TW201335253A - Urethane (meth)acrylate composition - Google Patents
Urethane (meth)acrylate composition Download PDFInfo
- Publication number
- TW201335253A TW201335253A TW101149823A TW101149823A TW201335253A TW 201335253 A TW201335253 A TW 201335253A TW 101149823 A TW101149823 A TW 101149823A TW 101149823 A TW101149823 A TW 101149823A TW 201335253 A TW201335253 A TW 201335253A
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- meth
- acrylate
- urethane
- carbon atoms
- Prior art date
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 147
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000000203 mixture Substances 0.000 title claims abstract description 58
- 238000003860 storage Methods 0.000 claims abstract description 37
- 239000003381 stabilizer Substances 0.000 claims abstract description 30
- 229920005862 polyol Polymers 0.000 claims description 54
- 125000004432 carbon atom Chemical group C* 0.000 claims description 53
- 239000003054 catalyst Substances 0.000 claims description 48
- 150000003077 polyols Chemical class 0.000 claims description 46
- 150000001875 compounds Chemical class 0.000 claims description 45
- 229910052751 metal Inorganic materials 0.000 claims description 36
- 239000002184 metal Substances 0.000 claims description 36
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 17
- 239000005056 polyisocyanate Substances 0.000 claims description 16
- 229920001228 polyisocyanate Polymers 0.000 claims description 16
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 11
- 125000005843 halogen group Chemical group 0.000 claims description 10
- 125000001188 haloalkyl group Chemical group 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 125000000304 alkynyl group Chemical group 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000001425 triazolyl group Chemical group 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000003282 alkyl amino group Chemical group 0.000 claims description 4
- 125000000962 organic group Chemical group 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 3
- 125000003172 aldehyde group Chemical group 0.000 claims description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 3
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 3
- 125000004427 diamine group Chemical group 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims 1
- -1 coatings Substances 0.000 description 47
- 238000004519 manufacturing process Methods 0.000 description 31
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 30
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 26
- 125000003118 aryl group Chemical group 0.000 description 13
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 125000001931 aliphatic group Chemical group 0.000 description 9
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 9
- 125000002723 alicyclic group Chemical group 0.000 description 8
- 239000003085 diluting agent Substances 0.000 description 8
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- 235000019441 ethanol Nutrition 0.000 description 8
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 125000000623 heterocyclic group Chemical group 0.000 description 6
- 150000005846 sugar alcohols Polymers 0.000 description 6
- 238000004448 titration Methods 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 5
- 229920005906 polyester polyol Polymers 0.000 description 5
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- 239000011347 resin Substances 0.000 description 5
- 239000012974 tin catalyst Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- PXBFMLJZNCDSMP-UHFFFAOYSA-N 2-Aminobenzamide Chemical compound NC(=O)C1=CC=CC=C1N PXBFMLJZNCDSMP-UHFFFAOYSA-N 0.000 description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000004383 yellowing Methods 0.000 description 4
- MZZYGYNZAOVRTG-UHFFFAOYSA-N 2-hydroxy-n-(1h-1,2,4-triazol-5-yl)benzamide Chemical compound OC1=CC=CC=C1C(=O)NC1=NC=NN1 MZZYGYNZAOVRTG-UHFFFAOYSA-N 0.000 description 3
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 3
- 101100220068 Arabidopsis thaliana CDA6 gene Proteins 0.000 description 3
- 0 C*(cc1*(N)=O)ccc1N Chemical compound C*(cc1*(N)=O)ccc1N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000004292 cyclic ethers Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
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- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical group O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- BHNHHSOHWZKFOX-UHFFFAOYSA-N 2-methyl-1H-indole Chemical compound C1=CC=C2NC(C)=CC2=C1 BHNHHSOHWZKFOX-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 2
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- 101000658622 Homo sapiens Testis-specific Y-encoded-like protein 2 Proteins 0.000 description 2
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
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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 2
- 239000006078 metal deactivator Substances 0.000 description 2
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
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- 238000010998 test method Methods 0.000 description 2
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- QZOPRMWFYVGPAI-UHFFFAOYSA-N 1-chloroindole Chemical compound C1=CC=C2N(Cl)C=CC2=C1 QZOPRMWFYVGPAI-UHFFFAOYSA-N 0.000 description 1
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- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
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- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical group CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- CQQXCSFSYHAZOO-UHFFFAOYSA-L [acetyloxy(dioctyl)stannyl] acetate Chemical compound CCCCCCCC[Sn](OC(C)=O)(OC(C)=O)CCCCCCCC CQQXCSFSYHAZOO-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 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 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- CWFOCCVIPCEQCK-UHFFFAOYSA-N chlorfenapyr Chemical compound BrC1=C(C(F)(F)F)N(COCC)C(C=2C=CC(Cl)=CC=2)=C1C#N CWFOCCVIPCEQCK-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl 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])* 0.000 description 1
- 125000006612 decyloxy group Chemical group 0.000 description 1
- JQZRVMZHTADUSY-UHFFFAOYSA-L di(octanoyloxy)tin Chemical compound [Sn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O JQZRVMZHTADUSY-UHFFFAOYSA-L 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000006232 ethoxy propyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PLONEVHFXDFSLA-UHFFFAOYSA-N ethyl hexanoate;tin(2+) Chemical compound [Sn+2].CCCCCC(=O)OCC PLONEVHFXDFSLA-UHFFFAOYSA-N 0.000 description 1
- WHRIKZCFRVTHJH-UHFFFAOYSA-N ethylhydrazine Chemical compound CCNN WHRIKZCFRVTHJH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002649 leather substitute Substances 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
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- YVZACCLFRNQBNO-UHFFFAOYSA-N pentylhydrazine Chemical compound CCCCCNN YVZACCLFRNQBNO-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 150000004060 quinone imines Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- MUQNAPSBHXFMHT-UHFFFAOYSA-N tert-butylhydrazine Chemical compound CC(C)(C)NN MUQNAPSBHXFMHT-UHFFFAOYSA-N 0.000 description 1
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 1
- 125000004149 thio group Chemical group *S* 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical class [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- SYRHIZPPCHMRIT-UHFFFAOYSA-N tin(4+) Chemical class [Sn+4] SYRHIZPPCHMRIT-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
- C08F2/40—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using retarding agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C08L75/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
本發明係有關於一種具有優良儲存安定性的胺基甲酸酯(甲基)丙烯酸酯組成物。 The present invention relates to a urethane (meth) acrylate composition having excellent storage stability.
胺基甲酸酯樹脂，由於在機械強度、耐擦傷性、耐磨耗性、柔軟性、伸張性、復元性、耐油性等良好，因此廣泛應用於彈性體、塗料、接著劑、合成皮革(人工皮革)、彈性繊維等。再者，使胺基甲酸酯(甲基)丙烯酸酯硬化而獲得的胺基甲酸酯樹脂這樣透明性高且霧度低的胺基甲酸酯樹脂，係被使用作為構成影像顯示裝置等之保護部的樹脂層。 Aurethane resin is widely used in elastomers, coatings, adhesives, synthetic leathers due to its good mechanical strength, scratch resistance, abrasion resistance, flexibility, stretchability, recovery, and oil resistance. Artificial leather), elastic 繊, etc. Further, a urethane resin obtained by curing a urethane (meth) acrylate such that the urethane resin is highly transparent and has a low haze is used as a video display device or the like. The resin layer of the protective portion.
另外，本說明書中，「(甲基)丙烯酸酯」係意指丙烯酸酯及甲基丙烯酸酯之至少一者，同様地，「(甲基)丙烯醯氧基」係意指丙烯醯氧基及甲基丙烯醯氧基之至少一者。 In the present specification, "(meth)acrylate" means at least one of acrylate and methacrylate, and "(meth)acryloxy" means "acrylomethoxy" and At least one of methacryloxyloxy groups.
又，本說明書中，「胺基甲酸酯(甲基)丙烯酸酯」係意指具有胺基甲酸酯鍵結的(甲基)丙烯酸酯。 In the present specification, "urethane (meth) acrylate" means a (meth) acrylate having a urethane bond.
為確保胺基甲酸酯(甲基)丙烯酸酯之硬化物的優良品質，有必要在能力所及下使用一定品質的胺基甲酸 酯(甲基)丙烯酸酯。尤其，黏度為重要的品質，使用安定地具有所欲黏度的胺基甲酸酯(甲基)丙烯酸酯即為關鍵。 In order to ensure the excellent quality of the cured product of urethane (meth) acrylate, it is necessary to use a certain quality of urethane for the ability. Ester (meth) acrylate. In particular, viscosity is an important quality, and it is critical to use a urethane (meth) acrylate which has a desired viscosity.
然而，在製造具所欲黏度的胺基甲酸酯(甲基)丙烯酸酯，會有儲存期間經時黏度變化的問題，特別是經時黏度下降(以下稱為「減黏」)的問題。 However, in the production of a urethane (meth) acrylate having a desired viscosity, there is a problem that the viscosity changes over time during storage, particularly a decrease in viscosity over time (hereinafter referred to as "reduction of viscosity").
為解決上述問題，有提出將合成胺基甲酸酯(甲基)丙烯酸酯時所用的有機錫觸媒換成使用鋅觸媒的方法(專利文獻1)。 In order to solve the above problems, there has been proposed a method of replacing an organotin catalyst used for synthesizing a urethane (meth) acrylate with a zinc catalyst (Patent Document 1).
[專利文獻1]日本專利公開案特開2010-215774號公報。 [Patent Document 1] Japanese Laid-Open Patent Publication No. 2010-215774.
然而，使用鋅觸媒時，會發生反應進行緩慢、反應不完全、反應生成物發生著色等諸多問題。也有不改變觸媒種類而抑制觸媒活性的方法被考量。但是，發明人等在試著使用代表性的減活劑時，有關減黏方面並無功效。因此，本發明係以提供不發生該等問題、且不發生減黏的儲存安定性良好的胺基甲酸酯(甲基)丙烯酸酯組成物為目的。 However, when a zinc catalyst is used, there are many problems such as a slow reaction, an incomplete reaction, and coloration of a reaction product. There are also methods for inhibiting the activity of the catalyst without changing the type of the catalyst. However, when the inventors tried to use a representative deactivator, there was no effect on the viscosity reduction. Therefore, the present invention has an object of providing a urethane (meth) acrylate composition having good storage stability without causing such problems and without reducing viscosity.
本發明人等，經種種檢討的結果，發現藉由使具
特定結構的化合物包含於胺基甲酸酯(甲基)丙烯酸酯中，可抑制胺基甲酸酯(甲基)丙烯酸酯組成物的減黏，而完成本發明。亦即，本發明係一種胺基甲酸酯(甲基)丙烯酸酯組成物，包含：胺基甲酸酯(甲基)丙烯酸酯(A)；及至少一種儲存安定劑(B)，其係相對於100質量份之胺基甲酸酯(甲基)丙烯酸酯(A)為0.0001~1質量份，且該儲存安定劑(B)係由下述式(1)~(5)中任一者所示之化合物所構成者：
[(在此，R1係氫原子、-OH或-NH2；R2係-O-或-NH-；R3係氫原子、碳數1~20之有機基、-NH2或-OH(但R2為-O-時R3不為-OH)；R4係選自於由氫原子、-OH、羧基、醛基、苯基、鹵素原子、-NO2、-NH2、-N3、碳數1~15之烷基、碳數2~15之烯基、碳數2~15之炔基、碳數1~15之鹵烷基、碳數1~15之烷氧基、碳數1~15之烷胺基、碳數1~15之烷硫基、碳數1~15之烷氧羰基及碳數1~15之烷羰基所構成群組中之基；R5係以下述式(11)表示之二醯胺殘基，
(式(11)中，R6係碳數1~15的伸烷基。)] (In the formula (11), R 6 is an alkylene group having 1 to 15 carbon atoms.)]
