CN113811555B - Urethane (meth) acrylate, neutralized product thereof, photocurable resin composition, and liquid composition - Google Patents
Urethane (meth) acrylate, neutralized product thereof, photocurable resin composition, and liquid composition Download PDFInfo
- Publication number
- CN113811555B CN113811555B CN202080034653.5A CN202080034653A CN113811555B CN 113811555 B CN113811555 B CN 113811555B CN 202080034653 A CN202080034653 A CN 202080034653A CN 113811555 B CN113811555 B CN 113811555B
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- China
- Prior art keywords
- diisocyanate
- acrylate
- meth
- compound
- urethane
- 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 125
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000000203 mixture Substances 0.000 title claims description 112
- 239000011342 resin composition Substances 0.000 title claims description 54
- 239000007788 liquid Substances 0.000 title claims description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 100
- -1 diisocyanate compound Chemical class 0.000 claims abstract description 66
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 62
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 40
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 40
- 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 claims abstract description 26
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 125000001302 tertiary amino group Chemical group 0.000 claims abstract description 21
- 229920000193 polymethacrylate Polymers 0.000 claims abstract description 18
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012948 isocyanate Substances 0.000 claims abstract description 7
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 239000000178 monomer Substances 0.000 claims description 43
- 239000000047 product Substances 0.000 claims description 29
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 14
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 11
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 8
- 125000002723 alicyclic group Chemical group 0.000 claims description 8
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- 150000001414 amino alcohols Chemical class 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 claims description 4
- IWSZDQRGNFLMJS-UHFFFAOYSA-N 2-(dibutylamino)ethanol Chemical compound CCCCN(CCO)CCCC IWSZDQRGNFLMJS-UHFFFAOYSA-N 0.000 claims description 3
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 3
- 125000005442 diisocyanate group Chemical group 0.000 claims description 3
- CFENKJQKDBNQRS-UHFFFAOYSA-N 1,18-diisocyanatooctadecane Chemical compound O=C=NCCCCCCCCCCCCCCCCCCN=C=O CFENKJQKDBNQRS-UHFFFAOYSA-N 0.000 claims description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 2
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 claims description 2
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 claims description 2
- ZGDSDWSIFQBAJS-UHFFFAOYSA-N 1,2-diisocyanatopropane Chemical compound O=C=NC(C)CN=C=O ZGDSDWSIFQBAJS-UHFFFAOYSA-N 0.000 claims description 2
- GNQKHBSIBXSFFD-UHFFFAOYSA-N 1,3-diisocyanatocyclohexane Chemical compound O=C=NC1CCCC(N=C=O)C1 GNQKHBSIBXSFFD-UHFFFAOYSA-N 0.000 claims description 2
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 claims description 2
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 2
- KIAZLPPFFCCZJS-UHFFFAOYSA-N 1,5-diisocyanato-2,3-dimethylbenzene Chemical compound CC1=CC(N=C=O)=CC(N=C=O)=C1C KIAZLPPFFCCZJS-UHFFFAOYSA-N 0.000 claims description 2
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 claims description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 2
- SIYBFAKKDKDECW-UHFFFAOYSA-N 1-ethoxy-2,4-diisocyanatobenzene Chemical compound CCOC1=CC=C(N=C=O)C=C1N=C=O SIYBFAKKDKDECW-UHFFFAOYSA-N 0.000 claims description 2
- DZDVHNPXFWWDRM-UHFFFAOYSA-N 2,4-diisocyanato-1-methoxybenzene Chemical compound COC1=CC=C(N=C=O)C=C1N=C=O DZDVHNPXFWWDRM-UHFFFAOYSA-N 0.000 claims description 2
- QZWKEPYTBWZJJA-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine-4,4'-diisocyanate Chemical compound C1=C(N=C=O)C(OC)=CC(C=2C=C(OC)C(N=C=O)=CC=2)=C1 QZWKEPYTBWZJJA-UHFFFAOYSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- VWYHWAHYVKZKHI-UHFFFAOYSA-N N=C=O.N=C=O.C1=CC(N)=CC=C1C1=CC=C(N)C=C1 Chemical compound N=C=O.N=C=O.C1=CC(N)=CC=C1C1=CC=C(N)C=C1 VWYHWAHYVKZKHI-UHFFFAOYSA-N 0.000 claims description 2
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 claims description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims description 2
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000539 dimer Substances 0.000 claims description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 38
- 239000005020 polyethylene terephthalate Substances 0.000 description 38
- 238000000576 coating method Methods 0.000 description 26
- 239000011248 coating agent Substances 0.000 description 24
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 17
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 11
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000003085 diluting agent Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 6
- 238000012719 thermal polymerization Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ZCZFEIZSYJAXKS-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COC(=O)C=C ZCZFEIZSYJAXKS-UHFFFAOYSA-N 0.000 description 2
- SSOONFBDIYMPEU-UHFFFAOYSA-N [3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COCC(CO)(CO)COC(=O)C=C SSOONFBDIYMPEU-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- DXUMYHZTYVPBEZ-UHFFFAOYSA-N 2,4,6-tris(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 DXUMYHZTYVPBEZ-UHFFFAOYSA-N 0.000 description 1
- UXCIJKOCUAQMKD-UHFFFAOYSA-N 2,4-dichlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC(Cl)=C3SC2=C1 UXCIJKOCUAQMKD-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
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- QRHHZFRCJDAUNA-UHFFFAOYSA-N 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=CC(OC)=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 QRHHZFRCJDAUNA-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-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
- ZWVHTXAYIKBMEE-UHFFFAOYSA-N 2-hydroxyacetophenone Chemical compound OCC(=O)C1=CC=CC=C1 ZWVHTXAYIKBMEE-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 description 1
- 125000004864 4-thiomethylphenyl group Chemical group 0.000 description 1
- HOSGXJWQVBHGLT-UHFFFAOYSA-N 6-hydroxy-3,4-dihydro-1h-quinolin-2-one Chemical group N1C(=O)CCC2=CC(O)=CC=C21 HOSGXJWQVBHGLT-UHFFFAOYSA-N 0.000 description 1
- ZMDDERVSCYEKPQ-UHFFFAOYSA-N Ethyl (mesitylcarbonyl)phenylphosphinate Chemical compound C=1C=CC=CC=1P(=O)(OCC)C(=O)C1=C(C)C=C(C)C=C1C ZMDDERVSCYEKPQ-UHFFFAOYSA-N 0.000 description 1
- 101000720524 Gordonia sp. (strain TY-5) Acetone monooxygenase (methyl acetate-forming) Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- JJLKTTCRRLHVGL-UHFFFAOYSA-L [acetyloxy(dibutyl)stannyl] acetate Chemical compound CC([O-])=O.CC([O-])=O.CCCC[Sn+2]CCCC JJLKTTCRRLHVGL-UHFFFAOYSA-L 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone 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
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical class NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- BOXSCYUXSBYGRD-UHFFFAOYSA-N cyclopenta-1,3-diene;iron(3+) Chemical class [Fe+3].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 BOXSCYUXSBYGRD-UHFFFAOYSA-N 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- UFUASNAHBMBJIX-UHFFFAOYSA-N propan-1-one Chemical compound CC[C]=O UFUASNAHBMBJIX-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
-
- 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
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Breeding Of Plants And Reproduction By Means Of Culturing (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
- Polyurethanes Or Polyureas (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
A urethane (meth) acrylate according to an embodiment of the present invention is a reaction product of an aminoalcohol component (a) having 1 hydroxyl group and 1 or more tertiary amino groups, at least 1 isocyanate component (B) selected from a diisocyanate compound (B1) and a polyisocyanate compound (B2) having 3 or more isocyanate groups, the isocyanate component (B) containing the polyisocyanate compound (B2), and a (meth) acrylate component (C) having 1 or more hydroxyl groups, the (meth) acrylate component (C) containing at least 1 selected from a dipentaerythritol poly (meth) acrylate (C1) having 1 or more hydroxyl groups and a pentaerythritol poly (meth) acrylate (C2) having 1 or more hydroxyl groups, the urethane (meth) acrylate having a weight average molecular weight of 1000 or more.
