JP4280147B2 - Radiation curable resin composition - Google Patents
Radiation curable resin composition Download PDFInfo
- Publication number
- JP4280147B2 JP4280147B2 JP2003365506A JP2003365506A JP4280147B2 JP 4280147 B2 JP4280147 B2 JP 4280147B2 JP 2003365506 A JP2003365506 A JP 2003365506A JP 2003365506 A JP2003365506 A JP 2003365506A JP 4280147 B2 JP4280147 B2 JP 4280147B2
- Authority
- JP
- Japan
- Prior art keywords
- meth
- acrylate
- curable resin
- resin composition
- radiation curable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 230000005855 radiation Effects 0.000 title claims description 37
- 239000011342 resin composition Substances 0.000 title claims description 33
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 101
- -1 phosphite triester Chemical class 0.000 claims description 43
- 150000001875 compounds Chemical class 0.000 claims description 32
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 5
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 150000003951 lactams Chemical class 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 24
- 239000000047 product Substances 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000003860 storage Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 150000002009 diols Chemical class 0.000 description 10
- 229920005862 polyol Polymers 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000005056 polyisocyanate Substances 0.000 description 9
- 229920001228 polyisocyanate Polymers 0.000 description 9
- 150000003077 polyols Chemical class 0.000 description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 8
- 239000004721 Polyphenylene oxide Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229920000570 polyether Polymers 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 150000001923 cyclic compounds Chemical class 0.000 description 6
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 229920001451 polypropylene glycol Polymers 0.000 description 6
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 5
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- 230000007774 longterm Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- BEIOEBMXPVYLRY-UHFFFAOYSA-N [4-[4-bis(2,4-ditert-butylphenoxy)phosphanylphenyl]phenyl]-bis(2,4-ditert-butylphenoxy)phosphane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(C=1C=CC(=CC=1)C=1C=CC(=CC=1)P(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C BEIOEBMXPVYLRY-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 125000000217 alkyl group Chemical group 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
- 239000011521 glass Substances 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 4
- 125000004437 phosphorous atom Chemical group 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VFBJXXJYHWLXRM-UHFFFAOYSA-N 2-[2-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]ethylsulfanyl]ethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCSCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 VFBJXXJYHWLXRM-UHFFFAOYSA-N 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- 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 3
- 230000000694 effects Effects 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000013307 optical fiber Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 238000012719 thermal polymerization Methods 0.000 description 3
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-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
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 2
- MSXXDBCLAKQJQT-UHFFFAOYSA-N 2-tert-butyl-6-methyl-4-[3-(2,4,8,10-tetratert-butylbenzo[d][1,3,2]benzodioxaphosphepin-6-yl)oxypropyl]phenol Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCCOP2OC3=C(C=C(C=C3C=3C=C(C=C(C=3O2)C(C)(C)C)C(C)(C)C)C(C)(C)C)C(C)(C)C)=C1 MSXXDBCLAKQJQT-UHFFFAOYSA-N 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- LFOXEOLGJPJZAA-UHFFFAOYSA-N [(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphoryl]-(2,6-dimethoxyphenyl)methanone Chemical compound COC1=CC=CC(OC)=C1C(=O)P(=O)(CC(C)CC(C)(C)C)C(=O)C1=C(OC)C=CC=C1OC LFOXEOLGJPJZAA-UHFFFAOYSA-N 0.000 description 2
- CGRTZESQZZGAAU-UHFFFAOYSA-N [2-[3-[1-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]-2-methylpropan-2-yl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropyl] 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCC(C)(C)C2OCC3(CO2)COC(OC3)C(C)(C)COC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 CGRTZESQZZGAAU-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- 150000008301 phosphite esters Chemical class 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 2
- AJEQPWZZVILXCR-UHFFFAOYSA-N (2,5-ditert-butyl-4-hydroxyphenyl) diethyl phosphite Chemical compound CCOP(OCC)OC1=CC(C(C)(C)C)=C(O)C=C1C(C)(C)C AJEQPWZZVILXCR-UHFFFAOYSA-N 0.000 description 1
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 1
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 1
- UYVWNPAMKCDKRB-UHFFFAOYSA-N 1,2,4,5-tetraoxane Chemical compound C1OOCOO1 UYVWNPAMKCDKRB-UHFFFAOYSA-N 0.000 description 1
- GJZFGDYLJLCGHT-UHFFFAOYSA-N 1,2-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(CC)C(CC)=CC=C3SC2=C1 GJZFGDYLJLCGHT-UHFFFAOYSA-N 0.000 description 1
- QWQFVUQPHUKAMY-UHFFFAOYSA-N 1,2-diphenyl-2-propoxyethanone Chemical compound C=1C=CC=CC=1C(OCCC)C(=O)C1=CC=CC=C1 QWQFVUQPHUKAMY-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- LAYAKLSFVAPMEL-UHFFFAOYSA-N 1-ethenoxydodecane Chemical compound CCCCCCCCCCCCOC=C LAYAKLSFVAPMEL-UHFFFAOYSA-N 0.000 description 1
- UKDKWYQGLUUPBF-UHFFFAOYSA-N 1-ethenoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOC=C UKDKWYQGLUUPBF-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- SDXHBDVTZNMBEW-UHFFFAOYSA-N 1-ethoxy-2-(2-hydroxyethoxy)ethanol Chemical compound CCOC(O)COCCO SDXHBDVTZNMBEW-UHFFFAOYSA-N 0.000 description 1
- CSCSROFYRUZJJH-UHFFFAOYSA-N 1-methoxyethane-1,2-diol Chemical compound COC(O)CO CSCSROFYRUZJJH-UHFFFAOYSA-N 0.000 description 1
- YHDVNSYMKOIPAK-UHFFFAOYSA-N 2,2,3-trimethyl-1,4-diazabicyclo[2.2.2]octane Chemical compound CC1C(N2CCN1CC2)(C)C YHDVNSYMKOIPAK-UHFFFAOYSA-N 0.000 description 1
- GELKGHVAFRCJNA-UHFFFAOYSA-N 2,2-Dimethyloxirane Chemical compound CC1(C)CO1 GELKGHVAFRCJNA-UHFFFAOYSA-N 0.000 description 1
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- ASUQXIDYMVXFKU-UHFFFAOYSA-N 2,6-dibromo-9,9-dimethylfluorene Chemical compound C1=C(Br)C=C2C(C)(C)C3=CC=C(Br)C=C3C2=C1 ASUQXIDYMVXFKU-UHFFFAOYSA-N 0.000 description 1
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 1
- MQFDMZNZEHTLND-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxy]benzoic acid Chemical compound CC(C)(C)OC1=CC=CC=C1C(O)=O MQFDMZNZEHTLND-UHFFFAOYSA-N 0.000 description 1
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- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- KQBSGRWMSNFIPG-UHFFFAOYSA-N trioxane Chemical compound C1COOOC1 KQBSGRWMSNFIPG-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl 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])[H] 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polymerisation Methods In General (AREA)
Description
本発明は、保存安定性が良く、高い密着力を有し、放射線硬化型接着剤や光ファイバ被覆材として有用な放射線硬化性樹脂組成物に関する。 The present invention relates to a radiation curable resin composition having good storage stability, high adhesion, and useful as a radiation curable adhesive or an optical fiber coating material.
紫外線に代表される放射線により硬化する放射線硬化性樹脂組成物は、硬化が速く、各種形状に対応できることから、塗料、インキ、接着剤、コーティング、光ファイバ被覆材等広範囲の用途に利用されている。各種電子部品や電気製品の接着においては、より高い密着力が求められており、放射線硬化性樹脂組成物には密着力向上の目的でシランカップリング剤が配合されている（特許文献１〜４）。
しかしながら、シランカップリング剤は、基本的性能として水酸基と反応することから、これを配合した放射線硬化性樹脂組成物は保存安定性が悪いという欠点を有している。従って、長期保存後も高い密着力を保持する放射線硬化性樹脂組成物が望まれていた。 However, since the silane coupling agent reacts with a hydroxyl group as a basic performance, the radiation curable resin composition containing the silane coupling agent has a drawback that the storage stability is poor. Accordingly, there has been a demand for a radiation curable resin composition that retains high adhesion even after long-term storage.