透過含有上述儲存安定劑(B)，本發明的組成物即便含有用有機錫觸媒製造的胺基甲酸酯(甲基)丙烯酸酯也不會減黏。 By containing the above-mentioned storage stabilizer (B), the composition of the present invention does not reduce viscosity even if it contains a urethane (meth)acrylate produced using an organic tin catalyst.
<胺基甲酸酯(甲基)丙烯酸酯(A)> <urethane (meth) acrylate (A)>
本發明中，胺基甲酸酯(甲基)丙烯酸酯(A)，係具有(甲基)丙烯醯氧基與胺基甲酸酯鍵結的化合物。胺基甲酸酯(甲基)丙烯酸酯(A)，係數量平均分子量為1,000~250,000者為佳，10,000~200,000較佳，20,000~150,000更佳。該分子量係可經由膠透層析(GPC)來測定。 In the present invention, the urethane (meth) acrylate (A) is a compound having a (meth) acryloxy group bonded to a urethane. The urethane (meth) acrylate (A) preferably has a coefficient average molecular weight of 1,000 to 250,000, preferably 10,000 to 200,000, more preferably 20,000 to 150,000. This molecular weight can be determined by gel permeation chromatography (GPC).
適宜的是，胺基甲酸酯(甲基)丙烯酸酯(A)係每1分子具有平均1個以上的丙烯醯氧基及甲基丙烯醯氧基之至少一者，且宜為1.8~4個。若該每1分子平均的(甲基)丙烯醯氧基的數量為1.8個以上，則在之後形成硬化物的時候，至少其中一部份具有交聯結構，因此易於避免在暴置於高溫下時硬化物流動而變形。另一方面，若為4個以下，則交聯密度不會過大，易於避免硬化物變脆。較佳係1.9個以上、3個以下；尤以1.9個以上、2.3個以下為佳。 It is preferable that the urethane (meth) acrylate (A) has an average of at least one of an acryloxy group and a methacryloxy group per molecule, and is preferably 1.8 to 4 One. If the number of (meth)acryloxy groups per molecule is 1.8 or more, at least one of the portions has a crosslinked structure when the cured product is formed later, so that it is easy to avoid exposure to high temperatures. The hardened material flows and deforms. On the other hand, if it is 4 or less, the crosslinking density will not be too large, and it is easy to prevent the hardened material from becoming brittle. It is preferably 1.9 or more and 3 or less; particularly preferably 1.9 or more and 2.3 or less.
胺基甲酸酯(甲基)丙烯酸酯(A)，係可以例如以下的方法獲得。首先，將多元醇與聚異氰酸酯以讓NCO/OH莫耳比成為1.01~5.的比率混合，在金屬觸媒的存在下進行 反應，獲得異氰酸酯封端預聚物。接著在此異氰酸酯封端預聚物中，以NCO/該反應性基莫耳比呈0.5~1.1為宜的比率、尤佳係呈0.9~1.02的比率，添加具有(甲基)丙烯醯氧基及對異氰酸酯具反應性之基的化合物(以下，亦稱為反應性(甲基)丙烯酸酯)添加並使其反應。若該莫耳比為前述下限值以上，則會有適當的分子量，並可達成良好的物性。又，若該莫耳比為前述上限值以下，不會有發生增黏問題的疑慮。 The urethane (meth) acrylate (A) can be obtained, for example, by the following method. First, the polyol and the polyisocyanate are mixed at a ratio such that the NCO/OH molar ratio becomes 1.01 to 5., in the presence of a metal catalyst. The reaction is carried out to obtain an isocyanate-terminated prepolymer. Next, in the isocyanate-terminated prepolymer, the (meth) propylene fluorenyl group is added at a ratio of NCO / the reactive base molar ratio of 0.5 to 1.1, and particularly preferably 0.9 to 1.02. A compound which is reactive with isocyanate (hereinafter also referred to as a reactive (meth) acrylate) is added and reacted. When the molar ratio is at least the above lower limit value, an appropriate molecular weight is obtained, and good physical properties can be achieved. Moreover, if the molar ratio is equal to or less than the above upper limit value, there is no doubt that the problem of viscosity increase may occur.
另外，以下除非特別指明，將異氰酸酯封端預聚物稱為預聚物。又，在本說明書中，有時候將異氰酸酯基稱為NCO。 Further, the isocyanate-terminated prepolymer is referred to as a prepolymer unless otherwise specified. Further, in the present specification, the isocyanate group is sometimes referred to as NCO.
使用一元醇代替上述多元醇，則可獲得每1分子具有平均1個(甲基)丙烯醯氧基的胺基甲酸酯(甲基)丙烯酸酯。又，使用一元醇與多元醇的混合物，亦可獲得每1分子具有平均超過1個之數量的(甲基)丙烯醯氧基的胺基甲酸酯(甲基)丙烯酸酯。 When a monohydric alcohol is used in place of the above polyol, a urethane (meth) acrylate having an average of one (meth) acryloxy group per molecule can be obtained. Further, a mixture of a monohydric alcohol and a polyhydric alcohol can also be used to obtain a urethane (meth) acrylate having an average of more than one (meth) acryloxy group per molecule.
每1分子平均的(甲基)丙烯醯氧基的數量未達2的胺基甲酸酯(甲基)丙烯酸酯，通常係經由使用多元醇與一元醇的混合物製造胺基甲酸酯(甲基)丙烯酸酯的方法、或是使用多元醇而不在多元醇的封端羥基的1部份導入(甲基)丙烯醯氧基的方法來製造。 A urethane (meth) acrylate having an average number of (meth) acryloxy groups per molecule of less than 2, usually by using a mixture of a polyol and a monohydric alcohol to produce a urethane (A) The method of using a acrylate, or a method of introducing a (meth) acryloxy group by using a polyol instead of a part of a blocked hydroxyl group of a polyol.
又，本發明的胺基甲酸酯(甲基)丙烯酸酯，並非如上所述，限定於使多元醇、聚異氰酸酯與反應性(甲基)丙烯酸酯發生反應而獲得者。例如，亦可將具有異氰酸酯基與(甲基) 丙烯醯氧基的化合物與多元醇或一元醇發生反應來製造胺基甲酸酯(甲基)丙烯酸酯。作為具有異氰酸酯基與(甲基)丙烯醯氧基的化合物，例如，可列舉異氰酸酯甲基丙烯酸烷基酯或異氰酸酯丙烯酸烷基酯。 Further, the urethane (meth) acrylate of the present invention is not limited to the above, and is limited to those obtained by reacting a polyol, a polyisocyanate and a reactive (meth) acrylate. For example, it is also possible to have an isocyanate group and (meth) A propylene oxime compound is reacted with a polyol or a monohydric alcohol to produce a urethane (meth) acrylate. Examples of the compound having an isocyanate group and a (meth) propylene fluorenyloxy group include an isocyanate alkyl methacrylate or an isocyanate alkyl acrylate.
本發明中的胺基甲酸酯(甲基)丙烯酸酯，係宜為如前所述的，使多元醇、聚異氰酸酯與反應性(甲基)丙烯酸酯發生反應而得的胺基甲酸酯(甲基)丙烯酸酯。反應性(甲基)丙烯酸酯中的對異氰酸酯具反應性的基宜為羥基；反應性(甲基)丙烯酸酯宜為(甲基)丙烯酸羥烷基酯。 The urethane (meth) acrylate in the present invention is preferably a urethane obtained by reacting a polyol, a polyisocyanate and a reactive (meth) acrylate as described above. (Meth) acrylate. The reactive (meth) acrylate is preferably a hydroxyl group responsive to isocyanate; the reactive (meth) acrylate is preferably a hydroxyalkyl (meth) acrylate.
本發明中的胺基甲酸酯(甲基)丙烯酸酯，較佳的是，使每1分子具有平均1.8~4個羥基的多元醇(i)、無黃變性二異氰酸酯(ii)、與(甲基)丙烯酸羥烷基酯(iii)發生反應而獲得的胺基甲酸酯(甲基)丙烯酸酯。 The urethane (meth) acrylate in the invention is preferably a polyol (i) having no average of 1.8 to 4 hydroxyl groups per molecule, a non-yellosed diisocyanate (ii), and ( A urethane (meth) acrylate obtained by reacting a hydroxyalkyl methacrylate (iii).
使多元醇(i)、無黃變性二異氰酸酯(ii)與(甲基)丙烯酸羥烷基酯(iii)發生反應而獲得的較佳胺基甲酸酯(甲基)丙烯酸酯(A)的一例，係可以下述方法調製。首先將前述聚氧伸烷基多元醇(i)與前述二異氰酸酯(ii)，以(i)中的-OH與(ii)中的-NCO基的莫耳比(NCO/OH的莫耳比)成為約1比1.2~2(NCO/OH=1.2~2)之比率的方式混合，在金屬觸媒存在下發生反應而獲得預聚物。NCO/OH的莫耳比係1.6~2較佳。接著在此預聚物中，以(iii)中的-OH與預聚物中的-NCO基的莫耳比(NCO/OH的莫耳比)成為約1比1(NCO/OH=1)之比率添加前述(甲基)丙烯酸羥烷基酯(iii)，在追加或不追加金屬觸媒下使其反應。 Preferred urethane (meth) acrylate (A) obtained by reacting polyol (i), non-yellowing diisocyanate (ii) with hydroxyalkyl (meth) acrylate (iii) For example, it can be modulated by the following method. First, the aforementioned polyoxyalkylene polyol (i) and the aforementioned diisocyanate (ii), the molar ratio of -OH in (i) to -NCO in (ii) (NCO/OH molar ratio) The mixture is mixed in a ratio of about 1 to 1.2 to 2 (NCO/OH = 1.2 to 2), and a prepolymer is obtained by reacting in the presence of a metal catalyst. The molar ratio of NCO/OH is preferably 1.6 to 2. Next, in this prepolymer, the molar ratio of -OH in (iii) to the -NCO group in the prepolymer (the molar ratio of NCO/OH) is about 1 to 1 (NCO/OH = 1). The hydroxyalkyl (meth) acrylate (iii) is added in a ratio, and the reaction is carried out with or without a metal catalyst.
作為多元醇，係可列舉聚氧伸烷基多元醇、聚碳酸酯多元醇及聚酯多元醇等，其等之混合物亦可。 Examples of the polyhydric alcohol include polyoxyalkylene polyols, polycarbonate polyols, and polyester polyols, and the like.