Description
Technical Field
The present invention relates to a urethane (meth) acrylate, a neutralized product thereof, a photocurable resin composition, and a liquid composition.
The present application claims priority based on Japanese application No. 2019-142965 filed in Japan on 8.8.2.2019, the contents of which are incorporated herein by reference.
Background
As the photocurable resin, a urethane (meth) acrylate having a urethane bond and a (meth) acryloyl group is known. When urethane (meth) acrylate is used, the urethane (meth) acrylate is generally diluted with an organic solvent or a reactive diluent. In recent years, it has been studied to dilute urethane (meth) acrylate with water to make it water-soluble.
As an aqueous composition containing a urethane (meth) acrylate, the following compositions are proposed.
(1) An emulsion coating material composition prepared from at least one monomer selected from (meth) acrylates of mono-or polypentaerythritol, a urethane poly (meth) acrylate compound having at least 2 radically polymerizable unsaturated double bonds in 1 molecule, a photopolymerization initiator, a radically polymerizable surfactant, and water (patent document 1).
(2) A photocurable resin composition comprising a polyfunctional urethane acrylate having an oxyalkylene group and a carboxyl group neutralized with an amino compound, a photopolymerization initiator, and water (patent document 2).
(3) An aqueous active energy ray-curable resin composition obtained by producing a carboxyl group-containing urethane (meth) acrylate in the presence of a water-soluble reactive diluent having a water mixing ratio of 100 wt% or more, converting the carboxyl group of the urethane (meth) acrylate into an amine salt, and then adding water to emulsify the amine salt (patent document 3).
(4) A water-dispersible curable resin composition obtained by dispersing at least 1 curable oligomer selected from urethane acrylate and epoxy acrylate in a water solvent in the presence of a reactive emulsifier (patent document 4).
(5) An active energy ray-curable emulsion composition containing an ethylenically unsaturated monomer, wherein a polyfunctional oligomer having 3 to 30 radical-polymerizable unsaturated groups is dispersed in an aqueous solvent in the presence of a polyfunctional reactive surfactant which is a urethane (meth) acrylate compound using a polyalkylene glycol derivative (patent document 5).
Documents of the prior art
Patent literature
Patent document 1: japanese unexamined patent publication Hei 9-137081
Patent document 2: japanese patent application laid-open No. Hei 11-209448
Patent document 3: japanese unexamined patent publication No. Hei 11-279242
Patent document 4: japanese unexamined patent publication No. 2000-159847
Patent document 5: japanese patent application laid-open No. 2008-303258
Disclosure of Invention
Problems to be solved by the invention
The compositions of patent documents 1 to 5 are all aqueous dispersions, not aqueous solutions, and are insufficient in homogeneity.
The purpose of the present invention is to provide a urethane (meth) acrylate which exhibits water solubility when neutralized, and a neutralized product thereof.
Another object of the present invention is to provide a photocurable resin composition that contains a water-soluble urethane (meth) acrylate and can be solubilized in water, and a liquid composition using the same.
Means for solving the problems
The present invention has the following aspects.
[1] A urethane (meth) acrylate which is a reaction product of an amino alcohol component (A) having 1 hydroxyl group and 1 or more tertiary amino groups, at least 1 isocyanate component (B) selected from a diisocyanate compound (B1) and a polyisocyanate compound (B2) having 3 or more isocyanate groups, and a (meth) acrylate component (C) having 1 or more hydroxyl groups,
the isocyanate component (B) comprises the polyisocyanate compound (B2), the (meth) acrylate component (C) comprises at least 1 selected from the group consisting of dipentaerythritol poly (meth) acrylate (C1) having 1 or more hydroxyl groups and pentaerythritol poly (meth) acrylate (C2) having 1 or more hydroxyl groups,
the urethane (meth) acrylate has a weight average molecular weight of 1000 or more.
[2] The urethane (meth) acrylate according to the above [1], wherein the amino alcohol component (A) is at least 1 selected from the group consisting of 2- (dimethylamino) ethanol, 2- (diethylamino) ethanol and 2- (dibutylamino) ethanol.
[3] The urethane (meth) acrylate according to the above [1] or [2], wherein the diisocyanate compound (B1) is at least 1 selected from an alicyclic diisocyanate compound and an aliphatic diisocyanate compound,
the polyisocyanate compound (B2) is at least 1 selected from the group consisting of an alicyclic polyisocyanate compound and an aliphatic polyisocyanate compound.
[4] The urethane (meth) acrylate according to any one of [1] to [3], wherein the polyisocyanate compound (B2) is polyhexamethylene diisocyanate.
[5] The urethane (meth) acrylate according to any one of the above [1] to [4], wherein the diisocyanate compound (B1) is hexamethylene diisocyanate.
[6] A neutralized product obtained by neutralizing a tertiary amino group based on the aminoalcohol component (A) in the urethane (meth) acrylate according to any one of [1] to [5] with a carboxylic acid.
[7] A photocurable resin composition comprising the neutralized product of [6] and a photopolymerization initiator.
[8] The photocurable resin composition according to [7], further comprising a monomer having a polymerizable unsaturated bond.
[9] The photocurable resin composition according to [8], wherein the (meth) acrylate component (C) comprises the dipentaerythritol poly (meth) acrylate (C1),
the monomer comprises dipentaerythritol hexa (meth) acrylate.
[10] The photocurable resin composition according to [9], wherein a hydroxyl value of a mixture of the dipentaerythritol poly (meth) acrylate (C1) and the dipentaerythritol hexa (meth) acrylate is 80mgKOH/g or more.
[11] The photocurable resin composition according to any one of the [8] to [10], wherein the (meth) acrylate component (C) comprises the pentaerythritol poly (meth) acrylate (C2),
the monomer comprises pentaerythritol tetra (meth) acrylate.
[12] The photocurable resin composition according to [11], wherein a hydroxyl value of a mixture of the pentaerythritol poly (meth) acrylate (C2) and the pentaerythritol tetra (meth) acrylate is 90mgKOH/g or more.
[13] A liquid composition comprising the photocurable resin composition according to any one of [7] to [12] and water.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a urethane (meth) acrylate which exhibits water solubility when neutralized, and a neutralized product thereof can be provided.
Further, the present invention can provide a photocurable resin composition which contains a water-soluble urethane (meth) acrylate and can be made water-soluble, and a liquid composition using the same.
Detailed Description
In the present specification, "(meth) acryloyl group" is a generic name of acryloyl group and methacryloyl group.
