JP4701846B2 - Curable composition - Google Patents
Curable composition Download PDFInfo
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- JP4701846B2 JP4701846B2 JP2005170502A JP2005170502A JP4701846B2 JP 4701846 B2 JP4701846 B2 JP 4701846B2 JP 2005170502 A JP2005170502 A JP 2005170502A JP 2005170502 A JP2005170502 A JP 2005170502A JP 4701846 B2 JP4701846 B2 JP 4701846B2
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- component
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- curable composition
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- composition
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- 239000000203 mixture Substances 0.000 title claims description 60
- 150000001875 compounds Chemical class 0.000 claims description 43
- 239000004593 Epoxy Substances 0.000 claims description 16
- 238000010538 cationic polymerization reaction Methods 0.000 claims description 13
- 239000003505 polymerization initiator Substances 0.000 claims description 12
- 125000003566 oxetanyl group Chemical group 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910002808 Si–O–Si Inorganic materials 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 description 13
- 229920000647 polyepoxide Polymers 0.000 description 13
- 238000002156 mixing Methods 0.000 description 12
- 125000002723 alicyclic group Chemical group 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 8
- -1 cyclic olefin compound Chemical class 0.000 description 8
- 239000000835 fiber Substances 0.000 description 7
- 239000000976 ink Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- RBHIUNHSNSQJNG-UHFFFAOYSA-N 6-methyl-3-(2-methyloxiran-2-yl)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2(C)OC2CC1C1(C)CO1 RBHIUNHSNSQJNG-UHFFFAOYSA-N 0.000 description 5
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000007142 ring opening reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 3
- UHHSHIQBMDUHIY-UHFFFAOYSA-N (3-methyl-7-oxabicyclo[4.1.0]heptan-4-yl) 3,4-dimethyl-7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1C2OC2CC(C)C1(C)C(=O)OC1CC2OC2CC1C UHHSHIQBMDUHIY-UHFFFAOYSA-N 0.000 description 2
- NLQMSBJFLQPLIJ-UHFFFAOYSA-N (3-methyloxetan-3-yl)methanol Chemical compound OCC1(C)COC1 NLQMSBJFLQPLIJ-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- BIDWUUDRRVHZLQ-UHFFFAOYSA-N 3-ethyl-3-(2-ethylhexoxymethyl)oxetane Chemical compound CCCCC(CC)COCC1(CC)COC1 BIDWUUDRRVHZLQ-UHFFFAOYSA-N 0.000 description 2
- BBDKZWKEPDTENS-UHFFFAOYSA-N 4-Vinylcyclohexene Chemical compound C=CC1CCC=CC1 BBDKZWKEPDTENS-UHFFFAOYSA-N 0.000 description 2
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- IDSLNGDJQFVDPQ-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-yl) hexanedioate Chemical compound C1CC2OC2CC1OC(=O)CCCCC(=O)OC1CC2OC2CC1 IDSLNGDJQFVDPQ-UHFFFAOYSA-N 0.000 description 2
- DJUWPHRCMMMSCV-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-ylmethyl) hexanedioate Chemical compound C1CC2OC2CC1COC(=O)CCCCC(=O)OCC1CC2OC2CC1 DJUWPHRCMMMSCV-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical group C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- GGAUUQHSCNMCAU-ZXZARUISSA-N (2s,3r)-butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C[C@H](C(O)=O)[C@H](C(O)=O)CC(O)=O GGAUUQHSCNMCAU-ZXZARUISSA-N 0.000 description 1
- JWZVNQGIGRCDRU-UHFFFAOYSA-N (3-butan-2-yloxetan-3-yl)methanol Chemical compound CCC(C)C1(CO)COC1 JWZVNQGIGRCDRU-UHFFFAOYSA-N 0.000 description 1
- BJYGGFGTOTUNJA-UHFFFAOYSA-N (3-butyloxetan-3-yl)methanol Chemical compound CCCCC1(CO)COC1 BJYGGFGTOTUNJA-UHFFFAOYSA-N 0.000 description 1
- FMUFFUZPAMYTLG-UHFFFAOYSA-N (3-propan-2-yloxetan-3-yl)methanol Chemical compound CC(C)C1(CO)COC1 FMUFFUZPAMYTLG-UHFFFAOYSA-N 0.000 description 1
- CUBVDBSVGQEYCB-UHFFFAOYSA-N (3-propyloxetan-3-yl)methanol Chemical compound CCCC1(CO)COC1 CUBVDBSVGQEYCB-UHFFFAOYSA-N 0.000 description 1
- AMONDPRIVREWOC-UHFFFAOYSA-N (3-tert-butyloxetan-3-yl)methanol Chemical compound CC(C)(C)C1(CO)COC1 AMONDPRIVREWOC-UHFFFAOYSA-N 0.000 description 1
- RVGLUKRYMXEQAH-UHFFFAOYSA-N 3,3-dimethyloxetane Chemical compound CC1(C)COC1 RVGLUKRYMXEQAH-UHFFFAOYSA-N 0.000 description 1
- BPRVZHZLXYVQOJ-UHFFFAOYSA-N 3-ethyl-3-(2-ethylhexyl)oxetane Chemical compound CCCCC(CC)CC1(CC)COC1 BPRVZHZLXYVQOJ-UHFFFAOYSA-N 0.000 description 1
- JUXZNIDKDPLYBY-UHFFFAOYSA-N 3-ethyl-3-(phenoxymethyl)oxetane Chemical compound C=1C=CC=CC=1OCC1(CC)COC1 JUXZNIDKDPLYBY-UHFFFAOYSA-N 0.000 description 1
- FNYWFRSQRHGKJT-UHFFFAOYSA-N 3-ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane Chemical compound C1OCC1(CC)COCC1(CC)COC1 FNYWFRSQRHGKJT-UHFFFAOYSA-N 0.000 description 1
- SLNCKLVYLZHRKK-UHFFFAOYSA-N 3-ethyl-3-[2-[(3-ethyloxetan-3-yl)methoxy]ethoxymethyl]oxetane Chemical compound C1OCC1(CC)COCCOCC1(CC)COC1 SLNCKLVYLZHRKK-UHFFFAOYSA-N 0.000 description 1
- DBOKHYVIOMXGKT-UHFFFAOYSA-N 3-ethyl-3-[3-[(3-ethyloxetan-3-yl)methoxy]propoxymethyl]oxetane Chemical compound C1OCC1(CC)COCCCOCC1(CC)COC1 DBOKHYVIOMXGKT-UHFFFAOYSA-N 0.000 description 1
- UWFHYGTWXNRUDH-UHFFFAOYSA-N 3-ethyl-3-[4-[(3-ethyloxetan-3-yl)methoxy]butoxymethyl]oxetane Chemical compound C1OCC1(CC)COCCCCOCC1(CC)COC1 UWFHYGTWXNRUDH-UHFFFAOYSA-N 0.000 description 1
- HWRAILPALQOXTB-UHFFFAOYSA-N 3-ethyl-3-[[3-[(3-ethyloxetan-3-yl)methoxy]-2,2-dimethylpropoxy]methyl]oxetane Chemical compound C1OCC1(CC)COCC(C)(C)COCC1(CC)COC1 HWRAILPALQOXTB-UHFFFAOYSA-N 0.000 description 1
- FRQGUZFVAWVQLA-UHFFFAOYSA-N 4-cyclohex-3-en-1-ylcyclohexene Chemical compound C1C=CCCC1C1CC=CCC1 FRQGUZFVAWVQLA-UHFFFAOYSA-N 0.000 description 1
- NIJZFHNDUJXJMR-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethanol Chemical compound C1C(CO)CCC2OC21 NIJZFHNDUJXJMR-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XBKBLLFQEZDLEP-UHFFFAOYSA-N C1(CC=CCC1)COC(=O)C(C(CC)C(=O)OCC1CC=CCC1)(C(=O)OCC1CC=CCC1)C(=O)OCC1CC=CCC1 Chemical compound C1(CC=CCC1)COC(=O)C(C(CC)C(=O)OCC1CC=CCC1)(C(=O)OCC1CC=CCC1)C(=O)OCC1CC=CCC1 XBKBLLFQEZDLEP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- 206010070835 Skin sensitisation Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- YFYPKPBOAHOTCM-UHFFFAOYSA-N [3-(2-methylpropyl)oxetan-3-yl]methanol Chemical compound CC(C)CC1(CO)COC1 YFYPKPBOAHOTCM-UHFFFAOYSA-N 0.000 description 1
- AUNAPVYQLLNFOI-UHFFFAOYSA-L [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O Chemical compound [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O AUNAPVYQLLNFOI-UHFFFAOYSA-L 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
