthene ketone, benzophenone etc., such as: in bitter almond oil camphor class, have the derivatives such as bitter almond oil camphor, benzoin methylether, benzoin iso-propylether; Methyl phenyl ketone, 2 is had in acetophenones, 2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1, the derivatives such as 1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinopropane-1-ketone, N, N-dimethylamino benzoylformaldoxime; The derivatives such as 2-methylanthraquinone, 2-chloroanthraquinone, 2-ethyl-anthraquinone, 2-tertiary butyl anthraquinone, 2-amyl anthraquinone, 2-aminoanthraquinone are had in Anthraquinones; The derivatives such as thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthones, CTX, ITX, 2,4-diisopropylthioxanthone are had in thioxanthene ketone; Benzophenone, 4-benzoyl-4'-dimethyl diphenyl sulfide, 4 is had in benzophenone, 4'-dichloro benzophenone, N, the derivatives such as N-dimethylamino benzophenone, methyl benzophenone, 4,4'-two (diethylamino) benzophenone, Michler's keton, 4-benzoyl-4'-dimethyl diphenyl sulfides; 2,4,6-trimethylbenzoyldiphenyl oxide compounds etc., can be used alone a kind or combinationally use two or more.
In addition, Photoepolymerizationinitiater initiater (C) also can be used together the known photosensitizerss such as tertiary amines.Specifically can enumerate: trolamine, tripropanol amine, triethylamine, N, N-dimethylamino ethyl benzoate, N, N-dimethylamino M-nitro benzoic acid isopentyl ester, 4-dimethylaminobenzoic acid pentyl ester etc.
Above-mentioned Photoepolymerizationinitiater initiater (C) can use a kind or be mixed with two or more, also can further and use known photosensitizers.In the total amount of photosensitive polymer combination, the usage ratio of Photoepolymerizationinitiater initiater (C) is about 0.5 ~ about 20 % by weight, is preferably about 1.0 ~ about 15 % by weight.
In photosensitive polymer combination of the present invention, use polymerizable unsaturated compound and/or solvent as thinner (D).The polymerizable unsaturated compound used as thinner (D) and/or solvent are to improve using for active-energy light for coating when solidified nature and/or photosensitive polymer combination use as resist ink.
As such polymerizable unsaturated compound, preferably there is the monomer class of active-energy light curability, can enumerate: vinylformic acid 2-hydroxy methacrylate, vinylformic acid 2-hydroxy propyl ester, N-pyrrolidone, N-acryloyl morpholine, N,N-DMAA, N, N-acrylamide, vinylformic acid N, N-dimethylamino ethyl ester, vinylformic acid N, N-dimethylamino propyl ester, methoxy polyethylene glycol acrylate, oxyethyl group polyethylene glycol acrylate, melamine acrylate, acrylate, vinylformic acid phenoxy-propyl, glycol diacrylate, propylene glycol diacrylate, poly-(propylene glycol) diacrylate, Viscoat 295, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol acrylate, glycerol diacrylate, isobornyl acrylate, (methyl) acrylic compound such as vinylformic acid dihydro dicyclopentadiene base oxygen base ethyl ester and the various methacrylic esters corresponding with these.These polymerizable unsaturated compounds can use a kind or and use two or more.
Usually preferably above-mentioned (methyl) acrylic compound, in (methyl) acrylic compound, preferably multifunctional (methyl) acrylic compound, usually more preferably 2 ~ 6 officials can (methyl) acrylic compound.
In the present invention, in order to form photosensitive polymer combination, the mode preferably containing polymerizable unsaturated compound.
The use level of this polymerizable unsaturated compound, relative to total amount 100 weight part of resin Y, is generally 3 ~ 200 weight parts, is preferably 5 ~ 200 weight parts, is more preferably about 5 ~ about 100 weight parts, more preferably 7 ~ 50 weight parts.
