CN110382575A - Actinic energy ray curable resion composition and smears - Google Patents
Actinic energy ray curable resion composition and smears Download PDFInfo
- Publication number
- CN110382575A CN110382575A CN201880014095.9A CN201880014095A CN110382575A CN 110382575 A CN110382575 A CN 110382575A CN 201880014095 A CN201880014095 A CN 201880014095A CN 110382575 A CN110382575 A CN 110382575A
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- Prior art keywords
- methyl
- acrylate
- acrylic acid
- mixture
- carbamate
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 428
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 321
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 126
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 101
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 93
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 93
- 239000011248 coating agent Substances 0.000 claims abstract description 91
- 238000000576 coating method Methods 0.000 claims abstract description 91
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 88
- GNBCKKSGQPLTRW-UHFFFAOYSA-N C(C=C)(=O)OC.C(N)(O)=O Chemical compound C(C=C)(=O)OC.C(N)(O)=O GNBCKKSGQPLTRW-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 23
- -1 (methyl) acrylic acid dipentaerythritol ester Chemical class 0.000 claims description 142
- 238000006243 chemical reaction Methods 0.000 claims description 82
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 54
- 239000011347 resin Substances 0.000 claims description 47
- 229920005989 resin Polymers 0.000 claims description 47
- 239000002253 acid Substances 0.000 claims description 40
- 150000002148 esters Chemical class 0.000 claims description 36
- 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 description 28
- QIDAPCPSDKKZEA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;2-methylprop-2-enoic acid Chemical class CC(=C)C(O)=O.OCC(CO)(CO)COCC(CO)(CO)CO QIDAPCPSDKKZEA-UHFFFAOYSA-N 0.000 claims description 20
- 230000003287 optical effect Effects 0.000 claims description 10
- 239000010409 thin film Substances 0.000 claims description 10
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical group CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- AWZKVJXQYAIKOD-UHFFFAOYSA-N but-2-ene carbamic acid Chemical group C(N)(O)=O.CC=CC AWZKVJXQYAIKOD-UHFFFAOYSA-N 0.000 claims description 4
- IQSHMXAZFHORGY-UHFFFAOYSA-N methyl prop-2-enoate;2-methylprop-2-enoic acid Chemical compound COC(=O)C=C.CC(=C)C(O)=O IQSHMXAZFHORGY-UHFFFAOYSA-N 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 38
- 239000010408 film Substances 0.000 description 122
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 77
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 60
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 50
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 49
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 45
- 239000003054 catalyst Substances 0.000 description 35
- 239000004615 ingredient Substances 0.000 description 33
- 239000003112 inhibitor Substances 0.000 description 32
- 238000006116 polymerization reaction Methods 0.000 description 32
- 229910052757 nitrogen Inorganic materials 0.000 description 29
- 239000002585 base Substances 0.000 description 24
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 21
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 19
- 239000002904 solvent Substances 0.000 description 19
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 18
- 238000007711 solidification Methods 0.000 description 18
- 230000008023 solidification Effects 0.000 description 18
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 17
- 150000005846 sugar alcohols Polymers 0.000 description 17
- 229920002799 BoPET Polymers 0.000 description 16
- 239000012975 dibutyltin dilaurate Substances 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 16
- 239000000178 monomer Substances 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 235000019441 ethanol Nutrition 0.000 description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 14
- 238000005984 hydrogenation reaction Methods 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- 150000001336 alkenes Chemical class 0.000 description 11
- 150000002513 isocyanates Chemical class 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- RKGVNLUAVXQJDL-UHFFFAOYSA-N benzene;prop-2-enoic acid Chemical compound OC(=O)C=C.C1=CC=CC=C1 RKGVNLUAVXQJDL-UHFFFAOYSA-N 0.000 description 8
- 125000005442 diisocyanate group Chemical group 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000012948 isocyanate Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 208000027418 Wounds and injury Diseases 0.000 description 7
- 238000005452 bending Methods 0.000 description 7
- KPTLPIAOSCGETM-UHFFFAOYSA-N benzene 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O.c1ccccc1 KPTLPIAOSCGETM-UHFFFAOYSA-N 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 230000001186 cumulative effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 5
- LWTMUSZXWXLIPB-UHFFFAOYSA-N C(C=C)(=O)O.NC(=O)OCC.N Chemical compound C(C=C)(=O)O.NC(=O)OCC.N LWTMUSZXWXLIPB-UHFFFAOYSA-N 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 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 5
- 150000001875 compounds Chemical class 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- 238000006845 Michael addition reaction Methods 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 150000002576 ketones Chemical class 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 238000003892 spreading Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 3
- KNSXNCFKSZZHEA-UHFFFAOYSA-N [3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C KNSXNCFKSZZHEA-UHFFFAOYSA-N 0.000 description 3
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- JJFFNQSUUAIWHB-UHFFFAOYSA-N carbamic acid;prop-2-enoic acid Chemical compound NC(O)=O.OC(=O)C=C JJFFNQSUUAIWHB-UHFFFAOYSA-N 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
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- 238000010894 electron beam technology Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000007046 ethoxylation reaction Methods 0.000 description 2
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- BPMFZUMJYQTVII-UHFFFAOYSA-N guanidinoacetic acid Chemical compound NC(=N)NCC(O)=O BPMFZUMJYQTVII-UHFFFAOYSA-N 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- RHGQOMYDGHIKFH-GNOQXXQHSA-K bis[[(z)-octadec-9-enoyl]oxy]bismuthanyl (z)-octadec-9-enoate Chemical compound [Bi+3].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O RHGQOMYDGHIKFH-GNOQXXQHSA-K 0.000 description 1