聚氧伸烷基多元醇，係宜為以起始劑使環狀醚開環加成聚合而獲得的聚氧伸烷基多元醇。作為起始劑，係以含羥基化合物為宜，一元醇或多元醇為宜，一元醇與多元醇的混合物、或羥基數相異之多元醇的混合物等亦可使用作為起始劑。作為環狀醚係宜為環氧烷或四氫呋喃。由於起始劑中的與環狀醚反應之活性氫的數量(例如，羥基的氫原子數)會成為所獲得之聚氧伸烷基多元醇的羥基數，則例如，從每1分子具有平均1.8~4個羥基的起始劑，可獲得每1分子具有平均1.8~4個羥基的聚氧伸烷基多元醇。 The polyoxyalkylene polyol is preferably a polyoxyalkylene polyol obtained by subjecting a cyclic ether to ring-opening addition polymerization with an initiator. As the initiator, a hydroxyl group-containing compound is preferred, a monohydric alcohol or a polyhydric alcohol is preferred, a mixture of a monohydric alcohol and a polyhydric alcohol, or a mixture of polyhydric alcohols having a different hydroxyl number may be used as a starter. The cyclic ether is preferably an alkylene oxide or a tetrahydrofuran. Since the amount of active hydrogen which reacts with the cyclic ether in the initiator (for example, the number of hydrogen atoms of the hydroxyl group) becomes the number of hydroxyl groups of the obtained polyoxyalkylene polyol, for example, it has an average value per molecule. An initiator of 1.8 to 4 hydroxyl groups can obtain a polyoxyalkylene polyol having an average of 1.8 to 4 hydroxyl groups per molecule.
作為聚氧伸烷基多元醇，例如，可列舉聚氧伸乙基多元醇、聚氧伸丙基多元醇、聚(氧伸乙基‧氧伸丙基)多元醇及聚氧四亞甲基多元醇等。適宜的聚氧伸烷基多元醇，係聚氧伸丙基多元醇及氧伸乙基封端之聚氧伸丙基多元醇。 Examples of the polyoxyalkylene polyol include polyoxyethylene ethyl alcohol, polyoxypropyl propylene polyol, poly(oxyethylidene ethoxypropyl) polyol, and polyoxytetramethylene. Polyols, etc. Suitable polyoxyalkylene polyols are polyoxyalkylene propylene polyols and oxygen-extended ethyl-terminated polyoxy-extension propylene polyols.
作為聚碳酸酯多元醇，例如，可列舉碳酸酯與二元醇的反應生成物。作為碳酸酯，具體而言，可列舉二苯基碳酸酯等二芳基碳酸酯，以及二甲基碳酸酯及二乙基碳酸酯等二烷基碳酸酯等。作為二元醇，係可列舉低分子量二元醇。低分子量二元醇係例如，可列舉分子量60~300程度的二元醇，具體例方面可列舉乙二醇、丙二醇、二乙二醇、二丙二醇、丁二醇、1,6-己二醇、2-甲基-1,8-辛二醇、壬二醇、環己烷二甲醇、新戊二醇及3-甲基-1,5-戊二醇等。 The polycarbonate polyol may, for example, be a reaction product of a carbonate and a glycol. Specific examples of the carbonate include a diaryl carbonate such as diphenyl carbonate, and a dialkyl carbonate such as dimethyl carbonate or diethyl carbonate. Examples of the diol include low molecular weight diols. Examples of the low molecular weight diols include diols having a molecular weight of about 60 to 300, and specific examples thereof include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butanediol, and 1,6-hexanediol. , 2-methyl-1,8-octanediol, decanediol, cyclohexanedimethanol, neopentyl glycol, and 3-methyl-1,5-pentanediol.
作為聚酯多元醇，例如，可列舉為選自於上述低分子 量二元醇中之至少1種、與二羧酸或其反應性衍生物之至少1種所構成之酸成分的反應物。酸成分方面，係例如可列舉已二酸、癸二酸、琥珀酸、馬來酸、苯二甲酸、六氫苯二甲酸及對苯二甲酸等二元酸或其酸酐等。又，亦可使用：使用3官能以上的聚羧酸或其反應性衍生物作為酸成分的一部份，而獲得的每1分子平均羥基數超過2個的聚酯多元醇。再者，作為聚酯多元醇，亦可使用：於前述多元醇等的起始劑使環狀酯開環加成聚合而獲得的每1分子平均羥基數為1.8~4個的聚酯多元醇。作為環狀酯係可列舉ε-己內酯等。 The polyester polyol is, for example, selected from the above low molecular weights. A reactant of at least one of the diols and an acid component composed of at least one of a dicarboxylic acid or a reactive derivative thereof. Examples of the acid component include dibasic acids such as adipic acid, sebacic acid, succinic acid, maleic acid, phthalic acid, hexahydrophthalic acid, and terephthalic acid, and anhydrides thereof. Further, a polyester polyol having a polyvalent carboxylic acid having a trifunctional or higher functional group or a reactive derivative thereof as a part of an acid component and having an average number of hydroxyl groups per molecule of more than two may be used. In addition, as the polyester polyol, a polyester polyol having an average number of hydroxyl groups per molecule of 1.8 to 4 obtained by ring-opening addition polymerization of a cyclic ester in an initiator such as a polyhydric alcohol may be used. . Examples of the cyclic ester system include ε-caprolactone and the like.
上述多元醇之中，係以聚氧伸烷基多元醇為宜；上述多元醇(i)方面，係使用每1分子具有平均1.8~4個羥基的聚氧伸烷基多元醇者為宜。較佳的是，使用每1分子具有平均1.9~3個羥基的聚氧伸烷基多元醇，尤其每1分子具有平均1.9~2.3個羥基者為佳。 Among the above polyols, a polyoxyalkylene polyol is preferred, and in the case of the above polyol (i), a polyoxyalkylene polyol having an average of 1.8 to 4 hydroxyl groups per molecule is preferably used. It is preferred to use a polyoxyalkylene polyol having an average of 1.9 to 3 hydroxyl groups per molecule, and particularly preferably having an average of 1.9 to 2.3 hydroxyl groups per molecule.
藉著讓胺基甲酸酯(甲基)丙烯酸酯具有聚氧伸烷基鏈，易於獲得即便在低溫區域柔軟性也很高的硬化物。構成該聚氧伸烷基鏈的氧伸烷基方面，係宜為氧伸乙基、氧伸丙基、氧四亞甲基等碳數2~4的氧伸烷基。聚氧伸烷基鏈，係亦可為由2種以上之氧伸烷基所構成，此時係尤其以氧伸乙基與氧伸丙基所構成者為宜。 By allowing the urethane (meth) acrylate to have a polyoxyalkylene chain, it is easy to obtain a cured product which is highly flexible even in a low temperature region. The oxygen-extended alkyl group constituting the polyoxyalkylene alkyl chain is preferably an oxygen-extended alkyl group having 2 to 4 carbon atoms such as an oxygen-extended ethyl group, an oxygen-extended propyl group or an oxytetramethylene group. The polyoxyalkylene chain may be composed of two or more kinds of oxygen-extended alkyl groups, and in particular, it is preferably composed of an oxygen-extended ethyl group and an oxygen-extended propyl group.
適宜的聚氧伸烷基多元醇，係聚氧伸丙基多元醇，以及於聚氧伸丙基多元醇使少量的環氧乙烷發生反應而獲得的氧伸乙基封端聚氧伸丙基多元醇，較佳的是氧伸乙基封 端聚氧伸丙基多元醇。由於氧伸乙基封端聚氧伸丙基多元醇係1級羥基的比率很高，故對異氰酸酯基的反應性很高。氧伸烷基為氧伸丙基所構成或氧伸丙基與少量氧伸乙基所構成，具有這樣的聚氧伸烷基鏈的胺基甲酸酯(甲基)丙烯酸酯係特別適宜的。 Suitable polyoxyalkylene polyols, polyoxyalkylene propylene polyols, and oxygen-extended ethyl-terminated polyoxypropylene-extended polypropylene obtained by reacting a small amount of ethylene oxide with polyoxypropylene propylene polyol Base polyol, preferably oxygen-extended ethyl Polyoxylated propyl polyol. Since the ratio of the oxygen-extended ethyl-terminated polyoxy-extension propyl polyol-based first-order hydroxyl group is high, the reactivity to the isocyanate group is high. The oxygen alkyl group is composed of an oxygen-extended propyl group or an oxygen-extended propyl group and a small amount of an oxygen-extended ethyl group. A urethane (meth) acrylate having such a polyoxyalkylene chain is particularly suitable. .
聚氧伸烷基多元醇的每1羥基的數量平均分子量(Mn)係宜為400~8000，故而，分子量係其1.8~4倍，即720~32,000為宜。尤其，每1羥基的數量平均分子量(Mn)係600~5000為佳。 The number average molecular weight (Mn) per one hydroxyl group of the polyoxyalkylene polyol is preferably from 400 to 8,000. Therefore, the molecular weight is 1.8 to 4 times, that is, 720 to 32,000. In particular, the number average molecular weight (Mn) per one hydroxyl group is preferably from 600 to 5,000.
多元醇的數量平均分子量，係可藉由依據JISK1557-1(2007年版)而測定的羥值A(KOHmg/g)與多元醇1分子內的羥基數B，並經由下列算式(1)而算出。 The number average molecular weight of the polyol can be calculated from the hydroxyl value A (KOH mg/g) measured in accordance with JIS K1557-1 (2007 edition) and the hydroxyl number B in the molecule of the polyol 1 and calculated by the following formula (1). .
多元醇的分子量=56.1×B×1000/A (1) The molecular weight of the polyol = 56.1 × B × 1000 / A (1)
上述與多元醇發生反應的聚異氰酸酯，並無特定限制，可使用具有2個以上異氰酸酯基的芳香族系、無黃變性芳香族系、脂環族系、脂肪族系等聚異氰酸酯，以及該等聚異氰酸酯之2種類以上的混合物等。作為具體例，係可列舉：二異氰酸甲苯酯(TDI)、二苯甲烷二異氰酸酯(MDI)等芳香族系；伸苯二甲基二異氰酸酯(XDI)等無黃變性芳香族系；異佛酮二異氰酸酯(IPDI)、4,4'-亞甲基雙(環己基異氰酸酯)等脂環族系；2,2,4-三甲基-己二異氰酸酯、己二異氰酸酯(HDI)等脂肪族系。 The polyisocyanate which reacts with the polyol is not particularly limited, and an aromatic, non-yellowing aromatic, alicyclic or aliphatic polyisocyanate having two or more isocyanate groups can be used, and these A mixture of two or more types of polyisocyanate. Specific examples thereof include aromatic systems such as toluene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI); and non-yellowing aromatic groups such as xylylene diisocyanate (XDI); Alicyclic groups such as ketone diisocyanate (IPDI), 4,4'-methylenebis(cyclohexyl isocyanate); fats such as 2,2,4-trimethyl-hexamethylene diisocyanate or hexamethylene diisocyanate (HDI) Family.