On the other hand, as solvent, can enumerate: the ketones such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone; The aromatic hydrocarbon such as toluene, dimethylbenzene; The Trivalin SF classes such as ethyl cellosolve, ethylene glycol butyl ether, Trivalin SF, diethylene glycol monobutyl ether; Ethyl acetate, butylacetate, cellosolve acetate, butyl cellosolve acetate, ethylcarbitol acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetic ester, TC acetic ester, diethylene glycol monobutyl ether acetic ester, propylene glycol monomethyl ether (PGMEA), DPGME acetic ester etc.These solvents can use a kind or and use two or more.
The polymerizable unsaturated compound used as thinner (D) or solvent can be used alone a kind or use with the form of mixture of more than two kinds.And the usage quantity of polymerizable unsaturated compound and/or solvent, relative to above-mentioned resin Y 100 weight part, the total amount of polymerizable unsaturated compound and/or solvent is about 10 ~ about 200 weight parts, is preferably about 20 ~ about 150 weight parts.Wherein, polymerizable unsaturated compound is the compound also giving the solidified nature of resin for active-energy light, its usage quantity is relative to above-mentioned resin Y 100 weight part, be generally more than 3 weight parts, be preferably more than 5 weight parts, be more preferably more than 7 weight parts, most preferably be more than 10 weight parts, time very few, luminous sensitivity becomes too low sometimes, on the other hand, during more than 200 weight part, when being used as resist ink by photosensitive polymer combination, viscosity becomes too low, and the characteristic sometimes as cured coating film becomes insufficient.Therefore, in the present invention, preferably and with appropriate polymerizable unsaturated compound and solvent, and fluid composition is prepared as to obtain such as good coating and cured coating film characteristic.
In addition, in photosensitive polymer combination of the present invention, in order to improve the characteristic such as adhesivity, hardness, as required, the inorganic fillers such as soft silica, calcium carbonate, magnesiumcarbonate, barium sulfate, clay, talcum, silica powder, mica powder can also be used: the tinting pigments such as phthalocyanine green, phthalocyanine blue, titanium oxide, carbon black; The various additive such as defoamer, flow agent, and the stopper such as quinhydrones, Resorcinol, catechol, pyrogallol, Hydroquinone monomethylether, tert-butyl catechol, thiodiphenylamine.
Photosensitive polymer combination of the present invention by preferably being coordinated with aforementioned proportion by above-mentioned each gradation composition, and utilizes the Homogeneous phase mixing such as three-roll mill and obtains.
As preferred photosensitive polymer combination of the present invention, following resin combination can be enumerated.
I. a photosensitive polymer combination, wherein:
(A) be 10 ~ 80 % by weight for the alkali developable resin-phase according to any one of the alkali developable resin according to any one of (1) ~ (9) in the means of dealing with problems or I ~ X of recording as the preferred resin Y of the invention described above for the total amount of composition
(B) epoxy resin is 1 ~ 50 % by weight relative to the total amount of composition,
(C) Photoepolymerizationinitiater initiater is 0.5 ~ 20 % by weight relative to the total amount of composition, and
(D) thinner is 10 ~ 200 weight parts relative to alkali developable resin 100 weight part.
II. the photosensitive polymer combination as described in above-mentioned I, wherein, epoxy resin is 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 epoxy resin containing biphenyl backbone.
IV. as the photosensitive polymer combination according to any one of above-mentioned I ~ III, wherein, relative to alkali developable resin 100 weight part, containing 3 ~ 200 weight part polymerizable unsaturated compounds as thinner.
V. the photosensitive polymer combination as described in above-mentioned IV, wherein, relative to alkali developable resin 100 weight part, the content of polymerizable unsaturated compound is 5 ~ 100 weight parts.
VI. the photosensitive polymer combination as described in above-mentioned IV or V, wherein, polymerizable unsaturated compound is (methyl) acrylic compound.
VII. as the photosensitive polymer combination according to any one of above-mentioned IV ~ VI, wherein, containing solvent as thinner, the total amount of polymerizable unsaturated compound and solvent, relative to alkali developable resin 100 weight part, is 10 ~ 200 weight parts.
