CN104350421A - Photosensitive composition and printed circuit board having hardened layer thereof - Google Patents
Photosensitive composition and printed circuit board having hardened layer thereof Download PDFInfo
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- CN104350421A CN104350421A CN201380028583.2A CN201380028583A CN104350421A CN 104350421 A CN104350421 A CN 104350421A CN 201380028583 A CN201380028583 A CN 201380028583A CN 104350421 A CN104350421 A CN 104350421A
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- carboxyl
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- photosensitive composite
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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
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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
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- 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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- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials For Photolithography (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
In order to enable formation of a hardened film on a printed circuit board enabling an image to be properly developed, insulation performance to be maintained for prolonged periods of time, and mechanical strength to be kept at exceptional levels, a photosensitive composition contains (A) a carboxyl-group-containing photosensitive compound, (B) a photopolymerization initiator, (C) an epoxy compound, and optionally (D) a photosensitive compound not having a carboxyl group, the amount of double bonds in the photosensitive composition when no organic solvent or filler is contained therein being at least 400 eq. Another embodiment is a photosensitive composition containing (A') a carboxyl-group-containing compound, (B) a photopolymerization initiator, and (C) an epoxy compound, wherein there are 1.5-4 eq of epoxy groups of the epoxy compound (C) per equivalent of carboxyl groups of the carboxyl-group-containing compound (A'), and the liquid components included in the photosensitive composition constituting 5-30 percent by mass of all components excepting organic solvents and fillers.
Description
Technical field
The present invention relates to photosensitive composite and there is the printed circuit board (PCB) of its cured layer.
Background technology
In printed circuit board (PCB), the base material of conductor layer with circuit pattern is formed with soldering-resistance layer.As the material of this soldering-resistance layer, proposed various photosensitive composite in the past.For example, Patent Document 1 discloses a kind of permanent resist photosensitive polymer combination, it comprises the polymkeric substance with carboxyl, the photopolymerizable compound with ethylenic unsaturated bond and Photoepolymerizationinitiater initiater.
But, in recent years, particularly when the photosensitive composites such as solder resist are used for vehicle-mounted printed circuit board (PCB), under high-temperature high-humidity environment, require to maintain insulativity for a long time, do not crack such physical strength.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2005-99647 publication (claims)
Summary of the invention
the problem that invention will solve
But, for existing photosensitive composite, when the content of photopolymerization monomer is many, under high-temperature high-humidity, exist and cannot maintain insulativity for a long time or produce the such problem of a large amount of crackle.
On the other hand, when reducing the content of photopolymerization monomer, therefore also there is pattern formation and become the such problem of difficulty in sensitivity decrease.
The present invention makes in view of the problem of foregoing prior art, and its basic object is to provide to be formed and can forms pattern well, can maintain insulativity for a long time and the photosensitive composite of the cured film of mechanical strength.
And then, the object of the present invention is to provide the printed circuit board (PCB) that the long-term reliability of the cured layer with the photosensitive composite possessing this excellent specific property is high.
for the scheme of dealing with problems
In order to reach aforementioned object, according to the 1st aspect of the present invention, a kind of photosensitive composite being provided, it is characterized in that, containing:
(A) containing carboxyl photosensitive compounds,
(B) Photoepolymerizationinitiater initiater and
(C) epoxy compound,
The double bond equivalent of this photosensitive composite is more than 400 under the state not containing organic solvent and filler.
In another way, a kind of photosensitive composite is provided, it is characterized in that, also not there is containing (D) photosensitive compounds of carboxyl except above-mentioned each composition.
According to preferred mode, not containing under the state of organic solvent and filler, the double bond equivalent of photosensitive composition be more than 400 and less than 680, be more preferably more than 450 and less than 650, more preferably more than 500 and less than 650.And then according to preferred mode, aforementioned (A) is below 30 quality % containing the containing ratio of (D) composition that carboxyl photosensitive compounds and (D) do not have in the blending constituent of the photosensitive compounds of carboxyl.According to preferred mode, relative to carboxyl 1 equivalent of aforementioned (A) carboxylated compound, the epoxy radicals of aforementioned (C) epoxy compound is more than 1.5 equivalents.
And then, according to the 2nd aspect of the present invention, a kind of photosensitive composite is provided, it is characterized in that, contain:
(A ') carboxylated compound,
(B) Photoepolymerizationinitiater initiater and
(C) epoxy compound,
Relative to carboxyl 1 equivalent of aforementioned (A ') carboxylated compound, the epoxy radicals of aforementioned (C) epoxy compound is more than 1.5 equivalents and below 4 equivalents, the containing ratio of liquid parts contained in this photosensitive composite is more than 5 quality % and below 30 quality % relative to the whole compositions except organic solvent and filler.
According to preferred mode, the quantity of the epoxy radicals of aforementioned (C) epoxy compound is 2.
And then according to the present invention, a kind of printed circuit board (PCB) is also provided, it is characterized in that, have and use photosensitive composition and the cured layer that formed.
the effect of invention
The photosensitive composite of the 1st aspect of the present invention is more than 400 as described previously by making the double bond equivalent of photosensitive composite under the state not containing organic solvent and filler, thus pattern can be formed well, even if also insulativity can be maintained for a long time under high-temperature high-humidity, and the generation of crackle can be suppressed.Therefore, by using the photosensitive composite with this excellent specific property to form the cured layer such as soldering-resistance layer, interlayer insulating film, thus the printed circuit board (PCB) that long-term reliability is high can be provided.
In addition, the photosensitive composite of the 2nd aspect of the present invention contains as previously mentioned: (A ') carboxylated compound, (B) Photoepolymerizationinitiater initiater, and (C) epoxy compound, relative to carboxyl 1 equivalent of aforementioned (A ') carboxylated compound, the epoxy radicals of aforementioned (C) epoxy compound is more than 1.5 equivalents and below 4 equivalents, the containing ratio of liquid parts contained in this photosensitive composite is more than 5 quality % and below 30 quality % relative to the whole compositions except organic solvent and filler, thus pattern can be formed well, even if also insulativity can be maintained for a long time under high-temperature high-humidity, and the generation of crackle can be suppressed.Therefore, by using the photosensitive composite with this excellent specific property to form the cured layer such as soldering-resistance layer, interlayer insulating film, thus the printed circuit board (PCB) that long-term reliability is high can be provided.
Accompanying drawing explanation
Fig. 1 is the schematic side view that 2 test tubes used are shown during the liquid state of embodiment and comparative example judges.
Embodiment
According to the research of the present inventor etc., find containing (A) containing the photosensitive composite of carboxyl photosensitive compounds, (B) Photoepolymerizationinitiater initiater and (C) epoxy compound or the photosensitive composite also containing (D) without the photosensitive compounds of carboxyl, and the double bond equivalent of this photosensitive composite is when being more than 400 under not containing the state of organic solvent and filler, problem of the present invention can be solved.
Find, the aforementioned photosensitive compounds without carboxyl, namely when the content of photo-sensitive monomer (photopolymerization monomer) is many, insulativity cannot be maintained for a long time under high-temperature high-humidity, on the other hand, desensitize the content of monomer time, sensitivity decrease, therefore pattern formation becomes the such problem of difficulty and is set to specific scope at the double bond equivalent of the total amount by the organic principle in photosensitive composite, namely can solve when the double bond equivalent of photosensitive composition is more than 400 under the state not containing organic solvent and filler, thus complete the present invention.
