CN101676800A - Phototonus resin combination, solder resist combination for printed wiring board and printed wiring board - Google Patents
Phototonus resin combination, solder resist combination for printed wiring board and printed wiring board Download PDFInfo
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- CN101676800A CN101676800A CN200910171055A CN200910171055A CN101676800A CN 101676800 A CN101676800 A CN 101676800A CN 200910171055 A CN200910171055 A CN 200910171055A CN 200910171055 A CN200910171055 A CN 200910171055A CN 101676800 A CN101676800 A CN 101676800A
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- wiring board
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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
- G03F7/0385—Macromolecular compounds which are rendered insoluble or differentially wettable using epoxidised novolak resin
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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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
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
- H05K3/061—Etching masks
- H05K3/064—Photoresists
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- Engineering & Computer Science (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials For Photolithography (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Abstract
The present invention provides a light-sensitive resin combination, a solder resist combination for a printed wiring board and a printed wiring board; the invention also provides a liquid resin combination having less descend of reflection index and color degradation of a white coated film caused by irradiation of UV in a hot process and capable of forming a pattern by a low exposure amount. The light-sensitive resin combination contains (A) active energy ray curing resin obtained by reaction of alicyclic ring cage epoxide having ethylene unsaturated bond with copolymerization resin, wherein the copolymerization resin is selected from monomer of acroleic acid and acrylic ester, and copolymer of monomer of methacrylic acid and metacrylic acid ester; (B) mercaptan series coumpound; (C) lightpolymerization initiator; (D) diluting agent; (E) red schorl type titanium oxide; and (F) epoxy series thermoset coumpound.
Description
Technical field
The present invention relates to the solder resist composition and the printed wiring board of photosensitive polymer combination, printed wiring board-use.
Background technology
Printed wiring board is to be used at the pattern that forms conductor circuit on the substrate and by electronic devices and components being welded in the plate that carries on the pad of this pattern, and the circuit part except that this pad is used as the soldering-resistance layer lining of permanent protection tunicle.By this, scolding tin adheres in unwanted part when preventing on printed wiring board welding electronic component, prevents simultaneously that circuit conductor directly is exposed in the air and is corroded because of oxidation or humidity.
Follow the demand of raising (fine and closely wovenization) of the wiring density of printed circuit board, also require the solder resist composition to have high resolution and high precision int, no matter be civilian substrate or industrial substrate, the photic solder resist method of lining better fluid (photographic process method) of positional precision, conductor edge portion has been proposed according to silk screen print method all.Such solder resist composition is recorded in for example following document.
In addition, also propose to have the photic solder resist composition of alkali developable (patent documentation 7) of available dilute alkaline aqueous solution development.
These liquid solder resist compositions are by introducing carboxyl and give photonasty and based on the development of dilute alkaline aqueous solution in epoxy acrylate.But, it is filmed expose, development treatment and after forming required corrosion-resisting pattern, usually make its heat curing, therefore generally make said composition further contain epoxy compound as the heat curing composition, make itself and the heat treated of introducing the carboxyl reaction in the above-mentioned epoxy acrylate, thereby form good etchant resists such as adaptation, hardness, thermotolerance, electrical insulating property.Under this situation, generally with epoxy resin and use hardener for epoxy resin.
Patent documentation 1: the Jap.P. spy opens clear 50-144431 communique
Patent documentation 2: the Jap.P. spy opens clear 49-5923 communique
Patent documentation 3: the Jap.P. spy opens clear 61-243869 communique
Patent documentation 4: the Jap.P. spy opens the 2001-233842 communique
Patent documentation 5: the Jap.P. spy opens the 2001-302871 communique
Patent documentation 6: the Jap.P. spy opens the 2003-280193 communique
Patent documentation 7: the Jap.P. spy opens the 2006-259150 communique
Patent documentation 8: the special hope of Jap.P. 2007-047295
Summary of the invention
Yet, particularly adopt under the situation of white solder resist, heating is sometimes filmed and variable color is taken place when it is solidified, takes place painted, light reflectivity decline.Adopt under the situation of white solder resist, the decline of variable color and reflectivity is obvious especially, therefore may cause commodity value to descend, and this problem has to be solved.On the other hand, the solder resist composition need be cured with lower exposure, has the difficult problem of antinomy.
In order to address this problem, it will be the photosensitive polymer combination of the photoresist of raw material as principal ingredient with alicyclic ring framework ring oxide that the applicant has disclosed in patent documentation 8.But the aspects such as variable color improvement of this compound after heating also also has further room for improvement.
The decline that problem of the present invention is to provide variable color that the white that caused by UV irradiation, thermal process films and reflectivity less and can hang down the liquid resin composition that exposure forms pattern.
