CN1690118A - Epoxy resin composition, ultraviolet rays-curable can-coating composition and its uses - Google Patents
Epoxy resin composition, ultraviolet rays-curable can-coating composition and its uses Download PDFInfo
- Publication number
- CN1690118A CN1690118A CN 200510066823 CN200510066823A CN1690118A CN 1690118 A CN1690118 A CN 1690118A CN 200510066823 CN200510066823 CN 200510066823 CN 200510066823 A CN200510066823 A CN 200510066823A CN 1690118 A CN1690118 A CN 1690118A
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- Prior art keywords
- compound
- epoxy
- epoxy resin
- weight
- acid
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 58
- 239000008199 coating composition Substances 0.000 title claims abstract description 39
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 32
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 32
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims abstract description 22
- 239000004065 semiconductor Substances 0.000 claims abstract description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 13
- 125000005843 halogen group Chemical group 0.000 claims abstract description 12
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 8
- 125000001424 substituent group Chemical group 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims description 189
- 239000004593 Epoxy Substances 0.000 claims description 132
- 238000004519 manufacturing process Methods 0.000 claims description 63
- 125000003700 epoxy group Chemical group 0.000 claims description 55
- 150000002148 esters Chemical group 0.000 claims description 44
- 229920005989 resin Polymers 0.000 claims description 36
- 239000011347 resin Substances 0.000 claims description 36
- 239000002253 acid Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000000576 coating method Methods 0.000 claims description 30
- 239000011248 coating agent Substances 0.000 claims description 28
- 150000007513 acids Chemical class 0.000 claims description 22
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 21
- 238000010538 cationic polymerization reaction Methods 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 19
- 239000003505 polymerization initiator Substances 0.000 claims description 19
- 125000001931 aliphatic group Chemical group 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- 230000004927 fusion Effects 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 230000005693 optoelectronics Effects 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 125000002091 cationic group Chemical group 0.000 claims description 7
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 230000005855 radiation Effects 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 abstract description 9
- 150000002118 epoxides Chemical class 0.000 abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 125000004430 oxygen atom Chemical group O* 0.000 abstract 2
- 239000007888 film coating Substances 0.000 abstract 1
- 238000009501 film coating Methods 0.000 abstract 1
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 125000004434 sulfur atom Chemical group 0.000 abstract 1
- ROWMQJJMCWDJDT-UHFFFAOYSA-N tribromomethane Chemical compound Br[C](Br)Br ROWMQJJMCWDJDT-UHFFFAOYSA-N 0.000 abstract 1
- ZBZJXHCVGLJWFG-UHFFFAOYSA-N trichloromethyl(.) Chemical compound Cl[C](Cl)Cl ZBZJXHCVGLJWFG-UHFFFAOYSA-N 0.000 abstract 1
- -1 3,4-epoxycyclohexyl methyl Chemical class 0.000 description 83
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 49
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 31
- 125000004432 carbon atom Chemical group C* 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 26
- 239000001993 wax Substances 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical group C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 150000001336 alkenes Chemical class 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 12
- 229910052731 fluorine Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 235000014113 dietary fatty acids Nutrition 0.000 description 10
- 238000006735 epoxidation reaction Methods 0.000 description 10
- 229930195729 fatty acid Natural products 0.000 description 10
- 239000000194 fatty acid Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 150000008065 acid anhydrides Chemical class 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 239000001294 propane Substances 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 7
- 125000001118 alkylidene group Chemical group 0.000 description 7
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 240000007930 Oxalis acetosella Species 0.000 description 6
- 235000008098 Oxalis acetosella Nutrition 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- OXQXGKNECHBVMO-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptane-4-carboxylic acid Chemical compound C1C(C(=O)O)CCC2OC21 OXQXGKNECHBVMO-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 229920005862 polyol Polymers 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 235000001510 limonene Nutrition 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- 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 4
- BUCJHJXFXUZJHL-UHFFFAOYSA-N 1-ethylcyclohexan-1-ol Chemical compound CCC1(O)CCCCC1 BUCJHJXFXUZJHL-UHFFFAOYSA-N 0.000 description 3
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000001924 cycloalkanes Chemical class 0.000 description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical group OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 125000002541 furyl group Chemical group 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- 150000002628 limonene derivativess Chemical class 0.000 description 3
- 150000002632 lipids Chemical class 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- CZPZWMPYEINMCF-UHFFFAOYSA-N propaneperoxoic acid Chemical compound CCC(=O)OO CZPZWMPYEINMCF-UHFFFAOYSA-N 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 230000001235 sensitizing effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000001544 thienyl group Chemical group 0.000 description 3
- 239000005028 tinplate Substances 0.000 description 3
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 2
- VTBOTOBFGSVRMA-UHFFFAOYSA-N 1-Methylcyclohexanol Chemical compound CC1(O)CCCCC1 VTBOTOBFGSVRMA-UHFFFAOYSA-N 0.000 description 2
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- QKMOFWOJEZZHFD-UHFFFAOYSA-N 1-pentylcyclohexan-1-ol Chemical compound CCCCCC1(O)CCCCC1 QKMOFWOJEZZHFD-UHFFFAOYSA-N 0.000 description 2
- PYLPYOPJKOJRNP-UHFFFAOYSA-N 1-propylcyclohexan-1-ol Chemical compound CCCC1(O)CCCCC1 PYLPYOPJKOJRNP-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- ZRNSSRODJSSVEJ-UHFFFAOYSA-N 2-methylpentacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(C)C ZRNSSRODJSSVEJ-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
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- 102100026735 Coagulation factor VIII Human genes 0.000 description 2
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
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- 239000005062 Polybutadiene Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 229910018286 SbF 6 Inorganic materials 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 2
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- 239000003063 flame retardant Substances 0.000 description 2
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- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000002075 main ingredient Substances 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
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- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000001802 myricyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- ULYOZOPEFCQZHH-UHFFFAOYSA-N n-(methoxymethyl)prop-2-enamide Chemical compound COCNC(=O)C=C ULYOZOPEFCQZHH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229960002969 oleic acid Drugs 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
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- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 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 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical group [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 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 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- WBHHMMIMDMUBKC-QJWNTBNXSA-N ricinoleic acid Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(O)=O WBHHMMIMDMUBKC-QJWNTBNXSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 235000019830 sodium polyphosphate Nutrition 0.000 description 1
- JXAZAUKOWVKTLO-UHFFFAOYSA-L sodium pyrosulfate Chemical class [Na+].[Na+].[O-]S(=O)(=O)OS([O-])(=O)=O JXAZAUKOWVKTLO-UHFFFAOYSA-L 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000012177 spermaceti Substances 0.000 description 1
- 229940084106 spermaceti Drugs 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 150000003866 tertiary ammonium salts Chemical class 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
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- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- NLSXASIDNWDYMI-UHFFFAOYSA-N triphenylsilanol Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(O)C1=CC=CC=C1 NLSXASIDNWDYMI-UHFFFAOYSA-N 0.000 description 1
- 229960002703 undecylenic acid Drugs 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- DJXRIQMCROIRCZ-XOEOCAAJSA-N vibegron Chemical compound C1([C@H]([C@@H]2N[C@H](CC=3C=CC(NC(=O)[C@H]4N5C(=O)C=CN=C5CC4)=CC=3)CC2)O)=CC=CC=C1 DJXRIQMCROIRCZ-XOEOCAAJSA-N 0.000 description 1
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- 238000010792 warming Methods 0.000 description 1
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- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
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Abstract
The present invention provides a method for preparing a liquid epoxy resin composition, a photoelectric semiconductor device, an ultraviolet curable can used coating composition and a film-coating metal can, wherein the liquid epoxy resin composition includes epoxy resin and solidifying agent and/or curing accelerator, and the invention is characterized in that the epoxy resin includes 100 to 20wtalicyclic epoxide (A) represented by the following general formula (I), in the formula, X is an oxygen atom, a sulfur atom, the bivalent radical of -SO-, -SO2-, -CH2-, -C(CH3)2-, -CBr2-, -C(CBr3)2-, -C(CF3)2-, -C(CCl3)2- or -CH(C6H5)-, or the single bound connected with two alicyclic rings, R<1> to R<18> may be the same or different and are each a hydrogen atom, a halogen atom, an oxygen atom or a hydrocarbon group which may contain a halogen atom or an alkoxy group which may contain a substituent group.
Description
The application is that international application no is PCT/JP 02/02778, and international filing date is national applications the dividing an application for the Chinese patent application of " manufacture method of epoxy compounds, composition epoxy resin and uses thereof and ultraviolet rays-curable can-coating composition and the metal canned manufacture method of filming " that number be 02800749.2 title after the PCT international application on March 22nd, 2002 enters China's stage.
Technical field
I of the present invention relates to the manufacture method of epoxy compounds.Specifically, relate to the low aliphatics percarboxylic acids of water content and make the oxidation of ester ring type olefin(e) compound make the manufacture method of alicyclic epoxy compound with ad hoc structure.The alicyclic epoxy compound of gained is used for purposes such as coating, ink, tackiness agent, sealing material and stablizer.
It is composition epoxy resin of main ingredient and uses thereof that II of the present invention relates to the alicyclic epoxy compound.More particularly, relate to the composition epoxy resin that can obtain humidity resistance and the good cured article of the transparency and be used for the semi-conductive purposes of sealed photoelectric by being heating and curing.
III of the present invention relates to ultraviolet rays-curable can-coating (can coating) composition and with the said composition manufacturing metal canned method of filming, said composition is a main ingredient with above-mentioned alicyclic epoxy compound, it can solidify by uviolizing, form film properties such as processibility, stopping property, hardness and scratch resistance well, particularly film outward appearance and withstand voltage hot (retort resistance) good filming.
Background technology
[background technology relevant with II] with I of the present invention
It is multiple commercially available that intramolecularly has the di-epoxy compounds of 2 alicyclic ring skeletons to have now.For example Celloxide 2021 (3 ', 4 ' epoxy cyclohexane carboxylic acid 3,4-epoxycyclohexyl methyl esters), Celloxide 3000 (1,2,8,9-two Huan Yangization limonenes), Celloxide 2081 (two ends are respectively with 3,4-epoxycyclohexyl methyl alcohol and 3,4-epoxy cyclohexane carboxylic acid is with ester bond bonded 6-caprolactone monomer or oligopolymer) (above all is the manufacturing of Daicel chemical industry).
Above-mentioned Celloxide 3000 has methyl constituting on the carbon of epoxy group(ing), so the reactivity of this epoxy group(ing) ratio is low when not having methyl.So alicyclic epoxy resin mainly uses in the occasion that preferentially reaches low viscosity and high Tg etc.
In addition, Celloxide 2021, Celloxide 2081 are because intramolecularly has ester group, thus the meeting hydrolysis, and its humidity resistance is than the epoxy basis of bisphenols.
Therefore, they are when using under the hot and humid degree and use under conditions such as generation strong acid, and the physical properties of cured article can variation sometimes.
The motion that improves these problems for example has: the spy opens the optoelectronic semiconductor encapsulating epoxy resin of having put down in writing the diglycidylether that contains Hydrogenated Bisphenol A in the flat 9-255764 communique, but its cured article has the problem on tint permanence, weathering resistance and the thermotolerance etc.; Put down in writing the optical stereo moulding resin combination of the alicyclic epoxy compound identical in the Te Kaiping 10-156952 communique, but be not used in the semi-conductive record of sealed photoelectric with the present invention.In addition, the spy opens the moulding (buildup) of the composition of having put down in writing the multivalence epoxy compounds that uses specific alicyclic epoxy compound and have the polyphenol skeleton in the 2000-63485 communique and uses solidification compound, but finds no the feature of the thermotolerance and the transparency.
On the other hand, the spy opens in the clear 48-29899 communique and puts down in writing, and by the X that synthesizes the represented alicyclic epoxy compound (A) of following (I) formula is-CH
2-compound, be cured reaction with itself and acid anhydrides, improve the physical properties of cured article so that it is comparable to former alicyclic ring epoxide.But use peroxybenzoic acid in this epoxy compounds synthetic is so this is difficult in industrial utilization.
In addition, the spy opens and has put down in writing in the clear 58-172387 communique by the synthetic percarboxylic acids of hydrogen peroxide, acid catalyst and organic acid, uses the organic solvent extraction percarboxylic acids then, carries out epoxidation with it.Its operating time is long, and the amount of waste is many, thereby operation is miscellaneous.And from the extraction efficiency and the cost consideration of percarboxylic acids, solvent is the material as benzene, sees it is bad from the toxicity aspect.Therefore, need intramolecularly to have and do not have epoxy compounds and effective manufacture method thereof of the alicyclic ring skeleton of ester group.
So process for epoxidation that the purpose of I of the present invention provides and uses effectively, economy and the little solvent of toxicity carry out the ester ring type olefin(e) compound.
And the purpose of II of the present invention provides the humidity resistance and the good optoelectronic semiconductor encapsulating epoxy resin composition of the transparency of cured article.
