CN101798432B - Curable resin composition and printed circuit board and reflection board using same - Google Patents
Curable resin composition and printed circuit board and reflection board using same Download PDFInfo
- Publication number
- CN101798432B CN101798432B CN2010101308295A CN201010130829A CN101798432B CN 101798432 B CN101798432 B CN 101798432B CN 2010101308295 A CN2010101308295 A CN 2010101308295A CN 201010130829 A CN201010130829 A CN 201010130829A CN 101798432 B CN101798432 B CN 101798432B
- Authority
- CN
- China
- Prior art keywords
- resin composition
- curable resin
- resin
- methyl
- mass parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention provides a curable resin composition and a printed circuit board and a reflection board using the same, in particular a curable resin composition capable of further improving the reflectivity of a curable substance, a printed circuit board with a welding resistant film using the resin composition and a reflection board using the resin composition. The curable resin composition is characterized by comprising resin containing alkene unsaturated group and carboxyl in 1 molecule, photo-polymerization initiator, photo-polymerization monomer, titanium oxide subjected to surface treatment by using alumina, barium sulfate and talc or barium sulfate talc, and organic solvent.
Description
Technical field
The printed substrate and the reflector that the present invention relates to curable resin composition and use this resin combination.Especially, relate to the curable resin composition that can form the soldering-resistance layer permanent mask, high-reflectivity that is suitable as printed substrate.And then relate to and use this curable resin composition to form the printed substrate that the soldering-resistance layer pattern forms on the surface of the base material that is formed with circuit and use this curable resin composition on base material, to form the reflector that reflection graphic patterns (cured article) forms.
Background technology
Printed substrate is normally removed the circuit card that forms wiring through the part that do not need that etching will be fitted in the Copper Foil of veneer sheet, through the position configuration electronic unit of scolding tin in regulation.In such printed substrate, the protective membrane of the circuit when using the soldering-resistance layer be applied to base material and be solidified to form as the scolding tin electronic unit.
Solder attachment arrived the unwanted part of printed substrate when this soldering-resistance layer prevented scolding tin, and prevented owing to the direct exposed to air of circuit conductor is caused because the deterioration that oxygen or moisture cause.And then soldering-resistance layer also plays the effect of the permanent protective membrane of printed substrate.Therefore, soldering-resistance layer requires each characteristics such as adaptation, electrical insulating property, solder heat resistance property, solvent resistance, chemical proofing.
In addition, in order to realize the densification of printed substrate, (granular, fine), multiple stratification and veneer (one board) change, its mounting means also develops into surface mounting technique (SMT) to make its miniaturization day by day.Therefore, soldering-resistance layer has also been improved in the requirement aspect granular, high resolving power, high precision, the high reliability.
As the technology of the pattern that forms such soldering-resistance layer, use can accurately form the photolithography of fine pattern.Particularly from the consideration grade of environment aspect, the photolithography of alkali developable (with reference to patent documentation 1,2) is just becoming main flow.
On the other hand; In recent years, the backlight liquid crystal display lamp of portable terminal, PC, TV etc. and the light source of lighting fixtures etc. will hang down the purposes that the luminous photodiode of electric power (LED) directly is installed on the printed substrate with soldering-resistance layer increases gradually.
Given this, in order more effectively to utilize the light of LED, the solder resist of various high-reflectivity has been proposed.For example, proposed through using specific titanium oxide to improve the solder resist (with reference to patent documentation 3) of degradation characteristic.
Yet patent documentation 3 described resin combinations are to improve the resin combination that degradation characteristic is a purpose, to have limitation aspect the further raising reflectivity.
In addition, also expectation with such improvement reflection characteristic be coated with the reflector purposes of film figure as display applications etc.
The prior art document
Patent documentation
Patent documentation 1: Japan special fair 1-54390 number
Patent documentation 2: Japan special fair 7-17737 number
Patent documentation 3: TOHKEMY 2007-322546 number
Summary of the invention
Invent problem to be solved
The objective of the invention is to the printed substrate and the reflector that the curable resin composition of the reflectivity that can further improve its cured article are provided and have the soldering-resistance layer that uses this resin combination.
The method that is used to deal with problems
Contrivers etc. further investigate to achieve these goals; The result finds; Through combination use with aluminum oxide carried out the surface-treated titanium oxide, with permanent white and talcum or permanent white or talcum; Can further improve the reflectivity of the cured article of resin combination, thereby expect the present invention.
Promptly; Curable resin composition of the present invention; It is characterized in that it comprises: 1 intramolecularly contain ethylenically unsaturated group and carboxyl resin, Photoepolymerizationinitiater initiater, photopolymerization monomer, carried out surface-treated titanium oxide, permanent white and talcum or permanent white or talcum, organic solvent with aluminum oxide.
The invention effect
According to the present invention, the curable resin composition that can further improve the reflectivity of its cured article can be provided.Consequently, curable resin composition of the present invention is useful in the purposes of the soldering-resistance layer of high-reflectivity, reflector.
Embodiment
Below, to curable resin composition of the present invention (below, also abbreviate " resin combination " as.) each constituent specify.
Contain the resin of ethylenically unsaturated group and carboxyl as 1 intramolecularly, just can use, do not limit especially so long as 1 intramolecularly has the resin of the ethylenically unsaturated group that is used for light solidified and the carboxyl that can enough weak alkaline aqueous solutions develops.Contain the resin of ethylenically unsaturated group and carboxyl as 1 such intramolecularly, the resin of enumerating below can suiting to use (can be in oligopolymer or the polymkeric substance any).That is,
(1) contains that carboxyl (methyl) acrylic acid series copolymer resins and 1 intramolecularly have the compound reaction of oxyethane ring and ethylenically unsaturated group and the photosensitive carboxy resin that contains that obtains;
(2) make the reaction of following multipolymer and unsaturated monocarboxylic; Secondary hydroxyl that is generated and saturated or unsaturated multi-anhydride react and the photosensitive carboxy resin that contains of acquisition, and wherein said multipolymer is the compound and the multipolymer with compound of unsaturated double-bond that 1 intramolecularly has 1 epoxy group(ing) and unsaturated double-bond respectively;
(3) after the reaction of hydroxyl polymer-containing and saturated or unsaturated multi-anhydride, react and the photosensitive hydroxyl of acquisition and the resin of carboxyl by this reaction carboxylic acid that generates and the compound that 1 intramolecularly has 1 epoxy group(ing) and unsaturated double-bond respectively.