そこで本発明者は、シランカップリング剤を含有する放射線硬化性樹脂組成物の保存安定性について検討してきたところ、エチレン性不飽和結合を有する重合性化合物、光重合開始剤及びシランカップリング剤を含有する放射線硬化性樹脂組成物に、特定の亜リン酸エステルを配合することにより、長期保存後も密着力が極めて高い硬化体を与える放射線硬化性樹脂組成物が得られることを見出した。
すなわち、本発明は、次の成分（Ａ）、（Ｂ）、（Ｃ）及び（Ｄ）：
（Ａ）エチレン性不飽和結合を有する重合性化合物、
（Ｂ）光重合開始剤、
（Ｃ）シランカップリング剤、
（Ｄ）（Ａ）成分と反応し得る官能基を有しない、成分（Ｂ）以外の亜リン酸エステル
を含有することを特徴とする放射線硬化性樹脂組成物を提供するものである。
Therefore, the present inventor has examined the storage stability of a radiation curable resin composition containing a silane coupling agent, and has obtained a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and a silane coupling agent. It has been found that a radiation curable resin composition that gives a cured product with extremely high adhesion even after long-term storage can be obtained by blending a specific phosphite with the radiation curable resin composition contained.
That is, the present invention includes the following components (A), (B), (C) and (D):
(A) a polymerizable compound having an ethylenically unsaturated bond,
(B) a photopolymerization initiator,
(C) a silane coupling agent,
(D) A radiation curable resin composition characterized by containing a phosphite other than the component (B) that does not have a functional group capable of reacting with the component (A).
本発明の放射線硬化性樹脂組成物により得られる硬化体は、基材に対する密着力が高い。また、保存安定性が良好であり、長期保存後も密着力の高い硬化体が得られる。従って、本発明組成物は、接着剤、光ファイバ被覆材、光学レンズ材、シート、フィルム材、各種コーティング剤、塗料等として特に有用である。 The cured product obtained from the radiation curable resin composition of the present invention has high adhesion to the substrate. Moreover, the storage stability is good, and a cured product having high adhesion even after long-term storage can be obtained. Accordingly, the composition of the present invention is particularly useful as an adhesive, an optical fiber coating material, an optical lens material, a sheet, a film material, various coating agents, a paint, and the like.
本発明放射線硬化性樹脂組成物における成分（Ａ）エチレン性不飽和結合を有する重合性化合物は、放射線照射によりウレタン（メタ）アクリレート等の成分と共重合可能な成分である。（Ａ）成分としては、例えば（Ａ１）重合性単官能化合物、又は（Ａ２）重合性多官能化合物が挙げられる。このような、（Ａ１）重合性単官能性化合物としては、Ｎ−ビニルピロリドン、Ｎ−ビニルカプロラクタム等のビニル基含有ラクタム、イソボルニル（メタ）アクリレート、ボルニル（メタ）アクリレート、トリシクロデカニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート等の脂環式構造含有（メタ）アクリレート、ベンジル（メタ）アクリレート、４−ブチルシクロヘキシル（メタ）アクリレート、アクリロイルモルホリン、ビニルイミダゾール、ビニルピリジン等が挙げられる。さらに、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ブチル（メタ）アクリレート、アミル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、イソアミル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ドデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、エトキシジエチレングリコール（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、メトキシエチレングリコール（メタ）アクリレート、エトキシエチル（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、メトキシポリプロピレングリコール（メタ）アクリレート、ジアセトン（メタ）アクリルアミド、イソブトキシメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、ｔ−オクチル（メタ）アクリルアミド、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、７−アミノ−３，７−ジメチルオクチル（メタ）アクリレート、Ｎ，Ｎ−ジエチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド、ヒドロキシブチルビニルエーテル、ラウリルビニルエーテル、セチルビニルエーテル、２−エチルヘキシルビニルエーテル、２−ヒドロキシー３−フェノキシプロピルアクリレート及び下記一般式で表される化合物等が挙げられる。 The component (A) polymerizable compound having an ethylenically unsaturated bond in the radiation curable resin composition of the present invention is a component copolymerizable with a component such as urethane (meth) acrylate by radiation irradiation. Examples of the component (A) include (A1) a polymerizable monofunctional compound or (A2) a polymerizable polyfunctional compound. Such (A1) polymerizable monofunctional compounds include vinyl group-containing lactams such as N-vinylpyrrolidone and N-vinylcaprolactam, isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meta ) And alicyclic structure-containing (meth) acrylates such as dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloylmorpholine, vinylimidazole, vinylpyridine and the like. . Furthermore, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) ) Acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) ) Acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodec (Meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate , Ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethyl (meth) Acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate , Diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7- Amino-3,7-dimethyloctyl (meth) acrylate, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, Examples thereof include 2-hydroxy-3-phenoxypropyl acrylate and compounds represented by the following general formula.
ＣＨ2＝Ｃ（Ｒ1）−ＣＯＯ（Ｒ2Ｏ）p−Ｃ6Ｈ4−Ｒ3 CH 2 = C (R 1) -COO (R 2 O) p -C 6 H 4 -R 3
（式中、Ｒ1は水素原子又はメチル基を示し、Ｒ2は炭素数２〜６、好ましくは２〜４のアルキレン基を示し、Ｒ3は水素原子又は炭素数１〜１２、好ましくは１〜９のアルキル基を示し、ｐは０〜１２、好ましくは１〜８の自然数を示す。） Wherein R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, and R 3 represents a hydrogen atom or 1 to 12 carbon atoms, preferably 1 -9 represents an alkyl group, and p represents a natural number of 0 to 12, preferably 1 to 8.)
これら（Ａ１）重合性単官能性化合物のうちＮ−ビニルピロリドン、Ｎ−ビニルカプロラクタム等のビニル基含有ラクタム、炭素数１０以上の脂肪族炭化水素基を有する単官能性（メタ）アクリレートが好ましい。ここで炭素数１０以上の脂肪族基としては、直鎖、分岐鎖及び脂環式のいずれも含まれ、炭素数は１０〜２４が好ましい。これらのうちイソボルニル（メタ）アクリレート、イソデシル（メタ）アクリレート、ラウリル（メタ）アクリレートがさらに好ましく、イソボルニル（メタ）アクリレート及び／又はイソデシル（メタ）アクリレートが特に好ましい。これら（Ｃ１）重合性単官能性化合物の市販品としてはＩＢＸＡ（大阪有機化学工業（株）製）、アロニックスＭ−１１０、Ｍ−１１１、Ｍ−１１３、Ｍ１１４、Ｍ−１１７、ＴＯ−１２１０（以上、東亞合成（株）製）、エポキシエステルＭ−６００Ａ（共栄社（株）製）を使用することができる。 Of these (A1) polymerizable monofunctional compounds, vinyl group-containing lactams such as N-vinylpyrrolidone and N-vinylcaprolactam, and monofunctional (meth) acrylates having an aliphatic hydrocarbon group having 10 or more carbon atoms are preferred. Here, as an aliphatic group having 10 or more carbon atoms, any of straight chain, branched chain and alicyclic is included, and the number of carbon atoms is preferably 10 to 24. Of these, isobornyl (meth) acrylate, isodecyl (meth) acrylate, and lauryl (meth) acrylate are more preferable, and isobornyl (meth) acrylate and / or isodecyl (meth) acrylate are particularly preferable. Commercially available products of these (C1) polymerizable monofunctional compounds include IBXA (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Aronix M-110, M-111, M-113, M114, M-117, TO-1210 ( As mentioned above, Toagosei Co., Ltd.) and epoxy ester M-600A (manufactured by Kyoeisha Co., Ltd.) can be used.