"(meth) acrylate" is a generic term for both acrylates and methacrylates.
"urethane (meth) acrylate" is a (meth) acrylate having a urethane bond.
"Poly (meth) acrylate" is a (meth) acrylate having 2 or more (meth) acryloyl groups.
The "weight average molecular weight" (hereinafter, also referred to as "Mw") is a value in terms of standard polystyrene measured by Gel Permeation Chromatography (GPC).
The "hydroxyl value" is the amount of potassium hydroxide required to acetylate hydroxyl groups in a sample, and to neutralize acetic acid used for acetylation, expressed in milligrams relative to 1.0g of the sample, is a standard indicating the content of hydroxyl groups in the sample. The hydroxyl value was measured according to JIS K0070: 1992.
Hereinafter, preferred embodiments of the present invention will be described, but the present invention is not limited to the following embodiments.
[ urethane (meth) acrylate ]
A urethane (meth) acrylate (hereinafter, also referred to as "present urethane (meth) acrylate") according to an embodiment of the present invention is a reaction product of an aminoalcohol component (a) (hereinafter, also referred to as "component a"), an isocyanate component (B) (hereinafter, also referred to as "component B"), and a (meth) acrylate component (C) having 1 or more hydroxyl groups (hereinafter, also referred to as "component C").
The reaction product contains units based on the (A) component, units based on the (B) component, and units based on the (C) component.
< component (A) >
(A) The component (A) has 1 hydroxyl group and 1 or more tertiary amino groups in the molecule.
(A) The number of tertiary amino groups contained in the component (a) is preferably 1 from the viewpoint of water solubility.
The component (A) includes, for example, (R) 1 ) 2 -N-R 2 The compound represented. Here, R is 1 Represents an alkyl group, R 2 Represents hydroxyalkyl. 2 of R in the formula 1 May be the same or different.
R 1 The polymer may be linear or branched. R 1 The number of carbon atoms of (b) is preferably 1 to 4 from the viewpoint of water solubility.
R 2 The polymer may be linear or branched. R 2 The number of carbon atoms of (2) is preferably 1 to 4 from the viewpoint of water solubility.
The component (a) is preferably at least 1 selected from the group consisting of 2- (dimethylamino) ethanol, 2- (diethylamino) ethanol, and 2- (dibutylamino) ethanol, from the viewpoint of water solubility.
(A) The component (A) may be used alone in 1 kind, or may be used in combination with 2 or more kinds.
< ingredient (B) >
(B) The component (B) is at least 1 selected from a diisocyanate compound (B1) and a polyisocyanate compound (B2) having 3 or more isocyanate groups (-N = C = O).
"diisocyanate Compound (B1)"
The diisocyanate compound (B1) may be any compound having 2 isocyanate groups in the molecule, and examples thereof include: aliphatic diisocyanate compounds, alicyclic diisocyanate compounds, and aromatic diisocyanate compounds.
Examples of the aliphatic diisocyanate compound include: hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, methylene diisocyanate, ethylene diisocyanate, butylene diisocyanate, propylene diisocyanate, octadecylene diisocyanate, 1, 4-tetramethylene diisocyanate, 1, 6-hexamethylene diisocyanate, 1, 10-decamethylene diisocyanate.
Examples of the alicyclic diisocyanate compound include: 4,4 '-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2, 4 (or 2, 6) -diisocyanate, 1,3- (isocyanatomethyl) cyclohexane, isophorone diisocyanate, dimer acid diisocyanate, 1, 3-cyclohexylene diisocyanate, 4' -methylene-bis (cyclohexyl isocyanate).
Examples of the aromatic diisocyanate include: toluene diisocyanate, 4' -diphenylmethane diisocyanate, xylylene diisocyanate, xylene diisocyanate, dianisidine diisocyanate, phenyl diisocyanate, halogenated phenyl diisocyanate, 1, 5-naphthalene diisocyanate, polymethylene polyphenylene diisocyanate, naphthalene diisocyanate, 3-phenyl-2-ethylene diisocyanate, cumene-2, 4-diisocyanate, 4-methoxy-1, 3-phenylene diisocyanate, 4-ethoxy-1, 3-phenylene diisocyanate, 2,4' -diisocyanate diphenyl ether, 5, 6-dimethyl-1, 3-phenylene diisocyanate, 4' -diisocyanate diphenyl ether, benzidine diisocyanate, 9, 10-anthracene diisocyanate, 4' -diisocyanatobenzyl ester, 3' -dimethyl-4, 4' -diisocyanate diphenylmethane, 2, 6-dimethyl-4, 4' -diisocyanatodiphenyl ester, 3' -dimethoxy-4, 4' -diisocyanatodiphenyl ester, 1, 4-anthracene diisocyanate, phenylene diisocyanate.
The above diisocyanate compounds may be allophanate compounds.
The diisocyanate compound (B1) is preferably at least 1 selected from the group consisting of an alicyclic diisocyanate compound and an aliphatic diisocyanate compound, from the viewpoint of suppressing yellowing.
Among the above, hexamethylene diisocyanate is preferable from the viewpoint of water solubility.
The diisocyanate compound (B1) may be used alone in 1 kind, or may be used in combination with 2 or more kinds.
"polyisocyanate Compound (B2)"
The polyisocyanate compound (B2) may be any compound having 3 or more isocyanate groups in the molecule, and examples thereof include: aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, and aromatic polyisocyanate compounds.
Examples of the aliphatic polyisocyanate compound include: polymers, biurets and adducts of aliphatic diisocyanate compounds.
Examples of the alicyclic polyisocyanate compound include: polymers, biurets and adducts of alicyclic diisocyanate compounds.
Examples of the aromatic polyisocyanate compound include: polymers of aromatic diisocyanate compounds, biuret compounds and adduct compounds, and triphenylmethane triisocyanate.
Specific examples of the aliphatic diisocyanate compound, the alicyclic polyisocyanate compound, and the aromatic polyisocyanate compound are as described above.
Examples of the polymer include a urea ester (isocyanurate).
The polyisocyanate compound (B2) is preferably at least 1 selected from the group consisting of an alicyclic polyisocyanate compound and an aliphatic polyisocyanate compound, from the viewpoint of suppressing yellowing.
Among the above, from the viewpoint of water solubility, polyhexamethylene diisocyanate (polymer of hexamethylene diisocyanate) is preferable, and hexamethylene diisocyanate uretate (uretate of hexamethylene diisocyanate) is particularly preferable.
The polyisocyanate compound (B2) may be used alone in 1 kind, or may be used in combination with 2 or more kinds.
(B) The component (B2) contains at least a polyisocyanate compound (B2) among the diisocyanate compound (B1) and the polyisocyanate compound (B2) from the viewpoint of water solubility of the neutralized product of the present urethane (meth) acrylate.
The proportion of the polyisocyanate compound (B2) to the total mass of the component (B) is preferably 50 mass% or more, more preferably 60 mass% or more, and still more preferably 70 mass% or more. The upper limit of the proportion is not particularly limited, and may be 100 mass%. When the ratio of the polyisocyanate compound (B2) is not less than the lower limit, the water solubility of the neutralized product of the present urethane (meth) acrylate is further excellent.