The present invention relates to photosensitive polymer combination, it is characterized in that, comprise:
(A) make alicyclic ring framework ring oxide with ethene unsaturated link and copolymerization resin carboxyl reaction and the active energy ray-curable resin, described copolymerization resin is the multipolymer that is selected from the monomer of acrylic acid and acrylate and is selected from the monomer of methacrylic acid and methacrylate;
(B) sulfur alcohol compound;
(C) Photoepolymerizationinitiater initiater;
(D) thinning agent;
(E) Titanium Dioxide Rutile Top grade; And
(F) epoxies heat-curable compounds.
In addition, the present invention relates to the solder resist composition of printed wiring board-use, it is characterized in that, form by described photosensitive polymer combination.
In addition, the present invention relates to have before the lift-launch electronic devices and components of cured film of this solder resist composition or carry electronic devices and components after printed wiring board.
The decline by UV irradiation, variable color that thermal process causes and reflectivity that the white that is formed by photosensitive polymer combination of the present invention is filmed is few, and can hang down exposure and form pattern.
Embodiment
Below, each composition of composition of the present invention is described.
[(A) make alicyclic ring framework ring oxide with ethene unsaturated link and the monomer that is selected from acrylic acid and acrylate and be selected from methacrylic acid and methacrylate monomer the copolymerization resin carboxyl reaction and the active energy ray-curable resin]
(A) be the active energy ray-curable resin that the reaction by described multipolymer and alicyclic ring framework ring oxide obtains.
Alicyclic ring framework ring oxide is meant compound or the resin with alicyclic ring skeleton and epoxy radicals, and skeleton is formed by ester ring type compound or its chain.Epoxide equivalent is not particularly limited, and using usually below 1000, better is 100～500 alicyclic ring framework ring oxide.About the ester ring type compound, can exemplify cyclohexane, cyclopentane.
In addition, alicyclic ring framework ring oxide has the ethene unsaturated link.This ethene unsaturated link can be the unsaturated link of acryloyl group, methacryl for example.
As alicyclic ring framework ring oxide, can exemplify Daisel chemical industry Co., Ltd (ダ イ セ Le chemical industry society) system " CELLOXIDE 2021P ", " CELLOXIDE 2000 ", " CELLOXIDE3000 ", " EHPE 3150 ", " EHPE 3150CE " etc.In addition, as compound name or resin name, can exemplify 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexane carboxylate, vinyl epoxy cyclohexane, 1,2-epoxy-4-vinyl cyclohexane, 1,2:8,9-diepoxy citrene, 2,1 of 2-two (methylol)-1-butanols, 2-epoxy-4-(2-Oxyranyle) cyclohexane addition product etc.
In addition, as the structural formula of alicyclic ring framework ring oxide, can exemplify following formula 1～formula 4.
Formula 1
Formula 2
Formula 3
Formula 4
Described copolymer resin be by be selected from acrylic acid and acrylate one or more monomer and be selected from the multipolymer that one or more the copolyreaction of monomer of methacrylic acid and methacrylate obtains.
For example, the multipolymer that obtains of the copolyreaction by acrylic acid and methacrylic acid is shown in following formula 5.
Formula 5
In addition, by acrylate and methacrylate the multipolymer that obtains of copolyreaction shown in following formula 6.R is an alkyl, better is methyl or ethyl.
Formula 6
The method for making of described multipolymer is not particularly limited, and can use existing method.In addition, the weight-average molecular weight of multipolymer better is 10000～30000, and two key equivalents better are 300～500.
Described multipolymer has 2 carboxyls at least in 1 molecule.The number of the carboxyl that exists in 1 molecule is not particularly limited, and better is 10～500.
Then, make the carboxyl of described multipolymer and the epoxy reaction of alicyclic ring framework ring oxide.Thus, by the reaction of epoxy radicals and carboxyl, shown in following formula 7, epoxy radicals is opened and is generated ester bond with hydroxyl.The active energy ray curable resin of gained has the ethene unsaturated link of the epoxy radicals of deriving from.Also has R
1Being hydrogen, alkyl or hydroxy alkyl, better is hydrogen or methyl.
Formula 7
In the reaction of described multipolymer and alicyclic ring framework ring oxide, better be the epoxy radicals that is had for 1 equivalent alicyclic ring framework ring oxide, the described multipolymer of counting 0.7～1.2 equivalent with the equivalents of carboxyl is reacted with it.If described multipolymer amount then may initiated gelization, the perhaps stability decreases of resin in the synthetic reaction of subsequent handling in equivalents less than 0.7 equivalent of carboxyl.In addition, if multipolymer is excessive, then unreacted carboxyl is remaining in a large number, and the various characteristics (for example water tolerance etc.) of solidfied material is descended.The reaction of alicyclic ring framework ring oxide and multipolymer better is to carry out under heated condition, and its temperature of reaction better is 80～140 ℃.If temperature of reaction surpasses 140 ℃, the then synthetic difficulty that may become; And during 80 ℃ of less thaies, reaction velocity may be slack-off, and is undesirable at the manufacture view of reality.
