CN110320749A - The manufacturing method of photosensitive polymer combination, dry film and printed circuit board - Google Patents
The manufacturing method of photosensitive polymer combination, dry film and printed circuit board Download PDFInfo
- Publication number
- CN110320749A CN110320749A CN201910212193.XA CN201910212193A CN110320749A CN 110320749 A CN110320749 A CN 110320749A CN 201910212193 A CN201910212193 A CN 201910212193A CN 110320749 A CN110320749 A CN 110320749A
- Authority
- CN
- China
- Prior art keywords
- photosensitive polymer
- polymer combination
- mass parts
- resin
- dry
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
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Classifications
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- 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
-
- 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)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
Abstract
There is provided the manufacturing method of a kind of photosensitive polymer combination, dry film and printed circuit board, the generation that above-mentioned photosensitive polymer combination can inhibit the contraction after coating or when dry or hang forms uniform dry coating after the drying, is able to suppress the generation of short circuit.Photosensitive polymer combination of the invention is characterized in that, it includes carboxy resin, thermosetting resin, photo-sensitive monomer and organic solvent is contained, above-mentioned organic solvent includes diethylene glycol monoethyl ether acetic acid esters, dipropylene glycol monomethyl ether and propylene glycol methyl ether acetate.
Description
Technical field
The present invention relates to photosensitive polymer combinations, more particularly to are suitable as the photoresist group of solder resist formation
Close object.In addition, the invention further relates to the dry films for having used the photosensitive polymer combination.Moreover, it relates to use
The manufacturing method of the printed circuit board of the photosensitive polymer combination.
Background technique
In general, in the printed circuit board used in electronic equipment etc., when electronic component is installed to printed circuit board,
In unnecessary portion, the region in addition to connecting hole on the substrate for being formed with circuit pattern is formed solder attachment in order to prevent
There is solder mask.
With in recent years by high-precision, the densification of the light and shortization bring printed circuit board of electronic equipment, mesh
Before, forming solder mask using following so-called photosensitive type solder resists just becomes mainstream, that is, the photosensitive resin coating group on substrate
Object and drying are closed, by the way that after exposing, develop and forming pattern, the resin after forming pattern using heating or light irradiation carries out formal
Solidification.
In the past, in the case where anticorrosive additive material to be applied on substrate, it is possible to can not equably be coated with resist material
Expect and crawling occurs.For example, there is resist layer when being applied to existing anticorrosive additive material on substrate by silk-screen printing
When can observe the unevenness of striated.For such technical task, following scheme is proposed: in the photonasty of biliquid mixed type
In composition, diethylene glycol monoethyl ether acetic acid esters, dipropylene glycol monomethyl ether and specific distillability are used as organic solvent
At least one of naphtha of shape (referring to patent document 1 with 2).
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2012-234141 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2014-066735 bulletin
Summary of the invention
Problems to be solved by the invention
But using the mixed organic solvents proposed in patent document 1 and 2, although at first sight can equably be coated with sense
Photosensitive resin composition, but discovery has following technical tasks: shrinking or hang after coating or when dry, after the drying without
Method forms uniform dry coating.In addition, there is also the technical tasks that short circuit occurs in the substrate using cured coating film, it is desirable to
Improved.
Therefore, it the purpose of the present invention is to provide a kind of photosensitive polymer combination, can inhibit after being coated with or when dry
Contraction or the generation that hangs, form uniform dry coating after the drying, be able to suppress the generation of short circuit.In addition, of the invention
Another object be to provide the dry film for having used above-mentioned photosensitive polymer combination.In addition, another object of the present invention is to
A kind of manufacturing method of printed circuit board is provided, above-mentioned photosensitive polymer combination is able to use and forms uniform solder mask.
Means for solving the problems
Present inventor has performed in-depth studies, as a result, it has been found that, short circuit is due to the solder of substrate or gold-plated bad, in turn
The reason is the contraction after composition coating or when dry or hangs.Present inventor has performed deeper into research, as a result send out
It is existing, in comprising the photosensitive polymer combination containing carboxy resin, thermosetting resin, photo-sensitive monomer and organic solvent, pass through
Share specific 3 kinds of substance conducts of diethylene glycol monoethyl ether acetic acid esters, dipropylene glycol monomethyl ether and propylene glycol methyl ether acetate
Organic solvent is able to solve the above subject.The present invention is based on above-mentioned technical ideas.
That is, photosensitive polymer combination of the invention is characterized in that, it includes contain carboxy resin, thermosetting resin, sense
Photosensitiveness monomer and organic solvent, above-mentioned organic solvent include diethylene glycol monoethyl ether acetic acid esters, dipropylene glycol monomethyl ether and the third two
Alcohol methyl ether acetate.
In mode of the invention, for photosensitive polymer combination, it is preferred that make to utilize rock at 25 DEG C of temperature
The viscosity of field flow cup NK-2 measurement is 40 seconds~100 seconds.
In mode of the invention, photosensitive polymer combination is preferred for the coating using flush coater or curtain coater.
In mode of the invention, photosensitive polymer combination is preferably used as solder resist and forms use.
The dry film of another way of the invention is characterized in that having support membrane and be formed on above-mentioned support membrane
The resin layer being made of the dry coating of above-mentioned photosensitive polymer combination.
Another way according to the present invention provides a kind of manufacturing method of printed circuit board, is the print for having solder mask
The manufacturing method of printed circuit board, which is characterized in that be applied to above-mentioned photosensitive polymer combination using flush coater or curtain coater
On substrate, its solidification is made by least any one in light and heat, forms solder mask.
The effect of invention
It according to the present invention it is possible to provide a kind of photosensitive polymer combination, can equably be coated with, and then can inhibit painting
Contraction when after cloth or dry or the generation to hang, form uniform dry coating after the drying, inhibit the generation of short circuit.According to
Another way of the invention can provide the dry film for having used above-mentioned photosensitive polymer combination.Another party according to the present invention
Formula can provide a kind of manufacturing method of printed circuit board, be able to use above-mentioned photosensitive polymer combination and formed uniformly
Solder mask.
Specific embodiment
[photosensitive polymer combination]
Photosensitive polymer combination of the invention is illustrated.Photosensitive polymer combination of the invention contains
Carboxy resin, thermosetting resin, photo-sensitive monomer (reactive diluent) and organic solvent (non-reactive diluent), can be with
Further include the other compositions such as Photoepolymerizationinitiater initiater, colorant, curing catalysts, filler and additive.In the present invention, lead to
It crosses and shares specific 3 kinds of substances as organic solvent (non-reactive diluent), photosensitive polymer combination can adjusted
Character is adjusted while viscosity, the generation for inhibiting the contraction after being coated with or when dry or hanging is formed uniform dry after the drying
Dry film inhibits the generation of short circuit.Hereinafter, being illustrated to each ingredient for constituting photosensitive polymer combination of the invention.
