CN103226291A - An ultraviolet curing transparent resin composition - Google Patents
An ultraviolet curing transparent resin composition Download PDFInfo
- Publication number
- CN103226291A CN103226291A CN2013100282925A CN201310028292A CN103226291A CN 103226291 A CN103226291 A CN 103226291A CN 2013100282925 A CN2013100282925 A CN 2013100282925A CN 201310028292 A CN201310028292 A CN 201310028292A CN 103226291 A CN103226291 A CN 103226291A
- Authority
- CN
- China
- Prior art keywords
- methyl
- resin composition
- transparent resin
- ultra
- violet solidified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Laminated Bodies (AREA)
Abstract
The invention provides an ultraviolet curing transparent resin composition. Plastic components such as polyethylene glycol terephthalate have excellent impermeability, and mechanical characteristics of lossless transparency, and bending resistance. The ultraviolet curing transparent resin composition is characterized by comprising (A) (methyl) acrylic acid series monomer, (B) light polymerization initiator, and (C) polyester resin.
Description
Technical field
The present invention relates to be applicable to flexible distributing board or printed wiring board and so on circuit board solder resist various resists such as (solder resist) etc. the transparent, UV hardening resin composition and be covered this transparent, UV hardening resin composition is solidified and the circuit board of solidfied material.
Background technology
At present, ultra-violet solidified resin composition is used as for example solder resist film of flexible distributing board sometimes.Flexible distributing board is used as the mounting substrate of light-emitting diode (LED) etc. sometimes, and at this moment, the solder resist film that requires to be formed at installed surface has the function that the reflection of light rate from light source is improved.Known for the cured film that improves ultra-violet solidified resin composition reflectivity and cooperate inorganic Chinese white.
On the other hand, according to the purposes of circuit board, the solder resist film that requires sometimes to be formed at installed surface has the transparency.In addition,, its visuognosis degree reduction aspect is considered, required the material of the high electrode protective membrane of the transparency yet from strong not hope for the touch panel of the front that is assembled in display body such as LCD electrode base board.Therefore, patent documentation 1 has proposed a kind of reactive epoxy carbonate and reactive polycarboxylate compound, this compound can provide have the transparency, the light deterioration is few and the solidfied material of the balance excellence of obdurability, thermotolerance, moisture-proof.
But, at present, comprise resin combination with transparency, filming of resin combination is insufficient to the adaptation of the polyethylene terephthalate plastics such as (PET) of the raw material that is used as flexible distributing board or various sheet materials etc., according to circumstances, filming from the problem of strippable substrate of PET system substrate coated in existence.
The prior art document
Patent documentation
Patent documentation 1:WO2006/109572
Summary of the invention
In view of the foregoing, the object of the present invention is to provide mechanical property such as the curved property of a kind of harmless transparency, folding and to the ultra-violet solidified transparent resin composition of the adaptation excellence of plastics member mades such as polyethylene terephthalate.
The solution of the present invention is a kind of ultra-violet solidified transparent resin composition, it is characterized in that, contains (A) (methyl) acrylic monomer, (B) Photoepolymerizationinitiater initiater, (C) vibrin.Unless cooperate the colorant (for example making the Chinese white of transparency forfeiture) that makes transparency forfeiture, the present invention is transparent resin combination, its solidfied material has the transparency.
The solution of the present invention is a kind of ultra-violet solidified transparent resin composition, it is characterized in that, with respect to 100 mass parts above-mentioned (A) (methyl) acrylic resin, contains 1.0 mass parts～50 mass parts above-mentioned (C) vibrin.
The solution of the present invention is a kind of ultra-violet solidified transparent resin composition, it is characterized in that, the number-average molecular weight of above-mentioned (C) vibrin is 5000～30000.
The solution of the present invention is a kind of ultra-violet solidified transparent resin composition, it is characterized in that, the glass temperature of above-mentioned (C) vibrin is 0～100 ℃.
The solution of the present invention is the solidfied material of above-mentioned ultra-violet solidified transparent resin composition.In addition, feature of the present invention is a kind of circuit board, has the tunicle that ultra-violet solidified transparent resin composition curing is obtained.
According to the solution of the present invention, by in ultra-violet solidified transparent resin composition, cooperating vibrin, can access a kind of ultra-violet solidified transparent resin composition, this ultra-violet solidified transparent resin composition can form mechanical property such as the harmless transparency, the curved property of folding and to the cured coating film of plastics systems such as polyethylene terephthalate base material adaptation excellence.In addition, according to the solution of the present invention, can access mechanical property such as the harmless transparency, the curved property of folding and to the solidfied material of plastics systems such as polyethylene terephthalate base material adaptation excellence.In addition, according to the solution of the present invention, can access have the harmless transparency, mechanical property such as the curved property of folding and to the circuit board of the curing tunicle of plastics systems such as polyethylene terephthalate base material adaptation excellence.
Embodiment
Next ultra-violet solidified transparent resin composition of the present invention is described.Ultra-violet solidified transparent resin composition of the present invention contains (A) (methyl) acrylic monomer, (B) Photoepolymerizationinitiater initiater, (C) vibrin, and above-mentioned each composition is as described below.
