CN106414556B - Hardening resin composition - Google Patents
Hardening resin composition Download PDFInfo
- Publication number
- CN106414556B CN106414556B CN201680000405.2A CN201680000405A CN106414556B CN 106414556 B CN106414556 B CN 106414556B CN 201680000405 A CN201680000405 A CN 201680000405A CN 106414556 B CN106414556 B CN 106414556B
- Authority
- CN
- China
- Prior art keywords
- methyl
- ingredient
- resin composition
- acrylate
- hardening resin
- 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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- 239000011342 resin composition Substances 0.000 title claims abstract description 39
- 239000004615 ingredient Substances 0.000 claims abstract description 50
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical class COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000126 substance Substances 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 24
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 15
- -1 (methyl) acryloxy Chemical group 0.000 description 40
- 150000001721 carbon Chemical group 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 239000000654 additive Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 238000010538 cationic polymerization reaction Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000004693 imidazolium salts Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- QZAYGJVTTNCVMB-UHFFFAOYSA-N serotonin Chemical compound C1=C(O)C=C2C(CCN)=CNC2=C1 QZAYGJVTTNCVMB-UHFFFAOYSA-N 0.000 description 4
- 230000008719 thickening Effects 0.000 description 4
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 150000003335 secondary amines Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- 239000004034 viscosity adjusting agent Substances 0.000 description 3
- NJXYTXADXSRFTJ-UHFFFAOYSA-N 1,2-Dimethoxy-4-vinylbenzene Chemical compound COC1=CC=C(C=C)C=C1OC NJXYTXADXSRFTJ-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 0 CC*(C(*(CC*COC(CCNC)=O)CC(*1CC*)=*)C=O)C1=C Chemical compound CC*(C(*(CC*COC(CCNC)=O)CC(*1CC*)=*)C=O)C1=C 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 2
- 150000003851 azoles Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 229960005222 phenazone Drugs 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229940076279 serotonin Drugs 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 125000000101 thioether group Chemical group 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- CTLDMRCJDQGAQJ-UHFFFAOYSA-N (1,1-dimethoxy-2-phenylethyl)benzene Chemical compound C=1C=CC=CC=1C(OC)(OC)CC1=CC=CC=C1 CTLDMRCJDQGAQJ-UHFFFAOYSA-N 0.000 description 1
- YBBLOADPFWKNGS-UHFFFAOYSA-N 1,1-dimethylurea Chemical class CN(C)C(N)=O YBBLOADPFWKNGS-UHFFFAOYSA-N 0.000 description 1
- URJFKQPLLWGDEI-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=[C]N1CC1=CC=CC=C1 URJFKQPLLWGDEI-UHFFFAOYSA-N 0.000 description 1
- XZKLXPPYISZJCV-UHFFFAOYSA-N 1-benzyl-2-phenylimidazole Chemical class C1=CN=C(C=2C=CC=CC=2)N1CC1=CC=CC=C1 XZKLXPPYISZJCV-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
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical class CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- 150000008614 2-methylimidazoles Chemical class 0.000 description 1
- 150000004941 2-phenylimidazoles Chemical class 0.000 description 1
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical class C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical class CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- QBJKMPPBWQMKGY-UHFFFAOYSA-N 3-(2-phenyl-1h-imidazol-5-yl)propanenitrile Chemical class N1C(CCC#N)=CN=C1C1=CC=CC=C1 QBJKMPPBWQMKGY-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229940123208 Biguanide Drugs 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004425 Makrolon Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
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- 239000005864 Sulphur Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- AGJXDKGTTMVHOU-UHFFFAOYSA-N [4-(hydroxymethyl)-1h-imidazol-5-yl]methanol Chemical compound OCC=1N=CNC=1CO AGJXDKGTTMVHOU-UHFFFAOYSA-N 0.000 description 1
- DZHAKMZHPZQEIN-UHFFFAOYSA-N [I].FC(F)F Chemical compound [I].FC(F)F DZHAKMZHPZQEIN-UHFFFAOYSA-N 0.000 description 1
- QFJVRMQMEQYFIB-UHFFFAOYSA-N [SH3+].[Br-].C1(=CC=CC=C1)[PH+](C1=CC=CC=C1)C1=CC=CC=C1.[Br-] Chemical compound [SH3+].[Br-].C1(=CC=CC=C1)[PH+](C1=CC=CC=C1)C1=CC=CC=C1.[Br-] QFJVRMQMEQYFIB-UHFFFAOYSA-N 0.000 description 1
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- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
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- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
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- WSDHIXAKVRLSPY-UHFFFAOYSA-N fluoroform;tris(4-methylphenyl)sulfanium Chemical compound FC(F)F.C1=CC(C)=CC=C1[S+](C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WSDHIXAKVRLSPY-UHFFFAOYSA-N 0.000 description 1
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- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 1
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- 150000003624 transition metals Chemical class 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- BAZVSMNPJJMILC-UHFFFAOYSA-N triadimenol Chemical compound C1=NC=NN1C(C(O)C(C)(C)C)OC1=CC=C(Cl)C=C1 BAZVSMNPJJMILC-UHFFFAOYSA-N 0.000 description 1
- UXVLEXMPXZXYSA-UHFFFAOYSA-N triazine-1,2-diamine Chemical compound NN1C=CC=NN1N UXVLEXMPXZXYSA-UHFFFAOYSA-N 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/38—Esters containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
- C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/0245—Block or graft polymers
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention provides a kind of hardening resin composition, contains (methyl) acrylate derivative of the Sulfide-containing Hindered of (A) specific structure, the multifunctional (methyl) acrylate that (B) weight average molecular weight is 200~50000.(A) mass ratio ((A)/(B)) of ingredient and (B) ingredient is 0.05~30.