VIII. as the photosensitive polymer combination according to any one of above-mentioned I ~ VII, wherein, relative to alkali developable resin 100 weight part, the inorganic filler of the scope also containing 1 ~ 100 weight part.
In addition, photosensitive polymer combination of the present invention is generally fluid composition, such as, solidified by following mode and obtain cured article.Namely, by screen painting method, spraying method, rolling method, electrostatic coating processes, the methods such as curtain coating method, printed wiring board is coated with composition of the present invention with the thickness of 10 ~ 160 μm, by film 60 ~ 110 DEG C of dryings, then, negative film is made directly to contact this film (or being placed on film with discontiguous state), then irradiation ultraviolet radiation makes composition expose, dissolve the unexposed part of removing with dilute alkaline aqueous solution and develop, then in order to improve every physical property further, and solidified fully by irradiation ultraviolet radiation and/or heating (such as 100 ~ 200 DEG C of heating 0.5 ~ 1.0 hour), thus obtain cured coating film.
Photosensitive polymer combination of the present invention is except being directly coated on the method on base material with liquid state, also can use with the form of dry film, this dry film on the films such as polyethylene terephthalate, is coated with solder resist in advance and the dry and film with solder mask layer that is that formed.Dry film has sequentially laminated with carrier film, solder mask layer and the structure of strippable mulch film that uses as required.
In order to use dry film to make protective membrane on printed wiring board, peel off mulch film, solder mask layer is overlapping with the base material being formed with circuit, use laminating machine etc. to fit, thus form solder mask layer on the base material being formed with circuit.As long as carry out exposure similar to the above to formed solder mask layer, develop, be heating and curing, just cured coating film can be formed.
Embodiment
Below, explain the present invention 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 " weight part " and " % by weight " respectively.
Synthesis example 1 (synthesis example of resin Y-1)
Drop into cresol novolac resin [Shonol CRG-951, Showa Highpolymer Co., Ltd's system, hydroxyl equivalent 118, softening temperature 96 DEG C, number-average molecular weight 750] 118 parts of (1.0 equivalent) and propylene glycol monomethyl ether 124.71 parts, be heated to 80 DEG C, by said mixture uniform dissolution.After confirming dissolving, add Racemic glycidol 37.04 parts (0.5 mole) and triphenylphosphine 0.47 part wherein, be heated to 120 DEG C and react about 8 hours, thus obtaining reaction product X (resin: intermediate X).By GPC (gel permeation chromatography) assaying reaction rate, the reactivity of result Racemic glycidol is 98%.Then, in the reaction solution containing this reaction product X, add trimellitic acid 1,2-anhydride 32.03 parts (0.17 mole), 100 DEG C of reactions about 6 hours, thus obtain curable resin of the present invention (Y-1) (solid substance acid number 100mgKOH/g, solid concentration 60%).The average molecular weight Mw of this resin Y-1 is 3,200.
Synthesis example 2 (synthesis example of resin Y-2)
Drop into biphenyl aralkyl type phenol resin [GPH-103, Nippon Kayaku K. K's system, hydroxyl equivalent 239, softening temperature 103 DEG C, phenolic hydroxyl group is all Resorcinol hydroxyl (Resorcinol hydroxyl 100%), weight-average molecular weight 3220] 239 parts of (1.0 equivalent) and propylene glycol monomethyl ether 222.04 parts, be heated to 80 DEG C, by said mixture uniform dissolution.After confirming dissolving, add Racemic glycidol 37.04 parts (0.5 mole) and triphenylphosphine 0.83 part wherein, be heated to 120 DEG C and react about 8 hours, thus obtaining reaction product X (resin: intermediate X).Measured by GPC and obtain reactivity, the reactivity of result Racemic glycidol is 98%.Then, in the reaction solution containing this reaction product X, add trimellitic acid 1,2-anhydride 57.02 parts (0.3 mole), 100 DEG C of reactions about 6 hours, thus obtain curable resin of the present invention (Y-2) (solid substance acid number 100mgKOH/g, solid concentration 60%).The average molecular weight Mw of this resin Y-2 is 15,000.