And then, according to the research of the present inventor etc., find, photosensitive composite containing (A ') carboxylated compound, (B) Photoepolymerizationinitiater initiater and (C) epoxy compound, relative to carboxyl 1 equivalent of aforementioned (A ') carboxylated compound, the epoxy radicals of aforementioned (C) epoxy compound is more than 1.5 equivalents and below 4 equivalents, the containing ratio of liquid parts contained in this photosensitive composite be more than 5 quality % relative to the whole compositions except organic solvent and filler and below 30 quality % time, problem of the present invention can be solved.Herein, be whether that the judgement of " liquid state " is carried out at 20 DEG C.
As previously mentioned, do not have the content of the photosensitive compounds of carboxyl, i.e. photo-sensitive monomer (photopolymerization monomer) many time, the such problem of insulativity cannot be maintained for a long time under easily occurring in high-temperature high-humidity, even if photosensitive composite of the present invention is also a small amount of not containing photo-sensitive monomer or containing sometimes, the worry that therefore this problem occurs is less.On the other hand, find, desensitize the content of monomer time, usual softening point improves, therefore dissolubility reduces, pattern is formed and becomes the epoxy radicals of the such problem of difficulty at aforementioned (C) epoxy compound and be more than 1.5 equivalents relative to carboxyl 1 equivalent of aforementioned (A ') carboxylated compound and below 4 equivalents, the containing ratio of liquid parts contained in this photosensitive composite be more than 5 quality % relative to the whole compositions except organic solvent and filler and below 30 quality % when can solve, thus complete the present invention.
Below, each constituent of photosensitive composite of the present invention is described.
Aforementioned containing the ethylenical unsaturated double bonds preferred source in carboxyl photosensitive compounds (A) from acrylic or methacrylic acid or their derivant.
On the other hand, as aforementioned carboxylated compound (A '), the known usual resin compound with carboxyl can be used in molecule.As containing carboxy resin, any person contained in carboxyl photoresist containing carboxy resin, have ethylenical unsaturated double bonds himself without ethylenical unsaturated double bonds all can use, be not limited to specific material, containing carboxyl photoresist from the aspect of photo-curable, resistance to developability more preferably.
As this concrete example containing carboxyl photosensitive compounds or carboxylated compound, can list and enumerate such compound (oligomer and polymkeric substance) below.
(1) by the unsaturated carboxylic acid such as (methyl) acrylic acid and styrene, α-methyl styrene etc. have the compound of unsaturated double-bond and phenyl ring copolymerization and obtain containing carboxy resin.
(2) what make to have the copolymerization of the compound of unsaturated double-bond and phenyl ring and being formed containing the compound in carboxy resin and molecule with more than 1 ethylenically unsaturated group and 1 epoxy radicals carries out reacting of obtaining by the unsaturated carboxylic acids such as (methyl) acrylic acid and styrene, α-methyl styrene etc. contains carboxyl photoresist.
(3) aromatic diisocyanate is utilized, and dihydromethyl propionic acid, dimethylolpropionic acids etc. are containing carboxyl diatomic alcohol compounds and polycarbonate-based polyvalent alcohol, polyethers system polyvalent alcohol, polyester-based polyols, polyolefin polyvalent alcohol, acrylic polyol, bisphenol-A system alkylene oxide addition product glycol, have the diol compounds such as the compound of phenolic hydroxyl group and alcohol hydroxyl group addition polymerization and carry out carried out end (methyl) polyacryl containing adding the compound in (methyl) hydroxyalkyl acrylates equimolecular with 1 hydroxyl and more than 1 (methyl) acryloyl group in the synthesis of carboxyl urethane resin contain carboxyl photonasty urethane resin.
(4) aliphatic diisocyanate is utilized, Branched fatty (cyclo) aliphatic diisocyanates, ester ring type diisocyanate, the diisocyanate such as aromatic diisocyanate, and bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, di-first phenol-type epoxy resin, united phenol-type epoxy resins etc. have (methyl) acrylate or the anhydride modified thing of its part of 2 functional epoxy resins of phenyl ring, obtain containing the addition polymerization of carboxyl diatomic alcohol compounds and diol compound containing carboxyl photonasty urethane resin.
(5) have in the reaction with same mole thing equimolecular adding compound, isophorone diisocyanate and the pentaerythritol triacrylate in (methyl) hydroxyalkyl acrylates equimolecular with 1 hydroxyl and more than 1 (methyl) acryloyl group in the synthesis of the resin of aforementioned (3) 1 isocyanate group and more than 1 (methyl) acryloyl group compound and carried out end (methyl) polyacryl containing carboxyl photonasty urethane resin.
(6) make 2 officials with phenyl ring as described later can or 2 officials can above polyfunctional epoxy resin react with (methyl) acrylic acid, 2 yuan of acid anhydrides such as addition phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride on the hydroxyl being present in side chain and obtain contain carboxyl photoresist.
(7) make the hydroxyl with 2 functional epoxy resins of phenyl ring as described later react with (methyl) acrylic acid with the polyfunctional epoxy resin that epichlorokydrin carries out epoxidation further, addition 2 yuan of acid anhydrides on the hydroxyl generated and obtain contain carboxyl photoresist.
(8) cyclic carbonates such as cyclic ether and/or propylene carbonate such as the multifunctional phenolic compounds addition of ethylene oxide as novolaks are made, the hydroxyl obtained (methyl) acrylic acid is carried out partial esterification, the multi-anhydride such as remaining hydroxyl and maleic anhydride, tetrabydrophthalic anhydride, trimellitic anhydride, pyromellitic dianhydride is reacted and obtain containing carboxyl photoresist.
(9) make to have in the further addition of resin (methyl) glycidyl acrylate of above-mentioned (1) ~ (8), (methyl) acrylic acid Alpha-Methyl ethylene oxidic ester equimolecular the compound of 1 epoxy radicals and more than 1 (methyl) acryloyl group containing carboxyl photoresist.
It should be noted that, in this instructions, (methyl) acrylate refers to the term being referred to as acrylate, methacrylate and their potpourri, and other similar expression is also same.
Foregoing containing carboxyl photosensitive compounds or carboxylated compound owing to there is multiple carboxyl on the side chain of trunk polymer, dilute alkaline aqueous solution therefore can be utilized to develop.
In addition, the aforementioned acid number containing carboxyl photosensitive compounds or carboxylated compound is the scope of 30 ~ 200mgKOH/g is suitable, is more preferably 30 ~ 150mgKOH/g, is particularly preferably the scope of 45 ~ 120mgKOH/g.During containing the acid number of carboxyl photosensitive compounds lower than 30mgKOH/g, alkali development becomes difficulty, on the other hand, during more than 200mgKOH/g, the dissolving in the exposure portion caused by developer solution advances, and therefore line is carefully to necessity, or according to circumstances exposure portion and unexposed portion Wu are differently dissolved by the developing stripping, the description of normal corrosion-resisting pattern becomes difficulty, therefore not preferred.
In addition, aforementioned containing carboxyl photosensitive compounds or carboxylated compound, such as use gel permeation chromatography (GPC) to measure time weight-average molecular weight Mw (weight-average molecular weight of polystyrene conversion) different according to resin matrix, preferably be in be greater than 4000 and be less than 150000 scope, be preferably in more than 5000 further and be less than 100000 scope.When weight-average molecular weight is less than 4000, non-adhesion behavior is poor sometimes, and the moisture-proof of the film after exposure is poor, and produce film during development and reduce, resolution is significantly deteriorated sometimes.On the other hand, when weight-average molecular weight is more than 150000, developability is obviously deteriorated sometimes, therefore not preferred.