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- 239000003086 colorant Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
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- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- PESYEWKSBIWTAK-UHFFFAOYSA-N cyclopenta-1,3-diene;titanium(2+) Chemical class [Ti+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 PESYEWKSBIWTAK-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- DGVMNQYBHPSIJS-UHFFFAOYSA-N dimagnesium;2,2,6,6-tetraoxido-1,3,5,7-tetraoxa-2,4,6-trisilaspiro[3.3]heptane;hydrate Chemical compound O.[Mg+2].[Mg+2].O1[Si]([O-])([O-])O[Si]21O[Si]([O-])([O-])O2 DGVMNQYBHPSIJS-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [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])* 0.000 description 1
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- 150000002118 epoxides Chemical class 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
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- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 150000005309 metal halides Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
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- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
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- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- SWYHWLFHDVMLHO-UHFFFAOYSA-N oxetan-3-ylmethanol Chemical compound OCC1COC1 SWYHWLFHDVMLHO-UHFFFAOYSA-N 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical group C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 150000002921 oxetanes Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- KTNLYTNKBOKXRW-UHFFFAOYSA-N phenyliodanium Chemical compound [IH+]C1=CC=CC=C1 KTNLYTNKBOKXRW-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
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- 239000004645 polyester resin Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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- 238000007789 sealing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 231100000370 skin sensitisation Toxicity 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Polyethers (AREA)
- Epoxy Resins (AREA)
Description
本発明は、活性エネルギー線照射によりカチオン重合を生じ迅速に硬化可能な組成物に関するものである。当該組成物は、コーティング用、塗料用並びにフレキソおよびグラビア等のインク用等の組成物として有用なものであり、かつ高湿度下においても活性エネルギー線により迅速に硬化可能なものである。 The present invention relates to a composition that can be rapidly cured by generating cationic polymerization by irradiation with active energy rays. The composition is useful as a composition for coating, paint, ink for flexo and gravure, and the like, and can be rapidly cured by active energy rays even under high humidity.
エポキシ化合物の硬化物は、一般に機械的性質、密着性、耐水性、耐食性、耐化学薬品性、耐熱性および電気特性等の点で優れた性能を有することから、接着剤、塗料、積層板、ＩＣ封止材および成形材料等の幅広い分野で用いられている。 A cured product of an epoxy compound generally has excellent performance in terms of mechanical properties, adhesion, water resistance, corrosion resistance, chemical resistance, heat resistance, electrical properties, etc. It is used in a wide range of fields such as IC sealing materials and molding materials.
例えばビスフェノール型エポキシ樹脂およびフェノールノボラック型エポキシ樹脂等に代表されるグリシジルエーテル型芳香族エポキシ樹脂は、硬化剤、場合によっては硬化促進剤を添加し、また必要により、タルク、チタンおよびシリカ等の充填剤を添加して、種々の硬化条件で硬化させて硬化物として使用されている。 For example, glycidyl ether type aromatic epoxy resins represented by bisphenol type epoxy resin and phenol novolac type epoxy resin are added with a curing agent, and in some cases a curing accelerator, and if necessary, talc, titanium, silica and the like are filled. An agent is added and cured under various curing conditions and used as a cured product.
しかしながら、上記のグリシジルエーテル型芳香族エポキシ樹脂からなる硬化物は、芳香核構造を有するために屋外における耐候性に問題がある。また、グリシジルエーテル型芳香族エポキシ樹脂の流動性が低いため、トルエン、キシレン、メチルエチルケトンおよび酢酸エチル等のような溶剤を添加して使用されることが多く、作業性、環境安全性に問題がある。 However, the cured product composed of the above glycidyl ether type aromatic epoxy resin has an aromatic nucleus structure and thus has a problem in outdoor weather resistance. In addition, since the fluidity of the glycidyl ether type aromatic epoxy resin is low, it is often used by adding a solvent such as toluene, xylene, methyl ethyl ketone, ethyl acetate, etc., and there is a problem in workability and environmental safety. .
このような溶剤を使用しなくても粘度の低いエポキシ樹脂としては、シクロヘキセンオキシド骨格を持つものが知られている。この骨格を有するエポキシ化合物はグリシジルエーテル型芳香族エポキシ化合物と同程度の反応性を有することを特徴として、現在さまざまな種類のものが市販されている。例えば分子内にこのような脂環骨格を持つ単官能エポキシ化合物としてモノエポキシ化４−ビニルシクロヘキセン、二官能エポキシ化合物として４−ビニルシクロヘキセンジエポキシドやリモネンジエポキシド等が挙げられる。 As an epoxy resin having a low viscosity without using such a solvent, one having a cyclohexene oxide skeleton is known. Epoxy compounds having this skeleton are characterized by having the same degree of reactivity as glycidyl ether type aromatic epoxy compounds, and various types are now commercially available. Examples of the monofunctional epoxy compound having such an alicyclic skeleton in the molecule include monoepoxidized 4-vinylcyclohexene and examples of the bifunctional epoxy compound include 4-vinylcyclohexene diepoxide and limonene diepoxide.
このような脂環骨格を有する化合物は、その製造工程ではハロゲン化物を使用しないことに起因してハロゲンフリーであり、電気特性に優れている。また脂環骨格を有する化合物を用いた樹脂の特徴である耐熱性および透明性を持たせることができる。この脂環骨格を有するエポキシ化合物またはそれを含む樹脂組成物は、コーティング、接着剤、インキ、シーラントの成分等の用途に用いられている。さらに有用な他の化合物を製造するための中間体としても有用であることが知られている。この脂環骨格を有するエポキシ化合物は、上記用途での使用にあたって十分な性能を有するが若干反応性が低く、硬化物の物性や反応性の低下が起こることがあった。このため、反応性の高い脂環エポキシ化合物の提供が望まれている。しかし、先に挙げたモノエポキシ化４−ビニルシクロヘキセンやリモネンジエポキシドは、室温において揮発性を有するため、作業環境上に問題があった。 Such a compound having an alicyclic skeleton is halogen-free due to the fact that no halide is used in the production process, and has excellent electrical characteristics. Moreover, the heat resistance and transparency which are the characteristics of the resin using the compound which has alicyclic skeleton can be provided. This epoxy compound having an alicyclic skeleton or a resin composition containing the same is used for applications such as coatings, adhesives, inks and sealant components. Furthermore, it is known to be useful as an intermediate for producing other useful compounds. The epoxy compound having an alicyclic skeleton has sufficient performance for use in the above-mentioned applications, but is slightly low in reactivity, and the physical properties and reactivity of the cured product may be lowered. For this reason, provision of a highly reactive alicyclic epoxy compound is desired. However, since the monoepoxidized 4-vinylcyclohexene and limonene diepoxide listed above have volatility at room temperature, there is a problem in the working environment.