作為上述無黃變性二異氰酸酯(ii)，係可使用選自於由脂肪族系二異氰酸酯、脂環族系二異氰酸酯及無黃 變性芳香族系二異氰酸酯所構成之群組中的二異氰酸酯。其等可單獨使用1種，亦可併用2種類以上。 The above-mentioned non-yellowing diisocyanate (ii) can be selected from aliphatic diisocyanates, alicyclic diisocyanates, and non-yellow A diisocyanate in a group consisting of denatured aromatic diisocyanates. These may be used alone or in combination of two or more.
反應性(甲基)丙烯酸酯中，作為對異氰酸酯具反應性的基，係可列舉為羥基、羧基、胺基、巰基等。其等之中係以羥基為佳，上述(甲基)丙烯酸羥烷基酯(iii)尤佳。作為(甲基)丙烯酸羥烷基酯(iii)的例子，係可列舉(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸4-羥丁酯等具有碳數2~6、較佳碳數2~4之羥烷基的(甲基)丙烯酸酯。又，亦可使用分子量較低的聚氧伸烷基二元醇的單(甲基)丙烯酸酯。聚氧伸烷基二元醇的數量平均分子量宜為400以下，尤其是200以下。其等係可單獨使用1種，亦可併用2種類以上。 Among the reactive (meth) acrylates, examples of the group reactive with isocyanate include a hydroxyl group, a carboxyl group, an amine group, and a decyl group. Among them, a hydroxyl group is preferred, and the above hydroxyalkyl (meth)acrylate (iii) is particularly preferred. Examples of the hydroxyalkyl (meth)acrylate (iii) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. A (meth) acrylate having a hydroxyalkyl group having 2 to 6 carbon atoms and preferably 2 to 4 carbon atoms, such as an ester. Further, a mono(meth)acrylate of a polyoxyalkylene glycol having a relatively low molecular weight can also be used. The number average molecular weight of the polyoxyalkylene glycol is preferably 400 or less, particularly 200 or less. These may be used alone or in combination of two or more.
較佳的是，(甲基)丙烯醯氧基全為丙烯醯氧基的胺基甲酸酯(甲基)丙烯酸酯，而且，使用具碳數2~6之羥烷基的丙烯酸羥烷基酯等作為反應性(甲基)丙烯酸酯者更佳。 Preferably, the (meth) propylene decyloxy group is a acryl methoxy group urethane (meth) acrylate, and a hydroxyalkyl group having a hydroxyalkyl group having 2 to 6 carbon atoms is used. Ester or the like is more preferred as the reactive (meth) acrylate.
在胺基甲酸酯(甲基)丙烯酸酯的合成中，所使用的金屬觸媒，係對羥基與異氰酸酯基的反應展現觸媒作用的金屬觸媒。一般而言，係使用有機金屬觸媒作為金屬觸媒，具體上，係選自於由錫、鐵、鉛、鉍、汞、鈦、鉿及鋯所構成之群組中至少1種金屬的有機化合物。但在本發明中，羧酸金屬鹽亦視為有機金屬化合物。 In the synthesis of urethane (meth) acrylate, the metal catalyst used is a metal catalyst which exhibits a catalytic action for the reaction of a hydroxyl group with an isocyanate group. In general, an organometallic catalyst is used as the metal catalyst, and specifically, it is selected from the group consisting of at least one metal selected from the group consisting of tin, iron, lead, antimony, mercury, titanium, cerium, and zirconium. Compound. However, in the present invention, the metal carboxylate salt is also regarded as an organometallic compound.
作為金屬觸媒，係以錫觸媒為宜，更適宜的錫觸媒係有機錫觸媒。作為有機錫觸媒係可列舉：羧酸的錫(II)鹽，例如錫(II)乙酸鹽、錫(II)辛酸鹽、錫(II)乙基己酸鹽及 錫(II)月桂酸鹽)；以及羧酸的錫(IV)鹽，例如二丁基錫二乙酸鹽、二月桂酸二丁錫、二丁基錫馬來酸鹽及二辛基錫二乙酸鹽。此類有機錫觸媒的特別適宜之例方面，係可列舉NEOSTANN U-500(註冊商標，日東化成公司製)、NEOSTANN U-100(註冊商標，日東化成公司製)。 As the metal catalyst, tin catalyst is preferred, and a suitable tin catalyst is an organic tin catalyst. Examples of the organotin catalyst include tin (II) salts of carboxylic acids, such as tin (II) acetate, tin (II) octoate, tin (II) ethyl hexanoate, and Tin (II) laurate); and tin (IV) salts of carboxylic acids, such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, and dioctyltin diacetate. A particularly suitable example of such an organic tin catalyst is NEOSTANN U-500 (registered trademark, manufactured by Nitto Kasei Co., Ltd.) and NEOSTANN U-100 (registered trademark, manufactured by Nitto Kasei Co., Ltd.).
在胺基甲酸酯(甲基)丙烯酸酯的製造中，金屬觸媒的使用量係可為在胺基甲酸酯(甲基)丙烯酸酯製造中作為觸媒通常所使用的量，在本發明的胺基甲酸酯(甲基)丙烯酸酯的製造中，係宜為相對於100質量份之多元醇、聚異氰酸酯與反應性(甲基)丙烯酸酯的合計量而為0.0001~1質量份者。較佳的是0.0005~0.1質量份。藉由使金屬觸媒的使用量在0.0001質量份以上，能夠使胺基甲酸酯化反應適當地進行；而藉由使其在1質量份以下，可以減少反應進行速度的調整及儲存安定劑的使用量。 In the production of urethane (meth) acrylate, the amount of the metal catalyst used may be an amount generally used as a catalyst in the manufacture of urethane (meth) acrylate. In the production of the urethane (meth) acrylate of the invention, it is preferably 0.0001 to 1 part by mass based on 100 parts by mass of the total amount of the polyol, the polyisocyanate and the reactive (meth) acrylate. By. It is preferably 0.0005 to 0.1 parts by mass. By using the amount of the metal catalyst in an amount of 0.0001 part by mass or more, the urethanization reaction can be appropriately carried out, and by setting it to 1 part by mass or less, the adjustment of the reaction progress rate and the storage stabilizer can be reduced. The amount of use.
所製造的胺基甲酸酯(甲基)丙烯酸酯中的金屬觸媒，就是在其製造時所使用的金屬觸媒，因此所製造的胺基甲酸酯(甲基)丙烯酸酯的金屬觸媒量，就等於上述相對於100質量份之多元醇、聚異氰酸酯與反應性(甲基)丙烯酸酯之合計量的金屬觸媒量。因此，相對於100質量份之胺基甲酸酯(甲基)丙烯酸酯100質量份，本發明之胺基甲酸酯(甲基)丙烯酸酯組成物中的金屬觸媒含量宜為0.0001~1質量份，較佳的是0.0005~0.1質量份。 The metal catalyst in the manufactured urethane (meth) acrylate is the metal catalyst used in the production thereof, and thus the metal touch of the manufactured urethane (meth) acrylate The amount of the medium is equal to the amount of the metal catalyst as described above in relation to 100 parts by mass of the polyol, the polyisocyanate and the reactive (meth) acrylate. Therefore, the metal catalyst content in the urethane (meth) acrylate composition of the present invention is preferably 0.0001 to 1 with respect to 100 parts by mass of 100 parts by mass of the urethane (meth) acrylate. The mass part is preferably 0.0005 to 0.1 part by mass.
在金屬觸媒存在下使多元醇與聚異氰酸酯發生反應而獲得之預聚物中的金屬觸媒含量，係相等於在預聚 物的製造中使用的相對於多元醇與聚異氰酸酯之合計量的金屬觸媒量。再者，於所得之預聚物使反應性(甲基)丙烯酸酯發生反應而製造胺基甲酸酯(甲基)丙烯酸酯的情況時，該預聚物中的金屬觸媒，就是使預聚物與反應性(甲基)丙烯酸酯發生反應的觸媒。因此，在使預聚物與反應性(甲基)丙烯酸酯發生反應時，可毋須另行追加金屬觸媒，就使含有著金屬觸媒的預聚物與反應性(甲基)丙烯酸酯發生反應。又，在使預聚物與反應性(甲基)丙烯酸酯發生反應的時候，也可以另行追加金屬觸媒。 The content of the metal catalyst in the prepolymer obtained by reacting the polyol with the polyisocyanate in the presence of a metal catalyst is equivalent to the prepolymerization The amount of metal catalyst used in the manufacture of the material relative to the total amount of the polyol and the polyisocyanate. Further, when the obtained prepolymer reacts with a reactive (meth) acrylate to produce a urethane (meth) acrylate, the metal catalyst in the prepolymer is such that A catalyst in which a polymer reacts with a reactive (meth) acrylate. Therefore, when the prepolymer is reacted with the reactive (meth) acrylate, the prepolymer containing the metal catalyst can be reacted with the reactive (meth) acrylate without additionally adding a metal catalyst. . Further, when the prepolymer is allowed to react with the reactive (meth) acrylate, a metal catalyst may be additionally added.
預聚物製造時的金屬觸媒量，係相對於100質量份之所得預聚物的量(亦即多元醇與聚異氰酸酯的合計量)為未達1質量份者為宜。使預聚物與反應性(甲基)丙烯酸酯發生反應之時的金屬觸媒量，係相對於100質量份之預聚物與反應性(甲基)丙烯酸酯之合計量(亦即，多元醇、聚異氰酸酯與反應性(甲基)丙烯酸酯的合計量)而如上所述，宜為0.0001~1質量份者。 The amount of the metal catalyst in the production of the prepolymer is preferably less than 1 part by mass based on 100 parts by mass of the amount of the prepolymer obtained (that is, the total amount of the polyol and the polyisocyanate). The amount of the metal catalyst at the time of reacting the prepolymer with the reactive (meth) acrylate is based on 100 parts by mass of the total amount of the prepolymer and the reactive (meth) acrylate (ie, plural The alcohol, the total amount of the polyisocyanate and the reactive (meth) acrylate) is preferably 0.0001 to 1 part by mass as described above.
在使預聚物與反應性(甲基)丙烯酸酯發生反應的情況下，當預聚物中的金屬觸媒少時，宜追加金屬觸媒。追加之金屬觸媒量，係宜相對於100質量份之預聚物與反應性(甲基)丙烯酸酯之合計量而為0.1質量份以下。 When the prepolymer is reacted with the reactive (meth) acrylate, when the metal catalyst in the prepolymer is small, a metal catalyst is preferably added. The amount of the metal catalyst to be added is preferably 0.1 part by mass or less based on 100 parts by mass of the total of the prepolymer and the reactive (meth) acrylate.