(A) (methyl) acrylic monomer
(methyl) acrylic monomer is not particularly limited, for example can enumerate acrylic acid, methacrylic acid, the methacrylic acid phenoxy ethyl, dimethacrylate diglycol ester, 2-hydroxyethyl methacrylate, acrylic acid 2-hydroxyl-3-phenoxy group propyl ester, two (trihydroxy methyl) propane tetraacrylate, phenol EO modification (methyl) acrylate, nonyl phenol PO modification (methyl) acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid octyl group ester, ethoxylation (methyl) acrylate, two (methyl) acrylic acid dipropylene glycol ester, 1,6-hexanediol (methyl) acrylate, ethoxylation O-phenylphenol (methyl) acrylate, phenoxy group polyglycol (methyl) acrylate, (methyl) acrylic acid 2-hydroxyl-3-acryloxy propyl ester, (methyl) acrylic acid cyclohexyl ester, (methyl) acrylic acid 2-methoxyl ethyl ester, (methyl) acrylic acid 2-ethoxy ethyl ester, (methyl) acrylic acid benzyl ester, (methyl) acrylic acid phenoxy ethyl, N-acryloxy ethyl hexahydrophthalic phthalimide, phthalic acid monohydroxy ethyl (methyl) acrylate, tristane dihydroxymethyl two (methyl) acrylate, Bisphenol F EO modification two (methyl) acrylate, 9, two [4-(the 2-acryloyl-oxy base oxethyl) phenyl] fluorenes of 9-, cyamelide modification two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, triethylene glycol two (methyl) acrylate, neopentyl two (methyl) acrylate, cyamelide modification three (methyl) acrylate, pentaerythrite three (methyl) acrylate, dihydroxy methylpropane four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc.Above-mentioned substance can use separately, also can use being mixed into more than 2 kinds to exercise.
(B) Photoepolymerizationinitiater initiater
Photoepolymerizationinitiater initiater so long as the general material that uses get final product, be not particularly limited, for example can enumerate the oxime series initiators, benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin n-butylether, the benzoin isobutyl ether, acetophenone, the dimethylamino benzoylformaldoxime, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, the 1-hydroxy cyclohexyl phenylketone, 2-methyl isophthalic acid-(4-(methyl mercapto) phenyl)-2-morpholinyl-propane-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-2-(hydroxyl-2-propyl group) ketone, benzophenone, to phenyl benzophenone, 4,4 '-the diethylamino benzophenone, dichloro benzophenone, 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, 2,4 diethyl thioxanthones, the benzil dimethyl ketal, the acetophenone dimethyl ketal, P-dimethylaminobenzoic acid ethyl ester etc.Above-claimed cpd can use separately, also can use being mixed into more than 2 kinds to exercise.
If to the ultraviolet light of ultra-violet solidified transparent resin composition illumination wavelength 300～400nm of the present invention, then above-mentioned Photoepolymerizationinitiater initiater promotes the photocuring of ultra-violet solidified transparent resin composition.The use level of Photoepolymerizationinitiater initiater can suitably be selected, and for example with respect to 100 mass parts (methyl) acrylic monomer, is preferably 5～20 mass parts, more preferably 6～15 mass parts.
(C) vibrin
Vibrin is to make the reaction of dicarboxylic acid and diol compound and the material that obtains.Think by cooperating vibrin, because the ester group of vibrin has the compatibility with plastics, so the adaptation of plastic basis material is improved.Vibrin is not particularly limited, and all can use.
Therefore, above-mentioned dicarboxylic acid is not particularly limited, and for example can use aliphatics, alicyclic or aromatic dicarboxylic acid.In addition, the carbon number of dicarboxylic acid is not particularly limited, and for example can use carbon number is 2～20 dicarboxylic acid.As above-mentioned dicarboxylic acid, for example can enumerate succinic acid, hexane diacid, azelaic acid, decanedioic acid, dodecanedioic acid, maleic acid, fumaric acid, glutaric acid, chlordene heptane dicarboxylic acid, cyclohexane dicarboxylic acid, phthalic acid, hexahydro-phthalic acid, m-phthalic acid, 4-sulfoisophthalic acid, 5-sulfoisophthalic acid, 5-sulfoisophthalic acid sodium salt, terephthalic acid (TPA), tetrahydrophthalic acid, tetrachlorophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid etc.Above-claimed cpd can use separately, also can use being mixed into more than 2 kinds to exercise.
In addition, above-mentioned diol compound is not particularly limited, and for example can enumerate ethylene glycol, propylene glycol, trimethylene, 1,4-butylene glycol, 1,3 butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 3-methyl isophthalic acid, 5-pentanediol, 2,2-dimethyl-1, ammediol, neopentyl glycol, 1,6-hexanediol, 2,2-diethyl-1, ammediol, 3,3-dihydroxymethyl heptane, 2-ethyl-2-butyl-1, ammediol, 1,12-dodecanediol, 1, C such as 18-octacosanol
2-C
22Alkanediol, 2-butene-1,4-glycol, 2,6-dimethyl-1-octene-3, aliphatic diols such as alkenediols such as 8-glycol; 1, alicyclic diols such as 4-cyclohexane diol, 1,4 cyclohexane dimethanol etc.Above-mentioned substance can use separately, also can use being mixed into more than 2 kinds to exercise.
The number-average molecular weight of vibrin is not particularly limited, and considers that from the easiness aspect that viscosity is adjusted its lower limit is preferably 5000, considers that from intermiscibility and coating aspect its lower limit is preferably 7500 especially.On the other hand, consider that from the dissolubility aspect its higher limit is preferably 30000, consider that from intermiscibility and coating aspect its higher limit is preferably 25000 especially.
The glass temperature of vibrin is not particularly limited, and considers that from the operability aspect its lower limit is preferably 0 ℃, consider from the suitable easiness aspect of cured coating film, its lower limit is preferably 30 ℃, considers from giving cured coating film flexibility aspect, is preferably 50 ℃ especially.On the other hand, consider that from the suitable easiness aspect of operability and cured coating film its higher limit is preferably 100 ℃, consider that from giving cured coating film flexibility aspect its higher limit is preferably 80 ℃ especially.