分子内に脂環骨格を持つ二官能エポキシ化合物としては、３，４−エポキシシクロヘキシルメチル−３’，４’−エポキシシクロヘキサンカルボキシレート、１，２，８，９−ジエポキシリモネン、ε−カプロラクトンオリゴマーの両端にそれぞれ３，４−エポキシシクロヘキシルメタノールと３，４−エポキシシクロヘキサンカルボン酸とがエステル結合したものやビス（３，４−エポキシシクロヘキシルメチル）アジペートが知られている。また、複数個の脂環式エポキシ基を有するものとしては、エポキシ化ブタンテトラカルボン酸テトラキス−３−シクロヘキセニルメチルエステルおよびそのε−カプロラクトン付加物が知られている。 Examples of the bifunctional epoxy compound having an alicyclic skeleton in the molecule include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 1,2,8,9-diepoxylimonene, and ε-caprolactone oligomer Known are ester-bonded 3,4-epoxycyclohexylmethanol and 3,4-epoxycyclohexanecarboxylic acid at both ends, and bis (3,4-epoxycyclohexylmethyl) adipate. As those having a plurality of alicyclic epoxy groups, epoxidized butanetetracarboxylic acid tetrakis-3-cyclohexenylmethyl ester and its ε-caprolactone adduct are known.
しかし、３，４−エポキシシクロヘキシルメチル−３’，４’−エポキシシクロヘキサンカルボキシレートやビス（３，４−エポキシシクロヘキシルメチル）アジペートおよびそのラクトン付加物、エポキシ化ブタンテトラカルボン酸テトラキス−３−シクロヘキセニルメチルエステルおよびそのε−カプロラクトン付加物等は、分子内にエステル基を持つため加水分解を生じることがある。このため、高温高湿下での使用や強酸が発生する条件等を用いた場合、硬化物の物性低下が起こることがある。 However, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate and its lactone adduct, epoxidized butanetetracarboxylic acid tetrakis-3-cyclohexenyl Methyl esters and their ε-caprolactone adducts and the like have an ester group in the molecule and may cause hydrolysis. For this reason, when the use under the condition of high temperature and high humidity or the generation of strong acid is used, the physical properties of the cured product may be deteriorated.
また、脂環式ジエポキシ化合物として、２つの脂環構造がメチレン基等で連結されている脂環式ジエポキシ化合物が知られている（例えば、特許文献１参照）。 As an alicyclic diepoxy compound, an alicyclic diepoxy compound in which two alicyclic structures are connected by a methylene group or the like is known (for example, see Patent Document 1).
下記式（５）を基本骨格とする化合物の製造例が報告（例えば、特許文献２参照）されている。また、下記式（５）を基本骨格とする化合物の用途が報告（例えば、特許文献３参照）されている。この報告では、式（５）を基本骨格とする化合物と熱カチオン重合開始剤、光カチオン重合開始剤、または酸無水物とを配合した組成物、更に他のエポキシ樹脂を配合した組成物が報告されている。そしてこれらの組成物は、電子部品封止用、電気絶縁油用安定剤、および電気絶縁用注型として使用できると記載されている。 A production example of a compound having the following formula (5) as a basic skeleton has been reported (for example, see Patent Document 2). Moreover, the use of the compound which has following formula (5) as a basic skeleton has been reported (for example, refer patent document 3). In this report, a composition containing a compound having the basic skeleton of formula (5) and a thermal cationic polymerization initiator, a photocationic polymerization initiator, or an acid anhydride, and a composition containing another epoxy resin are reported. Has been. It is described that these compositions can be used as electronic component sealing, electrical insulating oil stabilizers, and electrical insulation castings.
低粘度の組成物として、オキセタン環を有する化合物を用いた活性エネルギー線硬化型インクが開示されている（例えば、特許文献４参照）。オキセタン環を有する化合物は皮膚刺激性や感作性の問題がなく、またアクリルモノマーのラジカル重合の様に酸素による重合阻害を受けることがなく、比較的低出力の光源で硬化させることができるという特徴をもつ。 An active energy ray-curable ink using a compound having an oxetane ring is disclosed as a low-viscosity composition (see, for example, Patent Document 4). A compound having an oxetane ring has no problem of skin irritation and sensitization, and does not suffer from polymerization inhibition by oxygen unlike radical polymerization of acrylic monomers, and can be cured with a relatively low output light source. Has characteristics.
しかし、オキセタン環を有する化合物の硬化速度が雰囲気の湿度により低下してしまうことが報告されている（例えば、非特許文献１）。 However, it has been reported that the curing rate of a compound having an oxetane ring is reduced by the humidity of the atmosphere (for example, Non-Patent Document 1).
本発明は、酸素阻害を受けることなく重合することができ、コーティング用途、塗料用途、フレキソおよびグラビア等のインク用途等に使用することができ、且つ高湿度下においても活性エネルギー線照射により迅速に硬化可能な硬化性組成物を提供することである。 The present invention can be polymerized without being subjected to oxygen inhibition, can be used for coating applications, paint applications, ink applications such as flexo and gravure, etc., and rapidly by irradiation with active energy rays even under high humidity. It is to provide a curable composition that can be cured.
本発明者らは、上記課題を解決すべく鋭意研究を重ねた結果、下記一般式（１）で表される環状脂肪族エポキシ化合物（ａ成分）、下記一般式（３）で表される分子中にシロキサン結合とオキセタニル基とを有する化合物（ｂ成分）、および潜在性を有するカチオン重合開始剤（ｃ成分）を含有する硬化性組成物により目的を達成できることを見出し本発明を完成させた。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained a cycloaliphatic epoxy compound (component a) represented by the following general formula (1) and a molecule represented by the following general formula (3). The present invention has been completed by finding that the object can be achieved by a curable composition containing a compound having a siloxane bond and an oxetanyl group (component b) and a latent cationic polymerization initiator (component c).
式（１）において、Ｒ1〜Ｒ6は水素原子または炭素数１〜６の分岐を有しても良いアルキル基を示す。 In Formula (1), R < 1 > -R < 6 > shows the alkyl group which may have a hydrogen atom or a C1-C6 branch.
式（３）において、Ｘは下記一般式（４）で表わされるものであり、Ｙはメトキシ基および／またはエトキシ基であり、ｎは１〜１０の数であり、ａは０〜２の数であり、ｍは０〜３の数であり、そしてａおよびｍは（５−ａ−ｍ）／（ａ＋ｍ＋１）における値が０〜１を満たすものである。尚、ｎ、ａおよびｍは平均値を表す。 In the formula (3), X is represented by the following general formula (4), Y is a methoxy group and / or ethoxy group, n is a number from 1 to 10, and a is a number from 0 to 2 . Where m is a number from 0 to 3 and a and m are such that the value in (5-am) / (a + m + 1) satisfies 0 to 1. N, a and m represent average values.
式（４）において、Ｒ7は炭素数１〜１２の分岐および／または環状を有しても良いアルキル基を示す。
本発明の一つの態様として、ａ成分とｂ成分との合計を１００重量部としたときにおいて、ａ成分が３０〜９０質量部である上記記載の硬化性組成物である。
本発明の一つの態様として、上記記載の硬化性組成物に活性エネルギー線を照射してなるＳｉ−Ｏ−Ｓｉ結合を含む硬化物である。
In the formula (4), R 7 represents an alkyl group which may have a branched and / or cyclic structure having 1 to 12 carbon atoms.