In the middle of these; Preferably aforementioned (1) described photosensitive carboxy resin that contains, promptly (a) contains that carboxyl (methyl) acrylic acid series copolymer resins has the compound reaction of oxyethane ring and ethylenically unsaturated group with (b) 1 intramolecularly and the copolymerization with carboxyl of acquisition is a resin.
In this case, when particularly using the compound that generates by aliphatics polymerization property monomer to have the compound of oxyethane ring and ethylenically unsaturated group, can also suppress because the light deterioration that the aromatic nucleus of above-mentioned resin causes, so preferably as (b) 1 intramolecularly.
(a) containing carboxyl (methyl) acrylic acid series copolymer resins has the compound copolymerization of 1 unsaturated group and at least 1 carboxyl by (methyl) propenoate and 1 intramolecularly and obtains.As (methyl) propenoate that constitutes above-mentioned (a), can enumerate out (methyl) alkyl-acrylates such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) Bing Xisuandingzhi, (methyl) vinylformic acid pentyl ester, (methyl) NSC 11786; (methyl) esters of acrylic acid of (methyl) vinylformic acid-2-hydroxyl ethyl ester, (methyl) Propylene glycol monoacrylate, (methyl) vinylformic acid hydroxy butyl ester, caprolactone modification (methyl) vinylformic acid-hydroxyls such as 2-hydroxyl ethyl ester; Glycol modification (methyl) esters of acrylic acids such as methoxyl group Diethylene Glycol (methyl) propenoate, oxyethyl group Diethylene Glycol (methyl) propenoate, different octyloxy Diethylene Glycol (methyl) propenoate, methoxyl group triethylene glycol (methyl) propenoate, methoxy poly (ethylene glycol) (methyl) propenoate etc.These can use separately, also can mix more than 2 kinds and use.In addition, in this manual, (methyl) propenoate is the term of general designation propenoate and methacrylic ester, and other similarly show too.
In addition; The compound that has 1 unsaturated group and at least 1 carboxyl as 1 intramolecularly that constitutes above-mentioned (a); The modification unsaturated monocarboxylic that can enumerate out between vinylformic acid, methylacrylic acid, unsaturated group and the carboxylic acid by chain extension such as β-propyloic (methyl) propenoate, 2-acryloxy ethyl succsinic acid, 2-acryloxy ethyl hexahydrophthalic acid; Have the unsaturated monocarboxylic of ester bond through interior ester modified grade, have in modification unsaturated monocarboxylic and the toxilic acid equimolecular of ehter bond and comprise material of 2 above carboxyls etc.These can use separately also can mix more than 2 kinds and use.
Has the compound of oxyethane ring and ethylenically unsaturated group as (b) 1 intramolecularly, the preferred especially compound that generates by aliphatic monomer that uses.As its object lesson; Can enumerate out glycidyl (methyl) propenoate, Alpha-Methyl glycidyl (methyl) propenoate, 3; 4-epoxy group(ing) cyclohexyl methyl (methyl) propenoate, 3,4-epoxy group(ing) cyclohexyl ethyl (methyl) propenoate, 3,4-epoxy group(ing) cyclohexyl butyl (methyl) propenoate, 3; 4-epoxy group(ing) cyclohexyl methyl amino acrylates, 3,4-epoxy group(ing) cyclohexyl methyl (methyl) propenoate etc.These can use separately also can mix more than 2 kinds and use.
1 intramolecularly contains the acid number of the resin of ethylenically unsaturated group and carboxyl need be in the scope of 50～200mgKOH/g.During this acid number deficiency 50mgKOH/g, be difficult to remove the unexposed portion of resin combination with weak alkaline aqueous solution.In addition, when this acid number surpasses 200mgKOH/g, there are the problems such as water tolerance, electrical characteristic deterioration of the cured article of resin combination.
In addition, the weight-average molecular weight of this resin is preferably in 5000～100000 scope.During this weight-average molecular weight less than 5000, there is the tendency of the remarkable variation of touch dry property of filming of resin combination.In addition, this weight-average molecular weight surpasses at 100000 o'clock, and so the problem of the development property of generation tree oil/fat composition, the remarkable variation of storage stability is not preferred.
As the Photoepolymerizationinitiater initiater that uses among the present invention, can enumerate out bitter almond oil camphor and benzoin alkylether classes such as bitter almond oil camphor, benzoin methylether, ethoxybenzoin, benzoin iso-propylether; Methyl phenyl ketone, 2,2-dimethoxy-2-phenyl methyl phenyl ketone, 2,2-diethoxy-2-phenyl methyl phenyl ketone, 1,1-dichloroacetophenone, 2-hydroxyl-1-{4-(2-hydroxy-2-methyl-propionyl group)-2-methyl-propane-acetophenones such as 1-ketone; 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinyl-propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butane-1-ketone, N, N-dimethylamino benzoylformaldoxime, 2-(dimethylamino)-2-{ (4-aminomethyl phenyl) methyl }-1-{4-(4-morpholinyl) phenyl }-aminoacetophenone classes such as 1-butanone; Anthraquinone classes such as 2-methylanthraquinone, 2-ethyl-anthraquinone, 2-tertiary butyl anthraquinone, 1-chloroanthraquinone; 2,4-dimethyl-thioxanthone, 2,4-diethyl thioxanthone, 2-clopenthixal ketone, 2, thioxanthene ketones such as 4-di-isopropyl thioxanthone; Ketal classes such as methyl phenyl ketone dimethyl ketal, benzil dimethyl ketal; UVNUL MS-40,4,4 '-benzophenone or xanthene ketones such as two diethylamino UVNUL MS-40; 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(to the cyano-styrene base)-1,3, Lu such as 4-oxadiazole are for Jia oxadiazole based compound; 2; Two (the trichloromethyl)-6-(to methoxyl group-phenyl vinyl) of 4--1,3,5-triazines, 2; Two (the trichloromethyl)-6-of 4-are to methoxyl-styrene-s-triazine, 2; Two (the trichloromethyl)-6-(1-is to dimethylaminophenyl-1,3-butadiene base) of 4--halogenated methyls such as s-triazine-s-triazine based compound, { 1-[4-(thiophenyl)-2-(O-benzoyl oxime)] }-1,2-acetyl caproyl, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime) ethyl ketone etc.