In the reaction in thinning agent of alicyclic ring framework ring oxide and multipolymer, the incorporation of thinning agent better is 20～50% with respect to the gross mass of reaction system.
As the object lesson of (A), can exemplify Daisel chemical industry Co., Ltd's system " CYCLOMER-P (ACA) Z-251 ", " CYCLOMER-P (ACA) Z-250 ", " CYCLOMER-P (ACA) Z-300 ".Also have, " CYCLOMER-P (ACA) Z-251 " represents with the structural formula of above-mentioned formula 7.
[(B) sulfur alcohol compound]
(B) sulfur alcohol compound is meant the organic compound with sulfydryl, can exemplify 3-mercaptopropionic acid, mercaptopropionic acid methoxyl butyl ester, mercaptopropionic acid monooctyl ester, mercaptopropionic acid tridecyl ester, trimethylolpropane tris thiopropionate, trimethylolpropane tris (3-mercaptopropionic acid ester), pentaerythrite tetrathio propionic ester etc.Good especially is trimethylolpropane tris thiopropionate and/or pentaerythrite tetrathio propionic ester.
[(C) Photoepolymerizationinitiater initiater]
Get final product so long as be used for the Photoepolymerizationinitiater initiater of the photocuring of polyfunctional epoxy resin; be not particularly limited; can exemplify the oximes initiating agent; benzoin; benzoin methylether; benzoin ethyl ether; benzoin iso-propylether; benzoin n-butylether; the benzoin isobutyl ether; acetophenone; dimethylamino acetyl benzene; 2; 2-dimethoxy-2-phenyl acetophenone; 2; 2-diethoxy-2-phenyl acetophenone; 2-hydroxy-2-methyl-1-phenyl third-1-ketone; the 1-hydroxycyclohexylphenylketone; 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino-third-1-ketone; 4-(2-hydroxyl-oxethyl) phenyl-2-(hydroxyl-2-propyl group) ketone; benzophenone; to the phenyl benzophenone; 4; 4 '-diethylamino benzophenone; two chloro benzophenones; 2-methylanthraquinone; the 2-EAQ; 2-tert-butyl group anthraquinone; the 2-amino anthraquinones; 2-methyl thioxanthones; 2-ethyl thioxanthones; the 2-clopenthixal ketone; 2; 4-dimethyl thioxanthones; 2; the 4-diethyl thioxanthone; the dimethanol benzil that contracts; the dimethanol acetophenone that contracts; the ESCAROL 507 ethyl ester; 2; 4; 6-trimethylbenzoyl-diphenyl phosphine oxide; two (2; 4, the 6-trimethylbenzoyl)-phenyl phosphine oxide etc.These Photoepolymerizationinitiater initiaters can be used alone or in combination.
[(D) thinning agent]
(D) thinning agent constitutes by a kind in photopolymerization monomer and the organic solvent at least.Photopolymerization monomer is also referred to as reactive diluent, and it makes the photocuring of photoresist of above-mentioned (A) composition more abundant, is used to obtain to have acid resistance, the filming of thermotolerance, alkali resistance etc.Reactive diluent can preferably use the compound that has at least 2 two keys in 1 molecule.Viscosity and drying property for the composition of regulating the photoresist that comprises above-mentioned (A) composition can adopt the organic solvent as non-reactive diluent, if but do not have this needs, then can not adopt organic solvent.In addition, the light solidity of the photoresist of only above-mentioned (A) composition can not adopt photopolymerization monomer with regard under enough situations.
Representative example as this photopolymerization monomer (reactive diluent), can exemplify for example two (methyl) acrylic acid-1, the 4-butanediol ester, two (methyl) acrylic acid-1, the 6-butanediol ester, two (methyl) acrylic acid DOPCP, two (methyl) polyalkylene glycol acrylate ester, NPGA neopentyl glycol adipate two (methyl) acrylate, hydroxyl trimethylace tonitric DOPCP two (methyl) acrylate, two (methyl) acrylic acid, two cyclopentyl esters, caprolactone modification two (methyl) acrylic acid dicyclopentenyl ester, oxirane modified phosphate two (methyl) acrylate, allylation two (methyl) cyclohexyl acrylate, isocyanuric acid ester two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, three (methyl) acrylic acid dipentaerythritol ester, propionic acid modification three (methyl) acrylic acid dipentaerythritol ester, three (methyl) acrylic acid pentaerythritol ester, epoxy pronane modification trimethylolpropane tris (methyl) acrylate, three (acryloxy ethyl) isocyanuric acid ester, propionic acid modification five (methyl) acrylic acid dipentaerythritol ester, six (methyl) acrylic acid dipentaerythritol ester, caprolactone modification six (methyl) acrylic acid dipentaerythritol ester isoreactivity thinning agent.