Description
Technical field
The present invention relates to a kind of hardening resin composition, even if the hardening resin composition can be obtained on cold ground
The cured film that area is also excellent to the adhesion of base material and flexibility is excellent.
Background technology
In the past, in order to improve using adhesion of the epoxy resin as coating of principal component etc. to inorganic substrate, there is addition silane
The technology (Unexamined Patent 7-300491 bulletins) of coupling agent.However, the most low boiling point of silane coupling agent, needs to make an addition in large quantities
Thermosetting resin.Also, it is also insufficient by adding the adhesion improvement effect that silane coupling agent obtains, by also adding simultaneously
Such as the adhesions auxiliary agent such as salt, phosphate, polyurethane resin of titanium zirconium etc. could obtain the adhesion needed for realistic scale
Situation is also more.At this point, the addition of these adhesion auxiliary agents not only increases operation quantity, need also exist for selection and do not damage painting
Expect characteristic adhesion auxiliary agent type or its additive amount stringent optimized operation the problems such as.
Special open 2012-246464 bulletins disclose a kind of by multi-functional thiol's compound and the alcoxyl of specific Sulfide-containing Hindered
Base silane derivative and composition epoxy resin and the curability that there is the multifunctional polyenoid (polyene) of multiple double bonds to mix
Resin combination.The hardening resin composition, with using as silane coupling agent, without adding other adhesion auxiliary agents, energy
Enough excellent adhesions played to inorganic substrate.
Invention content
The technical problem to be solved in the present invention
However, understand such as special open 2012-246464 bulletins by multi-functional thiol's compound and specific Sulfide-containing Hindered
The alkoxyl silicone alkane derivatives and composition epoxy resin and curable resin that mixes of multifunctional polyenoid with multiple double bonds
Composition, although the excellent in stability of resin combination excellent to the adhesion of inorganic substrate, there are following technologies to ask
Topic：Cured film easily occurs slight crack (crack) in bending and lacks attaching due to shortage flexibility in cold district
Property.
Therefore, it is necessary to a kind of excellent and gained cured films even if adhesion of the cold district to base material to have softness
The material of property.
Solve the technological means of technical problem
In one aspect of the invention, hardening resin composition contains (methyl) third of Sulfide-containing Hindered shown in (A) following formula 1
Olefin(e) acid ester derivant, the multifunctional (methyl) acrylate that (B) weight average molecular weight is 200~50000, (A) ingredient and institute
The mass ratio ((A)/(B)) for stating (B) ingredient is 0.05~30.
[chemical formula 1]
A in formula is 1~2 integer, and b is 1~2 integer, a+b=3.R1For trivalent group, R shown in following formula 22For under
State divalent group shown in formula 3 or following formula 4；R3The alkyl for being 1~12 for carbon atom number,
[chemical formula 2]
R in formula4For-CH2-、-CH2CH2Or-CH2CH(CH3)-,
[chemical formula 3]
R5For hydrogen atom or methyl,
[chemical formula 4]
R5For hydrogen atom or methyl.
Another aspect of the present invention, hardening resin composition, can also be into other than (A)~(B) ingredients
One step contains (C) Photoepolymerizationinitiater initiater.Relative to 100 mass parts of gross mass of (A) ingredient and (B) ingredient, it is somebody's turn to do (C)
Ingredient is 0.01~10 mass parts.
