JP5670533B1 - Thermosetting resin composition, cured product thereof, and display member using the same - Google Patents
Thermosetting resin composition, cured product thereof, and display member using the same Download PDFInfo
- Publication number
- JP5670533B1 JP5670533B1 JP2013215600A JP2013215600A JP5670533B1 JP 5670533 B1 JP5670533 B1 JP 5670533B1 JP 2013215600 A JP2013215600 A JP 2013215600A JP 2013215600 A JP2013215600 A JP 2013215600A JP 5670533 B1 JP5670533 B1 JP 5670533B1
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- JP
- Japan
- Prior art keywords
- pigment
- resin composition
- manufactured
- thermosetting resin
- epoxy
- 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.)
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- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 38
- 239000011342 resin composition Substances 0.000 title claims abstract description 35
- 229920005989 resin Polymers 0.000 claims abstract description 41
- 239000003086 colorant Substances 0.000 claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 40
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 35
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003822 epoxy resin Substances 0.000 claims abstract description 21
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 21
- 229910052623 talc Inorganic materials 0.000 claims abstract description 13
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- 239000000454 talc Substances 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims description 43
- 239000011521 glass Substances 0.000 claims description 34
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 13
- 238000005034 decoration Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 abstract description 23
- 238000009413 insulation Methods 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000000049 pigment Substances 0.000 description 96
- 150000001875 compounds Chemical class 0.000 description 35
- 239000004593 Epoxy Substances 0.000 description 30
- 239000000203 mixture Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 21
- -1 3,4-epoxycyclohexyl Chemical group 0.000 description 20
- 239000000047 product Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 238000002156 mixing Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 239000000945 filler Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 8
- 150000004056 anthraquinones Chemical class 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 150000008065 acid anhydrides Chemical class 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 6
- 150000007519 polyprotic acids Polymers 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 239000002390 adhesive tape Substances 0.000 description 5
- 125000002723 alicyclic group Chemical group 0.000 description 5
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 235000010724 Wisteria floribunda Nutrition 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000001062 red colorant Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920004482 WACKER® Polymers 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 239000002318 adhesion promoter Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000008641 benzimidazolones Chemical class 0.000 description 3
- 239000000038 blue colorant Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 239000004843 novolac epoxy resin Substances 0.000 description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- 239000001060 yellow colorant Substances 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 239000000040 green colorant Substances 0.000 description 2
- WTIFIAZWCCBCGE-UUOKFMHZSA-N guanosine 2'-monophosphate Chemical compound C1=2NC(N)=NC(=O)C=2N=CN1[C@@H]1O[C@H](CO)[C@@H](O)[C@H]1OP(O)(O)=O WTIFIAZWCCBCGE-UUOKFMHZSA-N 0.000 description 2
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical class C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000001061 orange colorant Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VDCOSJPGDDQNJH-JVSYPLCOSA-N (8s,9s,10r,11r,13s,14s)-11-hydroxy-13-methyl-1,2,6,7,8,9,10,11,12,14,15,16-dodecahydrocyclopenta[a]phenanthrene-3,17-dione Chemical compound O=C1CC[C@@H]2[C@H]3[C@H](O)C[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 VDCOSJPGDDQNJH-JVSYPLCOSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- IBABXJRXGSAJLQ-UHFFFAOYSA-N 1,4-bis(2,6-diethyl-4-methylanilino)anthracene-9,10-dione Chemical compound CCC1=CC(C)=CC(CC)=C1NC(C=1C(=O)C2=CC=CC=C2C(=O)C=11)=CC=C1NC1=C(CC)C=C(C)C=C1CC IBABXJRXGSAJLQ-UHFFFAOYSA-N 0.000 description 1
- KTEFLEFPDDQMCB-UHFFFAOYSA-N 1,4-bis(4-butylanilino)-5,8-dihydroxyanthracene-9,10-dione Chemical compound C1=CC(CCCC)=CC=C1NC(C=1C(=O)C2=C(O)C=CC(O)=C2C(=O)C=11)=CC=C1NC1=CC=C(CCCC)C=C1 KTEFLEFPDDQMCB-UHFFFAOYSA-N 0.000 description 1
- OCQDPIXQTSYZJL-UHFFFAOYSA-N 1,4-bis(butylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NCCCC)=CC=C2NCCCC OCQDPIXQTSYZJL-UHFFFAOYSA-N 0.000 description 1
- OZQQAZPMNWJRDQ-UHFFFAOYSA-N 1,4-dihydroxy-5,8-bis(4-methylanilino)anthracene-9,10-dione Chemical compound C1=CC(C)=CC=C1NC(C=1C(=O)C2=C(O)C=CC(O)=C2C(=O)C=11)=CC=C1NC1=CC=C(C)C=C1 OZQQAZPMNWJRDQ-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- CKBFYMOTEJMJTP-UHFFFAOYSA-N 1,5-bis(3-methylanilino)anthracene-9,10-dione Chemical compound CC1=CC=CC(NC=2C=3C(=O)C4=CC=CC(NC=5C=C(C)C=CC=5)=C4C(=O)C=3C=CC=2)=C1 CKBFYMOTEJMJTP-UHFFFAOYSA-N 0.000 description 1
- CNRPDCKHCGUKDK-UHFFFAOYSA-N 1,8-bis(phenylsulfanyl)anthracene-9,10-dione Chemical compound C=12C(=O)C3=C(SC=4C=CC=CC=4)C=CC=C3C(=O)C2=CC=CC=1SC1=CC=CC=C1 CNRPDCKHCGUKDK-UHFFFAOYSA-N 0.000 description 1
- LAVARTIQQDZFNT-UHFFFAOYSA-N 1-(1-methoxypropan-2-yloxy)propan-2-yl acetate Chemical compound COCC(C)OCC(C)OC(C)=O LAVARTIQQDZFNT-UHFFFAOYSA-N 0.000 description 1
- WMWQTUBQTYZJRI-UHFFFAOYSA-N 1-(4-methoxyphenyl)-n,n-dimethylmethanamine Chemical compound COC1=CC=C(CN(C)C)C=C1 WMWQTUBQTYZJRI-UHFFFAOYSA-N 0.000 description 1
- GBAJQXFGDKEDBM-UHFFFAOYSA-N 1-(methylamino)-4-(3-methylanilino)anthracene-9,10-dione Chemical compound C1=2C(=O)C3=CC=CC=C3C(=O)C=2C(NC)=CC=C1NC1=CC=CC(C)=C1 GBAJQXFGDKEDBM-UHFFFAOYSA-N 0.000 description 1
- XUDJOVURIXHNRW-UHFFFAOYSA-N 1-amino-4-anilinoanthracene-9,10-dione Chemical compound C1=2C(=O)C3=CC=CC=C3C(=O)C=2C(N)=CC=C1NC1=CC=CC=C1 XUDJOVURIXHNRW-UHFFFAOYSA-N 0.000 description 1
- FUWDFGKRNIDKAE-UHFFFAOYSA-N 1-butoxypropan-2-yl acetate Chemical compound CCCCOCC(C)OC(C)=O FUWDFGKRNIDKAE-UHFFFAOYSA-N 0.000 description 1
- ZIKLJUUTSQYGQI-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxypropoxy)propane Chemical compound CCOCC(C)OCC(C)OCC ZIKLJUUTSQYGQI-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- NIDFGXDXQKPZMA-UHFFFAOYSA-N 14h-benz[4,5]isoquino[2,1-a]perimidin-14-one Chemical compound C1=CC(N2C(=O)C=3C4=C(C2=N2)C=CC=C4C=CC=3)=C3C2=CC=CC3=C1 NIDFGXDXQKPZMA-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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Abstract
【課題】絶縁性、耐熱性に優れ、表面平坦性、密着性、硬化性を高いレベルでバランス良く達成でき、且つ製造プロセス中に必要とされる高温絶縁抵抗性及び耐溶剤性が両方ともに優れた熱硬化性樹脂組成物、その硬化物、及びそれを用いたディスプレイ用部材を提供する。【解決手段】(a)熱硬化性成分としてのカルボキシル基含有樹脂と、(b)エポキシ樹脂と、(c)黒色着色剤と、(d)硫酸バリウム、シリカ及びタルクからなる群から選ばれる少なくとも1種と、を含むことを特徴とする熱硬化性樹脂組成物。【選択図】なしAn object of the present invention is to achieve excellent balance between insulation and heat resistance, surface flatness, adhesion and curability at a high level, as well as excellent high-temperature insulation resistance and solvent resistance required during the manufacturing process. A thermosetting resin composition, a cured product thereof, and a display member using the same are provided. At least selected from the group consisting of (a) a carboxyl group-containing resin as a thermosetting component, (b) an epoxy resin, (c) a black colorant, and (d) barium sulfate, silica, and talc. 1 type of thermosetting resin composition characterized by including. [Selection figure] None
Description
本発明は、表面平坦性、密着性、硬化性を高いレベルでバランス良く達成でき、且つ高温絶縁抵抗性及び耐溶剤性を両立する硬化物を形成できる熱硬化性樹脂組成物、及びその硬化物を備えたディスプレイ用部材を提供する。 The present invention relates to a thermosetting resin composition that can achieve a high level of surface flatness, adhesion, and curability, and that can form a cured product that has both high-temperature insulation resistance and solvent resistance, and the cured product thereof. There is provided a display member comprising:
近年、携帯電話機、個人携帯情報端末、ノートパソコンを始め、様々な電子機器の画面に操作部としてタッチパネル型入力装置(以下、単に「タッチパネル」と記す。)が取り込まれている。タッチパネルを備える液晶表示装置では、タッチパネルが、液晶表示装置の表示用パネルの偏光板上に位置合わせの上で搭載固定されている。ところで、携帯電話やタブレットではユーザー側から液晶表示部を見ると、透明ガラス全面に情報や画像が表示されるのではなく、基板の外周部分に、表示部を区画するように黒塗りまたは白塗りの枠部分があり、この枠部分の内側で情報が表示されている。 2. Description of the Related Art In recent years, touch panel type input devices (hereinafter simply referred to as “touch panels”) are incorporated as operation units on the screens of various electronic devices such as mobile phones, personal portable information terminals, and notebook computers. In a liquid crystal display device including a touch panel, the touch panel is mounted and fixed on the polarizing plate of the display panel of the liquid crystal display device after alignment. By the way, when viewing the liquid crystal display from the user side on mobile phones and tablets, information or images are not displayed on the entire surface of the transparent glass, but are painted black or white so as to partition the display on the outer periphery of the substrate. There is a frame part, and information is displayed inside the frame part.
この枠部分は加飾部と呼ばれるが、表示部分を4角形状に区画するとともに、見えると都合が悪い部分(タッチパネル用の配線部分等)を見られないように隠蔽する機能がある。加飾部は、直接目に触れるものとして携帯用端末機器表示部の外観装飾部材としても非常に重要であり、特にデザイン性が重視されていることから、その材料として色沢、密着性、硬化性を高いレベルでバランス良く達成でき、且つ加工プロセスに必要とされる高温絶縁抵抗及び耐溶剤性を両立する硬化物を形成できる熱硬化性樹脂組成物が求められている。 Although this frame portion is called a decoration portion, it has a function of partitioning the display portion into a quadrangular shape and concealing it so that a portion that is inconvenient (such as a wiring portion for a touch panel) cannot be seen. The decoration part is also very important as an exterior decoration member of the portable terminal device display part as something that can be directly touched by the eyes. There is a need for a thermosetting resin composition that can achieve good balance at a high level and that can form a cured product that satisfies both high-temperature insulation resistance and solvent resistance required for processing.