また（Ａ２）重合性多官能性化合物としては、特に制限はないが、好ましい例としてはポリエチレングリコールジアクリレート、トリシクロデカンジイルジメチレンジ（メタ）アクリレート、エチレンオキサイドを付加させたビスフェノールＡのジ（メタ）アクリレート、トリス（２−ヒドロキシエチル）イアオシアヌレートトリ（メタ）アクリレート、ヘキサンジオールジアクリレート（ＨＤＤＡ）等が挙げられる。これら（Ｃ２）重合性多官能性化合物の市販品として例えば、ライトアクリレート９ＥＧ−Ａ、及び、ライトアクリレート４ＥＧ−Ａ（共栄社化学（株）製）、ユピマーＵＶ、ＳＡ１００２（以上、三菱化学（株）製）、アロニックスＭ−２１５、Ｍ−３１５、Ｍ−３２５（以上東亞合成（株）製）が挙げられる。 The polymerizable polyfunctional compound (A2) is not particularly limited, but preferred examples include polyethylene glycol diacrylate, tricyclodecanediyldimethylene di (meth) acrylate, and bisphenol A di (A) added with ethylene oxide. And (meth) acrylate, tris (2-hydroxyethyl) iaocyanurate tri (meth) acrylate, hexanediol diacrylate (HDDA), and the like. As commercial products of these (C2) polymerizable polyfunctional compounds, for example, Light Acrylate 9EG-A and Light Acrylate 4EG-A (manufactured by Kyoeisha Chemical Co., Ltd.), Iupimer UV, SA1002 (above, Mitsubishi Chemical Corporation) Manufactured by), Aronix M-215, M-315, M-325 (manufactured by Toagosei Co., Ltd.).
これらの（Ａ１）重合性単官能化合物と（Ａ２）重合性多官能化合物を併用して用いることもできる。 These (A1) polymerizable monofunctional compound and (A2) polymerizable polyfunctional compound may be used in combination.
これらの（Ａ）成分は、本発明の放射線硬化性樹脂組成物中に１０〜９９重量％含有することが好ましく、２０〜８０重量％含有することがさらに好ましく、３０〜５０重量％含有することが特に好ましい。含有量が少なすぎると組成物の粘度が高くなり、組成物の取り扱い作業性が低下する。一方、含有量が多すぎると、低粘度により塗布形状の変化が起き、塗布が安定しない。 These components (A) are preferably contained in the radiation curable resin composition of the present invention in an amount of 10 to 99% by weight, more preferably 20 to 80% by weight, and more preferably 30 to 50% by weight. Is particularly preferred. When there is too little content, the viscosity of a composition will become high and the handling workability | operativity of a composition will fall. On the other hand, if the content is too large, the coating shape changes due to low viscosity, and the coating is not stable.
本発明放射線硬化性樹脂組成物には、（Ｂ）光重合開始剤が配合される。（Ｂ）光重合開始剤としては、例えば１−ヒドロキシシクロヘキシルフェニルケトン、２，２−ジメトキシ−２−フェニルアセトフェノン、キサントン、フルオレノン、ベンズアルデヒド、フルオレン、アントラキノン、トリフェニルアミン、カルバゾール、３−メチルアセトフェノン、４−クロロベンゾフェノン、４，４′−ジメトキシベンゾフェノン、４，４′−ジアミノベンゾフェノン、ミヒラーケトン、ベンゾインプロピルエーテル、ベンゾインエチルエーテル、ベンジルジメチルケタール、１−（４−イソプロピルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、チオキサントン、ジエチルチオキサントン、２−イソプロピルチオキサントン、２−クロロチオキサントン、２−メチル−１−〔４−（メチルチオ）フェニル〕−２−モルホリノ−プロパン−１−オン、２，４，６−トリメチルベンゾイルジフェニルホスフィンオキサイド、ビス−（２，６−ジメトキシベンゾイル）−２，４，４−トリメチルペンチルホスフィンオキサイド等が挙げられる。その市販品としては、イルガキュア１８４、３６９、６５１、５００、９０７、８１９、ＣＧＩ１７００、ＣＧＩ１７５０、ＣＧＩ１８５０、ＣＧＩ１８７０、ＣＧ２４６１、ダロキュア１１１６、１１７３（以上、チバ・スペシャルティ・ケミカルズ社製）；ＬＵＣＩＲＩＮ ＴＰＯ（ＢＡＳＦ社製）；ユベクリルＰ３６（ＵＣＢ社製）等が挙げられる。 (B) A photoinitiator is mix | blended with this radiation-curable resin composition. (B) Examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2- Methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2- Lorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like. The commercially available products include Irgacure 184, 369, 651, 500, 907, 819, CGI 1700, CGI 1750, CGI 1850, CGI 1870, CG 2461, Darocur 1116, 1173 (above, manufactured by Ciba Specialty Chemicals); LUCIRIN TPO (BASF) Manufactured by Ubekrill P36 (manufactured by UCB).
これらの（Ｂ）光重合開始剤のうち、アシルホスフィンオキサイド系光重合開始剤が着色防止の点で特に好ましい。アシルホスフィンオキサイド系光重合開始剤としては、２，４，６−トリメチルベンゾイルジフェニルホスフィンオキサイド、ビス−（２，６−ジメトキシベンゾイル）−２，４，４−トリメチルペンチルホスフィンオキサイド等が挙げられる。市販品としては、イルガキュア ８１９（チバ・スペシャルティ・ケミカルズ社製）、ＬＵＣＩＲＩＮ ＴＰＯ（ＢＡＳＦ社製）が挙げられる。 Of these (B) photopolymerization initiators, acylphosphine oxide photopolymerization initiators are particularly preferred from the standpoint of preventing coloring. Examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, and the like. Commercially available products include Irgacure 819 (manufactured by Ciba Specialty Chemicals) and LUCIRIN TPO (manufactured by BASF).
（Ｂ）光重合開始剤は、本発明の放射線硬化性樹脂組成物中に０．１〜１０重量％、さらに０．５〜５重量％、特に１〜３重量％含有するのが好ましい。 (B) The photopolymerization initiator is preferably contained in the radiation curable resin composition of the present invention in an amount of 0.1 to 10% by weight, more preferably 0.5 to 5% by weight, and particularly preferably 1 to 3% by weight.
本発明放射線硬化性樹脂組成物には、（Ｂ）光重合開始剤に加えて、熱重合開始剤、光増感剤を含有させることができる。熱重合開始剤としては、過酸化物、アゾ化合物等が挙げられ、具体的には、例えばベンゾイルパーオキサイド、ｔ−ブチル−オキシベンゾエート、アゾビスイソブチロニトリル等が挙げられる。また、光増感剤としては、例えばトリエチルアミン、ジエチルアミン、Ｎ−メチルジエタノールアミン、エタノールアミン、４−ジメチルアミノ安息香酸、４−ジメチルアミノ安息香酸メチル、４−ジメチルアミノ安息香酸エチル、４−ジメチルアミノ安息香酸イソアミル等が挙げられる。その市販品としては、ユベクリルＰ１０２、１０３、１０４、１０５（以上、ＵＣＢ社製）等が挙げられる。 The radiation curable resin composition of the present invention may contain a thermal polymerization initiator and a photosensitizer in addition to (B) the photopolymerization initiator. Examples of the thermal polymerization initiator include peroxides and azo compounds. Specific examples include benzoyl peroxide, t-butyl-oxybenzoate, and azobisisobutyronitrile. Examples of the photosensitizer include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate. An isoamyl acid etc. are mentioned. Examples of the commercially available products include Ubekrill P102, 103, 104, 105 (above, manufactured by UCB).
本発明の放射線硬化性樹脂組成物における（Ｃ）シランカップリング剤は、硬化体の基材に対する密着力を向上させる成分であり、当該シランカップリング剤としては、γ−アミノプロピルトリエトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−（メタ）アクリロキシプロピルトリメトキシシラン、ビニルトリクロロシラン、ビニルトリエトキシシラン、ビニルトリス（β−メトキシエトキシ）シラン、γ−グリシドキシプロピルトリメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルメチルジメトキシシラン、γ−クロロプロピルトリメトキシシラン、ビス−１，２−（トリエトキシシリル）エタン等が挙げられる。その市販品としては、ＳＨ６０６２、ＳＺ６０３０（以上、東レ・ダウコーニングシリコーン社製）、ＫＢＥ９０３、６０３、４０３（以上、信越化学工業（株）製）等が挙げられる。 The (C) silane coupling agent in the radiation curable resin composition of the present invention is a component that improves the adhesion of the cured product to the substrate, and the silane coupling agent includes γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-glycidoxypropyltrimethoxysilane, N- β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-chloropropyltrimethoxysilane, bis-1,2- (triethoxysilyl) ethane, etc. Can be mentioned. Examples of the commercially available products include SH6062, SZ6030 (above, manufactured by Toray Dow Corning Silicone), KBE903, 603, 403 (above, manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.