As long as in the molecule there is ethylenical unsaturated double bonds containing carboxyl photosensitive compounds, then use with can being not limited to the material of aforementioned list, a kind can be used also can to mix two or more to use.
As the Photoepolymerizationinitiater initiater used in the present invention (B), at least a kind of Photoepolymerizationinitiater initiater in the group being selected from and being made up of the oxime ester system Photoepolymerizationinitiater initiater with oxime ester base, alpha-aminoacetophenone system Photoepolymerizationinitiater initiater, acylphosphine oxide system Photoepolymerizationinitiater initiater can be used aptly.
As aforementioned oxime ester system Photoepolymerizationinitiater initiater, the Photoepolymerizationinitiater initiater with 2 oxime ester bases can be used in molecule aptly.
The compounding amount of this oxime ester system Photoepolymerizationinitiater initiater is preferably set to 0.02 ~ 10 quality % of total composition.During lower than 0.02 quality %, the photo-curable on copper is not enough, and film is peeled off, and the coating characteristics such as chemical proofing reduce.On the other hand, during more than 10 quality %, the light absorption on dry coating surface becomes violent, there is the tendency that deep curability reduces.
As aforementioned alpha-aminoacetophenone system Photoepolymerizationinitiater initiater, specifically, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-butane-1-ketone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone, N, N-dimethylamino benzoylformaldoxime etc. can be listed.
As aforementioned acylphosphine oxide system Photoepolymerizationinitiater initiater; specifically; can 2 be listed; 4,6-trimethyl benzoyl diphenyl base phosphine oxide, two (2,4; 6-trimethylbenzoyl)-phenyl phosphine oxide, two (2; 6-Dimethoxybenzoyl)-2,4,4-trimethyl-pentyl phosphine oxides etc.
The compounding amount of these alpha-aminoacetophenone system Photoepolymerizationinitiater initiaters, acylphosphine oxide system Photoepolymerizationinitiater initiater is preferably set to 0.5 ~ 15 quality % of total composition.During lower than 0.5 quality %, the photo-curable similarly on copper is not enough, and film is peeled off, and the coating characteristics such as chemical proofing reduce.On the other hand, during more than 15 quality %, can not get the effect reducing exhaust, and then the light absorption on dry coating surface becomes violent, there is the tendency that deep curability reduces.
In addition, as the Photoepolymerizationinitiater initiater that can be suitable in photosensitive composite of the present invention using, light-initiated auxiliary agent and sensitizer, benzoin compound, acetophenone compound, anthraquinone compounds, thioxanthone compounds, ketal compound, benzophenone cpd, tertiary amine compound and xanthone compound etc. can be listed.
As aforementioned benzoin compound, specifically, include, for example out benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether etc.
As foregoing acetophenone compound, specifically, include, for example out acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone etc.
As aforementioned anthraquinone compounds, specifically, include, for example out 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone etc.
As aforementioned thioxanthone compounds, specifically, include, for example out 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthones, CTX, 2,4-diisopropylthioxanthone etc.
As aforementioned ketal compound, specifically, include, for example out acetophenone dimethyl ketal, benzil dimethyl ketal etc.
As aforementioned benzophenone cpd; specifically, include, for example out benzophenone, 4-benzoyl diphenyl thioether, 4-benzoyl-4 '-dimethyl diphenyl sulfide, 4-benzoyl-4 '-ethyl diphenyl thioether, 4-benzoyl-4 '-propyl group diphenylsulfide etc.
As aforementioned tertiary amine compound, specifically, include, for example out ethanolamine compound, there is the compound of dialkyl amido benzene structure, such as, 4, 4 '-dimethylamino benzophenone, 4, the dialkyl amido benzophenone such as 4 '-diethylamino benzophenone, 7-(diethylamino)-4-methyl-2H-1-chromen-2-ones (7-(diethylamino)-4-methylcoumarin) etc. are containing the coumarin compound of dialkyl amido, EDMAB, 2-dimethyl amino benzoate, 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester, ESCAROL 507 isopentyl ethyl ester, 4-dimethylaminobenzoic acid 2-Octyl Nitrite etc.
In the middle of foregoing photo-polymerization initiating agent, light-initiated auxiliary agent and sensitizer, preferred thioxanthone compounds and tertiary amine compound.Particularly preferably comprise thioxanthone compounds from the aspect of deep curability.Wherein, the thioxanthone compounds such as 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthones, CTX, 2,4-diisopropylthioxanthone are preferably comprised.
As the compounding amount of this thioxanthone compounds, be preferably below the 15 quality % of total composition.When the compounding amount of thioxanthone compounds is more than 15 quality %, thick film curability reduces, and causes the cost increase of product.Be more preferably below 10 quality %.
In addition, as tertiary amine compound, preferably have the compound of dialkyl amido benzene structure, wherein particularly preferably dialkyl amido benzophenone cpd, maximum absorption wavelength are in the coumarin compound containing dialkyl amido and the cumarin ketone of 350 ~ 450nm.
As aforementioned dialkyl amido benzophenone cpd, 4, the toxicity of 4 '-diethylamino benzophenone is also low, is preferred.The aforementioned coumarin compound containing dialkyl amido is in the ultraviolet range of 350 ~ 410nm due to maximum absorption wavelength, therefore certainly can provide painted less, water white photosensitive composite, but also can provide and use coloring pigment and reflect the painted cured layer of coloring pigment self color.Particularly 7-(diethylamino)-4-methyl-2H-1-chromen-2-one shows excellent sensitization effect, so preferably for the laser of wavelength 400 ~ 410nm.
As the compounding amount of this tertiary amine compound, be preferably set to 0.1 ~ 15 quality % of total composition.When the compounding amount of tertiary amine compound is lower than 0.1 quality %, there is the tendency that cannot obtain sufficient sensitization effect.During more than 15 quality %, the light absorption on the dry coating surface of being caused by tertiary amine compound becomes violent, there is the tendency that deep curability reduces.
These Photoepolymerizationinitiater initiaters, light-initiated auxiliary agent and sensitizer can be used alone or use with the form of potpourri of more than two kinds.
The total amount of this Photoepolymerizationinitiater initiater, light-initiated auxiliary agent and sensitizer is aforementioned relative to 100 mass parts containing carboxyl photosensitive compounds or carboxylated compound, is preferably below 35 mass parts.During more than 35 mass parts, there is the tendency that deep curability reduces due to their light absorption.
It should be noted that, these Photoepolymerizationinitiater initiaters, light-initiated auxiliary agent and sensitizer are owing to absorbing specific wavelength, and therefore according to circumstances and sometimes sensitivity step-down, plays a role as ultraviolet light absorber.But they not only use to improve the sensitivity of composition.The light of specific wavelength can be absorbed as required, improve the photoreactivity on surface, make the wire shaped of resist and opening be changed to vertical, cone-shaped, reverse tapered shape, and improve the machining precision of line width, opening diameter.