Two～six above-mentioned senses and other multifunctional reactive diluents can use separately or in multiple mixed system.The addition of this reactive diluent better is 2.0～40 mass parts with respect to 100 mass parts (A) photoresist.If its addition is very few, then can't obtain sufficient photocuring, can't obtain enough characteristics at the aspects such as acid resistance of cured coating film; And if too much, then adhesion is strong, wiring diagram is attached to substrate easily during exposure, is difficult to obtain the cured coating film as target.From rerum naturas such as the acid resistance of light solidity, cured coating film and thermotolerances, prevent the angle of adhering to of wiring diagram to substrate, the addition of reactive diluent is more preferably 4.0～30 mass parts with respect to 100 mass parts (A) photoresist.
As above-mentioned organic solvent, can exemplify for example ketone such as methyl ethyl ketone, cyclohexanone, arene such as toluene, dimethylbenzene, alcohols such as methyl alcohol, isopropyl alcohol, cyclohexanol, ester ring type such as cyclohexane, methylcyclohexane hydro carbons, petroleum-type such as sherwood oil, naphtha solvent based, cellosolve such as cellosolve, butyl cellosolve class, carbitol such as carbitol, butyl carbitol class, acetate esters such as ethyl acetate, butyl acetate, cellosolve acetic acid esters, butyl cellosolve acetate, carbitol acetic acid esters, acetate of butyl carbitol etc.In the time of with an organic solvent, its use amount better is 40～500 mass parts with respect to 100 mass parts (A) photoresist.
[(E) Titanium Dioxide Rutile Top grade]
(E) Titanium Dioxide Rutile Top grade is the Titanium particles with rutile crystalline texture, and making films is white in color.The mean grain size of this particle is not particularly limited, and can be 0.01～1 μ m.In addition, the surface conditioning agent of Titanium Dioxide Rutile Top grade particle is also unqualified.
[(F) epoxies heat-curable compounds]
In photosensitive polymer combination, for it is filmed exposure and develop after enough tough the filming of back curings back acquisition (coating strength, thermotolerance, permanance, chemical resistance, environment resistant etc.) and add.
As the representative example of epoxies heat-curable compounds, have at least 1 epoxy radicals in preferred 1 molecule, better be the epoxy resin (comprising epoxy oligomer) of the epoxy radicals more than 2, but be not limited thereto.For example, can exemplify the bisphenol A type epoxy resin that bisphenol-A and epichlorokydrin is reacted and get in the presence of alkali, the epoxide of the resin that makes bisphenol-A and formaldehyde carry out condensation reaction and get, adopt brominated bisphenol A to replace the resin of bisphenol-A in these resins, phenolic resin varnish type epoxy resin (the phenol novolak type epoxy resin that makes epichlorokydrin and novolac resin react glycidyl ether and get, o-cresol phenolic epoxy varnish, p-t-butyl phenol phenolic varnish type etc.), the Bisphenol F type or the bisphenol-s epoxy resin that make the reaction of epichlorokydrin and Bisphenol F or bisphenol S and get, and has a 7-oxa-bicyclo[4.1.0 base, epoxy tristane (tricyclodecane oxide) base, the alicyclic epoxy resin of cyclopentane epoxide base etc., o-phthalic acid diglycidyl ester, the tetrahydrophthalic acid 2-glycidyl ester, the hexahydrophthalic acid 2-glycidyl ester, the diglycidyl P-hydroxybenzoic acid, glycidyl ester resins such as dimer acid ethylene oxidic ester, the four glycidyl group diaminodiphenyl-methane, glycidyl amine resinses such as triglycidyl group para-aminophenol, propylene glycol diglycidylether, polypropylene glycol diglycidyl ether, the polytetramethylene glycol diglycidyl ether, the glycerine polyglycidyl ether, trimethylolpropane polyglycidylether, resorcinolformaldehyde resin, 1, the 6-hexanediol diglycidyl ether, ethylene glycol diglycidylether, propylene glycol diglycidylether, sorbitol polyglycidylether, the sorbitan polyglycidyl ether, glycidyl ether resins such as pentaerythrite polyglycidyl ether, three (2, the 3-glycidyl) isocyanuric acid ester, triglycidyl group three (2-hydroxyethyl) isocyanuric acid ester etc. has the triglycidyl group isocyanuric acid ester of triazine ring, dicyclopentadiene-type epoxy resin etc.Heat-curable compounds (F) can use separately, also can multiple and usefulness.
In the photosensitive polymer combination of the present invention, (A) content of active energy ray-curable resin better is 10～50 quality %.
In addition, (B) content of sulfur alcohol compound better is more than 0.01 quality %, and the effect that prevents of the white variable color of filming etc. further improves by this.According to this viewpoint, (B) content of sulfur alcohol compound is more preferably more than 0.5 quality %, further is more preferably more than 1.0 quality %.In addition, (B) content of sulfur alcohol compound better is below 5.0 quality %, can not produce harmful effect to the storage stability of solder resist by this.According to this viewpoint, be more preferably below 2.0 quality %.