（Ｃ）シランカップリング剤は、密着力向上効果の点から、本発明放射線硬化性樹脂組成物中、０．１〜３．０重量％、さらに０．５〜２．０重量％、特に０．８〜１．２重量％含有するのが好ましい。 (C) The silane coupling agent is 0.1 to 3.0% by weight, more preferably 0.5 to 2.0% by weight, particularly 0%, in the radiation curable resin composition of the present invention, from the viewpoint of the effect of improving the adhesion. It is preferable to contain 8 to 1.2% by weight.
本発明放射線硬化性樹脂組成物における（Ｄ）亜リン酸エステルは、シランカップリング剤配合の放射線硬化性樹脂組成物の保存安定性を向上させ、長期保存後の密着力を維持させる作用を有するものである。かかる観点から、成分（Ｄ）の亜リン酸エステルは、（Ａ）成分と反応し得る官能基を有しないこと、及び成分（Ｂ）のような光重合開始能を有しないことが必要である。ここで、（Ａ）成分と反応し得る基としては、一級アミノ基、二級アミノ基、三級アミノ基等が挙げられる。 (D) Phosphite ester in the radiation curable resin composition of the present invention has an effect of improving the storage stability of the radiation curable resin composition containing a silane coupling agent and maintaining the adhesion after long-term storage. Is. From this point of view, the phosphite ester of component (D) needs not to have a functional group capable of reacting with component (A) and to have no photopolymerization initiating ability like component (B). . Here, examples of the group capable of reacting with the component (A) include a primary amino group, a secondary amino group, and a tertiary amino group.
このような成分（Ｄ）としては、（Ａ）成分と反応し得る基を有しない、（Ｂ）成分以外の亜リン酸トリエステル、例えば、次の一般式（１） As such a component (D), a phosphorous acid triester other than the component (B) having no group capable of reacting with the component (A), for example, the following general formula (1)
（Ｒ4Ｏ）3Ｐ・・・・（１） (R 4 O) 3 P (1)
（式中、Ｒ4は、同一又は異なって成分（Ａ）と反応しない有機基を示し、２又は３個のＲ4が酸素原子及びリン原子とともに環を形成していてもよい）
で表される亜リン酸トリエステルが挙げられる。ここでＲ4としては、リン原子、ハロゲン原子、ヒドロキシ基、アルコキシ基又はアルキル基が置換していてもよいアリール基、リン原子、ハロゲン原子、ヒドロキシ基、アルコキシ基又はアルキル基から置換していてもよいアラルキル基、アルキル基等が挙げられる。また、２又は３個のＲ4が酸素原子及びリン原子とともに環形成していてもよい。
(In the formula, R 4 is the same or different and represents an organic group that does not react with the component (A), and 2 or 3 R 4 may form a ring together with an oxygen atom and a phosphorus atom)
The phosphorous acid triester represented by these is mentioned. Here, R 4 is substituted from an aryl group, phosphorus atom, halogen atom, hydroxy group, alkoxy group or alkyl group which may be substituted by a phosphorus atom, halogen atom, hydroxy group, alkoxy group or alkyl group. Examples thereof include an aralkyl group and an alkyl group. Two or three R 4 groups may form a ring together with an oxygen atom and a phosphorus atom.
成分（Ｄ）の具体例としては、トリス（２，４−ジ−tert−ブチルフェニル）ホスファイト、ビス（２，４−（ビス１，１−ジメチルエチル）−６−メチルフェニル）エチルエステル亜リン酸、テトラキス（２，４−ジ−tert−ブチルフェニル）（１，１−ビフェニル）−４，４′−ジイルビスホスフォナイト、ビス（２，４−ジ−tert−ブチルフェニル）ペンタエリスリトールジホスファイト、２−メチル−４−ヒドロキシフェニルジエチルホスファイト、２−ｔ−ブチル−４−ヒドロキシフェニルジエチルホスファイト、２，５−ジ−ｔ−ブチル−４−ヒドロキシフェニルジエチルホスファイト、ビス（２，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）エチルホスファイト、トリス（２，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）ホスファイト、テトラキス（２，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）−２，５−ジ−ｔ−ブチル−ヒドロキシキノンジイル−ホスファイトや下記構造式（ｄ１）〜（ｄ８）で示される化合物等が挙げられる。 Specific examples of component (D) include tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4- (bis1,1-dimethylethyl) -6-methylphenyl) ethyl ester Phosphoric acid, tetrakis (2,4-di-tert-butylphenyl) (1,1-biphenyl) -4,4'-diylbisphosphonite, bis (2,4-di-tert-butylphenyl) pentaerythritol Diphosphite, 2-methyl-4-hydroxyphenyl diethyl phosphite, 2-t-butyl-4-hydroxyphenyl diethyl phosphite, 2,5-di-t-butyl-4-hydroxyphenyl diethyl phosphite, bis ( 2,5-di-tert-butyl-4-hydroxyphenyl) ethyl phosphite, tris (2,5-di-tert-butyl-4-hydroxyphenyl) Supite, tetrakis (2,5-di-t-butyl-4-hydroxyphenyl) -2,5-di-t-butyl-hydroxyquinonediyl-phosphite and the following structural formulas (d1) to (d8) Compounds and the like.
これらの（Ｄ）亜リン酸エステルは、Ｐｏｌｙｍｅｒ Ｄｅｇｒａｄａｔｉｏｎ ａｎｄ Ｓｔａｂｉｌｉｔｙ ７７ （２００２） ｐ２９に記載されている方法で合成することが出来る。（Ｄ）亜リン酸エステルの市販品としては、Ｉｒｇａｆｏｓ １６８、Ｉｒｇａｆｏｓ １６８ ＦＦ、Ｉｒｇａｆｏｓ ３８、Ｉｒｇａｆｏｓ Ｐ−ＥＰＱ、Ｉｒｇａｆｏｓ Ｐ−ＥＰＱ ＦＦ、Ｉｒｇａｆｏｓ Ｐ−ＥＰＱ ＦＤ、Ｉｒｇａｆｏｓ １２６、Ｉｒｇａｆｏｓ １２６ ＦＦ（チバ・スペシャルティ・ケミカルズ社製）、Ｓｕｍｉｌｉｚｅｒ ＧＰ（住友化学工業（株）製）等が挙げられる。 These (D) phosphites can be synthesized by the method described in Polymer Degradation and Stability 77 (2002) p29. (D) As commercially available phosphites, Irgafos 168, Irgafos 168 FF, Irgafos 38, Irgafos P-EPQ, Irgafos P-EPQ FF, Irgafos P-EPQ FD, Irgafos 126, Irgafos 126, Irgafos 126 Chemicals), Sumilizer GP (Sumitomo Chemical Co., Ltd.) and the like.
（Ｂ）亜リン酸エステルは、本発明放射線硬化性樹脂組成物中に０．１〜２．０重量％、さらに０．３〜１．０重量％、特に０．３〜０．５重量％含有するのが好ましい。含有量が少なすぎると保存安定性向上効果が得られず、多すぎると着色の原因となる。 (B) Phosphite is 0.1 to 2.0% by weight, more preferably 0.3 to 1.0% by weight, and particularly 0.3 to 0.5% by weight in the radiation curable resin composition of the present invention. It is preferable to contain. When the content is too small, the effect of improving the storage stability cannot be obtained, and when it is too much, coloring is caused.
本発明放射線硬化性樹脂組成物には、（Ｅ）ウレタン（メタ）アクリレートを含有するのが、速やかに硬化体を形成する点で好ましい。（Ｅ）ウレタン（メタ）アクリレートは、特に限定されないが、例えば、（ａ）ポリオール化合物、（ｂ）ポリイソシアネート化合物、及び（ｃ）水酸基含有（メタ）アクリレート化合物を反応させて得られる。 It is preferable that the radiation curable resin composition of the present invention contains (E) urethane (meth) acrylate in terms of quickly forming a cured product. (E) Urethane (meth) acrylate is not particularly limited, and can be obtained, for example, by reacting (a) a polyol compound, (b) a polyisocyanate compound, and (c) a hydroxyl group-containing (meth) acrylate compound.