As aforementioned epoxy compound (C), there is in preferred molecule the polyfunctional epoxy resin of multiple epoxy radicals, particularly preferably there is the polyfunctional epoxy resin of phenyl ring.As the concrete example of epoxy resin, bisphenol A type epoxy resin can be listed, brominated epoxy resin, phenolic resin varnish type epoxy resin, bisphenol f type epoxy resin, bisphenol-A epoxy resin, glycidyl amine type epoxy resin, hydantoins type epoxy resin, trihydroxy benzene methylmethane type epoxy resin, di-cresols type or united phenol-type epoxy resin or their potpourri, four hydroxy phenyl ethane type epoxy resin, hetero ring type epoxy resin, o-phthalic acid diglycidyl ester resin, four glycidyl group dimethylbenzene acyl group ethane resin, containing Naphthol-based Epoxy Resin, there is the epoxy resin of dicyclopentadiene skeleton, glycidyl methacrylate copolymerization system epoxy resin, and the copolymerization epoxy resin of N-cyclohexylmaleimide and glycidyl methacrylate, epoxide modified polybutadiene rubber derivant, CTBN modified epoxy etc., but be not limited to these.These epoxy resin can be used alone or in combination of two or more kinds.
The compounding amount of aforementioned epoxy compound, relative to carboxyl 1 equivalent in composition, is preferably scopes more than 1.5 equivalents, is more preferably more than 1.5 equivalents and scope below 5 equivalents, the scope more preferably more than 1.5 equivalents and below 4 equivalents.When the compounding amount of epoxy compound is lower than 1.5 equivalent, the insulativity of cured layer and crackle patience reduce, therefore not preferred.On the other hand, when the compounding amount of epoxy compound is more than 5 equivalent, developability reduces, therefore not preferred.
Photosensitive composite of the present invention can add such as imidazoles further, glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyano ethyl-2-phenylimidazole, the imdazole derivatives such as 1-(2-cyano ethyl)-2-ethyl-4-methylimidazole: dicyandiamide, benzyl dimethyl amine, 4-(dimethylamino)-N, N-dimethyl benzyl amine, 4-methoxyl-N, N-dimethyl benzyl amine, 4-methyl-N, the amines such as N-dimethyl benzyl amine: hexane diacid hydrazides, the hydrazine compounds such as decanedioic acid hydrazides: the phosphorus compounds such as triphenylphosphine etc. are as curing catalysts.Especially, as long as promote that there is the compound of cyclic ether group and the reaction of carboxyl, then these are not limited to.These catalyzer can be used alone or mix two or more to use.In addition, still the guanamines, methyl guanamines, benzoguanamine, the melamine, 2 that play function as adaptation imparting agent can be used, 4-diamido-6-methacryloxyethyl-s-triazine, 2-vinyl-2,4-diamido-s-triazine, 2-vinyl-4,6-diamido-s-triazine isocyanuric acid adduct, 2, these compounds and foregoing curing catalysts are preferably combinationally used by the Striazine derivatives such as 4-diamido-6-methacryloxyethyl-s-triazine isocyanuric acid adduct.The compounding amount of above-mentioned curing catalysts is that the ratio of common amount is just enough, such as, aforementioned relative to 100 mass parts containing carboxyl photosensitive compounds or carboxylated compound, is 0.1 ~ 20 mass parts, the ratio being preferably 0.5 ~ 15.0 mass parts.
As aforementioned photosensitive compounds (D) the i.e. photo-sensitive monomer without carboxyl, the compound that there is more than 1, preferably there are more than 2 ethylenical unsaturated double bonds can be used in molecule.Photo-sensitive monomer utilizes active energy beam to irradiate and photocuring, makes aforementioned insoluble in aqueous alkali containing carboxyl photosensitive compounds, or contributes to insoluble.As this compound, usual known polyester (methyl) acrylate, polyethers (methyl) acrylate, carbamate (methyl) acrylate, carbonic ester (methyl) acrylate, epoxy (methyl) acrylate can be used, specifically, the hydroxyalkyl acrylates class such as acrylic acid 2-hydroxy methacrylate, acrylic acid 2-hydroxy propyl ester can be listed; The diacrylate class of the glycol such as ethylene glycol, methoxyl TEG, polyglycol, propylene glycol; The acrylic amides such as N,N-DMAA, N hydroxymethyl acrylamide, N, N-dimethylaminopropylacryl acid amides; The acrylate classes such as acrylic acid N, N-dimethylamino ethyl ester, acrylic acid N, N-dimethylamino propyl ester; The multicomponent methacrylate classes such as polyvalent alcohol or their ethylene oxide adduct, propylene oxide adduct or 6-caprolactone addition product such as hexanediol, trimethylolpropane, pentaerythrite, dipentaerythritol, isocyanuric acid three hydroxyl ethyl ester; The multicomponent methacrylate classes such as the ethylene oxide adduct of phenoxy group acrylate, bisphenol a diacrylate and these phenols or propylene oxide adduct; The multicomponent methacrylate class of the glycidol ethers such as glycerin diglycidyl ether, T 55, trihydroxymethylpropanyltri diglycidyl ether, triglycidyl isocyanurate; Be not limited to above-mentioned, also can list and the polyvalent alcohols such as polyether glycol, PCDL, C-terminal polybutadiene, polyester polyol are directly carried out acroleic acid esterification or carry out the esters of acrylic acid of urethane acrylate and melamine acrylate and/or each methyl acrylic ester etc. corresponding with aforesaid propylene acid esters via diisocyanate.
And then, Epocryl that the send as an envoy to polyfunctional epoxy resins such as cresol novolak type epoxy resin and acrylic acid reacts and obtain can be enumerated, further the hydroxyl of this Epocryl is reacted with half carbamate compounds formed by diisocyanate such as hydroxy acrylate and isophorone diisocyanate such as pentaerythritol triacrylates and the epoxy amino formic ether acrylate compounds etc. that obtains.This epoxy acrylate system resin can improve photo-curable and not reduce dry to touch.
The foregoing photosensitive compounds without carboxyl is such as the compound of less than 4000 for measuring by GPC the weight-average molecular weight Mw obtained.
In addition, the compounding amount without the photosensitive compounds of carboxyl be whole photonasty composition (photosensitive compounds containing carboxyl photosensitive compounds+do not have carboxyl) below 30 quality %, be preferably more than 1 quality % and below 10 quality %, more preferably more than 1 quality %, below 5 quality % are suitable.
Photosensitive composite of the present invention can as required in order to improve and the adaptation of the base material such as polyamide and containing known usual sulfhydryl compound, closely sealed promoter.As sulfhydryl compound, 2 mercaptopropionic acid, trimethylolpropane tris (2-thiopropionate), 2 mercapto ethanol, 2-aminothiophenol, 3-sulfydryl-1 can be listed, 2,4-triazole, 3-mercapto-propyl trimethoxy silane etc. are containing mercaptosilane coupling agents etc.As closely sealed promoter, such as, there are benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thioketones, 5-amino-3-morpholinomethyl-thiazole-2-thioketones, 2-sulfydryl-5-methyl mercapto-thiadiazoles, triazole, tetrazolium, benzotriazole, carboxyl benzotriazole, containing amino benzotriazole, vinyl triazine etc.These can individually use, and also can combinationally use two or more.Its compounding amount is aforementioned relative to 100 mass parts to be below 10 mass parts containing carboxyl photosensitive compounds or carboxylated compound scope is suitable.When the compounding amount of these compounds exceedes above-mentioned scope, consume the epoxy radicals (with epoxy reaction) of the aforementioned epoxy compound needed for cross-linking reaction, cross-linking density reduces, therefore not preferred.
Mostly there is oxidative degradation once oxidation is just then chain in macromolecular material, cause the function of macromolecular material to reduce, therefore can add (1) in photosensitive composite of the present invention in order to anti-oxidation and can make the radical scavenger of the free radical ineffective treatment of generation or/and (2) can make the peroxide breakdown of generation be the antioxidants such as harmless material, the peroxide decomposer that can not produce new free radical.