[background technology relevant] with III of the present invention
So far, known ultraviolet-curable coating composition has: contain the cationically polymerizable compound of band epoxy group(ing) or vinyl and produced the cationic polymerization type coating of cationic cationic polymerization initiators by uviolizing and contain with the free-radical polymerised compound of free-radical polymerised unsaturated group and produced the radical polymerization mould assembly coating etc. of the radical polymerization initiator of free radical by uviolizing.
But, though radical polymerization mould assembly coating has curing speed feature faster, but it is insufficient with the stopping property and the processibility of base mateiral, and can be because of oxygen quenching solidify the solidified nature variation that makes the surface, need be with the equipment of inclosure nitrogen etc. when particularly using with film (2～8 microns) form.
On the other hand, cationic polymerization type coating is compared with radical polymerization mould assembly coating, though have good and do not need with the advantages such as equipment of enclosing nitrogen etc. with the stopping property of base mateiral and processibility, but curing speed is slow, therefore has film properties, particularly film outward appearance and withstand voltage hot inadequate problem.
In addition, any aggretion type film all have low irradiation dose (less than 100 millis burnt/centimetre
2) the following insufficient problem of solidified nature.
It is said this be because, for example the intramolecularly at the alicyclic epoxy thing that is fit to cationic curing often has ester bond, ester bond can and cationic substance (cation species) reaction and the polymerization of obstruction epoxide.
For example, put down in writing in the Te Kaiping 10-158581 communique and contained the ultraviolet rays-curable can-coating composition that compound, specific copolymer and the cationic polymerization initiators of trimethylene oxide ring are arranged in compound that the ester ring type epoxy group(ing) is arranged in the molecule, the molecule, but for above-mentioned reasons, it with aspects such as the withstand voltage hot relevant hardness in hot water, film outward appearance and shock-resistance on problem is also arranged.
So the purpose of III of the present invention provides ultraviolet rays-curable can-coating composition and the metal canned manufacture method of filming.
Summary of the invention
The present inventor furthers investigate for the purpose that solves the invention described above I, discovery is by making the compound epoxidation with 2 ester ring type olefin skeletals with the low aliphatics percarboxylic acids of water content, can solve the problem among the invention described above I, thereby finish I of the present invention.
The present inventor also furthers investigate for the purpose that solves the invention described above II, discovery has inside by use and does not have ester bond and constitute the alicyclic epoxy compound that does not have the structure of methyl on the carbon of ester ring type epoxy group(ing), can obtain the humidity resistance and the good optoelectronic semiconductor encapsulating epoxy resin composition of the transparency of cured article, just can solve the problem among the invention described above II, thereby finish II of the present invention.
In addition, the present invention also furthers investigate for the purpose that solves the invention described above III, find by use the alicyclic epoxy thing of ad hoc structure with specified rate, need not just can be with form of film with the equipment of enclosing nitrogen, and under low irradiation dose, be solidified to form the ultraviolet-curable coating composition by uviolizing, said composition is as the necessary processibility of can-coating, stopping property, film properties such as hardness and scratch resistance is good, film outward appearance and withstand voltage hot good particularly, and in uviolizing after heating film can show hardness in the good hot water, thereby finished III of the present invention.
Promptly, the 1st of the present invention is the manufacture method of the represented alicyclic epoxy compound (A) of following general formula (I), it is characterized in that this method is to be that the following aliphatics percarboxylic acids of 2 weight % makes the represented ester ring type olefin(e) compound epoxidation of following general formula (II) with water content
(in the formula, X for be selected from Sauerstoffatom, sulphur atom ,-SO-,-SO
2-,-CH
2-,-C (CH
3)
2-,-CBr
2-,-C (CBr
3)
2-,-C (CF
3)
2-,-C (CCl
3)
2-or-CH (C
6H
5)-divalent radical or the singly-bound that links to each other with 2 alicyclic rings, R
1～R
18Can be identical also can be different, be respectively hydrogen atom, halogen atom, maybe can have the alkyl of Sauerstoffatom or halogen atom, maybe can have substituent alkoxyl group.)
The 2nd of the present invention is manufacture method as the 1st described epoxy compounds of the present invention (A), and wherein said aliphatics percarboxylic acids is obtained by oxygen institute's oxidation by corresponding aldehyde.The 3rd of the present invention is manufacture method as the present invention the 1st or the 2nd described epoxy compounds (A), and the water content in the wherein said aliphatics percarboxylic acids is below the 0.8 weight %.The 4th of the present invention is that wherein said aliphatics percarboxylic acids is a peracetic acid as the manufacture method of any one described epoxy compounds (A) among the 1st～3 of the present invention.
The 5th of the present invention is the liquid epoxy resin composition that comprises Resins, epoxy and solidifying agent and/or curing catalyst, it is characterized in that, contains the represented alicyclic epoxy compound (A) of following general formula (I) of 100～20 weight % in this Resins, epoxy:
(in the formula, X be Sauerstoffatom, sulphur atom ,-SO-,-SO
2-,-CH
2-,-C (CH
3)
2-,-CBr
2-,-C (CBr
3)
2-,-C (CF
3)
2-,-C (CCl
3)
2-or-CH (C
6H
5)-divalent radical or the singly-bound that links to each other with 2 alicyclic rings, R
1～R
18Can be identical also can be different, be respectively hydrogen atom, halogen atom, maybe can have the alkyl of Sauerstoffatom or halogen atom, maybe can have substituent alkoxyl group.) the 6th of the present invention be as the 5th described liquid epoxy resin composition of the present invention, it is characterized in that the represented alicyclic epoxy compound (A) of general formula (I) is to be the epoxy compounds that the following percarboxylic acids of 1 weight % is made with water content.The 7th of the present invention is as the 5th or 6 described liquid epoxy resin composition of the present invention, it is characterized in that, described solidifying agent is the initiator of emitting the material that causes cationoid polymerisation by heating.The 8th of the present invention is as any one described liquid epoxy resin composition in the 5th～7 of the present invention, it is characterized in that described solidifying agent is a liquid anhydride.The 9th of the present invention is liquid epoxy resin composition, it be the curing catalyst (D) of the liquid anhydride class solidifying agent (C) of fusion 110～160 weight parts in the represented alicyclic epoxy compound (A) of the 5th the described general formula of the present invention (I) of 100 weight parts and 3～7 weight parts or also fusion be that the initiator (E) of emitting cationic substance by heating that 100 weight parts are counted 0.1～20 weight part forms with described alicyclic epoxy compound (A).The 10th of the present invention is that it is used for the sealed photoelectric semi-conductor as any one described liquid epoxy resin composition among the 5th～9 of the present invention.
The 11st of the present invention is opto-semiconductor device, and it is with the 10th described optoelectronic semiconductor encapsulating epoxy resin composition sealed photoelectric semiconductor element of the present invention.
In addition, the 12nd of the present invention is ultraviolet rays-curable can-coating composition, and it contains the represented alicyclic epoxy compound (A) of following general formula (I) of 10～100 weight parts, existing ester ring type epoxy group(ing) also has the compound of ester bond and/or has the epoxy compounds (B) of glycidyl in the molecule of 0～90 weight part, with compound (A) and (B) total amount 100 weight parts count the multipolymer (F) that has at least one glycidyl and/or ester ring type epoxy group(ing) in the molecule of 1～50 weight part, and 0.01～20 weight part produce cationic cationic polymerization initiators (G) by uviolizing:
(in the formula, X be Sauerstoffatom, sulphur atom ,-SO-,-SO
2-,-CH
2-,-C (CH
3)
2-,-CBr
2-,-C (CBr
3)
2-,-C (CF
3)
2-,-C (CCl
3)
2-or-CH (C
6H
5)-divalent radical or the singly-bound that links to each other with 2 alicyclic rings, R
1～R
18Can be identical also can be different, be respectively hydrogen atom, halogen atom, maybe can have the alkyl of Sauerstoffatom or halogen atom, maybe can have substituent alkoxyl group.)
The 13rd of the present invention is as the 12nd described ultraviolet rays-curable can-coating composition of the present invention, it is characterized in that described multipolymer (F) is to have the polymerizable unsaturated monomer of glycidyl and/or have the polymerizable unsaturated monomer of ester ring type epoxy group(ing) and the multipolymer of other polymerizable unsaturated monomer.The 14th of the present invention is as any one described ultraviolet rays-curable can-coating composition among the 12nd～13 of the present invention, it is characterized in that it also contains the oilness imparting agent of counting 0.01～10 weight part with total amount 100 weight parts of represented alicyclic epoxy compound (A) of following formula (I) and epoxy compounds (B).The 15th of the present invention is as any one described ultraviolet rays-curable can-coating composition in the 12nd～14 of the present invention, it is characterized in that it also contains the resin particle of counting 0.1～50 weight part with total amount 100 weight parts of represented alicyclic epoxy compound (A) of following formula (I) and epoxy compounds (B).The 16th of the present invention is as any one described ultraviolet rays-curable can-coating composition in the 12nd～15 of the present invention, it is characterized in that the represented alicyclic epoxy compound (A) of described general formula (I) is to be the liquid epoxy compounds of the following aliphatics percarboxylic acids manufacturing of 2 weight % with water content.The 17th of the present invention is the metal canned manufacture method of filming, it is characterized in that, it comprises with any one described ultraviolet rays-curable can-coating composition coating metal plate, resin film layer metal plate among the 12nd～16 of the present invention or the metal can that formed by these sheet metal formings, makes it to solidify by irradiation ultraviolet radiation then.
The preferred forms of invention
At first I of the present invention is elaborated.
Among the I of the present invention, the alicyclic epoxy compound (A) represented with above-mentioned general formula (I) is that the following aliphatics percarboxylic acids of 2 weight % is made the ester ring type olefin(e) compound oxidation of general formula (II) expression with water content.
As the ester ring type olefin(e) compound of raw material synthetic normally by the dehydration reaction of the compound that has corresponding hydroxyl.
The represented ester ring type olefin(e) compound of general formula (II) is opened clear 48-29899 communique, spy as the spy and is opened clear 58-172387 communique, spy and open as described in the 2000-169399 communique, for example can be synthesized by the compound with hexalin structure.Shown in (II), the ester ring type olefin(e) compound of gained is preferably with respect to having two keys on 3,4 of substituent X, preferably having hydroxyl with respect on 4 of substituent X as the compound that has hydroxyl of the raw material of ester ring type olefin(e) compound.
These compounds comprise the compound that contains the cyclohexane ring that is connected with hydroxyl at least more than 2 in the molecule for example since with above-mentioned identical reason, the present invention is effective especially for its dehydration reaction.
The compound that contains the cyclohexane ring that is connected with hydroxyl at least more than 2 in the molecule, for example can enumerate: the hydrogenation xenol, two (hydroxy-cyclohexyl) methane (dicyclohexanol methane), two (dimethyl hydroxyl cyclohexyl) methane (bis (dimethylcyclohexanol) methane), 1,2-two (hydroxy-cyclohexyl) ethane, 1,3-two (hydroxy-cyclohexyl) propane, 1,4-two (hydroxy-cyclohexyl) butane, 1,5-two (hydroxy-cyclohexyl) pentane, 1,6-two (hydroxy-cyclohexyl) hexane, 2,2-two (hydroxy-cyclohexyl) propane, two (hydroxy-cyclohexyl) phenylmethane, α, α-two (4-hydroxy-cyclohexyl)-4-(4-hydroxyl-α, the alpha-alpha-dimethyl cyclohexyl)-ethylbenzene, 3,3-two (hydroxy-cyclohexyl) pentane, 5,5-two (hydroxy-cyclohexyl) heptane, ten dihydro fluorenes glycol (dodecahydrofluorene diol), three (hydroxy-cyclohexyl) methane, three (hydroxy-cyclohexyl) ethane, 1,3,3-three (hydroxy-cyclohexyl) butane, four (hydroxy-cyclohexyl) ethane, 2,2-two [4,4 '-two (hydroxy-cyclohexyl) cyclohexyl] propane, A Hydrogenated Bisphenol A C (C: hexanaphthene), hydrogenation polyphenol etc. and their mixture.
The epoxidizing agent aliphatics percarboxylic acids that preferably water content is low that can when the double bond epoxidation of ester ring type olefin(e) compound, use.This is because if carry out epoxidation reaction in the presence of water, and the ring-opening reaction of epoxy group(ing) can take place, thereby has reduced the productive rate of epoxy compounds.
For this reason, the water content of aliphatics percarboxylic acids must be preferably below the 1 weight % for below the 2 weight %, more preferably below the 0.8 weight %, also will be preferably below the 0.6 weight %.
Water content of the present invention is the following aliphatics percarboxylic acids of 2 weight %, typically refers to the peracetic acid made through atmospheric oxidation by acetaldehyde etc. etc., and for example peracetic acid can and specially be opened the method manufacturing of putting down in writing among the clear 54-3006 with No. 1418465, German Patent communique.And also available hydrogen peroxide comes synthetic fat family percarboxylic acids by aliphatic carboxylic acid, is the following aliphatics percarboxylic acids of 2 weight % through distilling and use solvent extraction, making water content.