従来、このような熱硬化性樹脂組成物としては、例えば、特許文献1には、(A)ビスマレイミド−トリアジン樹脂と、(B)エポキシ樹脂と、(C)カーボンブラックとを含有する組成物が開示されている。 Conventionally, as such a thermosetting resin composition, for example, Patent Document 1 discloses a composition containing (A) a bismaleimide-triazine resin, (B) an epoxy resin, and (C) carbon black. Is disclosed.
近年、エポキシ樹脂を含有する硬化性樹脂組成物について要求される密着性のレベルが高まっており、とりわけ、硬化性と密着性とが両方ともに優れ、高温絶縁抵抗性及び耐溶剤性を両立することができる硬化性樹脂組成物が求められていた。しかしながら、上記特許文献1に記載されている従来の硬化性組成物は、密着性、硬化性を高いレベルでバランス良く達成でき、且つ高温絶縁抵抗性及び耐溶剤性を両立するものではなかった。
そこで、本発明は、絶縁性、耐熱性に優れ、表面平坦性、密着性、硬化性を高いレベルでバランス良く達成でき、且つ製造プロセス中に必要とされる高温絶縁抵抗性及び耐溶剤性が両方ともに優れた熱硬化性樹脂組成物、その硬化物、及びそれを用いたディスプレイ用部材を提供することを目的とする。
In recent years, the level of adhesion required for a curable resin composition containing an epoxy resin has increased, and in particular, both curability and adhesion are excellent, and both high-temperature insulation resistance and solvent resistance are compatible. There has been a demand for a curable resin composition that can be used. However, the conventional curable composition described in Patent Document 1 can achieve adhesion and curability at a high level in a well-balanced manner, and does not achieve both high-temperature insulation resistance and solvent resistance.
Therefore, the present invention is excellent in insulation and heat resistance, can achieve surface flatness, adhesion and curability at a high level in a well-balanced manner, and has high temperature insulation resistance and solvent resistance required during the manufacturing process. It is an object of the present invention to provide an excellent thermosetting resin composition, a cured product thereof, and a display member using the same.
本発明者らは、上記課題を解決するために鋭意検討した結果、特定のカルボキシル基含有樹脂、エポキシ樹脂、黒色着色剤、および、特定の絶縁性フィラーを含有する組成物が絶縁性、耐熱性、密着性および耐溶剤性に優れることを見出し、本発明を完成させた。
すなわち、本発明は、以下の(1)〜(5)を提供する。
As a result of intensive studies to solve the above problems, the present inventors have found that a composition containing a specific carboxyl group-containing resin, an epoxy resin, a black colorant, and a specific insulating filler is insulative and heat resistant. The present invention was completed by finding excellent adhesion and solvent resistance.
That is, the present invention provides the following (1) to (5).
(1) (a)熱硬化性成分としてのカルボキシル基含有樹脂と、(b)エポキシ樹脂と、(c)黒色着色剤と、(d)硫酸バリウム、シリカ及びタルクからなる群から選ばれる少なくとも1種と、を含むことを特徴とする熱硬化性樹脂組成物。 (1) (a) at least one selected from the group consisting of a carboxyl group-containing resin as a thermosetting component, (b) an epoxy resin, (c) a black colorant, and (d) barium sulfate, silica, and talc. A thermosetting resin composition comprising a seed.
(2) さらに、(e)黒色以外の着色剤を含むことを特徴とする(1)に記載の熱硬化性樹脂組成物。 (2) The thermosetting resin composition according to (1), further comprising (e) a colorant other than black.
(3) さらに、シランカップリング剤を含むことを特徴とする(1)又は(2)に記載の熱硬化性樹脂組成物。 (3) The thermosetting resin composition according to (1) or (2), further comprising a silane coupling agent.
(4) 基板上に形成したことを特徴とする(1)〜(3)の何れかに記載の熱硬化性樹脂組成物の硬化物。 (4) The cured product of the thermosetting resin composition according to any one of (1) to (3), which is formed on a substrate.
(5) 上記(4)に記載の硬化物を備えたことを特徴とするディスプレイ用部材。 (5) A display member comprising the cured product according to (4).
本発明によれば、絶縁性、耐熱性に優れ、表面平坦性、密着性、硬化性を高いレベルでバランス良く達成でき、且つ高温絶縁抵抗性及び耐溶剤性を両立できる硬化物を形成できる熱硬化性樹脂組成物を提供することができる。また、本発明の硬化性樹脂組成物は、表示装置に使用される加飾インキとして好適である。 According to the present invention, heat that can form a cured product that is excellent in insulation, heat resistance, can achieve surface flatness, adhesion, and curability at a high level in a balanced manner, and that can achieve both high-temperature insulation resistance and solvent resistance. A curable resin composition can be provided. Moreover, the curable resin composition of this invention is suitable as decorating ink used for a display apparatus.
本発明の硬化性樹脂組成物(以下、「本発明の組成物」ともいう。)は、(a)熱硬化性成分としてのカルボキシル基含有樹脂と、(b)エポキシ樹脂と、(c)黒色着色剤と、(d)硫酸バリウム、シリカ及びタルクからなる群から選ばれる少なくとも1種(以下、「絶縁性フィラー」ともいう。)とを含むものである。
以下、本発明の組成物に使用される各成分について詳細に説明する。
The curable resin composition of the present invention (hereinafter also referred to as “the composition of the present invention”) includes (a) a carboxyl group-containing resin as a thermosetting component, (b) an epoxy resin, and (c) black. It contains a colorant and (d) at least one selected from the group consisting of barium sulfate, silica and talc (hereinafter also referred to as “insulating filler”).
Hereinafter, each component used for the composition of this invention is demonstrated in detail.
〔(a)熱硬化性成分としてのカルボキシル基含有樹脂〕
本発明の熱硬化性樹脂組成物に含まれるカルボキシル基含有樹脂は、エポキシ樹脂と熱硬化反応するための成分であり、具体的には、下記に列挙するような樹脂が挙げられる。
(1)(メタ)アクリル酸などの不飽和カルボン酸と、それ以外の不飽和二重結合を有する化合物の1種類以上とを共重合させることにより得られるカルボキシル基含有共重合樹脂、
(2)(メタ)アクリル酸などの不飽和カルボン酸と、それ以外の不飽和二重結合を有する化合物の1種類以上との共重合体に、グリシジル(メタ)アクリレートや3,4−エポキシシクロヘキシルメチル(メタ)アクリレートなどのエポキシ基と不飽和二重結合を有する化合物や(メタ)アクリル酸クロライドなどによって、エチレン性不飽和基をペンダントとして付加させることによって得られるカルボキシル基含有樹脂、
(3)グリシジル(メタ)アクリレートや3,4−エポキシシクロヘキシルメチル(メタ)アクリレート等のエポキシ基と不飽和二重結合を有する化合物と、それ以外の不飽和二重結合を有する化合物との共重合体に、(メタ)アクリル酸などの不飽和カルボン酸を反応させ、生成した二級の水酸基に多塩基酸無水物を反応させて得られるカルボキシル基含有樹脂、
(4)無水マレイン酸などの不飽和二重結合を有する酸無水物と、それ以外の不飽和二重結合を有する化合物との共重合体に、2−ヒドロキシエチル(メタ)アクリレートなどの水酸基と不飽和二重結合を有する化合物を反応させて得られるカルボン酸含有樹脂、
(5)多官能エポキシ化合物と不飽和モノカルボン酸を反応させ、生成した水酸基に飽和又は不飽和多塩基酸無水物を反応させて得られるカルボキシル基含有樹脂、
(6)ポリビニルアルコール誘導体などの水酸基含有ポリマーに、飽和又は不飽和多塩基酸無水物を反応させた後、生成したカルボン酸に一分子中にエポキシ基と不飽和二重結合を有する化合物を反応させて得られるカルボキシル基含有樹脂、
(7)多官能エポキシ化合物と、不飽和モノカルボン酸と、一分子中に少なくとも1個のアルコール性水酸基と、エポキシ基と反応するアルコール性水酸基以外の1個の反応性基を有する化合物との反応生成物に、飽和又は不飽和多塩基酸無水物を反応させて得られるカルボキシル基含有樹脂、
(8)一分子中に少なくとも2個のオキセタン環を有する多官能オキセタン化合物に不飽和モノカルボン酸を反応させ、得られた変性オキセタン樹脂中の第一級水酸基に対して飽和又は不飽和多塩基酸無水物を反応させて得られるカルボキシル基含有樹脂、及び
(9)多官能エポキシ樹脂に不飽和モノカルボン酸を反応させた後、多塩基酸無水物を反応させて得られるカルボン酸含有樹脂に、更に、分子中に1個のオキシラン環と1個以上のエチレン性不飽和基を有する化合物を反応させて得られるカルボキシル基含有樹脂、などが挙げられるが、これらに限定されるものでは無い。
[(A) Carboxyl group-containing resin as thermosetting component]
The carboxyl group-containing resin contained in the thermosetting resin composition of the present invention is a component for thermosetting reaction with an epoxy resin, and specific examples thereof include the resins listed below.
(1) a carboxyl group-containing copolymer resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid and one or more other compounds having an unsaturated double bond;
(2) Glycidyl (meth) acrylate or 3,4-epoxycyclohexyl is a copolymer of an unsaturated carboxylic acid such as (meth) acrylic acid and one or more other compounds having an unsaturated double bond. A carboxyl group-containing resin obtained by adding an ethylenically unsaturated group as a pendant by a compound having an epoxy group and an unsaturated double bond, such as methyl (meth) acrylate, or (meth) acrylic acid chloride,
(3) Copolymerization of a compound having an unsaturated double bond with an epoxy group such as glycidyl (meth) acrylate or 3,4-epoxycyclohexylmethyl (meth) acrylate, and a compound having an unsaturated double bond other than that A carboxyl group-containing resin obtained by reacting an unsaturated carboxylic acid such as (meth) acrylic acid with the coalescence and reacting the resulting secondary hydroxyl group with a polybasic acid anhydride,
(4) To a copolymer of an acid anhydride having an unsaturated double bond such as maleic anhydride and a compound having an unsaturated double bond other than that, a hydroxyl group such as 2-hydroxyethyl (meth) acrylate; A carboxylic acid-containing resin obtained by reacting a compound having an unsaturated double bond;
(5) a carboxyl group-containing resin obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid and reacting the generated hydroxyl group with a saturated or unsaturated polybasic acid anhydride,
(6) After reacting a saturated or unsaturated polybasic acid anhydride with a hydroxyl group-containing polymer such as a polyvinyl alcohol derivative, the resulting carboxylic acid is reacted with a compound having an epoxy group and an unsaturated double bond in one molecule. Carboxyl group-containing resin obtained by
(7) a polyfunctional epoxy compound, an unsaturated monocarboxylic acid, at least one alcoholic hydroxyl group in one molecule, and a compound having one reactive group other than an alcoholic hydroxyl group that reacts with an epoxy group A carboxyl group-containing resin obtained by reacting a reaction product with a saturated or unsaturated polybasic acid anhydride,
(8) Saturated or unsaturated polybasic with respect to the primary hydroxyl group in the modified oxetane resin obtained by reacting an unsaturated monocarboxylic acid with a polyfunctional oxetane compound having at least two oxetane rings in one molecule. A carboxyl group-containing resin obtained by reacting an acid anhydride, and (9) a carboxylic acid-containing resin obtained by reacting an unsaturated monocarboxylic acid with a polyfunctional epoxy resin and then reacting with a polybasic acid anhydride. Furthermore, examples include, but are not limited to, a carboxyl group-containing resin obtained by reacting a compound having one oxirane ring and one or more ethylenically unsaturated groups in the molecule.