Relatively synthesis example 1 (synthesis example of curable resin Z)
Drop into cresol novolak type epoxy resin [EOCN-104s, Nippon Kayaku K. K's system, epoxy equivalent (weight) 219, softening temperature 90 DEG C] 219 parts of (1.0 equivalent), 72 parts, vinylformic acid (1.0 moles), as 2 of heat polymerization inhibitors, 6-ditertbutylparacresol 1.3 parts and propylene glycol monomethyl ether 216.65 parts, be heated to 95 DEG C, by said mixture uniform dissolution.After confirming dissolving, drop into triphenylphosphine 1.3 parts wherein, be heated to 100 DEG C and react about 24 hours, thus obtaining reaction product (solid substance below acid number 3.0mgKOH/g).Add Tetra Hydro Phthalic Anhydride 109.10 parts (0.72 mole) wherein, be heated to 98 DEG C and reaction about 6 hours, thus obtain the curable resin Z (solid substance acid number 100mgKOH/g, solid concentration 65%) that compares.The average molecular weight Mw of this curable resin Z is 6,500.
Embodiment 1 ~ 3 and comparative example 1:
Use by above-mentioned synthesis example 1 and 2 and compare the photoresist and polymkeric substance that synthesis example 1 obtains, according to the compounding ratio shown in table 1, utilizing three-roll mill mixing, thus the photosensitive polymer combination of preparation examples and comparative examples of the present invention.Diluted by each composition methyl ethyl ketone of the embodiment 1 ~ 3 prepared with mixing ratio shown in table 1 and comparative example 1, coating on a pet film and 80 DEG C of dryings 30 minutes, thus makes the dry film shape photosensitive polymer combination layer of thickness 20 μm.Predrying 30 minutes at 80 DEG C again, be then cooled to room temperature and obtain dry coating.Make the negative film with resist pattern adhere on this film, use ultraviolet exposure apparatus according with 350mJ/cm 2exposure, after removing negative film, uses 1% aqueous sodium carbonate, with 2.0kgf/cm 2spray pressure develop 60 seconds, be partly dissolved removing by unexposed.Afterwards, use hot air dryer, be heating and curing 60 minutes at 150 DEG C, thus preparation has the cured article overlay film of resist pattern.
Table 1. photosensitive polymer combination
* 1NC-3000H CA75: biphenyl phenolic resin varnish type epoxy resin [Nippon Kayaku K. K's system]
* 2Irg.907:2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinopropanone-1 [Irgacure907, Qi Ba Japanese firm system]
* 3DETEX-S:2,4-diethyl thioxanthone [KAYACURE DETEX-S, Nippon Kayaku K. K's system]
* 4TMPTA: Viscoat 295 [ラ イ ト ア Network リ レ ー ト TMP-A, Kyoeisha Chemical Co., Ltd.'s system]
Use the present invention with curing overlay film and each test film comparing product of obtaining in the above described manner, according to following shown test method, carry out developability, adhesivity, welding thermotolerance, the gold-plated property of chemically-resistant, resistance to PCT, flexure test, the test of cold-hot impact, HAST testing of characteristic, carry out the various evaluation of physical property of film.These evaluation results tested are shown in table 2 and table 3.Wherein, developability the pre-drying-time of 80 DEG C is changed into the various time beyond 30 minutes and the film obtained is evaluated as sample.
< developability >
To each dry coating pre-drying-time being set as 20 minutes, 40 minutes, 60 minutes, 80 minutes, 100 minutes, use the aqueous sodium carbonate of 1% with 2.0kgf/cm 2spray pressure develop 60 seconds, observe the presence or absence of film after development, and evaluate according to following benchmark.
Zero: after development, film is completely removed, and can develop completely.
×: have the film be not removed on a small quantity to remain after development, development is not exclusively.
< adhesivity >
According to the test method of JIS D 0202, the cured film cross cut of each test film is become chessboard trellis, then utilize scotch tape (セ ロ Ha Application テ ー プ) to carry out stripping test, the stripping state after visual judgement test.Evaluate according to following benchmark.