This method by atmospheric oxidations such as aldehyde can be synthesized the aliphatics percarboxylic acids of high density continuously in a large number, so in fact can obtain at an easy rate.
As the kind of aliphatics percarboxylic acids, available peroxyformic acid, peracetic acid, mistake isopropylformic acid, mistake trifluoroacetic acid etc.Wherein, peracetic acid is particularly preferred epoxidizing agent, because it can obtain at an easy rate industrial, and stability is also high.
Consumption as the aliphatics percarboxylic acids of epoxidizing agent does not have strict especially restriction, and the optimal dose under each situation depends on that used various epoxidizing agents, required epoxidation degree and used each are by variable factors such as epoxide.During the many compound of the epoxy group(ing) number in using 1 molecule, epoxidizing agent preferably with respect to alkylene to wait mole or to wait the above consumption adding of mole.But on the problem of economy and following side reaction, it is normally disadvantageous that its consumption surpasses 2 times of moles, and when using peracetic acid, its consumption is preferably 1～1.5 times of mole.
Epoxidation reaction is carried out under the condition of using or do not use inert solvent and conditioned reaction temperature according to the physical properties of device and raw material.
Inert solvent can be used for reducing material viscosity and makes it steady etc. by the dilution epoxidizing agent, epoxidizing agent during with peracetic acid inert solvent can use aromatics and ester class etc.
Particularly preferred solvent is hexane, hexanaphthene, toluene, ethyl acetate and methyl acetate.
According to the reactivity of used epoxidizing agent, determine the available range of reaction temperature.Be generally more than 0 ℃ to below 100 ℃.For preferred epoxidizing agent---peracetic acid, preferably 20～70 ℃.Delay of response below 20 ℃ can cause more than 70 ℃ that peracetic acid decomposes.
Epoxidizing agent can be according to the residual purpose that how much waits of unsaturated link(age) is changed with respect to the adding mol ratio of unsaturated link(age).
Reaction mixture is not needed special operation, for example mixture can be stirred 1～5 hour.The for example available following proper method of the method for separating obtained epoxide: make it sedimentary method with poor solvent, while in hot water, stir the method that drops into the epoxide redistillation except that method of desolvating and direct desolventizing.
Represented alicyclic epoxy compound (A) polymerization separately of the above-mentioned general formula of making by the manufacture method of I of the present invention (I), copolymerization or again with other compound reaction, generate the intermediate that is used for various coating, ink, tackiness agent, sealing agent, moulded products or uses other goods of these products.
The example of the end-use of the alicyclic epoxy compound (A) that use is made by the manufacture method of I of the present invention has: acid scavenger, coatings for furniture, decorative paint, beverages can and other can-coating, adhesive agent, the automobile base paint, sealing agent, overpainting, Word message or picture information ink, the electronic component sealing agent, be applicable to the photo-resist of exploitation printing plate or printed circuit board (PCB), the casting printing cylinder, glass based on unsaturated polyester and vinylbenzene, use carbon, the moulded products that graphite or other fibre-reinforced moulding adulterant or sheet forming adulterant are made, solvent, fire retardant, be used to make the intermediate of other useful compound of various end-uses such as medicine and medical treatment product.
In addition, the feature of the alicyclic epoxy compound of being made by the manufacture method of I of the present invention (A) is that its cured resin has used the compound with alicyclic ring skeleton, and it has thermotolerance, the transparency and good dielectric characteristics.
Below II of the present invention is elaborated.
II of the present invention relates to that the alicyclic epoxy compound (A) that above general formula (I) is represented is made the liquid epoxy resin composition of preferable alicyclic epoxy resin and with the opto-semiconductor device of this liquid epoxy resin composition sealed photoelectric semiconductor element.Each component in the said composition below is described.
Used alicyclic epoxy compound (A) is the compound that describes in detail as among the above-mentioned I of the present invention among the II of the present invention, is liquid state down at normal temperature (25 ℃) usually.
Liquid epoxy resin composition among the II of the present invention contains the above-mentioned alicyclic epoxy compound (A) of 100-20 weight %.
The compound that above-mentioned alicyclic epoxy compound (A) is made with the manufacture method that describes in detail among the invention described above I is better, but the compound that also available other manufacture method is made.Also available commercially available product.
And, above-mentioned alicyclic epoxy compound (A) in addition for example can and with following compound as alicyclic epoxy resin.
3,4-epoxy cyclohexane carboxylic acid-3,4-epoxy cyclohexyl, 3,4-epoxy-6-methylcyclohexanecarboxylic acid 3,4-epoxy-6-methylcyclohexyl methyl esters, hexanodioic acid two (3, the 4-epoxycyclohexyl) ester, an epoxidation (vinyl cyclohexene), two ring oxygen limonenes etc.
Can use following reactive diluent in the above-mentioned epoxy compounds.Viscosity was the following low viscosity cycloalkanes support glycol diglycidyl ether of 100 centipoises when low viscosity cycloalkanes support glycol diglycidyl ether for example was 25 ℃.Such cycloalkanes support glycol diglycidyl ether for example has cyclohexanedimethanol diglycidyl ether, cylohexanediol diglycidyl base ether.
In addition, also Racemic glycidol such as the bisphenol A-type of available liquid state, F type fundamental mode Resins, epoxy, bisphenol-A epoxy resin, glycidyl group amine type Resins, epoxy etc.
Even solid epoxy resin if the viscosity of the Resins, epoxy of its blending is below 40000 centipoises in the time of 45 ℃, then also can use.What spendable solid epoxy resin can be enumerated is, for example Solid Double phenol-type epoxy resin, phenolic resin varnish type epoxy resin, glycidyl ester, triglycidyl isocyanurate, EHPE-3150 (manufacturing of Daicel chemical industry).
These Resins, epoxy can use separately also and can two or more mixing use.
(solidifying agent (C))
Among the II of the present invention, the acid anhydrides that is used as solidifying agent can use and be selected from common solidifying agent as epoxy curing agent.
Used acid anhydrides preferably is liquid at normal temperatures among the II of the present invention, specifically, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methyl carbic anhydride etc. is for example arranged.
In addition, in the dysgenic scope of dipping generation not to the liquid epoxy resin composition of II of the present invention, can use to be the solid acid anhydrides under the normal temperature, for example Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, tetrahydrotoluene dicarboxylic anhydride etc.When using under the normal temperature, preferably it is dissolved in and is liquid acid anhydrides under the normal temperature, use for liquid mixture down as normal temperature to the solid acid anhydrides.
The combined amount of acid anhydrides has no particular limits for the significant quantity of performance solidifying agent (C) effect get final product, but is that the ratio of 0.5～1.5 anhydride equivalent is used better with the epoxy group(ing) of per 1 equivalent aforementioned epoxy resins component usually.
(curing catalyst (D))
Curing catalyst among the II of the present invention (D) is based on diazabicylo undecylene class curing catalyst, and it must account for 50 weight % at least in the total amount of curing catalyst (D).If the ratio of this diazabicylo undecylene class curing catalyst is worth less than this, just can not fully extend shelf life.From obtaining the viewpoint of enough shelf liveves, be preferably more than the 70 weight %.
Such diazabicylo undecylene class curing catalyst can exemplify 1,8-diazabicylo [5.4.0]-7-undecylene and salt thereof, especially preferably 1, the octylate of 8-diazabicylo [5.4.0]-7-undecylene.Curing catalyst (D) can be this independent diazabicylo undecylene class curing catalyst, also can be the mixture of following other used for epoxy resin curing catalyst (for example phosphorus such as Chang Yong tertiary amines curing catalyst and triphenyl phosphine are curing catalyst) of this class curing catalyst and 50 weight %.
This curing catalyst (D) uses in the ratio of counting 0.3～10 weight part with 100 weight part Resins, epoxy.If consumption is less than 0.3 weight part, solidifying facilitation effect can be insufficient, and if consumption more than 10 weight parts, the shelf lives can shorten.Therefore, from solidifying promotion property and shelf lives aspect consideration, particularly preferred blended amount is counted 1～5 weight part with 100 weight part epoxy resin ingredient.
Curing catalyst (D) is the compound that the function that promotes curing reaction is arranged when Resins, epoxy is solidified by acid anhydrides.
Used other curing catalyst (D) among the II of the present invention but exemplified by benzyl dimethyl amine, 2,4, the tertiary amine of 6-three (dimethylaminomethyl) phenol etc.; Imidazoles such as 2-ethyl-4-methylimidazole, 1-cyano ethyl-2-ethyl-4-methylimidazole; Organic phosphine compounds such as triphenyl phosphine; Tertiary ammonium salt; Quaternary ammonium salt; Phosphonium salt; Known compounds such as metal-salt such as stannous octoate.
The blended amount of this curing catalyst (D) is preferably being counted in the scope of 1～10 weight part with 100 weight part Resins, epoxy.
(cationic polymerization initiators (E))
On the other hand, among the II of the present invention available cationic polymerization initiators (E) as solidifying agent.
Cationic polymerization initiators (E) is the initiator by the material that adds heat release initiation cationoid polymerisation, and its blended amount is being counted in the scope of 0.05～5 weight part, preferred 0.1～3 weight part with 100 weight part Resins, epoxy.By fusion in this scope, can obtain well-behaved cured articles such as thermotolerance, the transparency and weathering resistance.
Cationic polymerization initiators (E) can exemplify aryl diazonium salts (for example PP-33 (Asahi Electro-Chemical Co. Ltd's manufacturing)), aryl salt (iodonium salt), aryl sulfonium salt (sulfonium salt) (FC-509 (manufacturing of 3M company) for example; UVE1014 (manufacturing of G.E. company); UVI-6974, UVI-6970, UVI-6990, UVI-6950 (manufacturing of UnionCarbide company); SP-170, SP-150 (Asahi Electro-Chemical Co. Ltd's manufacturing); SI-60L, SI-80L, SI-100L (three new chemical industrial companies make); Propadiene-ionic complex (for example CG-24-61 (manufacturing of Ciba Geigy company)).
In addition, initiator also have metals such as aluminium and titanium and acetylacetic ester or two ketones inner complex, comprise and the inner complex of the system of silanol or phenols can exemplify acetylacetonate aluminium silanol or phenols, as triphenyl silanol and bisphenol S etc.
(various additive)
In the liquid epoxy resin composition of II of the present invention, can not produce the various additives of fusion in the dysgenic scope to viscosity.
Such additive can exemplify silicone and fluorine is defoamer, γ-silane coupling agents such as glycidyl oxygen base propyl trimethoxy silicane etc.
The liquid epoxy resin composition of II of the present invention, the second-order transition temperature of its cured article and the transparency are high, and water-intake rate is low, is suitable for the resin combination of using as optoelectronic semiconductor.
In addition, the liquid epoxy resin composition of II of the present invention, particularly optoelectronic semiconductor sealing are with in the liquid epoxy resin composition, as required, but various additives commonly used in the optoelectronic semiconductor encapsulating epoxy resin composition up to now such as fusion weighting agent, fire retardant, defoamer, tinting material, silane coupling agent.
Below III of the present invention is elaborated.
III of the present invention is for the ultraviolet rays-curable can-coating composition of necessary component with the said composition manufacturing metal canned method of filming with the represented alicyclic epoxy compound (A) of above-mentioned general formula (I).
Below, each component in the ultraviolet rays-curable can-coating composition of III of the present invention is described.
The compound that the used preferred use of alicyclic epoxy compound (A) is made by the method that describes in detail among the invention described above I among the III of the present invention.This alicyclic epoxy compound (A) is in a liquid state under normal temperature (25 ℃) usually.
Though the preferred compound of being made by the method that describes in detail among the invention described above I that uses of above-mentioned alicyclic epoxy compound (A) also can use the compound of being made by other manufacture method.Also can use commercially available product.
In addition, also can and with the alicyclic epoxy resin except that above-mentioned alicyclic epoxy compound (A) of 0～80 weight %, for example have the ester ring type epoxy group(ing) that the compound of ester bond is also arranged in the molecule and/or have the epoxy compounds (B) of glycidyl.
Existing ester ring type epoxy group(ing) also has the compound of ester bond and/or has the epoxy compounds (B) of glycidyl so long as the compound of (preferred 1～2) ring grease formula epoxy group(ing) more than 1 is arranged in the molecule in the molecule, just can use with being not particularly limited.
Object lesson is: hexanodioic acid two (3, the 4-epoxycyclohexyl) ester, 3,4-epoxy cyclohexane carboxylic acid (3, the 4-epoxycyclohexyl) methyl esters, 3,4-epoxy-6-methylcyclohexanecarboxylic acid (3,4-epoxy-6-methylcyclohexyl) methyl esters, 1,2-two (3,4-epoxy cyclohexane carboxylic acid) glycol ester etc., these compounds can be singly with or be used in combination more than 2 kinds.