これらの例示の中で好ましいものとしては、上記(2)、(5)、(7)、(9)のカルボキシル基含有樹脂であり、特に上記(5)のカルボキシル基含有樹脂が、熱硬化性、硬化皮膜特性の面から好ましい。なお、ここで(メタ)アクリレートとは、アクリレート、メタクリレート及びそれらの混合物を総称する用語で、以下他の類似の表現についても同様である。 Among these examples, preferred are the carboxyl group-containing resins (2), (5), (7), and (9), and particularly the carboxyl group-containing resin (5) is thermosetting. From the viewpoint of cured film characteristics, it is preferable. Here, (meth) acrylate is a generic term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.
また、上記カルボキシル基含有樹脂の酸価は、好ましくは10〜150mgKOH/gの範囲であり、より好ましくは30〜100mgKOH/gの範囲である。カルボキシル基含有樹脂の酸価が10mgKOH/g以上であると、密着性がより良好となり、また、150mgKOH/g以下であると硬化物の熱安定性がより向上する。 The acid value of the carboxyl group-containing resin is preferably in the range of 10 to 150 mgKOH / g, more preferably in the range of 30 to 100 mgKOH / g. When the acid value of the carboxyl group-containing resin is 10 mgKOH / g or more, the adhesion becomes better, and when it is 150 mgKOH / g or less, the thermal stability of the cured product is further improved.
また、上記カルボキシル基含有樹脂の質量平均分子量は、樹脂骨格により異なるが、一般的に1000〜30000、さらには5000〜20000の範囲にあるものが好ましい。質量平均分子量が1000以上であると、タックフリー性能がより高まり、硬化物の硬度もより十分なものとなる。また、質量平均分子量が20000以下であると、密着性、硬化性をよりバランス良く達成することが可能となる。 Moreover, although the mass average molecular weight of the said carboxyl group-containing resin changes with resin frame | skeleton, generally what is in the range of 1000-30000, Furthermore, 5000-20000 is preferable. When the mass average molecular weight is 1000 or more, tack-free performance is further enhanced, and the hardness of the cured product is further sufficient. Further, when the mass average molecular weight is 20000 or less, it becomes possible to achieve better adhesion and curability.
このようなカルボキシル基含有樹脂の配合量は、全組成物の不揮発分100質量部に対して、好ましくは15〜60質量部、より好ましくは25〜50質量部である。15質量部以上の場合、深部硬化性がより十分となり、また、上記50質量部以下の場合、粘性が最適となり、塗布性等が低下することもない。 The blending amount of such a carboxyl group-containing resin is preferably 15 to 60 parts by mass, more preferably 25 to 50 parts by mass with respect to 100 parts by mass of the nonvolatile content of the entire composition. When the amount is 15 parts by mass or more, the deep-part curability becomes more sufficient, and when the amount is 50 parts by mass or less, the viscosity becomes optimal and the applicability is not lowered.
〔(b)エポキシ樹脂〕
本発明の熱硬化性樹脂組成物に使用される(b)エポキシ樹脂は、耐熱性を付与するための成分であり、芳香族骨格を有するエポキシ化合物を含むことが好ましい。芳香族骨格を有するエポキシ化合物は1種のみが用いられてもよく、2種以上が併用されてもよい。また、ガラス基材と成形体との密着性をより一層高める観点からは、エポキシ化合物は、脂環式骨格を有するエポキシ化合物を含むことが好ましい。脂環式骨格を有するエポキシ化合物は、1種のみが用いられてもよく、2種以上が併用されてもよい。また、変性エポキシ樹脂を併用してもよい。
[(B) Epoxy resin]
The (b) epoxy resin used in the thermosetting resin composition of the present invention is a component for imparting heat resistance, and preferably contains an epoxy compound having an aromatic skeleton. As for the epoxy compound which has an aromatic skeleton, only 1 type may be used and 2 or more types may be used together. Moreover, it is preferable that an epoxy compound contains the epoxy compound which has an alicyclic skeleton from a viewpoint of improving the adhesiveness of a glass base material and a molded object further. As for the epoxy compound which has alicyclic skeleton, only 1 type may be used and 2 or more types may be used together. Further, a modified epoxy resin may be used in combination.
芳香族骨格を有するエポキシ化合物としては、ビスフェノールA型エポキシ化合物、ビスフェノールF型エポキシ化合物、クレゾールノボラック型エポキシ化合物、フェノールノボラック型エポキシ化合物、芳香族骨格を有する多塩基酸化合物とエピクロロヒドリンとを反応させて得られるグリシジルエステル型エポキシ化合物、及び芳香族骨格を有するグリシジルエーテル型エポキシ化合物等が挙げられる。成形体の強度及び耐熱性をより一層高める観点からは、芳香族骨格を有するエポキシ化合物は、ビスフェノール骨格又はノボラック骨格を有することが好ましい。
芳香族骨格を有するエポキシ化合物のエポキシ当量は、好ましくは100以上1000以下である。該エポキシ当量が100以上であると、上記硬化性組成物の成形性がより一層良好になる。該エポキシ当量が1000以下であると、成形体の強度がより一層高くなる。
Examples of the epoxy compound having an aromatic skeleton include bisphenol A type epoxy compound, bisphenol F type epoxy compound, cresol novolac type epoxy compound, phenol novolac type epoxy compound, polybasic acid compound having aromatic skeleton and epichlorohydrin. Examples thereof include a glycidyl ester type epoxy compound obtained by reaction and a glycidyl ether type epoxy compound having an aromatic skeleton. From the viewpoint of further enhancing the strength and heat resistance of the molded article, the epoxy compound having an aromatic skeleton preferably has a bisphenol skeleton or a novolak skeleton.
The epoxy equivalent of the epoxy compound having an aromatic skeleton is preferably 100 or more and 1000 or less. When the epoxy equivalent is 100 or more, the moldability of the curable composition is further improved. When the epoxy equivalent is 1000 or less, the strength of the molded product is further increased.
上記脂環式骨格を有するエポキシ化合物の具体例としては、2−(3,4−エポキシ)シクロヘキシル−5,5−スピロ−(3,4−エポキシ)シクロヘキサン−m−ジオキサン、3,4−エポキシシクロヘキセニルメチル−3’,4’−エポキシシクロヘキセンカルボキシレート、ジシクロペンタジエンジオキシド、ビニルシクロヘキセンモノオキサイド、1,2−エポキシ−4−ビニルシクロヘキサン、1,2:8,9−ジエポキシリモネン、ε−カプロラクトン修飾テトラ(3,4−エポキシシクロヘキシルメチル)ブタンテトラカルボキシレート、2,2−ビス(ヒドロキシメチル)−1−ブタノールの1,2−エポキシ−4−(2−オキシラニル)シクロヘキサン付加物等が挙げられる。成形体の耐熱性をより一層高める観点から、脂環式骨格を有するエポキシ化合物は2,2−ビス(ヒドロキシメチル)−1−ブタノールの1,2−エポキシ−4−(2−オキシラニル)シクロヘキサン付加物が好ましい。 Specific examples of the epoxy compound having the alicyclic skeleton include 2- (3,4-epoxy) cyclohexyl-5,5-spiro- (3,4-epoxy) cyclohexane-m-dioxane, 3,4-epoxy. Cyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, dicyclopentadiene dioxide, vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane, 1,2: 8,9-diepoxy limonene, ε -Caprolactone-modified tetra (3,4-epoxycyclohexylmethyl) butanetetracarboxylate, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, etc. Can be mentioned. From the viewpoint of further improving the heat resistance of the molded product, an epoxy compound having an alicyclic skeleton is an addition of 1,2-epoxy-4- (2-oxiranyl) cyclohexane to 2,2-bis (hydroxymethyl) -1-butanol. Things are preferred.
上記脂環式骨格を有するエポキシ化合物の市販品として、例えば、長春人造樹脂廠(股)製のPNE−177(フェノールノボラック型エポキシ樹脂)、CNE−200EL(クレゾールノボラック型エポキシ樹脂)、BNE200D75(ビスフェノールA型ノボラックエポキシ樹脂)、ダイセル化学社製のセロキサイド2021、セロキサイド2021A、セロキサイド2021P、セロキサイド2081、セロキサイド2000、セロキサイド3000に例示される脂環式エポキシ、エポキシ基を有する(メタ)アクリレート化合物であるサイクロマーA200、サイクロマーM100、MGMAのようなメチルグリシジル基を有するメタクリレート、ダウケミカル社製サイラキュアなどが挙げられる。これらに限定されるものでは無い。 Examples of commercially available epoxy compounds having an alicyclic skeleton include PNE-177 (phenol novolac epoxy resin), CNE-200EL (cresol novolac epoxy resin), BNE200D75 (bisphenol) manufactured by Changchun Artificial Resin Co., Ltd. A-type novolac epoxy resin), Daicel Chemical Company's Celoxide 2021, Celoxide 2021A, Celoxide 2021P, Celoxide 2081, Celoxide 2000, Celoxide 3000, and a cyclo (cyclo) which is a (meth) acrylate compound having an epoxy group And methacrylate having a methyl glycidyl group such as MER A200, CYCLOMER M100, and MGMA, and Syracure manufactured by Dow Chemical Company. It is not limited to these.
エポキシ化合物の配合量は、熱の付与により適度に硬化するように適宜調整され、特に限定されるものではない。上記(a)カルボキシル基含有樹脂100質量部に対して、エポキシ化合物の配合量は好ましくは10質量部以上60質量部以下、より好ましくは20質量部以上50質量部以下、更に好ましくは25質量部以上45質量部以下である。エポキシ化合物の配合量が上記の範囲であると、加熱により硬化性組成物がより一層効果的に硬化し、成形体の耐熱性がより一層高くなる。 The compounding quantity of an epoxy compound is suitably adjusted so that it may harden | cure moderately by provision of heat, and is not specifically limited. The blending amount of the epoxy compound is preferably 10 parts by mass or more and 60 parts by mass or less, more preferably 20 parts by mass or more and 50 parts by mass or less, and further preferably 25 parts by mass with respect to 100 parts by mass of the (a) carboxyl group-containing resin. It is 45 parts by mass or more. When the blending amount of the epoxy compound is in the above range, the curable composition is more effectively cured by heating, and the heat resistance of the molded body is further increased.