Another aspect of the present invention, hardening resin composition is in addition to (A)~(B) ingredient or (A)~(C) ingredients
Except, it can also further contain the aminated compounds that (D) weight average molecular weight is 90~700.Relative to (A) ingredient and institute
100 mass parts of gross mass of (B) ingredient are stated, it is 0.01~50 mass parts to be somebody's turn to do (D) ingredient.
Hardening resin composition according to the present invention, with (methyl) acrylate derivative of specific Sulfide-containing Hindered
(A) for adhesion raising effect active ingredient while, balance well be added with specified molecular weight multifunctional (methyl)
Acrylate (B).It is therefore not necessary to other adhesion auxiliary agents etc. are added as using previous silane coupling agent, curability tree
The cured film of oil/fat composition can also realize the excellent adhesion to base material.Particularly, even if in cold district, gained cured film
Also the excellent adhesion and flexibility to base material have been given play to.
Specific embodiment
The hardening resin composition of the present invention optionally further contains using following (A) and (B) ingredient as neccessary composition
(C) and at least one of (D) ingredient.In addition, in the present invention, if without in addition illustrating, " molecular weight " refers to Weight-average molecular
Amount." (methyl) acrylate " is the general designation for including both acrylate and methacrylate, " (methyl) acryloxy "
It is the general designation for including acryloxy and (methyl) acryloxy.If without in addition illustrating, represent numberical range " 0 0~
×× " includes its upper limit value (" 00 ") and lower limiting value (" ×× "), that is, for correct, refers to " below more than 00 ××s ".
<(methyl) acrylate derivative ((A) ingredient) of Sulfide-containing Hindered>
(methyl) acrylate derivative of Sulfide-containing Hindered as (A) ingredient is compound shown in following formula 1.
[chemical formula 5]
A in formula is 1~2 integer, and b is 1~2 integer, a+b=3.R1For trivalent group, R shown in following formula 22For under
State divalent group shown in formula 3 or following formula 4；R3The alkyl for being 1~12 for carbon atom number,
[chemical formula 6]
R in formula4For-CH2-、-CH2CH2Or-CH2CH(CH3)-,
[chemical formula 7]
R5For hydrogen atom or methyl,
[chemical formula 8]
R5For hydrogen atom or methyl.
As the R in above-mentioned formula 13Carbon atom number be 1~12 alkyl, can enumerate straight chained alkyl, have side chain alkane
Base, cycloalkyl.
R in above-mentioned formula 24For mutually the same methylene, ethylidene or isopropylidene, ethylidene, isopropylidene because
Adhesion improvement effect is big and particularly preferred.
<Multifunctional (methyl) acrylate ((B) ingredient)>
Multifunctional (methyl) acrylate as (B) ingredient has (methyl) acryloxy in end, excellent as its
Example is selected, compound shown in following formula 5 can be enumerated.In addition, the multifunctional (methyl) acrylate as (B) ingredient both can be only
Be used alone a kind, can also two or more be used in mixed way.
[chemical formula 9]
The integer that c in formula is 2~30, R6For carbon atom number be 2~200 alkyl, carbon atom number be 2~300 only
The group or isocyanuric acid ester (isocyanurate) ring that are formed by ether oxygen (- O-) and alkyl or only by isocyanurate ring
The group formed with alkyl, R7For hydrogen atom or methyl.
In addition, as (B) multifunctional (methyl) acrylate, polymer-type can be also properly used.As polymerization
Object type multifunctional (methyl) acrylate, can enumerate following polymer：Having such as (methyl) acrylic acid can be anti-with epoxy group
(methyl) acrylate and (methyl) glycidyl acrylate of the group answered etc. have (methyl) acrylate of epoxy group
Homopolymer or copolymer reaction obtained from polymer；Having such as 2- methacrylic acids 2- isocyanatoethyl methacrylates can be with hydroxyl
(methyl) acrylate and (methyl) hydroxy-ethyl acrylate of the group of base reaction etc. have (methyl) acrylate of hydroxyl
Polymer obtained from homopolymer or copolymer reaction；Such as (methyl) glycidyl acrylate is made to have and can be reacted with carboxyl
Group (methyl) acrylate and (methyl) acrylic acid etc. have carboxyl (methyl) acrylate homopolymer or copolymerization
Polymer etc. obtained from object reaction.
(B) weight average molecular weight of multifunctional (methyl) acrylate is 200~50000, preferably 220~40000, more
Preferably 240~30000.(B) even if the weight average molecular weight of multifunctional (methyl) acrylate is less than 200, also there is no be related to
It is the problem of adhesion, but the tendency to smarten with volatility raising, foul smell, thus not preferred.On the other hand, if Weight-average molecular
Amount is more than 50000, although there is no adhesion is involved in the problems, such as, there is a possibility that the dissolubility reduction to other compositions,
It is thus not preferred.