Zero: do not peel off completely.
△: there is a little stripping in cross cut portion.
×: film has stripping.
< welds thermotolerance >
According to the test method of JIS C 6481, each test film is flooded 10 seconds in the solder bath of 280 DEG C, carry out 3 dippings, after taking-up, observe the change of outward appearance.Evaluate according to following benchmark.
Zero: the outward appearance of cured film is unchanged.
△: confirm cured film variable color.
×: cured film has tilting, stripping, solder to invade (half field dive り).
< chemically-resistant gold-plated property >
As the pre-treatment of test film, carry out each test film flooding in the acidic degreasing liquid of 30 DEG C → washing of dipping washing → soft etch processes → dipping → give catalyzer (flooding 7 minutes in the nickel plating catalyzer liquid of 30 DEG C) → flood the operation of washing.Then, as chemical nickel plating operation, carry out nickel-plating liquid (85 DEG C to each test film, pH 4.6) washing of middle dipping 20 minutes → acid dipping (under room temperature 10 volume % aqueous sulfuric acids) 1 minute → dipping, finally, as chemical gilding operation, each test film is passed through gold plating liquid (95 DEG C, pH6, the potassium auric cyanide 3 volume % aqueous solution) in the washing of dipping 10 minutes → dipping → with after the washing of the warm water immersions of 60 DEG C cleaning → fully → completely except anhydrating → operation of drying carries out chemical gilding, the change of outward appearance is observed for these test films and uses scotch tape to carry out stripping test, evaluate film.Evaluate according to following benchmark.
Zero: outward appearance is unchanged, there is no the stripping of resist completely.
△: although outward appearance is unchanged, observes the stripping of resist a little.
×: observe the tilting of resist, plating invades (メ ッ キ dive り), in stripping test, the stripping of resist is obvious.
< PCT tests >
Visual judgement is by each test film at 121 DEG C, and 2 normal atmosphere, place the outward appearance of the film after 100 hours under saturated vapo(u)r atmosphere.Evaluate according to following benchmark.
Zero: film is without expansion, stripping.
×: there are expansion, stripping.
< flexure test >
According to JIS K5400, use the Erichsen trier specified in JIS B7729A method, above-mentioned each photosensitive polymer combination to be coated on the steel plate of bonderize → dry → exposure → development → heating thus prepare test film.For obtained each test film, from the back side, steel ball is released, and measure when test film is out of shape until produce the release distance of breaking and peeling off of film.Evaluate and carry out according to following benchmark.
Zero: the distance releasing steel ball is more than 4mm, and does not produce breaking and peeling off of film.
△: the distance releasing steel ball is more than 2mm and is less than 4mm, and does not produce breaking and peeling off of film.
×: the distance releasing steel ball is less than 2mm, and produces breaking and peeling off of film.
< cold-hot impact test >
Make the evaluation substrate of solder resist cured coating film having and be formed with pierced pattern, zero pierced pattern.For obtained evaluation substrate, utilize cold shock testing device (Etac Inc.), by-55 DEG C/30 minutes ~ 150 DEG C/30 minutes as 1 circulation, carry out the resistance test of 1000 circulations, after test, by the cured film after visual observation process, and judge the production of crackle according to following benchmark.
Zero: the production rate of crackle is less than 30%
△: the production rate of crackle is 30% ~ 50%
×: the production rate of crackle is more than 50%
< HAST characteristic >
On the BT substrate being formed with comb-type electrode (live width/line-spacing=30 μm/30 μm), form solder resist cured coating film, thus be made evaluation substrate.This evaluation substrate is put into 130 DEG C, hot and humid groove under the environment of humidity 85%, apply voltage 5.5V, HAST test (insulativity test) in the groove carrying out the various time.According to following judgment standard, evaluate insulating resistance value in the groove of various time.