反應溫度，係因應所用原料及作為目標之胺基甲酸酯(甲基)丙烯酸酯(A)的結構或分子量等作適當設定即可，惟通常10~150℃為佳，較佳的是30~120℃。若反應溫度過低，則反應時間會變長，而對生產性有不良影響。又， 若反應溫度過高，則有誘發副反應等的可能性。反應時間，也是因應所用原料及作為目標之胺基甲酸酯(甲基)丙烯酸酯(A)的結構或分子量等作適當設定即可，惟通常1~70小時為佳，較佳的是2~30小時。若反應時間過短，則反應的控制會變得困難；若反應時間過長，則對生產性有不良影響。 The reaction temperature may be appropriately set depending on the raw material used and the structure or molecular weight of the target urethane (meth) acrylate (A), but it is usually preferably 10 to 150 ° C, preferably 30 ~120 °C. If the reaction temperature is too low, the reaction time becomes long and adversely affects productivity. also, If the reaction temperature is too high, there is a possibility that a side reaction or the like is induced. The reaction time is also appropriately set depending on the raw material used and the structure or molecular weight of the target urethane (meth) acrylate (A), but it is usually 1 to 70 hours, preferably 2 ~30 hours. If the reaction time is too short, the control of the reaction becomes difficult; if the reaction time is too long, the productivity is adversely affected.
<儲存安定劑(B)> <Storage stabilizer (B)>
本發明之胺基甲酸酯(甲基)丙烯酸酯組成物係包含：選自於由下述式(1)~(5)任一者所示之儲存安定劑(B)的群組中之1種類或2種類以上的混合物。 The urethane (meth) acrylate composition of the present invention comprises: a group selected from the group consisting of storage stabilizers (B) represented by any one of the following formulas (1) to (5). 1 type or a mixture of 2 or more types.
在此，R1係氫原子、-OH、或-NH2。較佳的是-OH或-NH2。又，R1為氫原子時，R4宜為-OH或-NH2。 Here, R 1 is a hydrogen atom, -OH, or -NH 2 . Preferred is -OH or -NH 2 . Further, when R 1 is a hydrogen atom, R 4 is preferably -OH or -NH 2 .
R2係-O-或-NH-，較佳係-NH-。 R 2 is -O- or -NH-, preferably -NH-.
R3係氫原子、碳數1~20之有機基、-NH2、或-OH(惟，R2為-O-時，R3不為-OH)。碳數1~20之有機基，係可列舉為可含有氧原子或鹵素原子的脂肪族基、脂環族基、芳香族基、雜原子環基或雜環基。該脂肪族基等之相關說明詳如後述。 R 3 is a hydrogen atom, an organic group having 1 to 20 carbon atoms, -NH 2 or -OH (except, when R 2 is -O-, R 3 is not -OH). The organic group having 1 to 20 carbon atoms may, for example, be an aliphatic group, an alicyclic group, an aromatic group, a hetero atom ring group or a heterocyclic group which may contain an oxygen atom or a halogen atom. The description of the aliphatic group and the like will be described later in detail.
R4係選自於由氫原子、-OH、羧基、醛基、苯基、鹵素原子、-NO2、-NH2、-N3、碳數1~15之烷基、碳數2~15之烯基、碳數2~15之炔基、碳數1~15之鹵烷基、碳數1~15之烷氧基、碳數1~15之烷胺基、碳數1~15之烷硫基、以及碳數1~15之烷氧基羰基、碳數1~15之烷基羰基所構成之群組的基，較佳的是氫原子、-OH、鹵素原子、-NO2、-NH2。R4為含烷基、烯基、炔基、鹵烷基或烷基的基時，其等基毋須為直鏈狀，分枝狀或環狀亦可。又，式(1)~(4)中，R4可為複數存在，此時，可為彼此相同亦可為相異。另一方面，在式(5)中，R4可為一個。又，烷胺基可為第2級、第3級任一者。 R 4 is selected from the group consisting of a hydrogen atom, -OH, a carboxyl group, an aldehyde group, a phenyl group, a halogen atom, -NO 2 , -NH 2 , -N 3 , an alkyl group having 1 to 15 carbon atoms, and a carbon number of 2 to 15. Alkenyl group, alkynyl group having 2 to 15 carbon atoms, haloalkyl group having 1 to 15 carbon atoms, alkoxy group having 1 to 15 carbon atoms, alkylamino group having 1 to 15 carbon atoms, and alkyl having 1 to 15 carbon atoms a group of a group consisting of a thio group and an alkoxycarbonyl group having 1 to 15 carbon atoms and an alkylcarbonyl group having 1 to 15 carbon atoms, preferably a hydrogen atom, -OH, a halogen atom, -NO 2 , - NH 2 . When R 4 is a group having an alkyl group, an alkenyl group, an alkynyl group, a haloalkyl group or an alkyl group, the base group thereof must be linear, branched or cyclic. Further, in the formulae (1) to (4), R 4 may be plural, and in this case, they may be the same or different. On the other hand, in the formula (5), R 4 may be one. Further, the alkylamine group may be either the second or third stage.
作為R3之脂肪族基，係可列舉烷基、烯基等碳數 1~20的烴基。該等烴基係可含有羰基、酯基、醚基、醯胺基、羧基、苯基、烷胺基、烷基醯胺基、醯亞胺基、鹵素原子等。而且亦可含有介於R2與脂肪族基間而鍵結的芳香族基、雜環基，可列舉如下式(6)或(7)所示之基。 Examples of the aliphatic group of R 3 include a hydrocarbon group having 1 to 20 carbon atoms such as an alkyl group or an alkenyl group. These hydrocarbon groups may contain a carbonyl group, an ester group, an ether group, a decylamino group, a carboxyl group, a phenyl group, an alkylamino group, a alkyl decylamino group, a quinone imine group, a halogen atom or the like. Further, an aromatic group or a heterocyclic group which is bonded between R 2 and an aliphatic group may be contained, and examples thereof include a group represented by the following formula (6) or (7).
作為脂環族基，係可列舉環戊基、環己基等，在脂環族上可有取代基亦可沒有取代基。作為取代基，係可列舉碳數1~碳數10的直鏈、分枝狀或環狀的烷基等。 Examples of the alicyclic group include a cyclopentyl group and a cyclohexyl group, and the alicyclic group may have a substituent or a substituent. Examples of the substituent include a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.
芳香族係可列舉直接鍵結於R2的苯基、萘基等，在芳香環上可有取代基。作為取代基，係可列舉碳數1~10之烷基、-OH、-NH2、-NO2、鹵素原子、碳數1~10之鹵烷基、或碳數1~10之烷氧基等。例如，可為以下式(8)或(9)所示之基。 The aromatic group may, for example, be a phenyl group or a naphthyl group directly bonded to R 2 , and may have a substituent on the aromatic ring. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms, -OH, -NH 2 , -NO 2 , a halogen atom, a halogen alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. Wait. For example, it may be a group represented by the following formula (8) or (9).
作為雜原子環基或雜環基，係可列舉吡咯基、咪唑基、吡唑基、三唑基、吲哚基、異吲哚基、吲唑基等，在雜原子環或雜環上可有取代基亦可沒有。作為取代基，係可列舉碳數1~5之烷基、-OH、-NH2、鹵基、碳數1~5之鹵烷基、-NO2、碳數2~4之炔基等。 Examples of the hetero atom ring group or the heterocyclic group include a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a triazolyl group, a fluorenyl group, an isodecyl group, a carbazolyl group, and the like, and a hetero atom ring or a heterocyclic ring may be used. There are also substituents. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, -OH, -NH 2 , a halogen group, a haloalkyl group having 1 to 5 carbon atoms, -NO 2 , an alkynyl group having 2 to 4 carbon atoms, and the like.
作為雜原子環基或雜環基，具體而言係可列舉以下式(10)表示的三唑基。 Specific examples of the hetero atom ring group or the heterocyclic group include a triazolyl group represented by the following formula (10).
在此，R7係碳數1~5之烷基、-OH、-NH2、鹵素原子、碳數1~5之鹵烷基、-NO2、或碳數2~4之炔基。 Here, R 7 is an alkyl group having 1 to 5 carbon atoms, -OH, -NH 2 , a halogen atom, a haloalkyl group having 1 to 5 carbon atoms, -NO 2 or an alkynyl group having 2 to 4 carbon atoms.
上述之基之中，作為R3係宜為氫原子及具電子吸引性之基，其中以上式(6)及(10)所示之基較佳，以式(10)所示之基特佳。 Among the above-mentioned groups, R 3 is preferably a hydrogen atom and an electron-attracting group, and the groups represented by the above formulas (6) and (10) are preferred, and the group represented by formula (10) is preferred. .
式(5)中，R5為以下述式(11)表示之二醯胺殘基。 In the formula (5), R 5 is a diamine residue represented by the following formula (11).
在此，R6係碳數1~15之伸烷基，且宜為碳數6~14之伸烷基。 Here, R 6 is an alkylene group having 1 to 15 carbon atoms, and is preferably an alkylene group having 6 to 14 carbon atoms.
於本發明中，發明人等在各種研討之後，發現了 R1與R2之官能基至關重要。亦即，發現了當R1為-OH或-NH2且R2為-O-或-NH-的時候，減黏抑制效果會大增。並發現了即使R1不為-OH或-NH2，若R4為-OH或-NH2，則會獲得減黏抑制效果。雖沒有限制本發明的用意，但關於其理由，認為是因為該等官能基對金屬觸媒有某種作用。 In the present invention, the inventors discovered various functional groups of R 1 and R 2 after various studies. That is, it was found that when R 1 is -OH or -NH 2 and R 2 is -O- or -NH-, the effect of reducing the viscosity is greatly increased. It was also found that even if R 1 is not -OH or -NH 2 , if R 4 is -OH or -NH 2 , a viscosity reduction inhibitory effect is obtained. Although the meaning of the present invention is not limited, the reason for this is considered to be because the functional groups have a certain effect on the metal catalyst.
以下，例示上述式(1)~(4)任一者所示之化合物。 Hereinafter, the compound represented by any one of the above formulas (1) to (4) will be exemplified.
1)R1為-OH、R2為-O-且R3為氫原子的化合物：[化8-1]
2)R1為-NH2、R2為-O-且R3為氫原子的化合物：
3)R1為-NH2、R2為-NH-且R3為氫原子或芳香族基的化合物：
4)R1為-OH、R2為-NH-且R3為氫原子的化合物：
5)R1為-OH、R2為-O-且R3為脂肪族基的化合物：
6)R1為-NH2、R2為-O-且R3為脂肪族基的化合物：
7)R1為-OH、R2為-NH-且R3為脂肪族基的化合物：
8)R1為-NH2、R2為-NH-且R3為脂肪族基的化合物：
9)R3為脂環族基的化合物：
10)R3為雜環基的化合物：
11)R1為-OH、R2為-O-且R3為芳香族基的化合物：
12)R1為-NH2、R2為-O-且R3為芳香族基的化合物：
13)R1為-OH、R2為-NH-且R3為芳香族基的化合物：
14)R3為-NH2的化合物：
15)R2為-NH-且R3為-OH的化合物：
16)R3為三唑基的化合物：
上述之中適宜的化合物，係R2為-NH-且R3之取代基為具電子吸引性之基的下述化合物。 A suitable compound among the above is a compound wherein R 2 is -NH- and the substituent of R 3 is an electron-attracting group.