この（Ｅ）ウレタン（メタ）アクリレートを製造する具体的方法としては、例えば（ａ）ポリオール、（ｂ）ポリイソシアネート化合物及び（ｃ）水酸基含有（メタ）アクリレートを一括して仕込んで反応させる方法；（ａ）ポリオール及び（ｂ）ポリイソシアネート化合物を反応させ、次いで（ｃ）水酸基含有（メタ）アクリレートを反応させる方法；（ｂ）ポリイソシアネート化合物及び（ｃ）水酸基含有（メタ）アクリレートを反応させ、次いで（ａ）ポリオールを反応させる方法；（ｂ）ポリイソシアネート化合物及び（ｃ）水酸基含有（メタ）アクリレートを反応させ、次いで（ａ）ポリオールを反応させ、最後にまた（ｃ）水酸基含有（メタ）アクリレートを反応させる方法などが挙げられる。 As a specific method for producing the (E) urethane (meth) acrylate, for example, (a) a polyol, (b) a polyisocyanate compound and (c) a hydroxyl group-containing (meth) acrylate are collectively charged and reacted; (A) a method of reacting a polyol and (b) a polyisocyanate compound, and then reacting (c) a hydroxyl group-containing (meth) acrylate; (b) reacting a polyisocyanate compound and (c) a hydroxyl group-containing (meth) acrylate, Next, (a) a method of reacting a polyol; (b) a polyisocyanate compound and (c) a hydroxyl group-containing (meth) acrylate are reacted, then (a) a polyol is reacted, and finally (c) a hydroxyl group-containing (meth) Examples include a method of reacting acrylate.
ここで用いる（ａ）ポリオールとしては、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール、ポリヘキサメチレングリコール、ポリヘプタメチレングリコール、ポリデカメチレングリコールのような一種のイオン重合性環状化合物を開環重合させて得られるポリエーテルジオール、又は二種以上のイオン重合性環状化合物を開環共重合させて得られるポリエーテルジオールが挙げられる。イオン重合性環状化合物としては、エチレンオキシド、プロピレンオキシド、ブテン−１−オキシド、イソブテンオキシド、オキセタン、３，３−ジメチルオキセタン、３，３−ビスクロロメチルオキセタン、テトラヒドロフラン、２−メチルテトラヒドロフラン、３−メチルテトラヒドロフラン、ジオキサン、トリオキサン、テトラオキサン、シクロヘキセンオキシド、スチレンオキシド、エピクロルヒドリン、グリシジルメタクリレート、アリルグリシジルエーテル、アリルグリシジルカーボネート、ブタジエンモノオキシド、イソプレンモノオキシド、ビニルオキセタン、ビニルテトラヒドロフラン、ビニルシクロヘキセンオキシド、フェニルグリシジルエーテル、ブチルグリシジルエーテル、安息香酸グリシジルエステル等の環状エーテル類が挙げられる。また、上記イオン重合性環状化合物と、エチレンイミン等の環状イミン類、γ−プロピオラクトン、グリコール酸ラクチド等の環状ラクトン酸、あるいはジメチルシクロポリシロキサン類とを開環共重合させたポリエーテルジオールを使用することもできる。上記二種以上のイオン重合性環状化合物の具体的な組み合わせとしては、テトラヒドロフランとプロピレンオキシド、テトラヒドロフランと２−メチルテトラヒドロフラン、テトラヒドロフランと３−メチルテトラヒドロフラン、テトラヒドロフランとエチレンオキシド、プロピレンオキシドとエチレンオキシド、ブテン−１−オキシドとエチレンオキシド、テトラヒドロフラン、ブテン−１−オキシド、エチレンオキシドの３元重合体等を挙げることができる。これらのイオン重合性環状化合物の開環共重合体はランダムに結合していてもよいし、ブロック状の結合をしていてもよい。本発明の硬化物に耐ジェリー性及び耐水性を付与する点から、これらのポリエーテルジオールのうち、ポリプロピレングリコールがより好ましく、ゲルパーミエーションクロマトグラフ法（ＧＰＣ法）によるポリスチレン換算の数平均分子量で１０００〜７０００のポリプロピレングリコールが特に好ましい。 The (a) polyol used here is a ring-opening polymerization of a kind of ion-polymerizable cyclic compound such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol. And polyether diol obtained by ring-opening copolymerization of two or more kinds of ion-polymerizable cyclic compounds. Examples of the ion polymerizable cyclic compound include ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide, oxetane, 3,3-dimethyloxetane, 3,3-bischloromethyloxetane, tetrahydrofuran, 2-methyltetrahydrofuran, and 3-methyl. Tetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrin, glycidyl methacrylate, allyl glycidyl ether, allyl glycidyl carbonate, butadiene monooxide, isoprene monooxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl glycidyl ether, butyl Cyclic ethers such as glycidyl ether and benzoic acid glycidyl ester Ethers, and the like. Polyether diol obtained by ring-opening copolymerization of the above ion polymerizable cyclic compound with cyclic imines such as ethyleneimine, cyclic lactone acids such as γ-propiolactone and glycolic acid lactide, or dimethylcyclopolysiloxanes. Can also be used. Specific combinations of the two or more ion-polymerizable cyclic compounds include tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, tetrahydrofuran and ethylene oxide, propylene oxide and ethylene oxide, butene-1- Examples thereof include terpolymers of oxide and ethylene oxide, tetrahydrofuran, butene-1-oxide, and ethylene oxide. The ring-opening copolymer of these ion-polymerizable cyclic compounds may be bonded at random or may be bonded in a block form. Of these polyether diols, polypropylene glycol is more preferable from the viewpoint of imparting jelly resistance and water resistance to the cured product of the present invention, and has a number average molecular weight in terms of polystyrene by gel permeation chromatography (GPC method). 1000 to 7000 polypropylene glycol is particularly preferred.
これらのポリエーテルジオールは、例えばＰＴＭＧ６５０、ＰＴＭＧ１０００、ＰＴＭＧ２０００（以上、三菱化学（株）製）、エクセノール １０２０、２０２０、３０２０、プレミノール ＰＭＬ−４００２、ＰＭＬ−５００５（以上、旭硝子（株）製）、ユニセーフ ＤＣ１１００、ＤＣ１８００、ＤＣＢ１０００（以上、日本油脂（株）製）、ＰＰＴＧ１０００、ＰＰＴＧ２０００、ＰＰＴＧ４０００、ＰＴＧ４００、ＰＴＧ６５０、ＰＴＧ１０００、ＰＧＴ２０００、ＰＴＧ−Ｌ１０００、ＰＴＧ−Ｌ２０００（以上、保土谷化学工業（株）製）、Ｚ−３００１−４、Ｚ−３００１−５、ＰＢＧ２０００（以上、第一工業製薬（株）製）、Ａｃｃｌａｉｍ ２２００、２２２０、３２０１、３２０５、４２００、４２２０、８２００、１２０００（以上、ライオンデール社製）等の市販品として入手することができる。 These polyether diols are, for example, PTMG650, PTMG1000, PTMG2000 (manufactured by Mitsubishi Chemical Corporation), Exenol 1020, 2020, 3020, Preminol PML-4002, PML-5005 (above, manufactured by Asahi Glass Co., Ltd.), Unisafe DC1100, DC1800, DCB1000 (above, manufactured by NOF Corporation), PPTG1000, PPTG2000, PPTG4000, PTG400, PTG650, PTG1000, PGT2000, PTG-L1000, PTG-L2000 (above, manufactured by Hodogaya Chemical Co., Ltd.), Z-3001-4, Z-3001-5, PBG2000 (above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Acclaim 2200, 2220, 3201, 3205, 4200, 4220, 8200 12000 (or, Lion Dale Corporation) may be commercially available, such as.
ポリオールとしては、上記ポリエーテルジオールが好ましいが、この他にポリエステルジオール、ポリカーボネートジオール、ポリカプロラクトンジオール等も用いることができ、これらのジオールをポリエーテルジオールと併用することもできる。これらの構造単位の重合様式は特に制限されず、ランダム重合、ブロック重合、グラフト重合のいずれであってもよい。 As the polyol, the above-mentioned polyether diol is preferable, but in addition to this, polyester diol, polycarbonate diol, polycaprolactone diol, and the like can also be used, and these diols can be used in combination with the polyether diol. The polymerization mode of these structural units is not particularly limited, and may be any of random polymerization, block polymerization, and graft polymerization.