The use level of vibrin is not particularly limited, and with respect to 100 mass parts (methyl) acrylic monomer, from positively giving the adaptation aspect of plastic basis material is considered that its lower limit is preferably 1.0 mass parts, is preferably 5.0 mass parts especially.On the other hand, with respect to 100 mass parts (methyl) acrylic monomer, consider that from the coating aspect higher limit of the use level of vibrin is preferably 50 mass parts, consider that from defoaming and levelability aspect the higher limit of the use level of vibrin is preferably 30 mass parts especially.
On market in the product sold, for example can enumerate " Elitel UE-3200G " that You Niji can (strain) as vibrin, " Elitel UE-3250 ", " Elitel UE-9100 ", " Elitel UE-3940 ", " Elitel UE-9885 ", " Elitel UE-3220 ", " Elitel UE-3223 ", " Elitel UE-3230 ", " Elitel UE-3231 ", " Elitel UE-3400 ", " Elitel UE-3410 ", " Elitel UE-3500 ", " Elitel UE-3510 ", " Elitel UE-3200 ", " Elitel UE-9200 ", " Elitel UE-3201 ", " Elitel UE-3203 ", " Elitel UE-3600 ", " Elitel UE-9600 ", " Elitel UE-3660 ", " Elitel UE-3690 ", " Elitel UE-9800 ", " Elitel UE-9900 ", " Elitel UE-3210 ", " Elitel UE-3215 ", " Elitel UE-3216 ", " Elitel UE-3620 ", " Elitel UE-3240 ", " Elitel UE-3250 ", " Elitel UE-3320 ", " Elitel UE-9820 ", " Elitel UE-3350 ", " Elitel UE-3370 ", " Elitel UE-3380 ", " Elitel UE-3300 ", " Elitel UE-3980 ", " Vylon103 " of Japan's weaving (strain), " Vylon200 ", " Vylon220 ", " Vylon226 ", " Vylon237 ", " Vylon240 ", " Vylon245 ", " Vylon270 ", " Vylon280 ", " Vylon290 ", " Vylon296 ", " Vylon300 ", " Vylon500 ", " Vylon550 ", " Vylon560 ", " Vylon600 ", " Vylon630 ", " Vylon637 ", " Vylon650 ", " Vylon660 ", " Vylon670 ", " Vylon802 ", " Vylon822 ", " Vylon885 ", " Vylon GK130 ", " Vylon GK140 ", " Vylon GK150 ", " VylonGK250 ", " Vylon GK330 ", " Vylon GK360 ", " Vylon GK570 ", " VylonGK590 ", " Vylon GK640 ", " Vylon GK680 ", " Vylon GK780 ", " VylonGK810 ", " Vylon GK880 ", " Vylon GK890 ", " Vylon BX1001 ", Hitachi changes into " Espel9940A " of industry (strain), " Espel9940B ", " Espel9940C-37 ", " Espel9940D ", " Espel9940E-37 ", " Espel9940Z-37 " etc.
In the ultra-violet solidified transparent resin composition of the present invention,, can also suitably cooperate (D) phosphorus compound, (E) (methyl) acrylated epoxy resin, (F) (methyl) acrylated urethane resin except above-mentioned each composition.
(D) phosphorus compound
If phosphorus compound is coupled in the ultra-violet solidified transparent resin composition of the present invention, then can gives flame retardancy.In the phosphorus compound, for example can enumerate three (chloroethyl) phosphate, three (2,3-two chloropropyls) phosphate, three (2-chloropropyl) phosphate, three (2, the 3-dibromopropyl) phosphate, three (bromine chloropropyl) phosphate, 2,3-dibromopropyl-2, Halogens such as 3-dichloro propyl phosphate, three (tribromo phenyl) phosphate, three (dibromo phenyl) phosphate, three (tribromo neopentyl) phosphate are phosphate; Non-halogen such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate are aliphatic phosphate ester; The triallyl phosphine; Triphenyl phosphate, tricresyl phosphate base diphenyl, di(2-ethylhexyl)phosphate tolyl phenylester, lindol, tricresyl phosphate (xylyl) ester, di(2-ethylhexyl)phosphate tolyl diphenyl, tricresyl phosphate (isopropyl phenyl) ester, p isopropylbenzoic acid base phenyl diphenyl, di(2-ethylhexyl)phosphate isopropyl phenyl phenylester, tricresyl phosphate (trimethylphenyl) ester, tricresyl phosphate (tert-butyl-phenyl) ester, phosphoric acid hydroxy phenyl diphenyl, octyl diphenyl phosphate, 3-glycidoxy propylidene diphenyl phosphine oxide, 3-glycidoxy diphenyl phosphine oxide, the diphenylacetylene phosphine oxide, 2-(9, the 10-dihydro-9-oxy is assorted-10-oxide-10-phospho hetero phenanthrene-10-yl) methylsuccinic acid is two-and (2-hydroxyethyl)-non-halogen such as ester polymer are aromatic phosphoric ester; The slaine of phosphinic acids such as three (diethyl) phosphinic acids aluminium, trimethyl ethyl phosphinic acids aluminium, three (diphenyl) phosphinic acids aluminium, two (diethyl) phosphinic acids zinc, two Methylethyl phosphinic acids zinc, two (diphenyl) phosphinic acids zinc, two (diethyl) phosphinic acids titanium, four (diethyl) phosphinic acids titanium, two Methylethyl phosphinic acids titanium, tetramethyl ethyl phosphinic acids titanium, two (diphenyl) phosphinic acids titanium, four (diphenyl) phosphinic acids titanium etc.
Wherein, suppress the carrying capacity of environment aspect considers from the generation that prevents bioxin, the phosphate that preferred non-halogen is, the slaine of phosphinic acids, from just not only effectively bringing into play flame retardancy, also effectively performance soldering thermotolerance, other metal solder thermotolerance aspects considerations, the slaine of preferred especially phosphinic acids on a small quantity.