1)R1為-OH、R2為-NH-且R3為芳香族基的化合物：
2)R2為-NH-且R3為NH2基的化合物：
3)R2為-NH-且R3為-OH的化合物：
4)R3為三唑基的化合物：
其等之中，較佳的儲存安定劑係下述式(12)所示之3-柳醯基胺基-1,2,4-三唑(ADK Stab CDA1，註冊商標，ADEKA公司製)；
下述式(13)所示之化合物；及
下述式(14)所示之十亞甲基二羧基二柳醯肼(ADK Stab CDA6，註冊商標，ADEKA公司製) Tetramethyldicarboxydiacene (ADK Stab CDA6, registered trademark, manufactured by ADEKA Co., Ltd.) represented by the following formula (14)
其等之中，式(13)所示之化合物，即使較大量地添加，亦不會減損胺基甲酸酯(甲基)丙烯酸酯之硬化物的透明性，以此點而言係為優良的。 Among them, the compound represented by the formula (13) does not detract from the transparency of the cured product of the urethane (meth) acrylate even if it is added in a large amount, and is excellent in terms of this point. of.
又，式(12)及(14)所示化合物係分子量大者，故不易揮發。 Further, since the compounds represented by the formulae (12) and (14) have a large molecular weight, they are less volatile.
本發明中，相對於胺基甲酸酯(甲基)丙烯酸酯100質量份，儲存安定劑係以為0.0001~1質量份、較佳0.0003~0.7質量份、更佳0.0005~0.5質量份被包含。儲存安定劑的量若為前述下限值以上，則會獲得充分的儲存安定性；若為前述上限值以下，則硬化物的透明性良好；即使添加逾前述上限值，不會得到呈比例的效果。另外，本發明中，儲存安定性意指在60℃下保存2個月時的儲存安定性為黏度下降率5%以內者，其測試法係詳述於實施例中。 In the present invention, the storage stabilizer is contained in an amount of 0.0001 to 1 part by mass, preferably 0.0003 to 0.7 part by mass, more preferably 0.0005 to 0.5 part by mass, per 100 parts by mass of the urethane (meth) acrylate. When the amount of the storage stabilizer is at least the above lower limit value, sufficient storage stability is obtained, and if it is at most the above upper limit value, the transparency of the cured product is good, and even if the above upper limit value is added, the cured product is not obtained. The effect of the ratio. Further, in the present invention, the storage stability means that the storage stability at 60 ° C for 2 months is within 5% of the viscosity reduction rate, and the test method is described in detail in the examples.
儲存安定劑，係藉由攪拌器等習知的混合方式而與胺基甲酸酯(甲基)丙烯酸酯混合。可與胺基甲酸酯(甲基)丙烯酸酯製造步驟接續而混合，在此種情況下，在確認異氰酸酯基是否消失，而達到所欲的理論NCO%之後添加。另外，異氰酸酯基的有無及含量係可經由FTIR、滴定法(JISK7301)等來確認。 The stabilizer is stored and mixed with a urethane (meth) acrylate by a conventional mixing method such as a stirrer. It can be mixed with the urethane (meth) acrylate production step, in which case it is added after confirming whether the isocyanate group disappears and reaches the desired theoretical NCO%. Further, the presence or absence and content of the isocyanate group can be confirmed by FTIR, titration (JISK7301) or the like.
再者，本發明之胺基甲酸酯(甲基)丙烯酸酯組成物，除了上述各成分外，可視需要在不損及本發明之目的的範圍內含有其他的添加劑，例如反應性稀釋劑、接著性賦予劑、抗氧化劑、紫外線吸收劑、光聚合起始劑、聚合抑制劑等。 Further, in addition to the above respective components, the urethane (meth) acrylate composition of the present invention may contain other additives such as a reactive diluent, as needed within a range not detracting from the object of the present invention. A further imparting agent, an antioxidant, an ultraviolet absorber, a photopolymerization initiator, a polymerization inhibitor, and the like.
反應性稀釋劑，係具有能夠與胺基甲酸酯(甲基)丙烯酸酯(A)共聚合之聚合性不飽和基、且黏度較胺基甲酸酯(甲基)丙烯酸酯(A)為低的化合物，所使用的目的，係藉由降低胺基甲酸酯(甲基)丙烯酸酯組成物全體的黏度，而提升組成物之塗佈性，及改良該組成物之硬化物的物性等。作為反應性稀釋劑，可列舉具有1個以上之(甲基)丙烯醯氧基、且沒有胺基甲酸酯鍵結的(甲基)丙烯酸酯。再者，不具有會與異氰酸酯基發生反應之基的反應性稀釋劑，可使用作為在製造胺基甲酸酯(甲基)丙烯酸酯(A)時的溶劑。作為溶劑而使用的反應性稀釋劑，不必與胺基甲酸酯(甲基)丙烯酸酯(A)分離，可作為胺基甲酸酯(甲基)丙烯酸酯組成物中的反應性稀釋劑。 The reactive diluent has a polymerizable unsaturated group copolymerizable with the urethane (meth) acrylate (A) and has a viscosity lower than that of the urethane (meth) acrylate (A). The low-level compound is used for the purpose of improving the coatability of the composition and improving the physical properties of the cured product of the composition by reducing the viscosity of the entire urethane (meth) acrylate composition. . The reactive diluent may, for example, be a (meth) acrylate having one or more (meth) acryloxy groups and no urethane linkage. Further, a reactive diluent which does not have a group which reacts with an isocyanate group can be used as a solvent in the production of the urethane (meth)acrylate (A). The reactive diluent used as the solvent does not have to be separated from the urethane (meth) acrylate (A), and can be used as a reactive diluent in the urethane (meth) acrylate composition.
具有1個以上之(甲基)丙烯醯氧基、且沒有會與異氰酸酯基發生反應之基的反應性稀釋劑方面，為了是低黏度，故分子量係125~600者為佳，可列舉為具有烷基之(甲基)丙烯酸酯、或具有脂環式烴基之(甲基)丙烯酸酯。具體而言，係例如可列舉(甲基)丙烯酸正十二烷酯、(甲基)丙烯酸正十八烷酯、(甲基)丙烯酸正二十二烷酯等具有碳數8~22之烷基的(甲基)丙烯酸烷酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸金剛烷酯等具有脂環式烴基的(甲基)丙烯酸酯。 In the case of a reactive diluent having one or more (meth) acryloxy groups and no reaction with an isocyanate group, in order to have a low viscosity, a molecular weight of from 125 to 600 is preferred, and A (meth) acrylate of an alkyl group or a (meth) acrylate having an alicyclic hydrocarbon group. Specific examples thereof include an alkylene having 10 to 22 carbon atoms such as n-dodecyl (meth)acrylate, n-octadecyl (meth)acrylate, and n-docosyl (meth)acrylate. A (meth) acrylate having an alicyclic hydrocarbon group such as an alkyl (meth) acrylate, isodecyl (meth) acrylate or adamantyl (meth) acrylate.
接著性賦予劑，係使胺基甲酸酯(甲基)丙烯酸酯組成物硬化時的接著性提升的化合物，係具有可與胺基甲酸酯(甲基)丙烯酸酯(A)共聚合之聚合性不飽和基、且具有用於提升接著性之極性基等的化合物。接著性提升劑，係 宜為較胺基甲酸酯(甲基)丙烯酸酯(A)為低黏度的化合物者，宜為上述反應性稀釋劑之範疇的化合物。作為接著性賦予劑，係宜為具有羥基等極性基的(甲基)丙烯酸酯，尤其宜為(甲基)丙烯酸羥烷基酯。具體而言，為具有1個或2個羥基的(甲基)丙烯酸酯，例如，作為具有1個羥基的(甲基)丙烯酸酯單體，係可列舉(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸2-羥丁酯、(甲基)丙烯酸4-羥丁酯、甲基丙烯酸6-羥己基酯等。作為具有2個羥基的(甲基)丙烯酸酯單體，係可列舉丙三醇單甲基丙烯酸酯、丙烯酸2,3-二羥丙酯等。 The further imparting agent is a compound which improves the adhesion at the time of curing the urethane (meth) acrylate composition, and is copolymerizable with the urethane (meth) acrylate (A). A polymerizable unsaturated group and a compound having a polar group or the like for enhancing adhesion. Subsequent enhancer It is preferred that the urethane (meth) acrylate (A) is a compound having a low viscosity, and it is preferably a compound of the above reactive diluent. The adhesiveness-imparting agent is preferably a (meth) acrylate having a polar group such as a hydroxyl group, and particularly preferably a hydroxyalkyl (meth)acrylate. Specifically, the (meth) acrylate having one or two hydroxyl groups is, for example, a (meth) acrylate monomer having one hydroxy group, and 2-hydroxyethyl (meth) acrylate is exemplified. 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl methacrylate, and the like. Examples of the (meth) acrylate monomer having two hydroxyl groups include glycerin monomethacrylate and 2,3-dihydroxypropyl acrylate.
紫外線吸收劑，具體而言，係例如可列舉二苯基酮系紫外線吸收劑、苯并三唑系紫外線吸收劑、受阻酚系紫外線吸收劑、柳酸酯系紫外線吸收劑、氰基丙烯酸酯系紫外線吸收劑、草醯胺苯系紫外線吸收劑、甲脒系紫外線吸收劑、三環系紫外線吸收劑、鎳錯鹽系紫外線吸收劑等。 Specific examples of the ultraviolet absorber include a diphenylketone ultraviolet absorber, a benzotriazole ultraviolet absorber, a hindered phenol ultraviolet absorber, a salicyl ester ultraviolet absorber, and a cyanoacrylate. An ultraviolet absorber, a chlorfenapyr ultraviolet absorber, a formazan-based ultraviolet absorber, a tricyclic ultraviolet absorber, a nickel-salt-based ultraviolet absorber, or the like.
作為光聚合起始劑，係例如可列舉苯偶姻、苯偶姻甲基醚、苯偶姻乙基醚及苯偶姻異丙基醚等苯偶姻及其烷基醚；苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、1,1-二氯苯乙酮、1-羥基苯乙酮、1-羥基環己基苯基酮及2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基丙-1-酮等苯乙酮；2-甲基蒽醌、2-乙基蒽醌、2-三級丁基蒽醌、1-氯蒽醌及2-戊基蒽醌等蒽醌；2,4-二甲基-9-氧硫、2,4-二乙基-9-氧硫、2-氯-9-氧硫及2,4-二異丙基-9-氧硫 等9-氧硫；苯乙酮二甲基縮酮及芐基二甲基縮酮等縮酮；2,4,6-三甲基苯甲醯基二苯基氧化膦等單醯基氧化膦及雙醯基氧化膦等氧化膦；二苯基酮等二苯基酮；以及酮等。 Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; and benzoin and alkyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophenone , 1-hydroxycyclohexyl phenyl ketone and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one and the like acetophenone; 2-methylindole , 2-ethyl hydrazine, 2-tertiary butyl hydrazine, 1-chloroindole and 2-pentyl hydrazine; 2,4-dimethyl-9-oxo-sulfur 2,4-diethyl-9-oxosulfur 2-chloro-9-oxosulfur And 2,4-diisopropyl-9-oxosulfur 9-oxosulfur a ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; a monodecylphosphine oxide such as 2,4,6-trimethylbenzimidyl diphenylphosphine oxide; a phosphine oxide such as phosphine; a diphenyl ketone such as diphenyl ketone; Ketones, etc.