[containing carboxy resin]
As carboxy resin is contained, the conventionally known various resins in molecule with carboxyl can be used.Photoresist
Composition can assign alkali-developable to photosensitive polymer combination by the inclusion of carboxy resin is contained.In particular, from photocuring
Property, set out in terms of resistance to developability, with the photoresist containing carboxyl of ethylenically unsaturated double bond preferably in molecule.Ethylenic bond
Unsaturated double-bond is preferred from acrylic or methacrylic acid or their derivative.It is unsaturated using only not having ethylenic bond
Double bond containing in the case where carboxy resin, by sharing the chemical combination in aftermentioned molecule with 2 or more ethylenically unsaturated groups
Object, i.e. photo-sensitive monomer make composition photonasty.
As the concrete example containing carboxy resin, can enumerate following compounds (can be appointing in oligomer and polymer
It is a kind of).
(1) pass through the unsaturated carboxylic acids such as (methyl) acrylic acid and styrene, α-methylstyrene, (methyl) acrylic acid lower
What the copolymerization of the compound containing unsaturated group such as Arrcostab, isobutene obtained contains carboxy resin.
(2) pass through aliphatic diisocyanate, Branched fatty (cyclo) aliphatic diisocyanates, ester ring type diisocyanate, aromatic series
The compound containing carboxylic diol such as the diisocyanate such as diisocyanate and dihydromethyl propionic acid, dimethylolpropionic acid and poly- carbonic acid
Ester system polyalcohol, polyether system polyalcohol, polyester-based polyols, polyolefin polyalcohol, acrylic acid series multiple alcohol, bisphenol-A system ring
Obtained from the polyadditions of diatomic alcohol compounds such as oxygen alkane addition product dihydric alcohol, compound with phenolic hydroxyl group and alcoholic extract hydroxyl group
Carboxylic carbamate resins.
(3) pass through diisocyanate and bisphenol A type epoxy resin, bisphenol-A epoxy resin, bisphenol F type epoxy tree
(the first of 2 functional epoxy resins such as rouge, bisphenol-s epoxy resin, union II toluene phenol-type epoxy resin, united phenol-type epoxy resin
Base) the anhydride modified object of acrylate or part thereof, compound containing carboxylic diol and diatomic alcohol compounds polyaddition and
Obtained carboxylic photonasty carbamate resins.
(4) intramoleculars such as (methyl) acrylic acid hydroxy alkyl ester are added in the synthesis of the resin of above-mentioned (2) or (3) has 1
A hydroxyl and 1 or more the compound of (methyl) acryloyl group and carry out end (methyl) it is acrylated obtained from it is carboxylic
Photonasty carbamate resins.
(5) isophorone diisocyanate and three propylene of pentaerythrite are added in the synthesis of the resin of above-mentioned (2) or (3)
Compound with 1 isocyanate group and 1 or more (methyl) acryloyl group in the molecules such as the reaction with same mole object of acid esters into
Carboxylic photonasty carbamate resins obtained from row end (methyl) is acrylated.
(6) it reacts 2 functions or multifunctional (solid-state) epoxy resin more than it with (methyl) acrylic acid, and is being present in
Photoresist containing carboxyl obtained from addition dibasic acid anhydride on the hydroxyl of side chain.
(7) the multifunctional ring for obtaining the further epoxidation of hydroxyl of 2 functions (solid-state) epoxy resin with epoxychloropropane
Oxygen resin is reacted with (methyl) acrylic acid, and the tree of photonasty containing carboxyl obtained from addition dibasic acid anhydride on the hydroxyl of generation
Rouge.
(8) make the dicarboxylic acids such as 2 function oxetane resins and adipic acid, phthalic acid, hexahydrophthalic acid anti-
It answers, and the binary such as addition phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride on the primary hydroxyl of generation
Contain carboxyl polyester resin obtained from acid anhydrides.
(9) make at least to have in 1 molecules such as the epoxide and p-hydroxyphenylethanol in 1 molecule with multiple epoxy groups
The compound of 1 alcoholic extract hydroxyl group and 1 phenolic hydroxyl group reacts with monocarboxylic acids containing unsaturated group such as (methyl) acrylic acid, and makes
The alcoholic extract hydroxyl group of resulting reaction product and maleic anhydride, tetrabydrophthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, oneself two
Photoresist containing carboxyl obtained from the reaction of the multi-anhydrides such as acid anhydrides.
(10) make in 1 molecule with multiple phenolic hydroxyl groups compound reacted with alkylene oxides such as ethylene oxide, propylene oxide and
The reaction product of acquisition is reacted with the monocarboxylic acid containing unsaturated group, and react resulting reaction product with multi-anhydride and
Obtained photoresist containing carboxyl.
(11) make the cyclic carbonates such as compound and ethylene carbonate, the propylene carbonate in 1 molecule with multiple phenolic hydroxyl groups
Ester compounds reaction obtained from reaction product reacted with the monocarboxylic acid containing unsaturated group, and make resulting reaction product and
Photoresist containing carboxyl obtained from multi-anhydride reaction.
(12) further addition in 1 intramolecular has 1 epoxy group and 1 or more on the resin of above-mentioned (1)~(11)
Photoresist containing carboxyl made of the compound of (methyl) acryloyl group.
It should be noted that in this specification, (methyl) acrylate be to acrylate, methacrylate and they
The term be referred to as of mixture, it is also identical about other similar statement.
Acid value containing carboxy resin is preferably 40mgKOH/g~150mgKOH/g.By making the acid value containing carboxy resin
40mgKOH/g or more, alkali development become good.In addition, by making acid value 150mgKOH/g hereinafter, can easily describe good
Good resist pattern.More preferably 50mgKOH/g~130mgKOH/g.
Weight average molecular weight containing carboxy resin is different according to resin matrix, it is often preferred that 2,000~150,000.It is logical
Crossing makes weight average molecular weight 2,000 or more, can be improved non-adhesion behavior, resolution ratio.In addition, by making weight average molecular weight 150,
000 hereinafter, can be improved developability, storage stability.More preferably 5,000~100,000.
In photosensitive polymer combination, the preferably 20 mass % in terms of solid component conversion of the blend amount containing carboxy resin
~40 mass %.By can be improved cured coating film intensity for 20 mass % or more.Additionally by for 40 mass % hereinafter, viscous
Property become appropriate, printing improves.More preferably 25 mass of mass %~35 %.