< ingredient (C) >
(C) Component (C) contains at least 1 selected from dipentaerythritol poly (meth) acrylate (C1) (hereinafter, also referred to as "compound (C1)") having 1 or more hydroxyl groups and pentaerythritol poly (meth) acrylate (C2) (hereinafter, also referred to as "compound (C2)") having 1 or more hydroxyl groups.
The compound (C1) is a compound in which 2 or more and 5 or less hydroxyl groups among 6 hydroxyl groups of dipentaerythritol are substituted with (meth) acryloyloxy groups. Specifically, there may be mentioned: dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate. These compounds (C1) may be used alone in 1 kind, or may be used in combination with 2 or more kinds.
The compound (C2) is a compound in which 2 or more and 3 or less hydroxyl groups among 4 hydroxyl groups of pentaerythritol are substituted with (meth) acryloyloxy groups. Specifically, there may be mentioned: pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate. These compounds (C2) may be used alone in 1 kind, or may be used in combination with 2 or more kinds.
When the component (C) contains the compound (C1), the component (C) preferably contains at least 1 selected from the group consisting of compounds having 2 or more hydroxyl groups, i.e., dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, and dipentaerythritol tetra (meth) acrylate, as the compound (C1), from the viewpoint of water solubility of the neutralized product of the present urethane (meth) acrylate. A compound having 2 or more hydroxyl groups and dipentaerythritol tetra (meth) acrylate may also be used in combination as the compound (C1).
When the component (C) contains the compound (C2), the component (C) preferably contains a compound having 2 or more hydroxyl groups, that is, pentaerythritol di (meth) acrylate, as the compound (C2) from the viewpoint of water solubility of the neutralized product of the present urethane (meth) acrylate. Pentaerythritol di (meth) acrylate and pentaerythritol tri (meth) acrylate may also be used in combination as compound (C2).
The larger the number of hydroxyl groups, the more the amount of tertiary amino groups introduced per 1 molecule of the present urethane (meth) acrylate increases, and the higher the water solubility of the neutralized product.
(C) The component (C) may further contain a (meth) acrylate having 1 or more hydroxyl groups in addition to the compound (C1) and the compound (C2). Examples of the (meth) acrylic acid ester include: dipentaerythritol mono (meth) acrylate, pentaerythritol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate.
The ratio of the total of the compound (C1) and the compound (C2) to the total mass of the component (C) is preferably 90 mass% or more, more preferably 95 mass% or more, and may be 100 mass%.
The urethane (meth) acrylate has a tertiary amino group derived from the component (A).
The content of the tertiary amino group in the present urethane (meth) acrylate is preferably 0.1 to 6% by mass, and more preferably 0.2 to 3% by mass, in terms of the proportion of the nitrogen atom in the tertiary amino group to the total mass of the present urethane (meth) acrylate. When the ratio of the nitrogen atom is not less than the lower limit, the water solubility of the neutralized product of the present urethane (meth) acrylate is further excellent. When the ratio of nitrogen atoms is not more than the above upper limit, a cured product having high surface hardness and excellent abrasion resistance and hard coating properties can be easily obtained. The proportion of the nitrogen atoms is determined by calculating the addition ratio.
The urethane (meth) acrylate has a polymerizable unsaturated bond (carbon-carbon double bond) because it has a (meth) acryloyl group derived from the component (C).
The double bond equivalent of the present urethane (meth) acrylate is preferably 125 to 250g/mol, more preferably 130 to 200g/mol. When the double bond equivalent is not less than the above lower limit, a cured product having high surface hardness and excellent abrasion resistance and hard coatability can be easily obtained. If the double bond equivalent is less than the above upper limit, the flexibility is more excellent.
"double bond equivalent" refers to the mass of each 1 mole of double bonds in a compound.
When the number of moles of the component (C) required for producing 1g of the present urethane (meth) acrylate is α mol and the number of polymerizable unsaturated bonds contained in the molecule of the component (C) 1 is β, the double bond equivalent weight is calculated from 1/(α × β).
When a plurality of compounds different in the number of polymerizable unsaturated bonds ((number of (meth) acryloyl groups)) are used in combination as the component (C), β is a weighted average value calculated from the number of polymerizable unsaturated bonds possessed by each compound and the presence ratio (molar ratio) of each compound. The presence ratio of each compound was determined from the addition ratio.
The urethane (meth) acrylate has an Mw of 1000 or more, preferably 1300 or more.
The Mw of the present urethane (meth) acrylate is preferably 20000 or less, more preferably 2000 or less.
The Mw of the present urethane (meth) acrylate is preferably 1000 to 20000, more preferably 1300 to 2000.
< method for producing urethane (meth) acrylate >
The present urethane (meth) acrylate can be produced by reacting (urethanizing) component (a), (B), and (C). When these components are reacted, the hydroxyl groups of the components (A) and (C) and the isocyanate groups of the component (B) form urethane bonds, and the present urethane (meth) acrylate is produced.
The reaction temperature of the carbamation reaction is, for example, 50 to 150 ℃ and further 60 to 100 ℃.
The reaction time of the urethanization reaction varies depending on the reaction temperature, the presence or absence of a catalyst, and the type of the catalyst, and is, for example, 6 to 48 hours, and further 12 to 36 hours.
The ratio of each component in the urethanization reaction can be appropriately selected in consideration of the number of hydroxyl groups of the components (a) and (C), physical properties after synthesis, and the like.
(B) The ratio (NCO/OH) of the number of isocyanate groups in component (A) to the total number of hydroxyl groups in component (C) is, for example, 0.5 to 2.
The proportion of the component (a) to the total mass of the components (a), (B), and (C) is preferably 3 to 30 mass%, and more preferably 3 to 15 mass%.
(B) The proportion of component (C) to the total mass of component (a), component (B) and component (C) is preferably 7 to 50% by mass, and more preferably 15 to 40% by mass.
(C) The proportion of the component (C) to the total mass of the components (a), (B), and (C) is preferably 50 to 90 mass%, and more preferably 65 to 80 mass%.
(A) The proportion of component (C) to the total mass of component (a) and component (C) is preferably 3 to 40% by mass, and more preferably 5 to 20% by mass.
The urethanization reaction can be carried out in the presence of dipentaerythritol hexa (meth) acrylate (hereinafter, also referred to as "DPH (M) a") or/and pentaerythritol tetra (meth) acrylate (hereinafter, also referred to as "PET (M) a").
When the component (C) contains the compound (C1), the urethanization reaction is typically carried out in the presence of DPH (M) a.
The compound (C1) is generally produced by esterification of dipentaerythritol with (meth) acrylic acid and is produced as a mixture with DPH (M) a. The mixture may contain a plurality of compounds (C1) having different numbers of (meth) acryloyl groups.
If the above-mentioned urethanization reaction is carried out using a mixture of the compound (C1) and DPH (M) a, DPH (M) a having no hydroxyl group does not react with the (B) component but remains as it is, thereby obtaining a mixture of the present urethane (meth) acrylate and DPH (M) a. DPH (M) a in the mixture does not react and remains as it is when the present urethane (meth) acrylate in the mixture is neutralized, and therefore can be used as a monomer of the photocurable resin composition.