〔(c)黒色着色剤〕
本発明の組成物に含まれる黒色着色剤は、黒色を十分に示し、上記カルボキシル基含有樹脂またはエポキシ樹脂と化学的に反応しないものであればよく、例えば、C.I.Pigment black 6、7、9および18等に示されるカーボンブラック系の着色剤、C.I.Pigment black 8、10等に示される黒鉛系の着色剤、C.I.Pigment black 11、12および27,Pigment Brown 35等で示される酸化鉄系の着色剤:例えば戸田工業社製KN−370の酸化鉄、三菱マテリアル社製13Mのチタンブラック、C.I.Pigment black 20等で示されるアンスラキノン系の着色剤、C.I.Pigment black13、25および29等で示される酸化コバルト系の着色剤、C.I.Pigment black 15および28等で示される酸化銅系の着色剤、C.I.Pigment black 14および26等で示されるマンガン系の着色剤、C.I.Pigment black 23等で示される酸化アンチモン系の着色剤、C.I.Pigment black 30等で示される酸化ニッケル系の着色剤、C.I.Pigment black 31、32で示されるペリレン系の着色剤、Pigment Black 1で示されるアニリン系の着色剤および硫化モリブデンや硫化ビスマスも好適な着色剤として例示できる。これらの着色剤は、単独で、または適宜組み合わせて使用される。
[(C) Black colorant]
The black colorant contained in the composition of the present invention may be any black colorant as long as it is sufficiently black and does not chemically react with the carboxyl group-containing resin or epoxy resin. For example, CIPigment black 6, 7, 9 and 18 Carbon black colorants such as CIPigment black 8, 10 etc., iron colorants such as CIPigment black 11, 12 and 27, Pigment Brown 35 etc .: for example Toda KN-370 iron oxide manufactured by Kogyo Co., Ltd., 13M titanium black manufactured by Mitsubishi Materials, anthraquinone-based colorant represented by CIPigment black 20, etc., cobalt oxide-based colorants represented by CIPigment black 13, 25, 29, etc. Copper oxide colorants such as CIPigment black 15 and 28, manganese colorants such as CIPigment black 14 and 26, CIPigment black 23, etc. Antimony oxide colorant shown, nickel oxide colorant shown as CIPigment black 30, etc., perylene colorant shown as CIPigment black 31, 32, aniline colorant shown as Pigment Black 1, and sulfurized Molybdenum and bismuth sulfide can also be exemplified as suitable colorants. These colorants are used alone or in appropriate combination.
特に好ましいのは、カーボンブラックであり、例えば、三菱化学社製のカーボンブラック、M−40、M−45、M−50、MA−8、MA−100、コロンビアケミカルカンパニー製のカーボンブラック1255等が挙げられる。
黒色着色剤の配合量は、多すぎると、絶縁性が低下し、コストアップにも繋がり、また少なすぎると、色沢または非透明性が不十分となる場合はある。好ましくは、本発明の熱硬化性組成物の不揮発分100質量部に対して1〜25質量部であり、より好ましくは、3〜20質量部である。
Particularly preferred is carbon black, such as carbon black manufactured by Mitsubishi Chemical Corporation, M-40, M-45, M-50, MA-8, MA-100, carbon black 1255 manufactured by Columbia Chemical Company, etc. Can be mentioned.
If the blending amount of the black colorant is too large, the insulating property is lowered, leading to an increase in cost, and if it is too small, the color or non-transparency may be insufficient. Preferably, it is 1-25 mass parts with respect to 100 mass parts of non volatile matters of the thermosetting composition of this invention, More preferably, it is 3-20 mass parts.
〔(d)硫酸バリウム、シリカ、タルクのいずれか少なくとも1種〕
本発明の熱硬化性樹脂組成物に使用される(d)硫酸バリウム、シリカ及びタルクからなる群から選ばれる少なくとも1種の絶縁性フィラーは、使用により、硬化物の高温絶縁抵抗性を改善するのみでなく、表面平坦性を上昇させ、加工プロセスの加熱による変形を抑制し、表面平坦性を維持するほか、かすり傷やマイクロクラックを有効に防止することができる。特に表面の平坦性も改善する観点からは、上記絶縁性フィラーは、硫酸バリウムを含むことが好ましい。また一方で、マイクロクラックを防止するための観点からは、上記絶縁性フィラーは、タルクおよびシリカのいずれか少なくとも1種を含むことがより好ましい。
[(D) At least one of barium sulfate, silica, and talc]
(D) At least one insulating filler selected from the group consisting of barium sulfate, silica and talc used in the thermosetting resin composition of the present invention improves the high-temperature insulation resistance of the cured product. In addition to increasing the surface flatness, suppressing deformation due to heating in the processing process and maintaining the surface flatness, it is possible to effectively prevent scratches and microcracks. In particular, from the viewpoint of improving surface flatness, the insulating filler preferably contains barium sulfate. On the other hand, from the viewpoint of preventing microcracks, the insulating filler more preferably contains at least one of talc and silica.
上記絶縁性フィラーの粒径として、硫酸バリウムの平均粒径は0.05〜5.00μmであること、シリカの平均粒径は0.1〜5.0μmであること、タルクの平均粒径は0.1〜5.0μmであることが好ましい。絶縁性フィラーの平均粒径は上記の範囲の上限値以下であると、分散性や表面平坦性がより向上する。また、絶縁性フィラーの平均粒径は上記の範囲の下限値以上であると、硬化性や高温抵抗性がより向上する。
上記絶縁性フィラーの合計配合量として、上記(a)カルボキシル基含有樹脂と(b)エポキシ樹脂との合計100質量部に対して、高温絶縁抵抗性がさらに向上することより、30〜70質量部であることが好ましく、40〜60質量部であることがより好ましい。また、硫酸バリウム、シリカ、タルクは市販のものを使用してもよい。
As the particle size of the insulating filler, the average particle size of barium sulfate is 0.05 to 5.00 μm, the average particle size of silica is 0.1 to 5.0 μm, and the average particle size of talc is It is preferable that it is 0.1-5.0 micrometers. When the average particle size of the insulating filler is not more than the upper limit of the above range, dispersibility and surface flatness are further improved. Moreover, sclerosis | hardenability and high temperature resistance improve more that the average particle diameter of an insulating filler is more than the lower limit of said range.
The total blending amount of the insulating filler is 30 to 70 parts by mass because the high-temperature insulation resistance is further improved with respect to 100 parts by mass in total of the (a) carboxyl group-containing resin and (b) the epoxy resin. It is preferable that it is 40-60 mass parts. Commercially available barium sulfate, silica, and talc may be used.
硫酸バリウムの市販品としては、沈降性硫酸バリウム ♯100、沈降性硫酸バリウム ♯300、沈降性硫酸バリウム SS−50、BARIACE B−30、BARIACE B−31、BARIACE B−32、BARIACE B−33、BARIACE B−34、BARIFINE BF−1、BARIFINE BF−10、BARIFINE BF−20、BARIFINE BF−40(堺化学工業社製)、表面処理硫酸バリウム B−30、B−34(堺化学工業社製)、W−1、W−6、W−10、C−300(竹原化学工業社製)などが挙げられる。
シリカの市販品としては、アエロジル50、アエロジル200、アエロジル380、アエロジルA300などのAシリーズ、RY300などのRYシリーズ(日本アエロジル社製);WACKER HDK S13、WACKER HDK V15、WACKER HDK N20(いずれも旭化成社製);「ファインシールB」(商品名、トクヤマ社製)、「ファインシール」(トクヤマ社製)、「サイリシア」(富士シリシア化学社製)、スノーテックスUP、スノーテックスOUP(日産化学工業社製)、Nipsil L−300、Nipsil KQ(日本シリカ工業社製)等が挙げられる。
タルクの市販品としては、LMS−100、LMS−200、LMS−300、LMS−3500、LMS−400、LMP−100、PKP−53、PKP−80、PKP−81(富士タルク工業社製)、D−600、D−800、D−1000、P−2、P−3、P−4、P−6、P−8、SG−95(日本タルク社製)等が挙げられる。これらは単独あるいは複数組み合わせても使用できる。
Commercially available products of barium sulfate include precipitated barium sulfate # 100, precipitated barium sulfate # 300, precipitated barium sulfate SS-50, BARIACE B-30, BARIACE B-31, BARIACE B-32, BARIACE B-33, BARIACE B-34, BARIFINE BF-1, BARIFINE BF-10, BARIFINE BF-20, BARIFINE BF-40 (manufactured by Sakai Chemical Industry), surface-treated barium sulfate B-30, B-34 (manufactured by Sakai Chemical Industry) , W-1, W-6, W-10, C-300 (manufactured by Takehara Chemical Industry Co., Ltd.) and the like.
As silica commercial products, Aerosil 50, Aerosil 200, Aerosil 380, Aerosil A300 and other A series, RY300 and other RY series (made by Nippon Aerosil Co., Ltd.); WACKER HDK S13, WACKER HDK V15, WACKER HDK N20 (all Asahi Kasei) “Fine Seal B” (trade name, manufactured by Tokuyama), “Fine Seal” (manufactured by Tokuyama), “Siricia” (manufactured by Fuji Silysia Chemical), Snowtex UP, Snowtex OUP (Nissan Chemical Industries) Nipsil L-300, Nipsil KQ (manufactured by Nippon Silica Kogyo Co., Ltd.) and the like.
As a commercial item of talc, LMS-100, LMS-200, LMS-300, LMS-3500, LMS-400, LMP-100, PKP-53, PKP-80, PKP-81 (manufactured by Fuji Talc Industrial Co., Ltd.), D-600, D-800, D-1000, P-2, P-3, P-4, P-6, P-8, SG-95 (made by Nippon Talc Co., Ltd.), etc. are mentioned. These can be used alone or in combination.
〔シランカップリング剤〕
本発明の熱硬化性樹脂組成物は、シランカップリング剤をさらに含むことが好ましい。カップリング剤の使用により、煮沸水中1時間でも耐え得るガラス基材との密着性が得られるのみならず、成形体において熱硬化性成分と絶縁性フィラーとの密着性が良好になる。シランカップリング剤は、1種のみが用いられてもよく、2種以上が併用されてもよい。
シランカップリング剤としては特に限定されないが、例えば、一般にエポキシシラン系カップリング剤、アミノシラン系カップリング剤、カチオニックシラン系カップリング剤、ビニルシラン系カップリング剤、アクリルシラン系カップリング剤、メルカプトシラン系カップリング剤およびこれらの複合系カップリング剤が挙げられる。
〔Silane coupling agent〕
The thermosetting resin composition of the present invention preferably further contains a silane coupling agent. Use of the coupling agent not only provides adhesion to a glass substrate that can withstand boiling water for 1 hour, but also improves adhesion between the thermosetting component and the insulating filler in the molded body. As for a silane coupling agent, only 1 type may be used and 2 or more types may be used together.
Although it does not specifically limit as a silane coupling agent, For example, generally an epoxy silane coupling agent, an aminosilane coupling agent, a cationic silane coupling agent, a vinyl silane coupling agent, an acrylic silane coupling agent, a mercaptosilane System coupling agents and composite coupling agents of these.