When using phosphate as phosphorus compound, the lower limit of the use level of phosphorus compound is 5 mass parts with respect to 100 mass parts (methyl) acrylic monomer, consider from guaranteeing sufficient flame retardancy aspect, be preferably 10 mass parts, its higher limit is 50 mass parts with respect to 100 mass parts (methyl) acrylic monomer, from positively suppressing to solidify the physical strength reduction aspect consideration of tunicle, be preferably 40 mass parts.On the other hand, when using the slaine of phosphinic acids as the organic compound of phosphorus element-containing, the lower limit of its use level is 3 mass parts with respect to 100 mass parts (methyl) acrylic monomer, consider from guaranteeing sufficient flame retardancy aspect, be preferably 4 mass parts, in addition, higher limit is 25 mass parts with respect to 100 mass parts (methyl) acrylic monomer, from positively suppressing to solidify the physical strength reduction aspect consideration of tunicle, be preferably 20 mass parts.
(E) (methyl) acrylated epoxy resin
(methyl) acrylated epoxy resin is partial esterification epoxy (methyl) acrylate that (methyl) acrylic acid is obtained with have the epoxy resin generation esterification of 2 above epoxy radicals in 1 molecule.(methyl) acrylated epoxy resin has (methyl) acrylic that can carry out free radical polymerization by the ultraviolet ray irradiation.Therefore, if in ultra-violet solidified transparent resin composition of the present invention, cooperate (methyl) acrylated epoxy resin, then can make (methyl) acrylated epoxy resin that cross-linking reaction take place each other by the ultraviolet ray irradiation, the cross-linking density of solidfied material improves, curable further improves, and gives the solidfied material folding curved property.
(methyl) acrylated epoxy resin is not particularly limited, preferably making the epoxy radicals with respect to epoxy resin is (methyl) acrylated epoxy resin that (methyl) acrylic acid of 50～100% equivalents and the epoxy resin generation esterification that has at least 2 above epoxy radicals in 1 molecule get, consider from the photonasty aspect, especially preferably make 80～100% equivalents (methyl) acrylic acid generation esterification and (methyl) acrylated epoxy resin.
Epoxy resin as the synthesis material of (methyl) acrylated epoxy resin, for example can enumerate bisphenol A type epoxy resin (bisphenol A-type liquid-state epoxy resin, bisphenol A-type modification flexibility epoxy resin, nuclear hydrogenated bisphenol A type liquid-state epoxy resin etc.), novolac-type epoxy resin (phenol-novolac-type epoxy resin, orthoresol-novolac-type epoxy resin, p-t-butyl phenol-novolac-type etc.), the Bisphenol F type or the bisphenol-s epoxy resin that make the reaction of chloropropylene oxide and Bisphenol F or bisphenol S and get, and then has a cyclohexene oxide base, the tristane oxide-base, the alicyclic epoxy resin of cyclopentene oxygen base etc., 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, diamantane type epoxy resin.Wherein, consider preferred bisphenol A type epoxy resin from the curved property aspect of folding.These compounds can use separately, also can use being mixed into more than 2 kinds to exercise.
The use level of (methyl) acrylated epoxy resin is thought of as 1～75 mass parts with respect to 100 mass parts (methyl) acrylic monomer from giving the curved property aspect of sufficient curable and folding, is preferably 3～50 mass parts.
(F) (methyl) acrylated urethane resin
(methyl) acrylated urethane resin so long as make (methyl) acrylic acid and urethane resin reaction and polyurethane (methyl) acrylate get final product, be not limited to specific compound.If (methyl) acrylated urethane resin is comprised in the ultra-violet solidified transparent resin composition, then can form the cured coating film of the curved property excellence of ductility and folding, so be effective to for example circuit board, particularly flexible distributing board.
Urethane resin be make the polyol compound reaction that has 2 above hydroxyls in the compound that has 2 above isocyanate group in 1 molecule and 1 molecule and.
The compound that has 2 above isocyanate group in 1 molecule is not particularly limited, for example can enumerate 1, hexamethylene-diisocyanate (HDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), trimethyl hexamethylene diisocyanate, hexamethyl amine diisocyanate, di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), toluene diisocyanate, 1,2-diphenylethane diisocyanate, 1,3-diphenyl propane diisocyanate, methyl diphenylene diisocyanate, diisocyanate such as dicyclohexyl methylene diisocyanate.Above-claimed cpd can use separately, also can use being mixed into more than 2 kinds to exercise.
The polyol compound that has 2 above hydroxyls in 1 molecule is not particularly limited, for example can enumerate ethylene glycol, propylene glycol, trimethylene, 1, the 4-butylene glycol, 1,3 butylene glycol, 1, the 2-butylene glycol, 1, the 5-pentanediol, the 3-methyl isophthalic acid, the 5-pentanediol, 2,2-dimethyl-1, ammediol, neopentyl glycol, 1, the 6-hexanediol, 2,2-diethyl-1, ammediol, 3,3-dihydroxymethyl heptane, 2-ethyl-2-butyl-1, ammediol, 1, the 12-dodecanediol, 1, C2-C22 alkanediols such as 18-octacosanol, the 2-butene-1, the 4-glycol, 2,6-dimethyl-1-octene-3, aliphatic diols such as alkenediols such as 8-glycol; 1, alicyclic diols such as 4-cyclohexane diol, 1,4 cyclohexane dimethanol; Glycerine, 2-methyl-2-hydroxymethyl-1, ammediol, 2,4-dihydroxy-3-hydroxymethyl pentane, 1,2,6-hexanetriol, trimethylolethane, trimethylolpropane, 2-methyl-2-hydroxymethyl-1, ammediol, 2,4-dihydroxy-3-(hydroxymethyl) pentane, 2, aliphatics triols such as two (the hydroxymethyl)-3-butanols of 2-; Tetramethylol methane, pentaerythrite, dipentaerythritol, xylitol etc. have the polyvalent alcohol of 4 above hydroxyls etc.Above-claimed cpd can use separately, also can use being mixed into more than 2 kinds to exercise.