One embodiment of the present invention is the curable composition as described above, wherein the a component is 30 to 90 parts by mass when the total of the a component and the b component is 100 parts by weight.
One embodiment of the present invention is a cured product containing a Si—O—Si bond formed by irradiating the curable composition described above with active energy rays.
本発明の組成物は、高湿度下においても高い硬化性を有していることから、広範な用途に用いることができる。例えば、フレキソおよびグラビア等のインク用、コーティング用並びに塗料用等の組成物として使用することがてきる。 Since the composition of the present invention has high curability even under high humidity, it can be used for a wide range of applications. For example, it can be used as a composition for inks such as flexo and gravure, coatings, and paints.
以下、本発明について詳細に説明する。
○ａ成分
上記一般式（１）で表される環状脂肪族エポキシ化合物をａ成分と称する。
式（１）のＲ1〜Ｒ6としては、水素原子または炭素数１〜６の分岐を有しても良いアルキル基であり、水素原子またはメチル基が好ましく、より好ましくは水素原子である。なお、Ｒ1〜Ｒ6にメチル基を有する場合、式（１）中のメチル基の個数としては２個以下が好ましく、この場合一つの環に偏らないものが好ましい。
式（１）の製造方法としては、ビス（３−シクロヘキセン）−１−イルのような環状オレフィン化合物を、塩化モリブデン（Ｖ）存在下でＥｔＣ（ＣＨ3）2ＯＯＨのような過酸化物によりエポキシ化する方法または過酢酸のような有機過カルボン酸により合成する方法等どのような方法でも使用することができる。この有機過カルボン酸は、カルボン酸と過酸化水素とから公知の方法で製造したものを使用することができる。
Hereinafter, the present invention will be described in detail.
○ a Component The cycloaliphatic epoxy compound represented by the general formula (1) is referred to as a component.
As R < 1 > -R < 6 > of Formula (1), it is a hydrogen atom or the alkyl group which may have a C1-C6 branch, A hydrogen atom or a methyl group is preferable, More preferably, it is a hydrogen atom. In addition, when it has a methyl group in R < 1 > -R < 6 >, as a number of the methyl group in Formula (1), 2 or less are preferable, and what is not biased to one ring in this case is preferable.
As a production method of the formula (1), a cyclic olefin compound such as bis (3-cyclohexene) -1-yl is formed by using a peroxide such as EtC (CH 3 ) 2 OOH in the presence of molybdenum chloride (V). Any method such as a method of epoxidation or a method of synthesis with an organic percarboxylic acid such as peracetic acid can be used. As this organic percarboxylic acid, one produced by a known method from carboxylic acid and hydrogen peroxide can be used.
○ｂ成分
本発明においてｂ成分は、分子中にシロキサン結合とオキセタニル基とを有する化合物であり、上記式（３）で表される化合物である。このシロキサン結合とは、ケイ素と酸素との結合（Ｓｉ−Ｏ）のことである。
○ b b components in the component present invention is a compound having a siloxane bond and an oxetanyl group in a molecule is a compound represented by the above following formula (3). This siloxane bond is a bond of silicon and oxygen (Si—O).
式（３）で表される化合物は、例えば下記式（７）と下記式（８）との脱アルコール反応により得ることができる。 The compound represented by the formula (3) can be obtained, for example , by a dealcoholization reaction between the following formula (7) and the following formula (8).
式（７）のＲ7は炭素数が１〜１２個の分岐および／または環状を有していても良いアルキル基を示す。 R 7 in formula (7) represents an alkyl group which may have a branched and / or cyclic structure having 1 to 12 carbon atoms.
式（７）で表されるものとしては、３−ヒドロキシメチル−３−メチルオキセタンおよび３−ヒドロキシメチル−３−エチルオキセタンなどが例示できる。 Examples of the compound represented by the formula (7) include 3-hydroxymethyl-3-methyloxetane and 3-hydroxymethyl-3-ethyloxetane.
式（８）としては、テトラメトキシシラン、テトラエトキシシラン等のテトラアルコキシシラン類またはこれらの部分縮合物などが好ましく、特に下記一般式（８）で表わされるものが好ましい。 As the formula (8), tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane or partial condensates thereof are preferable, and those represented by the following general formula (8) are particularly preferable.
式（８）のＹはメトキシ基および／またはエトキシ基を示し、ｎは１〜１０の数を示す。 Y of Formula (8) shows a methoxy group and / or an ethoxy group, and n shows the number of 1-10.
式（８）の数平均分子量は２６０〜１５５０程度のものが好ましい。式（８）において、ｎの値が１１を超えると、溶解性が悪くなるため好ましくない。このことから、式（８）において、ｎの数は１〜８が好ましく、更に好ましくは１〜６であり、特に好ましくは１〜５である。なお、式（８）のｎは、平均の値である。 The number average molecular weight of the formula (8) is preferably about 260 to 1550. In Formula (8), when the value of n exceeds 11, since solubility will worsen, it is unpreferable. From this, in the formula (8), the number of n is preferably 1 to 8, more preferably 1 to 6, and particularly preferably 1 to 5. Note that n in the formula (8) is an average value.
本発明に用いる式（３）で表される化合物は、式（７）と式（８）とを脱アルコール縮合反応させることにより得ることができるものであり、式（７）と式（８）との使用割合は、特に制限されない。なお、式（３）のＹを多く有するものである場合は、組成物を硬化させるときにシラノール基を生成するとともにメタノールまたはエタノールなどの揮発性化合物を生成しやすいため発泡することがある。このことから、式（３）は、式（４）が７０％以上有するものが好ましく、８０％以上有するものがより好ましく、９０％以上有するものが更に好ましく、特に好ましくは、下記式（９）のものである。 The compound represented by Formula (3) used in the present invention can be obtained by subjecting Formula (7) and Formula (8) to a dealcoholization condensation reaction. Formula (7) and Formula (8) The usage ratio is not particularly limited. In addition, when it has many Y of Formula (3), since it is easy to produce | generate volatile compounds, such as methanol or ethanol, while producing | generating a silanol group when hardening a composition, it may foam. From this, the formula (3) preferably has 70% or more of the formula (4), more preferably 80% or more, still more preferably 90% or more, particularly preferably the following formula (9) belongs to.
式（９）において、Ｒ7、Ｒ8、Ｒ9、Ｒ10は炭素数１〜１２の分岐および／または環状を有しても良いアルキル基を示す。ｌは、２〜１１の数を示す。 In the formula (9), R 7 , R 8 , R 9 and R 10 represent an alkyl group which may have a branched and / or cyclic structure having 1 to 12 carbon atoms. l shows the number of 2-11.
式（９）において、Ｒ7、Ｒ8、Ｒ9、Ｒ10は同一でもそれぞれ異なっていてもよく、好ましくは同一のものである。式（９）においてＲ7、Ｒ8、Ｒ9、Ｒ10は炭素数１〜１２のアルキル基が好ましく、より好ましくは炭素数１〜４であり、更に好ましくはメチル基またはエチル基である。
式（９）のｌとしては、２〜９が好ましく、より好ましくは２〜７であり、更に好ましくは２〜６である。
In the formula (9), R 7 , R 8 , R 9 and R 10 may be the same or different, preferably the same. In the formula (9), R 7 , R 8 , R 9 and R 10 are preferably an alkyl group having 1 to 12 carbon atoms, more preferably 1 to 4 carbon atoms, still more preferably a methyl group or an ethyl group.