In addition, as Photoepolymerizationinitiater initiater, it is that Photoepolymerizationinitiater initiater and monoacyl phosphine oxide are Photoepolymerizationinitiater initiater that special preferably combination is used two acylphosphine oxides.
As two acylphosphine oxides is Photoepolymerizationinitiater initiater, can enumerate out two (2,6-dichloro-benzoyl base) phenyl phosphine oxides, two (2,6-dichloro-benzoyl base)-2; 5-3,5-dimethylphenyl phosphine oxide, two (2,6-dichloro-benzoyl base)-4-propyl group phenyl phosphine oxide, two (2,6-dichloro-benzoyl base)-1-naphthyl phosphine oxide, two (2; 6-dimethoxy benzoyl-) phenyl phosphine oxide, two (2,6-dimethoxy benzoyl-)-2,4; 4-tri-methyl-amyl phosphine oxide, two (2,6-dimethoxy benzoyl-)-2,5-3,5-dimethylphenyl phosphine oxide, two (2; 4, the 6-trimethylbenzoyl) phenyl phosphine oxide, (2,5; The 6-trimethylbenzoyl)-2,4,4-tri-methyl-amyl phosphine oxide etc.In the middle of these, two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide (Ciba Japan K.K. manufacturing, trade(brand)name: IRGACURE 819) obtains easily and is practical.
As the monoacyl phosphine oxide is Photoepolymerizationinitiater initiater; Can enumerate out 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, 2; 6-dimethoxy benzoyl-diphenyl phosphine oxide, 2; 6-dichloro-benzoyl base diphenyl phosphine oxide, 2,4,6-trimethylbenzoyl phenyl methyl phosphite, 2-methyl benzoyl diphenyl phosphine oxide, pivaloyl phenyl phosphorous acid isopropyl esters etc.In the middle of these, 2,4, (Ciba Japan K.K. makes 6-trimethylbenzoyl diphenyl phosphine oxide, trade(brand)name: DAROCUR TPO) obtain easily and practicality.
Using above-mentioned pair of acylphosphine oxide through combination is that Photoepolymerizationinitiater initiater and aforementioned monoacyl phosphine oxide are Photoepolymerizationinitiater initiater, also can absorb required light even be combined with the filming of high-reflectivity of titanium oxide, can form high meticulous pattern.In addition, through changing their cooperation ratio, photosensitivity that can the inching resin combination.That is, the deep solidified nature of the substrate surface side that causes at the cross-sectional shape owing to pattern is not enough when being easy to produce undercutting (undercut), the ratio that can to improve above-mentioned pair of acylphosphine oxide be Photoepolymerizationinitiater initiater.In addition, because the surface cure property of filming is not enough, during the condition of surface variation of filming after causing developing, the ratio that can to improve aforementioned monoacyl phosphine oxide be Photoepolymerizationinitiater initiater.
Contain the resin of ethylenically unsaturated group and carboxyl with respect to 100 mass parts, 1 intramolecularly, the use level of Photoepolymerizationinitiater initiater is preferably 1～30 mass parts, 2～25 mass parts more preferably.During this use level less than 1 mass parts, the light solidified of resin combination reduces, and the pattern after exposure and the development is difficult to form, so not preferred.On the other hand, when this use level surpassed 30 mass parts, so the big and cost increase of the painted change of filming that Photoepolymerizationinitiater initiater causes was not preferred.
As the photopolymerization monomer that uses among the present invention, can enumerate out vinylformic acid-2-hydroxyl ethyl ester, vinylformic acid-acrylic acid hydroxy alkyl ester classes such as 2-hydroxy butyl ester; The mono acrylic ester class or the diacrylate class of glycol such as terepthaloyl moietie, methoxyl group TEG, polyoxyethylene glycol, Ucar 35; N, acrylic amides such as N-DMAA, N hydroxymethyl acrylamide; N, amino alkyl acrylates classes such as N-dimethyl amino ethyl acrylate; The multicomponent methacrylate class of polyvalent alcohols such as pinakon, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol, tris(2-hydroxy ethyl)isocyanurate or their oxyethane or propylene oxide adduct; Esters of acrylic acids such as the oxyethane of phenoxy propenoate, bisphenol a diacrylate and these phenols or propylene oxide adduct; The esters of acrylic acid of glycidyl ethers such as glycerine diglycidyl ether, trimethylolpropane tris glycidyl ether; The trimeric cyanamide propenoate; And/or the methyl acrylic ester corresponding with the aforesaid propylene esters of gallic acid etc.
Contain the resin of ethylenically unsaturated group and carboxyl with respect to 100 mass parts, 1 intramolecularly, the use level of these photopolymerization monomers is preferably 10～100 mass parts, 20～80 mass parts more preferably.When this use level surpasses 100 mass parts, reduce as the rerum natura of the soldering-resistance layer of cured article, so not preferred.On the other hand, during these use level less than 10 mass parts, resin combination does not have sufficient light solidified, can not obtain high meticulous pattern.
Carry out the surface-treated titanium oxide with aluminum oxide and can use in anatase type titanium oxide, the Titanium Dioxide (Rutile) Top grade any.Preferred especially Titanium Dioxide (Rutile) Top grade.Compare with Titanium Dioxide (Rutile) Top grade, anatase type titanium oxide is high at the reflectivity of the short wavelength side of ultra-violet region, therefore, consider from whiteness and reflectivity aspect, and be ideal as white pigment.Yet anatase type titanium oxide has photocatalytic activity, thereby this photolytic activity can cause the resin variable color in the resin combination.To this, to compare with anatase type titanium oxide, Titanium Dioxide (Rutile) Top grade is in the reflection differences of the short wavelength side of ultra-violet region, but has photolytic activity hardly, thereby, can suppress the deterioration of the resin in the resin combination, obtain stable cured article.
In addition, in Titanium Dioxide (Rutile) Top grade, can further suppress the deterioration of resin by the titanium oxide of chlorine manufactured, so preferred especially.
