JP2007262194A - Photocuring type composition - Google Patents
Photocuring type composition Download PDFInfo
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- JP2007262194A JP2007262194A JP2006087667A JP2006087667A JP2007262194A JP 2007262194 A JP2007262194 A JP 2007262194A JP 2006087667 A JP2006087667 A JP 2006087667A JP 2006087667 A JP2006087667 A JP 2006087667A JP 2007262194 A JP2007262194 A JP 2007262194A
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- acrylate
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- 239000000203 mixture Substances 0.000 title claims description 30
- 238000000016 photochemical curing Methods 0.000 title description 5
- 239000003999 initiator Substances 0.000 claims description 14
- 238000012719 thermal polymerization Methods 0.000 claims description 13
- 239000000853 adhesive Substances 0.000 claims description 10
- 230000001070 adhesive effect Effects 0.000 claims description 10
- 239000003505 polymerization initiator Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 7
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims 1
- 239000000446 fuel Substances 0.000 description 32
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 26
- 239000000565 sealant Substances 0.000 description 15
- -1 2-ethylhexyl Chemical group 0.000 description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 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 12
- 238000001723 curing Methods 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 10
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 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 6
- 229920000297 Rayon Polymers 0.000 description 6
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 125000001302 tertiary amino group Chemical group 0.000 description 6
- 239000007870 radical polymerization initiator Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- RJUVPCYAOBNZAX-VOTSOKGWSA-N ethyl (e)-3-(dimethylamino)-2-methylprop-2-enoate Chemical compound CCOC(=O)C(\C)=C\N(C)C RJUVPCYAOBNZAX-VOTSOKGWSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
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- 238000005259 measurement Methods 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
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- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
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- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
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- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
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- 238000010526 radical polymerization reaction Methods 0.000 description 2
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- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- 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 1
- WAVTZYKJTMZICQ-UHFFFAOYSA-N 2-(2-methylbutan-2-ylperoxy)propan-2-yl hydrogen carbonate Chemical compound CCC(C)(C)OOC(C)(C)OC(O)=O WAVTZYKJTMZICQ-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- NFWPZNNZUCPLAX-UHFFFAOYSA-N 4-methoxy-3-methylaniline Chemical compound COC1=CC=C(N)C=C1C NFWPZNNZUCPLAX-UHFFFAOYSA-N 0.000 description 1
- CDSULTPOCMWJCM-UHFFFAOYSA-N 4h-chromene-2,3-dione Chemical compound C1=CC=C2OC(=O)C(=O)CC2=C1 CDSULTPOCMWJCM-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000004849 alkoxymethyl group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 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
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 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
- 239000004744 fabric Substances 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 108700039708 galantide Proteins 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- SQGKLVBPYCDZLT-UHFFFAOYSA-N n,n-bis(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)N(CO)CO SQGKLVBPYCDZLT-UHFFFAOYSA-N 0.000 description 1
- HZHRYYYIOGLPCB-UHFFFAOYSA-N n,n-bis(hydroxymethyl)prop-2-enamide Chemical compound OCN(CO)C(=O)C=C HZHRYYYIOGLPCB-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- ADGJZVKOKVENDN-UHFFFAOYSA-N n-(butoxymethyl)-2-methylprop-2-enamide Chemical compound CCCCOCNC(=O)C(C)=C ADGJZVKOKVENDN-UHFFFAOYSA-N 0.000 description 1
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- YOZHLACIXDCHPV-UHFFFAOYSA-N n-(methoxymethyl)-2-methylprop-2-enamide Chemical compound COCNC(=O)C(C)=C YOZHLACIXDCHPV-UHFFFAOYSA-N 0.000 description 1
- ULYOZOPEFCQZHH-UHFFFAOYSA-N n-(methoxymethyl)prop-2-enamide Chemical compound COCNC(=O)C=C ULYOZOPEFCQZHH-UHFFFAOYSA-N 0.000 description 1
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- 239000003921 oil Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
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- 229920001451 polypropylene glycol Polymers 0.000 description 1
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- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
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- 239000010935 stainless steel Substances 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
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Landscapes
- Sealing Material Composition (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、ガソホール燃料フィルタ用接着剤、ガソホール燃料部品封止剤、ガソホール燃料部品シーリング剤、ガソホール燃料フィルタ濾紙のシール剤などに有用な一液可視光硬化型組成物に関する。 The present invention relates to a one-part visible light curable composition useful for an adhesive for gasohol fuel filters, a gasohol fuel part sealant, a gasohol fuel part sealant, a gasohol fuel filter filter paper sealant, and the like.
本発明は、アルコールをガソリンに混合した燃料であるガソホール（ｇａｓｏｈｏｌ、ｇａｓｏｌｉｎｅ、ａｌｃｏｈｏｌ）に優れた耐性を有する燃料フィルタ用接着剤、燃料部品封止剤、燃料部品シーリング剤などに有用な一液可視光硬化型組成物を提供する事に関する。 INDUSTRIAL APPLICABILITY The present invention is a one-part visible for a fuel filter adhesive, a fuel part sealant, a fuel part sealant, etc. having excellent resistance to gasohol (gasohol, gasoline, alcohol), which is a fuel in which alcohol is mixed with gasoline. The present invention relates to providing a photocurable composition.
従来からブラジルでは、サトウキビの発酵で得られるエタノールをガソリンに混合して利用し、原油依存を回避しようとする施策が行われてきた。また最近の原油高騰の影響もあり、米国においても州により混合割合は様々であるもののエタノールをガソリンに混合して使用している。この取り組みは中国やオーストラリアでも行われ、国内でも添加量は少ないがガソリンにエタノールを３％混合して使用するＥ３燃料使用の取り組みが始まるなど世界的に広がっている。メタノール添加も同様に検討されている。 Traditionally, in Brazil, measures have been taken to avoid dependence on crude oil by using ethanol obtained from sugarcane fermentation mixed with gasoline. In addition, due to the recent rise in crude oil prices, ethanol is mixed with gasoline in the United States, although the mixing ratio varies depending on the state. This effort is also being carried out in China and Australia, but it is spreading globally, such as the start of E3 fuel use in which 3% ethanol is mixed with gasoline, although there are few additions in Japan. Methanol addition is also being considered.
このような、ガソホール燃料周辺で使用される燃料フィルタ用接着剤、燃料部品封止剤、燃料部品シーリング剤には、耐ガソホール性に優れる一液や二液型の芳香族エポキシ系樹脂組成物が専ら利用されている。これは接着剤、封止剤、シーリング剤等として使用する際は常温〜中温で液状、かつ硬化後は高度の耐溶剤性を発揮する必要があるためである。 Such adhesives for fuel filters, fuel component sealants, and fuel component sealants used around gasohol fuel include one- and two-component aromatic epoxy resin compositions with excellent gasohol resistance. Used exclusively. This is because when used as an adhesive, sealant, sealing agent, etc., it must be liquid at room temperature to medium temperature and exhibit high solvent resistance after curing.
しかしながら、一液型の芳香族エポキシ系樹脂組成物は常温における貯蔵安定性が悪く製造後１ヶ月程度の間に使用するか輸送や貯蔵を低温に保つ必要がある等、利用が極めて煩雑である。二液型の芳香族エポキシ系樹脂組成物は貯蔵安定性には優れるが使用直前に主剤と硬化剤の計量、混合が必要で、使用後の塗布機器の入念な清掃等が必要であり、作業性が著しく悪い。自動で計量、混合、塗布、使用後の清掃をする機械、ディスペンサも多く利用されているが高度に信頼性が要求される自動車部品の品質を確実なものとするため計量誤差、混合不十分、塗布ムラ等を防ぐために頻繁にメンテナンスやオーバーホールを行っており、この清掃、メンテナンスに多大の時間、労力を費やしていると言う問題を抱えている。 However, the one-pack type aromatic epoxy resin composition is very complicated to use because it has poor storage stability at room temperature and needs to be used within about one month after production or transport and storage must be kept at a low temperature. . The two-pack type aromatic epoxy resin composition is excellent in storage stability, but it is necessary to weigh and mix the main agent and curing agent immediately before use, and it is necessary to carefully clean the application equipment after use. Sexually bad. Machines that automatically weigh, mix, apply, clean after use, and dispensers are also used a lot, but in order to ensure the quality of automobile parts that require high reliability, weighing errors, insufficient mixing, Maintenance and overhaul are frequently performed in order to prevent coating unevenness and the like, and there is a problem that a great deal of time and labor are spent on this cleaning and maintenance.
そのため光硬化樹脂を用い一液性でフィルタ製造に要する時間を短縮する提案もなされているが光ラジカル重合開始剤による硬化だけでは光が減衰するか、届かない深部は硬化不足となり信頼性高い耐ガソホール樹脂組成物の実現には至っていない。
解決しようとする課題は、アルコールをガソリンに混合した燃料であるガソホール燃料に対して耐性に優れる燃料フィルタ用接着剤、燃料部品封止剤、燃料部品シーリング剤などに有用な、一液性で貯蔵安定性や、深部硬化性に優れる光硬化型組成物を提供することである。 The problem to be solved is a one-component storage that is useful for adhesives for fuel filters, sealants for fuel parts, sealants for fuel parts, etc. that have excellent resistance to gasohol fuel, which is a mixture of alcohol and gasoline. It is to provide a photocurable composition that is excellent in stability and deep part curability.
請求項１の本発明は、光熱により深部硬化可能な耐ガソホール燃料性接着剤・注型硬化組成物であって、少なくとも（Ａ）（メタ）アクリロイル基を有するラジカル重合可能な化合物、（Ｂ）波長３８０〜１５００ｎｍの光を吸収することによりラジカルを発生する光重合開始剤、（Ｃ）１０時間半減期温度５０℃〜１２０℃である熱重合開始剤、とを含有することを特徴とする光硬化型組成物である。これにより、一液型であっても、光が届かない深部まで、硬化可能な耐ガソホール性にも優れる光硬化型組成物が得られる。 The present invention of claim 1 is a gasohol fuel-resistant adhesive / casting-curing composition that can be deeply cured by light heat, and comprises at least (A) a radically polymerizable compound having a (meth) acryloyl group, (B) Light comprising: a photopolymerization initiator that generates radicals by absorbing light having a wavelength of 380 to 1500 nm; and (C) a thermal polymerization initiator having a 10-hour half-life temperature of 50 ° C. to 120 ° C. It is a curable composition. Thereby, even if it is a one-pack type, the photocurable composition which is excellent also in the gasohol resistant property which can be hardened to the deep part which light does not reach is obtained.
本発明によれば、一液性であり深部硬化性に優れる光硬化型組成物が提供でき、アルコールをガソリンに混合した燃料であるガソホール燃料に対して耐性に優れる燃料フィルタ用接着剤、燃料部品封止剤、燃料部品シーリング剤などに有用な光硬化型組成物が提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the adhesive for fuel filters which can provide the photocurable composition which is one-component and is excellent in deep part sclerosis | hardenability, and is excellent in the resistance to the gasohol fuel which is the fuel which mixed alcohol with gasoline, Fuel component Photocurable compositions useful for sealants, fuel part sealants, and the like can be provided.
以下 本発明について説明する。 The present invention will be described below.
（メタ）アクリロイル基を有するラジカル重合可能な化合物としては、（メタ）アクリロイル基を一分子中に１〜６個有することが好ましく、アクリル酸またはメタクリル酸のアルキルエステルの例としてメチル（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、イソブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、イソプロピル（メタ）アクリレートなどが挙げられる。不飽和カルボン酸の例としてアクリル酸、メタクリル酸、マレイン酸、フマル酸、イタコン酸、モノアルキルイタコネート等がある。エポキシ基含有モノマーとしては、グリシジル（メタ）アクリレート、アリルグリシジルエーテル、メチルグリシジル（メタ）アクリレートを用いることができる。多官能性モノマーとしては、ジビニルベンゼン、ポリオキシエチレンジ（メタ）アクリレート、ポリオキシプロピレンジ（メタ）アクリレート、ブタンジオールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、、ジペンタエリスリトールヘキサ（メタ）アクリレート、ポリエステルポリ（メタ）アクリレート、ポリウレタンポリ（メタ）アクリレート等を用いることができる。これらの重合性不飽和基をもつ化合物は、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 The radically polymerizable compound having a (meth) acryloyl group preferably has 1 to 6 (meth) acryloyl groups in one molecule, and methyl (meth) acrylate as an example of an alkyl ester of acrylic acid or methacrylic acid. , Ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Lauryl (meth) acrylate, isopropyl (meth) acrylate, and the like. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, monoalkyl itaconate and the like. As the epoxy group-containing monomer, glycidyl (meth) acrylate, allyl glycidyl ether, or methyl glycidyl (meth) acrylate can be used. Polyfunctional monomers include divinylbenzene, polyoxyethylene di (meth) acrylate, polyoxypropylene di (meth) acrylate, butanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) ) Acrylate, dipentaerythritol hexa (meth) acrylate, polyester poly (meth) acrylate, polyurethane poly (meth) acrylate, and the like. These compounds having a polymerizable unsaturated group may be used alone or in combination of two or more.
接着剤、封止剤、シーリング剤等として当然、厚膜硬化が要求される。この点について紫外線ラジカル重合開始剤では、紫外光透過率が低く、減衰し、厚膜硬化することが不可能である事から極めて不利と言わざるを得ない。またその後の熱重合も紫外線照射による表面領域での重合硬化での発熱程度では進まず、深部硬化は期待できない。そこで波長３８０〜１５００ｎｍの光を吸収することによりラジカルを発生する光重合開始剤を使用する事により、ある程度深部領域まで重合硬化し、その光ラジカル重合の重合熱により熱重合開始剤の分解を促進し、さらにその重合熱により深部硬化を進める。最終的に最深部までの硬化が可能となり、この波長３８０〜１５００ｎｍの光を吸収することによりラジカルを発生する光重合開始剤を用いる事が本発明には欠かす事ができない。 Naturally, thick film curing is required as an adhesive, sealant, sealing agent and the like. In this regard, ultraviolet radical polymerization initiators must be extremely disadvantageous because the ultraviolet light transmittance is low, attenuates, and cannot be cured thick. Further, subsequent thermal polymerization does not proceed with the extent of heat generated by polymerization curing in the surface region due to ultraviolet irradiation, and deep curing cannot be expected. Therefore, by using a photopolymerization initiator that generates radicals by absorbing light with a wavelength of 380 to 1500 nm, it is polymerized and cured to a certain depth, and decomposition of the thermal polymerization initiator is accelerated by the polymerization heat of the photoradical polymerization. Further, deep curing is advanced by the polymerization heat. It is indispensable for the present invention to finally use a photopolymerization initiator that generates a radical by absorbing light having a wavelength of 380 to 1500 nm.
本発明における波長３８０〜１５００ｎｍの光を吸収することによりラジカルを発生する光重合開始剤は、３８０〜１５００ｎｍの領域の光エネルギ−で励起しラジカル発生するものであればいずれでも良く、例えばカンファ−キノン、ベンジル、３−ケトクマリンなどのα−ジケトン系の光開始剤を単独で使用することができる。また、これらα−ジケトン系の可視光開始剤と第１級，第２級または第３級アミンを還元剤として用いることもできる。更にα−ジケトン系の可視光開始剤に対して第１級，第２級または第３級アミンとカルボン酸の塩を還元剤として添加して用いることもできる。また、シアニン色素などのカチオン色素類の錯体とホウ素系増感剤との組合せなども挙げられる。
波長３８０〜１５００ｎｍの光を吸収することによりラジカルを発生する光重合開始剤の配合量は前記（メタ）アクリロイル基を一分子中に１〜６個有するラジカル重合可能な化合物１００重量部に対して０．０１〜１０重量部が好適である。０．０１重量部未満では本発明の特徴である可視光照射でも硬化不足となる。１０重量部を越えて添加しても重合速度は上がらず不経済となる。
The photopolymerization initiator that generates radicals by absorbing light having a wavelength of 380 to 1500 nm in the present invention may be any one that generates radicals by excitation with light energy in the region of 380 to 1500 nm. An α-diketone photoinitiator such as quinone, benzyl or 3-ketocoumarin can be used alone. These α-diketone-based visible light initiators and primary, secondary or tertiary amines can also be used as the reducing agent. Furthermore, a primary, secondary or tertiary amine and a carboxylic acid salt may be added to the α-diketone-based visible light initiator as a reducing agent. Moreover, the combination of the complex of cationic dyes, such as a cyanine dye, and a boron-type sensitizer is mentioned.
The amount of the photopolymerization initiator that generates radicals by absorbing light having a wavelength of 380 to 1500 nm is based on 100 parts by weight of the radically polymerizable compound having 1 to 6 (meth) acryloyl groups in one molecule. 0.01 to 10 parts by weight is preferred. If it is less than 0.01 part by weight, curing is insufficient even with visible light irradiation, which is a feature of the present invention. Even if it exceeds 10 parts by weight, the polymerization rate does not increase, which is uneconomical.
３８０〜１５００ｎｍの照射には、光源として、３８０〜１５００ｎｍの波長を出すものであれば特に制限なく使用でき、例えばハロゲンランプ、キセノンランプ、蛍光灯、太陽光、半導体レ−ザ−、発光ダイオ−ドなどが使用される。紫外光照射でも硬化はするが、表面領域で光が減衰し、深部では線量が不足し、重合を連鎖的に進めるまでには至らない可能性がある。よって減衰の少ない３８０〜１５００ｎｍの波長（可視光及び／又は近赤外光）が好ましい。照射条件は光硬化型組成物の厚みや組成などにより適宜選択できる。３００ｎｍ未満の高エネルギー照射を伴う光源は、浅い領域で光開始剤及び熱重合開始剤の分解を伴い本発明の効果を失わせるため、紫外域光線を高線量含まないものが、好ましい。 For irradiation of 380 to 1500 nm, any light source that emits a wavelength of 380 to 1500 nm can be used without particular limitation. For example, a halogen lamp, a xenon lamp, a fluorescent lamp, sunlight, a semiconductor laser, a light emitting diode Etc. are used. Although it is cured even by irradiation with ultraviolet light, light is attenuated in the surface region, the dose is insufficient in the deep part, and there is a possibility that polymerization does not proceed in a chain. Therefore, a wavelength of 380 to 1500 nm (visible light and / or near infrared light) with little attenuation is preferable. Irradiation conditions can be appropriately selected depending on the thickness and composition of the photocurable composition. The light source with high energy irradiation of less than 300 nm is preferably one that does not contain a high dose of ultraviolet rays in order to lose the effect of the present invention with decomposition of the photoinitiator and thermal polymerization initiator in a shallow region.
本発明における熱ラジカル重合開始剤は、１０時間の半減期温度が５０℃〜１２０℃の範囲内でラジカル発生可能なものであればいずれでも良く、例えばベンゾイルパーオキサイド（ＢＰＯ）、ジクミルパーオキサイド、メチルエチルケトンパーオキサイド、ラウロイルパーオキサイド、ビス−３，５，５−トリメチルヘキサノイルパーオキサイド、１．１−ジ−ｔ−ブチルパーオキシシクロヘキサン、ｔ−ブチルパーオキアセテート、ｔ−アミルパーオキシイソプロピルカーボネート、ｔ−ブチルパーオキシイソプロピルカーボネートやアゾビスイソブチロニトリル（ＡＩＢＮ）などが挙げられる。１０時間の半減期温度が５０℃以上、１２０℃以下であれば光重合開始剤による重合熱で分解が始まり熱重合が開始でき可視光が届かない深部であってもラジカル重合が進行し、貯蔵安定性があり、一液化が可能である。１０時間の半減期温度が１２０℃を越える熱重合開始剤では波長３８０〜１５００ｎｍの光を吸収することによりラジカルを発生する光重合開始剤による重合熱程度では分解が始まらず深部硬化はできない。
熱ラジカル重合開始剤の配合量は前記（メタ）アクリロイル基を一分子中に１〜６個有するラジカル重合可能な化合物１００重量部に対して０．０１〜１０部が好適である。０．０１未満では本発明の特徴である光重合後の熱重合による深部硬化が得られない。また１０を超えると貯蔵安定性が著しく低下する。これらの熱ラジカル重合開始剤は１種又は２種以上併用して使用する事もできる。
The thermal radical polymerization initiator in the present invention may be any as long as it can generate radicals within a 10-hour half-life temperature range of 50 ° C. to 120 ° C., for example, benzoyl peroxide (BPO), dicumyl peroxide. , Methyl ethyl ketone peroxide, lauroyl peroxide, bis-3,5,5-trimethylhexanoyl peroxide, 1.1-di-t-butylperoxycyclohexane, t-butylperoxyacetate, t-amylperoxyisopropyl carbonate , T-butylperoxyisopropyl carbonate, azobisisobutyronitrile (AIBN), and the like. If the half-life temperature for 10 hours is 50 ° C or higher and 120 ° C or lower, radical polymerization proceeds and is stored even in the deep part where the thermal polymerization can be started and visible light does not reach if the polymerization is initiated by the heat of polymerization by the photopolymerization initiator. It is stable and can be liquefied. A thermal polymerization initiator having a half-life temperature of more than 120 ° C. for 10 hours absorbs light having a wavelength of 380 to 1500 nm, and does not start to decompose and cannot be deeply cured by the polymerization heat generated by the photopolymerization initiator that generates radicals.
The amount of the thermal radical polymerization initiator is preferably 0.01 to 10 parts with respect to 100 parts by weight of the radical polymerizable compound having 1 to 6 (meth) acryloyl groups in one molecule. If it is less than 0.01, deep curing by thermal polymerization after photopolymerization, which is a feature of the present invention, cannot be obtained. On the other hand, when it exceeds 10, the storage stability is remarkably lowered. These thermal radical polymerization initiators can be used alone or in combination of two or more.
本発明の光硬化型組成物には上記以外の不飽和二重結合を有する重合性化合物も配合できる。例えば、不飽和ニトリルモノマーの例としてアクリロニトリル、メタクリロニトリル等が挙げられる。アミド基含有モノマーとしては、アクリルアミド、メタクリルアミド、Ｎ，Ｎ−メチレンビスアクリルアミド、ダイアセトンアクリルアミド、マレイン酸アミド、マレイミド等を用いることができる。メチロール基含有モノマーとしては、Ｎ−メチロールアクリルアミド、Ｎ−メチロールメタクリルアミド、ジメチロールアクリルアミド、ジメチロールメタクリルアミド等を用いることができる。アルコキシメチル基含有モノマーとしては、Ｎ−メトキシメチルアクリルアミド、Ｎ−メトキシメチルメタクリルアミド、Ｎ−ブトキシメチルアクリルアミド、Ｎ−ブトキシメチルメタクリルアミド等を用いることができる。ビニルエステルとしては、例えば、酢酸ビニル、プロピオン酸ビニル、オレフィン、例えば、ブタジエン、イソプレン、塩素含有ビニルモノマー、例えば、塩化ビニル、塩化ビニリデン、クロロプレン、その他スチレン等も用いることができる。またこの他にも波長３８０〜１５００ｎｍの光を吸収することによりラジカルを発生する光重合開始剤の促進剤として３級アミノ化合物等のアミン化合物なども配合する事ができる。更に消泡剤、レベリング剤、充填剤、揺変剤、老化防止剤等も適宜配合できる。これらは１種又は２種以上併用して使用できる。
以下実施例を挙げて本発明をさらに詳細に説明をする。
表１に実施例、比較例の評価結果を示す。
A polymerizable compound having an unsaturated double bond other than the above can also be added to the photocurable composition of the present invention. Examples of unsaturated nitrile monomers include acrylonitrile and methacrylonitrile. As the amide group-containing monomer, acrylamide, methacrylamide, N, N-methylenebisacrylamide, diacetone acrylamide, maleic acid amide, maleimide and the like can be used. As the methylol group-containing monomer, N-methylol acrylamide, N-methylol methacrylamide, dimethylol acrylamide, dimethylol methacrylamide and the like can be used. As the alkoxymethyl group-containing monomer, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-butoxymethylacrylamide, N-butoxymethylmethacrylamide and the like can be used. Examples of vinyl esters that can be used include vinyl acetate, vinyl propionate, olefins such as butadiene, isoprene, and chlorine-containing vinyl monomers such as vinyl chloride, vinylidene chloride, chloroprene, and other styrene. In addition, an amine compound such as a tertiary amino compound can also be blended as an accelerator for a photopolymerization initiator that generates radicals by absorbing light having a wavelength of 380 to 1500 nm. Furthermore, an antifoaming agent, a leveling agent, a filler, a thixotropic agent, an anti-aging agent and the like can be appropriately blended. These can be used alone or in combination of two or more.
Hereinafter, the present invention will be described in more detail with reference to examples.
Table 1 shows the evaluation results of Examples and Comparative Examples.
攪拌装置を有する５００ｍｌガラス製フラスコにＳＰ５００３（昭和高分子社（株）製、エポキシアクリレート樹脂）５０重量部、スチレン５０重量部、ＥＡ−１０２０（商品名、新中村化学（株）製、ビスフェノールＡ型エポキシアクリレート）１００重量部、ジペンタエリスリトールヘキサアクリレート（日本化薬（株）製、六官能アクリレート）１００重量部とを入れ、室温で３０分間攪拌後、光重合開始剤としてベンジル１重量部、促進剤として三級アミノ基を有するアクリルエステルＤＭ（商品名、三菱レイヨン（株）製、Ｎ，Ｎ’−ジメチルアミノエチルメタクリレート）２重量部、熱重合開始剤として１０時間の半減期温度が７３．６℃であるパーカドックスＣＨ−５０Ｌ（商品名、化薬アクゾ（株）製、ベンゾイルパーオキサイド）５重量部を添加・混合し、更に２０分攪拌混合して実施例１の組成物を得た。 In a 500 ml glass flask having a stirrer, 50 parts by weight of SP5003 (manufactured by Showa Polymer Co., Ltd., epoxy acrylate resin), 50 parts by weight of styrene, EA-1020 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., bisphenol A) Type epoxy acrylate) 100 parts by weight, dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., hexafunctional acrylate) 100 parts by weight, after stirring for 30 minutes at room temperature, 1 part by weight of benzyl as a photopolymerization initiator, Acrylic ester DM having a tertiary amino group as a promoter (trade name, manufactured by Mitsubishi Rayon Co., Ltd., N, N′-dimethylaminoethyl methacrylate) 2 parts by weight, and a half-life temperature of 10 hours as a thermal polymerization initiator is 73 Parkadox CH-50L (trade name, manufactured by Kayaku Akzo Co., Ltd., benzoyl peroxy) at 6 ° C Id) 5 parts by weight was added and mixed to obtain a composition of Example 1 was further mixed and stirred 20 minutes.
攪拌装置を有する５００ｍｌガラス製フラスコにポリセット１１２７（日立化成工業（株）製、アリル基含有不飽和ポリエステル樹脂）１００重量部、スチレン３０重量部、ＥＡ−１０２０（商品名、新中村化学（株）製ビスフェノールＡ型エポキシアクリレート）１００重量部、ジペンタエリスリトールヘキサアクリレート（日本化薬（株）製六官能アクリレート）１００重量部とを入れ、室温で３０分間攪拌後、光重合開始剤としてｄ，ｌ−カンファーキノン（東京化成（株）製）１重量部、促進剤として三級アミノ基を有するアクリルエステルＤＭ（商品名、三菱レイヨン（株）製、Ｎ，Ｎ’−ジメチルアミノエチルメタクリレート）２重量部、熱重合開始剤として１０時間の半減期温度が６６℃であるＡＩＢＮ（アゾビスイソブチロニトリル）１重量部を添加・混合し、更に２０分攪拌混合して実施例２の組成物を得た。 Polyset 1127 (manufactured by Hitachi Chemical Co., Ltd., allyl group-containing unsaturated polyester resin) 100 parts by weight, 500 parts by weight of styrene, EA-1020 (trade name, Shin-Nakamura Chemical Co., Ltd.) ) Bisphenol A type epoxy acrylate) 100 parts by weight, dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd. hexafunctional acrylate) 100 parts by weight, after stirring for 30 minutes at room temperature, d, 1 part by weight of l-camphorquinone (manufactured by Tokyo Chemical Industry Co., Ltd.), acrylic ester DM having a tertiary amino group as a promoter (trade name, N, N′-dimethylaminoethyl methacrylate, manufactured by Mitsubishi Rayon Co., Ltd.) 2 Part by weight, AIBN (azobisisobutyro) having a half-life temperature of 66 ° C. as a thermal polymerization initiator for 10 hours Tolyl) 1 part by weight was added and mixed to obtain a composition of Example 2 was further mixed and stirred 20 minutes.
攪拌装置を有する５００ｍｌガラス製フラスコにＳＰ５００３（昭和高分子（株）製、エポキシアクリレート樹脂）５０重量部、スチレン５０部、ＥＡ−１０２０（商品名、新中村化学（株）製ビスフェノールＡ型エポキシアクリレート）１００重量部、ジペンタエリスリトールヘキサアクリレート（日本化薬（株）製、六官能アクリレート）１００重量部とを入れ、室温で３０分間攪拌後、光重合開始剤としてベンジル１重量部、促進剤として三級アミノ基を有するアクリルエステルＤＥ（商品名、三菱レイヨン（株）製、Ｎ，Ｎ’−ジエチルアミノエチルメタクリレート）２重量部、熱重合開始剤として１０時間の半減期温度が７２．１℃であるパーブチルＯ（商品名、日本油脂（株）製、ｔ−ブチルパーオキシ−２−エチルヘキサノエート）１重量部を添加・混合し、更に２０分攪拌混合して実施例３の組成物を得た。 SP5003 (Showa Polymer Co., Ltd., epoxy acrylate resin) 50 parts by weight in a 500 ml glass flask having a stirrer, styrene 50 parts, EA-1020 (trade name, bisphenol A type epoxy acrylate manufactured by Shin-Nakamura Chemical Co., Ltd.) ) 100 parts by weight, 100 parts by weight of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., hexafunctional acrylate), and after stirring for 30 minutes at room temperature, 1 part by weight of benzyl as a photopolymerization initiator and as an accelerator Acrylic ester DE having a tertiary amino group (trade name, manufactured by Mitsubishi Rayon Co., Ltd., N, N′-diethylaminoethyl methacrylate) is 2 parts by weight, and a half-life temperature of 10 hours as a thermal polymerization initiator is 72.1 ° C. Perbutyl O (trade name, manufactured by NOF Corporation, t-butylperoxy-2-ethylhexanoe G) 1 part by weight was added and mixed to obtain a composition of Example 3 was further mixed and stirred 20 minutes.
攪拌装置を有する５００ｍｌガラス製フラスコにポリセット１１２７（日立化成工業（株）製、アリル基含有不飽和ポリエステル樹脂）１００重量部、スチレン３０重量部、ＥＡ−１０２０（商品名、新中村化学（株）製ビスフェノールＡ型エポキシアクリレート）１００重量部、ジペンタエリスリトールヘキサアクリレート（日本化薬（株）製六官能アクリレート）１００重量部とを入れ、室温で３０分間攪拌後、光重合開始剤としてｄ，ｌ−カンファーキノン（東京化成（株）製）１重量部、促進剤として三級アミノ基を有するアクリルエステルＤＥ（商品名、三菱レイヨン（株）製、Ｎ，Ｎ’−ジエチルアミノエチルメタクリレート）２重量部、熱重合開始剤として１０時間の半減期温度が６９．９℃であるパーヘキシルＯ（日本油脂（株）製、ｔ−ヘキシルパーオキシ−２−エチルヘキサノエート）１重量部を添加・混合し、更に２０分攪拌混合して実施例４の組成物を得た。
比較例１
Polyset 1127 (manufactured by Hitachi Chemical Co., Ltd., allyl group-containing unsaturated polyester resin) 100 parts by weight, 500 parts by weight of styrene, EA-1020 (trade name, Shin-Nakamura Chemical Co., Ltd.) ) Bisphenol A type epoxy acrylate) 100 parts by weight, dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd. hexafunctional acrylate) 100 parts by weight, after stirring for 30 minutes at room temperature, d, 1 part by weight of l-camphorquinone (manufactured by Tokyo Chemical Industry Co., Ltd.), 2 parts by weight of acrylic ester DE (trade name, manufactured by Mitsubishi Rayon Co., Ltd., N, N′-diethylaminoethyl methacrylate) having a tertiary amino group as an accelerator Perhexyl O (Japanese fats and oils) having a half-life temperature of 69.9 ° C. as a thermal polymerization initiator. Co., Ltd., t-hexylperoxy-2-ethylhexanoate) 1 part by weight was added and mixed, and further stirred and mixed for 20 minutes to obtain the composition of Example 4.
Comparative Example 1
攪拌装置を有する５００ｍｌガラス製フラスコにＳＰ５００３（昭和高分子（株）製、エポキシアクリレート樹脂）５０重量部、スチレン５０重量部、ＥＡ−１０２０（商品名、新中村化学（株）製ビスフェノールＡ型エポキシアクリレート）１００重量部、ジペンタエリスリトールヘキサアクリレート（日本化薬（株）製六官能アクリレート）１００重量部とを入れ、室温で３０分間攪拌後、光重合開始剤としてベンジル１重量部、促進剤として三級アミノ基を有するアクリルエステルＤＭ（商品名、三菱レイヨン（株）製、Ｎ，Ｎ’−ジメチルアミノエチルメタクリレート）２重量部を添加・混合し、更に２０分攪拌混合して比較例１の組成物を得た。
比較例２
SP5003 (Showa Polymer Co., Ltd., epoxy acrylate resin) 50 parts by weight in a 500 ml glass flask having a stirrer, styrene 50 parts by weight, EA-1020 (trade name, Shin Nakamura Chemical Co., Ltd. bisphenol A type epoxy) Acrylate) 100 parts by weight, dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd. hexafunctional acrylate) 100 parts by weight, after stirring at room temperature for 30 minutes, 1 part by weight of benzyl as a photopolymerization initiator, as an accelerator 2 parts by weight of an acrylic ester DM having a tertiary amino group (trade name, manufactured by Mitsubishi Rayon Co., Ltd., N, N′-dimethylaminoethyl methacrylate) was added and mixed, and the mixture was further stirred and mixed for 20 minutes. A composition was obtained.
Comparative Example 2
攪拌装置を有する５００ｍｌガラス製フラスコにポリセット１１２７（日立化成工業（株）製、アリル基含有不飽和ポリエステル樹脂）１００重量部、スチレン３０重量部、ＥＡ−１０２０（商品名、新中村化学（株）製ビスフェノールＡ型エポキシアクリレート）１００重量部、ジペンタエリスリトールヘキサアクリレート（日本化薬（株）製六官能アクリレート）１００重量部とを入れ、室温で３０分間攪拌後、熱重合開始剤としてパーカドックスＣＨ−５０Ｌ（商品名、化薬アクゾ（株）製、ベンゾイルパーオキサイド）５重量部、促進剤として三級アミノ基を有するアクリルエステルＤＭ（商品名、三菱レイヨン（株）製、Ｎ，Ｎ’−ジメチルアミノエチルメタクリレート）２重量部を添加・混合し、更に２０分攪拌混合して比較例２の組成物を得た。 Polyset 1127 (manufactured by Hitachi Chemical Co., Ltd., allyl group-containing unsaturated polyester resin) 100 parts by weight, 500 parts by weight of styrene, EA-1020 (trade name, Shin-Nakamura Chemical Co., Ltd.) ) Bisphenol A type epoxy acrylate) 100 parts by weight and 100 parts by weight of dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd. hexafunctional acrylate) were added and stirred at room temperature for 30 minutes, and then Parkadox as a thermal polymerization initiator. CH-50L (trade name, manufactured by Kayaku Akzo Co., Ltd., benzoyl peroxide) 5 parts by weight, acrylic ester DM having a tertiary amino group as a promoter (trade name, manufactured by Mitsubishi Rayon Co., Ltd., N, N ' -Dimethylaminoethyl methacrylate) 2 parts by weight are added and mixed, and further mixed by stirring for 20 minutes. It was obtained of the composition.
＜試験評価方法＞
（光硬化深さ測定）
内径１０ｍｍ、深さ１１５ｍｍのポリプロピレン製試験管に組成物を注入して満たし後、液面の５ｍｍ上から、（株）松風製ハロゲンランプグリップライトＩＩにより６７ｍＷ／ｃｍ２照度（３８０−４５０ｎｍ）で３０秒照射した。そのとき得られた硬化物を試験管から取り出し、液面からどれだけ深部硬化したかを測定した。このとき深部未硬化部はウェスで拭き取り、固化した硬化物の長さを光硬化深さとした。深さが大きいほど深部硬化良好である。なお 照明ランプ（三菱電機オスラム(株)製２５０Ｗ色温度５２００Ｋ ランプ型名ＨＱＩ−ＴＳ２５０Ｗ／Ｄメタルハライドランプ）で、上記と同じに、実施例１の配合を試験管に満たし、アルミニウムフォイルで側面遮光し、液面より１１０ｍｍ上から１３３ｍＷ／ｃｍ２で３０秒照射した結果は光硬化深さは１１５ｍｍ以上となった。
（ショアＤ硬度）
上記光硬化深さ測定の確認において得られた光硬化物の光照射面を表、その反対側を裏とし、光硬化物試験片の硬度をショアＤ硬度計（高分子計器(株)製）で測定した。光照射による重合熱と更に、それに続く熱ラジカル重合熱発生により硬化直後の硬化物の温度は高いので光照射硬化後に２３℃、５０％ＲＨの雰囲気で２時間、静置し温度が２３℃に冷却できた事を確認した後にショアＤ硬度を測定した。
（ガソホール浸せき試験）重量変化率、体積変化率
上記光硬化深さ測定の確認において得られた光硬化物を、下記に示す３種類の燃料を満たした肉厚１５ｍｍの耐圧ステンレス製容器に入れ８０℃で２００時間浸せきし、、浸せき後の重量変化率、体積変化率を測定した。３種類の燃料とはガソリン、ガソリン：メタノール＝８５：１５体積比の混合燃料であるＭ−１５、ガソリン：エタノール＝８０：２０体積比の混合燃料であるＥ−２０である。またこの際、体積変化は、ＪＩＳ Ｚ８８０７の４に従い測定した。
<Test evaluation method>
(Photocuring depth measurement)
After filling and filling the composition into a polypropylene test tube having an inner diameter of 10 mm and a depth of 115 mm, it was 67 mW / cm 2 illuminance (380-450 nm) from 5 mm above the liquid level using a Matsukaze halogen lamp grip light II. Irradiated for 30 seconds. The cured product obtained at that time was taken out from the test tube, and how deeply cured from the liquid surface was measured. At this time, the deep uncured part was wiped with waste cloth, and the length of the solidified cured product was defined as the photocured depth. The deeper the better, the deeper the depth. In addition, it is an illumination lamp (Mitsubishi Electric OSRAM Co., Ltd. 250W color temperature 5200K lamp model name HQI-TS250W / D metal halide lamp). As a result of irradiation at 133 mW / cm 2 for 30 seconds from 110 mm above the liquid surface, the photocuring depth was 115 mm or more.
(Shore D hardness)
The light irradiation surface of the photocured product obtained in the confirmation of the photocured depth measurement is the front side, and the opposite side is the back side. Measured with The temperature of the cured product immediately after curing is high due to the heat of polymerization due to light irradiation and the subsequent generation of heat of thermal radical polymerization. After confirming that cooling was possible, the Shore D hardness was measured.
(Gasohole immersion test) Rate of change in weight, rate of change in volume The photocured material obtained in the confirmation of the photocuring depth measurement is placed in a pressure resistant stainless steel container 15 mm thick and filled with the following three types of fuel. Immersion was carried out at 200 ° C. for 200 hours, and the weight change rate and volume change rate after immersion were measured. The three types of fuels are gasoline, M-15, which is a mixed fuel of gasoline: methanol = 85: 15 volume ratio, and E-20, which is a mixed fuel of gasoline: ethanol = 80: 20 volume ratio. At this time, the volume change was measured in accordance with 4 of JIS Z8807.
本発明によれば、一液性であり深部硬化性に優れる光硬化型組成物が提供できる。
例えばアルコールをガソリンに混合した燃料であるガソホール燃料に対して耐性に優れる燃料フィルタ用接着剤、燃料部品封止剤、燃料部品シーリング剤などに有用な光硬化型組成物が提供できる。
According to the present invention, it is possible to provide a photocurable composition that is one-component and excellent in deep part curability.
For example, it is possible to provide a photocurable composition useful for a fuel filter adhesive, a fuel part sealant, a fuel part sealant, and the like that has excellent resistance to gasohol fuel, which is a fuel in which alcohol is mixed with gasoline.
Claims (1)
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| JP2006087667A JP2007262194A (en) | 2006-03-28 | 2006-03-28 | Photocuring type composition |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150052177A (en) * | 2012-10-02 | 2015-05-13 | 가부시키가이샤 오토네트웍스 테크놀로지스 | (meth)acrylate composition |
| JP2017008132A (en) * | 2015-06-17 | 2017-01-12 | 株式会社東芝 | Resin composition, cured article and laminate coil for accelerator |
-
2006
- 2006-03-28 JP JP2006087667A patent/JP2007262194A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150052177A (en) * | 2012-10-02 | 2015-05-13 | 가부시키가이샤 오토네트웍스 테크놀로지스 | (meth)acrylate composition |
| KR101688342B1 (en) | 2012-10-02 | 2016-12-20 | 가부시키가이샤 오토네트웍스 테크놀로지스 | (meth)acrylate composition |
| JP2017008132A (en) * | 2015-06-17 | 2017-01-12 | 株式会社東芝 | Resin composition, cured article and laminate coil for accelerator |
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