For the antioxidant played a role as radical scavenger, include, for example out quinhydrones, 4-tert-butyl catechol, TBHQ, hydroquinone monomethyl ether, 2, 6-bis--t-butyl-p-cresol, 2, 2-methylene-bis-(4-methyl-6-tert-butylphenol), 1, 1, 3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1, 3, 5-trimethyl-2, 4, 6-tri-(3, 5-bis--tertiary butyl-4-hydroxy benzyl) benzene, 1, 3, 5-tri-(3 ', 5 '-two-tertiary butyl-4-hydroxy benzyl)-guanamine, 4, 6-(1H, 3H, 5H) the phenol system such as triketone, MEHQ (methoquinone), the quinone based compounds such as benzoquinones, two (2, 2, 6, 6-tetramethyl-4-piperidyl)-sebacate, the amine compounds etc. such as phenothiazine.
For the antioxidant played a role as peroxide decomposer, include, for example out the phosphorus series compounds such as triphenyl phosphite, pentaerythrite four lauryl thiopropionate, dilauryl thiodipropionate, 3, the chalcogenide compounds etc. such as 3 '-distearylthiodi-propionate.
Antioxidant as above can be used alone a kind or combine two or more use.
Photosensitive composite of the present invention can also use ultraviolet light absorber except above-mentioned antioxidant.
As this ultraviolet light absorber, benzophenone derivates, benzoate derivatives, benzotriazole derivatives, pyrrolotriazine derivatives, benzothiazole derivant, cinnamate derivates, anthranilate derivatives, dibenzoylmethane derivatives etc. can be enumerated.
Foregoing ultraviolet light absorber can be used alone a kind or combine two or more use, also can realize the stabilization of the molding obtained by photosensitive composite of the present invention by using with antioxidant combination.
And then, other adjuvant beyond aforesaid ingredients also can be added in photosensitive composite of the present invention in the scope not damaging effect of the present invention.As adjuvant, the known colorants etc. such as the defoamers such as known usual thickening agent, silicon-type, fluorine system, macromolecular and/or levelling agent, phthalocyanine blue, phthalocyanine green, dual-azo yellow, titanium dioxide, carbon black, naphthalene be black can be listed.And then, the silane coupling agents such as known usual thermal polymerization inhibitor, imidazoles system, thiazole system, triazole system, plastifier, gas-development agent, fire retardant, antistatic agent, aging resister, antibacterial/mildewproof agent etc. can be added as required.
[filler]
Can also further as required in order to improve the characteristics such as adaptation, hardness, thermotolerance and containing at least a kind of filler be selected from the group that is made up of inorganic filler and organic filler in photosensitive composite of the present invention.As inorganic filler, barium sulphate, calcium carbonate, barium titanate, monox, amorphous silica, talcum, clay, hydrotalcite, Nuo Yibao silica particles, mica powder etc. can be listed, as organic filler, silica flour, nylon powder, fluororesin powder etc. can be listed.And then, also can in order to obtain outward appearance, the anti-flammability and use the metal hydroxides such as titanium dioxide, metal oxide, aluminium hydroxide as extender pigment filler of white.In the middle of above-mentioned filler, what agent of low hygroscopicity, low volumetric expansion were excellent especially is silicon dioxide.Silicon dioxide can be fused silica, also for crystalline silica, can also be able to be their potpourri, when particularly having carried out surface-treated silicon dioxide with coupling agent etc., can improve electrical insulating property, so preferably.In addition, as above-mentioned filler, the fiber-reinforced materials etc. such as organobentonite, smectite, glass fibre, carbon fiber, boron nitride fiber can be listed.
Mean grain size (the D of filler
50) be less than 25 μm, be more preferably less than 10 μm, more preferably less than 3 μm be desirable.Herein, D
50refer to, use the laser diffraction and scattering formula particle size distribution method based on Mie scattering theory and the particle diameter of the volume-cumulative 50% obtained.More specifically, utilize laser diffraction and scattering formula particle size distribution device, make the size-grade distribution of particulate with volume reference, using its median particle diameter as mean grain size, thus can measure.Working sample can preferably use the sample utilizing ultrasound wave to be dispersed in water particulate.As laser diffraction formula particle size distribution device, the LA-500 etc. that Horiba Ltd manufactures can be used.These compounding amounts that are inorganic and/or organic filler are aforementioned relative to 100 mass parts be below 300 mass parts containing carboxyl photosensitive compounds or carboxylated compound is suitable, is preferably the ratio of 5 ~ 150 mass parts.When the compounding amount of filler exceedes aforementioned proportion, the folding resistance of cured film reduces, not preferably.
[organic solvent]
In photosensitive composite of the present invention, in order to make aforementionedly easily to dissolve containing carboxyl photosensitive compounds, epoxy compound or disperse, or in order to be adjusted to the viscosity being suitable for coating, can be with an organic solvent.As this organic solvent, ketone, aromatic hydrocarbon based, glycol ethers, glycol ethers acetate esters, ester class, alcohols, aliphatic hydrocarbon, petroleum solvent etc. can be listed.More specifically, be the ketone such as MEK, cyclohexanone; Toluene, dimethylbenzene, durene etc. are aromatic hydrocarbon based; The glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, Triethylene glycol ethyl ether; The ester classes such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetic acid esters, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, propandiol butyl ether acetic acid esters, 2-hydroxy-methyl isobutyl acid; The alcohols such as ethanol, propyl alcohol, ethylene glycol, propylene glycol; The aliphatic hydrocarbon such as octane, decane; The petroleum solvents etc. such as sherwood oil, naphtha, hydrogenated naphtha, solvent naphtha.This organic solvent can be used alone or uses with the form of potpourri of more than two kinds.The compounding amount of organic solvent suitably can set according to the viscosity expected.
Photosensitive composite of the present invention is such as adjusted to the viscosity being suitable for coating process with aforementioned organic solvents, be applied on base material by methods such as dip coating, flow coat method, rolling method, stick coating method, silk screen print method, curtain Tu Fa, organic solvent volatile dry (temporarily dry) contained in composition is made at the temperature of about 60 ~ 100 DEG C, thus the film that can cannot do not formed stickyly.In addition, be applied to by above-mentioned composition in carrier film, make it dry, batch in the form of a film, the product this coiled into pastes on base material, thus can form dry coating.Then, with contact (or cordless), utilize active energy beam optionally to expose by forming figuratum photomask or utilize the direct exposure machine of laser directly to carry out pattern exposure, utilize dilute alkaline aqueous solution (such as 0.3 ~ 3 quality % aqueous sodium carbonate) to develop to unexposed portion, form corrosion-resisting pattern.Then, high-pressure sodium lamp etc. is used, with cumulative exposure amount 500 ~ 2000mJ/cm
2irradiation ultraviolet radiation, can solidify completely.In addition, the temperature being such as heated to about 140 ~ 180 DEG C carries out heat curing, thus aforementioned containing carboxyl photosensitive compounds or the carboxyl of carboxylated compound and the epoxy reaction of epoxy compound, the cured coating film of each excellents such as thermotolerance, chemical proofing, resistance to hydroscopicity, adaptation, electrical characteristics can be formed.