シランカップリング剤の配合量は、前記(a)カルボキシル基含有樹脂と(b)エポキシ樹脂との合計100質量部に対して、0.1〜10質量部であることが好ましい。0.1質量部以上であると、その効果がより明らかとなり、また、10質量部以下であると、熱硬化性樹脂組成物の増粘がなく、またコスト的にも有利である。より好ましくは8質量部以下、さらに好ましくは1〜5質量部である。
シランカップリング剤の市販品としては、例えば、KA−1003、KBM−1003、KBE−1003、KBM−303、KBM−403、KBE−402、KBE−403、KBM−1403、KBM−502、KBM−503、KBE−502、KBE−503、KBM−5103、KBM−602、KBM−603、KBE−603、KBM−903、KBE−903、KBE−9103、KBM−9103、KBM−573、KBM−575、KBM−6123、KBE−585、KBM−703、KBM−802、KBM−803、KBE−846、KBE−9007(いずれも商品名、信越シリコーン社製)、Silquest A−186、Silquest A−187(いずれも商品名、モメンティブ・パフォーマンス・マテリアルズ社製)などを挙げることができる。これらは単独で又は2種以上を組み合わせて用いることができる。
It is preferable that the compounding quantity of a silane coupling agent is 0.1-10 mass parts with respect to a total of 100 mass parts of said (a) carboxyl group containing resin and (b) epoxy resin. When the amount is 0.1 parts by mass or more, the effect becomes more apparent. When the amount is 10 parts by mass or less, the thermosetting resin composition does not increase in viscosity and is advantageous in terms of cost. More preferably, it is 8 mass parts or less, More preferably, it is 1-5 mass parts.
Examples of commercially available silane coupling agents include KA-1003, KBM-1003, KBE-1003, KBM-303, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM- 503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9103, KBM-9103, KBM-573, KBM-575, KBM-6123, KBE-585, KBM-703, KBM-802, KBM-803, KBE-846, KBE-9007 (all trade names, manufactured by Shin-Etsu Silicone), Silquest A-186, Silquest A-187 (any Product name, Momentive performance Materials Co., Ltd.) and the like. These can be used alone or in combination of two or more.
また、本発明の組成物には、必要に応じて所望の物性または製造プロセスに使用される製造条件を調整するために以下のような添加剤を含むことができる。 In addition, the composition of the present invention may contain the following additives as necessary in order to adjust the desired physical properties or production conditions used in the production process.
[硬化触媒]
硬化速度の促進、または、加熱温度を低下させるために、硬化触媒を配合することができる。この硬化触媒としては、イミダゾール、2−メチルイミダゾール、2−エチルイミダゾール、2−エチル−4−メチルイミダゾール、2−フェニルイミダゾール、4−フェニルイミダゾール、1−シアノエチル−2−フェニルイミダゾール、1−(2−シアノエチル)−2−エチル−4−メチルイミダゾール等のイミダゾール誘導体;ジシアンジアミド、ベンジルジメチルアミン、4−(ジメチルアミノ)−N,N−ジメチルベンジルアミン、4−メトキシ−N,N−ジメチルベンジルアミン、4−メチル−N,N−ジメチルベンジルアミン等のアミン化合物、アジピン酸ジヒドラジド、セバシン酸ジヒドラジド等のヒドラジン化合物;トリフェニルホスフィン等のリン化合物等が挙げられる。市販されている硬化触媒としては、例えば四国化成工業社製の2MZ−A、2MZ−OK、2PHZ、2P4BHZ、2P4MHZ(いずれもイミダゾール系化合物の商品名)、サンアプロ社製のU−CAT3503N、U−CAT3502T(いずれもジメチルアミンのブロックイソシアネート化合物の商品名)、▲寧▼夏石嘴山民族化工集団公司製のTNK 110 Dyhard(ジシアンジアミド)、DBU、DBN、U−CATSA102、U−CAT5002(いずれも二環式アミジン化合物及びその塩)等が挙げられる。これらは単独で又は2種以上を混合して使用してもかまわない。
[Curing catalyst]
In order to accelerate the curing rate or to lower the heating temperature, a curing catalyst can be blended. Examples of the curing catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2 Imidazole derivatives such as -cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, Examples include amine compounds such as 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. Examples of commercially available curing catalysts include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., U-CAT3503N, U- CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), ▲ Ning ▼ NNK 110 Dyhard (Dicyandiamide), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic) Amidine compounds and salts thereof). These may be used alone or in admixture of two or more.
[光安定剤]
更に、本発明の熱硬化性樹脂組成物には、その硬化物の光劣化の減少を目的としてヒンダードアミン系光安定剤を配合することができる。
このヒンダードアミン系光安定剤としては、チヌビン622LD、チヌビン144;CHIMASSORB944LD、CHIMASSORB 119FL(以上いずれもBASFジャパン社製);MARK LA−57、LA−62、LA−67、LA−63、LA−68(以上いずれもADEKA社製);サノールLS−770、LS−765、LS−292、LS−2626、LS−1114、LS−744(以上いずれも三共ライフテック社製)等が挙げられる。
[Light stabilizer]
Furthermore, a hindered amine light stabilizer can be blended with the thermosetting resin composition of the present invention for the purpose of reducing photodegradation of the cured product.
As this hindered amine light stabilizer, Tinuvin 622LD, Tinuvin 144; CHIMASSORB 944LD, CHIMASSORB 119FL (all of which are manufactured by BASF Japan); MARK LA-57, LA-62, LA-67, LA-63, LA-68 ( These are all manufactured by ADEKA); Sanol LS-770, LS-765, LS-292, LS-2626, LS-1114, LS-744 (all of which are manufactured by Sankyo Lifetech).
[密着促進剤]
本発明の熱硬化性樹脂組成物には、層間の密着性、又はポリイミド等の基材との密着性を向上させるために密着促進剤を用いることができる。密着促進剤としては、例えば、ベンゾイミダゾール、ベンゾオキサゾール、ベンゾチアゾール、2−メルカプトベンゾイミダゾール、2−メルカプトベンゾオキサゾール、2−メルカプトベンゾチアゾール(商品名:川口化学工業社製アクセルM)、3−モルホリノメチル−1−フェニル−トリアゾール−2−チオン、5−アミノ−3−モルホリノメチル−チアゾール−2−チオン、2−メルカプト−5−メチルチオ−チアジアゾール、トリアゾール、テトラゾール、ベンゾトリアゾール、カルボキシベンゾトリアゾール、アミノ基含有ベンゾトリアゾール、シランカップリング剤などが挙げられる。これらは、それぞれ単独で用いてもよいし、2種以上組み合わせて用いてもよい。
[Adhesion promoter]
In the thermosetting resin composition of the present invention, an adhesion promoter can be used in order to improve adhesion between layers or adhesion to a substrate such as polyimide. Examples of the adhesion promoter include benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade name: Axel M manufactured by Kawaguchi Chemical Co., Ltd.), 3-morpholino. Methyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group Examples thereof include benzotriazole and silane coupling agents. These may be used alone or in combination of two or more.
[酸化防止剤]
本発明の硬化性樹脂組成物は、酸化を防ぐために、発生したラジカルを無効化するようなラジカル捕捉剤や、発生した過酸化物を無害な物質に分解し、新たなラジカルが発生しないようにする過酸化物分解剤などの酸化防止剤を含有することができる。本発明で用いられる酸化防止剤は、カルボキシル基含有樹脂やエポキシ樹脂等の酸化劣化を防止し、黄変を抑制することができる。上記酸化防止剤としては、フェノール系酸化防止剤、リン系酸化防止剤及びアミン系酸化防止剤等が挙げられる。なかでもフェノール系酸化防止剤が特に好ましい。酸化防止剤は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
[Antioxidant]
In order to prevent oxidation, the curable resin composition of the present invention decomposes the generated radical scavenger and the generated peroxide into harmless substances so as not to generate new radicals. Antioxidants such as peroxide decomposers can be included. The antioxidant used in the present invention can prevent oxidative deterioration of a carboxyl group-containing resin or an epoxy resin, and can suppress yellowing. Examples of the antioxidant include phenolic antioxidants, phosphorus antioxidants, and amine antioxidants. Of these, phenolic antioxidants are particularly preferred. An antioxidant may be used individually by 1 type and may be used in combination of 2 or more type.
[黒色着色剤以外の着色剤]
また、必要に応じて、黒色着色剤以外の1種以上の着色剤を添加することができる。そのほかの着色剤としては、公知慣用のものを使用することができ、顔料、染料、色素のいずれでもよい。例えば、青色着色剤、赤色着色剤、紫色着色剤、黄色着色剤、緑色着色剤、白色着色剤、オレンジ色着色剤、茶色着色剤を用いることができる。特に好ましいものとしては、青色着色剤および赤色着色剤の少なくとも一方、または双方を用いることができる。
[Colorants other than black colorants]
Moreover, 1 or more types of coloring agents other than a black coloring agent can be added as needed. As other colorants, known and commonly used colorants can be used, and any of pigments, dyes, and pigments may be used. For example, a blue colorant, a red colorant, a purple colorant, a yellow colorant, a green colorant, a white colorant, an orange colorant, and a brown colorant can be used. As a particularly preferable one, at least one or both of a blue colorant and a red colorant can be used.
青色着色剤としては、フタロシアニン系、アントラキノン系等の顔料系はピグメント(Pigment)、染料系はソルベント(Solvent)に分類されている化合物などがあり、具体的には、下記のようなカラーインデックス番号が付されているものを挙げることができる。
顔料系:Pigment Blue 15、Pigment Blue 15:1、Pigment Blue 15:2、Pigment Blue 15:3、Pigment Blue 15:4、Pigment Blue 15:6、Pigment Blue 16、Pigment Blue 60;
染料系:Solvent Blue 35、Solvent Blue 63、Solvent Blue 68、Solvent Blue 70、Solvent Blue 83、Solvent Blue 87、Solvent Blue 94、Solvent Blue 97、Solvent Blue 122、Solvent Blue 136、Solvent Blue 67、Solvent Blue 70;
等を使用することができる。上記以外にも金属置換もしくは無置換のフタロシアニン化合物も使用することができる。
Blue colorants include compounds such as pigments such as phthalocyanine and anthraquinone pigments, and compounds classified as solvent and dyes. Specifically, the color index numbers are as follows: Can be mentioned.
Pigment systems: Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60;
Dye system: Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70 ;
Etc. can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.
赤色着色剤としては、モノアゾ系、ジズアゾ系、アゾレーキ系、ベンズイミダゾロン系、ペリレン系、ジケトピロロピロール系、縮合アゾ系、アントラキノン系、キナクリドン系などがあり、具体的には、下記のようなカラーインデックス番号が付されているものを挙げることができる。
モノアゾ系:Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269;
ジスアゾ系:Pigment Red 37, 38, 41;
モノアゾレーキ系:Pigment Red 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 53:1, 53:2, 57:1, 58:4, 63:1, 63:2, 64:1, 68
ベンズイミダゾロン系:Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208;
ぺリレン系:Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224;
ジケトピロロピロール系:Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272;
縮合アゾ系:Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242;
アンスラキノン系:Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207;
キナクリドン系:Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.
Examples of the red colorant include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. The ones with the correct color index numbers.
Monoazo: Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151 , 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269;
Disazo: Pigment Red 37, 38, 41;
Monoazo lakes: Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57 : 1, 58: 4, 63: 1, 63: 2, 64: 1, 68
Benzimidazolone series: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208;
Perylenes: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224;
Diketopyrrolopyrrole: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272;
Condensed azo: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242;
Anthraquinone series: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207;
Kinacridone series: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.