As (methyl) acrylated urethane resin product sold on market, for example can enumerate " the purple light UV-1400B " of Japanese synthetic chemistry (strain), " purple light UV-1700B ", " purple light UV-6300B ", " purple light UV-7510B ", " purple light UV-7600B ", " purple light UV-7605B ", " purple light UV-7610B ", " purple light UV-7620EA ", " purple light UV-7630B " and " purple light UV-7640B ", on the root " the Art Resin UN-9000H " of industry (strain), " Art Resin UN-3320HA ", " Art Resin UN-3320HC ", " Art Resin UN-3320HS " and " Art Resin UN-901T ", " the NK Oligo U-4HA " of Xin Zhong village chemical industry (strain), " NK Oligo U-6HA ", " NK Oligo U-6LPA ", " NK Oligo U-15HA ", " NK Oligo UA-32P ", " NK Oligo U-324A " and " NK Oligo U-6H ", " EBECRYL1204 " of DIACELCYTEC (strain), " EBECRYL1205 ", " EBECRYL215 ", " EBECRYL230 ", " EBECRYL244 ", " EBECRYL245 ", " EBECRYL264 ", " EBECRYL265 ", " EBECRYL1280 ", " EBECRYL285 ", " EBECRYL8200 ", " EBECRYL8405 ", " EBECRYL8411 ", " EBECRYL8804 ", " EBECRYL9270 ", " KRM7735 ", " KRM8296 ", " EBECRYL1290 ", " EBECRYL1290K ", " EBECRYL5129 ", " EBECRYL210 ", " EBECRYL220 ", " EBECRYL284 ", " EBECRYL8210 ", " EBECRYL8402 " and " EBECRYL9260 ", " UX-2201 " of Japan's chemical drug (strain), " UX-2301 ", " UX-3204 ", " UX-3301 ", " UX-4101 ", " UX-0937 ", " UX-5000 ", " UX-5001 ", " UX-5002 ", " BEAMSET575 " of waste river chemical industry (strain), " M-313 " in East Asia synthetic (strain), " M-315 " and " M-1200 ", " AH-600 " of common prosperity society chemistry (strain) etc.
The skeleton of (methyl) acrylated urethane resin is not particularly limited, because the possibility that (methyl) acrylated urethane resin that (methyl) acrylic-functional number is many has cure shrinkage, ductility to reduce is so (methyl) acrylic-functional number in 1 molecule is preferably 2～4.In addition, if the value of weight-average molecular weight is little, take place wiring diagram film adhering to easily when then exposing to substrate, be difficult to obtain cured coating film as target, so its lower limit is preferably 1500, if weight-average molecular weight is big, then because there is the tendency of the curved property reduction of folding, so its higher limit is preferably 3000.
The use level of (methyl) acrylated urethane resin is 1～40 mass parts with respect to 100 mass parts (methyl) acrylic monomer, considers from the excellent aspect of balance of high ductibility and the curved property of folding, is preferably 2～25 mass parts.Should illustrate,, (methyl) acrylated urethane resin together can be cooperated with above-mentioned (methyl) acrylated epoxy resin in order to obtain the cured coating film of the curved property excellence of folding.
In the ultra-violet solidified transparent resin composition of the present invention, except above-mentioned each composition, can further contain various adding ingredients, for example various adjuvants, solvent etc. as required.In addition, impaired in the ultra-violet solidified transparent resin composition of the present invention in order to prevent the transparency, do not cooperate colorant, but when being colored as desirable color, can suitably cooperate colorants such as coloring pigment yet.
In the various adjuvants, can enumerate defoamers such as ethylene-based polymer, acrylate copolymer, for the levelling agent of the potpourri of polyether-modified dimethyl silicone polymer and polyethers etc.
Solvent uses for viscosity, the drying property of regulating ultra-violet solidified transparent resin composition.As solvent, for example can enumerate ketones such as methyl ethyl ketone, cyclohexanone, aromatic hydrocarbons such as toluene, dimethylbenzene, alcohols such as methyl alcohol, isopropyl alcohol, cyclohexanol, ester ring type such as cyclohexane, methylcyclohexane hydro carbons, oil such as sherwood oil, naphtha series solvent class, cellosolve such as cellosolve, butyl cellosolve class, carbitol such as carbitol, butyl carbitol class, acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetic acid esters, diethylene glycol monoethyl ether acetate, acetate of butyl carbitol etc.Use level when using solvent is preferably 1～500 weight portion with respect to 100 weight portions (methyl) acrylic monomer.
Colorant just can be not particularly limited use so long as not the material that destroys the transparency, when being colored as white, black, blueness, yellow etc., can cooperate white color agents, black colorant, blue colorant, yellow colorants etc. as required.
The manufacture method of the ultra-violet solidified transparent resin composition of the invention described above is not limited to specific method, after other compositions of for example can be with mentioned component (A)～(C) and using as required cooperate to scale, in room temperature by kneading device such as triple-roller mill, bowl mill, sand mill or stirring apparatuss such as high-speed mixer (Super mixer), planetary stirring machine carry out mixing or mixing is made.In addition, above-mentioned mixing or mix before, can carry out pre-mixing or premixed as required.