[photo-sensitive monomer]
It include photo-sensitive monomer in photosensitive polymer combination of the invention.Photo-sensitive monomer is with ethylenic bond unsaturation
The compound of double bond.As photo-sensitive monomer, it can be cited for example that known usual polyester (methyl) acrylate, polyethers (first
Base) acrylate, carbamate (methyl) acrylate, carbonic ester (methyl) acrylate, epoxy (methyl) acrylate
Deng.Specifically, can be from: the hydroxyalkyl acrylates class such as acrylic acid -2- hydroxyl ethyl ester, 2-hydroxypropyl acrylate；Second two
The diacrylate esters of the glycol such as alcohol, methoxyl group tetraethylene glycol, polyethylene glycol, propylene glycol；N, N- dimethylacrylamide, N- hydroxyl
Methacrylamide, N, the acrylic amides such as N- dimethylaminopropylacryl amide；N, N- dimethylaminoethylacryl acid
Ester, N, the amino alkyl acrylates class such as N- dimethylaminopropylacryl acid esters；Hexylene glycol, trimethylolpropane, Ji Wusi
The polyalcohols such as alcohol, dipentaerythritol, trihydroxy ethyl isocyanurate or their ethylene oxide adduct, propylene oxide addition
The multicomponent methacrylates class such as object or 6-caprolactone addition product；Phenoxy group acrylate, bisphenol a diacrylate and these phenol
The multicomponent methacrylates class such as ethylene oxide adduct or propylene oxide adduct of class；Diglycidyl ether, glycerol three
The glycidyl ethers such as glycidyl ether, trimethylolpropane tris glycidyl ether, triglycidyl group isocyanuric acid ester
Multicomponent methacrylate class；It is not limited to above-mentioned substance, by polyether polyol, polycarbonate glycol, C-terminal polybutadiene, is gathered
The polyalcohols such as ester polyol have directly carried out urethane acrylate by acroleic acid esterification or by diisocyanate
Esters of acrylic acid and melamine acrylate and each methyl acrylic ester corresponding with above-mentioned acrylate at least
It is suitable for selecting to use in any.Such photo-sensitive monomer can also be used as reactive diluent use.
Ring made of the polyfunctional epoxy resins such as cresol novolak type epoxy resin can also being made to react with acrylic acid
Oxypropylene acid ester resin；And then the hydroxies such as pentaerythritol triacrylate are made for the hydroxyl of the Epocryl
Epoxy amino first made of the half carbamate compounds reaction of the diisocyanate such as acid esters and isophorone diisocyanate
Acid esters acrylate compounds etc. are used as photo-sensitive monomer.Such epoxy acrylate system resin will not be such that dry to touch drops
It is low, it can be improved photo-curable.
About the blend amount of photo-sensitive monomer, in photosensitive polymer combination, in terms of solid component conversion, relative to containing
100 mass parts of carboxy resin, preferably 0.2 mass parts~60 mass parts, more preferably 0.2 mass parts~50 mass parts.Pass through
Make 0.2 mass parts of blend amount of photo-sensitive monomer or more, the photo-curable of photosensitive polymer combination improves.In addition, passing through
Make blend amount 60 below the mass, can be improved cured coating film hardness.
For photo-sensitive monomer, especially the non-photosensitive containing carboxyl without ethylenically unsaturated double bond is being used
It in the case where resin, in order to make composition photo-curable, needs to share photo-sensitive monomer, thus is effective.
[thermosetting resin]
Thermosetting resin used in the present invention can enumerate isocyanate compound, blocked isocyanate chemical combination
Object, amino resins, maleimide compound, benzoxazine resin, carbodiimides resin, cyclic carbonate compound, epoxy
Usual thermosetting resin known in compound, oxetane compound, episulfide resin etc..Preferred thermosetting among these
Property resin be epoxy resin.
As workable epoxy resin, it can be cited for example that bisphenol A type epoxy resin, bisphenol f type epoxy resin, hydrogenation
Bisphenol A type epoxy resin, brominated bisphenol a type epoxy resin, bisphenol-s epoxy resin, phenol novolak type epoxy resin, first
It is phenol phenolic resin varnish type epoxy resin, the phenolic resin varnish type epoxy resin of bisphenol-A, biphenyl type epoxy resin, naphthalene type epoxy resin, double
Cyclopeutadiene type epoxy resin, triphenylmenthane type epoxy resin etc..These epoxy resin can be used alone, and can also incite somebody to action
It is used in combination.
As commercially available epoxy resin, it can be cited for example that the jER828 of Mitsubishi chemical Co., Ltd's manufacture, 806,807,
YX-8000,8034, jER834, Nippon Steel & Sumitomo Metal Corporation manufacture YD-128, YDF-170, ZX-1059, ST-3000,
Dainippon Ink Chemicals's manufacture 830, the RE-306 etc. of 835,840,850, N-730A, N695 and Nippon Kayaku K. K's manufacture.
The equivalent of epoxy group about the epoxy resin in photosensitive polymer combination, in terms of solid component conversion, relatively
In the equivalent 1 of the carboxyl containing carboxy resin, preferably 0.3~3.0.More than for 0.3 equivalent, it can prevent in curing overlay film
The remaining of carboxyl can obtain good heat resistance, alkali resistance, electrical insulating property etc..On the other hand, by making above-mentioned blend amount
3.0 equivalents can ensure to solidify and cover well hereinafter, can prevent ring-type (sulphur) ether of low molecular weight from remaining in dry coating
Film strength etc..
[thermal curing catalyst]
It can mixed thermal curing catalyst in photosensitive polymer combination of the invention.It, can as thermal curing catalyst
With enumerate for example imidazoles, 2-methylimidazole, 2- ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2- phenylimidazole, 4- phenylimidazole,
The imdazole derivatives such as 1-cyanoethyl-2-phenylimidazole, 1- (2- cyanoethyl) -2-ethyl-4-methylimidazole；Dicyandiamide, benzyl two
Methylamine, 4- (dimethylamino)-N, N- dimethyl benzyl amine, 4- methoxyl group-N, N- dimethyl benzyl amine, 4- methyl-N, N- bis-
The hydrazine compounds such as the amine compounds such as methylbenzyl amine, adipic dihydrazide, sebacic dihydrazide；The phosphorus compounds such as triphenylphosphine
Deng.Alternatively, it is also possible to use guanamines, 2,4- diamino -6- methyl-1,3,5- triazines, benzoguanamine, melamine, 2,4- diamino
Base -6- methacryloxyethyl-s-triazine, 2- vinyl -2,4- diamino-s-triazine, 2- vinyl -4,6- diamino
Base-s-triazine isocyanuric acid adduct, 2,4- diamino -6- methacryloxyethyl-s-triazine isocyanuric acid add
At Striazine derivatives such as objects.