As having carried out the surface-treated Titanium Dioxide (Rutile) Top grade with aluminum oxide; Can use TIPAQUE R-820, TIPAQUE R-830, TIPAQUE R-930, TIPAQUE R-550, TIPAQUE R-630, TIPAQUE R-680, TIPAQUER-670, TIPAQUE R-680, TIPAQUE R-670, TIPAQUE R-780, TIPAQUE R-850, TIPAQUE CR-50, TIPAQUE CR-57, TIPAQUECR-80, TIPAQUE CR-90, TIPAQUE CR-93, TIPAQUE CR-95, TIPAQUE CR-97, TIPAQUE CR-60, TIPAQUE CR-63, TIPAQUECR-67, TIPAQUE CR-58, TIPAQUE CR-85, TIPAQUE UT771 (Ishihara Sangyo Kaisha; Ltd. manufacturing), Ti-Pure R-100, Ti-PureR-101, Ti-Pure R-102, Ti-Pure R-103, Ti-Pure R-104, Ti-PureR-105, Ti-Pure R-108, Ti-Pure R-900, Ti-Pure R-902, Ti-PureR-960, Ti-Pure R-706, Ti-Pure R-931 (Du Pont Kabushiki Kaisha manufacturing), TITON R-25, TITON R-21, TITON R-32, TITON R-7E, TITON R-5N, TITON R-61N, TITON R-62N, TITON R-42, TITON R-45M, TITON R-44, TITON R-49S, TITON GTR-100, TITON GTR-300 (Sakai Chemical Industry Co., Ltd. makes), TITANIX JR-300, TITANIX JR-403, TITANIX JR-405, TITANIXJR-600A, TITANIX JR-600E, TITANIX JR-602, TITANIXJR-602S, TITANIX JR-603, TITANIX JR-805 (Tayca Corporation manufacturing) etc.
In addition, as having carried out the surface-treated anatase type titanium oxide, can enumerate out TIPAQUE A-220 (Ishihara Sangyo Kaisha, Ltd. makes), TITANIX JA-4 (Tayca Corporation manufacturing) etc. with aluminum oxide.
Except carrying out the surface treatment, carried out the surface-treated titanium oxide with aluminum oxide and can also carry out surface treatment with other materials with aluminum oxide.Among the present invention, particularly will carry out the surface-treated titanium oxide and further carry out surface treatment, and can further improve the reflectivity of titanium oxide with zirconium white with aluminum oxide.
In above-mentioned titanium oxide; Carried out the surface-treated titanium oxide with zirconium white as carrying out again after the surface treatment with aluminum oxide; Can enumerate out TIPAQUE CR-57, TIPAQUE CR-97, TIPAQUE CR-67 (Ishihara Sangyo Kaisha; Ltd. manufacturing), R-61N, GTR-100, GTR-300 (Sakai Chemical Industry Co., Ltd. makes), TITANIX JR-603 (Tayca Corporation manufacturing).
With respect to 100 contained in resin combination mass parts nonvolatile component, the use level of having carried out surface-treated titanium oxide (comprise further and carried out the surface-treated titanium oxide with zirconium white) with aluminum oxide is preferably 30～80 mass parts, 30～70 mass parts more preferably.When this use level surpassed 80 mass parts, the light solidified of resin combination reduced, and curing depth reduces, so not preferred.On the other hand, during these use level less than 30 mass parts, the power of covering of resin combination diminishes, and can not obtain filming of high-reflectivity.
Through with the permanent white that uses among the present invention and talcum or permanent white or talcum and carried out the combination of surface-treated titanium oxide with aluminum oxide and used, help to improve the reflectivity of resin combination.
As such permanent white; Can enumerate out settleability permanent white #100, settleability permanent white #300, settleability permanent white SS-50, BARIACE B-30, BARIACEB-31, BARIACE B-32, BARIACE B-33, BARIACE B-34, BARIFINE BF-1, BARIFINE BF-10, BARIFINE BF-20, BARIFINE BF-40 (Sakai Chemical Industry Co.; Ltd. manufacturing), W-1, W-6, W-10, C-300 (Takehara Chemical Industrial Co., Ltd. makes) etc.
Contain the resin of ethylenically unsaturated group and carboxyl with respect to 100 mass parts, 1 intramolecularly, the use level of permanent white is preferably 0.5～50 mass parts, 1～30 mass parts more preferably.During this use level less than 0.5 mass parts, use for combination and to have carried out the surface-treated titanium oxide with aluminum oxide and improve reflectivity and do not have help.In addition, when this use level surpassed 50 mass parts, the concentration of this titanium oxide relatively tailed off, thereby reflectivity reduces.
As talcum; Can enumerate out LMS-100, LMS-200, LMS-300, LMS-3500, LMS-400, LMP-100, PKP-53, PKP-80, PKP-81 (FUJI TALC INDUSTRIAL CO.; LTD. manufacturing), D-600, D-800, D-1000, P-2, P-3, P-4, P-6, P-8, SG-95 (Nippon Talc Co., Ltd. makes) etc.They can multiple alone or in combination use.
Contain the resin of ethylenically unsaturated group and carboxyl with respect to 100 mass parts, 1 intramolecularly, the steatitic use level is preferably 0.5～50 mass parts, 1～30 mass parts more preferably.During this use level less than 0.5 mass parts, use for combination and to have carried out the surface-treated titanium oxide with aluminum oxide and improve reflectivity and do not have help.In addition, when this use level surpassed 50 mass parts, the concentration of this titanium oxide relatively tailed off, thereby reflectivity reduces.
The state that the organic solvent that uses among the present invention is used to that curable resin composition is in and is easy to be coated with is applied to base material with it, makes it dry and form and film then.As such organic solvent, can enumerate out ketones such as methylethylketone, pimelinketone; Toluene, YLENE, tetramethyl-benzene etc. are aromatic hydrocarbon based; Glycol ethers such as methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether, methyl carbitol, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol list ether, Triethylene glycol ethyl ether; The ester classes such as carboxylate of vinyl acetic monomer, N-BUTYL ACETATE, cellosolve acetic ester, diethylene glycol monoethyl ether acetic ester and above-mentioned glycol ethers; Alcohols such as ethanol, propyl alcohol, terepthaloyl moietie, Ucar 35; Aliphatic hydrocarbon such as octane, decane; Oil series solvents such as sherwood oil, petroleum naphtha, hydrogenated naphtha, solvent naphtha etc.
Aforementioned organic solvent can use separately or use as the mixture more than 2 kinds.Contain the resin of ethylenically unsaturated group and carboxyl with respect to 100 mass parts, 1 intramolecularly, the use level of organic solvent is preferably 20～300 mass parts.