Above-described molecule has in the compound of ester ring type epoxy group(ing), particularly suitablely exemplify 3,4-epoxy cyclohexane carboxylic acid 3,4-epoxycyclohexyl methyl esters, 3,4-epoxycyclohexyl methyl alcohol, 3, the compound that 4-epoxycyclohexyl ethyl trimethoxy silane or following formula are represented etc.
Or
Among the III of the present invention, the compound of trimethylene oxide ring is arranged in the useful molecules.
The used compound that has the trimethylene oxide ring in the coating composition of III of the present invention, be in the presence of cationic polymerization initiators, can carry out having at least in the molecule of ring-opening polymerization one, preferred 1～15, the more preferably compound of 1～4 following trimethylene oxide ring (hereinafter referred to as oxetane compound OXE) by uviolizing:
Specifically, for example following (4) represented compound, and the compound shown in back formula (10), (11) and (12).
In the following formula (4), R
6The expression hydrogen atom, fluorine atom, carbonatoms is 1～6 straight chain shape, chain or cyclic alkyl (methyl for example, ethyl, just or sec.-propyl, just, the XOR tertiary butyl, amyl group, hexyl, cyclohexyl etc.), carbonatoms is 1～6 straight chain shape or (for example props up the chain fluoroalkyl, one methyl fluoride, difluoromethyl, trifluoromethyl, 2,2, the 2-trifluoroethyl, the perfluor ethyl, perfluoro propyl, perfluoro butyl, perfluoro hexyl etc.), allyl group, aryl (phenyl for example, naphthyl, tolyl, xylyl etc.), aralkyl (benzyl for example, styroyl etc.), furyl or thienyl; R
7Valence mumber corresponding to the p value, expression hydrogen atom or 1～4 valency organic radical; Z represents Sauerstoffatom or sulphur atom; P is 1～4 integer.
R
7It is 1～30 straight chain shape, chain or ring-type 1～4 valency alkyl that 1～4 represented valency organic radical can exemplify the carbonatoms that can contain at least a heteroatoms that is selected from O, S, N and F and/or siloxane bond.
More particularly, R
71 represented valency base for example can be enumerated: carbonatoms is 1～6 straight chain shape, chain or cyclic alkyl (methyl for example, ethyl, just or sec.-propyl, just, the XOR tertiary butyl, amyl group, hexyl, cyclohexyl etc.), carbonatoms is 1～6 a straight chain shape or a chain alkoxyalkyl (methoxy ethyl for example, ethoxyethyl group, butoxyethyl group, ethoxyl methyl etc.), carbonatoms is 1～6 a straight chain shape or a chain fluoroalkyl (methyl fluoride for example, difluoromethyl, trifluoromethyl, 2,2, the 2-trifluoroethyl, the perfluor ethyl, perfluoro propyl, perfluoro butyl, perfluoro hexyl etc.), allyl group, aryl (phenyl for example, naphthyl, tolyl, xylyl etc.), aralkyl (benzyl for example, styroyl etc.), furyl, thienyl, contain epoxy group(ing) (glycidyl for example, 3,4-epoxycyclohexyl methyl etc.).
In addition, R
7Represented divalent base for example can be enumerated: straight chain shape, chain or cyclic alkylidene (particularly methylene radical, ethylidene, 1, the carbonatoms of 2-or trimethylene, butylidene, cyclohexylene etc. is 1～15 alkylidene group), carbonatoms be the represented group in 4～30, preferred 4～8 many (alkylene oxide) base (for example many (inferior ethoxy) base, many (inferior third oxygen) base etc.), phenylene, xylylene, following formula (5) and (6),
(in the formula, R
8Expression O, S, CH
2, NH, SO, SO
2, C (CF
3)
2Or C (CH
3)
2)
(in the formula, R
9The expression carbonatoms is 1～6 alkylidene group, arylidene or directly connects) carbonatoms that is formed by connecting by (gathering) siloxane chain of alkylidene group and alkylidene group be 2～30, preferred 2～6 group (for example, this alkylidene group is ethylidene or propylidene, the molecular weight of (gathering) siloxane chain is 130～15,000, be in particular 130～500 group, be preferably the represented group of following formula (7)) etc.
(in the formula, k represents 1～6 integer, and 1 is 2 or 3.)
Again, R
73 or 4 represented valency bases for example can be enumerated following formula (8)～(11) represented group.
(in the formula, R
10The expression carbonatoms is 1～6 alkyl, for example ethyl)
(in the formula, 4 R
11Can be identical also can be different, each represents that carbonatoms is 1～6 alkylidene group, for example ethylidene)
(in the formula, 2 R
12Can be identical also can be different, each represents that hydrogen atom, fluorine atom, carbonatoms are that 1～6 alkyl, carbonatoms are 1～6 fluoroalkyl, allyl group, aryl, furyl or thienyl)
R
7In 1～4 represented valency organic radical, 1 valency or divalent base are suitable (are p be 1 or 2 be suitable), and wherein, carbonatomss such as methyl, ethyl, propyl group, butyl, hexyl are 1～6 alkyl; Allyl group, glycidyl, vinyl; Carbonatoms such as ethoxyethyl group, methoxy ethyl is 1～6 alkoxyalkyl; Benzyl; Carbonatomss such as methylene radical, ethylidene, propylidene, butylidene, hexylidene are 1～6 alkylidene group; Right-xylyl; The represented group of following formula all is suitable.
In addition, in the preceding formula (4), R
6Be hydrogen atom; Carbonatomss such as methyl, ethyl, propyl group, butyl, hexyl are 1～6 alkyl; Allyl group is preferred, for hydrogen atom, methyl, ethyl more preferred.
Have in the molecule in the compound (OXE) of at least one trimethylene oxide ring (oxetane ring), below two kinds of compounds be suitable: (OXE-1): have each one at least of trimethylene oxide ring and hydroxyl, preferred in the molecule respectively with one compound; (OXE-2); Have at least 2 trimethylene oxide rings in the molecule or have the compound of trimethylene oxide ring and epoxy group(ing).
It is 1 and R that above-mentioned oxetane compound (OXE-1) can exemplify p
7The represented compound of compound, particularly following formula (4-1) of the aforementioned formula (4) during for hydrogen atom.
(in the formula, R
61Expression hydrogen atom, fluorine atom, carbonatoms are that 1～6 straight chain shape or branched-chain alkyl, carbonatoms are 1～6 straight chain shape or chain fluoroalkyl or allyl group.)
The typical example of the compound that following formula (4-1) is represented can be enumerated R
4The compound of the formula during for ethyl (4-1).
In addition, in the above-mentioned oxetane compound (OXE-2), the compound of the preceding formula (4) that the compound (hereinafter referred to as polyoxy heterocycle butane compound) that has at least 2 trimethylene oxide rings in the molecule can be enumerated p when being 2～4 integer, wherein, the represented compound of following formula (4-2) is preferred.
(in the formula, R
61Implication with aforementioned identical, R
71In the expression (4) to R
72～4 valency organic radicals of definition, q represents 2～4 integer.)
The typical example of the compound that following formula (4-2) is represented can be enumerated R
61Be ethyl and R
71Be 1,4-tetramethylene, ten dimethylenes, neighbour-,-or right-xylyl, R
9The compound of the formula (4-2) during for the group of the group of the following formula (6) of ethylidene or following formula (7).
Polyoxy heterocycle butane compound also can be enumerated following formula (12), (13) and (14) represented compound except the represented compound of following formula (4-2).
(in the formula, 2 R
61Can be identical also can be different, each expression and aforementioned identical implication are preferably ethyl especially.)
(in the formula, s represents 25～200 integer.)
In addition, in the aforementioned oxetane compound (OXE-2), the compound that has trimethylene oxide ring and epoxy group(ing) in the molecule is (hereinafter referred to as the oxetane compound that contains epoxy group(ing).) comprise each one of trimethylene oxide ring and epoxy group(ing) is arranged in the molecule, preferred molecular weight is less than 1000 compound, concrete example is as enumerating the represented compound of following formula (15).
(in the formula, R
13Expression contains the base of epoxy group(ing), R
61Identical with aforesaid implication.)
In addition, the typical example that contains the oxetane compound of epoxy group(ing) can be enumerated R in the following formula (15)
61Be ethyl and R
13Be glycidyl or 3, the compound during 4-epoxy group(ing) cyclohexyl methyl.
Above-described oxetane compound (OXE) can use separately, but also two or more is used in combination.Particularly preferably be to be used in combination aforesaid compound (OXE-1) and compound (OXE-2).And the oxetane compound of time spent (OXE-1) and (OXE-2) separately amount ranges be, total amount 100 weight parts in aforementioned epoxy compounds (A) and epoxy compounds (B), oxetane compound (OXE-1) is 1～75 weight part, be preferably 3～50 weight parts, and oxetane compound (OXE-2) is 1～75 weight part, is preferably 3～50 weight parts.
(multipolymer (F) that has at least one glycidyl and/or ester ring type epoxy group(ing) in the molecule)
Used multipolymer (F) in the coating composition of III of the present invention is the multipolymer that at least one glycidyl and/or ester ring type epoxy group(ing) are arranged in the molecule.
The monomer that contains epoxy group(ing) as this multipolymer raw material, be that the polymerizable unsaturated monomer that contains epoxy group(ing) gets final product, have no particular limits, representation example can be enumerated: glycidyl acrylate, glycidyl methacrylate, vinylformic acid methyl glycidyl ester, methacrylic acid methyl glycidyl ester, allyl glycidyl ether, vinyl glycidyl ether etc.Wherein, glycidyl acrylate, glycidyl methacrylate are to be fit to use.
As the monomer that contains the ester ring type epoxy group(ing) of this multipolymer raw material, but illustration Cyclomer A200 and M100 (manufacturing of Daicel chemistry (strain) society) etc.
Energy and above-mentioned other monomer that contains the monomer copolymerization of epoxy group(ing), be according to the required performance of gained multipolymer (F), in case of necessity can suitably used monomer, for example can enumerate: methyl acrylate, methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, vinylformic acid just-, the exclusive OR tert-butyl ester, methacrylic acid just-, the exclusive OR tert-butyl ester, Ethyl acrylate, N-Hexyl methacrylate, Octyl acrylate, Octyl methacrylate, lauryl acrylate, lauryl methacrylate(LMA), vinylformic acid octadecane ester, methacrylic acid octadecane ester, cyclohexyl acrylate, the carbonatoms of the acrylic or methacrylic acid of cyclohexyl methacrylate etc. is 1～24 alkyl or cycloalkanes ester; The carbonatoms of acrylic or methacrylic acid such as vinylformic acid 2-hydroxyl ethyl ester, methacrylic acid 2-hydroxyl ethyl ester, vinylformic acid 2-hydroxypropyl acrylate, methacrylic acid 2-hydroxypropyl acrylate, vinylformic acid 4-hydroxy butyl ester, methacrylic acid 4-hydroxy butyl ester is 1～8 hydroxy alkyl ester; The α of vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid, Ba Dousuan etc., β-ethylene linkage unsaturated carboxylic acid; Acrylamide or the Methacrylamide or their derivative of acrylamide, Methacrylamide, N methacrylamide, N-ethyl-methyl acrylamide, diacetone-acryloamide(DAA), N hydroxymethyl acrylamide, N-methylol methacrylamide, N-methoxymethyl acrylamide, N-butoxymethyl acrylamide etc.; Aromatic vinyl monomers such as vinylbenzene, Vinyl toluene, alpha-methyl styrene; (Shell chemistry society makes for propionate, vinyl-acetic ester, vinyl cyanide, methacrylonitrile, new vinyl acetate acid, Beova monomer; be branched vinyl fatty ester), other vinyl monomer of Cylaplane FM 0711, FM 0721, FM 0725 (above all is that Chisso society makes, and the polydimethylsiloxanemacromer macromer of methacryloyl is arranged for end) etc.
Multipolymer (F), can be by comprising the above-mentioned monomer of epoxy group(ing) and other used in case of necessity monomeric monomer component of containing, for example, obtain by the known polymerization process polymerization of solution polymerization, mass polymerization, letex polymerization, suspension polymerization etc. itself in the existence of radical polymerization initiator or not.The number-average molecular weight of multipolymer (F) is l, 000～100,000, be more preferably 2,000～50,000.
When aggregating into multipolymer (F), the proportioning of each monomer component is in monomer component total amount 100 weight parts, preferably in following scope.
The monomer that contains epoxy group(ing): 10～95 weight parts, preferred 20～80 weight parts.
Other monomer: 0～85 weight part, preferred 20～70 weight parts.
In the multipolymer (F), the concentration of epoxy group(ing) is preferably 0.1～7.0 equivalent/kilogram, more preferably 0.2～5.0 equivalent/kilogram.
When aggregating into multipolymer (F),, can improve the oilness of filming after homogeneity that gained films and the autoclaving by using the polydimethylsiloxanemacromer macromer of other monomer such as Cylaplane FM 0721 (manufacturing of Chisso society) etc.