In the composition of the present invention, (C) mass ratio of Photoepolymerizationinitiater initiater better is 0.1～10.0 quality %, is more preferably 0.2～5.0 quality %.
In the composition of the present invention, (D) mass ratio of thinning agent better is 1.0～10.0 quality %, is more preferably 3.0～6.0 quality %.
In the composition of the present invention, the mass ratio by making (E) Titanium Dioxide Rutile Top grade can improve the whiteness of filming more than 5 quality %.According to this viewpoint, mass ratio (E) is more preferably more than 20 quality %, further is more preferably more than 30 quality %.In addition, even mass ratio (E) surpasses 50 quality %, whiteness can not rise yet again, and has harmful effect at aspects such as intensity, so mass ratio (E) better is below 50 quality %, is more preferably below 40 quality %.
In the composition of the present invention, (F) mass ratio of epoxies heat-curable compounds better is 1.0～30 quality %, is more preferably 5.0～20 quality %.
In the photosensitive polymer combination of the present invention, except above-mentioned composition (A)～(F), for example can comprise coating such as defoamer, levelling agent as required with various adjuvants such as adjuvants.
Above-mentioned (A)～(F) and other compositions that adopt as required mix, mediate by mixing arrangements such as kneading devices such as three-roll grinder, bowl mill, sand mill or high-speed mixer, planetary-type mixers as required or mix, thereby can obtain photosensitive polymer combination of the present invention.
The photosensitive polymer combination of the present invention that obtains as mentioned above for example has on the printed wiring board that carries out the circuit pattern that etching forms by the Copper Foil to copper-clad laminate with required thickness, for example thickness coating of 5～100 μ m.As the method for coating, whole printing of silk screen print method adopted at present general most use, but comprises this method, so long as the coating process that can be coated with equably, how can to use method.For example, flush coater, hot melt coater, wire bar applicator, applicator, knife type coater, doctor knife coater, pneumatic doctor knife coater, curtain coater, roll coater, gravure coating machine, hectographic printing, dip coater, brushing and other usual ways can use.
After the coating,, promptly carry out predryingly, make the surface of filming be nonadherent state as required with prebake such as heat generator or far infrared line ovens.The temperature of prebake better is about 50～100 ℃.
Then, expose by the laser direct imaging that adopts LDI (laser direct imaging art, Laser Direct Imaging).Perhaps, use the negative film mask that does not see through active energy beam to expose by active energy beam.As the negative film mask, when active energy beam is ultraviolet ray, adopt the negative film film, adopt the metallicity mask during for electron ray, adopt the lead mask during for X ray, but owing to can use simple negative film film, so active energy beam adopts ultraviolet ray mostly in the printed wiring board manufacturing.The ultraviolet irradiation amount is about 10～1000mJ/cm
2
When making printed wiring board, for example the part driving fit beyond the pad of circuit pattern has the negative film film of the pattern of light transmission, quadrature is penetrated ultraviolet ray from it, thereby exposes, and films and develops by remove the territory, non-exposed area corresponding with this pad with dilute alkaline aqueous solution.This is removed can be dissolving, the swelling of unexposed portion, in peeling off etc. any.As employed dilute alkaline aqueous solution at this moment, be generally 0.5～5% aqueous sodium carbonate, but also can use other alkali.
Then, comprise under the situation of heat-curable compounds, for example heating such as dryers such as heat generator by 130～170 ℃ or far infrared line oven is for example 20～80 minutes, perhaps carries out ultraviolet ray irradiation, thereby carries out back curing, can form the welding resistance tunicle by this.
Can obtain the printed wiring board with soldering-resistance layer lining thus, electronic devices and components weld by jet flow welding method or reflow soldering method and connect, fixingly are equipped on this printed wiring board, form an electronic circuit cell.
Among the present invention, the printed wiring board after the printed wiring board that is coated with the welding resistance tunicle before this electronic devices and components carry, the electronic devices and components that carried electronic devices and components on this printed wiring board carry is included in its object.
Embodiment
(embodiment 1)
With following mass ratio each composition is mixed, make the solder resist composition.Detailed one-tenth component is as follows.