About the blend amount of thermal curing catalyst, in the composition comprising having cyclic annular (sulphur) ether in the molecules such as epoxy resin
In the case where the thermosetting component of base, in terms of solid component conversion, relative to the thermosetting property in molecule with cyclic annular (sulphur) ether
100 mass parts of ingredient, preferably 0.1 mass parts~20 mass parts, more preferably 0.5 mass parts~15.0 mass parts.
[organic solvent]
Organic solvent used in the present invention includes diethylene glycol monoethyl ether acetic acid esters, dipropylene glycol monomethyl ether and propylene glycol
This 3 kinds of methyl ether acetate.By sharing this specific 3 kinds of organic solvents, can equably photosensitive resin coating composition,
Furthermore it is possible to contraction after inhibiting coating or when dry or the generation to hang, form uniform dry coating after the drying, it can
Inhibit the generation of short circuit.
About the content of the organic solvent in photosensitive polymer combination, contain carboxy resin 100 relative to solid component
Mass parts, diethylene glycol monoethyl ether acetic acid esters are preferably 10 mass parts~60 mass parts, more preferably 15 mass parts~60 mass
Part, further preferably 20 mass parts~60 mass parts, dipropylene glycol monomethyl ether is preferably 10 mass parts~40 mass parts, more excellent
It is preferred to be selected as 15 mass parts~35 mass parts, further preferably 15 mass parts~30 mass parts, propylene glycol methyl ether acetate
For 50 mass parts~200 mass parts, more preferably 60 mass parts~170 mass parts, further preferably 70 mass parts~150 matter
Measure part.By sharing this specific 3 kinds of organic solvents with above-mentioned content, the contraction after being coated with or when dry can be further suppressed
Or the generation to hang, dry coating more evenly is formed after the drying, is able to suppress the generation of short circuit.On it should be noted that
Stating content further includes the organic solvent amount used in the preparation of photosensitive polymer combination, in the viscous of photosensitive polymer combination
Organic solvent amount used in degree adjusting.
The vapour pressure of 3 kinds of specific organic solvents, diethylene glycol monoethyl ether acetic acid esters used in the present invention are
0.16mmHg (25 DEG C), dipropylene glycol monomethyl ether are 0.40mmHg (25 DEG C), and propylene glycol methyl ether acetate is 3.92mmHg (25
℃).In the present invention, by sharing this specific 3 kinds of organic solvents with different vapour pressures, it is believed that the present invention can be obtained
Above-mentioned excellent effect.In this regard, though it is not necessarily clear, it can be presumed as follows.That is, each solvent caused by the difference of vapour pressure
The difference of evaporation rate form dry coating periodically, due to the formation, the surface state of dry coating becomes appropriate.
That is, contraction after coating can be further suppressed or when dry or the generation to hang, it is capable of forming more evenly dry after the drying
Dry film.As a result, thinking that the film after solidifying also becomes suitably, to be able to suppress the generation of substrate short circuit.But it only pushes away eventually
It surveys, this may not be defined in.
In the present invention, as organic solvent, other than above-mentioned specific 3 kinds, can also share more than one ketone,
Other organic solvents such as aromatic hydrocarbon, alcohols, aliphatic hydrocarbon and petroleum series solvent.Specifically, it can be cited for example that methyl
The ketones such as ethyl ketone, cyclohexanone；Toluene, dimethylbenzene, durene, SOLVESSO 150 etc. are aromatic hydrocarbon；Ethyl alcohol, propyl alcohol, second
The alcohols such as glycol, propylene glycol；The aliphatic hydrocarbons such as octane, decane；The stones such as petroleum ether, naphtha, hydrogenated naphtha, solvent naphtha
Oily series solvent etc..Relative to 100 mass parts containing carboxy resin, the content of other organic solvents in photosensitive polymer combination is excellent
Choosing is less than 10 mass parts, more preferably 0.1 mass parts~8 mass parts.
In the present invention, the viscosity that above-mentioned organic solvent adjusts photosensitive polymer combination can be used.For photonasty tree
For oil/fat composition, make when 25 DEG C of temperature of composition using the viscosity that rock field flow cup NK-2 is measured be preferably 40 seconds~
100 seconds (being equivalent to 0.13Pas~0.31Pas), more preferably 45 seconds~90 seconds (be equivalent to 0.15Pas~
0.29Pas), it is more preferably 50 seconds~80 seconds (being equivalent to 0.17Pas~0.25Pas).By making photonasty tree
Oil/fat composition has such viscosity, the generation that can be further suppressed the contraction after being coated with or when dry or hang, in drying
Dry coating more evenly is formed afterwards, is able to suppress the generation of short circuit.
[Photoepolymerizationinitiater initiater]
In the present invention, cause as the photopolymerization used to make above-mentioned photosensitive polymer combination carry out photopolymerization
Well known Photoepolymerizationinitiater initiater can be used in agent, it can be cited for example that oxime ester system Photoepolymerizationinitiater initiater, ring penta with oxime ester base
Diene titanium system Photoepolymerizationinitiater initiater, alpha-aminoacetophenone system Photoepolymerizationinitiater initiater, acylphosphine oxide system Photoepolymerizationinitiater initiater etc..Its
In, preferably alpha-aminoacetophenone system Photoepolymerizationinitiater initiater, acylphosphine oxide system Photoepolymerizationinitiater initiater.Photoepolymerizationinitiater initiater can be single
Solely using one kind, can also be shared two or more.
As alpha-aminoacetophenone system Photoepolymerizationinitiater initiater, specifically, 2- methyl-1-[4- (methyl mercapto) can be enumerated
Phenyl] -2- morpholinopropanone -1,2- benzyl -2- dimethylamino -1- (4- morphlinophenyl)-butane -1- ketone, 2- (dimethyl
Amino) -2- [(4- aminomethyl phenyl) methyl] -1- [4- (4- morpholinyl) phenyl] -1- butanone, N, N- dimethylamino benzoylformaldoxime
Deng.As commercially available product, Omnirad 369, the Omnirad 379, Omnirad 907 of the manufacture of IGM Resins company can be enumerated
Deng.
As acylphosphine oxide system Photoepolymerizationinitiater initiater, specifically, 2,4,6- trimethylbenzoyls two can be enumerated
Phenyl phosphine oxide, bis- (2,4,6- trimethylbenzoyl)-phenyl phosphine oxides, bis- (2,6- Dimethoxybenzoyls) -2,4,
4- trimethyl-pentyl phosphine oxide etc..As commercially available product, can enumerate the manufacture of IGM Resins company Omnirad TPO,
Omnirad 819 etc..