As l of Formula (9), 2-9 are preferable, More preferably, it is 2-7, More preferably, it is 2-6.
式（３）で表される化合物の製造は、例えば、式（７）と式（８）とを仕込み、加熱して生成するアルコールを留去しながら脱アルコール縮合反応することにより行なわれる。この反応温度は５０〜２５０℃程度であり、好ましくは８０〜２００℃であり、更に好ましくは９０〜１８０℃である。この時の反応時間は１〜１５時間程度である。この反応は、式（７）の重縮合反応を防止するため、および生成物が着色するのを防止するため実質的に無水条件下で行うのが好ましい。 The production of the compound represented by the formula (3) is carried out, for example, by charging the formula (7) and the formula (8) and carrying out a dealcoholization condensation reaction while distilling off the alcohol produced by heating. This reaction temperature is about 50 to 250 ° C, preferably 80 to 200 ° C, and more preferably 90 to 180 ° C. The reaction time at this time is about 1 to 15 hours. This reaction is preferably carried out under substantially anhydrous conditions in order to prevent the polycondensation reaction of formula (7) and to prevent the product from being colored.
上記の脱アルコール縮合反応は無触媒で行うことが好ましいが、反応促進のために従来公知の触媒の内、オキセタン環の開環反応を促進しないものを使用することができる。具体的には、ジブチル錫ジラウレート、オクチル酸錫などが挙げられる。また、上記反応は溶剤中でも、無溶剤でも行うこともできる。溶剤としては、式（７）と式（８）を溶解し、且つこれらに対し反応しない溶剤であれば特に制限はない。 The above dealcoholization condensation reaction is preferably carried out without a catalyst, but among the conventionally known catalysts, those that do not promote the oxetane ring-opening reaction can be used to promote the reaction. Specific examples include dibutyltin dilaurate and tin octylate. The above reaction can be performed in a solvent or without a solvent. The solvent is not particularly limited as long as it dissolves the formulas (7) and (8) and does not react with them.
本発明の硬化性組成物においてａ成分とｂ成分との合計が１００重量部のとき、ａ成分が３０〜９０重量部であり、好ましくは４０〜８０重量部であり、更に好ましくは５０〜７５重量部である。このａ成分が３０重量部未満であると高湿度下での硬化性が減少することがあり好ましくなく、ａ成分が９０重量部超であると、硬化性が低下することがあるため好ましくない。 When the sum of component a and component b is 100 parts by weight in the curable composition of the present invention, component a is 30 to 90 parts by weight, preferably 40 to 80 parts by weight, and more preferably 50 to 75 parts by weight. Parts by weight. If the a component is less than 30 parts by weight, the curability under high humidity may decrease, which is not preferable. If the a component exceeds 90 parts by weight, the curability may decrease, which is not preferable.
○ｃ成分
本発明のｃ成分としては、潜在性を有するカチオン重合開始剤であり、活性エネルギー線の照射により活性化されて酸成分を生成し、組成物中のａ成分やｂ成分等の開環重合性基のカチオン開環重合を誘発するように作用する。
C component The c component of the present invention is a latent cationic polymerization initiator, which is activated by irradiation with an active energy ray to produce an acid component, and opens the a component and b component in the composition. It acts to induce cationic ring-opening polymerization of the ring polymerizable group.
本発明のｃ成分としての光潜在性を有するカチオン重合開始剤は、活性エネルギー線、特に紫外線や可視光を照射されて活性化され開環重合性基の開環を誘発し得る限り任意の光カチオン重合開始剤が用いることができ、光カチオン重合開始剤としては、オニウム塩類および有機金属錯体類等を例示することができる。 The cationic polymerization initiator having photolatency as the component c of the present invention is any light as long as it is activated by irradiation with active energy rays, particularly ultraviolet rays or visible light, and can induce ring opening of the ring-opening polymerizable group. Cationic polymerization initiators can be used, and examples of the photocationic polymerization initiator include onium salts and organometallic complexes.
オニウム塩類としては、例えば、ジアゾニウム塩、スルホニウム塩およびヨードニウム塩が挙げられる。また、有機金属錯体類としては、例えば、鉄−アレン錯体、チタノセン錯体およびアリールシラノール−アルミニウム錯体等が挙げられる。市販品である、例えば、オプトマーＳＰ−１５０｛商品名、旭電化工業（株）製｝、オプトマーＳＰ−１７０｛商品名、旭電化工業（株）製｝、ＵＶＥ−１０１４（商品名、ゼネラルエレクトロニクス社製）およびＣＤ−１０１２（商品名、サートマー社製）等を利用することもできる。 Examples of onium salts include diazonium salts, sulfonium salts, and iodonium salts. Examples of organometallic complexes include iron-allene complexes, titanocene complexes, and arylsilanol-aluminum complexes. Commercially available products such as Optomer SP-150 {trade name, manufactured by Asahi Denka Kogyo Co., Ltd.}, Optomer SP-170 {trade name, manufactured by Asahi Denka Kogyo Co., Ltd.}, UVE-1014 (trade name, general electronics) And CD-1012 (trade name, manufactured by Sartomer) can be used.
上記潜在性カチオン重合開始剤の配合割合は、ａ成分およびｂ成分の合計量１００重量部に対し、０．０１〜５重量部の範囲とすることが好ましく、更に好ましくは０．１〜４重量部であり、特に好ましくは１〜３重量部である。この潜在性カチオン重合開始剤の配合割合が０．０１重量部未満の場合には、活性エネルギー線の作用により活性化しても、開環重合性基の開環反応を十分に進行させることができないことがあり、重合後の耐熱性および吸水率が不十分となる場合が有る。また、５重量部を超えて配合したとしても、重合を進行する作用はそれ以上高まらず、逆に耐熱性および吸水率が低下することがある。 The blending ratio of the latent cationic polymerization initiator is preferably in the range of 0.01 to 5 parts by weight, more preferably 0.1 to 4 parts by weight with respect to 100 parts by weight of the total amount of component a and component b. Part, particularly preferably 1 to 3 parts by weight. When the blending ratio of the latent cationic polymerization initiator is less than 0.01 parts by weight, the ring-opening reaction of the ring-opening polymerizable group cannot sufficiently proceed even when activated by the action of active energy rays. In some cases, heat resistance and water absorption after polymerization may be insufficient. Moreover, even if it mix | blends exceeding 5 weight part, the effect | action which advances superposition | polymerization does not increase any more, and heat resistance and a water absorption rate may fall conversely.
更に本発明は、本発明の硬化性組成物に活性エネルギー線を照射して得られる硬化物中にＳｉ−Ｏ−Ｓｉ結合を含むものである。即ち、本発明はＳｉ−Ｏ−Ｓｉ結合を含む硬化物である。 Furthermore, this invention contains a Si-O-Si bond in the hardened | cured material obtained by irradiating an active energy ray to the curable composition of this invention. That is, the present invention is a cured product containing Si—O—Si bonds.