The hydroxyl value of the mixture of the compound (C1) and DPH (M) A is preferably 80mgKOH/g or more. The higher the hydroxyl value of the mixture, the smaller the proportion of DPH (M) A. DPH (M) a alone is not water-soluble, but if the hydroxyl value of the mixture of the compound (C1) and DPH (M) a is 80mgKOH/g or more, a mixture of present urethane (meth) acrylate and DPH (M) a is obtained from the mixture, and the mixture of present urethane (meth) acrylate and DPH (M) a obtained by neutralizing the present urethane (meth) acrylate in the mixture easily becomes water-soluble.
The upper limit of the hydroxyl value of the mixture of the compound (C1) and DPH (M) A is not particularly limited, and is, for example, 130mgKOH/g.
When the component (C) contains the compound (C2), the urethanization reaction is typically carried out in the presence of PET (M) a.
In general, the compound (C2) is produced by esterification of pentaerythritol and (meth) acrylic acid, and is produced as a mixture with PET (M) a. The mixture can comprise a plurality of compounds (C2) having different amounts of (meth) acryloyl groups.
If the above-mentioned urethanization reaction is carried out using a mixture of the compound (C2) and PET (M) A, PET (M) A having no hydroxyl group does not react with the component (B) but remains as it is, thereby obtaining a mixture of the present urethane (meth) acrylate and PET (M) A. PET (M) a in the mixture does not react and remains as it is when the present urethane (meth) acrylate in the mixture is neutralized, and therefore can be used as a monomer of the photocurable resin composition.
The hydroxyl value of the mixture of the compound (C2) and PET (M) A is preferably 90mgKOH/g or more, more preferably 100mgKOH/g or more. The higher the hydroxyl value of the mixture, the lower the proportion of PET (M) A tends to be. PET (M) a alone is not water-soluble, but if the hydroxyl value of the mixture of compound (C2) and PET (M) a is 90mgKOH/g or more, a mixture of present urethane (meth) acrylate and PET (M) a is obtained from the mixture, and the mixture of present urethane (meth) acrylate and PET (M) a obtained by neutralizing the present urethane (meth) acrylate in the mixture easily becomes water-soluble.
The upper limit of the hydroxyl value of the mixture of the compound (C2) and the PET (M) A is not particularly limited, and is, for example, 290mgKOH/g.
The hydroxyl value of the mixture of the compound (C2) and PET (M) A is, for example, 90 to 290mgKOH/g, and may be further 100 to 290mgKOH/g.
The above-mentioned urethanization reaction is preferably carried out in the presence of a catalyst from the viewpoint of shortening the reaction time. As the catalyst, a known urethanization catalyst can be used, and examples thereof include: organic metal compounds such as dibutyltin acetate, dibutyltin dilaurate and dioctyltin dilaurate; and basic compounds such as triethylenediamine and triethylamine.
The amount of the catalyst to be used can be appropriately adjusted depending on the activity of the catalyst to be used, and is preferably 0.01 to 0.50% by mass, more preferably 0.03 to 0.30% by mass, and still more preferably 0.05 to 0.25% by mass, based on the total mass of the components (a) and (C).
The urethanization reaction is preferably carried out in the presence of a thermal polymerization inhibitor from the viewpoint of inhibiting the (meth) acryloyl group from reacting. As the thermal polymerization inhibitor, known thermal polymerization inhibitors can be used, and examples thereof include: 2, 6-di-tert-butyl-p-cresol and 4-methoxyphenol.
The amount of the thermal polymerization inhibitor to be used can be appropriately adjusted depending on the activity of the thermal polymerization inhibitor to be used, and is preferably 0.01 to 1.5% by mass, more preferably 0.03 to 1.0% by mass, and still more preferably 0.03 to 0.8% by mass, based on 100% by mass of the reactive product.
In the urethanization reaction, it is preferable that substantially all isocyanate groups in the component (B) are reacted with the component (a) or the component (C).
Measuring an infrared absorption spectrum of the reaction product, wherein the infrared absorption spectrum is measured at a wavelength of 2200 to 2300cm based on the isocyanate residue-derived wavelength not observed -1 The absorption of (B) can be judged by the reaction of substantially all isocyanate groups in the component (B) with the component (a) or the component (C).
[ neutralization of urethane (meth) acrylate ]
The neutralized product according to one embodiment of the present invention (hereinafter, also referred to as "present neutralized product") is obtained by neutralizing a tertiary amino group based on the component (a) in the present urethane (meth) acrylate with a carboxylic acid. Water solubility is exhibited by neutralization of the tertiary amino group with a carboxylic acid.
In the present neutralized product, the tertiary amino groups may be completely or partially neutralized. From the viewpoint of water solubility, the proportion of the tertiary amino groups neutralized with the carboxylic acid is preferably 80 mol% or more, more preferably 95 mol% or more, and may be 100 mol% based on 100 mol% of all the tertiary amino groups in the present neutralized product. The higher the proportion of tertiary amino groups neutralized with a carboxylic acid, the more excellent the water solubility tends to be.
All the tertiary amino groups in the neutralized product are the total of tertiary amino groups neutralized with a carboxylic acid and tertiary amino groups not neutralized with a carboxylic acid.
The carboxylic acid may be any carboxylic acid having a carboxyl group and capable of neutralizing a tertiary amino group, and examples thereof include: acetic acid, acrylic acid. These carboxylic acids may be used alone in 1 kind, or may be used in combination of 2 or more kinds. The carboxylic acid is preferably acetic acid or acrylic acid from the viewpoint of solubility in water.
The present neutralized product can be produced, for example, by contacting the present urethane (meth) acrylate with an aqueous carboxylic acid solution.
The temperature at the time of contact is, for example, 20 to 70 ℃. The contact time is, for example, 10 to 60 minutes.
Instead of the present urethane (meth) acrylate, a mixture of the present urethane (meth) acrylate with DPH (M) a or PET (M) a may also be used. In this case, a mixture of the present neutralized product with DPH (M) a or PET (M) a can be obtained.
[ Photocurable resin composition ]
A photocurable resin composition according to an embodiment of the present invention (hereinafter also referred to as "the present resin composition") includes the present neutralizer and a photopolymerization initiator.
The resin composition preferably further contains a monomer having a polymerizable unsaturated bond. The resin composition may further contain other components as required.
When light is irradiated to the present resin composition, the present resin composition is cured by intramolecular cleavage or hydrogen migration of the photopolymerization initiator to generate active species (radicals or cations) which act on the present urethane (meth) acrylate or monomer to cause polymerization or crosslinking reaction.
< photopolymerization initiator >
As the photopolymerization initiator, known photopolymerization initiators can be used, and examples thereof include: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, alpha-hydroxyacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-2-morpholinyl (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butanone, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 2,4, 6-trimethylbenzoylphenylethoxyphosphine oxide, benzophenone, methyl o-benzoylbenzoate, hydroxybenzophenone, 2-isopropylthioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, 2,4, 6-tris (trichloromethyl) -S-triazine, 2-methyl-4, 6-bis (trichloro) -S-triazine, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -S-triazine, ferrocenium complexes, ferrocenyl-diene compounds. These photopolymerization initiators may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
< monomer >
The monomer may be a monofunctional monomer having 1 polymerizable unsaturated bond, or may be a polyfunctional monomer having 2 or more polymerizable unsaturated bonds. It is also possible to use monofunctional monomers in combination with polyfunctional monomers.
The monomer may be a water-soluble monomer or a water-insoluble monomer. Water-soluble monomers and water-insoluble monomers may also be used in combination. The term "water-soluble monomer" means a monomer which becomes a homogeneous solution when mixed with water.