The cured article of curable resin composition of the present invention is needing as the purposes of the soldering-resistance layer of printed substrate under the stable on heating situation, gives Thermocurable through in resin combination, cooperating epoxy compounds, thereby can obtain thermotolerance.
As such epoxy compounds; Can enumerate out bisphenol-s epoxy resin, diglycidyl phthalate resin, triglycidyl group isocyanuric acid ester (Nissan ChemicalIndustries for example; Ltd. TEPIC-H (the β body of making; Have the structure that 3 epoxy group(ing) form at the same direction bonding of s-triazine ring skeleton face), TEPIC (mixture of β body and α body, α body possess the structure that 1 epoxy group(ing) and other 2 epoxy group(ing) form at the different directions bonding of s-triazine ring skeleton face) etc.) etc. the epoxy resin of thinner insoluble such as hetero ring type epoxy resin, di-toluene phenol-type epoxy resin, biphenyl type epoxy resin, four glycidyl group xylenol ethane resin; Bisphenol A type epoxy resin; Bisphenol-A epoxy resin; Bisphenol F type resin; Brominated bisphenol a type epoxy resin; Phenol phenolic varnish type or cresols phenolic resin varnish type epoxy resin; Alicyclic epoxy resin; The phenolic resin varnish type epoxy resin of dihydroxyphenyl propane; Inner complex type epoxy resin; Oxalic dialdehyde type epoxy resin; Contain aminoepoxy resin; Rubber modified epoxy resin; The Dicyclopentadiene (DCPD) phenol aldehyde type epoxy resin; Modifying epoxy resin by organosilicon; The epoxy resin of thinner solubilities such as 6-caprolactone modified epoxy etc.These epoxy resin can use separately or make up more than 2 kinds and use.
Contain the resin of ethylenically unsaturated group and carboxyl with respect to 100 mass parts, 1 intramolecularly, the use level of such epoxy compounds is preferably 5～70 mass parts, 5～60 mass parts more preferably.When the use level of epoxy compounds surpassed 70 mass parts, the unexposed portion of resin combination reduced the solvability of developing solution, and it is residual to be easy to generate development, therefore, is difficult to practicality.On the other hand; During these use level less than 5 mass parts; The carboxyl that 1 intramolecularly contains the resin of ethylenically unsaturated group and carboxyl remains in the cured article with unreacted state, thereby as solder resist the time, has the stable on heating tendency that is difficult to fully obtain cured article.
Carboxyl and the epoxy group(ing) of epoxy compounds that 1 intramolecularly contains the resin of ethylenically unsaturated group and carboxyl are reacted through ring-opening polymerization.In this case, will be the epoxy resin of processable when being used for resin combination to other materials in organic solvent, the resin combination, because the heat during dry when forming the filming of resin combination, the crosslinked of above-mentioned carboxyl and epoxy group(ing) carries out easily.Therefore, needs suppress this crosslinking reaction with the situation that prolongs time of drying under, it is desirable to use the epoxy resin of other materials in organic solvent, the resin combination separately as insoluble, perhaps its epoxy resin with processable is used.
Among the present invention, receive the purpose of the caused variable color of thermal degradation when, can cooperate inhibitor from reducing filming of resin combination.As aforementioned inhibitor, preferred hindered phenol based compound, but not special the qualification.As the hindered phenol based compound; Can enumerate out for example NOCRAC 200, NOCRAC M-17, NOCRAC SP, NOCRAC SP-N, NOCRAC NS-5, NOCRAC NS-6, NOCRACNS-30, NOCRAC 300, NOCRAC NS-7, NOCRAC DAH (OUCHISHINKO CHEMICAL INDUSTRIAL CO., LTD makes); MARKAO-30, MARK AO-40, MARK AO-50, MARK AO-60, MARKAO-616, MARK AO-635, MARK AO-658, MARK AO-15, MARKAO-18, MARK 328, MARK AO-37 ((strain) ADEKA manufacturing); IRGANOX 245, IRGANOX 259, IRGANOX 565, IRGANOX1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1081, IRGANOX 1098, IRGANOX 1222, IRGANOX 1330, IRGANOX1425WL (Ciba Japan K.K. manufacturing) etc.
Contain the resin of ethylenically unsaturated group and carboxyl with respect to 100 mass parts, 1 intramolecularly, the use level of aforementioned inhibitor is preferably below 25 mass parts, more preferably 0.4～15 mass parts.During this use level less than 0.4 mass parts, prevent to receive the effect of the caused variable color of thermal degradation when little because of filming of resin combination.When this use level surpasses 25 mass parts, can cause the development property reduction of resin combination, patterning is caused detrimentally affect.
In addition, to contain hindered amine in the curable resin composition of the present invention be photostabilizer through making, and can reduce the light deterioration of resin combination.
As hindered amine is photostabilizer, can enumerate out for example TINUVIN622LD, TINUVIN 144; CHIMASSORB 944LD, CHIMASSORB 119FL (Ciba Japan K.K. manufacturing); MARK LA-57, LA-62, LA-67, LA-63, LA-68 ((strain) ADEKA manufacturing) etc.
Contain the resin of ethylenically unsaturated group and carboxyl with respect to 100 mass parts, 1 intramolecularly, preferably adding the above-mentioned hindered amine of 0.1～10 mass parts is photostabilizer.
Through in curable resin composition of the present invention, containing dispersion agent, can improve dispersiveness, the settleability of titanium oxide.Can enumerate out for example ANTI-TERRA-U, ANTI-TERRA-U100, ANTI-TERRA-204, ANTI-TERRA-205, DISPERBYK-101, DISPERBYK-102, DISPERBYK-103, DISPERBYK-106, DISPERBYK-108, DISPERBYK-109, DISPERBYK-110, DISPERBYK-111, DISPERBYK-112, DISPERBYK-116, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-166, DISPERBYK-167, DISPERBYK-168, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-180, DISPERBYK-182, DISPERBYK-183, DISPERBYK-185, DISPERBYK-184, DISPERBYK-2000, DISPERBYK-2001, DISPERBYK-2009, DISPERBYK-2020, DISPERBYK-2025, DISPERBYK-2050, DISPERBYK-2070, DISPERBYK-2096, DISPERBYK-2150, BYK-P104, BYK-P104S, BYK-P105, BYK-9076, BYK-9077, BYK-220S (BYK Japan KK manufacturing), DISPARLON2150, DISPARLON1210, DISPARLONKS-860, DISPARLONKS-873N, DISPARLON 7004, DISPARLON 1830, DISPARLON 1860, DISPARLON 1850, DISPARLONDA-400N, DISPARLONPW-36, DISPARLONDA-703-50 (Kusumoto Chemicals; Ltd. manufacturing), FLOWLEN G-450, FLOWLEN G-600, FLOWLEN G-820, FLOWLEN G-700, FLOWLEN DOPA-44, FLOWLEN DOPA-17 (Kyoeisha Chemical Co., Ltd. makes).