(cationic polymerization initiators (G))
Used cationic polymerization initiators (G) among the III of the present invention, thus be the compound that produces the positively charged ion initiated polymerization by uviolizing.For example, can enumerate the represented fluorine antimonate of following formula (I)～(XV), five fluorine hydroxyls close stibnate, hexafluorophosphate, fluorine arsenate and other cationic polymerization initiators.
Ar
2I
+·X
-?????????????(I)
(in the formula, Ar represents the aryl such as phenyl, X
-Expression PF
6 -, SbF
6 -Or AsF
6-),
Ar
3S+·X
-?????????????(II)
(in the formula, Ar and X
-Have and above-mentioned identical implication),
(in the formula, R
20The expression carbonatoms is that 1～12 alkyl or carbonatoms are 1～12 alkoxyl group, and r represents 0～3 integer, X
-Have and above-mentioned identical implication),
(in the formula, Y
-Expression PF
6 -, SbF
6 -, AsF
6 -Or SbF
5(OH)
-),
(in the formula, X
-Have and above-mentioned identical implication)
(in the formula, X
-Have and above-mentioned identical implication)
(in the formula, X
-Have and above-mentioned identical implication)
(in the formula, R
21The expression carbonatoms is that 7～15 aralkyl or carbonatoms are 3～9 thiazolinyl, R
22The alkyl or the hydroxy phenyl of expression carbonatoms 1～7, R
23The carbonatoms that expression can contain Sauerstoffatom or sulphur atom is 1～5 alkyl, X
-Have and above-mentioned identical implication),
(in the formula, R
24And R
25Represent that independently of one another carbonatoms is that 1～12 alkyl or carbonatoms are 1～12 alkoxyl group),
(in the formula, R
24And R
25Have and above-mentioned identical implication)
Cationic polymerization initiators (G) can use commercially available product, commercially available product for example can be enumerated: UVACURE 1591 (manufacturing of U.S. UCB society), CD-1010, CD-1011, CD-1012, (manufacturing of U.S. Sartomer society), IRGACURE264 (manufacturing of Ciba Geigy society), CIT-1682 (Japanese Cao Da (society) manufacturing) etc.
In the above-mentioned cationic polymerization initiators,, have hexafluorophosphoric acid negatively charged ion (PF from viewpoints such as toxicity and versatilities
6 -) compound be preferred.
In the coating composition of III of the present invention, except as above-mentioned (A), (B) of essential component, (F) with (G) the component, but also fusion oilness imparting agent in case of necessity; Sensitizing agent; Pigment, dyestuffs such as the not serious obstruction solidified of its consumption tinting pigment, extender pigment; Modified resin such as polyol resin, resol, acrylic resin, polyester resin, polyolefin resin, Resins, epoxy, POLYBUTADIENE EPOXY RESIN; The organic resin particulate; Solvent etc.
Above-mentioned oilness imparting agent, mix in order to improve the oilness that gained films, for example can enumerate: for fatty acid ester wax, the silicon of the carboxylate of polyol compound and lipid acid is that wax, fluorine are that wax, polyolefin-wax, animal are wax classes such as wax, department of botany's wax.
Polyol compound as above-mentioned fatty acid ester wax stock, can enumerate: ethylene glycol, glycol ether, triglycol, Tetraglycol 99,1,3-or 1,4-butyleneglycol, neopentyl glycol, 1,6-hexylene glycol, glycerine, two or above Polyglycerine, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol etc.Wherein, the polyol compound that 3 above hydroxyls are arranged in 1 molecule is preferred, and wherein Polyglycerine, TriMethylolPropane(TMP), tetramethylolmethane are more suitable.
As the lipid acid of the another kind of raw material of above-mentioned fatty acid ester wax, can enumerate saturated or unsaturated fatty acids, preferred carbonatoms is 6～32 lipid acid.The object lesson of suitable fat acid can be enumerated: saturated fatty acid such as sad, n-nonanoic acid, capric acid, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, eicosanoic acid, docosoic, cerinic acid, montanic acid, myricyl acid; Decylenic acid, undecylenic acid, Zoomeric acid, oleic acid, linolic acid, linolenic acid, 9,11, unsaturated fatty acidss such as 13-punicic acid, spermaceti olefin(e) acid, erucic acid, sharp bank acid, ricinolic acid, arachidonic acid.
As fatty acid ester wax, the hydroxyl value of preferred above-mentioned polyol compound at least 1/3 by fatty acid esterification.
As silicon is wax, for example can enumerate: made by BYK Chemie society more than BYK-300, BYK-320, the BYK-330[]; Silhouette L-77, Silhouette L-720 and have Japan Unicar (strain) to make more than the Silhouette L-7602[]; Paintadd 29, Paintadd 32 and Paintadd M (above by the manufacturing of Dow Corning society]; Chemistry society of silicon KF-96[SHIN-ETSU HANTOTAI of SHIN-ETSU HANTOTAI makes] etc.And be wax as fluorine, for example can enumerate that ShamrockWax SST-1MG, Shamrock Wax SST-3 and Shamrock Wax Fluoroslip 231[are above to be made by Shamrock Chemicals society], POLYFLUO (poly-fluorine) 120,150,400[Micrpowders society make] etc.
As polyolefin-wax, it is above by the manufacturing of Shamrock Chemicals society for example can to enumerate Shamrock Wax S-394 and Shamrock Wax S-395[]; Hoechst Wax PE-520 and Hoechst Wax PE-521[are above to be made by Hoechst society]; Mitsui Hi-Wax[Mitsui Chemicals industry society makes] etc.And be wax as animal, for example can enumerate lanolin and beeswax etc.As department of botany's wax, for example can enumerate carnauba wax and beeswax etc.
Above-described oilness imparting agent can use separately, also can 2 kinds or multiple being used in combination.The blended amount of oilness imparting agent, so that the ester ring type epoxy group(ing) to be arranged in the molecule but do not have existing ester ring type epoxy group(ing) in the compound (A) of ester bond and the molecule that the compound of ester bond is also arranged or have total amount 100 weight parts of the epoxy compounds (B) of glycidyl, be generally below 10 weight parts, be preferably 0.1～5 weight part, more preferably 0.5～3 weight part.
In above-mentioned oilness imparting agent, silicon is that lubricated the giving property of wax before the back autoclaving is solidified in coating is good, and lubricated the giving property of fatty acid ester wax after the back autoclaving is solidified in coating is good.Therefore, fusion be selected from silicon be wax and fatty acid ester wax at least a better.Particularly, if and the compound of ester bond is also arranged or the total amount 100 weight part meters of the epoxy compounds (B) of glycidyl is arranged in order to existing ester ring type epoxy group(ing) in epoxy compounds (A) and the molecule, the silicon that is 0.01～5 weight part is the fatty acid ester wax of wax and 0.1～5 weight part, can form all good the filming of lubricated giving property of autoclaving front and back.
Aforementioned sensitizing agent mixes in order to improve ultra-violet solidified, for example can enumerate: Bi, perylene, acridine orange, thioxanthone, 2-clopenthixal ketone and benzoflavine etc.The blended amount of this sensitizing agent, total amount 100 weight parts in epoxy compounds (A) and epoxy compounds (B) are generally below 10 weight parts, are preferably below 3 weight parts.
In addition, during fusion modified resin, the consumption of this modified resin, so that the ester ring type epoxy group(ing) to be arranged in the molecule but do not have existing ester ring type epoxy group(ing) in the compound (A), molecule of ester bond that the compound of ester bond is also arranged and/or have total amount 100 weight parts of the epoxy compounds (B) of glycidyl, be generally 0.1～50 weight part, be preferably 5～20 weight parts especially.As modified resin, wherein the POLYBUTADIENE EPOXY RESIN aspects such as processibility, adhesivity of filming in improvement are effective especially.
As aforesaid organic resin particulate, the organic resin particulate of particle diameter in 50～500 nanometer range is preferred, for example can enumerate the crosslinked acrylic resin particulate of interior three-dimensional etc.As the organic resin particulate, can enumerate: the particulate that organic polymer is made after pulverizing; In the presence of the emulsifying agent in water through polymer particles drying that letex polymerization obtains, the particulate that obtains after pulverizing; In the presence of macromolecule stabilizer in organic solvent through polymer particles drying that dispersion polymerization obtains, the particulate that obtains after pulverizing etc.By fusion organic resin particulate in the coating composition of III of the present invention, can improve the adhesivity and the processibility of filming.When fusion organic resin particulate, the blended amount of this organic resin particulate is in total amount 100 weight parts of epoxy compounds (A) and epoxy compounds (B), and is in the scope of 0.1～50 weight part, good especially in the scope of 1～10 weight part usually.
(coating composition)
The coating composition of III of the present invention can be by mixing above-mentioned each component, and the coating composition that stirs into homogeneous is modulated.For example, can be by mixing each component, heat in case of necessity (for example about 50 ℃) for example stir about 10 minutes until evenly modulating with stirrers such as dissolver.
At this moment, the ester ring type epoxy group(ing) is arranged in the molecule but do not have existing ester ring type epoxy group(ing) in the alicyclic epoxy compound (A), molecule of ester bond that the compound of ester bond is also arranged and/or have the usage ratio of epoxy compounds (B), multipolymer (F) and the cationic polymerization initiators (G) of glycidyl can be as described below.
Promptly, the ester ring type epoxy group(ing) is arranged in the molecule but do not have the alicyclic epoxy compound (A) of ester bond and molecule in existing ester ring type epoxy group(ing) the compound of ester bond is arranged again and/or has the epoxy compounds (B) of glycidyl, total amount in the two is 100 weight parts, the consumption of alicyclic epoxy compound (A) is 10～90 weight parts, be preferably 20～70 weight parts, 30～60 weight parts more preferably, and the consumption of compound (B) is 10～90 weight parts, be preferably 30～80 weight parts, more preferably 40～70 weight parts.Total amount in both is 100 weight parts, alicyclic epoxy compound (A) if amount less than 10 weight parts, the hardness that gained is filmed, poor adhesion, if and the amount of alicyclic epoxy compound (A) surpasses 90 weight parts, the solidified nature of filming that forms by the uviolizing of low irradiation dose and withstand voltage hot poor.
The consumption of multipolymer (F), so that the ester ring type epoxy group(ing) to be arranged in the molecule but do not have existing ester ring type epoxy group(ing) in the alicyclic epoxy compound (A) of ester bond and the molecule that the compound of ester bond is arranged again and/or have total amount 100 weight parts of the epoxy compounds (B) of glycidyl, be generally 1～50 weight part, be preferably 3～30 weight parts, more preferably 5～20 weight parts.If the consumption of multipolymer (F) is less than 1 weight part, when the uviolizing of low irradiation dose, the reductions such as hardness, coating adhesion and hardness of film in hot water of filming after post-heating, if and the consumption of multipolymer (F) surpasses 50 weight parts, particularly the solidified nature of the uviolizing through hanging down irradiation dose is poor, hardness of film and withstand voltage hot low.
In addition, the consumption of cationic polymerization initiators (G), so that the ester ring type epoxy group(ing) to be arranged in the molecule but do not have existing ester ring type epoxy group(ing) in the alicyclic epoxy compound (A) of ester bond and the molecule that the compound of ester bond is also arranged and/or have total amount 100 weight parts of the epoxy compounds (B) of glycidyl, be generally 0.01～20 weight part, be preferably 0.1～10 weight part, more preferably 1～5 weight part.
The ultraviolet rays-curable can-coating composition of III of the present invention, have ultra-violet solidifiedly, it can be coated on the following material: tin plate, aluminium, non-tin-coated steel, iron, zinc, copper, steel plate galvanized, be coated with zinc and other metal alloy steel plate etc. become metal canned metal sheet (can handle and chemical treatments such as chromate treating through zinc phosphate on these metal sheets) by forming process; The resin film layer metal plate that resin moldings such as polyolefin resines such as vibrin, polyethylene and polypropylene, polyamide resin, Resins, epoxy, polyvinyl chloride such as laminated polyethylene terephthalate form on these metal sheets; Or,, form cured coating film then by uviolizing by the metal can that these sheet metal formings form.The thickness of coating can suitably be selected according to purposes, and usually, dry coating thickness is about 2～20 microns, more preferably 2～8 microns.
The ultraviolet rays-curable can-coating composition of III of the present invention, for example available roller painting, spraying method, spread coating, rod are coated with coating methods such as method, rolling method and silk screen print method and are coated with.Film when containing solvent, after the coating,, film then and solidify through uviolizing except that desolvating by modes such as heating, illuminate condition can be according to appropriate changes such as kind that is used for applied coating composition and thickness.The ultraviolet wavelength of irradiation is advisable in 200～600 nanometer range usually, can be according to the kind of cationic polymerization initiators etc., and the irradiating source of suitably selecting to have the high sensitive wavelength uses.