Next the coating process of the ultra-violet solidified transparent resin composition of the invention described above is described.Herein, to form the method for tunicle at coating ultra-violet solidified transparent resin composition of the present invention on the flexible base, board, more specifically to have the etching Copper Foil and coating ultra-violet solidified the transparent resin composition of the present invention and method that forms the solder resist film is that example describes on the flexible distributing board of the circuit pattern that forms.Adopt methods such as stencil printing, spraying process, on the flexible distributing board of the circuit pattern that forms having the etching Copper Foil, be coated with the ultra-violet solidified transparent resin composition of making as described above by desirable thickness.
Then, shine from the ultra-violet solidified transparent resin composition that is coated with, can on flexible distributing board, form cured coating film as target by making ultraviolet ray.
Embodiment
Next embodiments of the invention are described, but only otherwise exceed purport of the present invention, the present invention is not limited to these examples.
Embodiment 1～23, comparative example 1～4
Each composition shown in the following table 1 is cooperated in the cooperation ratio shown in the following table 1, use triple-roller mill it to be mixed and disperse, the ultra-violet solidified transparent resin composition that uses in modulation embodiment 1～23, the comparative example 1～4 in room temperature.Then, the ultra-violet solidified transparent resin composition of modulation is coated with as described below and makes test film.The numeric representation mass parts of the cooperation ratio in the table 1 should be described.
[table 1]
Should illustrate that the details of each composition is as described below in the table 1.
(A) (methyl) acrylic monomer
LIGHT ESTER PO: common prosperity society chemistry (strain) system, methacrylic acid phenoxy ethyl.
LIGHT ESTER 2EG: common prosperity society chemistry (strain) system, diethylene glycol dimethacrylate.
GE-610: Mitsubishi's gas chemistry (strain) system, 2-hydroxyethyl methacrylate.
M-5700: East Asia synthetic chemistry (strain) system, acrylic acid 2-hydroxyl-3-phenoxy group propyl ester.
EBECRYL767:DIACELCYTEC (strain) system, linear acrylate ester.
(B) Photoepolymerizationinitiater initiater
Irgacure184:CIBASpecialityChemicals (strain) system, 1-hydroxyl-cyclohexyl-phenyl-ketone.
Irgacure1173:CIBASpecialityChemicals (strain) system, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone.
Irgacure2529:CIBASpecialityChemicals (strain) system, 1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone.
(C) vibrin
Elitel UE-3690: You Niji can (strain) make the saturated copolymer polyester resin of thermoplasticity, 90 ℃ of glass temperatures, number-average molecular weight 14000.
Vylon240: Japan's weaving (strain) system, amorphous vibrin, 60 ℃ of glass temperatures, number-average molecular weight 15000.
Vylon GK640: Japan's weaving (strain) system, amorphous vibrin, 79 ℃ of glass temperatures, number-average molecular weight 18000.
(D) phosphorus compound
Diphenylacetylene phosphine oxide: sheet mountain chemical industry (strain) system.
ME-P8: three light (strain) systems, 2-(9, the 10-dihydro-9-oxy is assorted-10-oxide-10-phospho hetero phenanthrene-10-yl) methylsuccinic acid is two-(2-hydroxyethyl)-ester polymer.
Triallyl phosphine: Japan Science (strain) system.
(E) (methyl) acrylated epoxy resin
EBECRYL3708:DIACELCYTEC (strain) system, the potpourri of epoxy acrylate and acrylic acid 2-hydroxy methacrylate.
Miramer PE110:MIWON system, the phenyl epoxy acrylate.
Miramer PE250:MIWON system, the bisphenol type epoxy dimethylacrylate.
(F) (methyl) acrylated urethane resin
EBECRYL8405:DIACELCYTEC (strain) system, urethane acrylate.
M-1200: East Asia synthetic (strain) system, urethane acrylate.
AH-600: common prosperity society chemistry (strain) system, phenylglycidyl ether acrylate hexamethylene diisocyanate polyurethane prepolymer.
Adjuvant
UVX-189: this chemistry of nanmu (strain) system, ethylene-based polymer.
POLYFLOW No.90: common prosperity society chemistry (strain) system, acrylate copolymer.
BYK-361N:BYKJAPAN (strain) system, acrylate copolymer.
BYK-307:BYKJAPAN (strain) system, the potpourri of polyether-modified dimethyl silicone polymer and polyethers.
Coloring pigment
Lionol Blue FG-7351: Japan INK (strain) system, phthalocyanine compound.
Chromophtal Yellow AGR:CIBASpecialityChemicals (strain) system, anthraquinone compounds.
The test film production process
Ungrease treatment is carried out with isopropyl alcohol in the surface of polyethylene terephthalate film (PET film) (Supreme Being people DuPont society system, thickness 25 μ m), then, the ultra-violet solidified transparent resin composition of modulating as described above in the surface coated of having carried out ungrease treatment by stencil printing.Then, (300～400nm) are exposed to 1000mJ/cm to carry out ultraviolet ray with exposure device (Eyegraphic society system, UB093-5AM)
2The thickness of cured coating film is 15～20 μ m.
Estimate
(1) mist degree (mist value) (%)
Replace the PET film, use to be coated with on the surface of quartz glass substrate (50mm * 50mm, thickness 1mm) with the same method of above-mentioned test film production process and to form cured coating film, make test film.Based on JIS-K-7105, JIS-K-7136, use HITECH society of Hitachi system U-3310 spectrophotometer that this test film is measured mist degree.
(2) PET adaptation
For the test film of in above-mentioned test film production process, making, based on JIS-K5600-5-6, the gridiron pattern of 100 (10 * 10) 1mm is set on test film, use the Peeling test (disbonded test) of viscose paper, the tessellated state of peeling off of visual observations is estimated by following benchmark.
In zero: 100, do not observe more than 90 and peel off.