As above-mentioned base material, can use the copper-clad laminated board, polyamide film, PET film, glass substrate, ceramic substrate, wafer board etc. of printed circuit board (PCB), flexible printed circuit board and all grades (FR-4 etc.) being pre-formed with circuit, described copper-clad laminated board employs the compound substances such as paper-phenolics, paper-epoxy resin, glass cloth-epoxy resin, glass-polyamide, glass cloth/nonwoven fabrics-epoxy resin, glass cloth/paper-epoxy resin, synthon-epoxy resin, fluororesin tygon PPO cyanate.
The volatile dry carried out after being coated with photosensitive composite of the present invention can use heated air circulation type drying oven, IR stove, hot plate, convection oven etc. (method that the equipment that use possesses the thermal source of the air heat mode based on steam makes the hot air convection in dryer contact and utilize nozzle by heat blow to the mode of supporter) to carry out.
Be coated with photosensitive composite of the present invention and the dry coating obtained after volatile dry for as above, carry out exposing (irradiation of active energy beam).Exposure portion (utilizing the part that the active energy beam irradiates) solidification of dry coating.
Irradiate the exposure machine used as above-mentioned active energy beam, direct drawing apparatus (such as directly utilizing the laser direct imaging device of laser rendering image according to the cad data from computing machine) can be used, be equipped with the exposure machine of metal halide lamp, be equipped with the exposure machine of (surpassing) high-pressure sodium lamp, be equipped with the exposure machine of mercury short arc lamp or use the direct drawing apparatus of the UV-lamp such as (surpassing) high-pressure sodium lamp.As active energy beam, when using maximum wavelength to be in the laser of the scope of 350 ~ 410nm, gas laser, Solid State Laser.In addition, its exposure is different from thickness etc., usually can be set to 5 ~ 800mJ/cm
2, be preferably set to 5 ~ 700mJ/cm
2scope in.As above-mentioned direct drawing apparatus, such as, can use the equipment of Orbotech Ltd. manufacture, ORC MANUFACTURING CO., LTD. manufacture etc., as long as starting of oscillation maximum wavelength is the device of the laser of 350 ~ 410nm, then can use any device.
As aforementioned developing method, infusion process, spray process, spray-on process, spread coating etc. can be utilized, as developer solution, the aqueous alkalis such as potassium hydroxide, NaOH, sodium carbonate, sal tartari, sodium phosphate, sodium silicate, ammonia, amine can be used.
Photosensitive composite of the present invention, except can be coated directly onto the method on base material with liquid state except, can also to be coated with photosensitive composite in advance and dry and the form of the dry film of dry coating that is that formed uses to have on the films such as polyethylene terephthalate.The situation that photosensitive composite of the present invention is made dry film to use below is shown.
Dry film has the structure of strippable coverlay stacking gradually carrier film, dry coating and use as required.Dry coating is such as being applied to the photosensitive composite of alkali-developable on carrier film or coverlay and dry and layer that is that obtain.After forming dry coating on a carrier film, coverlay is laminated thereon, or forms dry coating on coverlay, this duplexer is laminated in carrier film, then can obtain dry film.
As carrier film, the thermoplastic films such as the mylar of the thickness of 2 ~ 150 μm can be used.
Dry coating can utilize knife type coater, lip coating machine, comma coater, film painting machine etc. are uniformly applied to also dry on carrier film or coverlay by the photosensitive composite of alkali-developable with the thickness of 10 ~ 150 μm and are formed.
As coverlay, can use polyethylene film, polypropylene film etc., the bonding force that the bonding force of coverlay and dry coating is less than carrier film and dry coating is good.
Diaphragm (permanent diaphragm) is made on a printed circuit for use dry film; peel off coverlay; dry coating is overlapping with the base material being formed with circuit, use laminating machine etc. to paste, thus form dry coating on the base material being formed with circuit.For formed dry coating, carry out exposing in the same manner as aforementioned, develop, be heating and curing, then can form cured layer.Carrier film before exposure or exposure after stripping.
It should be noted that, photosensitive composite of the present invention is suitable for the permanent overlay film material as printed circuit board (PCB), especially suitable to soldering-resistance layer material, interlayer dielectic.
Embodiment
Below, illustrate that embodiment and comparative example are to illustrate the present invention, but the present invention is originally just not limited to following embodiment.It should be noted that, below, " % " and " part " is quality criteria in case of no particular description.
Synthesis example 1
Drop into possessing thermometer, in autoclave that nitrogen gatherer holds concurrently alkylene oxide gatherer and stirring apparatus phenolic varnish type cresol resin that Showa Highpolymer Co., Ltd manufactures (trade name " Shonol CRG951 ", OH equivalent: 119.4) 119.4 parts, 1.19 parts, potassium hydroxide, toluene 119.4 parts, nitrogen displacement is carried out while stirring, heat temperature raising in system.Then, slowly epoxypropane 63.8 parts is dripped, with 125 ~ 132 DEG C, 0 ~ 4.8kg/cm
2react 16 hours.Then, be cooled to room temperature, in this reaction solution, add mixing 89% phosphatase 11 .56 part, in and potassium hydroxide, obtain nonvolatile component 62.1%, the solution of the epoxypropane addition reaction of phenolic varnish type cresol resin that hydroxyl value is 182.2g/eq..It is the product of average about 1.08 mol of alkylene oxide relative to the addition of phenolic hydroxyl group 1 equivalent.
The solution 293.0 parts of the alkylene oxide addition reaction of obtained phenolic varnish type cresol resin, 43.2 parts, acrylic acid, methane-sulforic acid 11.53 parts, methylnaphthohydroquinone 0.18 part, toluene 252.9 parts are put into possess stirring machine, thermometer, air be blown in the reactor of pipe, be blown into air with the speed of 10ml/ minute, react 12 hours at 110 DEG C while stirring.The water generated by reaction distillates the water of 12.6 parts with the form of the azeotropic mixture with toluene.Then, be cooled to room temperature, by the reaction solution 15% sodium hydrate aqueous solution 35.35 parts neutralization obtained, then wash.Then, utilize evaporator to be heated up in a steamer on toluene limit diethylene glycol monoethyl ether acetic acid esters 118.1 parts displacement limit, obtain phenolic varnish type acrylic ester resin solution.Then, obtained phenolic varnish type acrylic ester resin solution 332.5 parts, chromium naphthenate 0.8 part, naphthenic acid lithium 0.4 part are put into possess stirring machine, thermometer, air be blown in the reactor of pipe, air is blown into the speed of 10ml/ minute, slowly add tetrabydrophthalic anhydride 60.8 parts while stirring, react 6 hours at 95 ~ 101 DEG C, take out after cooling.What so obtain is nonvolatile component 70.9%, solid constituent acid number 82.1mgKOH/g containing carboxyl photosensitive compounds.
Embodiment 1 ~ 9 and comparative example 1 ~ 3
According to the compounding each composition of the ratio shown in table 1 and table 2, after stirring, utilize 3 roller mills to disperse, obtain photosensitive composite.
[table 1]
[table 2]
Acid number in aforementioned table 1 and table 2, epoxide equivalent, double bond equivalent are measured by following method.
< is relative to the determination method > of the acid number of organic principle total amount
By photosensitive composite at 70 DEG C dry 24 hours, remove organic solvent, obtain solid constituent.In solid constituent, add acetone make its dissolution/dispersion, utilize hydro-extractor from solid constituent separating filler.Use and be separated the organic principle of filler, measure acid number according to JIS K2501.The acid number so obtained is the acid number relative to organic principle total amount.
< is relative to the determination method > of the epoxide equivalent of organic principle total amount
In the same manner as measuring the situation of acid number, obtain the organic principle being separated filler.Use this organic principle, measure the 1st equivalent according to JIS K7236.