Zero: after 240 hours, at 108 more than Ω
×: after 240 hours, at 108 below Ω
Table 2 developability evaluation result
80 DEG C of time of drying (minute) Embodiment 1 Embodiment 2 Embodiment 3 Comparative example 1
20 ○ ○ ○ ○
40 ○ ○ ○ ○
60 ○ ○ ○ ×
80 ○ ○ ○ ×
100 ○ ○ ○ ×
120 ○ ○ ○ ×
The various evaluation result of table 3
Test subject Embodiment 1 Embodiment 2 Embodiment 3 Comparative example 1
Adhesivity ○ ○ ○ ○
Welding thermotolerance ○ ○ ○ ×
The gold-plated property of chemically-resistant ○ ○ ○ △
Resistance to PCT ○ ○ ○ ×
Flexible ○ ○ ○ △
Cold-hot impact ○ ○ ○ ×
HAST characteristic ○ ○ ○ ×
From the evaluation result of table 2 and table 3, alkali developable resin of the present invention is compared with known epoxies photoresist, drying property, alkali-developable are excellent, and adhesivity, welding thermotolerance, the gold-plated property of chemically-resistant, resistance to PCT, flexibility, cold-hot impact, the HAST characteristic etc. of its cured article are excellent.
Synthesis example 3 (synthesis example of resin Y-3)
Drop into the record according to No. 8-143648, Japanese Unexamined Patent Publication, phenol resins [the hydroxyl equivalent 134g/ equivalent of Resorcinol is contained with the biphenyl phenolic varnish type being roughly used as the phenol of phenolic compound and Resorcinol to manufacture relative to the ratio of phenol 9 moles of Resorcinols 1 mole, softening temperature 93.4 DEG C, the ratio of Resorcinol hydroxyl (the total phenolic hydroxyl group number in Resorcinol hydroxyl value/phenol resins (a1)) × 100}=about 20%] 134 parts (hydroxyl equivalent: 1.0 equivalents), propylene glycol monomethyl ether 179.56 parts, be heated to 80 DEG C, the mixture that uniform dissolution is above-mentioned.After confirming dissolving, drop into Racemic glycidol 14.82 parts (0.2 mole), triphenylphosphine 0.45 part wherein, be heated to 120 DEG C and react about 8 hours, thus obtaining reaction product X (resin: intermediate X).Measured by GPC and obtain reactivity, the reactivity of result Racemic glycidol is 98%.Then, in the reaction solution containing this reaction product X, add trimellitic acid 1,2-anhydride 30.74 parts (0.16 mole), 100 DEG C of reactions about 6 hours, thus obtain curable resin of the present invention (Y-3) (solid concentration 50%, solid substance acid number 100mgKOH/g).The average molecular weight Mw of this resin Y-3 is 1,900.
Synthesis example 4 (synthesis example of resin Y-4)
Drop into the biphenyl phenolic varnish type resorcinol resin [hydroxyl equivalent 102 synthesized according to the embodiment 1 of No. 7-292066, Japanese Unexamined Patent Publication, softening temperature 85.2 DEG C] 102 parts of (1.0 equivalent) and propylene glycol monomethyl ether 192.09 parts, be heated to 80 DEG C, by said mixture uniform dissolution.After confirming dissolving, add Racemic glycidol 37.04 parts (0.5 mole), triphenylphosphine 0.42 part wherein, be heated to 120 DEG C and react about 8 hours, thus obtaining reaction product X (resin: intermediate X).Measured by GPC and obtain reactivity, the reactivity of result Racemic glycidol is 98%.Then, in the reaction solution containing this reaction product X, add Tetra Hydro Phthalic Anhydride 51.05 parts (0.34 mole), 100 DEG C of reactions about 6 hours, thus obtain curable resin of the present invention (Y-4) (solid concentration 50%, solid substance acid number 100mgKOH/g).The average molecular weight Mw of this resin Y-4 is 1,200.