In addition, (methyl) the acrylate equivalent of (B) multifunctional (methyl) acrylate is 80~6000g/mol, preferably
For 80~4500g/mol, more preferably 85~3000g/mol.If (methyl) acrylate equivalent is less than 80g/mol, by
Superfluous, the mercapto with (methyl) acrylate derivative of (A) Sulfide-containing Hindered in (methyl) acryloxy of per unit volume
Unreacted (methyl) acryloxy largely remains, thus has under the toughness of the cured film formed by hardening resin composition
The worry that drop, adhesion decline.On the other hand, if (methyl) acrylate equivalent is more than 6000g/mol, due to (methyl) third
Alkene acyloxy concentration significantly reduces, and declines with the reaction efficiency of the mercapto of (methyl) acrylate derivative of (A) Sulfide-containing Hindered,
Thus there is the toughness of the cured film formed by hardening resin composition to decline, the worry that adhesion declines.
<Photoepolymerizationinitiater initiater ((C) ingredient)>
In order to promote reacting for mercapto and (methyl) acryloxy, (C) ingredient Photoepolymerizationinitiater initiater is added, can be reduced
Light needed for curing in solidification compound irradiates.As Photoepolymerizationinitiater initiater, optical free radical polymerization can be enumerated and caused
Agent, light cationic polymerization initiator, time cation polymerization initiator etc..Photopolymerization radical initiator is preferred for shortening reaction
During the time, light cationic polymerization initiator be preferred for reduce cure shrinkage when, time cation polymerization initiator be preferred for
Circuit is when assigning cementability in fields.
As optical free radical polymerization initiator, such as 2,2- dimethoxy -1,2- diphenylethane -1- ketone, 1- can be enumerated
Hydroxy-cyclohexyl-phenyl -one, 2- hydroxy-2-methyl -1- phenyl-propan -1- ketone, 1- [4- (2- hydroxyl-oxethyls)-phenyl] -
2- hydroxy-2-methyl -1- propane -1- ketone, 2- hydroxyls -1- { 4- [4- (2- hydroxy-2-methyls-propiono)-benzyl]-phenyl } -
2- methyl-propan -1- ketone, 2- methyl-1s-[4- (methyl mercapto) phenyl] -2- morpholino propane -1- ketone, bis- (2,4,6- trimethyls
Benzoyl)-phenyl phosphine oxide, 2,4,6- trimethylbenzoy-diphenies-phosphine oxide etc..
As light cationic polymerization initiator, such as bis- (4- tert-butyl-phenyls) iodine hexafluorophosphates, bis- (4- can be enumerated
Tert-butyl-phenyl) iodine fluoroform sulphonate, cyclopropyl diphenyl sulfonium tetrafluoroborate, diphenyl iodine hexafluorophosphate, two
Phenyl-iodide hexafluoro arsenate, bis- (the trichloromethyl) -1,3,5- triazines of 2- (3,4 dimethoxy styrene base) -4,6-, triphen
Base sulfonium tetrafluoroborate, triphenyl phosphonium bromide sulfonium, tri-p-tolylsulfonium hexafluorophosphate, tri-p-tolylsulfonium fluoroform sulphonate
Deng.
As time cation polymerization initiator, such as acetophenone-O- benzoyls oxime, nifedipine, 2- (9- oxygen Xanthones can be enumerated
Ton -2- bases) tri- azabicyclic [4.4.0] decyl- 5- alkene of propionic acid 1,5,7-, 2- nitrobenzophenone methyl 4- methacryloxy piperazines
Pyridine -1- carboxylates, 1,2- diisopropyls -3- [bis- (dimethylamino) methylene] guanidine 2- (3- benzoylphenyls) propionate,
- 4,4,5,5 tetramethyl biguanides normal-butyl triph-enylborate of 1,2- dicyclohexyls etc..
<Aminated compounds ((D) ingredient)>
Aminated compounds as (D) ingredient is to promote reacting for (catalysis) mercapto and (methyl) acryloxy
And it adds.Specifically, by containing (D) ingredient, mercapto can be made to be reacted at low temperature with (methyl) acryloxy, because
This can make the curable resin containing (A) ingredient and (B) ingredient carry out low-temperature setting.It, can as the aminated compounds of (D) ingredient
Enumerate the monofunctional amines or have multiple that weight average molecular weight is 90~700, preferably 100~690, more preferably 110~680
The polyamines of amino.Aminated compounds weight average molecular weight less than 90 in the case of, the raising of the volatility of aminated compounds, not only
The reason of making to form foul smell and hole (void), due also to amine concentration when being heating and curing reduces, is difficult to cross-linking reaction,
Adhesion easily declines.If the weight average molecular weight of aminated compounds, more than 700, water resistance reduces, adhesion easily declines.