With respect to 100 mass parts titanium oxide, the use level of dispersion agent is 0.1～10 mass parts, be preferably 0.5～5 mass parts.
In addition, in resin combination, can also use curing catalyst, hot stopper, thickening material, skimmer, flow agent, coupling agent, flame retardant etc. as required.
Below, as an example that uses curable resin composition of the present invention, the manufacturing of the printed substrate during for use resin combination in soldering-resistance layer describes.In addition, certainly, the present invention also can be used for except the soldering-resistance layer purposes in the purposes such as reflector.
Can making as follows of printed substrate of the present invention:
At first, as required, curable resin composition of the present invention is diluted, is adjusted to the viscosity that is suitable for coating process.
Then, be coated with methods such as method, spraying method, rolling method through silk screen print method, curtain, this resin combination that has carried out viscosity adjustment is applied on the printed substrate that is formed with circuit.Then, for example making organic solvent volatile dry contained in the resin combination of this coating under 70～90 ℃ the temperature, form tack-free filming.
Then, across photomask, with active energy beam to this exposure of filming optionally.And, with alkaline aqueous solution to unexposed development in filming to form corrosion-resisting pattern.And then, under 100～200 ℃,, form the soldering-resistance layer pattern with this etchant resist pattern thermofixation.
In addition, as the radiation source that is used for above-mentioned exposure, can use low pressure mercury lamp, medium pressure mercury lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, xenon lamp or metal halide lamp etc.In addition, laser beam etc. also can be used as active ray.
As developing solution is alkaline aqueous solution, uses the aqueous sodium carbonate of 0.5～5 quality % usually, but also can use other alkaline aqueous solutions.As other alkaline aqueous solutions, can enumerate out the for example alkaline aqueous solution of Pottasium Hydroxide, sodium hydroxide, salt of wormwood, sodium phosphate, water glass, ammonium, amine etc.
More than, printed substrate of the present invention, reflector contain the titanium oxide of high-reflectivity through use curable resin composition of the present invention makes, thereby reflectivity is high and have a high meticulous pattern.
Embodiment
Below, embodiment being shown and comparative example specifies the present invention, the present invention is not limited to these certainly.
Synthesizing of resin solution 1:
(NOFCORPORATION makes, trade(brand)name: PERBUTYL O), be heated to 90 ℃ as the tert-butyl peroxide-2-ethylhexanoate of polymerization starter as the diethylene glycol dimethyl ether of solvent and 21.4g in 2 liters of removable flasks that possess stirrer, TM, reflux exchanger, tap funnel and nitrogen ingress pipe, to add 900g.After the heating; With in this flask, dripped 309.9g methylacrylic acid, 116.4g TEB 3K in 3 hours, (DAICELCHEMICAL INDUSTRIES, LTD. makes 109.8g lactone modified methacrylic acid-2-hydroxyl ethyl ester, trade(brand)name: PLACCEL FM1) with two (4-tert-butylcyclohexyl) peroxy dicarbonates (NOF CORPORATION manufacturing, the trade(brand)name: PEROYL TCP) of 21.4g as polymerization starter.Then, its further slaking was obtained to contain the carboxyl copolymer resins in 6 hours.In addition, this is reflected under the nitrogen atmosphere and carries out.
Then; Add 363.9g 3 in the carboxyl copolymer resins to resulting above-mentioned containing; CYCLOMER A200), 3.6g is as the dimethyl benzyl amine of ring opening catalyst, the 1.80g hydroquinone monomethyl ether as stopper (DAICEL CHEMICALINDUSTRIES, LTD. make 4-epoxy group(ing) cyclohexyl methyl propenoate, trade(brand)name:.Then, be heated 100 ℃ and also stir the opening that carries out epoxy group(ing).After 16 hours, the acid number that obtains comprising solids component is that 108.9mgKOH/g, weight-average molecular weight are 25000, do not have the solution that contains carboxy resin 53.8 quality % (nonvolatile component) of aromatic nucleus.Below, this reaction soln is called resin solution 1.
The cooperation of embodiment 1～9 and comparative example 1～8:
Cooperate each composition and stirring according to table 1, utilize 3 roll-type roller mills to make its dispersion, thereby make each curable resin composition.Numeral mass parts in the table.
Photoepolymerizationinitiater initiater 1: two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide IRGACURE819 (Ciba Japan K.K. manufacturing)
Photoepolymerizationinitiater initiater 2:2,4,6-trimethylbenzoyl diphenyl phosphine oxide
Photopolymerization monomer: dipentaerythritol acrylate
Titanium oxide 1 (carrying out the surface treatment rutile-type): TITANIXJR-600E (Tayca Corporation manufacturing) with aluminum oxide
Titanium oxide 2 (carrying out the surface treatment rutile-type): TITANIX JR-603 (Tayca Corporation manufacturing) with aluminum oxide+zirconium white
Titanium oxide 3 (no surface treatment rutile-type): TITANIX JR (TaycaCorporation manufacturing)
Permanent white: settleability permanent white #100 (Sakai ChemicalIndustry Co., Ltd. makes)
Talcum: LMS-200 (FUJI TALC INDUSTRIAL CO., LTD. makes)
Silicon-dioxide: FB-3SDC (DENKI KAGAKU KOGYOKABUSHIKI KAISHA manufacturing)
Organic solvent: Trivalin SF acetic ester
Epoxy compounds (biphenyl type): YX-4000 (Japan Epoxy ResinsCo., Ltd. makes)
Solidifying agent: Dyhard RU 100
Skimmer (organic silicone oil): KS-66 (Shin-Etsu Silicones manufacturing)
For each curable resin composition of embodiment 1～9 and comparative example 1～8, each property test of the soldering-resistance layer that is described below, and estimate.