Embodiment 4 ~ 7 and comparative example 2:
Use by above-mentioned synthesis example 2,3,4 respectively and above-mentionedly compare resin Y-2, Y-3, Y-4 and curable resin Z that synthesis example 1 obtains, three-roll mill is utilized to mix according to the allotment ratio shown in table 4, the photosensitive polymer combination of preparation examples and comparative examples of the present invention.Diluted by each composition methyl ethyl ketone of the embodiment 4 ~ 7 prepared with the mixing ratio shown in table 4 and comparative example 2, coating on a pet film and 80 DEG C of dryings 30 minutes, thus makes the photosensitive polymer combination layer of the dry film shape of thickness 20 μm.Then, at 80 DEG C after predrying 30 minutes, cool to room temperature thus obtain dry coating.Make the negative film with resist pattern adhere on this film, use ultraviolet exposure apparatus according, with 350mJ/cm 2exposure, after removing negative film, uses 1% aqueous sodium carbonate, with 2.0kgf/cm 2spray pressure develop 60 seconds, be partly dissolved removing by unexposed.Afterwards, use hot air dryer, be heating and curing 60 minutes at 150 DEG C, thus make the cured article overlay film (test film of the present invention and compare with test film) with resist pattern.
Table 4 photoresist forms
* 1NC-3000H CA75: biphenyl phenolic resin varnish type epoxy resin [Nippon Kayaku K. K's system]
* 2Irg.907:2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinopropanone-1 [Irgacure907, Qi Ba Japanese firm system]
* 3DETEX-S:2,4-diethyl thioxanthone [KAYACURE DETEX-S, Nippon Kayaku K. K's system]
* 4DPTA: dipentaerythritol acrylate [KAYARAD DPHA, Nippon Kayaku K. K's system]
Use 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, carry out developability, adhesivity, welding thermotolerance, the gold-plated property of chemically-resistant, resistance to PCT, flexure test, carry out the various evaluation of physical property of film.These evaluation results tested are shown in table 5 and table 6.Wherein, developability the pre-drying-time of 80 DEG C is changed into the various time beyond 30 minutes and the film obtained is evaluated as sample.Metewand is identical with the situation of table 2.
Table 5 developability evaluation result
80 DEG C of time of drying (minute) Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Comparative example 2
20 ○ ○ ○ ○ ○
40 ○ ○ ○ ○ ○
60 ○ ○ ○ ○ ×
80 ○ ○ ○ ○ ×
100 ○ ○ ○ × ×
120 ○ ○ ○ × ×
The various evaluation result of table 6
Test subject Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Comparative example 2
Adhesivity ○ ○ ○ ○ ○
Welding thermotolerance ○ ○ ○ ○ ×
The gold-plated property of chemically-resistant ○ ○ ○ ○ △
Resistance to PCT ○ ○ ○ ○ ×
Flexible ○ ○ ○ ○ △
Cold-hot impact ○ ○ ○ ○ ×
HAST characteristic ○ ○ ○ ○ ×
From the evaluation result of table 5 and table 6, alkali developable resin of the present invention is compared with known epoxies photoresist, drying property, alkali-developable are excellent, and adhesivity, welding thermotolerance, the gold-plated property of chemically-resistant, resistance to PCT, flexibility, cold-hot impact, the HAST characteristic etc. of its cured article are excellent.
Particularly, comprise the alkali developable resin of the present invention that biphenyl phenolic varnish type contains the phenol resins of Resorcinol, in alkali developable resin of the present invention, in drying property and alkali-developable, more excellent than other.
Industrial applicability
Drying property, the alkali-developable of photosensitive polymer combination of the present invention are excellent, and adhesivity, each characteristic good such as welding thermotolerance, the gold-plated property of chemically-resistant, resistance to PCT, flexibility, cold-hot impact, HAST characteristic etc. of film after solidification.Can with low cost and productivity forms cured film well, therefore, except may be used for the purposes etc. of the ultraviolet hardening printing-ink using active energy ray-curable, be also useful in the solder resist, resist, plating resist application, interlayer dielectic etc. that use when manufacturing printed wiring board.

Claims (21)

1. an alkali developable resin, the hydroxyl in its reaction product X obtained by making to have in molecule the compound (b) of alcoholic extract hydroxyl group and 1 epoxy group(ing) and the hydroxyl reaction of phenol resins (a) reacts with saturated and/or unsaturated multi-anhydride (c) further and obtains.