As monofunctional amines, primary amine, secondary amine or tertiary amine can be enumerated.As polyamines, primary amine, secondary amine, tertiary amine, compound can be enumerated
Amine.Serotonin refers to have the amine of more than two kinds in primary amine groups, secondary amine, tertiary amine groups.As such serotonin, can enumerate
Imidazolinium compounds, imidazolium compounds, N substituted piperazine like compound, N, N- dimethyl urea derivatives etc..In addition, amine compounds were both
1 kind can be only used alone, can also two or more be used in mixed way.
In addition, in order to adjust catalytic activity, aminated compounds also can in advance with organic acid forming salt.As advance and amine
The organic acid of compound reaction, can enumerate carbon atom number be 1~20, the stearic acid or 2- second in molecule with 1~5 carboxyl
The aliphatic carboxylic acids such as base caproic acid, carbon atom number be 1~20, Pyromellitic Acid, the inclined benzene front three in molecule with 1~10 carboxyl
The aromatic carboxylic acids such as acid, benzoic acid or isocyanuric acid.
In aminated compounds, overbasic imidazolium compounds is best suited for the curing under low temperature.In addition it is also possible to it uses
Imidazolium compounds coated with phenolic resin etc..
The imidazolium compounds is compound shown in following formula 6.
[chemical formula 10]
R9For cyano, carbon atom number be 1~10 alkyl, by 2,3- diamino triazine replace carbon atom number be 1~10
Alkyl, carbon atom number be 1~4 alkoxy or hydrogen atom, R8、R10、R11Alkyl, carbon atom number 1 for carbon atom number 1~20
~4 alkoxy or hydrogen atom, R8~R11Alkyl when combination forms ring for carbon atom number 2~8.
Specifically, 2-methylimidazole, 2- undecyl imidazoles, 2- heptadecyl imidazoles, 2- phenylimidazoles, 1 can be enumerated,
2- methylimidazoles, 2- phenyl -4-methylimidazole, 1 benzyl 2 methyl imidazole, 1- benzyl -2- phenylimidazoles, 2- ethyls -4-
Methylimidazole, 1- (2- cyano ethyls) -2-methylimidazole, 1- (2- cyano ethyls) -2- undecyl imidazoles, 1- (2- cyano second
Base) -2-ethyl-4-methylimidazole, 1- (2- cyano ethyl -2- phenylimidazoles, 1- (2- cyano ethyls) -2- ethyl -4- methyl miaows
Azoles, 2,3- dihydro -1H- pyrroles [1,2-a] benzimidazole, 2,4- diamino -6- [2-methylimidazole base-(1)] ethyl-s- three
Piperazine, 2,4- diamino -6- [2- undecyl imidazoles base-(1 ')]-ethyl-s-triazine, 2,4- diamino -6- [2 '-ethyl -4 ' -
Methylimidazolyl-(1 ')]-ethyl-S- triazines, 2 pheny1 4,5 dihydroxymethyl imidazole, 2- phenyl -4- methyl -5- methylol miaows
Azoles.
<Ratio of components (equilibrium addition)>
Hardening resin composition is with (methyl) acrylate derivative of (A) Sulfide-containing Hindered and (B) multifunctional (methyl) third
The mode that the mass ratio ((A)/(B)) of olefin(e) acid ester is 0.05~30 is added.Herein, " (A)/(B) " refers to (A) Sulfide-containing Hindered
The value of the quality of (methyl) acrylate derivative divided by the quality of (B) multifunctional (methyl) acrylate.In (A)/(B) deficiencies
0.05 or more than 30 in the case of, there are adhesion decline tendency.Best (A)/(B) value is because of hardening resin composition institute
It is required that characteristic, (methyl) acrylate derivative of (A) Sulfide-containing Hindered or the type of (B) multifunctional (methyl) acrylate and
It is different.Hardening resin composition curing after characteristic strictly (the mercaptan radix) in by hardening resin composition Unit Weight/
The value of ((methyl) acryloyl-oxy radix) (hereinafter referred to as mercaptan/alkene ratio) influences.For example, if mercaptan/alkene is than 0.5~1.5
In the range of, then close crosslinking is easily formed, and easily form tough solidfied material.On the other hand, if mercaptan/alkene ratio is more than 0.1
Less than 0.5 or less than 2.0 more than 1.5, then soft adhesive object can be obtained.If mercaptan/alkene is than less than 0.1 or being more than
2.0, then gelation is difficult to, there are the tendencies that adhesion declines.