Examples of monofunctional monomers include: hydroxyl group-containing monofunctional (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl acrylate, and 4-hydroxybutyl acrylate, acryloylmorpholine, dimethylacrylamide, and isobornyl acrylate.
Examples of the polyfunctional monomer include: hydroxyl group-containing polyfunctional (meth) acrylates such as pentaerythritol di-or tri (meth) acrylate, dipentaerythritol di-, tri-, tetra-or penta (meth) acrylate, DPH (M) A, PET (M) A, tripropylene glycol diacrylate and trimethylolpropane triacrylate. These monomers may be used alone in 1 kind, or may be used in combination with 2 or more kinds.
The monomer preferably contains a polyfunctional monomer from the viewpoint of forming a cured film excellent in surface hardness. The polyfunctional monomer is preferably a monomer having 3 or more polymerizable unsaturated bonds, and particularly preferably DPH (M) a or PET (M) a from the viewpoint of hardness.
In the case where the component (C) contains the compound (C1), the monomer preferably contains DPH (M) a.
When the component (C) contains the compound (C2), the monomer preferably contains PET (M) a.
< other ingredients >
As other components, there may be mentioned: additives such as thermal polymerization inhibitors, ultraviolet absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, anti-aging agents, antibacterial agents, fungicides, antifoaming agents, leveling agents, fillers, tackifiers, adhesion-imparting agents, thixotropy-imparting agents, luminescent materials, and the like.
< content of each component >
The total content of the urethane (meth) acrylate and the monomer is preferably 20 to 70% by mass, and more preferably 30 to 60% by mass, based on the total mass of the resin composition.
The proportion of the present urethane (meth) acrylate to the total content of the present urethane (meth) acrylate and the monomer is preferably 1 to 30% by mass, and more preferably 1 to 20% by mass. When the ratio of the present urethane (meth) acrylate is not less than the lower limit, the present resin composition easily exhibits water solubility even when a water-insoluble monomer (DPH (M) a, PET (M) a, or the like) is contained as a monomer.
When the component (C) forming the present urethane (meth) acrylate in the present resin composition contains the compound (C1) and the monomer contains DPH (M) a, the content of DPH (M) a is preferably such that the hydroxyl value of the mixture of the compound (C1) and DPH (M) a becomes 80mgKOH/g or more. The higher the hydroxyl value of the mixture, the smaller the proportion of DPH (M) A. DPH (M) A alone is not water-soluble, but if the hydroxyl value of the mixture of the compound (C1) and DPH (M) A is 80mgKOH/g or more, the resin composition easily exhibits water solubility.
The upper limit of the hydroxyl value of the mixture of the compound (C1) and DPH (M) A is not particularly limited, and is, for example, 130mgKOH/g.
In the case where the component (C) forming the present urethane (meth) acrylate in the present resin composition contains the compound (C2) and the monomer contains PET (M) a, the content of PET (M) a is preferably such an amount that the hydroxyl value of the mixture of the compound (C2) and PET (M) a becomes 90mgKOH/g or more, more preferably such an amount that the hydroxyl value of the mixture of the compound (C2) and PET (M) a becomes 100mgKOH/g or more. The higher the hydroxyl value of the mixture, the lower the proportion of PET (M) A tends to be. Although PET (M) A alone is not water-soluble, the resin composition is easily water-soluble if the hydroxyl value of the mixture of the compound (C2) and PET (M) A is 90mgKOH/g or more.
The upper limit of the hydroxyl value of the mixture of the compound (C2) and PET (M) A is not particularly limited, but is, for example, 290mgKOH/g.
The hydroxyl value of the mixture of the compound (C2) and PET (M) A is, for example, 90 to 290mgKOH/g, and may be further 100 to 290mgKOH/g.
The content of the photopolymerization initiator is preferably 0.5 to 7.0% by mass, and more preferably 1 to 5% by mass, based on the total mass of the present resin composition. When the content of the photopolymerization initiator is not less than the lower limit, the photocurable property of the resin composition is more excellent, and when the content is not more than the upper limit, the storage stability of the resin composition is more excellent.
The resin composition can be produced by mixing the urethane (meth) acrylate, the photopolymerization initiator, and, if necessary, the monomer and other components. The order of mixing the components is not particularly limited. When the monomer contains DPH (M) a, the present resin composition may be produced using a mixture of the present urethane (meth) acrylate and DPH (M) a. When the monomer contains PET (M) a, the resin composition can also be produced using a mixture of the present urethane (meth) acrylate and PET (M) a.
The resin composition can be cured by irradiation with light to produce a cured product.
Examples of the light include: visible light, ultraviolet light, plasma, infrared, ionizing radiation, and the like. Among these lights, ultraviolet rays are preferable from the viewpoint of wide spread of irradiation devices.
The irradiation conditions of light can be appropriately selected according to the light source used. When ultraviolet rays are irradiated, the cumulative light amount is, for example, 50 to 1000mJ/cm 2 。
[ liquid composition ]
The liquid composition according to one embodiment of the present invention (hereinafter, also referred to as "the present liquid composition") includes the present resin composition and water. Typically, the present liquid composition is in the form of an aqueous solution.
The content of the present resin composition in the present liquid composition is, for example, 10 to 60% by mass based on the total mass of the present liquid composition.
The present liquid composition may optionally further contain a non-reactive diluent other than water. The non-reactive diluent is a compound which has no polymerizable unsaturated bond and is liquid at ordinary temperature. As the other non-reactive diluent, a diluent compatible with water is preferable, and for example, there can be mentioned: methanol, ethanol, isopropanol, propylene glycol monomethyl ether.
In consideration of the concept of aqueous property, the content of the other non-reactive diluent in 100% by mass of the present liquid composition is preferably 15% by mass or less, and particularly preferably 0% by mass.
The present liquid composition can be used, for example, for forming a coating film made of a cured product of the present resin composition. The present liquid composition is applied to the surface of an arbitrary substrate, dried to form a coating film composed of the present resin composition, and the coating film is irradiated with light to be cured, thereby obtaining a coating film (cured coating film) composed of a cured product of the present resin composition.
Examples of the substrate include: resin, film, sheet, and molded article. Examples of the resin include: polyesters such as polyethylene terephthalate (PET), polycarbonate resins, and ABS resins.
As the coating method, a known coating method can be suitably used, and examples thereof include: spray coating, spin coating, gravure coating.
The drying conditions may be any conditions as long as the non-reactive diluent such as water can be removed, and examples thereof include conditions of 0.5 to 10 minutes at 60 to 110 ℃.
The irradiation conditions of light are as described above.
The thickness of the coating film (after drying) can be set to, for example, 1 to 10 μm.
Examples
The present invention will be specifically described below with reference to examples.
Hereinafter, "part" means "part by mass" and "%" means "% by mass".
"dipentaerythritol acrylate mixture" is a mixture of a plurality of dipentaerythritol acrylates having different numbers of acryloyl groups, and a mixture containing dipentaerythritol polyacrylate having a hydroxyl group and dipentaerythritol hexaacrylate (DPHA) and having a hydroxyl value of 80mgKOH/g is used.