（Ｅ）ウレタン（メタ）アクリレートの合成に用いられる（ｂ）ポリイソシアネートとしては、芳香族ジイソシアネート、脂環族ジイソシアネート、脂肪族ジイソシアネート等が挙げられる。具体的化合物としては、芳香族ジイソシアネート及び脂環式ジイソシアネート、より好ましくは、２，４−トリレンジイソシアネート及びイソホロンジイソシアネートが挙げられる。これらのジイソシアネート化合物は単独で用いても、２種以上併用しても良い。 (E) As polyisocyanate used for the synthesis | combination of urethane (meth) acrylate, aromatic diisocyanate, alicyclic diisocyanate, aliphatic diisocyanate, etc. are mentioned. Specific examples of the compound include aromatic diisocyanate and alicyclic diisocyanate, and more preferably 2,4-tolylene diisocyanate and isophorone diisocyanate. These diisocyanate compounds may be used alone or in combination of two or more.
（Ｅ）ウレタン（メタ）アクリレートの合成に用いられる（ｃ）水酸基含有（メタ）アクリレートとしては、ポリイソシアネートのイソシアネート基との反応性の点から、水酸基が第一級炭素原子に結合した水酸基含有（メタ）アクリレート（第一水酸基含有（メタ）アクリレートという）及び水酸基が第二級炭素原子に結合した水酸基含有（メタ）アクリレート（第二水酸基含有（メタ）アクリレートという）が好ましい。 (E) As a hydroxyl group-containing (meth) acrylate used for the synthesis of urethane (meth) acrylate, from the viewpoint of reactivity with the isocyanate group of polyisocyanate, a hydroxyl group containing a hydroxyl group bonded to a primary carbon atom A (meth) acrylate (referred to as a primary hydroxyl group-containing (meth) acrylate) and a hydroxyl group-containing (meth) acrylate (referred to as a secondary hydroxyl group-containing (meth) acrylate) in which the hydroxyl group is bonded to a secondary carbon atom are preferred.
第一水酸基含有（メタ）アクリレートとして、例えば、２−ヒドロキシエチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、１，６−ヘキサンジオールモノ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ネオペンチルグリコールモノ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、トリメチロールエタンジ（メタ）アクリレート等が挙げられる。 Examples of the primary hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, Examples include dipentaerythritol penta (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, and trimethylolethane di (meth) acrylate.
第二水酸基含有（メタ）アクリレートとして、例えば、２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、２−ヒドロキシ−３−フェニルオキシプロピル（メタ）アクリレート、４−ヒドロキシシクロヘキシル（メタ）アクリレート等が挙げられ、さらに、アルキルグリシジルエーテル、アリルグリシジルエーテル、グリシジル（メタ）アクリレート等のグリシジル基含有化合物と、（メタ）アクリル酸との付加反応により得られる化合物が挙げられる。これら水酸基含有（メタ）アクリレート化合物は１種単独で、あるいは２種以上組み合わせて使用できる。 As the secondary hydroxyl group-containing (meth) acrylate, for example, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 4-hydroxycyclohexyl (meta) ) Acrylates, and the like, and compounds obtained by addition reaction of glycidyl group-containing compounds such as alkyl glycidyl ether, allyl glycidyl ether, glycidyl (meth) acrylate and (meth) acrylic acid. These hydroxyl group-containing (meth) acrylate compounds can be used alone or in combination of two or more.
（Ｅ）ウレタン（メタ）アクリレートの合成に用いる（ａ）ポリオール、（ｂ）ポリイソシアネート化合物及び水酸基含有（メタ）アクリレートの使用割合は、ポリオールに含まれる水酸基１当量に対してポリイソシアネート化合物に含まれるイソシアネート基が１．１〜２当量、水酸基含有（メタ）アクリレートの水酸基が０．１〜１当量となるようにするのが好ましい。 (E) The proportion of (a) polyol, (b) polyisocyanate compound and hydroxyl group-containing (meth) acrylate used for the synthesis of urethane (meth) acrylate is included in the polyisocyanate compound with respect to 1 equivalent of hydroxyl group contained in the polyol. It is preferable that the isocyanate group to be prepared is 1.1 to 2 equivalents, and the hydroxyl group of the hydroxyl group-containing (meth) acrylate is 0.1 to 1 equivalent.
また（Ｅ）ウレタン（メタ）アクリレートの合成においてポリオールとともにジアミンを併用することも可能であり、このようなジアミンとしてはエチレンジアミン、テトラメチレンジアミン、ヘキサメチレンジアミン、パラフェニレンジアミン、４，４′−ジアミノジフェニルメタン等のジアミンやヘテロ原子を含むジアミン、ポリエーテルジアミン等が挙げられる。 It is also possible to use a diamine together with a polyol in the synthesis of (E) urethane (meth) acrylate. Examples of such diamine include ethylenediamine, tetramethylenediamine, hexamethylenediamine, paraphenylenediamine, 4,4'-diamino. Examples thereof include diamines such as diphenylmethane, diamines containing a hetero atom, and polyether diamines.
水酸基含有（メタ）アクリレートの一部をイソシアネート基に付加しうる官能基を持った化合物、又はアルコール類に置き換えて用いることもできる。イソシアネート基に付加しうる官能基を持った化合物としては、例えば、γ−アミノプロピルトリエトキシシラン、γ−メルカプトプロピルトリメトキシシランなどを挙げることができる。これらの化合物を使用することにより、ガラス等の基材への密着性をさらに高めることができる。アルコール類としては、例えば、メタノール、エタノール、イソプロピルアルコール、ｎ−ブチルアルコール、ｔ−ブチルアルコール、などを挙げることができる。これらの化合物を使用することにより、樹脂のヤング率を調節することができる。 A part of the hydroxyl group-containing (meth) acrylate may be replaced with a compound having a functional group that can be added to an isocyanate group, or an alcohol. Examples of the compound having a functional group that can be added to an isocyanate group include γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, and the like. By using these compounds, the adhesion to a substrate such as glass can be further enhanced. Examples of alcohols include methanol, ethanol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol, and the like. By using these compounds, the Young's modulus of the resin can be adjusted.
（Ｅ）ウレタン（メタ）アクリレートの合成においては、ナフテン酸銅、ナフテン酸コバルト、ナフテン酸亜鉛、ジブチル錫ジラウレート、トリエチルアミン、１，４−ジアザビシクロ〔２．２．２〕オクタン、２，６，７−トリメチル−１，４−ジアザビシクロ〔２．２．２〕オクタン等のウレタン化触媒を、反応物の総量に対して０．０１〜１重量％用いるのが好ましい。また、反応温度は、通常５〜９０℃、特に１０〜８０℃が好ましい。 (E) In the synthesis of urethane (meth) acrylate, copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyltin dilaurate, triethylamine, 1,4-diazabicyclo [2.2.2] octane, 2,6,7 It is preferable to use 0.01 to 1% by weight of a urethanization catalyst such as trimethyl-1,4-diazabicyclo [2.2.2] octane based on the total amount of the reaction product. Moreover, reaction temperature is 5-90 degreeC normally, Especially 10-80 degreeC is preferable.
（Ｅ）ウレタン（メタ）アクリレートの好ましい分子量は、硬化物の良好な破断伸び及び放射線硬化性樹脂組成物の適度な粘度を得る観点から、ＧＰＣ法によるポリスチレン換算の数平均分子量で通常５００〜４０，０００であり、より好ましくは７００〜３０，０００である。 The preferred molecular weight of (E) urethane (meth) acrylate is usually from 500 to 40 in terms of polystyrene-reduced number average molecular weight by the GPC method from the viewpoint of obtaining a good elongation at break of the cured product and an appropriate viscosity of the radiation curable resin composition. 000, more preferably 700 to 30,000.
（Ｅ）ウレタン（メタ）アクリレートは、硬化物のヤング率、破断伸び等の良好な力学特性及び放射線硬化性樹脂組成物の適度な粘度を得る観点から、本発明の放射線硬化性樹脂組成物中に、０〜８５重量％、さらに３０〜６５重量％、特に３０〜５５重量％含有することが好ましい。８５重量％を超えると放射線硬化性樹脂組成物の粘度が６．０Ｐａ・ｓを超えてしまうため作業性も低下し、また硬化物の耐水性も悪化する。放射線硬化性樹脂組成物の粘度は１．０〜６．０Ｐａ・ｓが好ましい。 (E) Urethane (meth) acrylate is included in the radiation curable resin composition of the present invention from the viewpoint of obtaining good mechanical properties such as Young's modulus of the cured product and elongation at break and an appropriate viscosity of the radiation curable resin composition. 0 to 85% by weight, more preferably 30 to 65% by weight, and particularly preferably 30 to 55% by weight. If it exceeds 85% by weight, the viscosity of the radiation curable resin composition exceeds 6.0 Pa · s, so that workability is lowered and the water resistance of the cured product is also deteriorated. The viscosity of the radiation curable resin composition is preferably 1.0 to 6.0 Pa · s.