In addition, hardening resin composition is multifunctional relative to (methyl) acrylate derivative of (A) Sulfide-containing Hindered and (B)
Gross mass ((A)+(B)) 100 mass parts of (methyl) acrylate, added with 0.01~10 mass parts (C) Photoepolymerizationinitiater initiater.
In the case of relative to the additive amount of ((A)+(B)) 100 mass parts (C) ingredient less than 0.01 mass parts, need largely tired
Product light quantity, progress mercapto are reacted with (methyl) acryloxy, if more than 10 mass parts, reduced there are crosslink density,
The situation that adhesion declines.
In addition, in the case where adding (D) aminated compounds into hardening resin composition, relative to (A) Sulfide-containing Hindered
(methyl) acrylate derivative and (B) multifunctional (methyl) acrylate gross mass ((A)+(B)) 100 mass parts, add
Add 0.01~50 mass parts, preferably add 0.01~45 mass parts (D) aminated compounds.(D) additive amount of ingredient relative to
In the case that ((A)+(B)) is less than 0.01, the function as catalyst is insufficient, does not realize and cures promotion as caused by heating,
If more than 50 mass parts, the storage stability of hardening resin composition declines.
<The formation of cured film>
Hardening resin composition is cured by being coated on base material, can form cured film.Curable resin group
It closes object and the adhesion to base material has been given play to by the thioether group of (methyl) acrylate derivative of (A) Sulfide-containing Hindered.Therefore, as
Base material, it is excellent for forming the adhesion improvement effect of base material of chemical bond (chemical affinity is high) with thioether group, such as：Transition
Metal or the inorganic substrates such as its alloy or silicon compound, phosphorus compound, sulphur compound or boron compound；With unsaturated bond
The organic matter of (including aromatic rings), the organic matter that there is the organic matter or plasma or UV ozone treatments of hydroxyl or carboxyl to cross
Wait organic substrates.Specifically, as inorganic substrate, glass, silicon, various metals etc. can be enumerated.As organic substrate, preferably arrange
Lift poly- (methyl) acrylic resin, Triafol T (TAC) resinoid, polyethylene terephthalate (PET) or poly-
The polyester resins such as mutual-phenenyl two acid bromide two alcohol ester, polycarbonate resin, polyimide based resin, polyethylene or polypropylene etc.
Polyolefin resin, makrolon, polyimides, ABS resin, polyvinyl alcohol, vinyl chloride resin, polyacetals etc..It is in addition, solid
The property changed resin combination has specific alkyl, thus cured film due to (methyl) acrylate derivative of (A) Sulfide-containing Hindered
Flexibility is excellent.Therefore, even if under cold conditions, cured film also easy followed base material is excellent to the adhesion of base material.So as to
The coating of flexible parent metal that can be used under cold conditions particularly suitablely.
Hardening resin composition can be cured by the irradiation of light.As irradiation light, it is (ultraviolet UV can be enumerated
Line), EB (electron beam) isoreactivity energy line etc..It, can be in addition, hardening resin composition is in the case of containing (C) ingredient
By the commonly required 2500mJ/cm wanted2The light irradiation amount of left and right is reduced to 100mJ/cm2Left and right.In addition, curable resin combines
Object can cure in the case of containing (D) ingredient in a low temperature of 80 DEG C or so.Also, hardening resin composition containing
In the case of having (C) ingredient and (D) ingredient, additionally it is possible to pair of the curing process by light irradiation and the curing process by heating
Heavy industry sequence is cured.
In order to which reaction system is made uniformly, to be easily coated, hardening resin composition can be with after organic solvent diluting
It uses.As such organic solvent, alcohols solvent, aromatic hydrocarbon solvent, ether solvent, esters solvent and ether-ether can be enumerated
Class solvent, ketones solvent, phosphoric acid ester solvent.Relative to 100 mass parts hardening resin compositions, these organic solvents add
Dosage is preferably controlled to less than 10000 mass parts, but substantially solvent volatilizees when forming cured film, because without to cured film
Physical property cause big influence.