"pentaerythritol acrylate mixture" is a mixture of a plurality of pentaerythritol acrylates having different numbers of acryloyl groups, and a mixture containing pentaerythritol polyacrylate having a hydroxyl group and pentaerythritol tetraacrylate (PETA) and having a hydroxyl value of 100mgKOH/g is used.
The ratio of urethane acrylate to DPHA in the urethane acrylate and DPHA-containing mixture and the ratio of urethane acrylate to PETA in the urethane acrylate and PETA-containing mixture are the area ratios of GPC (gel permeation chromatography), respectively.
Production example 1
501 parts of dipentaerythritol acrylate mixture, 50 parts of 2- (dimethylamino) ethanol, 0.2 parts of dibutyltin dilaurate, 0.8 parts of 2, 6-di-tert-butyl-p-cresol, and 249 parts of hexamethylene diisocyanate were put into a four-necked flask equipped with a thermometer, a cooling tube, and a stirring device, and after sufficient stirring, the temperature was raised to 70 ℃ and the mixture was stirred and heated for about 24 hours to effect reaction. After the reaction, it was confirmed by infrared absorption spectroscopy that the isocyanate residue was not observed gradually. A mixture containing urethane acrylate and DPHA (hereinafter, also referred to as "a mixture containing urethane acrylate and DPHA") was thus obtained. The ratio of urethane acrylate to DPHA in the mixture containing urethane acrylate, DPHA, i.e. urethane acrylate: DPHA is 37:63.
production examples 2 to 3 and comparative production examples 1 to 4
A mixture containing urethane acrylate and DPHA or a mixture containing urethane acrylate and PETA (hereinafter, also referred to as "a mixture containing urethane acrylate and PETA") was obtained in the same manner as in production example 1, except that the kind and amount of the material charged into the four-necked flask were changed in accordance with the composition shown in table 1. In comparative production example 2, the comparative product was used in place of component (C), and thus the obtained mixture contained no DPHA and no PETA. The ratio of urethane acrylate to DPHA or PETA in the urethane acrylate, DPHA-containing mixture or urethane acrylate, PETA-containing mixture of each production example is shown in table 1.
[ example 1]
Into a flask equipped with a stirrer, 35 parts of the urethane acrylate-and DPHA-containing mixture obtained in production example 1, 1.1 parts of a photopolymerization initiator (2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone, product name "Omnirad 2959" manufactured by IGM Resins b.v., inc. (hereinafter, simply referred to as "Omnirad 2959"), 1.8 parts of 80% acetic acid, and 66 parts of water were charged, and stirred for about 1 hour to obtain a liquid composition. The stirred liquid composition was transparent and pale yellow.
The obtained liquid composition was coated on a film-like easy-to-adhere PET having a thickness of 100 μm so that the film thickness after drying was 5 μm, and dried at 100 ℃ to form a coating film. Thereafter, the coating film was irradiated with a cumulative light amount of 500mJ/cm 2 Thereby obtaining a cured coating film.
[ examples 2 to 4]
Liquid compositions were obtained in the same manner as in example 1, except that the kinds and amounts of the materials charged into the flasks were changed to the compositions shown in table 2. In Table 2, "ACMO" represents acryloylmorpholine. The stirred liquid composition was transparent and pale yellow.
The obtained liquid composition was coated on a film-like easy-to-adhere PET having a thickness of 100 μm so that the film thickness after drying was 5 μm, and dried at 100 ℃ to form a coating film. Thereafter, the coating film was irradiated with a cumulative light amount of 500mJ/cm 2 Thereby obtaining a cured coating film.
Comparative examples 1 to 4
Liquid compositions were obtained in the same manner as in example 1, except that the kinds and amounts of the materials charged into the flasks were changed to the compositions shown in table 2. The liquid composition still caused phase separation after stirring and did not become transparent.
[ evaluation ]
The following evaluations were made for the liquid compositions and cured coatings of the examples. The results are shown in table 2. In comparative examples 1 to 4 in which the water solubility was evaluated as B, evaluations other than water solubility were not performed.
< Water solubility >
The water solubility of the photocurable resin composition (the remaining part of the liquid composition of each example after water removal) was evaluated according to the following criteria.
A: the liquid composition became transparent after stirring for about 1 hour, and did not separate after standing for 7 days.
B: the liquid composition did not become transparent after stirring for about 1 hour.
< curability >
The curability of the photocurable resin composition was evaluated according to the following criteria.
A: the integrated quantity of light for irradiation is 500mJ/cm 2 The ultraviolet ray of (3) is followed by curing of the coating film.
B: the integrated quantity of light for irradiation is 500mJ/cm 2 The coating film was not cured after the UV irradiation.
Here, the occurrence of curing of the coating film was confirmed by the loss of the tacky feel.
Hardness of pencil
The pencil hardness of the surface of the cured coating film was measured in accordance with JIS K5600-5-4.
< leveling >
The leveling property of the liquid composition was evaluated according to the following criteria.
A: when the liquid composition is coated on an easily bondable PET, a cured coating film having a smooth surface can be obtained without occurrence of shrinkage or the like.
B: when the liquid composition is applied to an easily bondable PET, shrinkage or the like occurs, and a cured coating film having a smooth surface cannot be obtained.
[ Table 1]
[ Table 2]
In examples 1 to 4 using the urethane acrylate and DPHA-containing mixtures or urethane acrylate and PETA-containing mixtures obtained in production examples 1 to 3, the photocurable resin compositions showed water solubility. The photocurable resin composition is excellent in curability, surface hardness of a cured coating film, and leveling of a liquid composition.
In comparative examples 1 to 4 using the urethane acrylate and DPHA-containing mixtures or urethane acrylate and PETA-containing mixtures obtained in comparative production examples 1 to 4, the photocurable resin compositions did not show water solubility.
[ industrial applicability ]
The urethane (meth) acrylate of the present invention exhibits water solubility when neutralized, and can be solubilized with water. By the aqueous solution, the leveling property is improved as compared with the case of an aqueous dispersion, and the surface smoothness of the coating film and the physical properties (such as surface hardness) of the coating film after curing can be expected to be improved.
The urethane (meth) acrylate of the present invention can be used as a hard coating agent, a crosslinking agent, and the like.