It can also be shared with above-mentioned Photoepolymerizationinitiater initiater and use light-initiated auxiliary agent or sensitizer.As light-initiated auxiliary agent or
Sensitizer, can enumerate benzoin compound, acetophenone compound, anthraquinone compounds, thioxanthone compounds, ketal compound,
Benzophenone cpd, tertiary amine compound and xanthone compound etc..Particularly preferably use 2,4- dimethyl thioxanthone, 2,4-
The thioxanthone compounds such as diethyl thioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone.By the inclusion of
Thioxanthone compounds can be improved deep curability.As commercially available product, DETX, ITX as thioxanthone compounds can be enumerated
(LAMBSON company manufacture) etc..These compounds are also used as Photoepolymerizationinitiater initiater use sometimes, but preferably draw with photopolymerization
Hair agent is shared and is used.In addition, light-initiated auxiliary agent or sensitizer can be used alone, can also share two or more.
It should be noted that these Photoepolymerizationinitiater initiaters, light-initiated auxiliary agent and sensitizer be due to absorbing specific wavelength, because
And according to circumstances sensitivity decrease, there is the case where working as ultraviolet absorbing agent.But these reagents are not only used
In the purpose for the sensitivity for improving composition.It can according to need the light for making it absorb specific wavelength, improve the light reaction on surface
Property, while the wire shaped of resist and opening to be changed to vertical, taper, back taper, improve the processing essence of line width and opening diameter
Degree.
[colorant]
Also it may include colorant in photosensitive polymer combination.As colorant, red, blue, green, Huang Denggong can be used
The colorant known can be any one of pigment, dyestuff, pigment.But from reduction environmental pressure and to the influence of human body
Aspect set out, preferably do not contain halogen.
As red stain, there is monoazo system, bisazo system, azo lake system, benzimidazolone system, is, diketone
Base pyrrolopyrrole system, condensation azo system, anthraquinone system, quinacridone etc., refer to specifically, can enumerate with following colors
Number (C.I.；The Society of Dyers and Colourists distribution) serial number substance.
As monoazo system red stain, can enumerate paratonere 1,2,3,4,5,6,8,9,12,14,15,16,17,
21、22、23、31、32、112、114、146、147、151、170、184、187、188、193、210、245、253、258、266、
267,268,269 etc..In addition, pigment red 37,38,41 etc. can be enumerated as bisazo system red stain.In addition, conduct
Monoazo color lake system red stain, can enumerate pigment red 4 8:1,48:2,48:3,48:4,49:1,49:2,50:1,52:1,
52:2,53:1,53:2,57:1,58:4,63:1,63:2,64:1,68 etc..In addition, as benzimidazolone system red stain,
Paratonere 171,175,176,185,208 etc. can be enumerated.In addition, solvent red can be enumerated as being red stain
135,179, pigment red 123,149,166,178,179,190,194,224 etc..In addition, red as diketopyrrolopyrrolecocrystals system
Chromatic colorant agent can enumerate paratonere 254,255,264,270,272 etc..In addition, as condensation azo system red stain, it can
To enumerate paratonere 220,144,166,214,220,221,242 etc..In addition, can be enumerated as anthraquinone system red stain
Paratonere 168,177,216, solvent red 149,150,52,207 etc..In addition, as quinacridone red stain, Ke Yiju
Pigment red 122,202,206,207,209 etc. out.
As blue colorant, there are phthalocyanine system, anthraquinone system, pigment system is the compound for being classified as pigment (Pigment),
It can be cited for example that pigment blue 15,15:1,15:2,15:3,15:4,15:6,16,60.As dyestuff system, solvent blue can be used
35,63,68,70,83,87,94,97,122,136,67,70 etc..In addition to the foregoing, can also use metal replace or not
Substituted phthalocyanine compound.
As yellow colorants, monoazo system, bisazo system, condensation azo system, benzimidazolone system, different Yin can be enumerated
Diindyl quinoline ketone system, anthraquinone system etc., for example, as anthraquinone system yellow colorants, can enumerate solvent yellow 16 3, pigment yellow 24,108,
193,147,199,202 etc..As isoindolinone system yellow colorants, can enumerate pigment yellow 110,109,139,179,
185 etc..As condensation azo system yellow colorants, pigment yellow 93,94,95,128,155,166,180 etc. can be enumerated.As
Benzimidazolone system yellow colorants can enumerate pigment Yellow 12 0,151,154,156,175,181 etc..In addition, as single idol
Nitrogen system yellow colorants, can enumerate pigment yellow 1,2,3,4,5,6,9,10,12,61,62,62:1,65,73,74,75,97,
100,104,105,111,116,167,168,169,182,183 etc..In addition, as bisazo system yellow colorants, Ke Yiju
Pigment Yellow 12,13,14,16,17,55,63,81,83,87,126,127,152,170,172,174,176,188,198 etc. out.
In addition to this, the colorant of purple, orange, brown, black, white etc. can also be added.Specifically, pigment black can be enumerated
1,6,7,8,9,10,11,12,13,18,20,25,26,28,29,30,31,32, pigment violet 19,23,29,32,36,38,42,
Solvent violet 13,36, C.I. pigment orange 1,5,13,14,16,17,24,34,36,38,40,43,46,49,51,61,63,64,71,
73, pigment brown 23,25, carbon black, titanium oxide etc..
[other compositions]
In photosensitive polymer combination, for characteristics such as adaptation, mechanical strength, the linear expansion coefficients for improving solidfied material
Purpose, can according to need further mixed inorganic filler.Such as barium sulfate, barium titanate, silica powder, micro- can be used
Known in powdery silica, amorphous silicon oxide, talcum, clay, magnesium carbonate, calcium carbonate, aluminium oxide, aluminium hydroxide, mica powder etc.
Usual inorganic filler.
It, as needed can further mixed fire retardant, closely sealed promotor, anti-oxidant in photosensitive polymer combination
The ingredients such as agent, ultraviolet absorbing agent, dispersing agent.Well known substance in field of electronic materials can be used in they.Furthermore it is possible to mixed
In defoaming agent and levelling agent with silicone-based, fluorine system, macromolecular etc. at least any one, imidazoles system, thiazole system, triazole system
Deng silane coupling agent, antirust agent, fluorescent whitening agent etc. known in usual additive kind at least any one.