In addition, in order to adjust the purpose of viscosity, hardening resin composition of the invention can also add titanium dioxide
The viscosity modifiers such as Si powder.Relative to 100 mass parts hardening resin compositions, preferably by the addition of these viscosity modifiers
Amount control is less than 300 mass parts.If the additive amount of viscosity modifier is more than 300 mass parts, adhesion may decline.
In addition, the hardening resin composition of the present invention can also be added available for the various of common coating or binding agent
Additive.As such additive, can enumerate for make coated face smooth surfactant, for extending pot life
Aluminium salt etc..It is less than 80 matter preferably by the control of the additive amount of these additives relative to 100 mass parts hardening resin compositions
Measure part.If the additive amount of these additives is more than 80 mass parts, adhesion may decline.
Embodiment
Embodiment and comparative example are enumerated below, and more specific description is carried out to hardening resin composition.The present embodiment and ratio
It is as follows compared with each ingredient used in example.In addition, Mw represents weight average molecular weight.
<(A) ingredient>
(A-1：(methyl) acrylate derivative of Sulfide-containing Hindered)
[chemical formula 11]
(A-2：(methyl) acrylate derivative of Sulfide-containing Hindered)
[chemical formula 12]
(A-3：(methyl) acrylate derivative of Sulfide-containing Hindered)
[chemical formula 13]
(A-4：(methyl) acrylate derivative of Sulfide-containing Hindered)
[chemical formula 14]
(A-5：(methyl) acrylate derivative of Sulfide-containing Hindered)
[chemical formula 15]
(A-6：Multi-thiol compound)
[chemical formula 16]
(A-7：Multi-thiol compound)
[chemical formula 17]
(A-8：The alkoxyl silicone alkane derivatives of Sulfide-containing Hindered)
[chemical formula 18]
(A-9：The alkoxyl silicone alkane derivatives of Sulfide-containing Hindered)
[chemical formula 19]
(A-10：(methyl) acrylate derivative of Sulfide-containing Hindered)
[chemical formula 20]
<(B) ingredient)：Multifunctional (methyl) acrylate>
(B-1, Mw：5000)
[chemical formula 21]
(n average out to 13)
(B-2, Mw：246)
[chemical formula 22]
(B-3, Mw：352)
[chemical formula 23]
(B-4, Mw：22000)
Using following D-3 as catalyst, on the copolymer of glycidyl methacrylate and cyclohexyl methacrylate
The polymer of equimolar addition methacrylic acid (carries out what reprecipitation obtained with hexane to the methyl isobutyl ketone solution of 50wt%
White solid)
(B-5, Mw：45000)
Using following D-3 as catalyst, on the copolymer of glycidyl methacrylate and cyclohexyl methacrylate
The polymer of equimolar addition methacrylic acid (carries out what reprecipitation obtained with hexane to the methyl isobutyl ketone solution of 50wt%
White solid)
<(C) ingredient：Photoepolymerizationinitiater initiater>
(C-1, Mw：204)
1- hydroxy-cyclohexyl-phenyl -one
(C-2, Mw：348)
2,4,6- trimethylbenzoy-diphenies-phosphine oxide
(C-3, Mw：407)
2- (9- oxygen xanthene -2- bases) propionic acid 1,5,7- tri- azabicyclic [4.4.0] decyl- 5- alkene
<(D) ingredient：Aminated compounds>
(D-1, Mw：110)
[chemical formula 24]
(D-2, Mw：102)
N, N- dimethyl -1,3- propane diamine
(D-3, Mw：680)
[chemical formula 25]
(n1, n2, n3 be 1~5 integer, average out to 3.5 mixture)
(A)~(D) ingredients are mixed with mixing ratio shown in table 1 below~table 4 respectively, are stirred with spatula (spatula) to equal
It is even, obtain the sample of the hardening resin composition of each embodiment and comparative example.Each curing to gained embodiment and comparative example
Property resin combination sample carry out following adhesion 1 (room temperature adhesion), adhesion 2 (cold district adhesion), flexibility and
Storage stability is evaluated.As a result it is shown in 1~table of table 4.
[making of evaluation test film]
The evaluation of adhesion 1, adhesion 2 and flexibility is obtained with test film by following manner.With die coating machine (Die
Coater) each sample of hardening resin composition is coated on 100 μm of thickness on the PET film of 25mm wide, is weighed on it
After folded other PET film, cured with condition of cure shown in 1~table of table 4, obtain evaluation test film.In addition, as PET film, make
With eastern beautiful (strain) Lumirror U46-100 processed.Light irradiation has used UV plants of formula meetings of Heraeus NobleLight Fusion
The UV lamp system " light hammer 6 " of society's manufacture, light bulb has used H light bulbs.