(1) reflectivity
Pass through silk screen print method; Use the version of 100 order polyester (twill system); The full pattern (the whole face of substrate) of the curable resin composition of embodiment 1～9, comparative example 1～8 is printed onto on the FR-4 copper clad laminate of size and thick 1.6mm of 100mm * 150mm, and to make thickness be 40 μ m.Then, use the heated air circulation type drying oven that they are following dry 30 minutes at 80 ℃.Then, use use in printed circuit board exposure machine HMW-680GW ((strain) ORC MANUFACTURING CO., LTD. makes), with 700mJ/cm
2The accumulation light quantity with the mode that stays the square negative pattern of 30mm they are carried out ultraviolet exposure.Then, as developing solution, utilize the use in printed circuit board developing machine that they were developed for 60 seconds down at 30 ℃ with the aqueous sodium carbonate of 1 quality %.Then, use the heated air circulation type drying oven that they are carried out thermofixation in 60 minutes under 150 ℃, make the test film that testing of characteristic is used.
Use color colour-difference meter CR-400 (Konica Minolta Sensing, Inc. makes) to measure the Y value of the XYZ table color method of resulting each test film, should be worth as reflectivity.Its result is shown in table 2.
Can know from the result shown in the table 2; Compare with comparative example 1, combination uses the titanium oxide that carried out handling with aluminum oxide and permanent white or steatitic embodiment 1～4 and combination to use titanium oxide and the permanent white and the steatitic embodiment 9 that have carried out processing with aluminum oxide to improve reflectivity all quite a lot ofly.In addition, also find: changed the use level of titanium oxide embodiment 5～7, use the effect that the embodiment 8 of the titanium oxide that carries out after the surface treatment again crossing with zirconia treatment with aluminum oxide is also visible and embodiment 1～4 is same.Particularly, can confirm, through can further improving reflectivity with the zirconia treatment titanium oxide.In addition, do not find that comparative example has big effect to improving reflectivity.
(2) solder heat resistance property
The rosin series solder flux is applied to through on each test film made from aforementioned (1) same method, it was flow through for 10 seconds in 260 ℃ solder bath.Then, with these test films of propylene glycol methyl ether acetate washing, and make its drying.Then, these test films are carried out the stripping test of zellglas self adhesive tape, estimate peeling off of filming.Its result is shown in table 2.
(3) solvent resistance
To in propylene glycol methyl ether acetate, flood 30 minutes through each test film made from aforementioned (1) same method, make its drying.Then, these test films are carried out the stripping test of zellglas self adhesive tape, estimate peeling off and variable color of filming.Its result is shown in table 2.
(4) pencil hardness test
Be pressed into through on each test film made from aforementioned (1) same method with about 45 ° angle from the pencil of B to 9H what the core point polished, record does not produce the hardness of the pencil of peeling off of filming.Its result is shown in table 2.
(5) insulation resistance test
Except the comb-type electrode B sample that uses IPC B-25 test pattern substitutes the FR-4 copper clad laminate, with aforementioned (1) same condition under each test film of making.This test film is applied the bias voltage of DC 500V, measure insulating resistance value.Its result is shown in table 2.
The metewand of aforementioned (3) solder heat resistance property, aforementioned (4) solvent resistance, aforementioned (5) pencil hardness test is described below.
Zero ... do not have peeling off of filming, variable color
* ... peeling off of filming, variable color are arranged
Result as shown in table 2 can know that curable resin composition of the present invention has the desired good thermotolerance of soldering-resistance layer, solvent resistance, adaptation and electrical insulating property.
As above detailed description; When curable resin composition of the present invention reaches capacity (also can not improve reflectivity even will be coupled in the heat-curing resin than the more titanium oxide of limiting quantity) in the use level of titanium oxide, also can reflectivity further be improved through cooperating permanent white or talcum or permanent white and talcum.And, use that soldering-resistance layer that curable resin composition of the present invention forms is few because of the variable color that light or thermal conductance cause, high-reflectivity is excellent.
Claims (4)
1. curable resin composition is characterized in that it comprises:
1 intramolecularly contain ethylenically unsaturated group and carboxyl resin,
Photoepolymerizationinitiater initiater,
Photopolymerization monomer,
With aluminum oxide carried out the surface-treated titanium oxide,
Permanent white and talcum or permanent white or talcum,
Organic solvent,
Epoxy compounds,
With respect to 100 contained in compsn mass parts nonvolatile component, the use level that said use aluminum oxide has carried out the surface-treated titanium oxide is 30～80 mass parts.
2. curable resin composition according to claim 1 is characterized in that, has saidly carried out the surface-treated titanium oxide with aluminum oxide and has further carried out surface treatment with zirconium white.
3. printed substrate, it possesses:
Be formed with circuit base material and
The soldering-resistance layer that uses claim 1 or 2 described curable resin compositions on this base material, to form.