Photosensitive polymer combination of the invention is particularly suitable for forming cured film in the printed circuit boards, can be used as
For solder mask formation, interlayer dielectic, marking ink, coating, solder dam, the through-hole or via hole for filling printed circuit board
Through hole or recess portion hole portion packing material.Among these, solder resist can be suitable for use as and form use.In addition, of the invention
Photosensitive polymer combination can for one-pack-type, or dual liquid type more than.
[dry film]
Photosensitive polymer combination of the invention may be the form of dry film, the dry film have support (carrier) film and
The resin layer being made of the dry coating of above-mentioned photosensitive polymer combination being formed on the support membrane.It, will in dry film
Photosensitive polymer combination of the invention is adjusted to viscosity appropriate with above-mentioned organic solvent diluting, using comma coater,
Knife type coater, lip type coating machine, bar coater, extrusion coating machine, reversed coating machine, transfer roll coater, gravure coater, spray
Painting machine etc. is coated on a carrier film with uniform thickness, usually in 50 DEG C~130 DEG C of at a temperature of 1 minute~30 points of drying
Clock, it is hereby achieved that film.Coating film thickness is not particularly limited, usually with the film thickness gauge after drying 1 μm~150 μm, it is excellent
The range for being selected in 10 μm~60 μm is suitable for selection.
As support membrane, as long as well known support membrane can use without particular limitation, it can be suitable for use example
Such as polyethylene terephthalate, polyethylene naphthalate polyester film, polyimide film, polyamidoimide film,
The film that polypropylene screen, polystyrene film etc. are made of thermoplastic resin.Among these, from heat resistance, mechanical strength, treatability etc.
Aspect is set out, preferably polyester film.Alternatively, it is also possible to which the laminate of these films is used as support membrane.
In addition, above-mentioned thermoplastic resin film is preferably in uniaxial direction or double from improving mechanical strength aspect
The film that axis direction is stretched.
The thickness of support membrane is not particularly limited, such as can be 10 μm~150 μm.
After forming the resin layer being made of the dry coating of photosensitive polymer combination of the invention on support membrane, in turn
For the purpose of preventing dust to be attached to resin layer surface, the protection (cover) that can preferably be removed in the surface lamination of resin layer
Film.As the protective film that can be removed, such as polyethylene film, polytetrafluoroethylene film, polypropylene screen, surface treated can be used
Paper etc., as long as the bonding force of resin layer and protective film is less than the bonding force of resin layer and support membrane when removing protective film
It can.
The thickness of protective film is not particularly limited, such as can be 10 μm~150 μm.
The measuring method that the various organic solvents for including in dry film of the invention can use degassing as shown below is come true
Recognize.As the measuring method of degassing, firstly, will be on dry film laminating to copper clad laminate using vacuum laminator.Next, using taking
The exposure device for being loaded with metal halide lamp carries out whole face exposure to the substrate, by support membrane after dry film removing, with 30 DEG C
Atomisation pressure is the 1 mass %Na of 0.2MPa2CO3Aqueous solution develops, the resist film after forming development.Using made
The heating desorption apparatus (TDU) manufactured to GERSTEL company is added in powder sample acquisition by the resist of work.Later, for
150 DEG C of thermal extraction temperature carries out the obtained ingredient that deaerates for 10 minutes, is trapped using liquid nitrogen in -60 DEG C.Utilize Agilent
The gas chromatography mass spectrometer (6890N/5973N) of Technologies company manufacture carries out separation point to the degassing ingredient trapped
Analysis quantifies the peak of the solvent composition detected with n-dodecane conversion, is able to confirm that by the presence at above-mentioned peak various
Organic solvent.
[manufacturing method of printed circuit board]
The manufacturing method of printed circuit board of the invention is, using flush coater or curtain coater by above-mentioned photosensitive resin composition
Object is applied on substrate, is made its solidification by least any one in light and heat, is formed solder mask.Hereinafter, about solder mask
Forming method is illustrated an example.
About solder mask, photosensitive polymer combination is adjusted to be suitble to the viscosity of coating method, utilizes flush coater or curtain
Painting machine whole face is applied on the substrate for being formed with circuit, about 60 DEG C~100 DEG C at a temperature of make to include in composition it is organic
Solvent volatile dry (interim dry), thus, it is possible to form dry coating non-stick.Film thickness after drying is preferably 30 μm~
50μm.Later, by contact (or cordless), through forming figuratum photomask optionally by active-energy
Ray is exposed, and unexposed portion is developed using dilute alkaline aqueous solution (such as 0.3%~3% aqueous sodium carbonate) and is formed anti-
Lose agent pattern.In addition, be for example heated to about 140 DEG C~180 DEG C of temperature and make its heat cure, thus, it is possible to formed heat resistance,
The excellent cured coating film of the various characteristics such as chemical resistance, resistance to hygroscopicity, adaptation, electrology characteristic.
In the case where dry film, after being conformed on substrate in such a way that resin layer is contacted with substrate using laminating machine etc.,
Carrier film is peeled, thus forms resin layer on substrate.After being carried out similarly exposure with the above method, by support membrane from dry film
It removes and develops, thus form resist pattern on substrate.
It is formed with substrate used in the substrate of circuit as above-mentioned, can enumerate and use high-frequency circuit copper-clad
The coating foil laminated board and polyimide film, PET film, glass substrate, ceramics of all grades (FR-4 etc.) of materials such as product plate
Substrate, chip plate etc., wherein copper-clad product plate has used paper-phenolic resin, paper-epoxy resin, glass cloth-asphalt mixtures modified by epoxy resin
Rouge, glass-polyimides, glass cloth/non-woven fabrics-epoxy resin, glass cloth/paper-epoxy resin, synthetic fibers-epoxy resin,
Fluororesin polyethylene PPO cyanate etc..
In addition, as active energy beam irradiation used in radiation source, low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp,
Ultrahigh pressure mercury lamp, xenon lamp or metal halide lamp etc. are appropriate.In addition to this, it also can use laser beam etc. as activity
Energy-ray.
As above-mentioned developing method, infusion process, spray process, spray-on process, spread coating etc. can be used, it, can as developer solution
To use the dilute alkali aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium metasilicate, ammonia, amine etc..
Embodiment
Next, enumerating embodiment, the present invention will be described in more detail, and however, the present invention is not limited to these examples.