○ｄ成分
本発明の組成物には、ａ成分、ｂ成分、およびｃ成分以外に必要に応じて他のエポキシ化合物（ｄ成分という）を添加することができる。このｄ成分とは、ａ成分以外のエポキシ化合物のことである。
本発明の組成物に用いるｄ成分としては、ジシクロペンタジエンオキサイド、リモネンジオキサイド、４−ビニルシクロヘキセンジオキサイド、３，４−エポキシシクロヘキシルメチル−３’，４’−エポキシシクロヘキサンカルボキシレート、ジ（３，４−エポキシシクロヘキシル）アジペート、（３，４−エポキシシクロヘキシル）メチルアルコール、（３，４−エポキシ−６−メチルシクロヘキシル）メチル−３，４−エポキシ−６−メチルシクロヘキサンカルボキシレート、エチレン１，２−ジ（３，４−エポキシシクロヘキサンカルボン酸）エステル、（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、フェニルグリシジルエーテル、ビスフェノールＡ型エポキシ樹脂、ハロゲン化ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ｏ−、ｍ−、ｐ−クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、多価アルコールのポリグリシジルエーテル等が例示できる。
O component In addition to the component a, component b, and component c, another epoxy compound (referred to as component d) can be added to the composition of the present invention as necessary. This d component is an epoxy compound other than the a component.
Examples of the component d used in the composition of the present invention include dicyclopentadiene oxide, limonene dioxide, 4-vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, di (3 , 4-epoxycyclohexyl) adipate, (3,4-epoxycyclohexyl) methyl alcohol, (3,4-epoxy-6-methylcyclohexyl) methyl-3,4-epoxy-6-methylcyclohexanecarboxylate, ethylene 1,2 -Di (3,4-epoxycyclohexanecarboxylic acid) ester, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, phenylglycidyl ether, bisphenol A type epoxy resin, halogenated bisphenol A type epoxy resin, Scan phenol F type epoxy resin, o-, m-, p-cresol novolak type epoxy resin, phenol novolak type epoxy resins, polyglycidyl ethers of polyhydric alcohols can be exemplified.
本発明におけるｄ成分の好ましい化合物として、ジシクロペンタジエンオキサイド、リモネンジオキサイド、３，４−エポキシシクロヘキシルメチル−３’，４’−エポキシシクロヘキサンカルボキシレート、ジ（３，４−エポキシシクロヘキシル）アジペート、（３，４−エポキシシクロヘキシル）メチルアルコール、（３，４−エポキシ−６−メチルシクロヘキシル）メチル−３，４−エポキシ−６−メチルシクロヘキサンカルボキシレート、エチレン１，２−ジ（３，４−エポキシシクロヘキサンカルボン酸）エステル等が挙げられる。 Preferred compounds of the d component in the present invention include dicyclopentadiene oxide, limonene dioxide, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, di (3,4-epoxycyclohexyl) adipate, 3,4-epoxycyclohexyl) methyl alcohol, (3,4-epoxy-6-methylcyclohexyl) methyl-3,4-epoxy-6-methylcyclohexanecarboxylate, ethylene 1,2-di (3,4-epoxycyclohexane) Carboxylic acid) esters and the like.
本発明の組成物へのｄ成分の配合割合は、ａ成分およびｂ成分の合計量１００重量部に対し、５０重量部以下であり、好ましくは４０重量部以下であり、更に好ましくは３０重量部以下である。ｄ成分を５０重量部超で配合した場合、配合物の粘度が上昇してしまい、本発明の目的を達成できないことがある。
本発明の組成物における単官能のものの配合割合は、ａ成分およびｂ成分の合計を１００重量部としたとき、またはａ成分、ｂ成分およびｄ成分の合計を１００重量部としたとき、単官能のものは５０重量部以下にすることが好ましく、更に好ましくは４０重量部以下である。単官能のものが５０重量部超の場合は、硬化物の硬度が弱くなることがあるため好ましくない。
The blending ratio of component d in the composition of the present invention is 50 parts by weight or less, preferably 40 parts by weight or less, more preferably 30 parts by weight with respect to 100 parts by weight of the total amount of component a and component b. It is as follows. When the component d is blended in an amount exceeding 50 parts by weight, the viscosity of the blend increases, and the object of the present invention may not be achieved.
The blending ratio of the monofunctional component in the composition of the present invention is such that when the total of component a and component b is 100 parts by weight, or the sum of component a, component b and component d is 100 parts by weight, The amount is preferably 50 parts by weight or less, more preferably 40 parts by weight or less. If the monofunctional compound is more than 50 parts by weight, the hardness of the cured product may be weak, which is not preferable.
○ｅ成分
本発明の組成物には、式（２）以外のオキセタニル基を有する化合物（ｅ成分）を添加することもできる。このｅ成分は、ｄ成分と併用して用いても良い。
ｅ成分として、オキセタニル基を１個有する化合物として３，３−ジメチルオキセタン、３−ヒドロキシメチルオキセタン、３−メチル−３−ヒドロキシメチルオキセタン、３−エチル−３−ヒドロキシメチルオキセタン、３−エチル−３−フェノキシメチルオキセタン、３−ｎ−プロピル−３−ヒドロキシメチルオキセタン、３−イソプロピル−３−ヒドロキシメチルオキセタン、３−ｎ−ブチル−３−ヒドロキシメチルオキセタン、３−イソブチル−３−ヒドロキシメチルオキセタン、３−ｓｅｃ−ブチル−３−ヒドロキシメチルオキセタン、３−ｔｅｒｔ−ブチル−３−ヒドロキシメチルオキセタン、３−エチル−３−（２−エチルヘキシル）オキセタン等があり、オキセタニル基を２個以上有する化合物としてビス（３−エチル−３−オキセタニルメチル）エーテル、１，２−ビス［（３−エチル−３−オキセタニルメトキシ）］エタン、１，３−ビス［（３−エチル−３−オキセタニルメトキシ）］プロパン、１，３−ビス［（３−エチル−３−オキセタニルメトキシ）］−２，２−ジメチル−プロパン、１，４−ビス（３−エチル−３−オキセタニルメトキシ）ブタン、１，６−ビス（３−エチル−３−オキセタニルメトキシ）ヘキサン等が挙げられる。
本発明の組成物へのｅ成分の配合割合は、ａ成分およびｂ成分の合計量１００重量部に対し、５０重量部以下であり、好ましくは４０重量部以下であり、更に好ましくは３０重量部以下である。ｅ成分を５０重量部超で配合した場合、本発明の目的を達成できないことがあり好ましくない。
○ e Component A compound having an oxetanyl group other than the formula (2) (e component) may be added to the composition of the present invention. This e component may be used in combination with the d component.
As the component e, as a compound having one oxetanyl group, 3,3-dimethyloxetane, 3-hydroxymethyloxetane, 3-methyl-3-hydroxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3 -Phenoxymethyloxetane, 3-n-propyl-3-hydroxymethyloxetane, 3-isopropyl-3-hydroxymethyloxetane, 3-n-butyl-3-hydroxymethyloxetane, 3-isobutyl-3-hydroxymethyloxetane, 3 -Sec-butyl-3-hydroxymethyloxetane, 3-tert-butyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyl) oxetane, and the like. As a compound having two or more oxetanyl groups, bis ( 3-ethyl-3 Oxetanylmethyl) ether, 1,2-bis [(3-ethyl-3-oxetanylmethoxy)] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy)] propane, 1,3-bis [( 3-ethyl-3-oxetanylmethoxy)]-2,2-dimethyl-propane, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) ) Hexane and the like.
The blending ratio of the component e to the composition of the present invention is 50 parts by weight or less, preferably 40 parts by weight or less, more preferably 30 parts by weight with respect to 100 parts by weight of the total amount of the components a and b. It is as follows. When the component e is added in an amount exceeding 50 parts by weight, the object of the present invention may not be achieved, which is not preferable.