△: in 100,50 90 of above less thaies are not observed and are peeled off.
*: in 100,50 of less thaies are not observed and are peeled off.
(3) the curved property of folding
For the test film of in above-mentioned test film production process, making, repeatedly carry out 180 ° of bendings repeatedly with the lock seam machine, range estimation and film with the transparent cured of * 200 observation by light microscope this moment in the crack situation occurred, the number of times in crack does not take place in mensuration.
(4) insulation resistance (Ω)
Replace the PET film, by and the same method of above-mentioned test film production process go up coating at comb shape test pattern (100 μ m between live width 100 μ m, line) and form cured coating film, make test film.This test film is applied direct current 50V in the atmosphere of 85 ℃ of temperature, humidity 85%, place after 1000 hours, this test film is fetched into outside the groove, measure insulating resistance value.
Evaluation result is shown in table 2.
[table 2]
Shown in the evaluation result of each embodiment of above-mentioned table 2,, then do not destroy the curved property of folding, mist degree and be yet the transparency and the PET adaptation improves if in (methyl) acrylic monomer, cooperate vibrin.In addition, if observe cooperation (methyl) acrylated epoxy resin by embodiment 12～14,18, then the tendency that property further improves is bent in folding, if observe cooperation (methyl) acrylated urethane resin by embodiment 15～17,19～23, then the further tendency of raising of property is bent in folding.In addition, among the embodiment, no matter whether cooperate phosphorus compound, (methyl) acrylated epoxy resin, (methyl) acrylated urethane resin, insulating resistance value is all not destroyed, and insulativity is also good.
On the other hand, by the result of comparative example as can be known,, then can't obtain PET adaptation to cured coating film if in (methyl) acrylic monomer, do not cooperate vibrin.
Utilizability on the industry
The solidfied material of PET adaptation excellence because ultra-violet solidified transparent resin composition of the present invention can access mechanical property such as the curved property of harmless folding, the transparency; so for example at the insulation tunicle of circuit board, solder resist film, touch panel with fields such as diaphragm, value height.
Claims (6)
1. a ultra-violet solidified transparent resin composition is characterized in that, contains (A) (methyl) acrylic monomer, (B) Photoepolymerizationinitiater initiater, (C) vibrin.
2. ultra-violet solidified transparent resin composition as claimed in claim 1 is characterized in that, with respect to 100 mass parts described (A) (methyl) acrylic monomer, contains 1.0 mass parts～50 mass parts described (C) vibrin.
3. ultra-violet solidified transparent resin composition as claimed in claim 1 or 2 is characterized in that, the number-average molecular weight of described (C) vibrin is 5000～30000.
4. as each the described ultra-violet solidified transparent resin composition in the claim 1～3, it is characterized in that the glass temperature of described (C) vibrin is 0～100 ℃.
5. the solidfied material of a ultra-violet solidified transparent resin composition is the solidfied material of each the described ultra-violet solidified transparent resin composition in the claim 1～4.
6. a circuit board has the tunicle that each the described ultra-violet solidified transparent resin composition curing in the claim 1～4 is got.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012015499A JP5897915B2 (en) | 2012-01-27 | 2012-01-27 | UV curable transparent resin composition |
| JP2012-015499 | 2012-01-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103226291A true CN103226291A (en) | 2013-07-31 |
Family
ID=48836787
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013100282925A Pending CN103226291A (en) | 2012-01-27 | 2013-01-25 | An ultraviolet curing transparent resin composition |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5897915B2 (en) |
| CN (1) | CN103226291A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107179652A (en) * | 2016-03-11 | 2017-09-19 | 奇美实业股份有限公司 | Positive photosensitive polysiloxane composition and application thereof |
| CN107652875A (en) * | 2017-10-24 | 2018-02-02 | 沈阳顺风新材料有限公司 | A kind of UV fireproof coatings and preparation method thereof |
| CN111269640A (en) * | 2020-04-15 | 2020-06-12 | 山东和秀新材料有限公司 | UV (ultraviolet) curing coating for wood board and preparation method thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101491974B1 (en) | 2013-12-31 | 2015-02-10 | 도레이케미칼 주식회사 | Resin composition of ultraviolet stiffening type for plastic surface treatment and plastic surface treatment method |
| JP2016022411A (en) * | 2014-07-17 | 2016-02-08 | しげる工業株式会社 | Manufacturing method for coating on coated material of synthetic resin and decorative article with coating-applied coated material of synthetic resin |
| JP2018090654A (en) * | 2016-11-30 | 2018-06-14 | 東洋インキＳｃホールディングス株式会社 | Light transmissive resin composition |
| WO2017170795A1 (en) * | 2016-03-30 | 2017-10-05 | 東洋インキＳｃホールディングス株式会社 | Resin composition and electronic element |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0919873A1 (en) * | 1997-11-28 | 1999-06-02 | Hitachi Chemical Co., Ltd. | Photo curable resin composition and photosensitive element |
| JP2003292857A (en) * | 2002-04-08 | 2003-10-15 | Toyobo Co Ltd | Actinic energy ray-reactive electrical insulation ink and laminate using the same |
| CN1892427A (en) * | 2005-07-06 | 2007-01-10 | 株式会社有泽制作所 | Photosensitive thermosetting resin composition, and photosensitive cover lay and flexible printed wiring board using the composition |
| CN101675089A (en) * | 2007-04-27 | 2010-03-17 | 日本化药株式会社 | (meth)acrylate compound, resin composition containing the same, cured product of the resin composition, and energy ray-curable resin composition for optical lens sheet and cured product thereof |