また、本発明の放射線硬化性樹脂組成物には上記成分以外に各種添加剤、例えば着色剤、光安定剤、酸化防止剤、熱重合禁止剤、レベリング剤、界面活性剤、保存安定剤、可塑剤、滑剤、溶媒、フィラー、老化防止剤、濡れ性改良剤、塗面改良剤等を必要に応じて配合することができる。ここで光安定剤としては、例えばチヌビン ２９２、１４４、６２２ＬＤ（以上、チバ・スペシャルティ・ケミカルズ社製）、サノールＬＳ７７０（三共（株）製）、ＴＭ−０６１（住友化学工業（株）製）、ＳＥＥＳＯＲＢ１０１、ＳＥＥＳＯＲＢ１０３、ＳＥＥＳＯＲＢ７０９（以上、シプロ化成（株）製）、Ｓｕｍｉｓｏｒｂ１３０（住友化学工業（株）製）等が挙げられる。酸化防止剤としては、例えばＳｕｍｉｌｉｚｅｒ ＧＡ−８０（住友化学工業（株）製）、Ｉｒｇａｎｏｘ１０１０、Ｉｒｇａｎｏｘ１０３５（チバ・スペシャリティ・ケミカルズ（株）製）が挙げられる。 In addition to the above components, the radiation curable resin composition of the present invention includes various additives such as colorants, light stabilizers, antioxidants, thermal polymerization inhibitors, leveling agents, surfactants, storage stabilizers, plasticizers. An agent, a lubricant, a solvent, a filler, an anti-aging agent, a wettability improver, a coating surface improver and the like can be blended as necessary. Here, as the light stabilizer, for example, Tinuvin 292, 144, 622LD (above, manufactured by Ciba Specialty Chemicals), Sanol LS770 (manufactured by Sankyo Corporation), TM-061 (manufactured by Sumitomo Chemical Co., Ltd.), SEESORB 101, SEESORB 103, SEESORB 709 (manufactured by Sipro Kasei Co., Ltd.), Sumisorb 130 (manufactured by Sumitomo Chemical Co., Ltd.), and the like. Examples of the antioxidant include Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.), Irganox 1010, and Irganox 1035 (manufactured by Ciba Specialty Chemicals Co., Ltd.).
本発明の放射線硬化性樹脂組成物は、放射線によって硬化される。ここで放射線とは、赤外線、可視光線、紫外線、Ｘ線、α線、β線、γ線、電子線等であるが、特に紫外線が好ましい。 The radiation curable resin composition of the present invention is cured by radiation. Here, the radiation includes infrared rays, visible rays, ultraviolet rays, X-rays, α rays, β rays, γ rays, electron rays, and the like, and ultraviolet rays are particularly preferable.
以下に本発明を実施例により具体的に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
ウレタン（メタ）アクリレートの合成例１
撹拌機を備えた反応容器に、数平均分子量が４０００のポリプロピレングリコール８９２．９ｇ、トリレンジイソシアネート５０．８ｇ、２，６−ジ−ｔ−ブチル−ｐ−クレゾール０．２３ｇ、フェノチアジン０．０８ｇを仕込み、これらを撹拌しながら液温度が１５℃となるまで冷却した。ジブチル錫ジラウレート０．８ｇを添加した後、撹拌しながら液温度を１時間かけて３５℃まで徐々に上げた。その後、液温度を５０℃に上げて反応させた。残留イソシアネート基濃度が０．６６重量％（仕込量に対する割合；以下同じ）以下となった後、メタノール０．６gを添加した後、1時間撹拌し、２−ヒドロキシエチルアクリレート１５．１ｇを添加し、液温度約６０℃にて撹拌し、反応させた。残留イソシアネート基濃度が０．１重量％以下になった時を反応終了とし、ウレタン（メタ）アクリレートを得た（これをＵＡ−１とする）。
Synthesis example 1 of urethane (meth) acrylate
In a reaction vessel equipped with a stirrer, 892.9 g of polypropylene glycol having a number average molecular weight of 4000, 50.8 g of tolylene diisocyanate, 0.23 g of 2,6-di-t-butyl-p-cresol, and 0.08 g of phenothiazine were added. The solution was stirred and cooled until the liquid temperature reached 15 ° C. while stirring. After adding 0.8 g of dibutyltin dilaurate, the liquid temperature was gradually raised to 35 ° C. over 1 hour with stirring. Thereafter, the liquid temperature was raised to 50 ° C. for reaction. After the residual isocyanate group concentration was 0.66% by weight (ratio to the charged amount; the same applies hereinafter), 0.6 g of methanol was added, and the mixture was stirred for 1 hour, and 15.1 g of 2-hydroxyethyl acrylate was added. The mixture was stirred at a liquid temperature of about 60 ° C. for reaction. The reaction was terminated when the residual isocyanate group concentration was 0.1% by weight or less, and urethane (meth) acrylate was obtained (this is referred to as UA-1).
ウレタン（メタ）アクリレートの合成例２
撹拌機を備えた反応容器に、数平均分子量が２０００のポリプロピレングリコール８３２．２ｇ、イソホロンジイソシアネート１２９．５ｇ、２，６−ジ−ｔ−ブチル−ｐ−クレゾール０．２４ｇ、フェノチアジン０．０８ｇを仕込み、これらを撹拌しながら液温度が１５℃となるまで冷却した。ジブチル錫ジラウレート０．８ｇを添加した後、撹拌しながら液温度を１時間かけて３５℃まで徐々に上げた。その後、液温度を５０℃に上げて反応させた。残留イソシアネート基濃度が１．４４重量％（仕込量に対する割合；以下同じ）以下となった後、２−ヒドロキシエチルアクリレート３６．７ｇを添加し、液温度約６０℃にて撹拌し、反応させた。次に、メタノール０．５ｇを滴下し、液温度約６０℃にて撹拌し、反応させた。残留イソシアネート基濃度が０．１重量％以下になった時を反応終了とし、ウレタン（メタ）アクリレートを得た（これをＵＡ−２とする）。
Synthesis example 2 of urethane (meth) acrylate
A reaction vessel equipped with a stirrer is charged with 832.2 g of polypropylene glycol having a number average molecular weight of 2000, 129.5 g of isophorone diisocyanate, 0.24 g of 2,6-di-t-butyl-p-cresol, and 0.08 g of phenothiazine. These were cooled until the liquid temperature became 15 ° C. while stirring. After adding 0.8 g of dibutyltin dilaurate, the liquid temperature was gradually raised to 35 ° C. over 1 hour with stirring. Thereafter, the liquid temperature was raised to 50 ° C. for reaction. After the residual isocyanate group concentration became 1.44% by weight (ratio to the charged amount; the same applies hereinafter), 36.7 g of 2-hydroxyethyl acrylate was added, and the mixture was stirred at a liquid temperature of about 60 ° C. for reaction. . Next, 0.5 g of methanol was added dropwise, and the mixture was stirred at a liquid temperature of about 60 ° C. for reaction. The reaction was terminated when the residual isocyanate group concentration was 0.1% by weight or less, and urethane (meth) acrylate was obtained (this is referred to as UA-2).
実施例１〜９及び比較例１〜４
撹拌機を備えた反応容器に表１に示す配合比（重量部）で化合物を仕込み、均一な溶液になるまで液温度５０℃で撹拌し、実施例及び比較例の組成物を得た。
Examples 1-9 and Comparative Examples 1-4
The compounds were charged in a reaction vessel equipped with a stirrer at a blending ratio (parts by weight) shown in Table 1, and stirred at a liquid temperature of 50 ° C. until a uniform solution was obtained, thereby obtaining compositions of Examples and Comparative Examples.