(A) Daisel chemical industry Co., Ltd's system " CYCLOMER-P (ACA) Z-251 " 40 quality %
(B) trimethylolpropane tris thiopropionate 0.05 quality %
(C) acylphosphanes class Photoepolymerizationinitiater initiater (Ciba company (チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ society) system " IRGACURE 819 ") 0.3 quality %
(D) thinning agent (DPHA) 5 quality %
(E) Titanium Dioxide Rutile Top grade (Ishihara Sangyo Kaisha, Ltd. (the former industry of stone society) system " CR-80 ") 35 quality %
(F) epoxies heat-curable compounds (Dainippon Ink. ﹠ Chemicals Inc's (big Japanese イ Application キ chemical industry society) system " EPICLON 860 ") 10 quality %
Remainder is as follows:
Defoamer, KS-66 (organosilicon Co., Ltd. of SHIN-ETSU HANTOTAI (シ リ コ one Application society of SHIN-ETSU HANTOTAI) system)
Thixotropic agent, AEROSIL R-97 (Japanese A Luo gill Co., Ltd. (Japanese ア エ ロ ジ Le society) system)
DICY-7 (japan epoxy resin Co., Ltd. (ジ ヤ パ Application エ Port キ シ レ ジ Application society) system)
ア one コ ソ Le Block DPM (the (Association of Kyowa Hakkokogyo Co., Ltd is with development ferment industry society) system)
EDGAC (Daisel chemical industry Co., Ltd's system)
Solvesso 150 (Exxon Mobil Corporation (エ Network ソ Application モ one PVC Le society))
Talcum
Barium sulphate
Melamine
(embodiment 2)
Make the composition of following composition similarly to Example 1.Wherein, except that (A)～(F), identical with embodiment 1.
(A) Daisel chemical industry Co., Ltd's system " CYCLOMER-P (ACA) Z-251 " 40 quality %
(B) trimethylolpropane tris thiopropionate 1 quality %
(C) acylphosphanes class Photoepolymerizationinitiater initiater (Ciba corporate system " IRGACURE 819 ") 0.3 quality %
(D) thinning agent (DPHA) 5 quality %
(E) Titanium Dioxide Rutile Top grade (Ishihara Sangyo Kaisha, Ltd.'s system " CR-80 ") 35 quality %
(F) epoxies heat-curable compounds (Dainippon Ink. ﹠ Chemicals Inc's system " EPICLON860 ") 10 quality %
(embodiment 3)
Make the composition of following composition similarly to Example 1.Wherein, except that (A)～(F), identical with embodiment 1.
(A) Daisel chemical industry Co., Ltd's system " CYCLOMER-P (ACA) Z-251 " 40 quality %
(B) trimethylolpropane tris thiopropionate 5 quality %
(C) acylphosphanes class Photoepolymerizationinitiater initiater (Ciba corporate system " IRGACURE 819 ") 0.3 quality %
(D) thinning agent (DPHA) 5 quality %
(E) Titanium Dioxide Rutile Top grade (Ishihara Sangyo Kaisha, Ltd.'s system " CR-80 ") 35 quality %
(F) epoxies heat-curable compounds (Dainippon Ink. ﹠ Chemicals Inc's system " EPICLON860 ") 10 quality %
(embodiment 4)
Make the composition of following composition similarly to Example 1.Wherein, except that (A)～(F), identical with embodiment 1.
(A) Daisel chemical industry Co., Ltd's system " CYCLOMER-P (ACA) Z-251 " 40 quality %
(B) pentaerythrite tetrathio propionic ester 1 quality %
(C) acylphosphanes class Photoepolymerizationinitiater initiater (Ciba corporate system " IRGACURE 819 ") 0.3 quality %
(D) thinning agent (DPHA) 5 quality %
(E) Titanium Dioxide Rutile Top grade (Ishihara Sangyo Kaisha, Ltd.'s system " CR-80 ") 35 quality %
(F) epoxies heat-curable compounds (Dainippon Ink. ﹠ Chemicals Inc's system " EPICLON860 ") 10 quality %
(embodiment 5)
Make the composition of following composition similarly to Example 1.Wherein, except that (A)～(F), identical with embodiment 1.
(A) Daisel chemical industry Co., Ltd's system " CYCLOMER-P (ACA) Z-251 " 40 quality %
(B) trimethylolpropane tris thiopropionate 1 quality %
(C) acylphosphanes class Photoepolymerizationinitiater initiater (Ciba corporate system " IRGACURE TPO ") 0.3 quality %
(D) thinning agent (DPHA) 5 quality %
(E) Titanium Dioxide Rutile Top grade (Ishihara Sangyo Kaisha, Ltd.'s system " CR-80 ") 35 quality %
(F) epoxies heat-curable compounds (japan epoxy resin Co., Ltd. system " jER 807 ") 10 quality %
(comparative example 1)
Make the composition of following composition similarly to Example 1.Wherein, (A)～(F) with embodiment 1 replaces with following composition.
(G) the active energy ray-curable resin 40 quality % that obtain by alicyclic ring framework ring epoxy resins (Daisel chemical industry Co., Ltd's system " EHPE-3150 ") reaction
(B) do not contain the trimethylolpropane tris thiopropionate
(C) acylphosphanes class Photoepolymerizationinitiater initiater (Ciba corporate system " IRGACURE 819 ") 0.3 quality %
(D) thinning agent (DPHA) 5 quality %
(E) Titanium Dioxide Rutile Top grade (Ishihara Sangyo Kaisha, Ltd.'s system " CR-80 ") 35 quality %
(F) epoxies heat-curable compounds (Dainippon Ink. ﹠ Chemicals Inc's system " EPICLON860 ") 10 quality %
(comparative example 2)
Make the composition of following composition similarly to Example 1.Wherein, (A)～(F) with embodiment 1 replaces with following composition.