2. alkali developable resin as claimed in claim 1, is characterized in that, makes above-claimed cpd (b) with the ratio reaction relative to phenolic hydroxyl group 1 equivalent of phenol resins (a) being 0.1 ~ 0.9 mole.
3. alkali developable resin as claimed in claim 1 or 2, is characterized in that, makes above-mentioned multi-anhydride (c) with the ratio reaction relative to alcoholic extract hydroxyl group 1 equivalent of reaction product X being 0.05 ~ 0.9 mole.
4. the alkali developable resin according to any one of claims 1 to 3, wherein, relative to the total phenolic hydroxyl group number in phenol resins (a), the ratio of phenolic hydroxyl group residual in alkali developable resin is 10 ~ 90%.
5. the alkali developable resin according to any one of Claims 1 to 4, wherein, phenol resins (a) is the phenol resins (a) containing biphenyl backbone.
6. the alkali developable resin according to any one of Claims 1 to 5, wherein, phenol resins (a) is the phenol resins (a1) shown in following general formula (1):
In formula, m1, m2 and m3 are the integer of 1 or 2 independently of one another, and n represents the integer of 0 ~ 10.
7. alkali developable resin as claimed in claim 6, wherein, phenol resins (a1) is the phenol resins wherein containing Resorcinol structure.
8. alkali developable resin as claimed in claim 7, wherein, the hydroxyl equivalent of the phenol resins containing Resorcinol structure is 70 ~ 170g/ equivalent.
9. the alkali developable resin according to any one of claim 1 ~ 8, wherein, compound (b) is Racemic glycidol.
10. the alkali developable resin according to any one of claim 1 ~ 9, wherein, described multi-anhydride (c) is for having the acid anhydrides of the polyprotonic acid of 2 or 3 carboxyls.
11. 1 kinds of photosensitive polymer combinations, is characterized in that, contain:
Alkali developable resin (A) according to any one of claim 1 ~ 10,
(B) epoxy resin,
(C) Photoepolymerizationinitiater initiater and
(D) thinner.
12. photosensitive polymer combinations as claimed in claim 11, it is characterized in that, thinner is polymerizable unsaturated compound and/or solvent.
13. photosensitive polymer combinations as described in claim 11 or 12, is characterized in that,
(A) alkali developable resin-phase is 10 ~ 80 % by weight for the total amount of composition;
(B) epoxy resin is 1 ~ 50 % by weight relative to the total amount of composition;
(C) Photoepolymerizationinitiater initiater is 0.5 ~ 20 % by weight relative to the total amount of composition; And
(D) thinner is 10 ~ 200 weight parts relative to alkali developable resin 100 weight part.
14. photosensitive polymer combinations according to any one of claim 11 ~ 13, wherein, relative to alkali developable resin 100 weight part, the scope using 5 ~ 200 % by weight contains polymerizable unsaturated compound as thinner.
15. photosensitive polymer combinations as claimed in claim 14, wherein, polymerizable unsaturated compound is (methyl) acrylic compound.
The cured article of the photosensitive polymer combination according to any one of 16. claims 11 ~ 15.
The cured article of 17. photosensitive polymer combinations as claimed in claim 16, it carries out patterning and the cured article that obtains for using the photolithography that light can be utilized to carry out superstructure technologies.
18. 1 kinds of base materials, it has the layer of claim 16 or cured article according to claim 17.
19. 1 kinds of article, it has base material according to claim 18.
The formation method of 20. 1 kinds of cured coating films, it is characterized in that, photosensitive polymer combination according to any one of claim 11 ~ 15 is coated on printed wiring board and forms film, carry out exposing, developing, then make it solidify by irradiation ultraviolet radiation and/or heating.
21. purposes for the manufacture of alkali developable resin according to claim 1 with the reaction product X of phenolic hydroxyl group and alcoholic extract hydroxyl group, described reaction product X obtains by making to have in molecule the compound (b) of alcoholic extract hydroxyl group and 1 epoxy group(ing) and the hydroxyl reaction of phenol resins (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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