測定方法
（硬化速度）
液状組成物を３８１μｍのアプリケーターを用いてガラス上に塗布し、３．５ｋＷメタルハライドランプ（オーク社製ＳＭＸ−３５００／Ｆ−ＯＳ）を用いて空気雰囲気下で５００ｍＪ／ｃｍ2と、２０ｍＪ／ｃｍ2の照射量で紫外線を照射し、厚さ約２００μｍの硬化膜を得た。５００ｍＪ／ｃｍ2と、２０ｍＪ／ｃｍ2の照射量で得られたフィルムの弾性率を測定し、その比を硬化速度とし評価した。
Measuring method (curing speed)
The liquid composition was coated on a glass using an applicator for 381, and 500 mJ / cm 2 under air atmosphere using a 3.5kW metal halide lamp (Oak Co. SMX-3500 / F-OS) , 20mJ / cm 2 The cured film having a thickness of about 200 μm was obtained by irradiating with ultraviolet rays at a dose of. The elasticity modulus of the film obtained by the irradiation amount of 500 mJ / cm < 2 > and 20 mJ / cm < 2 > was measured, and the ratio was evaluated as a curing rate.
（温水浸漬時の密着力）
液状組成物（製造初期品もしくは、常温で１年保管後品）を３８１μｍのアプリケーターを用いてガラス上に塗布し、更にその上にガラス板を乗せ、３．５ｋＷメタルハライドランプ（オーク社製ＳＭＸ−３５００／Ｆ−ＯＳ）を用いて空気雰囲気下で１Ｊ／ｃｍ2の照射量で紫外線を照射し試験片を得た。その試験片を６０℃の温水に７日間浸漬した。剥離の有無を目視で評価した。剥離が無い場合を良好とし、剥離が認められた場合を不良とした。
(Adhesion when immersed in warm water)
A liquid composition (manufactured initial product or product stored at room temperature for one year) was applied onto glass using a 381 μm applicator, and a glass plate was placed thereon, and a 3.5 kW metal halide lamp (SMX- manufactured by Oak Co., Ltd.) was applied. 3500 / F-OS) was irradiated with ultraviolet rays at an irradiation amount of 1 J / cm 2 in an air atmosphere to obtain a test piece. The test piece was immersed in warm water at 60 ° C. for 7 days. The presence or absence of peeling was visually evaluated. The case where there was no peeling was determined to be good, and the case where peeling was observed was determined to be defective.
Ｍ１１３：ノニルフェニルＥＯ変性アクリレート（東亞合成（株）製）
ＩＢＸＡ：インボルニルアクリレート（大阪有機化学工業（株）製）
ＡＣＭＯ：アクリロイルモルホリン
ＨＤＤＡ：ヘキサンジオールジアクリレート
ＴＰＧＤＡ：トリプロピレングリコールジアクリレート（昭和高分子（株）製）
ＶＲ−７７：ビスフェノールＡエポキシアクリレート（昭和高分子（株）製）
ＬＵＣＩＲＩＮ ＴＰＯ：２，４，６−トリメチルベンゾイルジフェニルホスフィンオキサイド（ＢＡＳＦ社製）
Ｉｒｇａｃｕｒｅ ８１９：ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド（チバ・スペシャルティ・ケミカルズ社製）
Ｉｒｇａｃｕｒｅ １８４：１−ヒドロキシシクロヘキシルフェニルケトン（チバ・スペシャルティ・ケミカルズ社製）
ＳＺ６０３０：γ−メタクリロキシプロピルトリメトキシシラン（東レ・ダウコーニングシリコーン社製）
ＳＨ６０６２：γ−メルカプトトリメトキシシラン（東レ・ダウコーニングシリコーン社製）
ＧＰ：Ｓｕｍｉｌｉｚｅｒ ＧＰ（住友化学工業（株）製）
Ｉｒｇａｆｏｓ ３８：ビス〔２，４−ビス（１，１−ジメチルエチル）−６−メチルフェニル〕エチルエステルフォスファイト（チバ・スペシャルティ・ケミカルズ社製）
Ｉｒｇａｆｏｓ １２６ ＦＦ：ビス（２，４−ｔｅｒｔ−ブチルフェニル）ペンタエリスリトールジフォスファイト（チバ・スペシャルティ・ケミカルズ社製）
Ｉｒｇａｆｏｓ １６８：トリス（２，４−ジ−ｔ−ブチルフェニル）フォスファイト（チバ・スペシャルティ・ケミカルズ社製）
ＳＥＥＳＯＲＢ １０１：２−ヒドロキシ−４−メトキシベンゾフェノン（シプロ化成（株）製）
Ｉｒｇａｎｏｘ １０３５：２，２−チオ−ジエチレンビス〔３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート〕（チバ・スペシャルティ・ケミカルズ社製）
ＧＡ−８０：Ｓｕｍｉｌｉｚｅｒ ＧＡ−８０（住友化学工業（株）製）
M113: Nonylphenyl EO-modified acrylate (manufactured by Toagosei Co., Ltd.)
IBXA: Inbornyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
ACMO: acryloylmorpholine HDDA: hexanediol diacrylate TPGDA: tripropylene glycol diacrylate (manufactured by Showa Polymer Co., Ltd.)
VR-77: bisphenol A epoxy acrylate (manufactured by Showa Polymer Co., Ltd.)
LUCIRIN TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (BASF)
Irgacure 819: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Ciba Specialty Chemicals)
Irgacure 184: 1-hydroxycyclohexyl phenyl ketone (Ciba Specialty Chemicals)
SZ6030: γ-methacryloxypropyltrimethoxysilane (Toray Dow Corning Silicone)
SH6062: γ-mercaptotrimethoxysilane (Toray Dow Corning Silicone)
GP: Sumilizer GP (manufactured by Sumitomo Chemical Co., Ltd.)
Irgafos 38: bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphite (manufactured by Ciba Specialty Chemicals)
Irgafos 126 FF: bis (2,4-tert-butylphenyl) pentaerythritol diphosphite (Ciba Specialty Chemicals)
Irgafos 168: Tris (2,4-di-t-butylphenyl) phosphite (Ciba Specialty Chemicals)
SEESORB 101: 2-hydroxy-4-methoxybenzophenone (manufactured by Cypro Kasei Co., Ltd.)
Irganox 1035: 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals)
GA-80: Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.)
表１から明らかなように、成分（Ｃ）を含有する放射線硬化性樹脂組成物は基材に対する密着力が向上するが、その安定性は悪い（比較例１、２）。これに対し、これに成分（Ｄ）を配合すると安定性が向上し、長期保存後も高い密着力を維持していることがわかる。 As is apparent from Table 1, the radiation curable resin composition containing the component (C) has improved adhesion to the substrate, but its stability is poor (Comparative Examples 1 and 2). On the other hand, when a component (D) is mix | blended with this, stability improves and it turns out that the high adhesive force is maintained after a long-term storage.
Claims (3)
（Ａ）エチレン性不飽和結合を有する重合性化合物、
（Ｂ）アシルホスフィンオキサイド系光重合開始剤、
（Ｃ）シランカップリング剤、
（Ｄ）（Ａ）成分と反応し得る官能基を有さず、かつ光重合開始能を有しない亜リン酸トリエステル
を含有することを特徴とする放射線硬化性樹脂組成物。 The following components (A), (B), (C) and (D):
(A) a polymerizable compound having an ethylenically unsaturated bond,
(B) an acylphosphine oxide photopolymerization initiator,
(C) a silane coupling agent,
(D) (A) without the organic functional groups capable of reacting with component, and radiation curable resin composition characterized by containing a phosphite triester having no photopolymerization initiating ability.
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| JP5201792B2 (en) * | 2005-09-28 | 2013-06-05 | Ｊｓｒ株式会社 | Liquid curable resin composition |
| JP4710596B2 (en) * | 2005-12-26 | 2011-06-29 | Ｊｓｒ株式会社 | Radiation curable resin composition for optical member and optical member |
| TW200916130A (en) * | 2007-10-02 | 2009-04-16 | Alcon Inc | Ophthalmic and otorhinolaryngological device materials containing an alkylphenol ethoxylate |
| CN102892796B (en) * | 2010-05-21 | 2015-04-29 | 电气化学工业株式会社 | Composition and adhesive |
| KR101848401B1 (en) * | 2010-10-08 | 2018-04-12 | 덴카 주식회사 | Resin composition |
| WO2014115210A1 (en) * | 2013-01-28 | 2014-07-31 | 日本曹達株式会社 | Coating agent |
| KR101852509B1 (en) | 2013-03-15 | 2018-04-26 | 동우 화인켐 주식회사 | Colored photosensitive resin composition |
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