此等光聚合起始劑係可單獨使用，亦可與苯甲酸系及胺系等增感劑組合而使用。 These photopolymerization initiators may be used singly or in combination with a sensitizer such as a benzoic acid or an amine.
作為聚合抑制劑，係例如可列舉氫醌、三級丁基氫醌、氫醌單甲基醚、2,6-二-三級丁基-4-甲基酚、2,4,6-三-三級丁基酚、苯醌、酚噻等有機系聚合抑制劑。 Examples of the polymerization inhibitor include hydroquinone, tertiary butyl hydroquinone, hydroquinone monomethyl ether, 2,6-di-tertiary butyl-4-methylphenol, and 2,4,6-trid. - Tert-butyl phenol, benzoquinone, phenolic thiophene Organic polymerization inhibitors.
另外，並未看出此等聚合抑制劑的種類或一般所使用的添加量對減黏有所影響。 In addition, it is not seen that the type of the polymerization inhibitor or the amount of addition generally used has an effect on the viscosity reduction.
[實施例] [Examples]
以下，由實施例及比較例說明本發明。另外，於以下記載中，「份」係意指「質量份」。 Hereinafter, the present invention will be described by way of examples and comparative examples. In addition, in the following description, "part" means "mass part."
由以下方法測定胺基甲酸酯(甲基)丙烯酸酯的特性。 The properties of the urethane (meth) acrylate were determined by the following method.
(NCO測定方法) (NCO measurement method)
依據JISK7301，以滴定法測定。 According to JIS K7301, it is determined by titration.
(GPC測定條件) (GPC measurement conditions)
使用機種：HLC-8220 GPC(TOSOH公司製) Model: HLC-8220 GPC (manufactured by TOSOH)
數據處理裝置：GPC-8020 model II(TOSOH公司製) Data processing device: GPC-8020 model II (manufactured by TOSOH Corporation)
使用管柱：TSK-GEL Super Multipore HZ 4000×22500×2(TOSOH公司製) Use the column: TSK-GEL Super Multipore HZ 4000×22500×2 (manufactured by TOSOH)
管柱溫度：40℃；感測器：RI；溶劑：四氫呋喃；流 速0.35ml/分 Column temperature: 40 ° C; sensor: RI; solvent: tetrahydrofuran; stream Speed 0.35ml / min
試料濃度：0.05質量%；注入量：20μl Sample concentration: 0.05% by mass; Injection amount: 20 μl
標準曲線作成用標準樣本：聚苯乙烯([Easical]PS-2[Polystyrene Standards]，Polymer Laboratories公司製) Standard curve preparation standard sample: polystyrene ([Easical] PS-2 [Polystyrene Standards], manufactured by Polymer Laboratories)
(製造例1：胺基甲酸酯丙烯酸酯1的製造) (Production Example 1: Production of urethane acrylate 1)
於配備有攪拌機的3000ml反應容器，裝入平均羥基數2、數量平均分子量4000之氧伸乙基封端聚氧伸丙基多元醇1840g、異佛酮二異氰酸酯(IPDI)128g、作為觸媒之二月桂酸二辛基錫(U500：日東化成公司製)160mg，在氮氣環境下，以70℃反應約7小時。再於反應混合物中裝入丙烯酸2-羥乙酯(2-HEA)28g、作為聚合抑制劑之2,5-二-三級丁基氫醌(DTBHQ)600mg、作為追加觸媒之二月桂酸二丁錫(U100：日東化成公司製)540mg，於氮氣環境下，以70℃反應約2小時後，羥由上述滴定法確認NCO的消失。由GPC測定胺基甲酸酯丙烯酸酯1的數量平均分子量(Mn)，結果為25,000。 In a 3000 ml reaction vessel equipped with a stirrer, 1840 g of an oxygen-extended ethyl-terminated polyoxy-extension propylene polyol having an average number of hydroxyl groups of 2 and a number average molecular weight of 4000, and 128 g of isophorone diisocyanate (IPDI) were charged as a catalyst. 160 mg of dioctyltin dilaurate (U500: manufactured by Nitto Kasei Co., Ltd.) was reacted at 70 ° C for about 7 hours under a nitrogen atmosphere. Further, 28 g of 2-hydroxyethyl acrylate (2-HEA) and 600 mg of 2,5-di-tert-butylhydroquinone (DTBHQ) as a polymerization inhibitor were added to the reaction mixture, and dilauric acid was added as an additional catalyst. Dibutyltin (U100: manufactured by Nitto Kasei Co., Ltd.) was 540 mg, and after reacting at 70 ° C for about 2 hours in a nitrogen atmosphere, the disappearance of NCO was confirmed by the above titration method. The number average molecular weight (Mn) of the urethane acrylate 1 was determined by GPC and found to be 25,000.
(製造例2：胺基甲酸酯丙烯酸酯2的製造) (Production Example 2: Production of urethane acrylate 2)
在配備有攪拌機的2000ml反應容器中，裝入平均羥基數2、數量平均分子量4000的氧伸乙基封端聚氧伸丙基多元醇991g、丙烯酸異莰酯(IBXA)447g、己二異氰酸酯(HDI)45g、作為觸媒之二月桂酸二辛基錫(U500：日東化成公司製)16mg、作為追加觸媒之二月桂酸二丁錫(U100：日東化成公司製)260mg，在氮氣環境下，於80℃反應約25小時。再於反應混合物中，裝入丙烯酸2-羥乙酯3.1g、作為聚 合抑制劑之2,5-二-三級丁基氫醌310mg，在氮氣環境下，於80℃反應約8小時後，由滴定法確認NCO的消失。由GPC測定胺基甲酸酯丙烯酸酯2的數量平均分子量Mn，結果為53,000。 In a 2000 ml reaction vessel equipped with a stirrer, 991 g of an oxygen-extended ethyl-terminated polyoxy-extension propyl polyol having an average number of hydroxyl groups of 2 and a number average molecular weight of 4000, 447 g of isodecyl acrylate (IBXA), and hexamethylene diisocyanate were placed. Hg) 45g, 16mg of dioctyltin dilaurate (U500: manufactured by Nitto Kasei Co., Ltd.) as a catalyst, and 260mg of dibutyltin dilaurate (U100: manufactured by Nitto Chemical Co., Ltd.) as an additional catalyst, under nitrogen atmosphere It was reacted at 80 ° C for about 25 hours. Further, 3.1 g of 2-hydroxyethyl acrylate was added to the reaction mixture as a poly The inhibitor 2,5-di-tertiary butylhydroquinone 310 mg was reacted at 80 ° C for about 8 hours under a nitrogen atmosphere, and the disappearance of NCO was confirmed by titration. The number average molecular weight Mn of the urethane acrylate 2 was determined by GPC and found to be 53,000.
(製造例3：胺基甲酸酯丙烯酸酯3的製造) (Production Example 3: Production of urethane acrylate 3)
在配備有攪拌機的2000ml反應容器中，裝入平均羥基數2、數量平均分子量4000的氧伸乙基封端聚氧伸丙基多元醇800g、丙烯酸異莰酯360g、己二異氰酸酯38g、作為觸媒之二月桂酸二辛基錫(U500(日東化成公司製)4mg，在氮氣環境下，於80℃反應約25小時。再於反應溶液中，裝入丙烯酸2-羥乙酯3.3g、作為聚合抑制劑之2,5-二-三級丁基氫醌250mg，在氮氣環境下，於80℃反應約8小時後，由滴定法確認NCO的消失。由GPC測定胺基甲酸酯丙烯酸酯3的數量平均分子量Mn，結果為55,000。 In a 2000 ml reaction vessel equipped with a stirrer, 800 g of an oxygen-extended ethyl-terminated polyoxy-extension propyl polyol having an average number of hydroxyl groups of 2 and a number average molecular weight of 4000, 360 g of isodecyl acrylate, and 38 g of hexamethylene diisocyanate were charged as a touch. 4 mg of dioctyltin dilaurate (U500 (manufactured by Nitto Kasei Co., Ltd.) was reacted in a nitrogen atmosphere at 80 ° C for about 25 hours. Further, 3.3 g of 2-hydroxyethyl acrylate was added to the reaction solution. 250 mg of 2,5-di-tert-butylhydroquinone of a polymerization inhibitor, and the reaction of the NCO was confirmed by titration after reacting at 80 ° C for about 8 hours under a nitrogen atmosphere. The urethane acrylate was determined by GPC. The number average molecular weight Mn of 3 was 55,000.
(製造例4：胺基甲酸酯丙烯酸酯4的製造) (Production Example 4: Production of urethane acrylate 4)
在配備有攪拌機的2000ml反應容器中，裝入平均羥基數2、數量平均分子量4000的氧伸乙基封端聚氧伸丙基多元醇990g、丙烯酸異莰酯447g、己二異氰酸酯45g、作為觸媒之雙(乙醯丙酮酸)鋅(以下稱為Zn(acac)2)26mg，在氮氣環境下，於70℃反應5小時。再於反應溶液中，裝入丙烯酸2-羥乙酯2.7g，作為聚合抑制劑之2,5-二-三級丁基氫醌300mg，在氮氣環境下，於70℃反應9小時後，由滴定法確認殘留NCO。由GPC測定胺基甲酸酯丙烯酸酯4的數量平均分子量Mn，結果為55,000。 In a 2000 ml reaction vessel equipped with a stirrer, 990 g of an oxygen-extended ethyl-terminated polyoxy-extension propyl polyol having an average number of hydroxyl groups of 2 and a number average molecular weight of 4000, 447 g of isodecyl acrylate, and 45 g of hexamethylene diisocyanate were charged as a touch. 26 mg of zinc (acetyl acetonate) zinc (hereinafter referred to as Zn(acac) 2) was reacted at 70 ° C for 5 hours under a nitrogen atmosphere. Further, 2.7 g of 2-hydroxyethyl acrylate was added to the reaction solution, and 300 mg of 2,5-di-tert-butylhydroquinone as a polymerization inhibitor was reacted at 70 ° C for 9 hours under a nitrogen atmosphere. The residual NCO was confirmed by titration. The number average molecular weight Mn of the urethane acrylate 4 was determined by GPC and found to be 55,000.
(實施例1) (Example 1)
將100份之於製造例1合成的胺基甲酸酯丙烯酸酯1、及作為儲存安定劑之3-柳醯基胺基-1,2,4-三唑(CDA1(ADEKA公司製))0.5份，利用自轉公轉式攪拌機混合，得到胺基甲酸酯丙烯酸酯組成物。 100 parts of urethane acrylate 1 synthesized in Production Example 1 and 0.5 part of 3-lyonylamino-1,2,4-triazole (CDA1 (made by ADEKA)) as a storage stabilizer The mixture was mixed using a rotary revolution mixer to obtain a urethane acrylate composition.
(實施例2) (Example 2)
將100份之於製造例2合成的胺基甲酸酯(甲基)丙烯酸酯2、及作為儲存安定劑之十亞甲基二羧基二柳醯肼(CDA6(ADEKA公司製))0.02份，經由自轉公轉式攪拌機混合，得到胺基甲酸酯丙烯酸酯組成物。 100 parts of urethane (meth) acrylate 2 synthesized in Production Example 2, and 0.02 parts of decamethylidene dicarboxy saponin (CDA6 (made by ADEKA)) as a storage stabilizer. The mixture was mixed by a rotary revolution mixer to obtain a urethane acrylate composition.