<preparation containing carboxy resin>
(manufacture of varnish A)
By cresol novolak type epoxy resin (Nippon Kayaku K. K's manufacture, EOCN-104S, epoxide equivalent 220g/
Eq) 220 mass parts (1 equivalent), 200.4 mass parts of diethylene glycol monoethyl ether acetic acid esters (hereinafter also referred to CA) are put into flask,
It is heated to 90 DEG C and stirs, dissolved.Obtained solution is temporarily cooled to 60 DEG C, 72 mass parts of acrylic acid are added, and (1 rubs
You), 0.5 mass parts of methylnaphthohydroquinone, 2 mass parts of triphenylphosphine, be heated to 100 DEG C, make its react about 12 hours, obtaining acid value is
The reactant of 0.2mgKOH/g.80.6 mass parts of tetrabydrophthalic anhydride (0.53 mole) is added thereto, is heated to 90 DEG C,
It reacts it about 6 hours, obtains the resin solution A that solid component acid value is 85mgKOH/g, solid component concentration is 64.9%.
Hereinafter referred to as varnish A.
(manufacture of varnish B)
As organic solvent, use propylene glycol methyl ether acetate (hereinafter also referred to PMA) instead of CA, in addition to this into
The capable preparation with varnish A similarly operates, and obtains resin solution B.Hereinafter referred to as varnish B.
<preparation of photosensitive polymer combination>
[embodiment 1]
According to the varnish A of the above-mentioned preparation of ratio shown in table 1 (mass parts) mixture, Photoepolymerizationinitiater initiater, colorant, inorganic
Filler, additive, photo-sensitive monomer (reactive diluent), thermosetting resin, curing catalysts and organic solvent (non-reaction
Property diluent), later using blender premixing after, be kneaded using three-roll mill, by PMA adjust viscosity, prepare
Photosensitive polymer combination (solder mask composition) 1.About 3 kinds of organic solvent (dipropylene glycol in photosensitive polymer combination 1
Monomethyl ether (hereinafter also referred to DPM), CA, PMA) content, relative to 100 mass parts containing carboxy resin of solid component, DPM is
20 mass parts, CA are 54 mass parts, PMA is 140 mass parts.
[embodiment 2]
The proportion for changing each ingredient as shown in table 1, prepares photosensitive polymer combination similarly to Example 1 in addition to this
2.About the content of 3 kinds of organic solvents (DPM, CA, PMA) in photosensitive polymer combination 2, contain carboxylic relative to solid component
100 mass parts of base resin, DPM is 25 mass parts, CA is 54 mass parts, PMA is 140 mass parts.
[embodiment 3]
The proportion for changing each ingredient as shown in table 1, prepares photosensitive polymer combination similarly to Example 1 in addition to this
3.About the content of 3 kinds of organic solvents (DPM, CA, PMA) in photosensitive polymer combination 3, contain carboxylic relative to solid component
100 mass parts of base resin, DPM is 20 mass parts, CA is 54 mass parts, PMA is 140 mass parts.
[embodiment 4]
Instead of varnish A using above-mentioned preparation varnish B, change the proportion of each ingredient as shown in table 1, in addition to this with reality
It applies example 1 and is prepared as photosensitive polymer combination 4.About in photosensitive polymer combination 43 kinds of organic solvents (DPM, CA,
PMA content), relative to 100 mass parts containing carboxy resin of solid component, DPM is 20 mass parts, CA is 25 mass parts, PMA
For 169 mass parts.
[embodiment 5]
The proportion for changing each ingredient as shown in table 1, prepares photosensitive polymer combination similarly to Example 1 in addition to this
5.About the content of 3 kinds of organic solvents (DPM, CA, PMA) in photosensitive polymer combination 5, contain carboxylic relative to solid component
100 mass parts of base resin, DPM is 20 mass parts, CA is 54 mass parts, PMA is 80 mass parts.
[embodiment 6]
The proportion for changing each ingredient as shown in table 1, prepares photosensitive polymer combination similarly to Example 1 in addition to this
6.About the content of 3 kinds of organic solvents (DPM, CA, PMA) in photosensitive polymer combination 6, contain carboxylic relative to solid component
100 mass parts of base resin, DPM is 25 mass parts, CA is 54 mass parts, PMA is 80 mass parts.
[embodiment 7]
The proportion for changing each ingredient as shown in table 1, prepares photosensitive polymer combination similarly to Example 1 in addition to this
7.About the content of 3 kinds of organic solvents (DPM, CA, PMA) in photosensitive polymer combination 7, contain carboxylic relative to solid component
100 mass parts of base resin, DPM is 20 mass parts, CA is 54 mass parts, PMA is 80 mass parts.
[embodiment 8]
Instead of varnish A using above-mentioned preparation varnish B, change the proportion of each ingredient as shown in table 1, in addition to this with reality
It applies example 1 and is prepared as photosensitive polymer combination 8.About in photosensitive polymer combination 83 kinds of organic solvents (DPM, CA,
PMA content), relative to 100 mass parts containing carboxy resin of solid component, DPM is 20 mass parts, CA is 25 mass parts, PMA
For 109 mass parts.
[embodiment 9]
The proportion for changing each ingredient as shown in table 1, prepares photosensitive polymer combination similarly to Example 1 in addition to this
9.About the content of 3 kinds of organic solvents (DPM, CA, PMA) in photosensitive polymer combination 9, contain carboxylic relative to solid component
100 mass parts of base resin, DPM is 20 mass parts, CA is 54 mass parts, PMA is 160 mass parts.
[embodiment 10]
The proportion for changing each ingredient as shown in table 1, prepares photosensitive polymer combination similarly to Example 1 in addition to this
10.About the content of 3 kinds of organic solvents (DPM, CA, PMA) in photosensitive polymer combination 10, relative to containing for solid component
100 mass parts of carboxy resin, DPM is 20 mass parts, CA is 54 mass parts, PMA is 62 mass parts.
[embodiment 11]
Instead of varnish A using above-mentioned preparation varnish B, change the proportion of each ingredient as shown in table 1, in addition to this with reality
It applies example 1 and is prepared as photosensitive polymer combination 11.About in photosensitive polymer combination 11 3 kinds of organic solvents (DPM,
CA, PMA) content, relative to 100 mass parts containing carboxy resin of solid component, DPM is 20 mass parts, CA be 25 mass parts,
PMA is 169 mass parts.
[comparative example 1]
The proportion for changing each ingredient as shown in table 1, prepares photosensitive polymer combination similarly to Example 1 in addition to this
12 (no PMA).About the content of 3 kinds of organic solvents (DPM, CA, PMA) in photosensitive polymer combination 12, relative to solid
100 mass parts containing carboxy resin of ingredient, DPM is 108 mass parts, CA is 84 mass parts, PMA is 0 mass parts.