| JP2010169809A (en) * | 2009-01-21 | 2010-08-05 | Hitachi Chem Co Ltd | Photosensitive resin composition, and photosensitive film and photosensitive permanent resist using the same |
| JP2011148962A (en) * | 2009-12-21 | 2011-08-04 | Toyobo Co Ltd | Active energy ray-reactive and curable adhesive composition, label and bottle |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5713444A (en) * | 1980-06-27 | 1982-01-23 | Tamura Kaken Kk | Photosensitive composition |
| JP3390099B2 (en) * | 1994-12-14 | 2003-03-24 | 三洋化成工業株式会社 | UV curable resin composition for Fresnel lens and transmission screen |
| JP2002105340A (en) * | 2000-09-29 | 2002-04-10 | Toyobo Co Ltd | Active energy ray-curable liquid resin composition |
| JP2004010855A (en) * | 2002-06-11 | 2004-01-15 | Nippon Paint Co Ltd | Active energy ray-curable impregnant composition and sheet impregnated therewith |
| JP4882300B2 (en) * | 2004-07-29 | 2012-02-22 | Ｄｉｃ株式会社 | Active energy ray-curable resin composition for shaping, shaping sheet and shaped article |
| JP5567290B2 (en) * | 2009-05-12 | 2014-08-06 | 太陽ホールディングス株式会社 | Photosensitive resin composition, dry film and cured product thereof, and printed wiring board using them |
-
2012
- 2012-01-27 JP JP2012015499A patent/JP5897915B2/en active Active
-
2013
- 2013-01-25 CN CN2013100282925A patent/CN103226291A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0919873A1 (en) * | 1997-11-28 | 1999-06-02 | Hitachi Chemical Co., Ltd. | Photo curable resin composition and photosensitive element |
| JP2003292857A (en) * | 2002-04-08 | 2003-10-15 | Toyobo Co Ltd | Actinic energy ray-reactive electrical insulation ink and laminate using the same |
| CN1892427A (en) * | 2005-07-06 | 2007-01-10 | 株式会社有泽制作所 | Photosensitive thermosetting resin composition, and photosensitive cover lay and flexible printed wiring board using the composition |
| CN101675089A (en) * | 2007-04-27 | 2010-03-17 | 日本化药株式会社 | (meth)acrylate compound, resin composition containing the same, cured product of the resin composition, and energy ray-curable resin composition for optical lens sheet and cured product thereof |
| JP2010169809A (en) * | 2009-01-21 | 2010-08-05 | Hitachi Chem Co Ltd | Photosensitive resin composition, and photosensitive film and photosensitive permanent resist using the same |
| JP2011148962A (en) * | 2009-12-21 | 2011-08-04 | Toyobo Co Ltd | Active energy ray-reactive and curable adhesive composition, label and bottle |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107179652A (en) * | 2016-03-11 | 2017-09-19 | 奇美实业股份有限公司 | Positive photosensitive polysiloxane composition and application thereof |
| CN107179652B (en) * | 2016-03-11 | 2022-02-08 | 奇美实业股份有限公司 | Positive photosensitive polysiloxane composition and application thereof |
| CN107652875A (en) * | 2017-10-24 | 2018-02-02 | 沈阳顺风新材料有限公司 | A kind of UV fireproof coatings and preparation method thereof |
| CN111269640A (en) * | 2020-04-15 | 2020-06-12 | 山东和秀新材料有限公司 | UV (ultraviolet) curing coating for wood board and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5897915B2 (en) | 2016-04-06 |
| JP2013155246A (en) | 2013-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103226291A (en) | An ultraviolet curing transparent resin composition | |
| CN101675089B (en) | (meth)acrylate compound, resin composition containing the same, cured product of the resin composition, and energy ray-curable resin composition for optical lens sheet and cured product thereof | |
| JP5996894B2 (en) | Transparent resin composition for insulating film formation | |
| CN102520585A (en) | Alkali soluble transparent resin composition | |
| CN102520582A (en) | White curable resin composition | |
| CN103257526A (en) | UV curing transparent resin composition | |
| CN111886300A (en) | Curable composition for inkjet printing, cured product thereof, and electronic component having cured product | |
| CN103869617A (en) | Active radiation hardenable resin composition, and spacer and/or color filter protective layer for display element using the same | |
| CN108594600A (en) | Active energy ray curable adhensive compositions and use its laminated body | |
| KR20200139632A (en) | Curable resin composition, dry film, cured product and printed wiring board | |
| JP2010006905A (en) | Polyester resin, photocurable-heat curable resin composition, photocurable-heat curable layer, ink, adhesive and printed circuit board | |
| JP2015129074A (en) | Composition for reinforcing glass end face, glass plate material, and method of producing glass plate material | |
| KR102424000B1 (en) | Polyurethane compound and active energy ray curable resin composition containing same, and use thereof | |
| JP2010006949A (en) | Photocurable and thermosetting resin composition, photocurable and thermosetting layer, ink, adhesive, and printed circuit board | |
| CN110297392A (en) | Photosensitive polymer combination | |
| KR102480646B1 (en) | Active energy ray curable resin composition with white color and cured product thereof, and printed wiring board | |
| JP3489911B2 (en) | Ink composition | |
| JP4994712B2 (en) | Peripheral sealant for etching glass substrate and cured product thereof | |
| CN106604947A (en) | Reactive polyester compound and active energy ray-curable resin composition using same | |
| JP6918163B2 (en) | Photosensitive resin composition | |
| JP2001151848A (en) | Method for producing active energy ray-curable urethane composition | |
| CN111650811A (en) | White photosensitive film and preparation method and application thereof | |
| JP2008231149A (en) | Composition for touch feeling-coating | |
| KR20230107571A (en) | Curable resin composition and dry film | |
| JP2021050292A (en) | Composition that gives cured article having elasticity and ultraviolet laser processability, and thermosetting sheet of the composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130731 |