(G) by alicyclic ring framework ring oxide (example: Daisel chemical industry Co., Ltd's system, EHPE-3150) the active energy ray-curable resin 40 quality % that obtain of reaction
(B) trimethylolpropane tris thiopropionate 1 quality %
(C) acylphosphanes class Photoepolymerizationinitiater initiater (Ciba corporate system " IRGACURE 819 ") 0.3 quality %
(D) thinning agent (DPHA) 5 quality %
(E) Titanium Dioxide Rutile Top grade (Ishihara Sangyo Kaisha, Ltd.'s system " CR-80 ") 35 quality %
(F) epoxies heat-curable compounds (Dainippon Ink. ﹠ Chemicals Inc's system " EPICLONN-860 ") 10 quality %
Disperse by three-roll grinder each filler mixing, make photosensitive polymer combination embodiment, comparative example.The sensitivity of filming of said composition, line are residual, variable color, reflectivity the results are shown in table 1.
Substrate manufacture operation and evaluation method when carrying out these evaluations are as follows.
Surface treatment: polishing
Coating: 20～23 μ m when the thickness of filming is dry
Predrying: 75 ℃-20 minutes (interior 25 minutes of batch-type furnace)
Exposure: 300mJ/cm on the resist
2(the system HMW-680GW of ORC Mfg. Co., Ltd. (オ one Network society))
Develop: 1%Na
2CO
3-30 minutes-0.1MPas * 90 seconds
Solidify the back: 150 ℃-60 minutes (interior 70 minutes of batch-type furnace)
Variable color is estimated: 260 ℃ of heating after 90 minutes, and the variable color of filming by the visual inspection evaluate cure
Reflectivity is estimated: the reflectivity of record 450nm
Irradiation back: shielded the UV irradiation (150J) of the wavelength below the 400nm by optical filter after, measure the reflectivity of cured coating film
Heating back: after 90 minutes, measure the reflectivity of cured coating film 260 ℃ of heating
Sensitivity:
As test board, with above-mentioned each the routine photosensitive polymer combination of the thickness of about 35 μ m (before dry) coating, make it dry and make each coated substrates, 21 rank exposure guide rules with 400mJ/cm by silk screen print method
2Exposure carry out ultraviolet exposure, use 1% aqueous sodium carbonate to carry out 90 seconds development with the expulsion pressure of 0.1MPas, estimate with the exponent number of the residual fully maximum of filming.Exponent number is big more, represents that then sensitometric characteristic is good more.
Line is residual: with copper thickness be the QFP pattern of 50 μ m as test board, by silk screen print method above-mentioned each routine photosensitive polymer combination of thickness (before dry) coating, make dried coating film and make each coated substrates, with 400mJ/cm with about 35 μ m
2Exposure carry out ultraviolet exposure.At this moment, use live width to be 40～150 μ m, to have carried out the exposed film of dividing with the unit of 10 μ m.The aqueous sodium carbonate of use 1% carries out 90 seconds development with the expulsion pressure of 0.1MPas, estimates the residual minimum feature of filming.Live width is more little, represents that then sensitometric characteristic is good more.
[table 1]
Among the embodiment 1,2,3,4,5, line is residual little as can be known, and the variable color that white is filmed is inhibited, and the variation of the reflectivity after irradiation back, the heating is also little.
Relative with it, in the comparative example 1,2, line is residual relatively poor relatively, and the variable color that white is filmed is big, and the variation of the reflectivity after the heating is also big.That is, in the present embodiment, inner photonasty is good as can be known, and the reflectivity after the variable color that white is filmed, the heating descends and is inhibited, and the commodity value of solder resist composition significantly improves.
Claims (5)
1. photosensitive polymer combination is characterized in that, comprises:
(A) make alicyclic ring framework ring oxide with ethene unsaturated link and copolymerization resin carboxyl reaction and the active energy ray-curable resin, described copolymerization resin is the multipolymer that is selected from the monomer of acrylic acid and acrylate and is selected from the monomer of methacrylic acid and methacrylate;
(B) sulfur alcohol compound;
(C) Photoepolymerizationinitiater initiater;
(D) thinning agent;
(E) Titanium Dioxide Rutile Top grade; And
(F) epoxies heat-curable compounds.
2. photosensitive polymer combination as claimed in claim 1 is characterized in that, the content of described (B) sulfur alcohol compound is 0.01～5.0 quality %.