[comparative example 2]
Instead of varnish A using above-mentioned preparation varnish B, change the proportion of each ingredient as shown in table 1, in addition to this with reality
It applies example 1 and is prepared as photosensitive polymer combination 13 (no CA).About 3 kinds of organic solvents in photosensitive polymer combination 13
The content of (DPM, CA, PMA), relative to 100 mass parts containing carboxy resin of solid component, DPM is 10 mass parts, CA is 0 matter
Measure part, PMA is 182 mass parts.
[comparative example 3]
Instead of varnish A using above-mentioned preparation varnish B, change the proportion of each ingredient as shown in table 1, in addition to this with reality
It applies example 1 and is prepared as photosensitive polymer combination 14 (no DPM).It is organic molten about 3 kinds in photosensitive polymer combination 14
The content of agent (DPM, CA, PMA), relative to 100 mass parts containing carboxy resin of solid component, DPM is 0 mass parts, CA 45
Mass parts, PMA are 147 mass parts.
[table 1]
<viscosity evaluation>
About the photosensitive polymer combination 1~14 prepared in above-described embodiment and comparative example, make the temperature of composition
25 DEG C, viscosity (second) is measured using rock field flow cup NK-2.Measurement result is shown in table 2.
<unevenness evaluation>
Using the photosensitive polymer combination 1~14 (wherein 11 except) prepared in above-described embodiment and comparative example, utilize
After curtain coater is applied on the copper clad laminate for be formed with circuit, the circuit part of substrate is observed by visual observation.
According to the unevenness that following benchmark evaluations are coated with, table 2 is showed the results of the evaluation.
[evaluation criteria]
ο: nothing is unevenly coated between circuit.
Δ: the position that can not be coated between circuit is 2 points hereinafter, there is no problem (2 points or less) on practical.
×: the position that can not be coated between circuit is 3 points or more, is coated with bad.
<shrinking evaluation>
It is 20 μ according to dry film thickness using the photosensitive polymer combination 1~14 prepared in above-described embodiment and comparative example
The mode of m is applied on the copper clad laminate for being formed with circuit, observes the contraction situation of the solder resist on copper circuit by visual observation.It needs
It is carried out it is noted that the coating of each composition is based respectively on the method recorded in table 2.
According to the contraction of following benchmark evaluation solder resists, table 2 is showed the results of the evaluation.
[evaluation criteria]
ο: ungauged regions can be equably applied on copper circuit.
Δ: slightly shrinking, and produces a small amount of unevenness on copper circuit, but it is practical on without problem be coated with.
×: there is contraction, a part of copper circuit exposes.
<hang evaluation>
It is 20 μ according to dry film thickness using the photosensitive polymer combination 1~14 prepared in above-described embodiment and comparative example
The mode of m is applied on the copper clad laminate for being formed with circuit, is laid flat and is dried at room temperature for 10 minutes.It should be noted that each
The coating of composition is based respectively on the method recorded in table 2 and carries out.Later, it erects and leans against on special frame, utilize heated air circulation type
Drying oven is 15 minutes dry with 80 DEG C, observes hanging for the solder resist on copper circuit by visual observation.
According to hanging for following benchmark evaluation solder resists, table 2 is showed the results of the evaluation.
[evaluation criteria]
ο: it without hanging, can equably be applied on copper circuit.
Δ: a part hangs, and the difference of film thickness can be observed in top and lower part, but practical goes up that there is no problem.
×: generation significantly hangs, and copper circuit exposes.
<electrical insulating property evaluation>
Using the photosensitive polymer combination 1~14 prepared in above-described embodiment and comparative example, it is coated with as L/S=50/50 μ
The combed B pattern of m, is solidified.It is carried out it should be noted that the coating of each composition is based respectively on the method recorded in table 2.
For the comb-type electrode, carry out 7 days 25 DEG C~65 DEG C circulations, 90%R.H. warming and humidifying under the conditions of apply the inclined of DC100V
The processing of pressure, the resistance value (Ω) after humidification, after applying 500V with value measurement in 1 minute.
According to the electrical insulating property of following benchmark evaluation cured coating films, table 2 is showed the results of the evaluation.
[evaluation criteria]
ο: 1 × 1012Ω or more.
Δ: 1 × 1011Ω is more than and less than 1012Ω。
×: less than 1 × 1011Ω。
[table 2]
By above-mentioned experimental result it is found that photosensitive polymer combination of the invention can inhibit the contraction after being coated with or when dry
Or the generation to hang, dry coating is uniform after the drying.In addition we know, photosensitive polymer combination of the invention is utilizing curtain coating
It also can be without being unevenly coated between circuit when machine is coated.Furthermore it is found that using photosensitive resin composition of the invention
The electrical insulating property (inhibition that short circuit occurs) for the cured coating film that object is formed is excellent.
Claims (6)
1. a kind of photosensitive polymer combination, which is characterized in that it includes contain carboxy resin, thermosetting resin, photo-sensitive monomer
And organic solvent, the organic solvent include diethylene glycol monoethyl ether acetic acid esters, dipropylene glycol monomethyl ether and propylene glycol monomethyl ether
Acetic acid esters.
2. photosensitive polymer combination as described in claim 1, wherein make the temperature 25 of the photosensitive polymer combination
DEG C when using rock field flow cup NK-2 measurement viscosity be 40 seconds~100 seconds.
3. photosensitive polymer combination as claimed in claim 1 or 2 is used for the coating using flush coater or curtain coater.
4. photosensitive polymer combination according to any one of claims 1 to 3 is used as solder resist and forms use.
5. a kind of dry film, which is characterized in that it have support membrane and be formed on the support membrane by claim 1,2 and 4
Any one of described in photosensitive polymer combination dry coating constitute resin layer.
6. a kind of manufacturing method of printed circuit board, is the manufacturing method for having the printed circuit board of solder mask, feature exists
In,
Photosensitive polymer combination according to any one of claims 1 to 4 is applied to substrate using flush coater or curtain coater
On, its solidification is made by least any one in light and heat, forms solder mask.
Applications Claiming Priority (4)
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| JP2018-063037 | 2018-03-28 | ||
| JP2018063037 | 2018-03-28 | ||
| JP2018-247798 | 2018-12-28 | ||
| JP2018247798A JP7254511B2 (en) | 2018-03-28 | 2018-12-28 | Photosensitive resin composition, dry film, and method for producing printed wiring board |
Publications (1)
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|---|---|
| CN110320749A true CN110320749A (en) | 2019-10-11 |
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ID=68112805
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| CN201910212193.XA Pending CN110320749A (en) | 2018-03-28 | 2019-03-20 | The manufacturing method of photosensitive polymer combination, dry film and printed circuit board |
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| TWI819237B (en) * | 2020-09-08 | 2023-10-21 | 健鼎科技股份有限公司 | Printed circuit board manufacturing method |
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