On the other hand, except not using tetraethylammonium bromide, to operate equally with the assay method of the 1st equivalent, measure the 2nd equivalent.
Deduct the 2nd equivalent from the 1st equivalent, calculate " epoxide equivalent relative to organic principle total amount ".
The assay method > of < double bond equivalent
In the same manner as measuring the situation of acid number, obtain the organic principle being separated filler.After this organic principle and morpholine are reacted, add acetic anhydride and react with unreacted morpholine.Utilize the reaction product of perchloric acid titration organic principle and morpholine, calculate the 3rd equivalent thus.
Deduct the 1st equivalent from the 3rd equivalent, calculate " the double bond equivalent relative to organic principle total amount ".
The decision method > of < liquid parts
Liquid judgement makes " the liquid confirmation method " of the attached sheet the 2nd of (Heisei autonomous province in the first year makes No. 1) to carry out according to the province of the test and proterties that relate to dangerous goods.
(1) device
Water Tank with Temp.-controlled: use and possess stirring machine, well heater, thermometer, automatic temperature regulator (can with ± 0.1 DEG C of control temperature) and the degree of depth is the tank of more than 150mm.
It should be noted that, the judgement of liquid parts all uses YAMATO SCIENTIFIC CO., LTD. the Low Constant Temperature Water Baths (model BU300) manufactured and the combination of Constant Temperature Devices ThermoMate (model BF500), about 22 liters of tap water are put into Low Constant Temperature Water Baths (model BU300), connect the power supply being assembled in its ThermoMate (model BF500), be set as design temperature (20 DEG C), utilize ThermoMate (model BF500) by water temperature inching to design temperature ± 0.1 DEG C, as long as but the device that can carry out same adjustment just can use arbitrarily.
Test tube:
As test tube, use as shown in Figure 1: test tube 1a is used in liquid judgement, it is the test tube of internal diameter 30mm, the highly flat cylinder type clear glass of 120mm, makes graticule 2,3 respectively, by airtight for test tube mouth rubber plug 4a in the position of the height of 55mm and 85mm at the bottom of pipe; Temperature measuring test tube 1b, its with liquid judgement test tube 1a, there is same size and in the same manner as make graticule, utilize central authorities output for inserting/the rubber plug 4b in the hole of support temperature meter inserts thermometer 5 by airtight for test tube mouth in rubber plug 4b.Below, the graticule of the height of 55mm at the bottom of pipe is called " A line ", the graticule of the height of 85mm is called " B line " at the bottom of pipe.
As thermometer 5, use the thermometer (SOP-58 range ability 20 ~ 50 DEG C) of the kryoscopy of regulation in JIS B7410 (1982) " petroleum-type test glass thermometer ", as long as but the device of the temperature range of 0 ~ 50 DEG C can be measured.
(2) implementation step tested
The sample placing more than 24 hours under the atmospheric pressure of temperature 20 ± 5 DEG C is put into respectively the temperature measuring test tube 1b shown in (b) of liquid state judgement test tube 1a and Fig. 1 shown in (a) of Fig. 1 until A line.2 test tubes 1a, 1b are erectly rested in Low Constant Temperature Water Baths in undersurface mode with B line.Make the lower end of thermometer 30mm below A line.
This state is kept 10 minutes from specimen temperature reaches design temperature 20 ± 0.1 DEG C.After 10 minutes, taken out by liquid state judgement test tube 1a, flatly fell immediately on the testing table of level in Low Constant Temperature Water Baths, the front end measuring invisible spectro liquid level with stopwatch moves to the time of B line from A line, and record.For sample, be that situation within 90 seconds is judged to be liquid state, situation more than 90 seconds is judged to be solid-state by the time measured at a set temperature.
For each photosensitive composite, following making tests substrate, carries out following evaluating characteristics.Show the result in table 3 and table 4.
< tests the making > of substrate
Utilizing silk screen print method to use 100 object polyester half tones to be applied to the whole face of the thickness of 20 ~ 30 μm by photosensitive composite is formed on the printed circuit board of copper pattern, use the hot-air drier of 80 DEG C by dried coating film after 60 minutes, the negative film with corrosion-resisting pattern is sealed at film, use ultraviolet exposure apparatus according (ORC MANUFACTURING CO., LTD., model HMW-680GW), irradiate exposure 500mJ/cm
2ultraviolet.Then, utilize the aqueous sodium carbonate of 1% with 60 seconds, 2.5kg/cm
2spray and develop.Then, for this substrate, utilize high-pressure sodium lamp with cumulative exposure amount 1000mJ/cm
2irradiation ultraviolet radiation solidifies completely, and at 160 DEG C, heating carries out Post RDBMS in 1 hour, makes evaluation substrate.
The test of insulativity, anti-thread breakage, patternability (developability) and viscosity is carried out as follows.
Insulation resistance > in <PCBT
Use the comb-type electrode B sample of IPCB-25, make with above-mentioned condition and evaluate substrate, this comb-type electrode is applied to the bias voltage of DC30V, use PCT device (ESPEC Co., Ltd. the HAST YSTEM TPC-412MD manufactured), 121 DEG C, process under the condition of humidity 97%, measure resistance value and be reduced to 1.0 × 10
7the time of below Ω.Need the situation of more than 300 hours can be evaluated as well.
<TCT corner crack >
After the substrate of copper cash pattern being formed with 2mm being coated with photosensitive composition, carrying out as described above exposing, developing, carry out Ultraviolet radiation, heat curing, be produced on evaluation substrate copper cash being formed with the square corrosion-resisting pattern of 7 3mm.This evaluation substrate is put in the cold-hot circulating machine carrying out temperature cycles between-65 DEG C and 150 DEG C, carries out TCT (Thermal Cycle Test; Thermal cycling test).Then, observe the outward appearance of 1000 circulation times, counting crackle number.Crackle number be less than 30/68 situation can be evaluated as well.It should be noted that, the numerical value " 68 " of denominator means 4 angle (4) × 17, namely 68 angles of the corrosion-resisting pattern that 3mm is square, and the numerical value " 30 " of molecule represents the generation number of crackle.
< patternability >
Utilize the state after the visual judgement exposure of magnifier, development.Result as shown in Table 3 and Table 4, in embodiment 1 ~ 9, comparative example 1 ~ 3, pattern be formed as possibility.
< viscosity >
Utilize serigraphy to be applied in whole for photosensitive composite face respectively and formed on figuratum copper clad laminate, in the heated air circulation type drying oven of 80 DEG C, drying 30 minutes, naturally cools to room temperature.Place PET system on the substrate and bear film, (HMW-GW20) that utilize ORC Co., Ltd. to manufacture crimps 1 minute at reduced pressure conditions, then, evaluates the coherent condition of film when peeling off negative film.
Good: during stripping film, there is no resistance, film is not left a trace.
Bad: during stripping film, to there is resistance, film is left a trace.
[table 3]
[table 4]
As shown in table 3, pattern can be formed well in embodiment 1 ~ 9, under high-temperature high-humidity, also can maintain insulativity for a long time, and inhibit the generation of crackle.But as shown in table 4, the double bond equivalent deducting the composition in its entirety of filler in photosensitive composite, lower than in the comparative example 1 ~ 3 of 400, cannot maintain insulativity for a long time, and the generation of crackle is also many under high-temperature high-humidity.
utilizability in industry
Hardening resin composition of the present invention or its dry film are suitable for the permanent overlay film material as printed circuit board (PCB), especially can be advantageously used for soldering-resistance layer material, interlayer dielectic.
description of reference numerals
The liquid judgement test tube of 1a
1b temperature measuring test tube
2 graticules (A line)
3 graticules (B line)
4a, 4b rubber plug
5 thermometers
Claims (7)
1. a photosensitive composite, is characterized in that, contains:
(A) containing carboxyl photosensitive compounds,
(B) Photoepolymerizationinitiater initiater and
(C) epoxy compound,
The double bond equivalent of this photosensitive composite is more than 400 under the state not containing organic solvent and filler.