[adhesion 1 (room temperature adhesion)]
After above-mentioned evaluation test film is stood 24 hours at 25 DEG C, within 5 minutes, provided with JIS K6854-3
T-shaped stripping method be measured, evaluated as follows.
◎：Tensile strength is more than 5N/25mm (rupture of PDT films)
○：Tensile strength is more than 5N/25mm (PDT films do not rupture)
×：Less than 5N/25mm
[adhesion 2 (cold district adhesion)]
After above-mentioned evaluation test film is stood 24 hours at -10 DEG C, within 5 minutes, provided with JIS K6854-3
T-shaped stripping method be measured, evaluated as follows.
◎：Tensile strength is more than 5N/25mm (rupture of PDT films)
○：Tensile strength is more than 5N/25mm (PDT films do not rupture)
×：Less than 5N/25mm
[flexibility]
After above-mentioned evaluation test film is stood 24 hours at -10 DEG C, within 5 minutes, the stick in a diameter of 8mm is rolled up
It with visual observation, was evaluated as follows upper 1 minute.
○：0 slight crack
×：1 or more slight crack
[storage stability]
It is (firm mixed to measure the sample of the hardening resin composition of each embodiment and comparative example viscosity mixed 25 DEG C firm
Viscosity after conjunction), and measured again with the viscosity (viscosity after heating) after heating 12 hours at 40 DEG C, the viscosity after heating is removed
With firm mixed viscosity, thickening rate is calculated, is evaluated as follows.In addition, viscosity is glued with Toki Sangyo Co., Ltd.'s R types
Degree meter is measured with following conditions.
The rotor used：1°34’×R24
Measurement range：0.5183~103.7Pas
◎：Thickening rate 1.0~1.8
○：Thickening rate 1.8~10
×：Thickening rate is outside above range
In the hardening resin composition of embodiment 1-1~1-13, the high attaching under room temperature and cold conditions is confirmed
Property, good flexibility and excellent storage stability.In the solidification compound of embodiment 2-1~2-5, confirm and pass through
A small amount of light is irradiated and is cured, high adhesion, good flexibility and excellent storage stability under room temperature and cold conditions.
In the hardening resin composition of embodiment 3-1~3-5, confirm and cured by a small amount of illumination and low-temperature heat, room temperature and
High adhesion, good flexibility and excellent storage stability under cold conditions.On the other hand, (A) ingredient relative to
(B) the very few comparative example 1-1 of ingredient and (A) ingredient are relative in the excessive comparative example 1-2 of (B) ingredient, not only in cold item
Adhesion is poor under part, and the adhesion under room temperature is also poor.Used without above-mentioned formula 1 structure compound as (A) into
In the comparative example 1-3~1-7 divided, the adhesion under cold conditions is poor.
Claims (3)
1. a kind of hardening resin composition, contains：
(A) (methyl) acrylate derivative of Sulfide-containing Hindered shown in following formula 1,
(B) weight average molecular weight is 200~50000 multifunctional (methyl) acrylate,
Mass ratio (A)/(B) of (A) ingredient and (B) ingredient is 0.05~30,
[chemical formula 1]
A in formula is 1~2 integer, and b is 1~2 integer, a+b=3；R1For trivalent group, R shown in following formula 22For following formula
3 or following formula 4 shown in divalent group；R3The alkyl for being 1~12 for carbon atom number,
[chemical formula 2]
R in formula4For-CH2-、-CH2CH2Or-CH2CH(CH3)-,
[chemical formula 3]
R5For hydrogen atom or methyl,
[chemical formula 4]
R5For hydrogen atom or methyl.
2. hardening resin composition according to claim 1, relative to the total of (A) ingredient and (B) ingredient
100 mass parts of quality contain 0.01~10 mass parts (C) Photoepolymerizationinitiater initiater.
3. hardening resin composition according to claim 1 or 2, relative to (A) ingredient and (B) ingredient
100 mass parts of gross mass contain the aminated compounds that 0.01~50 mass parts (D) weight average molecular weight is 90~700.
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| JP5355845B2 (en) | 2006-02-24 | 2013-11-27 | 太陽ホールディングス株式会社 | Photocurable resin composition and cured product thereof. |
| JP5012005B2 (en) * | 2006-12-27 | 2012-08-29 | Ｄｉｃ株式会社 | Fluorine-containing composition and fluorine-containing polyfunctional thiol |
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| US20140319734A1 (en) * | 2013-04-24 | 2014-10-30 | The Board Of Regents Of The University Of Texas System | Real time manufacturing of softening polymers |
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