As the ultraviolet irradiation source, for example can enumerate: high voltage mercury lamp, ultrahigh pressure mercury lamp, xenon lamp, carbon arc, metal halide lamp and sunlight etc.The illuminate condition of filming normally, dosage be 10～1,000 milli burnt/centimetre
2, specially suitable be 50～500 millis burnt/centimetre
2
In addition, can be after uviolizing, as required to the heating of filming.By heating, reduce the unreacted reactant in filming, and relax by the curing of coating of uviolizing with by what forming process produced and be coated with membrane strain.By heating, can improve the hardness and the adhesivity of filming sometimes.Above-mentioned heating was carried out under 150～250 ℃ atmosphere temperature 1～30 minute usually.
The ultraviolet rays-curable can-coating composition of III of the present invention, contain the alicyclic epoxy compound (A) that the ester ring type epoxy group(ing) is arranged in the molecule but do not have ester bond, existing ester ring type epoxy group(ing) has the compound of ester bond again and/or has the epoxy compounds (B) of glycidyl in the molecule, and multipolymer (F) is as the film-forming resin component, it is in the presence of cationic polymerization initiators (G), need not use the equipment of enclosing nitrogen, even the uviolizing by low irradiation dose also can be solidified by cationoid polymerisation effectively, formed filming as the necessary processibility of can-coating, adhesivity, hardness, film performances such as scratch resistance are good, and appearance of film, withstand voltage hot.
Therefore, the coating composition of III of the present invention is particularly suitable as the coating that the can outside is used.
Below, with reference to embodiment, specify the present invention, but the present invention should not be limited to this.
" part " in the example and " % " represent " weight part " and " weight % " respectively.
The embodiment of＜I of the present invention 〉
Production Example 1
Being equipped with that air is blown into mouthful, in 300 milliliters of stainless steel reactor of gas dispersion porous plate and cooling jacket, dropping into the 10% acetaldehyde-ethyl acetate solution that contains cobaltous acetate with 114 kilograms/hour, be blown into pressurized air simultaneously, react in 45 ℃.Reaction solution contains 10.1% peracetic acid, 2.2% acetaldehyde monoperacetate and 2.0% acetate.This solution and sodium polyphosphate are dropped in the distillation tower together, concentrate, obtain peracetic acid solution.In this peracetic acid solution, peracetic acid concentration is 29.1%, and moisture is 0.47%.
Example I-1: alicyclic epoxy compound (A-1) synthetic
In 1 liter of strap clamp cover flask that agitator, cooling tube, thermometer, nitrogen ingress pipe are housed, add 36 gram water, 12.0 gram sodium pyrosulfates, 500 gram isopropylidenes-4,4 '-two hexalin (Aldrich manufacturing) and 500 grams carry out dehydration reaction as the Solvesso 150 (Exxon chemistry system) of solvent under 100 ℃.
When no longer distilling water outlet, reaction finishes.With vapor-phase chromatography reaction solution is analyzed, generate productive rate and be 96% 2,2-two (3 ', 4 '-cyclohexenyl) propane.Use separating funnel, with 500 milliliters of ion-exchange water washing gained reaction solutions, the underpressure distillation organic layer obtains 2 of 387.0 gram water white transparency liquid state then, 2-two (3 ', 4 '-cyclohexenyl) propane, and its purity is 96.1%.
Overlapping in the flask with aforementioned 1 liter of identical strap clamp, drop into 100 grams this 2,2-two (3 ', 4 '-cyclohexenyl) propane, 300 gram ethyl acetate, when gas phase partly is blown into nitrogen, with the ethyl acetate solution of the anhydrous in fact peracetic acid that makes in the 307.2 gram Production Examples 1 of dripping in about 2 hours (peracetic acid concentration: 29.1%, water content: 0.47%), making the temperature in the reaction system is 30 ℃.After peracetic acid splashes into and finishes, under 30 ℃, made it ageing 3 hours, to finish reaction.Liquid when 30 ℃ of following washed reactions stop is removed low-boiling point material under 70 ℃/20 mmhg again, obtains 99.4 gram epoxy compoundss.In the epoxy compounds 2, the purity of 2-two (3 ', 4 '-epoxycyclohexyl) propane is 93.4%.
The character of resulting product is, the Oxyranyle oxygen concn is 11.3%, and viscosity is 3,550 centipoises (25 ℃); By
1As seen HNMR has been disappeared by the peak that internal double bonds produced near δ 4.5～5ppm, has generated the peak of the proton that is produced by epoxy group(ing) near δ 2.9～3.1ppm.
Example I-2: alicyclic epoxy compound (A-2) synthetic
In 1 liter of strap clamp cover flask that agitator, cooling tube, thermometer, nitrogen ingress pipe are housed, add 300 grams, 4,4 '-two hexalin methane, 600 gram toluene and 3 gram tosic acid, under 100 ℃, carry out dehydration reaction.
When no longer distilling water outlet, reaction finishes.With vapor-phase chromatography reaction solution is analyzed, the generation productive rate is two (3, the 4-cyclohexenyl) methane of 96%.Use separating funnel, with 500 milliliters of ion-exchange water washing gained reaction solutions, underpressure distillation organic layer then obtains 269 two (3, the 4-cyclohexenyl) methane that restrain the water white transparency liquid state.
In the 1 liter strap clamp cover flask identical with example I-1, drop into 100 grams this two (3, the 4-cyclohexenyl) methane and 200 gram ethyl acetate, when gas phase partly is blown into nitrogen, (peracetic acid concentration: 29.1%), making the temperature in the reaction system is 25 ℃ with the ethyl acetate solution of the anhydrous in fact peracetic acid that makes in the 276.2 gram Production Examples 1 of dripping in about 3 hours.After peracetic acid splashes into and finishes, under 30 ℃, made it ageing 4 hours, to finish reaction.Liquid when 30 ℃ of following washed reactions stop is removed low-boiling point material under 70 ℃/30 mmhg again, obtains 106.4 gram epoxy compoundss.The purity of two in the epoxy compounds (3, the 4-epoxycyclohexyl) methane is 91.8%.
The character of resulting product is, the Oxyranyle oxygen concn is 13.8%, and viscosity is 2,590 centipoises (25 ℃); By
1HNMR determines, has been disappeared by the peak that two key produced near δ 4.5～5ppm, has generated the peak of the proton that is produced by epoxy group(ing) near δ 2.9～3.3ppm.
Example I-3
Except using beyond 400 gram A Hydrogenated Bisphenol A sulfones (i.e. 4,4 '-two hexalin sulfones) and 500 Solvesso 150 of gram as solvent, all the other are identical with example I-1, and acquisition 330 restrains two (3,4-two cyclohexenyls) sulfones, and its purity is 92.2%.
100 these reactants of gram are overlapped in the flask with 300 gram ethyl acetate inputs and aforementioned 1 liter of identical strap clamp, when gas phase partly is blown into nitrogen, (peracetic acid concentration: 29.1%), making the temperature in the reaction system is 40 ℃ with the ethyl acetate solution that splashed into 242.7 gram peracetic acid in about 2 hours.After peracetic acid splashes into and finishes, under 40 ℃, made it ageing 4 hours, to finish reaction.The thick liquid of washing under 30 ℃ is removed low-boiling point material under 70 ℃/30 mmhg again, obtains 97.0 gram epoxy compoundss.The purity of two in the epoxy compounds (3, the 4-epoxycyclohexyl) sulfone is 90.3%.
The character of resulting product is, the Oxyranyle oxygen concn is 10.8%, and viscosity is 6,700 centipoises (25 ℃); By
1HNMR determines, has been disappeared by the peak that two key produced near δ 4.5～5ppm, has generated the peak of the proton that is produced by epoxy group(ing) near δ 2.9～3.3ppm.
Comparative Example I-1
Being 60% superoxol, 200 gram propionic acid and 0.3 gram sulfuric acid with 167.7 gram concentration mixed 3 hours in 30 ℃, and synthetic perpropionic acid extracts with 700 gram benzene then, and acquisition concentration is the benzole soln (moisture 4.5%) of 16.9% perpropionic acid.
With synthetic 2 in the 100 gram example I-1,2-two (cyclohexenyl) propane drops in 1 liter of used in the example I-1 strap clamp cover flask.With the benzole soln that splashed into the above-mentioned perpropionic acid of 578.8 grams in about 1 hour therein, making the temperature in the reaction system is 30 ℃.Splash into finish after, under 30 ℃, made it ageing 4 hours, to finish reaction.The thick liquid of washing under 40 ℃ is removed low-boiling point material under 70 ℃/20 mmhg again, obtains 81.8 gram epoxy compoundss.In the epoxy compounds 2,2-two (3 ', 4 '-the oxirane ring hexenyl) purity of propane is 52%.
The character of resulting product is, the Oxyranyle oxygen concn is 6.4%, and viscosity is 14,560 centipoises (25 ℃); By
1HNMR determines, has been disappeared by the peak that two key produced near δ 4.5～5ppm, has generated the peak from the proton of epoxy group(ing) near δ 2.9～3.3ppm.
Comparative Example I-2
300 gram 60% hydrogen peroxide and 280 gram acetate were mixed 3 hours in 30 ℃, and synthetic peracetic acid extracts with 1000 gram ethyl acetate then, and acquisition concentration is the ethyl acetate solution (moisture 8.5%) of 21.8% peracetic acid.
With synthetic 2 in the 100 gram example I-1,2-two (3 ', 4 '-cyclohexenyl) propane drops in 1 liter of used in the example I-1 strap clamp cover flask.With the ethyl acetate solution (moisture 8.5%) that splashed into the peracetic acid of 410.0 grams above-mentioned 21.8% in about 2 hours therein, making the temperature in the reaction system is 30 ℃.Splash into finish after, under 30 ℃, made it ageing 4 hours, to finish reaction.The thick liquid of washing under 20 ℃ is removed low-boiling point material under 70 ℃/20 mmhg again, obtains 65.7 gram epoxy compoundss.In the epoxy compounds 2,2-two (3 ', 4 '-epoxycyclohexyl) purity of propane is 37.8%.
The character of resulting product is, the Oxyranyle oxygen concn is 4.87%, and viscosity is 16,000 centipoises (25 ℃); By
1HNMR determines, has been disappeared by the peak that two key produced near δ 4.5～5ppm, has generated the peak from the proton of epoxy group(ing) near δ 2.9～3.3ppm.
By I of the present invention, can use the little solvent of toxicity, carry out the epoxidation of ester ring type olefin(e) compound effectively, economically.
The embodiment of II of the present invention
The composition epoxy resin among each embodiment of II of the present invention and the physical properties of cured article thereof are estimated according to method shown below.
[thermotolerance]
Make the thermotolerance sample composition in 120 ℃ following 1 hour+160 ℃ following 3 hours (example II-7～II-8, Comparative Example I I-2 in 100 ℃ following 1 hour+160 ℃ following 3 hours) carry out thermofixation, obtain test film (long 10 millimeters, wide 5 millimeters, thick 5 millimeters), measure second-order transition temperature with hot mechanical determinator (TMA) (manufacturing of SeikoInstruments society).Its result is according to following standard evaluation.
More than zero: 140 ℃.
△: more than 130 ℃, less than 140 ℃.
*: less than 130 ℃.
Second-order transition temperature is the sample composition more than 140 ℃, and thermotolerance is good.
[wet fastness]
The wet fastness sample composition is carried out thermofixation under the above-mentioned thermal test condition identical with sample, obtain test film (long 50 millimeters, wide 50 millimeters, thick 3 millimeters), under the condition of 120 ℃, 2 normal atmosphere and 50 hours, this test film is carried out humidification with pressure cooking device (Sabai Espec society system), obtain the weight increase of the test film behind the humidification according to following formula.
Weight increase (%)=(W-W0)/W0 * 100
W0 is the weight before the humidification, and W is the weight behind the humidification.Its result is according to following standard evaluation.
◎: less than 1.2%.
More than zero: 1.2%, less than 1.5%.
△: more than 1.5, less than 2.0%.
*: more than 2.0.
Weight increase is less than 1.5% sample composition, and wet fastness is good.
[light transmission]
Use composition epoxy resin, in 120 ℃ following 1 hour+160 ℃ following 3 hours (example II-7～II-8, Comparative Example I I-2 in 100 ℃ following 1 hour+160 ℃ following 3 hours) be cured, form thick 1 millimeter cured article.
With its transmittance when wavelength is 600 nanometers of spectrophotometric determination.
Example II-1～II-8
With constituting each component of the optoelectronic semiconductor encapsulating epoxy resin composition of II of the present invention,, and mix equably with ratio (weight part) fusion shown in the Table II-1.
In example II-1, II-2, II-5, II-6 and II-7, use the alicyclic epoxy compound of making among the previous embodiment I-1 (A-1).
And in example II-3, II-4 and II-8, use the alicyclic epoxy compound of making among the previous embodiment I-2 (A-2).
Comparative Example I I-1～II-2
To measuring shelf lives and dipping property in the same manner with composition and the embodiment that the ratio (weight part) shown in the Table II-1 is blended into by each component.It the results are shown in Table II-1.