2. photosensitive composite according to claim 1, is characterized in that, does not also have the photosensitive compounds of carboxyl containing (D).
3. photosensitive composite according to claim 2, it is characterized in that, the containing ratio that described (A) does not have the photosensitive compounds of carboxyl containing described (D) that carboxyl photosensitive compounds and described (D) do not have in the blending constituent of the photosensitive compounds of carboxyl is below 30 quality %.
4. the photosensitive composite according to any one of claims 1 to 3, is characterized in that, relative to described (A) carboxyl 1 equivalent containing carboxyl photosensitive compounds, the epoxy radicals of described (C) epoxy compound is more than 1.5 equivalents.
5. a photosensitive composite, is characterized in that, contains:
(A ') carboxylated compound,
(B) Photoepolymerizationinitiater initiater and
(C) epoxy compound,
Relative to carboxyl 1 equivalent of described (A ') carboxylated compound, the epoxy radicals of described (C) epoxy compound is more than 1.5 equivalents and below 4 equivalents, the containing ratio of liquid parts contained in this photosensitive composite is more than 5 quality % and below 30 quality % relative to the whole compositions except organic solvent and filler.
6. photosensitive composite according to claim 5, is characterized in that, the quantity of the epoxy radicals of described (C) epoxy compound is 2.
7. a printed circuit board (PCB), is characterized in that, has and uses photosensitive composite according to any one of claim 1 ~ 6 and the cured layer that formed.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012122325 | 2012-05-29 | ||
| JP2012-122325 | 2012-05-29 | ||
| JP2013085450A JP6240399B2 (en) | 2012-05-29 | 2013-04-16 | Photosensitive composition and printed wiring board having cured layer thereof |
| JP2013-085451 | 2013-04-16 | ||
| JP2013-085450 | 2013-04-16 | ||
| JP2013085451A JP2014006499A (en) | 2012-05-29 | 2013-04-16 | Photosensitive composition and print wiring board having cured layer thereof |
| PCT/JP2013/062951 WO2013179863A1 (en) | 2012-05-29 | 2013-05-08 | Photosensitive composition and printed circuit board having hardened layer thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104350421A true CN104350421A (en) | 2015-02-11 |
| CN104350421B CN104350421B (en) | 2019-06-04 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201380028583.2A Active CN104350421B (en) | 2012-05-29 | 2013-05-08 | Photosensitive composite and printed circuit board with its cured layer |
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| Country | Link |
|---|---|
| JP (2) | JP2014006499A (en) |
| KR (1) | KR102050126B1 (en) |
| CN (1) | CN104350421B (en) |
| TW (1) | TWI620016B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106916262A (en) * | 2015-12-25 | 2017-07-04 | 太阳油墨（苏州）有限公司 | Hole landfill hardening resin composition and its solidfied material and printed circuit board (PCB) |
| CN106916261A (en) * | 2015-12-25 | 2017-07-04 | 太阳油墨（苏州）有限公司 | Hole landfill hardening resin composition and its solidfied material and printed circuit board (PCB) |
| CN107533294A (en) * | 2016-03-16 | 2018-01-02 | 互应化学工业株式会社 | Liquid solder mask agent composition and printed substrate |
| CN109073969A (en) * | 2016-03-31 | 2018-12-21 | 太阳油墨制造株式会社 | Hardening resin composition, dry film, solidfied material and printed circuit board |
| CN110320752A (en) * | 2018-03-28 | 2019-10-11 | 太阳油墨制造株式会社 | Photosensitive polymer combination, dual liquid type photosensitive polymer combination, dry film and printed circuit board |
| CN110317316A (en) * | 2019-07-02 | 2019-10-11 | 戚玉侠 | A kind of preparation method of synthetic leather antibacterial resistant polyurethane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5997860B1 (en) | 2016-03-16 | 2016-09-28 | 互応化学工業株式会社 | Liquid solder resist composition and printed wiring board |
| JP6154942B1 (en) * | 2016-07-11 | 2017-06-28 | 互応化学工業株式会社 | Liquid solder resist composition and printed wiring board |
| JP7013666B2 (en) * | 2017-03-29 | 2022-02-01 | 昭和電工マテリアルズ株式会社 | Manufacturing method of photosensitive resin composition, photosensitive element, printed wiring board and printed wiring board |
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- 2013-04-16 JP JP2013085450A patent/JP6240399B2/en active Active
- 2013-05-08 CN CN201380028583.2A patent/CN104350421B/en active Active
- 2013-05-08 KR KR1020147036115A patent/KR102050126B1/en active IP Right Grant
- 2013-05-20 TW TW102117740A patent/TWI620016B/en active
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| CN101281367A (en) * | 2007-04-06 | 2008-10-08 | 太阳油墨制造株式会社 | Solder resist compound and cured product thereof |
| JP2011118400A (en) * | 2008-12-12 | 2011-06-16 | Sekisui Chem Co Ltd | Photosensitive composition and solder resist composition |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106916262A (en) * | 2015-12-25 | 2017-07-04 | 太阳油墨（苏州）有限公司 | Hole landfill hardening resin composition and its solidfied material and printed circuit board (PCB) |
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| CN106916261B (en) * | 2015-12-25 | 2020-05-19 | 太阳油墨（苏州）有限公司 | Curable resin composition for filling holes, cured product thereof, and printed wiring board |
| CN107533294A (en) * | 2016-03-16 | 2018-01-02 | 互应化学工业株式会社 | Liquid solder mask agent composition and printed substrate |
| CN107533294B (en) * | 2016-03-16 | 2018-10-30 | 互应化学工业株式会社 | Liquid solder mask agent composition and printed wiring board |
| CN109073969A (en) * | 2016-03-31 | 2018-12-21 | 太阳油墨制造株式会社 | Hardening resin composition, dry film, solidfied material and printed circuit board |
| CN109073969B (en) * | 2016-03-31 | 2022-09-13 | 太阳油墨制造株式会社 | Curable resin composition, dry film, cured product, and printed wiring board |
| CN110320752A (en) * | 2018-03-28 | 2019-10-11 | 太阳油墨制造株式会社 | Photosensitive polymer combination, dual liquid type photosensitive polymer combination, dry film and printed circuit board |
| CN110320752B (en) * | 2018-03-28 | 2023-12-29 | 太阳控股株式会社 | Photosensitive resin composition, two-liquid photosensitive resin composition, dry film and printed circuit board |
| CN110317316A (en) * | 2019-07-02 | 2019-10-11 | 戚玉侠 | A kind of preparation method of synthetic leather antibacterial resistant polyurethane |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201407281A (en) | 2014-02-16 |
| JP6240399B2 (en) | 2017-11-29 |
| JP2014006499A (en) | 2014-01-16 |
| JP2014006498A (en) | 2014-01-16 |
| KR102050126B1 (en) | 2019-11-28 |
| CN104350421B (en) | 2019-06-04 |
| KR20150017361A (en) | 2015-02-16 |
| TWI620016B (en) | 2018-04-01 |
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