4. reflector, it possesses:
Base material and
The claim 1 that on this base material, forms or the cured article of 2 described curable resin compositions.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009085909A JP6054012B2 (en) | 2009-03-31 | 2009-03-31 | Curable resin composition and printed wiring board and reflector using the same |
| JP2009-085909 | 2009-03-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101798432A CN101798432A (en) | 2010-08-11 |
| CN101798432B true CN101798432B (en) | 2012-10-10 |
Family
ID=42594284
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101308295A Active CN101798432B (en) | 2009-03-31 | 2010-03-11 | Curable resin composition and printed circuit board and reflection board using same |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6054012B2 (en) |
| KR (1) | KR100987542B1 (en) |
| CN (1) | CN101798432B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5147820B2 (en) * | 2009-12-24 | 2013-02-20 | 株式会社タムラ製作所 | White solder resist composition for spray painting |
| JP2011248322A (en) * | 2010-04-26 | 2011-12-08 | Sekisui Chem Co Ltd | Photosensitive composition, solder resist composition and substrate |
| JP5806492B2 (en) * | 2011-03-31 | 2015-11-10 | 太陽インキ製造株式会社 | Curable resin composition, dry film and printed wiring board using the same |
| JP5688129B1 (en) * | 2013-09-30 | 2015-03-25 | 太陽インキ製造株式会社 | Curable composition for printed wiring board, cured coating film using the same, and printed wiring board |
| JP2016100182A (en) * | 2014-11-21 | 2016-05-30 | スタンレー電気株式会社 | Display device |
| EP3054350B1 (en) | 2014-12-10 | 2018-04-11 | Goo Chemical Co., Ltd. | Liquid solder resist composition and coated printed wiring board |
| JP6321059B2 (en) * | 2015-02-18 | 2018-05-09 | 株式会社タムラ製作所 | Photosensitive resin composition |
| CN106918988B (en) * | 2015-12-25 | 2021-04-20 | 太阳油墨（苏州）有限公司 | Curable resin composition, and reflective film and printed wiring board using same |
| WO2017135751A1 (en) | 2016-02-05 | 2017-08-10 | 주식회사 엘지화학 | Resin composition having photocurability and thermosetting property, and dry film solder resist |
| JP2018048268A (en) * | 2016-09-21 | 2018-03-29 | 日本ゼオン株式会社 | Polyvinyl chloride resin composition, polyvinyl chloride resin molding and laminate |
| KR20190043896A (en) * | 2017-10-19 | 2019-04-29 | 삼성전기주식회사 | Photo curable and thermo curable resin composition and cured product thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101266398A (en) * | 2007-03-16 | 2008-09-17 | 北京传世唯信科技有限责任公司 | Composition for back projection screen and preparation method of integral back projection screen |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5203916A (en) * | 1992-04-10 | 1993-04-20 | Kerr-Mcgee Chemical Corporation | Titanium dioxide pigment and method of preparation |
| JP2000181058A (en) | 1998-12-18 | 2000-06-30 | Hitachi Chem Co Ltd | Photosensitive resin composition |
| JP2005258460A (en) * | 1999-09-17 | 2005-09-22 | Hitachi Chem Co Ltd | Photosensitive resin composition, photosensitive element using the same, process for producing resist pattern, and process for producing printed circuit board |
| WO2001073510A1 (en) | 2000-03-29 | 2001-10-04 | Kanagawa University | Photocurable/thermosetting resin composition, photosensitive dry film formed therefrom, and method of forming pattern with the same |
| WO2006004158A1 (en) | 2004-07-07 | 2006-01-12 | Taiyo Ink Mfg. Co., Ltd. | Photocurable/thermosetting resin composition, dry film using same, and cured product thereof |
| JP2007332166A (en) * | 2004-09-29 | 2007-12-27 | Taiyo Ink Mfg Ltd | Photo-curable white ink composition |
| TWI395057B (en) * | 2006-03-29 | 2013-05-01 | Taiyo Holdings Co Ltd | A photohardenable thermosetting resin composition and a cured product thereof, and a printed circuit board |
| JP5066376B2 (en) * | 2007-02-27 | 2012-11-07 | 株式会社タムラ製作所 | Solder resist composition for printed wiring board and printed wiring board |
| JP4994922B2 (en) * | 2007-04-06 | 2012-08-08 | 太陽ホールディングス株式会社 | Solder resist composition and cured product thereof |
| JP5089426B2 (en) * | 2008-02-15 | 2012-12-05 | 電気化学工業株式会社 | Alkali-developable photocurable / thermosetting solder resist composition and metal base circuit board using the same |
| JP2009194222A (en) * | 2008-02-15 | 2009-08-27 | Denki Kagaku Kogyo Kk | White alkali-developable photocurable and thermosetting solder resist composition, and metal-base circuit substrate using the same |
-
2009
- 2009-03-31 JP JP2009085909A patent/JP6054012B2/en active Active
-
2010
- 2010-02-25 KR KR1020100016902A patent/KR100987542B1/en active IP Right Grant
- 2010-03-11 CN CN2010101308295A patent/CN101798432B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101266398A (en) * | 2007-03-16 | 2008-09-17 | 北京传世唯信科技有限责任公司 | Composition for back projection screen and preparation method of integral back projection screen |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101798432A (en) | 2010-08-11 |
| JP2010235798A (en) | 2010-10-21 |
| KR100987542B1 (en) | 2010-10-12 |
| JP6054012B2 (en) | 2016-12-27 |
| KR20100109367A (en) | 2010-10-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101798432B (en) | Curable resin composition and printed circuit board and reflection board using same | |
| TWI408150B (en) | A solder resist composition and a printed circuit board using the same | |
| CN103732001B (en) | Solder mask and printed circuit board (PCB) | |
| JP4538484B2 (en) | Photocurable thermosetting resin composition and printed wiring board using the same | |
| TWI527838B (en) | Solder resist composition and printed circuit board | |
| CN102227681A (en) | Curable resin composition and reflective sheet | |
| TWI484290B (en) | Solder resist composition and printed wiring board | |
| JP5636209B2 (en) | Solder resist composition and printed wiring board | |
| JP2010235799A (en) | Curable resin composition and printed wiring board and reflector using the same | |
| CN102844711A (en) | Solder resist composition and printed-circuit board | |
| JP5663506B2 (en) | Solder resist composition | |
| JP6078595B2 (en) | Curable resin composition and printed wiring board and reflector using the same | |
| JP2011227308A (en) | Solder resist composition and print circuit board | |
| JP2014206752A (en) | Solder resist composition and printed wiring board | |
| JP2011215384A (en) | Solder resist composition and printed-circuit board | |
| JP5618516B2 (en) | Insulating photocurable thermosetting resin composition and printed wiring board | |
| CN106918988B (en) | Curable resin composition, and reflective film and printed wiring board using same | |
| JP5775943B2 (en) | Solder resist layer and printed wiring board |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Taiyo Ink Mfg.Co., Ltd. Assignor: Taiyo Ink Manufacturing Co., Ltd. Contract record no.: 2010990000679 Denomination of invention: Curable resin composition and printed circuit board and reflection board using same License type: Common License Open date: 20100811 Record date: 20100830 |
|
| EC01 | Cancellation of recordation of patent licensing contract |
Assignee: Taiyo Ink Mfg.Co., Ltd. Assignor: Taiyo Ink Manufacturing Co., Ltd. Contract record no.: 2010990000679 Date of cancellation: 20110302 |
|
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Taiyo Ink Mfg.Co., Ltd. Assignor: Taiyo Holding Co., Ltd. Contract record no.: 2011990000116 Denomination of invention: Curable resin composition and printed circuit board and reflection board using same License type: Common License Open date: 20100811 Record date: 20110302 |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |