JP6241727B2 - Urethane (meth) acrylate composition - Google Patents
Urethane (meth) acrylate composition Download PDFInfo
- Publication number
- JP6241727B2 JP6241727B2 JP2013226283A JP2013226283A JP6241727B2 JP 6241727 B2 JP6241727 B2 JP 6241727B2 JP 2013226283 A JP2013226283 A JP 2013226283A JP 2013226283 A JP2013226283 A JP 2013226283A JP 6241727 B2 JP6241727 B2 JP 6241727B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- meth
- acrylate
- urethane
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims description 57
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title claims description 31
- 239000000203 mixture Substances 0.000 title claims description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 37
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical group NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 30
- 125000001931 aliphatic group Chemical group 0.000 claims description 24
- 125000002723 alicyclic group Chemical group 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 13
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 8
- 150000005846 sugar alcohols Polymers 0.000 claims description 8
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 45
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 32
- 238000000034 method Methods 0.000 description 30
- 230000015572 biosynthetic process Effects 0.000 description 27
- 238000003786 synthesis reaction Methods 0.000 description 27
- -1 carboxymethylpentamethylene group Chemical group 0.000 description 26
- 125000006353 oxyethylene group Chemical group 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 13
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 12
- 239000005056 polyisocyanate Substances 0.000 description 12
- 229920001228 polyisocyanate Polymers 0.000 description 12
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000007664 blowing Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 8
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 8
- 238000005452 bending Methods 0.000 description 7
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 5
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 4
- 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 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 206010052428 Wound Diseases 0.000 description 3
- 208000027418 Wounds and injury Diseases 0.000 description 3
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- 229940105990 diglycerin Drugs 0.000 description 3
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- 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 2
- MYKLQMNSFPAPLZ-UHFFFAOYSA-N 2,5-dimethylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C(C)=CC1=O MYKLQMNSFPAPLZ-UHFFFAOYSA-N 0.000 description 2
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-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
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 208000032544 Cicatrix Diseases 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 2
- HEBKCHPVOIAQTA-QWWZWVQMSA-N D-arabinitol Chemical compound OC[C@@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-QWWZWVQMSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229930195725 Mannitol Natural products 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- JVWLUVNSQYXYBE-UHFFFAOYSA-N Ribitol Natural products OCC(C)C(O)C(O)CO JVWLUVNSQYXYBE-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 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
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- HEBKCHPVOIAQTA-NGQZWQHPSA-N d-xylitol Chemical compound OC[C@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-NGQZWQHPSA-N 0.000 description 2
- FLLHZLOYVPKTTJ-UHFFFAOYSA-N dibenzyl tetrasulphide Natural products C=1C=CC=CC=1CSSSSCC1=CC=CC=C1 FLLHZLOYVPKTTJ-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- FBPFZTCFMRRESA-UHFFFAOYSA-N hexane-1,2,3,4,5,6-hexol Chemical compound OCC(O)C(O)C(O)C(O)CO FBPFZTCFMRRESA-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 239000000594 mannitol Substances 0.000 description 2
- 235000010355 mannitol Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- HEBKCHPVOIAQTA-ZXFHETKHSA-N ribitol Chemical compound OC[C@H](O)[C@H](O)[C@H](O)CO HEBKCHPVOIAQTA-ZXFHETKHSA-N 0.000 description 2
- 231100000241 scar Toxicity 0.000 description 2
- 230000037387 scars Effects 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 239000000811 xylitol Substances 0.000 description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 2
- 235000010447 xylitol Nutrition 0.000 description 2
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- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- WCBPJVKVIMMEQC-UHFFFAOYSA-N 1,1-diphenyl-2-(2,4,6-trinitrophenyl)hydrazine Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1NN(C=1C=CC=CC=1)C1=CC=CC=C1 WCBPJVKVIMMEQC-UHFFFAOYSA-N 0.000 description 1
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- HSKPJQYAHCKJQC-UHFFFAOYSA-N 1-ethylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CC HSKPJQYAHCKJQC-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- QYXHDJJYVDLECA-UHFFFAOYSA-N 2,5-diphenylcyclohexa-2,5-diene-1,4-dione Chemical compound O=C1C=C(C=2C=CC=CC=2)C(=O)C=C1C1=CC=CC=C1 QYXHDJJYVDLECA-UHFFFAOYSA-N 0.000 description 1
- UHZLTTPUIQXNPO-UHFFFAOYSA-N 2,6-ditert-butyl-3-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1C(C)(C)C UHZLTTPUIQXNPO-UHFFFAOYSA-N 0.000 description 1
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- OFYFURKXMHQOGG-UHFFFAOYSA-J 2-ethylhexanoate;zirconium(4+) Chemical compound [Zr+4].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O OFYFURKXMHQOGG-UHFFFAOYSA-J 0.000 description 1
- WVRHNZGZWMKMNE-UHFFFAOYSA-N 2-hydroxy-1-[2-(2-methylpropyl)phenyl]-2-phenylethanone Chemical compound CC(C)CC1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 WVRHNZGZWMKMNE-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- NACPTFCBIGBTSJ-UHFFFAOYSA-N 2-hydroxy-2-phenyl-1-(2-propan-2-ylphenyl)ethanone Chemical compound CC(C)C1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 NACPTFCBIGBTSJ-UHFFFAOYSA-N 0.000 description 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- LUQZKEZPFQRRRK-UHFFFAOYSA-N 2-methyl-2-nitrosopropane Chemical compound CC(C)(C)N=O LUQZKEZPFQRRRK-UHFFFAOYSA-N 0.000 description 1
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- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
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- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
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- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 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
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- 230000001678 irradiating effect Effects 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
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- 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 1
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- 150000005309 metal halides Chemical class 0.000 description 1
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- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical group CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- JYIYPKOJFKMEKS-UHFFFAOYSA-N n-(2,2-dimethyl-1-phenylpropylidene)hydroxylamine Chemical compound CC(C)(C)C(=NO)C1=CC=CC=C1 JYIYPKOJFKMEKS-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 125000005628 tolylene group Chemical group 0.000 description 1
- JUYONNFUNDDKBE-UHFFFAOYSA-J tri(oct-2-enoyloxy)stannyl oct-2-enoate Chemical compound [Sn+4].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O JUYONNFUNDDKBE-UHFFFAOYSA-J 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
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- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
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- 125000006839 xylylene group Chemical group 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
本発明は、自己修復性を有し、優れた表面硬度、耐屈曲性を兼ね備えた硬化膜を形成することのできる、ウレタン（メタ）アクリレート組成物に関する。 The present invention relates to a urethane (meth) acrylate composition that has a self-healing property and can form a cured film having excellent surface hardness and bending resistance.
従来、プラスチックは、軽量で透明性、成形加工性に優れ安価であることから、種々の分野で使用されている。一方でプラスチックは、一般的に柔軟で硬度が低く、傷がつきやすいため、表面にコーティングを施す場合が多い。特に、表面を硬質化し傷がつきにくくするハードコートが一般的に普及している。ハードコートの材質は硬く、傷つきにくい特性が必要となるが、硬い材料とするほど柔軟性に乏しくなる傾向がある。 Conventionally, plastics are used in various fields because they are lightweight, transparent, excellent in moldability and inexpensive. On the other hand, plastics are generally flexible, low in hardness, and easily scratched, so that the surface is often coated. In particular, hard coats that harden the surface and are less likely to be scratched are generally prevalent. The material of the hard coat is required to be hard and not easily damaged. However, the harder the material, the lower the flexibility.
架橋密度を高め、表面硬度を高めたハードコート層を形成する手法として、例えばペンタエリスリトールトリアクリレート等の分子内に少なくとも２以上の（メタ）アクリロイル基と水酸基を有する多官能（メタ）アクリレートと、イソホロンジイソシアネート等のポリイソシアネートを反応させた多官能ウレタン（メタ）アクリレートを含有する樹脂組成物を用いる方法が知られている（特許文献１）。この方法によれば、高硬度化による耐擦傷性は達成されるものの、柔軟性は乏しく耐屈曲性が十分でないために加工性が低下するという問題がある。 As a method of forming a hard coat layer with increased crosslink density and increased surface hardness, for example, polyfunctional (meth) acrylate having at least two (meth) acryloyl groups and hydroxyl groups in the molecule such as pentaerythritol triacrylate, A method using a resin composition containing a polyfunctional urethane (meth) acrylate obtained by reacting a polyisocyanate such as isophorone diisocyanate is known (Patent Document 1). According to this method, although the scratch resistance due to the increase in hardness is achieved, there is a problem that the workability is lowered because the flexibility is poor and the bending resistance is not sufficient.
他方、塗膜に自己修復性を付与し耐擦傷性を高める技術も知られている。ここで自己修復性とは、擦過傷もしくは圧力によるへこみ傷に対して、一時的には他の平面と比べて傷として存在するが、その塗膜の弾性により経時的に傷を修復する機能のことをいう。最近では、塗膜に傷をつけないための塗膜の硬質化とともに、自己修復性による傷の回復性を付与する技術があり、ジペンタエリスリトールペンタアクリレートとヘキサメチレンジイソシアネートのイソシアヌレート変性体とのウレタンアクリレート、及びペンタエリスリトールトリアクリレートを含有する樹脂組成物を用いる方法（特許文献２）が知られている。この方法によれば塗膜は高い硬度を示すものの、傷の復元性試験では、１００℃で１０分間の加熱が行われている。傷の修復のためとはいえこのような加熱を行えば、熱に弱いプラスチック基材であれば変形を来す恐れがあることから、当該方法は、自己修復性の面で問題があると考えられる。また、１分子中に２以上のヒドロキシル基を有するポリオールと、ヘキサメチレンジイソシアネートなどのポリイソシアネートと２‐ヒドロキシエチルアクリレートを反応させたウレタン（メタ）アクリレートを用いる方法（特許文献３）も知られている。この方法では自己修復性の発現は認められるものの、硬度については満足いくものではない。また、２−ヒドロキシエチルアクリレートと、ヘキサメチレンジイソシアネートのアロファネート変性ポリイソシアネートとのウレタンアクリレートを含有する樹脂組成物を用いる方法（特許文献４）が知られている。この方法では、硬度についての検討はあるものの更なる向上が必要であり、また自己修復性を有していない。さらに、ペンタエリスリトールトリアクリレートと２−ヒドロキシエチルアクリレートと、ヘキサメチレンジイソシアネートのアロファネート変性ポリイソシアネートとのウレタンアクリレートを含有する樹脂組成物を用いる方法（特許文献５）が知られている。この方法では、硬化物の可撓性、耐擦傷性について検討されているが、硬度や自己修復性は満足いくものではない。 On the other hand, a technique for imparting self-repairing property to the coating film and improving scratch resistance is also known. Here, self-repairing is a function to repair scratches over time due to the elasticity of the coating film, which temporarily exists as scratches compared to other planes against scratches or dents caused by pressure. Say. Recently, there has been a technique to harden the coating film so as not to damage the coating film, as well as to provide scratch recovery by self-healing, and it has been found that dipentaerythritol pentaacrylate and the isocyanurate modified form of hexamethylene diisocyanate A method of using a resin composition containing urethane acrylate and pentaerythritol triacrylate (Patent Document 2) is known. According to this method, the coating film exhibits high hardness, but in the scratch resilience test, heating is performed at 100 ° C. for 10 minutes. Even if it is used to repair wounds, this method may be problematic in terms of self-healing because it may cause deformation if it is a plastic substrate that is weak against heat. It is done. Also known is a method using a polyol having two or more hydroxyl groups in one molecule and urethane (meth) acrylate obtained by reacting polyisocyanate such as hexamethylene diisocyanate and 2-hydroxyethyl acrylate (Patent Document 3). Yes. Although the self-healing property is observed by this method, the hardness is not satisfactory. Further, a method using a resin composition containing urethane acrylate of 2-hydroxyethyl acrylate and hexamethylene diisocyanate allophanate-modified polyisocyanate is known (Patent Document 4). In this method, although there is a study on hardness, further improvement is necessary, and it does not have self-healing properties. Furthermore, a method using a resin composition containing urethane acrylate of pentaerythritol triacrylate, 2-hydroxyethyl acrylate and hexamethylene diisocyanate allophanate-modified polyisocyanate is known (Patent Document 5). In this method, the flexibility and scratch resistance of the cured product have been studied, but the hardness and self-repairability are not satisfactory.
本発明が解決しようとする課題は、自己修復性と優れた硬度を有し、各種製品の表面の傷付きを防止し、かつ良好な耐屈曲性を示す硬化膜を与えることができる、ウレタン（メタ）アクリレート組成物を提供することにある。 The problem to be solved by the present invention is a urethane (which has a self-repairing property and excellent hardness, can prevent scratches on the surface of various products, and can provide a cured film exhibiting good bending resistance. It is to provide a (meth) acrylate composition.
本発明者らは、上記課題を解決するために鋭意検討した結果、特定構造のウレタン（メタ）アクリレートと特定構造の（メタ）アクリロイル基含有化合物を、特定の比率で組み合わせたウレタン（メタ）アクリレート組成物が、上記目的を達成することを見出した。
すなわち、本発明は、以下のとおりである。
［１］ 下記（Ａ）及び（Ｂ）成分を含有し、（Ａ）成分／（Ｂ）成分の質量比が４０／６０〜６０／４０である、ウレタン（メタ）アクリレート組成物。
（Ａ）下記一般式（１）で表される、アロファネート基含有ウレタン（メタ）アクリレート
As a result of intensive studies to solve the above problems, the present inventors have found that a urethane (meth) acrylate in which a urethane (meth) acrylate having a specific structure and a (meth) acryloyl group-containing compound having a specific structure are combined at a specific ratio. It has been found that the composition achieves the above objective.
That is, the present invention is as follows.
[1] A urethane (meth) acrylate composition containing the following components (A) and (B) and having a mass ratio of (A) component / (B) component of 40/60 to 60/40.
(A) Allophanate group-containing urethane (meth) acrylate represented by the following general formula (1)
（式中、Ｒ１及びＲ４は、それぞれ同一でも異なっていてもよく、水素原子又はメチル基、Ｒ２は炭素数１〜２０の２価の脂肪族、脂環式、又は芳香族炭化水素基、Ｒ３は炭素数１〜２０の脂肪族、脂環式、又は芳香族炭化水素基、Ａ１Ｏ及びＡ２Ｏは、それぞれ同一でも異なっていてもよく、炭素数２〜４のオキシアルキレン基、ｍ及びｎは、同一でも異なっていてもよく、オキシアルキレン基の繰り返し単位数を表す２〜１０の数である。）
（Ｂ）下記一般式（２）で表される、（メタ）アクリロイル基含有化合物
(In the formula, R 1 and R 4 may be the same as or different from each other; a hydrogen atom or a methyl group; R 2 is a divalent aliphatic, alicyclic, or aromatic hydrocarbon having 1 to 20 carbon atoms; Group, R 3 is an aliphatic, alicyclic, or aromatic hydrocarbon group having 1 to 20 carbon atoms, A 1 O and A 2 O may be the same or different, and an oxy having 2 to 4 carbon atoms The alkylene group, m and n may be the same or different, and are 2 to 10 numbers representing the number of repeating units of the oxyalkylene group.
(B) A (meth) acryloyl group-containing compound represented by the following general formula (2)
（式中、Ｒ５は水素原子又はメチル基、Ｘは炭素数３〜１０の脂肪族多価アルコールの水酸基を除いた残基を示し、ｓ＋ｔは脂肪族多価アルコールの水酸基の数を示す３〜６の数であり、ｓ＝３〜６、ｔ＝０又は１である。） (In the formula, R 5 represents a hydrogen atom or a methyl group, X represents a residue excluding the hydroxyl group of an aliphatic polyhydric alcohol having 3 to 10 carbon atoms, and s + t represents the number of hydroxyl groups of the aliphatic polyhydric alcohol 3 ˜6, s = 3-6, t = 0 or 1)
本発明のウレタン（メタ）アクリレート組成物を塗布して形成される硬化膜は、硬度が高いうえに自己修復性にすぐれ、傷が発生しても短時間で修復され、受傷前の表面に復元しやすい。また、耐屈曲性にも優れるため、曲面への施行にもよくなじみ、クラックの発生を来すことがない。さらに、基材への密着性がよいため、合成樹脂成形品をはじめとする各種製品の表面被覆剤として極めて有用である。 The cured film formed by applying the urethane (meth) acrylate composition of the present invention has high hardness and excellent self-healing properties. Even if a scratch occurs, it is repaired in a short time and restored to the surface before being damaged. It's easy to do. Moreover, since it is excellent also in bending resistance, it is well suited to enforcement on curved surfaces and does not cause cracks. Furthermore, since it has good adhesion to the substrate, it is extremely useful as a surface coating agent for various products including synthetic resin molded products.
以下、本発明を詳細に説明する。なお、本明細書中で記載する「（メタ）アクリレート」とは、アクリレート及び／又はメタクリレートを表す用語である。
＜（Ａ）成分：アロファネート基含有ウレタン（メタ）アクリレート＞
上記一般式（１）で表される本発明のアロファネート基含有ウレタン（メタ）アクリレートにおいて、Ｒ１及びＲ４は水素原子又はメチル基であるが、硬化速度の観点から水素原子が好ましい。これらＲ１及びＲ４はそれぞれ同一でも異なっていてもよい。Ｒ２は炭素数１〜２０の２価の脂肪族、脂環式又は芳香族炭化水素である。
脂肪族炭化水素基としては、テトラメチレン基、カルボキシメチルペンタメチレン基、ヘキサメチレン基、オクタメチレン基等が挙げられる。脂環式炭化水素基としては、メチルシクロへキシレン基、シクロヘキサンジイルビスメチレン基、下記一般式（３）で表される基等が挙げられる。
Hereinafter, the present invention will be described in detail. In addition, "(meth) acrylate" described in this specification is a term representing acrylate and / or methacrylate.
<(A) component: Allophanate group containing urethane (meth) acrylate>
In the allophanate group-containing urethane (meth) acrylate of the present invention represented by the above general formula (1), R 1 and R 4 are a hydrogen atom or a methyl group, but a hydrogen atom is preferred from the viewpoint of curing speed. R 1 and R 4 may be the same or different. R 2 is a C 1-20 divalent aliphatic, alicyclic or aromatic hydrocarbon.
Examples of the aliphatic hydrocarbon group include a tetramethylene group, a carboxymethylpentamethylene group, a hexamethylene group, and an octamethylene group. Examples of the alicyclic hydrocarbon group include a methylcyclohexylene group, a cyclohexanediyl bismethylene group, and a group represented by the following general formula (3).
芳香族炭化水素基としては、トリレン基、キシリレン基等が挙げられる。Ｒ２は自己修復性と硬度がより高い物性で両立する観点から、脂肪族又は脂環式炭化水素基が好ましく、直鎖状の脂肪族炭化水素基がより好ましい。 Examples of the aromatic hydrocarbon group include a tolylene group and a xylylene group. R 2 is preferably an aliphatic or alicyclic hydrocarbon group, more preferably a linear aliphatic hydrocarbon group from the viewpoint of achieving both self-repairing properties and higher physical properties.
Ｒ３は炭素数１〜２０の脂肪族、脂環式、又は芳香族炭化水素基である。脂肪族炭化水素基としては、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基、オクチル基、デシル基、ドデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、エイコシル基等が挙げられる。脂環式炭化水素基としては、シクロぺンチル基、シクロヘキシル基などが挙げられる。芳香族炭化水素基としては、フェニル基、ベンジル基等が挙げられる。これらの中でも、炭素数１〜１０の脂肪族炭化水素基が好ましく、炭素数２〜６の直鎖状の脂肪族炭化水素基がより好ましい。 R 3 is an aliphatic, alicyclic, or aromatic hydrocarbon group having 1 to 20 carbon atoms. Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, and an eicosyl group. Examples of the alicyclic hydrocarbon group include a cyclopentyl group and a cyclohexyl group. Examples of the aromatic hydrocarbon group include a phenyl group and a benzyl group. Among these, a C1-C10 aliphatic hydrocarbon group is preferable, and a C2-C6 linear aliphatic hydrocarbon group is more preferable.
Ａ１Ｏ及びＡ２Ｏは炭素数２〜４の直鎖又は分岐状のオキシアルキレン基であり、例えば、オキシエチレン基、オキシプロピレン基、オキシブチレン基、オキシテトラメチレン基等が挙げられる。これらの中でも、自己修復性と硬度の観点から、オキシエチレン基が好ましい。これらＡ１Ｏ及びＡ２Ｏは、それぞれ同一でも異なっていてもよい。
ｍ及びｎは、オキシアルキレン基の繰り返し単位数を表す２〜１０の数であり、３〜６の範囲であることが好ましい。これらｍ及びｎは、それぞれ同一でも異なっていてもよく、オキシアルキレン基は、それぞれ二種類以上をランダム状やブロック状に含んでいてもよい。ｍ又はｎが２未満であると傷が修復せずに傷跡が残りやすく、かつ、耐屈曲性に劣る。他方、ｍ又はｎが１０を超えると傷が修復せずに傷跡が残りやすくなる。上記の範囲であることにより、後述する一般式（２）で表される（メタ）アクリロイル基含有化合物と組合せることで良好な自己修復性、硬度、耐屈曲性を得ることができる。
A 1 O and A 2 O are linear or branched oxyalkylene groups having 2 to 4 carbon atoms, and examples thereof include an oxyethylene group, an oxypropylene group, an oxybutylene group, and an oxytetramethylene group. Among these, an oxyethylene group is preferable from the viewpoints of self-repairability and hardness. These A 1 O and A 2 O may be the same or different.
m and n are 2 to 10 numbers representing the number of repeating units of the oxyalkylene group, and preferably in the range of 3 to 6. These m and n may be the same or different, and the oxyalkylene group may contain two or more types in a random or block form. If m or n is less than 2, the scratches are not repaired and scars are likely to remain, and the flex resistance is poor. On the other hand, if m or n exceeds 10, the scratches are not repaired and scars remain easily. By being in the above range, good self-healing properties, hardness, and bending resistance can be obtained by combining with the (meth) acryloyl group-containing compound represented by the general formula (2) described later.
本発明のアロファネート基含有ウレタン（メタ）アクリレートは、具体的には、下記一般式（４）で表されるアロファネート基含有ポリイソシアネート（ａ−１）と、下記一般式（５）で表されるポリオキシアルキレンモノ（メタ）アクリレート（ａ−２）を反応させることによって得られる化合物である。 The allophanate group-containing urethane (meth) acrylate of the present invention is specifically represented by the allophanate group-containing polyisocyanate (a-1) represented by the following general formula (4) and the following general formula (5). It is a compound obtained by reacting polyoxyalkylene mono (meth) acrylate (a-2).
（式中、Ｒ２は炭素数１〜２０の２価の脂肪族、脂環式又は芳香族炭化水素基、Ｒ３は炭素数１〜２０の脂肪族、脂環式、又は芳香族炭化水素基である。） (Wherein R 2 is a divalent aliphatic, alicyclic or aromatic hydrocarbon group having 1 to 20 carbon atoms, and R 3 is an aliphatic, alicyclic or aromatic hydrocarbon group having 1 to 20 carbon atoms. Group.)
（式中、Ｒ６は上記一般式（１）におけるＲ１又はＲ４であり、水素原子又はメチル基、Ａ３Ｏは上記一般式（１）におけるＡ１Ｏ又はＡ２Ｏであり、炭素数２〜４のオキシアルキレン基、ｐは上記一般式（１）におけるｍ又はｎであり、オキシアルキレン基の繰り返し単位数を表す２〜１０の数である。） (In the formula, R 6 is R 1 or R 4 in the above general formula (1), a hydrogen atom or a methyl group, A 3 O is A 1 O or A 2 O in the above general formula (1), carbon (The oxyalkylene group of formula 2-4, p is m or n in the general formula (1), and is a number of 2-10 representing the number of repeating units of the oxyalkylene group.)
前記アロファネート基含有ポリイソシアネート（ａ−１）は、上記一般式（４）で表される化合物であれば、特に限定されない。一般的には公知の方法に従って、脂肪族、脂環式、又は芳香族炭化水素基を有するモノアルコールと、該モノアルコール中の水酸基当量に対してイソシアネート当量が過剰となる量の脂肪族、脂環式、又は芳香族ジイソシアネートを、２−エチルヘキサン酸ジルコニウム等のアロファネート化触媒の存在下でアロファネート化反応させることによって得られる化合物である。
一般に入手可能な市販品としては、例えば、上記一般式（１）におけるＲ２がヘキサメチレン基である住化バイエルウレタン（株）製「デュラネートＸＰ２５８０」、旭化成ケミカルズ（株）製「ＬＶＡ−２０９」、「ＬＶＡ−２１０」、「ＶＡ−２１１」や、Ｒ２が一般式（３）で表される脂環式炭化水素基である住化バイエルウレタン（株）製「デスモジュールＸＰ２５６５」等が挙げられる。これら（ａ−１）成分は、単独でも二種類以上併用してもよい。
The allophanate group-containing polyisocyanate (a-1) is not particularly limited as long as it is a compound represented by the general formula (4). In general, according to a known method, a monoalcohol having an aliphatic, alicyclic, or aromatic hydrocarbon group, and an amount of the aliphatic or fatty acid in which the isocyanate equivalent is excessive with respect to the hydroxyl group equivalent in the monoalcohol It is a compound obtained by subjecting a cyclic or aromatic diisocyanate to an allophanatization reaction in the presence of an allophanatization catalyst such as zirconium 2-ethylhexanoate.
As commercially available products, for example, “Duranate XP2580” manufactured by Sumika Bayer Urethane Co., Ltd., in which R 2 in the above general formula (1) is a hexamethylene group, “LVA-209” manufactured by Asahi Kasei Chemicals Corporation. , “LVA-210”, “VA-211”, “Desmodur XP2565” manufactured by Sumika Bayer Urethane Co., Ltd., in which R 2 is an alicyclic hydrocarbon group represented by the general formula (3), and the like. It is done. These components (a-1) may be used alone or in combination of two or more.
前記ポリオキシアルキレン（メタ）アクリレート（ａ−２）は、上記一般式（５）で表される化合物であれば特に限定されず、一般的には公知の方法に従って、（メタ）アクリル酸又は水酸基含有（メタ）アクリレートに、三フッ化ホウ素・ジエチルエーテル錯体等の触媒の存在下で、炭素数２〜４のアルキレンオキサイド又はテトラヒドロフランを開環重合させることによって得られる化合物である。
具体的な化合物としては、例えば、ポリオキシエチレン（平均付加モル数２〜１０）モノ（メタ）アクリレート、ポリオキシプロピレン（平均付加モル数２〜１０）モノ（メタ）アクリレート、ポリオキシブチレン（平均付加モル数２〜１０）モノ（メタ）アクリレート、ポリオキシエチレン・ポリオキシプロピレン（平均付加モル数２〜１０）モノ（メタ）アクリレート、ポリオキシエチレン・ポリオキシテトラメチレン（平均付加モル数２〜１０）モノ（メタ）アクリレート、ポリオキシプロピレン・ポリオキシテトラメチレン（平均付加モル数２〜１０）モノ（メタ）アクリレート等が挙げられる。これら（ａ−２）成分は、単独でも二種類以上を併用してもよい。
The polyoxyalkylene (meth) acrylate (a-2) is not particularly limited as long as it is a compound represented by the above general formula (5), and is generally (meth) acrylic acid or a hydroxyl group according to a known method. It is a compound obtained by ring-opening polymerization of an alkylene oxide or tetrahydrofuran having 2 to 4 carbon atoms in the presence of a catalyst such as boron trifluoride / diethyl ether complex or the like in (meth) acrylate.
Specific examples of the compound include polyoxyethylene (average addition mole number 2 to 10) mono (meth) acrylate, polyoxypropylene (average addition mole number 2 to 10) mono (meth) acrylate, polyoxybutylene (average Addition mole number 2 to 10) mono (meth) acrylate, polyoxyethylene / polyoxypropylene (average addition mole number 2 to 10) mono (meth) acrylate, polyoxyethylene / polyoxytetramethylene (average addition mole number 2 to 2) 10) Mono (meth) acrylate, polyoxypropylene / polyoxytetramethylene (average added mole number 2 to 10) mono (meth) acrylate, and the like. These components (a-2) may be used alone or in combination of two or more.
本発明のアロファネート基含有ウレタン（メタ）アクリレートは、前記アロファネート基含有ポリイソシアネート（ａ−１）と前記ポリオキシアルキレンモノ（メタ）アクリレート（ａ−２）をウレタン化反応させることによって得られる化合物である。
（ａ−１）成分と（ａ−２）成分の配合比率は、（ａ−１）成分中のイソシアネート基１当量に対して（ａ−２）成分の水酸基が通常０．１〜１０当量であり、０．５〜５当量が好ましく、０．９〜１．２当量がより好ましい。
反応温度は通常１０〜１５０℃であり、３０〜１２０℃が好ましく、４０〜８０℃がより好ましい。反応の終点はイソシアネート基を示す２２７０ｃｍ−１の赤外吸収スペクトルの消失や、ＪＩＳ Ｋ ７３０１に記載の方法でイソシアネート基の含有量を求めることで確認することができる。後者の方法では、イソシアネート化合物の含有量を算出し、反応生成物の質量の０．５質量％以下、好ましくは０．１質量％以下になった時を終了とする。
なお、前記ウレタン化反応では反応速度を促進する目的としてジブチルスズジラウレート等のスズ化合物や、トリエチルアミン等のアミンを触媒として用いてもよい。
The allophanate group-containing urethane (meth) acrylate of the present invention is a compound obtained by urethanating the allophanate group-containing polyisocyanate (a-1) and the polyoxyalkylene mono (meth) acrylate (a-2). is there.
The mixing ratio of the component (a-1) and the component (a-2) is such that the hydroxyl group of the component (a-2) is usually 0.1 to 10 equivalents with respect to 1 equivalent of the isocyanate group in the component (a-1). Yes, 0.5 to 5 equivalents are preferable, and 0.9 to 1.2 equivalents are more preferable.
The reaction temperature is usually 10 to 150 ° C, preferably 30 to 120 ° C, more preferably 40 to 80 ° C. The end point of the reaction can be confirmed by disappearance of the infrared absorption spectrum at 2270 cm −1 indicating the isocyanate group or by determining the content of the isocyanate group by the method described in JIS K 7301. In the latter method, the content of the isocyanate compound is calculated, and the process ends when the mass of the reaction product is 0.5 mass% or less, preferably 0.1 mass% or less.
In the urethanization reaction, a tin compound such as dibutyltin dilaurate or an amine such as triethylamine may be used as a catalyst for the purpose of accelerating the reaction rate.
ウレタン化反応は、触媒、重合禁止剤の存在下で行われる。ウレタン化触媒は、ナフテン酸コバルト、ナフテン酸亜鉛、塩化第一スズ、塩化第二スズ、テトラ−ｎ−ブチルスズ、トリ−ｎ−ブチルスズアセテート、ｎ−ブチルスズトリクロライド、トリメチルスズハイドロオキシド、ジメチルスズジクロライド、ジブチルスズアセテート、ジブチルスズジラウレート、ジブチルスズジエチルヘキソエート、ジブチルスズサルファイト、オクテン酸スズ等が挙げられる。これらの触媒を使用する場合、原料の総質量に対し１０〜１０００ｐｐｍとなる範囲で使用するのが好ましい。 The urethanization reaction is performed in the presence of a catalyst and a polymerization inhibitor. Urethane catalyst is cobalt naphthenate, zinc naphthenate, stannous chloride, stannic chloride, tetra-n-butyltin, tri-n-butyltin acetate, n-butyltin trichloride, trimethyltin hydroxide, dimethyltin dichloride , Dibutyltin acetate, dibutyltin dilaurate, dibutyltin diethylhexoate, dibutyltin sulfite, tin octenoate and the like. When using these catalysts, it is preferable to use in the range used as 10-1000 ppm with respect to the total mass of a raw material.
重合禁止剤の例としては、ヒドロキノン、ヒドロキノンモノメチルエーテル、モノ−ｔｅｒｔ−ブチルヒドロキノン、カテコール、ｐ−ｔｅｒｔ−ブチルカテコール、２，６−ジ−ｔｅｒｔ−ブチル−ｍ−クレゾール、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール、ピロガロール、β−ナフトール等のフェノール類、ベンゾキノン、２，５−ジフェニル−ｐ−ベンゾキノン、ｐ−トルキノン、ｐ−キシロキノン等のキノン類；ニトロベンゼン、ｍ−ジニトロベンゼン、２−メチル−２−ニトロソプロパン、α−フェニル−ｔｅｒｔ−ブチルニトロン、５，５−ジメチル−１−ピロリン−１−オキシド等のニトロ化合物又はニトロソ化合物；クロラニル−アミン、ジフェニルアミン、ジフェニルピクリルヒドラジン、フェノール−α−ナフチルアミン、ピリジン、フェノチアジン等のアミン類；ジチオベンゾイルスルフィド、ジベンジルテトラスルフィド等のスルフィド類等が挙げられる。これらの重合禁止剤は、一種のみを用いてもよく、また、二種以上を混合して用いてもよい。
重合禁止剤の使用量は、原料の総質量に対して、１０〜１００００ｐｐｍ（質量基準）が好ましく、より好ましくは１００〜１０００ｐｐｍである。
ウレタン化反応における反応温度は２０〜９０℃が好ましく、反応時間は１〜３０時間が好ましい。
また、ウレタン化反応において有機溶剤を使用しても良い。有機溶剤の例としては、トルエン、キシレン等の芳香族炭化水素系溶剤；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤；酢酸エチル、酢酸プロピル、酢酸イソブチル、酢酸ブチル等のエステル系溶剤が挙げられる。
Examples of polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, mono-tert-butylhydroquinone, catechol, p-tert-butylcatechol, 2,6-di-tert-butyl-m-cresol, 2,6-di- Phenols such as tert-butyl-4-methylphenol, pyrogallol, β-naphthol, quinones such as benzoquinone, 2,5-diphenyl-p-benzoquinone, p-toluquinone, p-xyloquinone; nitrobenzene, m-dinitrobenzene, Nitro compounds or nitroso compounds such as 2-methyl-2-nitrosopropane, α-phenyl-tert-butylnitrone, 5,5-dimethyl-1-pyrroline-1-oxide; chloranil-amine, diphenylamine, diphenylpicrylhydrazine, Phenol-α- Fuchiruamin, pyridine, amines such as phenothiazine; dithio benzoylsulfamoyl sulfide, sulfides such as dibenzyl tetrasulfide and the like. These polymerization inhibitors may be used alone or in combination of two or more.
As for the usage-amount of a polymerization inhibitor, 10-10000 ppm (mass reference | standard) is preferable with respect to the total mass of a raw material, More preferably, it is 100-1000 ppm.
The reaction temperature in the urethanization reaction is preferably 20 to 90 ° C., and the reaction time is preferably 1 to 30 hours.
Further, an organic solvent may be used in the urethanization reaction. Examples of organic solvents include aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as ethyl acetate, propyl acetate, isobutyl acetate, and butyl acetate Is mentioned.
＜（Ｂ）成分：（メタ）アクリロイル基含有化合物＞
本発明に用いる（メタ）アクリロイル基含有化合物（（Ｂ）成分）は前記一般式（２）で表され、該式において、Ｒ５は水素原子又はメチル基である。
Ｘは炭素数３〜１０の脂肪族多価アルコールの水酸基を除いた残基を示し、ｓ＋ｔは脂肪族多価アルコールの水酸基の数を示し３〜６の数である。脂肪族多価アルコールとして、グリセリン、ジグリセリン、トリグリセリン、トリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、またアラビトール、キシリトール、リビトールなどのペンチトール、ソルビトール、マンニトールなどのヘキシトールなどであり、好ましくはトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトールである。
（メタ）アクリロイル基の数を表すｓは３〜６の範囲、好ましくは４〜６の数であり、（メタ）アクリル酸とエステル結合を形成していない水酸基の数を表すｔは０又は１であり、この範囲にある（メタ）アクリロイル基含有化合物を用いることで硬化物の架橋密度が高くなり、得られる硬化膜の強度が向上するとともに、硬化膜の自己修復性を両立することが可能となる。
<(B) component: (meth) acryloyl group-containing compound>
The (meth) acryloyl group-containing compound (component (B)) used in the present invention is represented by the general formula (2), in which R 5 is a hydrogen atom or a methyl group.
X represents a residue excluding the hydroxyl group of the aliphatic polyhydric alcohol having 3 to 10 carbon atoms, and s + t represents the number of the hydroxyl group of the aliphatic polyhydric alcohol, which is a number of 3 to 6. Examples of aliphatic polyhydric alcohols include glycerin, diglycerin, triglycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, pentitol such as arabitol, xylitol, ribitol, hexitol such as sorbitol, mannitol, etc. Of these, trimethylolpropane, pentaerythritol and dipentaerythritol are preferable.
S representing the number of (meth) acryloyl groups is in the range of 3 to 6, preferably 4 to 6, and t representing the number of hydroxyl groups not forming an ester bond with (meth) acrylic acid is 0 or 1. By using a (meth) acryloyl group-containing compound in this range, it is possible to increase the crosslink density of the cured product, improve the strength of the resulting cured film, and achieve both self-healing properties of the cured film. It becomes.
（メタ）アクリロイル基含有化合物として、グリセリントリ（メタ）アクリレート、ジグリセリントリ（メタ）アクリレート、ジグリセリンテトラ（メタ）アクリレート、トリグリセリンテトラ（メタ）アクリレート、トリグリセリンペンタ（メタ）アクリレート、トリメチロールエタントリ（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、ジトリメチロールプロパンテトラ（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、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ペンタ（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、アラビトール、キシリトール、及びリビトールなどのペンチトールのテトラアクリレート又はペンタアクリレート、ソルビトールやマンニトールなどのヘキシトールのペンタアクリレート又はヘキサアクリレートなどが挙げられる。これらは単独で用いてもよいし、又は２種以上を組み合わせてもよい。その中でも、優れた硬度の観点から、トリメチロールプロパントリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールヘキサアクリレートのうちの、１種又は２種以上が好ましく用いられる。 As a (meth) acryloyl group-containing compound, glycerin tri (meth) acrylate, diglycerin tri (meth) acrylate, diglycerin tetra (meth) acrylate, triglycerin tetra (meth) acrylate, triglycerin penta (meth) acrylate, trimethylol Ethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Tetraacrylate or pen of pentitol such as dipentaerythritol hexa (meth) acrylate, arabitol, xylitol, and ribitol Acrylate, etc. pentaacrylate or hexaacrylate hexitol such as sorbitol or mannitol. These may be used alone or in combination of two or more. Among these, from the viewpoint of excellent hardness, one or more of trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate are preferably used.
＜ウレタン（メタ）アクリレート組成物＞
本発明のウレタン（メタ）アクリレート組成物は、前記の（Ａ）成分：アロファネート基含有ウレタン（メタ）アクリレートと、（Ｂ）成分：（メタ）アクリロイル基含有化合物を含有する組成物である。
（Ａ）成分と（Ｂ）成分の比率は、（Ａ）成分／（Ｂ）成分の質量比が４０／６０〜６０／４０であり、４５／５５〜５５／４５が好ましい。この比率にあるウレタン（メタ）アクリレート組成物は、自己修復性、硬度、耐屈曲性に優れた硬化塗膜を得ることができる。
本発明のウレタン（メタ）アクリレート組成物は、各種重合開始剤を配合して重合性ウレタン（メタ）アクリレート組成物とすることができる。
<Urethane (meth) acrylate composition>
The urethane (meth) acrylate composition of this invention is a composition containing said (A) component: Allophanate group containing urethane (meth) acrylate and (B) component: (meth) acryloyl group containing compound.
As for the ratio of the component (A) to the component (B), the mass ratio of the component (A) / the component (B) is 40/60 to 60/40, and preferably 45/55 to 55/45. The urethane (meth) acrylate composition in this ratio can provide a cured coating film excellent in self-restoring property, hardness, and bending resistance.
The urethane (meth) acrylate composition of the present invention can be made into a polymerizable urethane (meth) acrylate composition by blending various polymerization initiators.
重合開始剤としては、例えば光硬化を目的とした場合は、光重合開始剤が配合される。光重合開始剤の例としては、イソプロピルベンゾインエーテル、イソブチルベンゾインエーテル、ベンゾフェノン、ミヒラーケトン、ｏ−ベンゾイルメチルベンゾエート、アセトフェノン、２，４−ジエチルチオキサントン、２−クロロチオキサントン、エチルアントラキノン、ｐ−ジメチルアミノ安息香酸イソアミルエステル、ｐ−ジメチルアミノ安息香酸エチルエステル、１−ヒドロキシシクロヘキシルフェニルケトン（例えば、ＢＡＳＦ社製のイルガキュア１８４）、２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オン（例えば、ＢＡＳＦ社製のダロキュア１１７３）、２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン（例えば、ＢＡＳＦ社製のイルガキュア６５１）、２−ベンジル−２−ジメチルアミノ−１（４−モルフォリノフェニル）−ブタノン−１、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シド、メチルベンジルホルメートなどがある。
本発明のウレタン（メタ）アクリレート組成物には、上記の他にも、本発明の効果を損なわない範囲で、必要に応じて、有機溶剤やレベリング剤、紫外線吸収剤、光安定剤、消泡剤、シランカップリング剤、酸化防止剤、着色剤などを適宜配合することができる。
As the polymerization initiator, for example, for the purpose of photocuring, a photopolymerization initiator is blended. Examples of photopolymerization initiators include isopropyl benzoin ether, isobutyl benzoin ether, benzophenone, Michler ketone, o-benzoylmethyl benzoate, acetophenone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, ethylanthraquinone, p-dimethylaminobenzoic acid Isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, 1-hydroxycyclohexyl phenyl ketone (for example, Irgacure 184 manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (for example, BASF) Darocur 1173), 2,2-dimethoxy-1,2-diphenylethane-1-one (for example, Irgacure 651 manufactured by BASF), 2-benzyl-2-dimethylamino- (4-morpholinophenyl) - butanone-1, bis (2,4,6-trimethylbenzoyl) - phenyl phosphine oxide, and the like methylbenzyl formate.
In the urethane (meth) acrylate composition of the present invention, in addition to the above, an organic solvent, a leveling agent, an ultraviolet absorber, a light stabilizer, an antifoam, as long as the effects of the present invention are not impaired. An agent, a silane coupling agent, an antioxidant, a colorant and the like can be appropriately blended.
本発明のウレタン（メタ）アクリレート組成物は、（Ａ）成分、（Ｂ）成分、及び必要に応じて重合開始剤のほか、種々の添加剤を加え、常法により均一に混合することによって得られる。
本発明のウレタン（メタ）アクリレート組成物を基材へ塗工する方法は、公知の方法で行うことができ、ディッピングコート、スプレーコート、フローコート、シャワーコート、ロールコート、スピンコート、刷毛塗りなどが挙げられる。これらコーティングにおける塗膜の厚さは、硬化後、通常０．１〜４００μｍであり、好ましくは、１〜２００μｍである。
本発明のウレタン（メタ）アクリレート組成物は、熱線、紫外線、赤外線、可視光線、Ｘ線、放射線、電子線などの活性エネルギー線を照射することにより、架橋し、硬化膜を形成させることができる。特に光硬化では高圧水銀ランプ、メタルハライドランプ等が使用することができ、照射する雰囲気は、空気中でもよいし、窒素、アルゴンなどの不活性ガス中でもよい。
The urethane (meth) acrylate composition of the present invention is obtained by adding various additives in addition to the (A) component, the (B) component, and, if necessary, a polymerization initiator, and mixing them uniformly by a conventional method. It is done.
The method of applying the urethane (meth) acrylate composition of the present invention to a substrate can be performed by a known method, such as dipping coating, spray coating, flow coating, shower coating, roll coating, spin coating, brush coating, etc. Is mentioned. The thickness of the coating film in these coatings is usually 0.1 to 400 μm, preferably 1 to 200 μm after curing.
The urethane (meth) acrylate composition of the present invention can be crosslinked to form a cured film by irradiation with active energy rays such as heat rays, ultraviolet rays, infrared rays, visible rays, X-rays, radiations, and electron beams. . In particular, a high-pressure mercury lamp, a metal halide lamp, or the like can be used for photocuring, and the irradiation atmosphere may be air or an inert gas such as nitrogen or argon.
本発明のウレタン（メタ）アクリレート組成物は、塗料、コーティング剤等として使用される。携帯電話筐体、パソコン筐体、オーディオ機器やＯＡ機器等のプラスチック製品、タッチパネル、液晶画面等の電子材料部品、冷蔵庫、掃除機、電子レンジ等の家電製品、階段、床、机、椅子、ダンス、その他の家具等の木工製品、自動車の内外装、サングラスや矯正用メガネレンズ等の光学レンズの保護層等、表面の傷防止が求められる用途に好適に用いることができる。 The urethane (meth) acrylate composition of the present invention is used as a paint, a coating agent or the like. Mobile phone housing, personal computer housing, plastic products such as audio equipment and OA equipment, electronic material parts such as touch panels and liquid crystal screens, home appliances such as refrigerators, vacuum cleaners, microwave ovens, stairs, floors, desks, chairs, dance Further, it can be suitably used for applications requiring prevention of scratches on the surface, such as other woodwork products such as furniture, interior and exterior of automobiles, protective layers for optical lenses such as sunglasses and glasses for correction.
以下、実施例及び比較例を挙げて、前記実施形態を更に具体的に説明するが、本発明はこれに限定されるものではない。
＜合成例１＞
［アロファネート基含有ウレタンアクリレート（Ａ−１）の合成］
撹拌装置、空気導入管、温度計を備えた四つ口フラスコに、（ａ−１）成分として、アロファネート基含有ポリイソシアネート（デスモジュールＸＰ２５８０、住化バイエルウレタン（株）製、イソシアネート基含有率２０．０％、以下、「ＸＰ２５８０」という。一般式（４）で表されるアロファネート基含有ポリイソシアネート（ａ−１）においてＲ２がヘキサキサメチレン基、Ｒ３がブチル基である化合物）４３部、（ａ−２）成分としてポリオキシエチレンモノアクリレート（オキシエチレン基の繰り返し単位数４．５、水酸基価２０２ｍｇＫＯＨ／ｇ、以下、「ＰＥＧ２００ＭＡ」という。）５７部、ジブチルスズジラウレート（以下、「ＤＢＴＤＬ」という。）０．０２部、ハイドロキノンモノメチルエーテル（以下、「ＭＥＨＱ」という。）０．０４部を投入した。なお、この時のイソシアネート基／水酸基の当量比は１．０である。
次に、空気を吹き込みながら内温を６０℃に保持して５時間反応させた後、ＪＩＳ Ｋ ７３０１の方法で、イソシアネート基含有率が０．１％以下となり、イソシアネート基が水酸基とほぼ全て反応してウレタン結合が形成されたことを確認して、アロファネート基含有ウレタンアクリレート（Ａ−１）を１００部得た。
得られたウレタンアクリレート（Ａ−１）は、一般式（１）においてＲ１及びＲ４が水素原子、Ｒ２がヘキサメチレン基、Ｒ３がブチル基、Ａ１Ｏ及びＡ２Ｏがオキシエチレン基、並びにｍ及びｎが４．５である化合物であり、２５℃における粘度は下表１に示す通り１０Ｐａ・ｓ、ゲルパーミエーションクロマトグラフィーで測定した数平均分子量（標準ポリエチレングリコール換算）は１０００であった。
Hereinafter, although the embodiment will be described more specifically with reference to examples and comparative examples, the present invention is not limited thereto.
<Synthesis Example 1>
[Synthesis of Allophanate Group-Containing Urethane Acrylate (A-1)]
In a four-necked flask equipped with a stirrer, an air introduction tube, and a thermometer, as component (a-1), an allophanate group-containing polyisocyanate (Desmodur XP2580, manufactured by Sumika Bayer Urethane Co., Ltd., isocyanate group content 20 0.0%, hereinafter referred to as “XP2580.” Compound in which R 2 is a hexaxamethylene group and R 3 is a butyl group in the allophanate group-containing polyisocyanate (a-1) represented by the general formula (4)) 43 parts As component (a-2), polyoxyethylene monoacrylate (number of repeating units of oxyethylene group 4.5, hydroxyl value 202 mgKOH / g, hereinafter referred to as “PEG200MA”) 57 parts, dibutyltin dilaurate (hereinafter referred to as “DBTDL”) 0.02 part, hydroquinone monomethyl ether (hereinafter referred to as “ME”) Q "that.) Was charged with 0.04 parts. At this time, the equivalent ratio of isocyanate group / hydroxyl group is 1.0.
Next, after reacting for 5 hours while blowing the air while maintaining the internal temperature at 60 ° C., the isocyanate group content becomes 0.1% or less by the method of JIS K 7301, and the isocyanate groups are almost completely reacted with the hydroxyl groups. As a result, 100 parts of allophanate group-containing urethane acrylate (A-1) was obtained.
The obtained urethane acrylate (A-1) has the following general formula (1): R 1 and R 4 are hydrogen atoms, R 2 is a hexamethylene group, R 3 is a butyl group, and A 1 O and A 2 O are oxyethylene. Group and m and n are 4.5 compounds, the viscosity at 25 ° C. is 10 Pa · s as shown in Table 1 below, and the number average molecular weight (converted to standard polyethylene glycol) measured by gel permeation chromatography is 1000 Met.
＜合成例２＞
［アロファネート基含有ウレタンアクリレート（Ａ−２）の合成］
撹拌装置、空気導入管、温度計を備えた四つ口フラスコに、（ａ−１）成分として、合成例１で使用したＸＰ２５８０を３７部、（ａ−２）成分としてポリオキシエチレンモノアクリレート（オキシエチレン基の繰り返し単位数６、水酸基価１６５ｍｇＫＯＨ／ｇ、以下、「ＰＥＧ２６０ＭＡ」という。）を６３部、ＤＢＴＤＬを０．０２部、ＭＥＨＱを０．０４部投入した。なお、この時のイソシアネート基／水酸基の当量比は１．０である。
次に、空気を吹き込みながら内温を６０℃に保持して５時間反応させた後、ＪＩＳ Ｋ ７３０１の方法で、イソシアネート基含有率が０．１％以下となり、イソシアネート基が水酸基とほぼ全て反応してウレタン結合が形成されたことを確認して、アロファネート基含有ウレタンアクリレート（Ａ−２）を１００部得た。
得られたウレタンアクリレート（Ａ−２）は、一般式（１）においてＲ１及びＲ４が水素原子、Ｒ２がヘキサメチレン基、Ｒ３ブチル基、Ａ１Ｏ及びＡ２Ｏがオキシエチレン基、並びにｍ及びｎが６である化合物であり、２５℃における粘度は下表１に示す通り９Ｐａ・ｓ、ゲルパーミエーションクロマトグラフィーで測定した数平均分子量は１４００であった。
<Synthesis Example 2>
[Synthesis of Allophanate Group-Containing Urethane Acrylate (A-2)]
In a four-necked flask equipped with a stirrer, an air introduction pipe, and a thermometer, 37 parts of XP2580 used in Synthesis Example 1 as component (a-1) and polyoxyethylene monoacrylate (a-2) as component (a-2) 63 parts of oxyethylene group repeating unit, hydroxyl value of 165 mgKOH / g, hereinafter referred to as “PEG260MA”), 0.02 part of DBTDL, and 0.04 part of MEHQ were added. At this time, the equivalent ratio of isocyanate group / hydroxyl group is 1.0.
Next, after reacting for 5 hours while blowing the air while maintaining the internal temperature at 60 ° C., the isocyanate group content becomes 0.1% or less by the method of JIS K 7301, and the isocyanate groups are almost completely reacted with the hydroxyl groups. As a result, 100 parts of allophanate group-containing urethane acrylate (A-2) was obtained.
In the obtained urethane acrylate (A-2), R 1 and R 4 are hydrogen atoms, R 2 is a hexamethylene group, R 3 butyl group, A 1 O and A 2 O are oxyethylene groups in the general formula (1). And the viscosity at 25 ° C. was 9 Pa · s as shown in Table 1 below, and the number average molecular weight measured by gel permeation chromatography was 1400.
＜合成例３＞
［アロファネート基含有ウレタンアクリレート（Ａ−３）の合成］
撹拌装置、空気導入管、温度計を備えた四つ口フラスコに、（ａ−１）成分として、合成例１で使用したＸＰ２５８０を５４部、（ａ−２）成分としてポリオキシエチレンモノアクリレート（オキシエチレン基の繰り返し単位数２、水酸基価３２６ｍｇＫＯＨ／ｇ、以下、「ＰＥＧ９０ＭＡ」という。）を４６部、ＤＢＴＤＬを０．０２部、ＭＥＨＱを０．０４部投入した。なお、この時のイソシアネート基／水酸基の当量比は１．０である。
次に、空気を吹き込みながら内温を６０℃に保持して５時間反応させた後、ＪＩＳ Ｋ ７３０１の方法で、イソシアネート基含有率が０．１％以下となり、イソシアネート基が水酸基とほぼ全て反応してウレタン結合が形成されたことを確認して、アロファネート基含有ウレタンアクリレート（Ａ−３）を１００部得た。
得られたウレタンアクリレート（Ａ−３）は、一般式（１）においてＲ１及びＲ４が水素原子、Ｒ２がヘキサメチレン基、Ｒ３がブチル基、Ａ１Ｏ及びＡ２Ｏがオキシエチレン基、並びにｍ及びｎが２である化合物であり、２５℃における粘度は下表１に示す通り１２Ｐａ・ｓ、ゲルパーミエーションクロマトグラフィーで測定した数平均分子量は８００であった。
<Synthesis Example 3>
[Synthesis of Allophanate Group-Containing Urethane Acrylate (A-3)]
In a four-necked flask equipped with a stirrer, an air introduction tube, and a thermometer, 54 parts of XP2580 used in Synthesis Example 1 as component (a-1) and polyoxyethylene monoacrylate (a-2) as component (a-2) 46 parts of oxyethylene group repeating unit number 2, hydroxyl value 326 mgKOH / g, hereinafter referred to as “PEG90MA”), 0.02 part of DBTDL, and 0.04 part of MEHQ were added. At this time, the equivalent ratio of isocyanate group / hydroxyl group is 1.0.
Next, after reacting for 5 hours while blowing the air while maintaining the internal temperature at 60 ° C., the isocyanate group content becomes 0.1% or less by the method of JIS K 7301, and the isocyanate groups are almost completely reacted with the hydroxyl groups. As a result, 100 parts of allophanate group-containing urethane acrylate (A-3) was obtained.
In the obtained urethane acrylate (A-3), in general formula (1), R 1 and R 4 are hydrogen atoms, R 2 is a hexamethylene group, R 3 is a butyl group, and A 1 O and A 2 O are oxyethylene. The group was a compound having m and n of 2, the viscosity at 25 ° C. was 12 Pa · s as shown in Table 1 below, and the number average molecular weight measured by gel permeation chromatography was 800.
＜合成例４＞
［アロファネート基含有ウレタンアクリレート（Ａ−４）の合成］
撹拌装置、空気導入管、温度計を備えた四つ口フラスコに、（ａ−１）成分として、合成例１で使用したＸＰ２５８０を３３部、（ａ−２）成分としてポリオキシエチレンモノアクリレート（オキシエチレン基の繰り返し単位数８、水酸基価１２９ｍｇＫＯＨ／ｇ、以下、「ＰＥＧ３６０ＭＡ」という。）を６７部、ＤＢＴＤＬを０．０２部、ＭＥＨＱを０．０４部投入した。なお、この時のイソシアネート基／水酸基の当量比は１．０である。
次に、空気を吹き込みながら内温を６０℃に保持して５時間反応させた後、ＪＩＳ Ｋ ７３０１の方法で、イソシアネート基含有率が０．１％以下となり、イソシアネート基が水酸基とほぼ全て反応してウレタン結合が形成されたことを確認して、アロファネート基含有ウレタンアクリレート（Ａ−４）を１００部得た。
得られたウレタンアクリレート（Ａ−４）は、一般式（１）においてＲ１及びＲ４が水素原子、Ｒ２がヘキサメチレン基、Ｒ３がブチル基、Ａ１Ｏ及びＡ２Ｏがオキシエチレン基、並びにｍ及びｎが８である化合物であり、２５℃における粘度は下表１に示す通り７Ｐａ・ｓ、ゲルパーミエーションクロマトグラフィーで測定した数平均分子量は１８００であった。
<Synthesis Example 4>
[Synthesis of Allophanate Group-Containing Urethane Acrylate (A-4)]
In a four-necked flask equipped with a stirrer, an air introduction tube, and a thermometer, 33 parts of XP2580 used in Synthesis Example 1 as component (a-1) and polyoxyethylene monoacrylate (a-2) as component (a-2) The number of oxyethylene group repeating units was 8, the hydroxyl value was 129 mgKOH / g, hereinafter referred to as “PEG360MA”), 67 parts, DBTDL was 0.02 part, and MEHQ was 0.04 part. At this time, the equivalent ratio of isocyanate group / hydroxyl group is 1.0.
Next, after reacting for 5 hours while blowing the air while maintaining the internal temperature at 60 ° C., the isocyanate group content becomes 0.1% or less by the method of JIS K 7301, and the isocyanate groups are almost completely reacted with the hydroxyl groups. As a result, 100 parts of allophanate group-containing urethane acrylate (A-4) was obtained.
In the obtained urethane acrylate (A-4), in general formula (1), R 1 and R 4 are hydrogen atoms, R 2 is a hexamethylene group, R 3 is a butyl group, A 1 O and A 2 O are oxyethylene. The group was a compound having m and n of 8, the viscosity at 25 ° C. was 7 Pa · s as shown in Table 1 below, and the number average molecular weight measured by gel permeation chromatography was 1800.
＜合成例５＞
［アロファネート基含有ウレタンアクリレート（Ａ−５）の合成］
撹拌装置、空気導入管、温度計を備えた四つ口フラスコに、（ａ−１）成分として、アロファネート基含有ポリイソシアネート（デスモジュールＸＰ２５６５、住化バイエルウレタン（株）製、イソシアネート基含有率１２．０％、以下、「ＸＰ２５６５」という。一般式（４）で表されるアロファネート基含有ポリイソシアネート（ａ−１）においてＲ２が一般式（３）で表される脂環式炭化水素基、Ｒ３がブチル基である化合物）５０部、（ａ−２）成分としてＰＥＧ２６０ＭＡを５０部、ＤＢＴＤＬを０．０２部、ＭＥＨＱを０．０４部投入した。なお、この時のイソシアネート基／水酸基の当量比は１．０である。
次に、空気を吹き込みながら内温を６０℃に保持して５時間反応させた後、ＪＩＳ Ｋ ７３０１の方法で、イソシアネート基含有率が０．１％以下となり、イソシアネート基が水酸基とほぼ全て反応してウレタン結合が形成されたことを確認して、アロファネート基含有ウレタンアクリレート（Ａ−５）を１００部得た。
得られたウレタンアクリレート（Ａ−５）は、一般式（１）においてＲ１及びＲ４が水素原子、Ｒ２が一般式（３）で表される脂環式炭化水素基、Ｒ３がブチル基、Ａ１Ｏ及びＡ２Ｏがオキシエチレン基、並びにｍ及びｎが６である化合物であり、２５℃における粘度は下表１に示す通り５０Ｐａ・ｓ、ゲルパーミエーションクロマトグラフィーで測定した数平均分子量は１３００であった。
<Synthesis Example 5>
[Synthesis of Allophanate Group-Containing Urethane Acrylate (A-5)]
In a four-necked flask equipped with a stirrer, an air introduction tube, and a thermometer, as component (a-1), an allophanate group-containing polyisocyanate (Desmodur XP2565, manufactured by Sumika Bayer Urethane Co., Ltd., isocyanate group content 12 0.0%, hereinafter referred to as “XP2565.” In the allophanate group-containing polyisocyanate (a-1) represented by the general formula (4), R 2 is an alicyclic hydrocarbon group represented by the general formula (3), 50 parts of a compound in which R 3 is a butyl group), 50 parts of PEG260MA, 0.02 part of DBTDL, and 0.04 part of MEHQ were added as the component (a-2). At this time, the equivalent ratio of isocyanate group / hydroxyl group is 1.0.
Next, after reacting for 5 hours while blowing the air while maintaining the internal temperature at 60 ° C., the isocyanate group content becomes 0.1% or less by the method of JIS K 7301, and the isocyanate groups are almost completely reacted with the hydroxyl groups. Then, 100 parts of allophanate group-containing urethane acrylate (A-5) was obtained after confirming that a urethane bond was formed.
In the obtained urethane acrylate (A-5), R 1 and R 4 in the general formula (1) are hydrogen atoms, R 2 is an alicyclic hydrocarbon group represented by the general formula (3), and R 3 is butyl. Group, A 1 O and A 2 O are oxyethylene groups, and m and n are 6 compounds, and the viscosity at 25 ° C. is 50 Pa · s, as measured by gel permeation chromatography, as shown in Table 1 below. The average molecular weight was 1300.
＜合成例６＞
［アロファネート基含有ウレタンアクリレート（Ａ−６）の合成］
撹拌装置、空気導入管、温度計を備えた四つ口フラスコに、（ａ−１）成分として、合成例５で使用したＸＰ２５６５を４３部、（ａ−２）成分としてＰＥＧ３６０ＭＡを５７部、ＤＢＴＤＬを０．０２部、ＭＥＨＱを０．０４部投入した。なお、この時のイソシアネート基／水酸基の当量比は１．０である。
次に、空気を吹き込みながら内温を６０℃に保持して５時間反応させた後、ＪＩＳ Ｋ ７３０１の方法で、イソシアネート基含有率が０．１％以下となり、イソシアネート基が水酸基とほぼ全て反応してウレタン結合が形成されたことを確認して、アロファネート基含有ウレタンアクリレート（Ａ−６）を１００部得た。
得られたウレタンアクリレート（Ａ−６）は、一般式（１）においてＲ１及びＲ４が水素原子、Ｒ２が一般式（３）で表される脂環式炭化水素基、Ｒ３がブチル基、Ａ１Ｏ及びＡ２Ｏがオキシエチレン基、並びにｍ及びｎが８である化合物であり、２５℃における粘度は下表１に示す通り１６Ｐａ・ｓ、ゲルパーミエーションクロマトグラフィーで測定した数平均分子量は１６５０であった。
<Synthesis Example 6>
[Synthesis of Allophanate Group-Containing Urethane Acrylate (A-6)]
In a four-necked flask equipped with a stirrer, an air inlet tube, and a thermometer, 43 parts of XP2565 used in Synthesis Example 5 as component (a-1), 57 parts of PEG360MA as component (a-2), DBTDL 0.02 part and MEHQ 0.04 part were added. At this time, the equivalent ratio of isocyanate group / hydroxyl group is 1.0.
Next, after reacting for 5 hours while blowing the air while maintaining the internal temperature at 60 ° C., the isocyanate group content becomes 0.1% or less by the method of JIS K 7301, and the isocyanate groups are almost completely reacted with the hydroxyl groups. As a result, 100 parts of allophanate group-containing urethane acrylate (A-6) was obtained.
In the obtained urethane acrylate (A-6), R 1 and R 4 in the general formula (1) are hydrogen atoms, R 2 is an alicyclic hydrocarbon group represented by the general formula (3), and R 3 is butyl. Group, A 1 O and A 2 O are oxyethylene groups, and m and n are 8, and the viscosity at 25 ° C. is 16 Pa · s as shown in Table 1 below, measured by gel permeation chromatography. The average molecular weight was 1650.
＜比較合成例１＞
［アロファネート基含有ウレタンアクリレート（Ａ’−１）の合成］
撹拌装置、空気導入管、温度計を備えた四つ口フラスコに、（ａ−１）成分として、合成例１で使用したＸＰ２５８０を６３部、（ａ’−２）成分として２−ヒドロキシエチルアクリレート（オキシエチレン基の繰り返し単位数１、水酸基価４８３ｍｇＫＯＨ／ｇ、以下、「ＨＥＡ」という。）を３７部、ＤＢＴＤＬを０．０２部、ＭＥＨＱを０．０４部投入した。なお、この時のイソシアネート基／水酸基の当量比は１．０である。
次に、空気を吹き込みながら内温を６０℃に保持して５時間反応させた後、ＪＩＳ Ｋ ７３０１の方法で、イソシアネート基含有率が０．１％以下となり、イソシアネート基が水酸基とほぼ全て反応してウレタン結合が形成されたことを確認して、アロファネート基含有ウレタンアクリレート（Ａ’−１）を１００部得た。
得られたウレタンアクリレート（Ａ’−１）は、一般式（１）においてＲ１及びＲ４が水素原子、Ｒ２がヘキサメチレン基、Ｒ３がブチル基、Ａ１Ｏ及びＡ２Ｏがオキシエチレン基、並びにｍ及びｎが１である化合物であり、２５℃における粘度は下表２に示す通り１１Ｐａ・ｓ、ゲルパーミエーションクロマトグラフィーで測定した数平均分子量は７００であった。
<Comparative Synthesis Example 1>
[Synthesis of Allophanate Group-Containing Urethane Acrylate (A′-1)]
In a four-necked flask equipped with a stirrer, an air introduction tube, and a thermometer, 63 parts of XP2580 used in Synthesis Example 1 as component (a-1) and 2-hydroxyethyl acrylate as component (a′-2) 37 parts of oxyethylene group repeating unit number 1, hydroxyl value 483 mg KOH / g (hereinafter referred to as “HEA”), 0.02 part of DBTDL, and 0.04 part of MEHQ were added. At this time, the equivalent ratio of isocyanate group / hydroxyl group is 1.0.
Next, after reacting for 5 hours while blowing the air while maintaining the internal temperature at 60 ° C., the isocyanate group content becomes 0.1% or less by the method of JIS K 7301, and the isocyanate groups are almost completely reacted with the hydroxyl groups. As a result, 100 parts of allophanate group-containing urethane acrylate (A′-1) was obtained.
The obtained urethane acrylate (A′-1) is represented by the general formula (1) in which R 1 and R 4 are hydrogen atoms, R 2 is a hexamethylene group, R 3 is a butyl group, and A 1 O and A 2 O are oxy. It is a compound having an ethylene group and m and n of 1, the viscosity at 25 ° C. was 11 Pa · s as shown in Table 2 below, and the number average molecular weight measured by gel permeation chromatography was 700.
＜比較合成例２＞
［アロファネート基含有ウレタンアクリレート（Ａ’−２）の合成］
撹拌装置、空気導入管、温度計を備えた四つ口フラスコに、（ａ−１）成分として、合成例４で使用したＸＰ２５６５を３８部、（ａ’−２）成分としてポリオキシエチレンモノアクリレート（オキシエチレン基の繰り返し単位数１１、水酸基価９８ｍｇＫＯＨ／ｇ、以下、「ＰＥＧ４８０ＭＡ」という。）を６２部、ＤＢＴＤＬを０．０２部、ＭＥＨＱを０．０４部投入した。なお、この時のイソシアネート基／水酸基の当量比は１．０である。
次に、空気を吹き込みながら内温を６０℃に保持して５時間反応させた後、ＪＩＳ Ｋ ７３０１の方法で、イソシアネート基含有率が０．１％以下となり、イソシアネート基が水酸基とほぼ全て反応してウレタン結合が形成されたことを確認して、アロファネート基含有ウレタンアクリレート（Ａ’−２）を１００部得た。
得られたウレタンアクリレート（Ａ’−２）は、一般式（１）においてＲ１及びＲ４が水素原子、Ｒ２が一般式（３）で表される脂環式炭化水素基、Ｒ３がブチル基、Ａ１Ｏ及びＡ２Ｏがオキシエチレン基、並びにｍ及びｎが１１である化合物であり、２５℃における粘度は下表２に示す通り９Ｐａ・ｓ、ゲルパーミエーションクロマトグラフィーで測定した数平均分子量は２１００であった。
<Comparative Synthesis Example 2>
[Synthesis of Allophanate Group-Containing Urethane Acrylate (A′-2)]
In a four-necked flask equipped with a stirrer, an air introduction tube, and a thermometer, 38 parts of XP2565 used in Synthesis Example 4 as component (a-1) and polyoxyethylene monoacrylate as component (a′-2) (Repeat unit number of oxyethylene group 11, hydroxyl value 98 mgKOH / g, hereinafter referred to as “PEG480MA”) 62 parts, DBTDL 0.02 part, MEHQ 0.04 part. At this time, the equivalent ratio of isocyanate group / hydroxyl group is 1.0.
Next, after reacting for 5 hours while blowing the air while maintaining the internal temperature at 60 ° C., the isocyanate group content becomes 0.1% or less by the method of JIS K 7301, and the isocyanate groups are almost completely reacted with the hydroxyl groups. As a result, 100 parts of allophanate group-containing urethane acrylate (A′-2) was obtained.
In the obtained urethane acrylate (A′-2), in general formula (1), R 1 and R 4 are hydrogen atoms, R 2 is an alicyclic hydrocarbon group represented by general formula (3), and R 3 is It is a compound in which butyl group, A 1 O and A 2 O are oxyethylene groups, and m and n are 11, and the viscosity at 25 ° C. was measured by gel permeation chromatography as shown in Table 2 below. The number average molecular weight was 2100.
＜比較合成例３＞
［ウレタンアクリレート（Ａ’−３）の合成］
撹拌装置、空気導入管、温度計を備えた四つ口フラスコに、（ａ’−１）成分として、ヘキサメチレンジイソシアネートのイソシアヌレート変性ポリイソシアネート（デュラネートＴＰＡ−１００、旭化成ケミカルズ（株）製、イソシアネート基含有率２３．１％、以下、「ＴＰＡ−１００」という。）を３９部、（ａ−２）成分としてＰＥＧ２００ＭＡを６１部、ＤＢＴＤＬを０．０２部、ＭＥＨＱを０．０４部投入した。なお、この時のイソシアネート基／水酸基の当量比は１．０である。
次に、空気を吹き込みながら内温を６０℃に保持して５時間反応させた後、ＪＩＳ Ｋ ７３０１の方法で、イソシアネート基含有率が０．１％以下となり、イソシアネート基が水酸基とほぼ全て反応してウレタン結合が形成されたことを確認して、ウレタンアクリレート（Ａ’−３）を１００部得た。
得られたウレタンアクリレート（Ａ’−３）は、一分子中に繰り返し単位数が４．５のオキシエチレン基を有するがアロファネート基は有さず、上記一般式（１）に含まれない化合物であり、２５℃における粘度は下表２に示す通り１６Ｐａ・ｓ、ゲルパーミエーションクロマトグラフィーで測定した数平均分子量は２３００であった。
<Comparative Synthesis Example 3>
[Synthesis of Urethane Acrylate (A′-3)]
Isocyanurate-modified polyisocyanate of hexamethylene diisocyanate (Duranate TPA-100, manufactured by Asahi Kasei Chemicals Co., Ltd.) as a component (a′-1) in a four-necked flask equipped with a stirrer, an air introduction tube and a thermometer The group content was 23.1%, hereinafter referred to as “TPA-100”), 39 parts, and as the component (a-2), 61 parts of PEG200MA, 0.02 part of DBTDL, and 0.04 part of MEHQ were added. At this time, the equivalent ratio of isocyanate group / hydroxyl group is 1.0.
Next, after reacting for 5 hours while blowing the air while maintaining the internal temperature at 60 ° C., the isocyanate group content becomes 0.1% or less by the method of JIS K 7301, and the isocyanate groups are almost completely reacted with the hydroxyl groups. As a result, 100 parts of urethane acrylate (A′-3) was obtained.
The obtained urethane acrylate (A′-3) is a compound that has an oxyethylene group having 4.5 repeating units in one molecule but no allophanate group and is not included in the general formula (1). Yes, the viscosity at 25 ° C. was 16 Pa · s as shown in Table 2 below, and the number average molecular weight measured by gel permeation chromatography was 2300.
＜実施例１〜７、比較例１〜６＞
［光硬化型ウレタン（メタ）アクリレート組成物の調製］
合成例１で得た（Ａ−１）１０部、（メタ）アクリロイル基含有化合物としてペンタエリスリトールテトラアクリレート（式（２）で表される（メタ）アクリロイル基含有化合物において、Ｒ５が水素原子、Ｘが炭素数５の４価の脂肪族多価アルコールであるペンタエリスリトールの水酸基を除いた基、ｓ＝４、ｔ＝０である化合物）１０部、光重合開始剤として１‐ヒドロキシシクロヘキシルフェニルケトン（イルガキュア１８４、ＢＡＳＦ社製、以下、「Ｉｒｇａｃｕｒｅ１８４」という。）０．６部、添加剤としてポリエーテル変性ポリジメチルシロキサン（ＢＹＫ−３５７０、ビックケミー・ジャパン（株）製、以下、「ＢＹＫ−３５７０」という。）０．０４部、有機溶剤としてメチルエチルケトン（以下、「ＭＥＫ」という。）３０部を均一に混ぜ、樹脂固形分４０％の光硬化型ウレタンアクリレート組成物１を調製した。
同様に、合成例１〜６で得た（Ａ−１）〜（Ａ−６）、比較合成例１〜３で得た（Ａ’−１）〜（Ａ’−３）、表３に示す（Ｂ）成分、Ｉｒｇａｃｕｒｅ１８４、ＢＹＫ−３５７０、ＭＥＫを用い、表４及び表５に示す割合（質量部）で混ぜ、光硬化型ウレタン（メタ）アクリレート組成物２〜１４を調製した。
<Examples 1-7, Comparative Examples 1-6>
[Preparation of photocurable urethane (meth) acrylate composition]
10 parts of (A-1) obtained in Synthesis Example 1, pentaerythritol tetraacrylate ((meth) acryloyl group-containing compound represented by formula (2) as a (meth) acryloyl group-containing compound, R 5 is a hydrogen atom, X is a group excluding the hydroxyl group of pentaerythritol, which is a tetravalent aliphatic polyhydric alcohol having 5 carbon atoms, a compound where s = 4 and t = 0), 10 parts, 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator (Irgacure 184, manufactured by BASF Corporation, hereinafter referred to as “Irgacure 184”) 0.6 parts, polyether-modified polydimethylsiloxane (BYK-3570, manufactured by BYK Japan Japan Co., Ltd.) as an additive, “BYK-3570” 0.04 part, methyl ethyl ketone as organic solvent (hereinafter referred to as “MEK”) 30 parts were mixed uniformly to prepare a photocurable urethane acrylate composition 1 having a resin solid content of 40%.
Similarly, (A-1) to (A-6) obtained in Synthesis Examples 1 to 6, (A′-1) to (A′-3) obtained in Comparative Synthesis Examples 1 to 3, and shown in Table 3. (B) Components, Irgacure 184, BYK-3570, and MEK were used and mixed at the ratios (parts by mass) shown in Tables 4 and 5 to prepare photocurable urethane (meth) acrylate compositions 2-14.
＜光硬化型ウレタン（メタ）アクリレート組成物の硬化膜層を有するフィルムの作製＞
易接着ＰＥＴフィルム（コスモシャインＡ４３００、膜厚１００μｍ、東洋紡績（株）製）上に、上記で得られた光硬化型樹脂組成物を、乾燥膜厚で２５μｍとなるよう塗工し、８０℃で１分間乾燥して有機溶剤を蒸発させた。次に、紫外線照射装置（ヘレウス・ノーブルライト・フュージョン・ユーブイ（株）製、光源：Ｈバルブ）を用いて積算光量５００ｍＪ／ｃｍ２の紫外線を照射することで、光硬化型樹脂組成物の硬化膜層を有するフィルムを得た。作製したフィルムについて下記評価を実施した結果を、下表４及び５に示す。
<Preparation of a film having a cured film layer of a photocurable urethane (meth) acrylate composition>
On the easy-adhesive PET film (Cosmo Shine A4300, film thickness 100 μm, manufactured by Toyobo Co., Ltd.), the photocurable resin composition obtained above was applied to a dry film thickness of 25 μm, and 80 ° C. And dried for 1 minute to evaporate the organic solvent. Next, the photocurable resin composition is cured by irradiating with an ultraviolet ray with an integrated light amount of 500 mJ / cm 2 using an ultraviolet ray irradiation device (manufactured by Heraeus Noblelight Fusion Ubuy Co., Ltd., light source: H bulb). A film having a membrane layer was obtained. The following evaluation results are shown in Tables 4 and 5 below for the produced films.
＜密着性＞
ＪＩＳ Ｋ ５６００に準拠し、作製した硬化膜層を有するフィルムを、カッターナイフで１ｍｍ四方の碁盤目を１００個作製し、市販のセロハンテープを表面に密着させた後に一気に剥がしたとき、剥離せずに残った碁盤目の個数を、下記の基準により判定した。
◎：残存した碁盤目の個数が１００個
○：残存した碁盤目の個数が９０〜９９個
△：残存した碁盤目の個数が６０〜８９個
×：残存した碁盤目の個数が６０個未満
＜鉛筆硬度＞
ＪＩＳ Ｋ ５６００に準拠し、作製した硬化膜層を有するフィルムを、４５°の角度で７５０ｇの荷重をかけ、多様な硬度の鉛筆で引っ掻き、硬化膜に生じた傷の有無を目視にて確認することで判定した。
<Adhesion>
In accordance with JIS K 5600, when a film having a cured film layer prepared was manufactured with 100 cutters of 1 mm square with a cutter knife and a cellophane tape on the market was adhered to the surface, it was not peeled off at once. The number of grids remaining on the board was determined according to the following criteria.
A: The number of remaining grids is 100. ○: The number of remaining grids is 90 to 99. Δ: The number of remaining grids is 60 to 89. X: The number of remaining grids is less than 60 < Pencil hardness>
In accordance with JIS K 5600, a film having a cured film layer produced was applied with a load of 750 g at an angle of 45 °, scratched with pencils of various hardness, and the presence or absence of scratches on the cured film was confirmed visually. It was judged by that.
＜自己修復性＞
作製した硬化膜層を有するフィルムに、２３℃、６０％ＲＨの条件下、真鍮ブラシにより１ｋｇの荷重をかけて１０往復擦ったとき、硬化物の表面状態を目視によって下記の基準により判定した。
◎：傷が３分以内に復元する。または傷がつかない。
○：３分後に傷が認められるが、６０℃恒温槽内に１分間保持することにより復元する。
×：３分後に傷が認められ、６０℃恒温槽内に１分間保持しても傷が復元しない。
＜耐屈曲性＞
ＪＩＳ Ｋ ５６００に準拠し、作製した硬化膜層を有するフィルムの硬化膜面が外側になるように円筒に巻きつけたときの、硬化膜の状態を下記基準により判定した。
○：直径１ｍｍの円筒でクラックが生じない。
△：直径１ｍｍの円筒ではクラックが生じるが、直径４ｍｍの円筒ではクラックが生じない。
×：直径４ｍｍの円筒でクラックが生じる。
<Self-healing>
When the film having the cured film layer thus produced was rubbed 10 times with a brass brush under a condition of 23 ° C. and 60% RH for 10 reciprocations, the surface state of the cured product was visually determined according to the following criteria.
A: The wound is restored within 3 minutes. Or it is not scratched.
○: Scratches are observed after 3 minutes, but are restored by holding in a constant temperature bath at 60 ° C. for 1 minute.
X: Scratches are observed after 3 minutes, and the scratches are not restored even if kept in a 60 ° C. constant temperature bath for 1 minute.
<Flexibility>
In accordance with JIS K 5600, the state of the cured film when it was wound around a cylinder so that the cured film surface of the produced film having the cured film layer was on the outside was determined according to the following criteria.
○: Cracks do not occur in a cylinder having a diameter of 1 mm.
Δ: Crack occurs in a cylinder having a diameter of 1 mm, but no crack occurs in a cylinder having a diameter of 4 mm.
X: A crack occurs in a cylinder having a diameter of 4 mm.
上表４に示したとおり、本発明の実施例１〜８の光硬化型樹脂硬化物は、一旦付いた傷が経時的に復元して消失する特性を有し、鉛筆硬度、耐屈曲性、密着性に優れていた。
他方、上表５の比較例１及び２に示すように、一般式（１）においてｍ及びｎが本発明の範囲を外れる化合物を用いた場合、傷復元性及び硬度を両立することができなかった。比較例３のようにアロファネート基を有しない化合物を用いた場合、傷復元性、耐屈曲性を満足しなかった。また、比較例４及び５に示すように一般式（２）で表される化合物の含有量が本発明の範囲を外れる場合、密着性、鉛筆硬度、耐屈曲性のいずれかを満足しなかった。
また、比較例６に示すようにアロファネート基含有ウレタンアクリレート単独では自己修復性が十分でなく、鉛筆硬度が劣っていた。
As shown in Table 4 above, the photo-curing resin cured products of Examples 1 to 8 of the present invention have characteristics that the scratches once attached are restored over time and disappear, and pencil hardness, flex resistance, Excellent adhesion.
On the other hand, as shown in Comparative Examples 1 and 2 in Table 5 above, when m and n in the general formula (1) are out of the scope of the present invention, it is impossible to achieve both flaw resilience and hardness. It was. When a compound having no allophanate group as in Comparative Example 3 was used, the scratch recovery property and flex resistance were not satisfied. Further, as shown in Comparative Examples 4 and 5, when the content of the compound represented by the general formula (2) is out of the range of the present invention, any of adhesion, pencil hardness, and bending resistance is not satisfied. .
Moreover, as shown in Comparative Example 6, the allophanate group-containing urethane acrylate alone was not sufficient in self-healing property and inferior in pencil hardness.
Claims (1)
（Ａ）成分
下記一般式（１）で表される、アロファネート基含有ウレタン（メタ）アクリレート
（Ｂ）成分
下記一般式（２）で表される、（メタ）アクリロイル基含有化合物
A urethane (meth) acrylate composition containing the following components (A) and (B) and having a mass ratio of (A) component / (B) component of 40/60 to 60/40.
Component (A) Allophanate group-containing urethane (meth) acrylate represented by the following general formula (1)
(B) Component (meth) acryloyl group-containing compound represented by the following general formula (2)
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