○その他の任意成分
本発明の組成物には、更に必要に応じて次の成分を添加配合することができる。
（１）粉末状の補強剤や充填剤、例えば酸化アルミニウム、酸化マグネシウム等の金属酸化物、炭酸カルシウム、炭酸マグネシウム等の金属炭酸塩、ケイソウ土粉、塩基性ケイ酸マグネシウム、焼成クレイ、微粉末シリカ、溶融シリカ、結晶シリカ等のケイ素化合物、水酸化アルミニウム等の金属水酸化物、その他、カオリン、マイカ、石英粉末、グラファイト、二硫化モリブデン等、さらに繊維質の補強剤や充填剤、たとえばガラス繊維、セラミック繊維、カーボンファイバー、アルミナ繊維、炭化ケイ素繊維、ボロン繊維、ポリエステル繊維及びポリアミド繊維等である。これらは本発明の組成物１００重量部に対して、１０〜９００重量部配合することができる。
（２）難燃剤、例えばブロム化合物及びトリフェニルホスフェイト等である。これらは本発明の組成物１００重量部に対して、０．１〜２０重量部配合することができる。
（３）さらに、成形品等における樹脂の性質を改善する目的で種々の硬化性モノマー、オリゴマー及び合成樹脂を配合することができる。例えば、モノエポキシ等のエポキシ樹脂用希釈剤、フェノール樹脂、アルキド樹脂、メラミン樹脂、フッ素樹脂、塩化ビニル樹脂、アクリル樹脂、シリコーン樹脂、ポリエステル樹脂等の１種又は２種以上の組み合わせを挙げることができる。これら樹脂類の配合割合は、本発明の組成物の本来の性質を損なわない範囲の量、すなわち本発明の組成物１００重量部に対して、５０重量部以下が好ましい。
Other optional components The composition of the present invention may further contain the following components as necessary.
(1) Powdery reinforcing agents and fillers, for example, metal oxides such as aluminum oxide and magnesium oxide, metal carbonates such as calcium carbonate and magnesium carbonate, diatomaceous earth powder, basic magnesium silicate, calcined clay, fine powder Silicon compounds such as silica, fused silica and crystalline silica, metal hydroxides such as aluminum hydroxide, kaolin, mica, quartz powder, graphite, molybdenum disulfide, etc., and fibrous reinforcing agents and fillers such as glass Examples thereof include fibers, ceramic fibers, carbon fibers, alumina fibers, silicon carbide fibers, boron fibers, polyester fibers, and polyamide fibers. These can be blended in an amount of 10 to 900 parts by weight based on 100 parts by weight of the composition of the present invention.
(2) Flame retardants such as bromine compounds and triphenyl phosphate. These can be blended in an amount of 0.1 to 20 parts by weight with respect to 100 parts by weight of the composition of the present invention.
(3) Furthermore, various curable monomers, oligomers, and synthetic resins can be blended for the purpose of improving the properties of the resin in a molded article or the like. For example, a diluent for epoxy resin such as monoepoxy, phenol resin, alkyd resin, melamine resin, fluororesin, vinyl chloride resin, acrylic resin, silicone resin, polyester resin, etc. it can. The blending ratio of these resins is preferably 50 parts by weight or less with respect to an amount within a range not impairing the original properties of the composition of the present invention, that is, 100 parts by weight of the composition of the present invention.
本発明の組成物及び任意成分の配合手段としては、ミキサーによる混合；加熱溶融混合、ロール、ニーダーによる溶融混練；および適当な有機溶剤を用いての混合等が挙げられる。 Examples of the blending means of the composition of the present invention and optional components include mixing with a mixer; heat-melt mixing, melt kneading with a roll or kneader; and mixing with an appropriate organic solvent.
本発明の組成物は、高湿度下においても活性エネルギー線を照射しても硬化させることができる。この高湿度とは、相対湿度６０％（％ＲＨ）以上の条件であり、更には７０％ＲＨ超の条件である。但し、結露しない条件であり、好ましくは９５％ＲＨ以下であり、更に好ましくは９０％ＲＨ以下である。
即ち、本発明の組成物は７０％ＲＨ超の条件でも低エネルギーの活性エネルギー線を照射して硬化することができるものであり、また本発明の組成物は６０％ＲＨ以上の条件でも低エネルギーの活性エネルギー線を照射して硬化することができるものである。
The composition of the present invention can be cured even when irradiated with active energy rays even under high humidity. This high humidity is a condition where the relative humidity is 60% (% RH) or more, and more than 70% RH. However, it is a condition that does not cause condensation, preferably 95% RH or less, and more preferably 90% RH or less.
That is, the composition of the present invention can be cured by irradiating with a low energy active energy ray even under a condition of more than 70% RH, and the composition of the present invention is low energy even under a condition of 60% RH or more. It can be cured by irradiation with active energy rays.
本発明の組成物は、活性エネルギー線の照射で硬化させることができる。この活性エネルギー線の照射により重合を行う場合に用いることのできる光源としては特に限定されるものではない。この光源としては、波長４００ｎｍ以下に発光分布を有する、例えば、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、ケミカルランプ、ブラックライトランプ、マイクロウェーブ励起水銀灯およびメタルハライドランプ等を用いることができる。組成物への照射強度は、目的とする製品毎に制御されるものであって特に限定されるものではない。例えば、ｃ成分の活性化に有効な光波長領域（光重合開始剤によって異なるが、通常３００〜４２０ｎｍの光が用いられる）の光照射強度が０．１〜１００ｍＷ／ｃｍ2であることが好ましい。組成物への照射強度が０．１ｍＷ／ｃｍ2未満であると、反応時間が長くなり過ぎ、１００ｍＷ／ｃｍ2を超えると、ランプから輻射される熱および組成物の重合時の発熱により、得られる硬化物の凝集力の低下や黄変あるいは支持体の劣化が生じる恐れがある。 The composition of the present invention can be cured by irradiation with active energy rays. There is no particular limitation on the light source that can be used when polymerization is carried out by irradiation with this active energy ray. As this light source, for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a black light lamp, a microwave excitation mercury lamp, a metal halide lamp, or the like having a light emission distribution at a wavelength of 400 nm or less can be used. . The irradiation intensity to the composition is controlled for each target product and is not particularly limited. For example, it is preferable that the light irradiation intensity in the light wavelength region effective for the activation of the c component (which varies depending on the photopolymerization initiator, but usually 300 to 420 nm is used) is 0.1 to 100 mW / cm 2. . When the irradiation intensity to the composition is less than 0.1 mW / cm 2 , the reaction time becomes too long, and when it exceeds 100 mW / cm 2 , it is obtained due to heat radiated from the lamp and heat generated during polymerization of the composition. There is a risk that the cohesive strength of the cured product may be reduced, yellowing or deterioration of the support may occur.