紫色着色剤としては、具体的には、Pigment Violet 19, 23, 29, 32, 36, 37, 38, 42; Solvent Violet 13, 36; C.I.Pigment brown 25 ;C.I.Pigment black 1、C.I. Pigment black 7,Pigment Violet 37(ジオキサジン系)等が挙げられる。 Specific examples of purple colorants include Pigment Violet 19, 23, 29, 32, 36, 37, 38, 42; Solvent Violet 13, 36; CIPigment brown 25; CIPigment black 1, CI Pigment black 7, Pigment Violet 37 (dioxazine type) etc. are mentioned.
黄色着色剤としては、モノアゾ系、ジスアゾ系、縮合アゾ系、ベンズイミダゾロン系、イソインドリノン系、アントラキノン系等があり、具体的には以下の着色剤が挙げられる。モノアゾ系:Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62:1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, 183;
ジスアゾ系:Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198;
縮合アゾ系:Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180;
ベンズイミダゾロン系:Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181;
イソインドリノン系:Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185;
アントラキノン系:Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.
Examples of the yellow colorant include monoazo series, disazo series, condensed azo series, benzimidazolone series, isoindolinone series, anthraquinone series and the like, and specific examples include the following colorants. Monoazo: Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116 , 167, 168, 169, 182, 183;
Disazo: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198;
Condensed azo: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180;
Benzimidazolone series: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181;
Isoindolinone: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185;
Anthraquinone series: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.
緑色着色剤としては、フタロシアニン系、アントラキノン系があり、具体的には、Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28等を使用することができる。上記以外にも金属置換もしくは無置換のフタロシアニン化合物も使用することができる。 Examples of the green colorant include phthalocyanine series and anthraquinone series. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, and the like can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.
オレンジ色着色剤としては、具体的には、C.I.ピグメントオレンジ1、C.I.ピグメントオレンジ5、C.I.ピグメントオレンジ13、C.I.ピグメントオレンジ14、C.I.ピグメントオレンジ16、C.I.ピグメントオレンジ17、C.I.ピグメントオレンジ24、C.I.ピグメントオレンジ34、C.I.ピグメントオレンジ36、C.I.ピグメントオレンジ38、C.I.ピグメントオレンジ40、C.I.ピグメントオレンジ43、C.I.ピグメントオレンジ46、C.I.ピグメントオレンジ49、C.I.ピグメントオレンジ51、C.I.ピグメントオレンジ61、C.I.ピグメントオレンジ63、C.I.ピグメントオレンジ64、C.I.ピグメントオレンジ71、C.I.ピグメントオレンジ73等が挙げられる。 Specific examples of the orange colorant include CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, and CI Pigment Orange. 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI pigment orange 71, CI pigment orange 73, and the like.
茶色着色剤としては、具体的には、C.I.ピグメントブラウン23、C.I.ピグメントブラウン25等が挙げられる。 Specific examples of the brown colorant include C.I. Pigment Brown 23 and C.I. Pigment Brown 25.
白色の着色剤としては、C.I.ピグメントホワイト4に示される酸化亜鉛、C.I.ピグメントホワイト6に示される酸化チタン、C.I.ピグメントホワイト7に示される硫化亜鉛が挙げられるが、着色力と無毒性という点から特に好ましいのは酸化チタンであり例えば、富士チタン工業社製TR−600、TR−700、TR−750、TR−840、石原産業社R−550、R−580、R−630、R−820、CR−50、CR−60、CR−90、チタン工業社製KR−270、KR−310、KR−380等のルチル型酸化チタン、富士チタン工業社製TA−100、TA−200、TA−300、TA−500、石原産業社製A100、A220、チタン工業社製KA−15、KA−20、KA−35、KA−90等のアナターゼ型酸化チタンが挙げられる。 Examples of the white colorant include zinc oxide shown in CI Pigment White 4, titanium oxide shown in CI Pigment White 6, and zinc sulfide shown in CI Pigment White 7, but particularly from the viewpoint of coloring power and non-toxicity. Preferred is titanium oxide, for example, TR-600, TR-700, TR-750, TR-840, Ishihara Sangyo R-550, R-580, R-630, R-820, CR manufactured by Fuji Titanium Industry Co., Ltd. -50, CR-60, CR-90, rutile titanium oxide such as KR-270, KR-310, KR-380 manufactured by Titanium Industry Co., Ltd., TA-100, TA-200, TA-300 manufactured by Fuji Titanium Industry Co., Ltd. TA-500, A100, A220 manufactured by Ishihara Sangyo Co., Ltd., KA-15, KA-20, KA-35, KA-90 manufactured by Titanium Industry Co., Ltd. Emissions, and the like.
[有機溶剤]
さらに、本発明の熱硬化性樹脂組成物は、組成物の希釈、又は基板やキャリアフィルムに塗布するための粘度調整のため、希釈剤として有機溶剤を使用することができる。
このような有機溶剤としては、ケトン類、芳香族炭化水素類、グリコールエーテル類、グリコールエーテルアセテート類、エステル類、アルコール類、脂肪族炭化水素、石油系溶剤などを挙げることができる。より具体的には、メチルエチルケトン、シクロヘキサノン等のケトン類;トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類;セロソルブ、メチルセロソルブ、ブチルセロソルブ、カルビトール、メチルカルビトール、ブチルカルビトール、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールジエチルエーテル、トリエチレングリコールモノエチルエーテル等のグリコールエーテル類;酢酸エチル、酢酸ブチル、ジプロピレングリコールメチルエーテルアセテート、プロピレングリコールメチルエーテルアセテート、プロピレングリコールエチルエーテルアセテート、プロピレングリコールブチルエーテルアセテートなどのエステル類;エタノール、プロパノール、エチレングリコール、プロピレングリコール等のアルコール類;オクタン、デカン等の脂肪族炭化水素;石油エーテル、石油ナフサ、水添石油ナフサ、ソルベントナフサ等の石油系溶剤などが挙げられる。このような有機溶剤は、1種を単独で用いてもよく、2種以上の混合物として用いてもよい。有機溶剤の配合量としては、特に制限されるものではなく、必要に応じて適宜に添加すればよい。
[Organic solvent]
Furthermore, the thermosetting resin composition of this invention can use an organic solvent as a diluent for the dilution of a composition, or the viscosity adjustment for apply | coating to a board | substrate or a carrier film.
Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Esters such as propylene glycol butyl ether acetate; ethanol, propano , Ethylene glycol, alcohols such as propylene glycol; octane, aliphatic hydrocarbons decane; petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and petroleum solvents such as solvent naphtha. Such an organic solvent may be used individually by 1 type, and may be used as a 2 or more types of mixture. The blending amount of the organic solvent is not particularly limited, and may be appropriately added as necessary.
本発明の熱硬化性樹脂組成物は、例えば前記有機溶剤で塗布方法に適した粘度に調整し、基材上に、ディップコート法、フローコート法、ロールコート法、バーコーター法、スクリーン印刷法、カーテンコート法等の方法により塗布し、約50〜300℃の温度で組成物中に含まれる有機溶剤を揮発乾燥(仮乾燥)させることにより、タックフリーの塗膜を形成できる。 The thermosetting resin composition of the present invention is adjusted to a viscosity suitable for the coating method using, for example, the organic solvent, and on the substrate, dip coating method, flow coating method, roll coating method, bar coater method, screen printing method A tack-free coating film can be formed by applying the organic solvent contained in the composition at a temperature of about 50 to 300 ° C. by volatile drying (temporary drying).
[湿潤分散剤]
組成物の微小凹部への充填性、硬化皮膜の表面平滑性、組成物の消泡性または表面張力を調整するために、本発明の熱硬化性樹脂組成物には、湿潤分散剤を含有することができる。その市販品としては、例えば、ビックケミー・GMBH社製湿潤分散剤BYK−110、BYK−111、BYK−183等が挙げられる。湿潤分散剤は単独または2種以上を併用してもよい。湿潤分散剤の配合量としては、全組成物(固形分)100質量部に対して、好ましくは0.01〜5質量部、より好ましくは1〜5質量部である。
[Wet dispersant]
The thermosetting resin composition of the present invention contains a wetting and dispersing agent in order to adjust the filling property of the composition into the minute recesses, the surface smoothness of the cured film, the defoaming property or surface tension of the composition. be able to. Examples of the commercially available products include BYK-110, BYK-111, BYK-183, etc. manufactured by Big Chemie GMBH. The wetting and dispersing agents may be used alone or in combination of two or more. The amount of the wetting and dispersing agent is preferably 0.01 to 5 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the total composition (solid content).
[レベリング剤]
レベリング剤としては、例えば、ポリアクリレート系重合体、ポリエーテル変性ジメチルポリシロキサン共重合物、ポリエステル変性ジメチルポリシロキサン共重合物、ポリエーテル変性メチルアルキルポリシロキサン共重合物、アラルキル変性メチルアルキルポリシロキサン共重合物およびポリエーテル変性メチルアルキルポリシロキサン共重合物等が挙げられる。レベリング剤は、単独でも2種以上を組み合わせて用いてもよい。レベリング剤の配合量として、前記(a)カルボキシル基含有樹脂と(b)エポキシ樹脂との合計100質量部に対して、好ましくは0.01〜5質量部、より好ましくは1〜5質量部である。
[Leveling agent]
Examples of leveling agents include polyacrylate polymers, polyether-modified dimethylpolysiloxane copolymers, polyester-modified dimethylpolysiloxane copolymers, polyether-modified methylalkylpolysiloxane copolymers, and aralkyl-modified methylalkylpolysiloxane copolymers. Examples thereof include a polymer and a polyether-modified methyl alkyl polysiloxane copolymer. Leveling agents may be used alone or in combination of two or more. As a compounding quantity of a leveling agent, Preferably it is 0.01-5 mass parts with respect to a total of 100 mass parts of said (a) carboxyl group containing resin and (b) epoxy resin, More preferably, it is 1-5 mass parts. is there.
[消泡剤]
消泡剤の具体例としては、市販されている非シリコーン系の破泡性ポリマー溶液からなる消泡剤としてビックケミー・ジャパン社製のBYK(登録商標)−054、−055、−057、−1790などが挙げられ、シリコーン系の消泡剤としてはビックケミー・ジャパン社製のBYK(登録商標)−063、−065、−066N、−067A、−077、及び、東レ・ダウコーニングシリコーン社製のジメチルシリコーンオイル SH200シリーズ、などが挙げられる。
[Defoamer]
Specific examples of the antifoaming agent include BYK (registered trademark) -054, -055, -057, and -1790 manufactured by Big Chemie Japan Co., Ltd. as an antifoaming agent comprising a commercially available non-silicone-based foam-breaking polymer solution. Examples of the silicone-based antifoaming agent include BYK (registered trademark) -063, -065, -066N, -067A, -077 manufactured by Big Chemie Japan, and dimethyl manufactured by Toray Dow Corning Silicone. Silicone oil SH200 series, etc. are mentioned.