(實施例3) (Example 3)
將100份之於製造例3合成的胺基甲酸酯(甲基)丙烯酸酯3、及作為儲存安定劑之0.0005份的CDA6，經由自轉公轉式攪拌機混合，得到胺基甲酸酯丙烯酸酯組成物。 100 parts of the urethane (meth) acrylate 3 synthesized in the production example 3 and 0.0005 parts of CDA6 as a storage stabilizer were mixed by a rotary rpm mixer to obtain a urethane acrylate composition. Things.
(實施例4) (Example 4)
將100份之於製造例2合成的胺基甲酸酯(甲基)丙烯酸酯2、及作為儲存安定劑之0.5份的CDA1，經由自轉公轉式攪拌機混合，得到胺基甲酸酯丙烯酸酯組成物。 100 parts of the urethane (meth) acrylate 2 synthesized in Production Example 2 and 0.5 part of CDA1 as a storage stabilizer were mixed by a rotary rpm mixer to obtain a urethane acrylate composition. Things.
(實施例5) (Example 5)
將100份之於製造例2合成的胺基甲酸酯(甲基)丙烯酸酯2、及作為儲存安定劑之0.5份的CDA6，經由自轉公轉式攪拌機混合，得到胺基甲酸酯丙烯酸酯組成物。 100 parts of the urethane (meth) acrylate 2 synthesized in Production Example 2 and 0.5 part of CDA 6 as a storage stabilizer were mixed by a rotary rpm mixer to obtain a urethane acrylate composition. Things.
(實施例6) (Example 6)
將100份之於製造例2合成的胺基甲酸酯(甲基)丙烯酸酯2、及作為儲存安定劑之0.1份的2-羥基苯甲醯胺(HBA)，經由自轉公轉式攪拌機混合，得到胺基甲酸酯丙烯酸酯組成物。 100 parts of the urethane (meth) acrylate 2 synthesized in Production Example 2 and 0.1 part of 2-hydroxybenzamide (HBA) as a storage stabilizer were mixed by a rotary revolution mixer. A urethane acrylate composition is obtained.
(實施例7) (Example 7)
將100份之於製造例2合成的胺基甲酸酯(甲基)丙烯酸酯2、及作為儲存安定劑之0.1份的2,4-二羥基苯甲醯胺(DHBA)，經由自轉公轉式攪拌機混合，得到胺基甲酸酯丙烯酸酯組成物。 100 parts of the urethane (meth) acrylate 2 synthesized in Production Example 2 and 0.1 part of 2,4-dihydroxybenzamide (DHBA) as a storage stabilizer were subjected to autorotation The mixer was mixed to obtain a urethane acrylate composition.
(實施例8) (Example 8)
將100份之於製造例2合成的胺基甲酸酯(甲基)丙烯酸酯2、及作為儲存安定劑之0.1份的2-胺基苯甲醯胺(ABA)，經由自轉公轉式攪拌機混合，得到胺基甲酸酯丙烯酸酯組成物。 100 parts of the urethane (meth) acrylate 2 synthesized in Production Example 2 and 0.1 part of 2-aminobenzamide (ABA) as a storage stabilizer were mixed by a rotary revolution mixer. A urethane acrylate composition is obtained.
(實施例9) (Example 9)
將100份之於製造例2合成的胺基甲酸酯(甲基)丙烯酸酯2、及作為儲存安定劑之0.1份的3-羥基-2-萘甲醯胺(HNA)，經由自轉公轉式攪拌機混合，得到胺基甲酸酯丙烯酸酯組成物。 100 parts of the urethane (meth) acrylate 2 synthesized in Production Example 2 and 0.1 part of 3-hydroxy-2-naphthylguanamine (HNA) as a storage stabilizer were subjected to autorotation The mixer was mixed to obtain a urethane acrylate composition.
(實施例10) (Embodiment 10)
將100份之於製造例2合成的胺基甲酸酯(甲基)丙烯酸 酯2、及作為儲存安定劑之0.1份的苯甲醯胺，經由自轉公轉式攪拌機混合，得到胺基甲酸酯丙烯酸酯組成物。 100 parts of the urethane (meth) acrylate synthesized in Production Example 2 The ester 2 and 0.1 part of benzamide as a storage stabilizer were mixed by a rotary revolution mixer to obtain a urethane acrylate composition.
(實施例11) (Example 11)
將100份之於製造例2合成的胺基甲酸酯(甲基)丙烯酸酯、及作為儲存安定劑之0.1份的柳酸甲酯，經由自轉公轉式攪拌機混合，得到胺基甲酸酯組成物。 100 parts of the urethane (meth) acrylate synthesized in Production Example 2 and 0.1 part of methyl sulphate as a storage stabilizer were mixed by a spin-rotation mixer to obtain a urethane composition. Things.
(比較例1~3) (Comparative examples 1 to 3)
將製造例1、2及4合成的胺基甲酸酯丙烯酸酯，在未添加任何物質下，作為比較例1~3。 The urethane acrylates synthesized in Production Examples 1, 2 and 4 were used as Comparative Examples 1 to 3 without adding any substance.
(比較例4) (Comparative Example 4)
將100份之於製造例1合成的胺基甲酸酯丙烯酸酯100份、與作為儲存安定劑之作為金屬減活劑而市售的1,2-雙(3,5-二-三級丁基-4-羥基氫桂皮基)肼(IRGANOX MD-1024(註冊商標，BASF公司製))0.5份，經由自轉公轉式攪拌機混合，得到比較組成物。 100 parts of 100 parts of urethane acrylate synthesized in Production Example 1 and 1,2-bis(3,5-di-tertiary) commercially available as a metal deactivator as a storage stabilizer 0.5 parts of thioglycolic acid sulfonate (IRGANOX MD-1024 (registered trademark, manufactured by BASF Corporation)) was mixed by a rotary automixer to obtain a comparative composition.
(儲存安定性的評價) (evaluation of storage stability)
將各胺基甲酸酯丙烯酸酯組成物的黏度，以實施例1、2、11及比較例1~4為60℃下、實施例3~10為25℃下，在製造後立即以E型黏度計測定，作為各自的初始黏度。接著，將80g的各組成物裝入100ml玻璃製樣本瓶並密閉，以80℃恆溫槽保持3天後，再以和初始黏度相同的條件測定黏度，經由下式求得黏度減少率(%)。 The viscosity of each urethane acrylate composition was 60 ° C in Examples 1, 2, 11 and Comparative Examples 1 to 4, and 25 ° C in Examples 3 to 10, and E type immediately after the production. Viscosity meter was measured as the initial viscosity of each. Next, 80 g of each composition was placed in a 100 ml glass sample bottle, sealed, and kept in a constant temperature bath at 80 ° C for 3 days, and then the viscosity was measured under the same conditions as the initial viscosity, and the viscosity reduction rate (%) was determined by the following formula. .
[(儲存後黏度-初始黏度)/初始黏度]×100 [(post-storage viscosity - initial viscosity) / initial viscosity] × 100
試驗結果記載於下表1~3。 The test results are shown in Tables 1 to 3 below.
(硬化性) (hardenability)
對實施例4及5的胺基甲酸酯丙烯酸酯組成物，由以下方法檢視硬化特性。 The urethane acrylate compositions of Examples 4 and 5 were examined for curing properties by the following method.
試驗法：在3mm厚的玻璃板之間以0.7mm之厚度夾住胺基甲酸酯丙烯酸酯組成物，作成硬化特性測定樣本。使用化學燈，以照度2mW，從樣本上方照射10分鐘。將玻璃板拿開，由指觸評價硬化性，結果確認了任一實施例的組成物均毫無問題地硬化了。 Test method: A urethane acrylate composition was sandwiched between 3 mm thick glass plates at a thickness of 0.7 mm to prepare a sample for determining the hardening property. A chemical lamp was used to illuminate the sample for 10 minutes with an illumination of 2 mW. The glass plate was taken away, and the hardenability was evaluated by finger touch, and as a result, it was confirmed that the composition of any of the examples was hardened without any problem.
如表3所示，不含儲存安定劑的組成物(比較例1~3)無論何者黏度變化都很大，尤其，含有使用鋅觸媒製造之胺基甲酸酯丙烯酸酯的比較例3之組成物大為增黏。比較例4雖為受阻酚系金屬減活劑，但減黏程度高。相對於其等，實施例1~9的胺基甲酸酯丙烯酸酯組成物，即使在加速試驗中均止於約10%以下的黏度減少率。 As shown in Table 3, the composition containing no stabilizer (Comparative Examples 1 to 3) had a large change in viscosity, in particular, Comparative Example 3 containing a urethane acrylate produced using a zinc catalyst. The composition is greatly thickened. Although Comparative Example 4 is a hindered phenol-based metal deactivator, the degree of viscosity reduction is high. With respect to these, the urethane acrylate compositions of Examples 1 to 9 all had a viscosity reduction rate of about 10% or less even in the accelerated test.
實施例10、11，相較於實施例2~9雖減黏抑制效果低了 少許，但與比較例2相比還是有明顯的減黏抑制效果，實用上，可謂在實際保存環境下係為不會有問題的水準。 In Examples 10 and 11, the viscosity reduction inhibition effect was lower than that of Examples 2 to 9. A little, but compared with Comparative Example 2, there is still a significant effect of reducing the viscosity. In practical terms, it can be said that it is not a problem in the actual storage environment.
本發明之胺基甲酸酯(甲基)丙烯酸酯組成物，黏度不會經時變化，故作為需要精密加工的胺基甲酸酯(甲基)丙烯酸酯組成物係為有用的。具體而言，可使用於塗佈劑、印墨、接著劑、抗蝕材、密封材等的硬化性樹脂成分，形成影像顯示裝置之保護部的樹脂層用的硬化性樹脂成分等各種用途。 Since the urethane (meth) acrylate composition of the present invention does not change its viscosity over time, it is useful as a urethane (meth) acrylate composition which requires precision processing. Specifically, the curable resin component used for the coating agent, the ink, the adhesive, the resist, the sealing material, and the like can be used for various purposes such as a curable resin component for a resin layer in a protective portion of a video display device.
另外，在此引用2011年12月26日申請之日本特許出願2011-283712號專利申請案所提出之說明書、申請專利範圍及摘要的全部內容，納入作為本發明說明書之揭示內容。 In addition, the entire contents of the specification, the patent application, and the abstract of the patent application of the Japanese Patent Application No. 2011-283712, filed on Dec.
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| EP4092002A4 (en) | 2020-01-14 | 2023-10-18 | Sumitomo Electric Industries, Ltd. | RESIN COMPOSITION, AND OPTICAL FIBERS AS WELL AS METHOD FOR MANUFACTURING THEM |
| US12265250B2 (en) | 2020-01-14 | 2025-04-01 | Sumitomo Electric Industries, Ltd. | Resin composition, optical fiber, and method for producing optical fiber |
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