And, under the identical condition of embodiment, make each composition curing and embodiment measure thermotolerance, wet fastness and the light transmission of this cured article in the same manner.It the results are shown in Table II-2.In Comparative Example I I-1, use the alicyclic epoxy compound of making among the previous embodiment I-1 (A-1), in Comparative Example I I-2, the alicyclic epoxy compound of making among use and the previous embodiment I-2 (A-2).
Table II-1
| Example II | Comparative Example I I | |||||||||
| ??-1 | ??-2 | ??-3 | ??-4 | ??-5 | ??-6 | ??-7 | ??-8 | ??-1 | ??-2 | |
| The compound of Production Example 2 | ??90 | ??85 | ??40 | ??40 | ??50 | ??10 | ||||
| The compound of Production Example 3 | ??60 | ??30 | ??40 | ??15 | ||||||
| ??CEL-2021P | ??10 | ??20 | ??50 | ??40 | ??50 | ??40 | ??80 | |||
| ??CEL-3000 | ??5 | |||||||||
| ??EHPE-3150 | ??20 | ??20 | ||||||||
| ??TEPIC | ??30 | |||||||||
| ??Epikote?828 | ??15 | ??30 | ??20 | ??20 | ??85 | |||||
| Ethylene glycol | ??2 | ??2 | ??2 | ??2 | ??2 | ??2 | ??2 | |||
| ??MH-700 | ??96.6 | ??124.9 | ??150.8 | ??98.1 | ??127.1 | ??140.6 | ??119.8 | |||
| ??DBU | ??1 | ??1.5 | ??1 | ??1 | ??1.5 | ??1 | ??1.5 | |||
| ??SI-100L | ??2 | |||||||||
| ??AI(ACAC) 3 | ??1 | ??1 | ||||||||
| Bisphenol S | ??3 | ??3 | ||||||||
(1) Celloxide 2021P (trade(brand)name) is (CEL-2021P): Daicel chemical industry society makes, and 3,4-epoxy cyclohexane carboxylic acid 3,4-epoxy cyclohexyl, epoxy equivalent (weight) 134.
(2) Celloxide 3000 (trade(brand)name) (CEL-3000): Daicel chemical industry society makes, two Huan Yangization limonenes, epoxy equivalent (weight) 94.
(3) EHPE-3150: Daicel chemical industry society makes, alicyclic epoxy resin, epoxy equivalent (weight) 168.
(4) isocyanuric acid three-glycidyl ester (trade(brand)name) TEPIC: produce chemical society daily and make.
(5) Epikote 828 (trade(brand)name): oiling Shell Epoxy society makes, and bisphenol A type epoxy resin is liquid in the time of 25 ℃, epoxy equivalent (weight) 187.
(6) methyl hexahydro phthalic anhydride (trade(brand)name) MH-700: new Japanese physics and chemistry society makes.
(7) 1,8-diazabicylo [5.4.0] undecylenes-7 (DBU): and the pure medicine of light society makes.
(8) sulfonium salt cation curing catalysts (trade(brand)name) SI-100L: three new chemical societies make.
(9) praseodynium aluminium (Al (AcAc)
3): Daicel chemical industry society makes.
Table II-2 evaluation result
| Example II | Comparative Example I I | |||||||||
| ??-1 | ??-2 | ??-3 | ??-4 | ??-5 | ??-6 | ??-7 | ??-8 | ??-1 | ??-2 | |
| Thermotolerance (℃) | ??148 | ??142 | ??155 | ??151 | ??146 | ??141 | ??144 | ??141 | ??152 | ??129 |
| Wet fastness | ??◎ | ??◎ | ??○ | ??○ | ??◎ | ??◎ | ??◎ | ??◎ | ??△ | ??○ |
| Light transmission | ??91.8 | ??88.9 | ??93.8 | ??89.1 | ??95.7 | ??91.1 | ??93.5 | ??90.3 | ??90.1 | ??72.1 |
By the optoelectronic semiconductor encapsulating epoxy resin composition of II of the present invention, can obtain humidity resistance and the good cured article of the transparency.
The embodiment of III of the present invention
(manufacturing of the multipolymer (F) of at least one epoxy group(ing) is arranged in the molecule)
Production Example III-1
In the flask that stirrer and water cooler are housed, drop into 500 parts of toluene, when stirring, be warming up to 95 ℃.Keep uniform temp, simultaneously, with splashing into therein in 4 hours by 150 parts of glycidyl methacrylate, 250 parts of n-BMAs and 50 part 2,2 '-Diisopropyl azodicarboxylate is pre-mixed the mixture that dissolving forms, carry out polymerization, remove toluene through underpressure distillation then, obtain multipolymer (F).
The number-average molecular weight of the multipolymer of gained (F) is 2500, and the Oxyranyle oxygen concn is 1.4%.
Production Example III-2～III-3
In Production Example III-1, except shown in the Table III composed as follows-1 of the mixture that splashes into and Production Example III-1 carry out polymerization in the same manner, obtain various multipolymers.Shown in the number-average molecular weight of the multipolymer of gained, trimethylene oxide ring concentration and the glycidyl concentration following Table III-1.The amount of each component is represented with weight part in the Table III-1.
Table III-1 Production Example
| ??III-1 | ??III-2 | ??III-3 | |
| ??GMA 1) | ??100 | ??200 | |
| ??CYMA-200 2) | ??150 | ||
| ??n-BMA 3) | ??150 | ??100 | ??200 |
| ??MMA | ??200 | ??250 | ??150 |
| ??BA | ??200 | ??150 | ??100 |
| ??HEMA | ??50 | ||
| ??AIBN 4) | ??50 | ??50 | ??50 |
| Number-average molecular weight | ??5000 | ??3000 | ??4500 |
| The Oxyranyle oxygen concn | ??1.4 | ??2.7 | ??1.8 |
1) GMA: glycidyl methacrylate
2) CYMA-200: methacrylic acid epoxy cyclohexyl, trade(brand)name Cyclomer A-200, (manufacturing of Daicel chemistry (strain) society)
3) n-BMA: n-BMA
4) AIBN:2,2 '-Diisopropyl azodicarboxylate
5) HEMA: methacrylic acid 2-hydroxyl ethyl ester
EXAMPLE III-1～III-7 and Comparative Example I II-1～III-2
With 3,4-epoxy cyclohexane carboxylic acid 3, R in 4-epoxycyclohexyl methyl esters (being expressed as CEL-2021P in the Table III-2), 3-ethyl-3-methylol trimethylene oxide (being expressed as OXE in the Table III-2), the aforementioned formula (12)
61All be compound (being expressed as E-DOA in the Table III-2), the multipolymer of each Production Example gained, the UVACURE 1591 (U.S. UCB society manufacturing of ethyl, the photo-induced cationic polymerization initiator that PF6 is arranged), be that (Dow Corning society makes for ten glyceryl ethers (12 hydroxyls are arranged in 1 molecule) of 10 Polyglycerine and 1 part and 0.2 part Paintadd M of fatty acid ester wax that 10 moles of lauric acid reactions form by 1 mole of polymerized degree, silicon wax) mix, remain on 50 ℃ and stirred 20 minutes down, obtain ultraviolet rays-curable can-coating composition.
In EXAMPLE III-1, III-2, III-4 and III-5, use the alicyclic epoxy compound of making among the previous embodiment I-1 (A-1).
And in EXAMPLE III-3, III-6 and III-7, use the alicyclic epoxy compound of making among the previous embodiment I-2 (A-2).
In Comparative Example I II-1～III-2, alicyclic epoxy compound (A-1), alicyclic epoxy compound (A-2) do not use.
Table III-2
| EXAMPLE III | Comparative Example I II | ||||||||
| ??-1 | ??-2 | ??-3 | ??-4 | ??-5 | ??-6 | ??-7 | ??-1 | ??-2 | |
| ??E-DOA 1) | ??60 | ??75 | ??20 | ??45 | |||||
| ??E-DOA-f 2) | ??30 | ??80 | ??15 | ||||||
| ??CEL-2021P 3) | ??40 | ??15 | ??40 | ??70 | ??40 | ??30 | ??45 | ||
| ??CEL-3000 4) | ??10 | ??15 | ??10 | ??15 | ??15 | ??5 | |||
| ??OXE 5) | ??15 | ??10 | ??30 | ??10 | ??10 | ||||
| Production Example 1 | ??30 | ??20 | ??50 | ??40 | |||||
| Production Example 2 | ??25 | ??20 | ??40 | ||||||
| Production Example 3 | ??40 | ??40 | |||||||
| Fatty acid ester wax | ??1 | ??1 | ??1 | ??1 | ??1 | ??1 | ??1 | ??1 | ??1 |
| ??UVACURE-1591 6) | ??7 | ??6 | ??7 | ??8 | ??6 | ??8.5 | ??6 | ??6 | ??7 |
1) E-DOA: synthetic alicyclic epoxy compound (A-1) in the example I-1
2) E-DOA-f: synthetic epoxy compounds (A-2) in the example I-2
3) CEL-2021P:3,4-epoxy cyclohexane carboxylic acid 3,4-epoxycyclohexyl methyl esters (manufacturing of Daicel chemistry (strain) society)
4) CEL-3000:1,2,8,9-two Huan Yangization limonenes (manufacturing of Daicel chemistry (strain) society)
5) OXE:3-ethyl-3-methylol trimethylene oxide (manufacturing of emerging product society of space portion)
6) UVACURE-1591: the cationic catalyst of sulfonium salt system (Daicel-UCB Co., Ltd. makes)
Test is coated with the manufacturing of lamina membranacea
Each coating composition with gained among the foregoing description III-1～III-7 and the Comparative Example I II-1～III-2, be coated on thick 0.20 millimeter non-tin plate (TFS) and at hot pressing on 0.2 millimeter tin plate of being altogether unjustifiable on the PET steel plate that forms of 12 micron thickness PET homopolymer (polyethylene terephthalate) sheet materials, the dry film thickness that separate application is 5 microns, use high voltage mercury lamp (160 watts/centimetre), carrying out uviolizing from being coated with lamina membranacea 15 centimeters, make energy dose be 80 millis burnt/centimetre
2, make curing of coating, form test and be coated with lamina membranacea.
Each test to gained is coated with lamina membranacea, tests according to following test method.And test is all carried out under 20 ℃.
Test method
Pencil hardness: on test the filming of coated plate,, carry out pencil test, estimate and use method of Tearing according to JIS K-54008.4.2 (1990) regulation.
Shock-resistance (Du Pon ' t formula): according to JIS K-54008.3.2 (1990), use DuPon ' t shock-testing machine, test is coated with the reverse side of lamina membranacea from coated surface, be 3/8 inch at the shock point diameter, the loading of dropping hammer is that 500 grams and height of the fall are under 30 centimetres the condition, impact processing, use the microscopic examination working position, estimate according to following standard.
◎: do not see the crack fully and film and peel off.
Zero: see slightly crack, but do not see filming and peel off.
△: see tangible crack, but do not see filming and peel off.
*: seeing films peels off.
Adhesivity: according to JIS K-54008.5.2 (1990) checker adhesive tape method, be coated with being coated with on the lamina membranacea face of lamina membranacea in test, make 100 1.5 millimeters * 1.5 millimeters grid, on this surface, adhere to cellotape, sharply peel, estimate the state of grid then according to following surface.
◎: do not see fully and peeling off.
Zero: the edge of seeing grid is slightly peeled off.
△: slightly peel off at the position beyond the grid edge.
*: see significantly and peeling off.
Hardness in the hot water: in 200 ℃ test was coated with the lamina membranacea heating after 1 minute, dipping is 10 minutes in 80 ℃ warm water, measures its pencil hardness in 80 ℃ of warm water.
Evaluation is carried out according to the method for Tearing among the JIS K-54008.4.2 (1990).
Each coating composition to gained among previous embodiment III-1～III-7 and the Comparative Example I II-1～III-2 carries out uniformity test in accordance with the following methods.
Homogeneity: with each coating composition, making dry film thickness with roller painting (coating (natural coating) naturally) coating on the PET steel plate is 5 microns, be to carry out uviolizing under 0.5 second the condition from being applied to uviolizing, visual assessment is coated with the face outward appearance when solidifying.Evaluation is carried out according to following standard.
◎: do not see roller marks being arranged on filming, smoothness is good.
Zero: see film on roller marks slightly, smoothness is good
△: see that suitable roller marks are arranged on filming, some is poor for smoothness.
*: seeing has remarkable roller marks on filming, and smoothness is obviously poor.
Test-results
Above-mentioned test the results are shown in following table III-3.