3. photosensitive polymer combination as claimed in claim 1 or 2 is characterized in that, described (B) sulfur alcohol compound comprises at least one side in trimethylolpropane tris thiopropionate and the pentaerythrite tetrathio propionic ester.
4. the solder resist composition of printed wiring board-use is characterized in that, is formed by each the described photosensitive polymer combination in the claim 1～3.
5. before the lift-launch electronic devices and components or carry printed wiring board behind the electronic devices and components, it is characterized in that having the cured film of the described solder resist composition of claim 4.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008216320 | 2008-08-26 | ||
| JP2008216320 | 2008-08-26 | ||
| JP2009158642A JP5485599B2 (en) | 2008-08-26 | 2009-07-03 | Photosensitive resin composition, solder resist composition for printed wiring board, and printed wiring board |
| JP2009158642 | 2009-07-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101676800A true CN101676800A (en) | 2010-03-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910171055A Pending CN101676800A (en) | 2008-08-26 | 2009-08-25 | Phototonus resin combination, solder resist combination for printed wiring board and printed wiring board |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR101727101B1 (en) |
| CN (1) | CN101676800A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2011125820A1 (en) * | 2010-03-31 | 2011-10-13 | 太陽ホールディングス株式会社 | Solder resist composition and printed circuit board |
| JP2011215384A (en) * | 2010-03-31 | 2011-10-27 | Taiyo Holdings Co Ltd | Solder resist composition and printed-circuit board |
| JP2011227308A (en) * | 2010-04-20 | 2011-11-10 | Taiyo Holdings Co Ltd | Solder resist composition and print circuit board |
| CN102483571A (en) * | 2009-09-10 | 2012-05-30 | 积水化学工业株式会社 | Photosensitive composition and printed wiring board |
| CN102520582A (en) * | 2010-08-18 | 2012-06-27 | 株式会社田村制作所 | White curable resin composition |
| CN102762627A (en) * | 2011-02-14 | 2012-10-31 | 积水化学工业株式会社 | Two-liquid mixing first and second liquids and method for producing printed circuit board |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3054350B1 (en) | 2014-12-10 | 2018-04-11 | Goo Chemical Co., Ltd. | Liquid solder resist composition and coated printed wiring board |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000256429A (en) * | 1999-03-11 | 2000-09-19 | Daicel Chem Ind Ltd | Active energy ray-curable unsaturated resin composition |
| JP4673996B2 (en) * | 2001-03-29 | 2011-04-20 | 株式会社タムラ製作所 | Photosensitive resin composition |
| JP2003295435A (en) * | 2002-03-28 | 2003-10-15 | Tamura Kaken Co Ltd | Photosensitive resin composition |
| TWI285298B (en) * | 2003-01-14 | 2007-08-11 | Sumitomo Chemical Co | Photosensitive resin composition |
-
2009
- 2009-07-21 KR KR1020090066222A patent/KR101727101B1/en active IP Right Grant
- 2009-08-25 CN CN200910171055A patent/CN101676800A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102483571A (en) * | 2009-09-10 | 2012-05-30 | 积水化学工业株式会社 | Photosensitive composition and printed wiring board |
| CN102483571B (en) * | 2009-09-10 | 2013-10-23 | 积水化学工业株式会社 | Photosensitive composition and printed wiring board |
| WO2011125820A1 (en) * | 2010-03-31 | 2011-10-13 | 太陽ホールディングス株式会社 | Solder resist composition and printed circuit board |
| JP2011215384A (en) * | 2010-03-31 | 2011-10-27 | Taiyo Holdings Co Ltd | Solder resist composition and printed-circuit board |
| CN102844711A (en) * | 2010-03-31 | 2012-12-26 | 太阳控股株式会社 | Solder resist composition and printed-circuit board |
| JP2011227308A (en) * | 2010-04-20 | 2011-11-10 | Taiyo Holdings Co Ltd | Solder resist composition and print circuit board |
| CN102520582A (en) * | 2010-08-18 | 2012-06-27 | 株式会社田村制作所 | White curable resin composition |
| CN102762627A (en) * | 2011-02-14 | 2012-10-31 | 积水化学工业株式会社 | Two-liquid mixing first and second liquids and method for producing printed circuit board |
| CN102762627B (en) * | 2011-02-14 | 2014-03-26 | 积水化学工业株式会社 | Two-liquid mixing first and second liquids and method for producing printed circuit board |
| CN106019827A (en) * | 2015-03-25 | 2016-10-12 | 积水化学工业株式会社 | First liquid and second liquid of two-liquid mixing type and method for manufacturing printed wiring board |
| CN110791150A (en) * | 2018-08-03 | 2020-02-14 | 株式会社田村制作所 | Curable resin composition for inkjet, printed wiring board, and method for producing printed wiring board |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20100024893A (en) | 2010-03-08 |
| KR101727101B1 (en) | 2017-04-14 |
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