本発明の組成物への活性エネルギー線の照射時間は、目的とする製品毎に制御されるものであって特に限定されるものではない。例えば、前記光波長領域での光照射強度と光照射時間の積として表される積算光量が３〜５，０００ｍＪ／ｃｍ2となるように設定されることが好ましく、更に好ましくは５〜５００ｍＪ／ｃｍ2であり、特に好ましくは１０〜２４０ｍＪ／ｃｍ2である。組成物への積算光量が３ｍＪ／ｃｍ2未満であると、ｃ成分よりの活性種の発生が十分でなく、得られる硬化物の特性の低下が生じるおそれがあり、５，０００ｍＪ／ｃｍ2を超えると、照射時間が非常に長時間となり、生産性向上のためには不利なものとなる。また、活性エネルギー線照射後０．１〜数分後には、ほとんどの組成物はカチオン重合により指触乾燥するが、カチオン重合反応を促進するために加熱を併用することも場合によっては好ましい。 The irradiation time of the active energy ray to the composition of the present invention is controlled for each target product and is not particularly limited. For example, it is preferable that the integrated light amount expressed as the product of the light irradiation intensity and the light irradiation time in the light wavelength region is set to 3 to 5,000 mJ / cm 2 , more preferably 5 to 500 mJ / cm 2 , particularly preferably 10 to 240 mJ / cm 2 . When the integration quantity of the composition is less than 3 mJ / cm 2, the active species generation than c component is not sufficient, there is a fear that reduction of the characteristic of the cured product obtained results, the 5,000 mJ / cm 2 If exceeded, the irradiation time becomes very long, which is disadvantageous for improving productivity. In addition, most of the composition is dry to the touch by cationic polymerization after 0.1 to several minutes after irradiation with active energy rays, but it is also preferable in some cases to use heating in combination to promote the cationic polymerization reaction.
本発明の組成物には、着色剤、顔料、染料等を含有させることができる。例えば二酸化チタン、鉄黒、モリブデン赤、紺青、群青、カドミウム黄、カドミウム赤等を本発明の組成物に配合してインクジェット、フレキソ、あるいはグラビア等のインクとして用いることもできる。 The composition of the present invention may contain a colorant, a pigment, a dye and the like. For example, titanium dioxide, iron black, molybdenum red, bitumen, ultramarine blue, cadmium yellow, cadmium red, and the like can be blended in the composition of the present invention and used as inks for inkjet, flexo, gravure and the like.
○実施形態
式（１）で表される環状脂肪族エポキシ化合物（ａ成分）、式（２）で表される構造単位とＳｉ−Ｏ−Ｓｉ結合とを含有する化合物および／または式（３）で表される化合物（ｂ成分）、潜在性を有するカチオン重合開始剤（ｃ成分）、および必要に応じて添加する他のエポキシ化合物（ｄ成分）および／またはｅ成分を含有する硬化性組成物である。
Embodiments Cycloaliphatic epoxy compound represented by formula (1) (component a), compound containing structural unit represented by formula (2) and Si—O—Si bond and / or formula (3) A curable composition containing a compound represented by the formula (component b), a latent cationic polymerization initiator (component c), and other epoxy compound (component d) and / or component e added as necessary It is.
＜実施例＞
以下に、実施例及び比較例を挙げて本発明をさらに詳しく説明するが、本発明はこれに限定されるものではない。なお、各例中の部は重量部を意味する。
<Example>
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, the part in each example means a weight part.
＜合成例１＞
下記式（１０）により表されるジシクロヘキシル−３，３’−ジエポキシド（ＤＣＨＤＥ）は、公知の方法（例えば、V. P. Yur've, G. A. Gailyunas, G. A. Tolstikov, F. G. Valyamova, Neftekhimiya, 12(3), 353-7, (1972)）に従い、この前駆体であるビシクロヘキシル−３，３’−ジエンをエポキシ化して合成した。
<Synthesis Example 1>
Dicyclohexyl-3,3′-diepoxide (DCHDE) represented by the following formula (10) can be obtained by a known method (for example, VP Yur've, GA Gailyunas, GA Tolstikov, FG Valyamova, Neftekhimiya, 12 (3), 353 -7, (1972)), this precursor bicyclohexyl-3,3′-diene was synthesized by epoxidation.
＜実施例１〜２及び比較例１〜８＞
合成例１で合成したＤＣＨＤＥ、３−エチル−３−（２−エチルヘキシロキシメチル）オキセタン（ＥＨＯＸ、東亞合成製）、オキセタニルシリケート（ＯＸ−ＳＣ、東亞合成製）、３，４−エポキシシクロヘキシルメチル−３’，４’−エポキシシクロヘキサンカルボキシレート（ＵＶＲ−６１１０）、３−エチル−３−ヒドロキシメチルオキセタン（ＯＸＡ）、および光開始剤としてヨードニウム塩系光潜在カチオン開始剤であるビス（ドデシルフェニルヨードニウム）ヘキサフルオロアンチモン塩（ＵＶ−９３８０Ｃ、ＧＥ東芝シリコーン製）を表１および表２に示した配合比で混合し、均一になるように室温で充分攪拌混合して硬化性組成物を得た。
実施例および比較例に示した硬化性組成物の粘度、硬化性、膜強度は下記の方法により測定し、表１および表２にあわせて示した。
粘度測定：配合後の組成物の粘度を２５℃においてＥ型粘度計にて測定した。
硬化性：組成物を＃３のバーコーターによりボンデライト鋼板上に約５μｍの厚さで塗布し、表１および表２に記載の湿度下に５分間放置した後、紫外線照射（フュージョンＵＶシステム社製：Ｆ−４５０、Ｈ−バルブ）を行い、指触により硬化を確認した。なお、硬化に必要な最小のエネルギー（ｍＪ／ｃｍ2）を示した。
膜強度：相対湿度５０％で作製した硬化膜の強度をＪＩＳ Ｋ−５４００の試験法に従って手かき法で行った。
<Examples 1-2 and Comparative Examples 1-8>
DCHDE synthesized in Synthesis Example 1, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane (EHOX, manufactured by Toagosei), O xenon Tani Le silicate (OX-SC, manufactured by Toagosei), 3,4-epoxy Cyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (UVR-6110), 3-ethyl-3-hydroxymethyloxetane (OXA), and bis (dodecyl), an iodonium salt-based photolatent cationic initiator as a photoinitiator (Phenyliodonium) hexafluoroantimony salt (UV-9380C, manufactured by GE Toshiba Silicones) was mixed at the blending ratio shown in Tables 1 and 2, and sufficiently stirred at room temperature to obtain a curable composition. It was.
The viscosity, curability, and film strength of the curable compositions shown in Examples and Comparative Examples were measured by the following methods, and are shown in Table 1 and Table 2.
Viscosity measurement: The viscosity of the composition after blending was measured with an E-type viscometer at 25 ° C.
Curability: The composition was applied on a bonderite steel plate with a # 3 bar coater to a thickness of about 5 μm, and allowed to stand for 5 minutes under the humidity described in Tables 1 and 2, and then irradiated with ultraviolet rays (manufactured by Fusion UV System Co., Ltd.). : F-450, H-bulb), and curing was confirmed by finger touch. In addition, the minimum energy (mJ / cm < 2 >) required for hardening was shown.
Film strength: The strength of a cured film produced at a relative humidity of 50% was measured by a hand-drawn method according to the test method of JIS K-5400.
表１及び２に示したように、実施例１〜２の組成物から作製した塗膜は硬く、その硬化に必要なエネルギーは小さいことが分かる。 As shown in Tables 1 and 2 , it can be seen that the coating films prepared from the compositions of Examples 1 and 2 are hard and the energy required for the curing is small.
本発明の組成物は、高湿度下においても高い硬化性を有しているため、広範な用途に応用展開が可能である。例えば、フレキソおよびグラビア等のインク用、コーティング用並びに塗料用等の組成物として有用であり、かつ高湿度下においても活性エネルギー線により迅速に硬化可能なものである。 Since the composition of the present invention has high curability even under high humidity, it can be applied to a wide range of applications. For example, it is useful as a composition for inks such as flexo and gravure, coating, and paint, and can be rapidly cured by active energy rays even under high humidity.
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| JP2005138389A (en) * | 2003-11-06 | 2005-06-02 | Sumitomo Bakelite Co Ltd | Transparent laminate and plastic substrate for display element using it |
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