Claims (15)
1. A urethane (meth) acrylate which is a reaction product of an amino alcohol component (A) having 1 hydroxyl group and 1 or more tertiary amino groups, at least 1 isocyanate component (B) selected from a diisocyanate compound (B1) and a polyisocyanate compound (B2) having 3 or more isocyanate groups, and a (meth) acrylate component (C) having 1 or more hydroxyl groups,
the amino alcohol component (A) is composed of (R) 1 ) 2 -N-R 2 A compound represented by the formula R 1 Represents an alkyl group having 1 to 4 carbon atoms, 2R 1 Which may be the same or different, R 2 Represents a hydroxyalkyl group having 1 to 4 carbon atoms,
the diisocyanate compound (B1) is at least one selected from the group consisting of an aliphatic diisocyanate compound which is at least one selected from the group consisting of hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, methylene diisocyanate, ethylene diisocyanate, butylene diisocyanate, propylene diisocyanate, octadecylene diisocyanate, 1, 4-tetramethylene diisocyanate, 1, 6-hexamethylene diisocyanate, 1, 10-decamethylene diisocyanate and allophanate bodies thereof, the alicyclic diisocyanate compound is at least one selected from the group consisting of 4,4' -methylenebis (cyclohexyl isocyanate), methylcyclohexane-2, 4 (or 2, 6) -diisocyanate, 1,3- (isocyanatomethyl) cyclohexane, isophorone diisocyanate, dimer acid diisocyanate, 1, 3-cyclohexylene diisocyanate, 4' -methylene-bis (cyclohexyl isocyanate), and allophanate bodies thereof, and the aromatic diisocyanate compound is at least one selected from the group consisting of tolylene diisocyanate, 4' -diphenylmethane diisocyanate, xylylene diisocyanate, xylene diisocyanate, dianisidine diisocyanate, phenyl diisocyanate, halogenated phenyl diisocyanate, 1, 5-naphthalene diisocyanate, 3-phenyl-2-ethylene diisocyanate, cumene-2, 4-diisocyanate, 4-methoxy-1, 3-phenylene diisocyanate, 4-ethoxy-1, 3-phenylene diisocyanate, 2,4 '-diisocyanate diphenyl ether, 5, 6-dimethyl-1, 3-phenylene diisocyanate, 4' -diisocyanate diphenyl ether, benzidine diisocyanate, 9, 10-anthracene diisocyanate, 4 '-benzyl diisocyanate, 3' -dimethyl-4, 4 '-diisocyanate diphenylmethane, 2, 6-dimethyl-4, 4' -diphenyl diisocyanate, 3 '-dimethoxy-4, 4' -diphenyl diisocyanate, 1, 4-anthracene diisocyanate, phenylene diisocyanate, and allophanate thereof,
the polyisocyanate compound (B2) is at least one selected from the group consisting of an aliphatic polyisocyanate compound, an alicyclic polyisocyanate compound and an aromatic polyisocyanate compound, the aliphatic polyisocyanate compound is at least one selected from the group consisting of a polymer, a biuret compound and an adduct of the aliphatic diisocyanate compound, the alicyclic polyisocyanate compound is at least one selected from the group consisting of a polymer, a biuret compound and an adduct of the alicyclic diisocyanate compound, the aromatic polyisocyanate compound is at least one selected from the group consisting of a polymer, a biuret compound and an adduct of the aromatic diisocyanate compound and triphenylmethane triisocyanate,
the isocyanate component (B) contains the polyisocyanate compound (B2),
the (meth) acrylate component (C) contains at least 1 selected from dipentaerythritol poly (meth) acrylate (C1) having 1 or more hydroxyl groups and pentaerythritol poly (meth) acrylate (C2) having 1 or more hydroxyl groups,
the urethane (meth) acrylate has a weight average molecular weight of 1000 or more.
2. The urethane (meth) acrylate according to claim 1, wherein the amino alcohol component (a) is at least 1 selected from the group consisting of 2- (dimethylamino) ethanol, 2- (diethylamino) ethanol, and 2- (dibutylamino) ethanol.
3. The urethane (meth) acrylate according to claim 1 or 2, wherein the diisocyanate compound (B1) is at least 1 selected from the group consisting of the alicyclic diisocyanate compound and the aliphatic diisocyanate compound,
the polyisocyanate compound (B2) is at least 1 selected from the alicyclic polyisocyanate compound and the aliphatic polyisocyanate compound.
4. The urethane (meth) acrylate according to claim 1 or 2, wherein the polyisocyanate compound (B2) is a polymer of hexamethylene diisocyanate.
5. The urethane (meth) acrylate according to claim 1 or 2, wherein the diisocyanate compound (B1) is hexamethylene diisocyanate.
6. The urethane (meth) acrylate according to claim 3, wherein the diisocyanate compound (B1) is hexamethylene diisocyanate.
7. The urethane (meth) acrylate according to claim 4, wherein the diisocyanate compound (B1) is hexamethylene diisocyanate.
8. A neutralized product obtained by neutralizing the tertiary amino group based on the aminoalcohol component (A) in the urethane (meth) acrylate according to any one of claims 1 to 7 with a carboxylic acid.
9. A photocurable resin composition comprising the neutralized product of claim 8 and a photopolymerization initiator.
10. The photocurable resin composition according to claim 9, further comprising a monomer having a polymerizable unsaturated bond.
11. The photocurable resin composition according to claim 10, wherein the (meth) acrylate component (C) comprises the dipentaerythritol poly (meth) acrylate (C1),
the monomer comprises dipentaerythritol hexa (meth) acrylate.
12. The photocurable resin composition according to claim 11, wherein a hydroxyl value of a mixture of the dipentaerythritol poly (meth) acrylate (C1) and the dipentaerythritol hexa (meth) acrylate is 80mgKOH/g or more.
13. The photocurable resin composition according to any one of claims 10-12, wherein the (meth) acrylate component (C) comprises the pentaerythritol poly (meth) acrylate (C2),
the monomer comprises pentaerythritol tetra (meth) acrylate.
14. The photocurable resin composition according to claim 13, wherein a hydroxyl value of a mixture of the pentaerythritol poly (meth) acrylate (C2) and the pentaerythritol tetra (meth) acrylate is 90mgKOH/g or more.
15. A liquid composition comprising the photocurable resin composition according to any one of claims 9-14 and water.
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| JP2019-142965 | 2019-08-02 | ||
| JP2019142965 | 2019-08-02 | ||
| PCT/JP2020/028789 WO2021024842A1 (en) | 2019-08-02 | 2020-07-28 | Urethane (meth)acrylate, neutralized product of same, photocurable resin composition and liquid composition |
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| CN113811555A CN113811555A (en) | 2021-12-17 |
| CN113811555B true CN113811555B (en) | 2023-03-10 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010202777A (en) * | 2009-03-04 | 2010-09-16 | Toyo Ink Mfg Co Ltd | Active energy line curable composition |
| WO2014106939A1 (en) * | 2013-01-07 | 2014-07-10 | 宇部興産株式会社 | Aqueous resin dispersion and use of same |
| WO2017161607A1 (en) * | 2016-03-24 | 2017-09-28 | 万华化学集团股份有限公司 | Waterborne radiation curing urethane acrylate composition, preparation method therefor and coating |
| WO2018181972A1 (en) * | 2017-03-31 | 2018-10-04 | 日本合成化学工業株式会社 | Active energy ray-curable resin composition and coating agent |
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2020
- 2020-07-28 CN CN202080034653.5A patent/CN113811555B/en active Active
- 2020-07-28 JP JP2021537236A patent/JP7040842B2/en active Active
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010202777A (en) * | 2009-03-04 | 2010-09-16 | Toyo Ink Mfg Co Ltd | Active energy line curable composition |
| WO2014106939A1 (en) * | 2013-01-07 | 2014-07-10 | 宇部興産株式会社 | Aqueous resin dispersion and use of same |
| WO2017161607A1 (en) * | 2016-03-24 | 2017-09-28 | 万华化学集团股份有限公司 | Waterborne radiation curing urethane acrylate composition, preparation method therefor and coating |
| WO2018181972A1 (en) * | 2017-03-31 | 2018-10-04 | 日本合成化学工業株式会社 | Active energy ray-curable resin composition and coating agent |
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| JPWO2021024842A1 (en) | 2021-02-11 |
| WO2021024842A1 (en) | 2021-02-11 |
| JP7040842B2 (en) | 2022-03-23 |
| CN113811555A (en) | 2021-12-17 |
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