When Table III-3 base mateiral is TFS
| EXAMPLE III | Comparative Example I II | ||||||||
| ??-1 | ??-2 | ??-3 | ??-4 | ??-5 | ??-6 | ??-7 | ??-1 | ??-2 | |
| Pencil hardness | ??2H | ??2H | ??2H | ??2H | ??2H | ??H | ??2H | ??HB | ??H |
| Shock-resistance | ??◎ | ??◎ | ??○ | ??◎ | ??○ | ??◎ | ??○ | ??△ | ??△ |
| Adhesivity | ??◎ | ??○ | ??◎ | ??○ | ??○ | ??○ | ??◎ | ??○ | ??○ |
| Hardness in the hot water | ??H | ??H | ??H | ??H | ??HB | ??HB | ??H | ??F | ??H |
When Table III-4 base mateiral is the PET steel plate
| EXAMPLE III | Comparative Example I II | ||||||||
| ??-1 | ??-2 | ??-3 | ??-4 | ??-5 | ??-6 | ??-7 | ??-1 | ??-2 | |
| Pencil hardness | ??2H | ??2H | ??H | ??2H | ??2H | ??H | ??2H | ??HB | ??H |
| Shock-resistance | ??◎ | ??○ | ??◎ | ??○ | ??◎ | ??◎ | ??◎ | ??○ | ??○ |
| Adhesivity | ??○ | ??◎ | ??○ | ??○ | ??◎ | ??○ | ??◎ | ??△ | ??△ |
| Hardness in the hot water | ??HB | ??H | ??HB | ??H | ??H | ??H | ??H | ??F | ??H |
| Homogeneity | ??○ | ??○ | ??○ | ??○ | ??◎ | ??○ | ??◎ | ??○ | ??△ |
The ultraviolet rays-curable can-coating composition of III of the present invention can be solidified by the uviolizing of low irradiation dose, and the film performance of the processibility of its cured article, adhesivity, hardness and scratch resistance etc. is good, and particularly appearance of film and heat-resisting pressure are good.
Claims (13)
1. liquid epoxy resin composition, it comprises Resins, epoxy and solidifying agent and/or curing catalyst, it is characterized in that, contains the represented alicyclic epoxy compound (A) of following general formula (I) of 100～20 weight % in the described Resins, epoxy:
In the formula, X be Sauerstoffatom, sulphur atom ,-SO-,-SO
2-,-CH
2-,-C (CH
3)
2-,-CBr
2-,-C (CBr
3)
2-,-C (CF
3)
2-,-C (CCl
3)
2-or-CH (C
6H
5)-divalent radical or the singly-bound that links to each other with 2 alicyclic rings, R
1～R
18Can be identical also can be different, be respectively hydrogen atom, halogen atom, maybe can have the alkyl of Sauerstoffatom or halogen atom, maybe can have substituent alkoxyl group.
2. liquid epoxy resin composition as claimed in claim 1 is characterized in that, the represented alicyclic epoxy compound (A) of described general formula (I) is to be the epoxy compounds of the following percarboxylic acids manufacturing of 2 weight % with water content.
3. liquid epoxy resin composition as claimed in claim 1 or 2 is characterized in that, described solidifying agent is the initiator of emitting the material that causes cationoid polymerisation by heating.
4. as any one described liquid epoxy resin composition in the claim 1～3, it is characterized in that described solidifying agent is a liquid anhydride.
5. liquid epoxy resin composition, it is characterized in that, it be the curing catalyst (D) of the liquid anhydride class solidifying agent (C) of fusion 110～160 weight parts in the alicyclic epoxy compound (A) represented and 3～7 weight parts in the described general formula of the claim 6 of 100 weight parts (I) or also fusion be that the initiator (E) of emitting cationic substance by heating that 100 weight parts are counted 0.1～20 weight part forms with described alicyclic epoxy compound (A).
6. as any one described liquid epoxy resin composition in the claim 1～5, it is used for the sealed photoelectric semi-conductor.
7, opto-semiconductor device, it uses the described optoelectronic semiconductor encapsulating epoxy resin composition of claim 6 sealed photoelectric semiconductor element.
8. ultraviolet rays-curable can-coating composition, it contain existing ester ring type epoxy group(ing) in the molecule of the represented alicyclic epoxy compound (A) of the following general formula (I) of 10～100 weight parts, 0～90 weight part the compound of ester bond is also arranged and/or have glycidyl epoxy compounds (B), with compound (A) and (B) total amount 100 weight parts count and have at least one glycidyl and/or ester ring type epoxy group(ing) in the molecule of 1～50 weight part
Multipolymer (F) and 0.01～20 weight part produce cationic cationic polymerization initiators (G) by uviolizing:
In the formula, X be Sauerstoffatom, sulphur atom ,-SO-,-SO
2-,-CH
2-,-C (CH
3)
2-,-CBr
2-,-C (CBr
3)
2-,-C (CF
3)
2-,-C (CCl
3)
2-or-CH (C
6H
5)-divalent radical or the singly-bound that links to each other with 2 alicyclic rings, R
1～R
18Can be identical also can be different, be respectively hydrogen atom, halogen atom, maybe can have the alkyl of Sauerstoffatom or halogen atom, maybe can have substituent alkoxyl group.
9. ultraviolet rays-curable can-coating composition as claimed in claim 8, it is characterized in that described multipolymer (F) is to have the polymerizable unsaturated monomer of glycidyl and/or have the polymerizable unsaturated monomer of ester ring type epoxy group(ing) and the multipolymer of other polymerizable unsaturated monomer.
10. ultraviolet rays-curable can-coating composition as claimed in claim 8 or 9, it is characterized in that it also contains the oilness imparting agent of counting 0.01～10 weight part with total amount 100 weight parts of represented alicyclic epoxy compound (A) of following formula (I) and epoxy compounds (B).
11. as any one described ultraviolet rays-curable can-coating composition in the claim 8～10, it is characterized in that it also contains the resin particle of counting 0.1～50 weight part with total amount 100 weight parts of represented alicyclic epoxy compound (A) of following formula (I) and epoxy compounds (B).
12. as any one described ultraviolet rays-curable can-coating composition in the claim 8～11, it is characterized in that the represented alicyclic epoxy compound (A) of described general formula (I) is to be the epoxy compounds of the following aliphatics percarboxylic acids manufacturing of 2 weight % with water content.
The metal canned manufacture method 13. film, it is characterized in that, it comprises makes it to solidify by irradiation ultraviolet radiation with any one described ultraviolet rays-curable can-coating composition coating metal plate, resin film layer metal plate in the claim 8～12 or the metal can that formed by these sheet metal formings then.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001084195A JP4663893B2 (en) | 2001-03-23 | 2001-03-23 | Method for producing epoxy compound |
| JP200184195 | 2001-03-23 | ||
| JP2001143835 | 2001-05-14 | ||
| JP2001193430 | 2001-06-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB028007492A Division CN1243744C (en) | 2001-03-23 | 2002-03-22 | Process for producing epoxy compound, epoxy resin composition and use thereof, ultraviolet-curable can coating composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1690118A true CN1690118A (en) | 2005-11-02 |
| CN1325559C CN1325559C (en) | 2007-07-11 |
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ID=18939901
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|---|---|---|---|
| CNB2005100668235A Expired - Fee Related CN1325559C (en) | 2001-03-23 | 2002-03-22 | Epoxy resin composition, ultraviolet rays-curable can-coating composition and its uses |
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| JP (1) | JP4663893B2 (en) |
| CN (1) | CN1325559C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI402285B (en) * | 2006-03-10 | 2013-07-21 | Adeka Corp | A hardening composition for optical material and optical waveguide device |
| CN109738257A (en) * | 2019-02-28 | 2019-05-10 | 山东科技大学 | A kind of preparation method of fine coal coal petrography mating plate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5226162B2 (en) * | 2001-05-14 | 2013-07-03 | 株式会社ダイセル | Liquid epoxy resin composition and use thereof |
| US20060009547A1 (en) | 2002-09-05 | 2006-01-12 | Hisashi Maeshima | Process for preparation of alicyclic diepoxy compound, curable epoxy resin compositions, epoxy resin compositions for the encapsulation of electronic components, stabilizers for electrical insulating oils, and casting epoxy resin compositions for electrical insulation |
| JP4622348B2 (en) * | 2003-07-07 | 2011-02-02 | 住友ベークライト株式会社 | Transparent composite composition |
| JP4553572B2 (en) * | 2003-11-12 | 2010-09-29 | ダイセル化学工業株式会社 | UV curable adhesive and its adhesive |
| JP4650003B2 (en) * | 2004-01-28 | 2011-03-16 | 住友ベークライト株式会社 | Transparent composite sheet and display element substrate using the same |
| JP4563053B2 (en) * | 2004-03-08 | 2010-10-13 | ダイセル化学工業株式会社 | Poly (meth) acrylate resin, method for producing the same, and curable resin composition |
| JP4823892B2 (en) * | 2004-03-18 | 2011-11-24 | ダイセル化学工業株式会社 | High-purity alicyclic epoxy compound, production method thereof, curable epoxy resin composition, cured product thereof, and use |
| JP4496828B2 (en) * | 2004-04-09 | 2010-07-07 | 住友ベークライト株式会社 | Manufacturing method of transparent composite substrate |
| JP4489549B2 (en) * | 2004-09-29 | 2010-06-23 | ダイセル化学工業株式会社 | Method for producing high purity 2,2-bis (3'-cyclohexenyl) propane |
| JP5329043B2 (en) | 2004-12-16 | 2013-10-30 | 株式会社ダイセル | Thermosetting epoxy resin composition and use thereof |
| JP4688503B2 (en) | 2005-01-07 | 2011-05-25 | ダイセル化学工業株式会社 | High purity alicyclic diepoxy compound and process for producing the same |
| WO2006077693A1 (en) * | 2005-01-21 | 2006-07-27 | Konica Minolta Medical & Graphic, Inc. | Polymerizable actinic radiation curable composition, polymerization method, actinic radiation curable ink and image formation method, and ink jet recording apparatus and epoxy compound |
| WO2007119743A1 (en) * | 2006-04-18 | 2007-10-25 | Daicel Chemical Industries, Ltd. | Process for production of cyclic olefins |
| JP5143449B2 (en) * | 2007-03-02 | 2013-02-13 | 株式会社ダイセル | Thermal or active energy ray curable adhesive |
| JP5638812B2 (en) * | 2010-02-01 | 2014-12-10 | 株式会社ダイセル | Curable epoxy resin composition |
| JP5675230B2 (en) | 2010-09-03 | 2015-02-25 | 株式会社ダイセル | Thermosetting epoxy resin composition and use thereof |
| JP5832740B2 (en) | 2010-11-30 | 2015-12-16 | 株式会社ダイセル | Curable epoxy resin composition |
| JP5832821B2 (en) * | 2011-08-18 | 2015-12-16 | 株式会社ダイセル | Epoxy compound and method for producing the same |
| JP5926130B2 (en) * | 2012-06-20 | 2016-05-25 | 株式会社ダイセル | Method for producing diolefin compound and method for producing diepoxy compound containing the same |
| KR20150090073A (en) * | 2012-11-27 | 2015-08-05 | 주식회사 다이셀 | Method for producing microstructure and photocurable composition for nanoimprinting |
| WO2014181699A1 (en) * | 2013-05-10 | 2014-11-13 | 株式会社ダイセル | Curable epoxy resin composition and cured product thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3075955A (en) * | 1960-03-31 | 1963-01-29 | Union Carbide Corp | Polyepoxy sulfones |
| US3271371A (en) * | 1960-03-31 | 1966-09-06 | Union Carbide Corp | Cured diepoxy sulfone and polyfunctional amine compositions |
| GB996064A (en) * | 1960-08-24 | 1965-06-23 | Union Carbide Corp | Improvements in and relating to epoxy resins |
| US3764814A (en) * | 1972-03-27 | 1973-10-09 | United Aircraft Corp | Control for auxiliary power unit |
| DE2752920A1 (en) * | 1977-11-26 | 1979-05-31 | Akzo Gmbh | PROCESS FOR THE MANUFACTURING OF EPOXIDS |
| DE3211305A1 (en) * | 1982-03-26 | 1983-09-29 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING 2,2-DICYCLOHEXENYL PROPANDY POXIDE |
| JP3844824B2 (en) * | 1996-11-26 | 2006-11-15 | 株式会社Ａｄｅｋａ | Energy ray-curable epoxy resin composition, resin composition for optical three-dimensional modeling, and optical three-dimensional modeling method |
| US6287748B1 (en) * | 1998-07-10 | 2001-09-11 | Dsm N.V. | Solid imaging compositions for preparing polyethylene-like articles |
-
2001
- 2001-03-23 JP JP2001084195A patent/JP4663893B2/en not_active Expired - Fee Related
-
2002
- 2002-03-22 CN CNB2005100668235A patent/CN1325559C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI402285B (en) * | 2006-03-10 | 2013-07-21 | Adeka Corp | A hardening composition for optical material and optical waveguide device |
| CN109738257A (en) * | 2019-02-28 | 2019-05-10 | 山东科技大学 | A kind of preparation method of fine coal coal petrography mating plate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4663893B2 (en) | 2011-04-06 |
| JP2002275169A (en) | 2002-09-25 |
| CN1325559C (en) | 2007-07-11 |
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