〔基板〕
本発明に使用される基板としては、ポリイミドフィルム、PETフィルムなどの樹脂フィルム、ガラス基板、セラミック基板、金属基板、ウエハ板等を挙げることができる。この中でもポリイミドフィルム、PETフィルムなどの樹脂フィルム、ガラス基板を好ましく用いることができる。基板の材質及び形状は、目的とする成形物の用途や性能により選択され、必要により、単独又は2種類以上の材質及び形状を組み合わせることができる。密着性の観点から、ガラス基板がより好ましい。
〔substrate〕
As a board | substrate used for this invention, resin films, such as a polyimide film and PET film, a glass substrate, a ceramic substrate, a metal substrate, a wafer board, etc. can be mentioned. Among these, a polyimide film, a resin film such as a PET film, and a glass substrate can be preferably used. The material and shape of the substrate are selected depending on the intended use and performance of the molded product, and if necessary, two or more kinds of materials and shapes can be combined. From the viewpoint of adhesion, a glass substrate is more preferable.
〔製造・混合方法〕
本発明の熱硬化性樹脂組成物は、上記の必須成分および必要に応じて使用される他の添加成分を均一に混合すれば、製造できる。混合方法としては、公知の方法が使用でき、特に限定されない。分散機を使用せずに混合する方法、ニーダー、ロール、アトライター、ビーズミルなどの各種分散機で機械的に混合する方法のいずれでもよい。
特に好ましい方法としては、予め前記絶縁性フィラーと溶剤と分散剤とを配合し、ロールミル等の分散機で分散した分散液を、他の硬化性樹脂成分と混合し、または必要に応じて再度ロールミル分散して得る方法、若しくは予め一部の樹脂成分と前記絶縁性フィラーと溶剤と分散剤とを配合しロールミル等の分散機で分散した分散液を、他の硬化性樹脂成分と混合し、または必要に応じて再度ロールミル分散して得る方法が挙げられる。
また、着色剤を添加する際には、分散性の観点から、水又は有機溶剤などに、予め着色剤などの粉体類を分散させた混合液に、着色剤分散剤を溶解又は微分散させた液を添加及び混合することが好ましい。
[Production / mixing method]
The thermosetting resin composition of the present invention can be produced by uniformly mixing the above essential components and other additive components used as necessary. A known method can be used as the mixing method, and is not particularly limited. Any of a method of mixing without using a disperser and a method of mechanically mixing with various dispersers such as a kneader, a roll, an attritor, and a bead mill may be used.
As a particularly preferable method, the insulating filler, a solvent, and a dispersing agent are blended in advance, and the dispersion liquid dispersed with a disperser such as a roll mill is mixed with other curable resin components, or, if necessary, a roll mill again. A method obtained by dispersing, or by mixing a part of the resin component, the insulating filler, the solvent, and a dispersing agent in advance and dispersing with a dispersing machine such as a roll mill, or other curable resin component, or The method of obtaining by roll mill dispersion again as needed is mentioned.
In addition, when adding the colorant, from the viewpoint of dispersibility, the colorant dispersant is dissolved or finely dispersed in a mixed liquid in which powders such as the colorant are previously dispersed in water or an organic solvent. It is preferable to add and mix the solution.
〔塗布方法〕
このようにして熱硬化性樹脂組成物を所定の組成で調製した後、例えば、有機溶剤で塗布方法に適した粘度に調整し、基材上に、例えば、ディップコート法、フローコート法、ロールコート法、バーコーター法、スクリーン印刷法、カーテンコート法等の方法により塗布することができる。この中でも、フローコート法、ロールコート法、バーコーター法、スクリーン印刷法が好ましく使用され、スクリーン印刷法が特に好ましく使用される。
[Coating method]
Thus, after preparing a thermosetting resin composition with a predetermined composition, it adjusts to the viscosity suitable for the coating method with an organic solvent, for example, on a base material, for example, a dip coat method, a flow coat method, a roll It can be applied by a method such as a coating method, a bar coater method, a screen printing method, or a curtain coating method. Among these, the flow coating method, the roll coating method, the bar coater method, and the screen printing method are preferably used, and the screen printing method is particularly preferably used.
以下、実施例を示して本発明について具体的に説明するが、本発明はこれらの実施例のみに限定されるものではない。尚、以下において特に断りのない限り、「部」は質量部を
、「%」は質量%を意味する。
EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated concretely, this invention is not limited only to these Examples. In the following description, “part” means part by mass and “%” means mass% unless otherwise specified.
(実施例1〜8、参考例1及び比較例1〜3)
下記表1に示す種々の成分を表1に示す割合(質量部)にて配合し、攪拌機にて予備混合した後、3本ロールミルで混練し、熱硬化性樹脂組成物のペーストを調製した。
(Examples 1-8, Reference Example 1 and Comparative Examples 1-3)
Various components shown in Table 1 below were blended in the proportions (parts by mass) shown in Table 1, premixed with a stirrer, and then kneaded with a three-roll mill to prepare a thermosetting resin composition paste.
*2 PNE177、長春人造樹脂廠(股)製エポキシ樹脂 エポキシ当量:172〜182
*3 BNE200D75、長春人造樹脂廠(股)製エポキシ樹脂(固形分75%) エポキシ当量:198〜218
*4 1255、コロンビアケミカルカンパニー製
*5 B-30、堺化学工業社製 平均粒径:0.3μm 表面処理硫酸バリウム
*6 Nipsil L300 、日本シリカ工業社製 平均粒径2.2μm
*7 SG-95、日本タルク社製 含水ケイ酸マグネシウム 平均粒径(D50):2.5μm
*8 TNK 110 Dyhard、▲寧▼夏石嘴山民族化工(集団)公司製、ジシアンジアミド
*9 BYK-183、BYK-ChemieGmbH製、顔料親和性基をもつ高分子量ブロックコポリマー
*10 BYK-110、BYK-ChemieGmbH製、酸性基含有共重合体
*11 DEAC、Polynt UKLtd.製 ジエチレングリコールモノエチルエーテルアセテート
*12 BYK-354、BYK-ChemieGmbH製、ポリアクリレート系レベリング剤
*13 Silquest A-187 モメンティブ・パフォーマンス・マテリアルズ社製、有機シラン
*14 Cromophtal Violet B、BASFジャパン社製、紫色着色剤(Pigment Violet 37)
*15 OSTAPLAST YELLOW AGR、 Synthesia,a,s製、アントラキノン、黄色着色剤
*16 Irgazin DPP Red Ultra Opaque、BASFジャパン社製、赤色着色剤
*17 R-KB-6、バイエルAG社製、アルミナにより表面処理されたルチル型酸化チタン
* 2 PNE177, Changchun Artificial Resin (Crotch) epoxy resin Epoxy equivalent: 172-182
* 3 BNE200D75, an epoxy resin made by Changchun Plastic Resin Co., Ltd. (solid) (solid content 75%) Epoxy equivalent: 198-218
* 4 1255, manufactured by Columbia Chemical Company
* 5 B-30, manufactured by Sakai Chemical Industry Co., Ltd. Average particle size: 0.3 μm Surface-treated barium sulfate
* 6 Nipsil L300, Nippon Silica Kogyo Co., Ltd. average particle size 2.2μm
* 7 SG-95, manufactured by Nippon Talc Co., Ltd. Hydrous magnesium silicate Average particle diameter (D50): 2.5μm
* 8 TNK 110 Dyhard, ▲ Ning ▼ Natsuishi Foshan Ethnic Chemicals (Group) Ltd., Dicyandiamide
* 9 BYK-183, BYK-Chemie GmbH, high molecular weight block copolymer with pigment affinity group
* 10 BYK-110, BYK-Chemie GmbH, acidic group-containing copolymer
* 11 Diethylene glycol monoethyl ether acetate manufactured by DEAC, Polynt UK Ltd.
* 12 BYK-354, BYK-Chemie GmbH, polyacrylate leveling agent
* 13 Silquest A-187 Momentive Performance Materials, Organosilane
* 14 Cromophtal Violet B, manufactured by BASF Japan, purple colorant (Pigment Violet 37)
* 15 OSTAPLAST YELLOW AGR, manufactured by Synthesia, a, s, anthraquinone, yellow colorant
* 16 Irgazin DPP Red Ultra Opaque, manufactured by BASF Japan, red colorant
* 17 R-KB-6, manufactured by Bayer AG, rutile titanium oxide surface-treated with alumina
(評価ガラス基板の作製)
上記実施例1〜8、参考例1及び比較例1〜3で得られた熱硬化性樹脂組成物のペーストをそれぞれ420メッシュのスクリーンを用いてスクリーン印刷にて硬化皮膜の膜厚が乾燥後約6μmとなるようにガラス基板(セントラル硝子社社製ソーダライムガラス、厚さ0.7mm)に塗工し、塗工されたガラス基板をオーブン(ヤマト科学社製、DH−62)に入れて、150℃で30分間加熱ベークを行ない、6μmの硬化皮膜が形成された評価ガラス基板を作製した。
前記各熱硬化性樹脂組成物の硬化皮膜が形成されたガラス基板を用いて、以下のような種々の特性について下記の方法で評価した。
(Production of evaluation glass substrate)
The paste of the thermosetting resin composition obtained in Examples 1 to 8, Reference Example 1 and Comparative Examples 1 to 3 was screen printed using a 420-mesh screen, and the thickness of the cured film was about after drying. It is applied to a glass substrate (Soda Lime Glass manufactured by Central Glass Co., Ltd., thickness 0.7 mm) so as to be 6 μm, and the coated glass substrate is placed in an oven (DH-62 manufactured by Yamato Scientific Co., Ltd.) Baking was performed at 150 ° C. for 30 minutes to prepare an evaluation glass substrate on which a 6 μm cured film was formed.
Using the glass substrate on which the cured film of each thermosetting resin composition was formed, the following various properties were evaluated by the following methods.
<光遮蔽性(OD値)>
ガラス基板の皮膜側を測定器に向けて透過濃度計(サカタインクスエンジニアリング社製、型番:X−Rite 361T、光源波長:400〜800nm)に装着してOD値を以下のように評価した。
○:OD値が4超
△:OD値が3以上4以下
×:OD値が3未満
<Light shielding (OD value)>
The glass substrate was attached to a transmission densitometer (manufactured by Sakata Inx Engineering, model number: X-Rite 361T, light source wavelength: 400-800 nm) with the film side facing the measuring device, and the OD value was evaluated as follows.
○: OD value is more than 4 △: OD value is 3 or more and 4 or less ×: OD value is less than 3
<熱湯耐性(熱湯試験)>
ガラス基板を60分間、100℃の沸騰水中に浸漬した後に、取り出して表面の水分を除去してから、目視で水の浸入または皮膜の析出を確認した。次に、透明粘着テープ(ニチバン社製、横幅:18mm)を完全に評価ガラス基板の皮膜側に付着させ、直ちにテープの一端をガラス基板に対して直角に保ちながら瞬間的に引き離し、目視で以下のように皮膜を評価した。
○:変化が確認されなかった。
△:わずかな変化が確認された。
×:水の浸入または皮膜の剥離が確認された。
<Hot water resistance (hot water test)>
After immersing the glass substrate in boiling water at 100 ° C. for 60 minutes, the glass substrate was taken out and the surface moisture was removed, and then water intrusion or film deposition was visually confirmed. Next, a transparent adhesive tape (manufactured by Nichiban Co., Ltd., width: 18 mm) is completely attached to the film side of the evaluation glass substrate, and immediately pulled apart while keeping one end of the tape at right angles to the glass substrate. The film was evaluated as follows.
○: No change was confirmed.
Δ: A slight change was confirmed.
X: Water permeation or film peeling was confirmed.
<耐高温クラック性>
ガラス基板を、DENG YNG高温オーブン(登盈儀器社製、型番:DH−400)に入れて、280℃で1時間加熱し、電子顕微鏡(50倍、オリンパス社製、型番:MEASURING MICROSCOPE STM−MJS2)を使用し、ガラス基板の皮膜表面を以下のように評価した。
○:クラックなし
△:クラック発生率が0超10%未満
×:クラック発生率が10%以上
<High temperature crack resistance>
The glass substrate is placed in a DENG YNG high-temperature oven (manufactured by Torigi Kikai Co., Ltd., model number: DH-400), heated at 280 ° C. for 1 hour, and electron microscope (50 times, Olympus, model number: MEASURING MICROSCOPE STM-MJS2). ) And the film surface of the glass substrate was evaluated as follows.
○: No crack △: Crack generation rate is more than 0 and less than 10% ×: Crack generation rate is 10% or more
<高温絶縁抵抗性>
ガラス基板をオーブンにて280℃で60分間ベークし、抵抗計(Agilent Technologes製、ハイレジスタンスメータ4339B、コンポーネント・テスト・フィクスチャ16339A)の正極、負極を、正極と負極との距離が0.5cmとなるようにそれぞれガラス基板の皮膜に挟め、電圧:500V、時間:60秒間という条件で皮膜の抵抗を測定し、以下のように皮膜の抵抗を評価した。
○:抵抗1010Ω超
△:抵抗が1010以上108Ω以下
×:抵抗が108Ω未満
<High temperature insulation resistance>
The glass substrate was baked in an oven at 280 ° C. for 60 minutes, and the positive electrode and negative electrode of the resistance meter (manufactured by Agilent Technologies, high resistance meter 4339B, component test fixture 16339A) were separated by a distance of 0.5 cm between the positive electrode and the negative electrode. The film resistance was measured under the conditions of voltage: 500 V, time: 60 seconds, and the film resistance was evaluated as follows.
○: Resistance of more than 10 10 Ω Δ: Resistance of 10 10 or more and 10 8 Ω or less ×: Resistance of less than 10 8 Ω
<表面平坦性>
表面粗さ測定計(小阪研究室製、型番:SE3500)を用いて、測定長さ:2.5mm、縦倍率:1000、横倍率:100、カットオフ:0.8mm、速度:0.5mm/sという条件で皮膜表面の粗さ(ピークの最大高さ、RmaxD)を3回測定し、以下のように評価した。
○:RmaxDが1.5μm未満
△:RmaxDが1.5以上2μm未満
×:RmaxDが2μm以上
<Surface flatness>
Using a surface roughness meter (manufactured by Kosaka Laboratory, model number: SE3500), measurement length: 2.5 mm, longitudinal magnification: 1000, lateral magnification: 100, cutoff: 0.8 mm, speed: 0.5 mm / The surface roughness (maximum peak height, RmaxD) was measured three times under the condition of s, and evaluated as follows.
○: RmaxD is less than 1.5 μm Δ: RmaxD is 1.5 or more and less than 2 μm ×: RmaxD is 2 μm or more
<鉛筆硬度テスト>
JIS K5400(1990版)に準拠して、鉛筆硬度計(東洋精機社製、型番:C221A)各ガラス基板に、芯の先が平らになるように研がれた4B〜9Hの鉛筆を、約45°の角度で押し付けて、皮膜の剥がれが生じない鉛筆の硬さを記録した。
<Pencil hardness test>
In accordance with JIS K5400 (1990 version), a pencil hardness tester (manufactured by Toyo Seiki Co., Ltd., model number: C221A) about 4B to 9H pencil sharpened on each glass substrate so that the tip of the core becomes flat, Pressing at an angle of 45 °, the hardness of the pencil at which no film peeling occurred was recorded.
<耐硫酸性>
25℃でガラス基板を10vol%硫酸水溶液に30分間浸漬して、水で洗浄を行った後に、水分を除去して、目視で水の浸入または皮膜の溶出を確認した。次に、透明粘着テープ(ニチバン社製、横幅:18mm)を完全に評価ガラス基板の皮膜側に付着させ、直ちにテープの一端をガラス基板に対して直角に保ちながら瞬間的に引き離し、目視で以下のように皮膜を評価した。
○:変化が確認されなかった。
△:わずかな変化が確認された。
×:水の浸入または皮膜の剥離が確認された。
<Sulfuric acid resistance>
After immersing the glass substrate in a 10 vol% sulfuric acid aqueous solution at 25 ° C. for 30 minutes and washing with water, the moisture was removed, and the intrusion of water or the elution of the film was visually confirmed. Next, a transparent adhesive tape (manufactured by Nichiban Co., Ltd., width: 18 mm) is completely attached to the film side of the evaluation glass substrate, and immediately pulled apart while keeping one end of the tape at right angles to the glass substrate. The film was evaluated as follows.
○: No change was confirmed.
Δ: A slight change was confirmed.
X: Water permeation or film peeling was confirmed.
<耐塩酸性>
25℃でガラス基板を10vol%塩酸水溶液に30分間浸漬して、水で洗浄を行った後に、水分を除去して、目視で水の浸入または皮膜の溶出を確認した。次に、透明粘着テープ(ニチバン社製、横幅:18mm)を完全に評価ガラス基板の皮膜側に付着させ、直ちにテープの一端をガラス基板に対して直角に保ちながら瞬間的に引き離し、目視で以下のように皮膜を評価した。
○:変化が確認されなかった。
△:わずかな変化が確認された。
×:水の浸入または皮膜の剥離が確認された。
<Hydrochloric acid resistance>
The glass substrate was immersed in a 10 vol% hydrochloric acid aqueous solution at 25 ° C. for 30 minutes and washed with water. Then, the water was removed, and water intrusion or film elution was visually confirmed. Next, a transparent adhesive tape (manufactured by Nichiban Co., Ltd., width: 18 mm) is completely attached to the film side of the evaluation glass substrate, and immediately pulled apart while keeping one end of the tape at right angles to the glass substrate. The film was evaluated as follows.
○: No change was confirmed.
Δ: A slight change was confirmed.
X: Water permeation or film peeling was confirmed.
<耐アルカリ性>
25℃でガラス基板を10vol%NaOH水溶液に30分間浸漬して、水で洗浄を行った後に、水分を除去して、目視で水の浸入または皮膜の溶出を確認した。次に、透明粘着テープ(ニチバン社製、横幅:18mm)を完全に評価ガラス基板の皮膜側に付着させ、直ちにテープの一端をガラス基板に対して直角に保ちながら瞬間的に引き離し、目視で以下のように皮膜を評価した。
○:変化が確認されなかった。
△:わずかな変化が確認された。
×:水の浸入または皮膜の剥離が確認された。
<Alkali resistance>
After immersing the glass substrate in a 10 vol% NaOH aqueous solution at 25 ° C. for 30 minutes and washing with water, the water was removed, and water permeation or film elution was confirmed visually. Next, a transparent adhesive tape (manufactured by Nichiban Co., Ltd., width: 18 mm) is completely attached to the film side of the evaluation glass substrate, and immediately pulled apart while keeping one end of the tape at right angles to the glass substrate. The film was evaluated as follows.
○: No change was confirmed.
Δ: A slight change was confirmed.
X: Water permeation or film peeling was confirmed.
<耐溶剤性>
キンバリークラーク製のレンズペーパーに、少量のアルコール(95vol%)、ジプロピレングリコールモノメチルエーテル(DPM)(100vol%)、イソプロピルアルコール(IPA)(100vol%)を付け、溶剤が付けられたレンズペーパーを用いてガラス基板の皮膜を約20回繰り返して拭いた後に、皮膜の表面を目視で観察した。
○:変化が確認されなかった。
△:わずかな変化が確認された。
×:皮膜が剥離した。
<Solvent resistance>
Use a lens paper to which a small amount of alcohol (95 vol%), dipropylene glycol monomethyl ether (DPM) (100 vol%), isopropyl alcohol (IPA) (100 vol%) is attached to a lens paper made by Kimberly Clark. After the glass substrate film was wiped about 20 times repeatedly, the surface of the film was visually observed.
○: No change was confirmed.
Δ: A slight change was confirmed.
X: The film peeled off.
<密着性(碁盤目付着性試験方法)>
JISK5400に準拠して、サンプルの皮膜に、1mmの碁盤目100個(10×10)を作り、碁盤目上に透明粘着テープ(ニチバン社製、幅:18mm)を完全に付着させ、直ちにテープの一端をガラス基板に対して直角に保ちながら瞬間的に引き離し、完全に剥がれないで残った碁盤目の数を調べた。
下記表2には、残った碁盤目の数を分子として、碁盤目の全数(100個)を分母として結果を記載した。
○:碁盤目が100%残存した。
△:碁盤目が95%以上100%未満残存した。
×:碁盤目が95%未満残存した。
前記各評価試験の結果を表2にまとめて示す。
<Adhesion (cross-cut adhesion test method)>
In accordance with JISK5400, 100 1 mm grids (10 × 10) are made on the sample film, and a transparent adhesive tape (Nichiban Co., Ltd., width: 18 mm) is completely adhered on the grids. While keeping one end at a right angle to the glass substrate, it was pulled away instantaneously, and the number of grids remaining without being completely peeled was examined.
Table 2 below shows the results with the number of remaining grids as the numerator and the total number of grids (100) as the denominator.
○: 100% of the grid pattern remained.
(Triangle | delta): 95% or more and less than 100% remain | survived.
X: A grid of less than 95% remained.
The results of each evaluation test are summarized in Table 2.
表2に示すように、本実施形態に係る実施例1〜8はいずれも、密着性、表面平坦性、硬化性を高いレベルでバランス良く達成でき、且つ高温絶縁抵抗性及び耐溶剤性を両立するものであった。特に硫酸バリウムの配合量が特定の量(カルボキシル基含有樹脂とエポキシ樹脂との合計量100質量部に対して、30〜70質量部)であると、高温絶縁抵抗性がさらに良くなることが確認された。一方、カルボキシル基含有樹脂を含まない組成物を用いた比較例1、硫酸バリウムを含まない組成物を用いた比較例2、及び、エポキシ樹脂を含まない組成物を用いた比較例3はいずれも、密着性、表面平坦性、硬化性を高いレベルでバランス良く達成できない上に、高温絶縁抵抗性及び耐溶剤性を両立することができないものであった。 As shown in Table 2, all of Examples 1 to 8 according to this embodiment can achieve adhesion, surface flatness, and curability at a high level in a well-balanced manner, and achieve both high-temperature insulation resistance and solvent resistance. It was something to do. It is confirmed that the high-temperature insulation resistance is further improved particularly when the blending amount of barium sulfate is a specific amount (30 to 70 parts by mass with respect to 100 parts by mass of the total amount of the carboxyl group-containing resin and the epoxy resin). It was done. Meanwhile, Comparative Example 1 using a composition containing no carboxyl group-containing resin, Comparative Example 2 using a composition containing no barium sulfate, and Comparative Example 3 using a composition containing no epoxy resin are all used. In addition, adhesion, surface flatness, and curability cannot be achieved in a well-balanced manner at a high level, and high-temperature insulation resistance and solvent resistance cannot be achieved at the same time.
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