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- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- HPAFOABSQZMTHE-UHFFFAOYSA-N phenyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPAFOABSQZMTHE-UHFFFAOYSA-N 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
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- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
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- 229920000642 polymer Chemical class 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
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- 229920005672 polyolefin resin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
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- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
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- 239000003381 stabilizer Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 1
- MVQLEZWPIWKLBY-UHFFFAOYSA-N tert-butyl 2-benzoylbenzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 MVQLEZWPIWKLBY-UHFFFAOYSA-N 0.000 description 1
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 1
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- ALHBQZRUBQFZQV-UHFFFAOYSA-N tin;tetrahydrate Chemical compound O.O.O.O.[Sn] ALHBQZRUBQFZQV-UHFFFAOYSA-N 0.000 description 1
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 description 1
- KOECRLKKXSXCPB-UHFFFAOYSA-K triiodobismuthane Chemical compound I[Bi](I)I KOECRLKKXSXCPB-UHFFFAOYSA-K 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
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- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- 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
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
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- 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
- 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
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L75/04—Polyurethanes
- C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
- C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
Abstract
The present invention provides a kind of actinic energy ray curable resion composition, carbamate (methyl) acrylate composition that is small containing cure shrinkage and being not easy to crimp and can be formed hardness and bendability also excellent cured coating film；The actinic energy ray curable resion composition contains carbamate (methyl) acrylate composition [I], carbamate (methyl) acrylate composition [I] is that the hydroxyl of (methyl) acrylate in mixture (A) is reacted with the isocyanate group of polyisocyanates (CA) and generated, the mixture (A) is the mixture of (methyl) acrylate of the reaction product as pentaerythrite Yu (methyl) acrylic acid, and the hydroxyl value of said mixture (A) is 200mgKOH/g or more.
Description
Technical field
The present invention relates to the active energy ray-curable trees for containing carbamate (methyl) acrylate composition
Oil/fat composition and smears, more specifically, when being related to forming cured coating film, cure shrinkage is small thus is not easy to crimp, Jin Erneng
Form the actinic energy ray curable resion composition of hardness and the superior film of bendability and the painting using this composition
Cloth agent.
Background technique
In the past, actinic energy ray curable resion composition by radiation, ultraviolet light of very short time etc. because that can be lived
Property energy-ray irradiation complete solidification, be thus widely used for as smears, bonding agent or the anchor coating agent for various substrates
Deng use, carbamate (methyl) acrylate based compound, polyfunctional monomer are used as cure component therein.But it will
Actinic energy ray curable resion composition is especially as smears, and especially hard coating smears is in use, have hair
The problem of cure shrinkage of raw film, cured coating film easily crimps, it is desirable to have be not easy curling person.
In addition, hard coating uses smears also to use as protective film in the bending section of molded product, display etc., therefore want
The plastic film for foring cured coating film is asked to be not susceptible to the bendability of cracking etc. bending.
It is not easy the phenomenon that crimping for above-mentioned, for cure shrinkage to be inhibited, it is thus proposed that: it is added in curable resin
The hardening resin composition of fine inorganic particles is (referring for example to patent document 1.), containing as cure component through high molecular weight
The hardening resin composition of carbamate (methyl) acrylate of change is (referring for example to patent document 2.), and then someone mentions
The hydroxyl and polyisocyanic acid in (methyl) acrylic acid adduct out containing the pentaerythrite for making hydroxyl value 130mgKOH/g or more
The isocyanate group of ester based compound is reacted and curable resin group obtained by carbamate (methyl) acrylate of generation
Object is closed (referring for example to patent document 3.).
In addition, as keeping marresistance more preferable and it has been known that there is will for example contain by the method for hard conating more high rigidity
Six acrylic acid dipentaerythritol esters and eight acrylic acid tripentaerythritol esters and three second of the resin combination generated at 80 μm of thickness
It is coated with and makes its solidification with 12 μm of film thickness on Atriacetyl cellulose film, to obtain the film of the hardness with pencil hardness 5H or so
Technology (referring for example to patent document 4.).
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2010-77292 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2010-180319 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2012-229412 bulletin
Patent document 4: Japanese Unexamined Patent Publication 2009-286924 bulletin
Summary of the invention
Problems to be solved by the invention
But the public technology of above patent document 1, if considering, the compatibility of fine inorganic particles and curable resin is had
The problem of a possibility that organic solvent that can be used is limited or the surface of film is abnormal is increased, or in general, it is inorganic
Fine grained is expensive, therefore being compounded with the resin of fine inorganic particles, coating also becomes expensive, the usage of curable resin in reality
It is limited to special purposes.
In addition, the public technology of above patent document 2, the carbamate (first for making to use as cure component
Base) autofrettage of acrylate polymeric quantization becomes reaction of high order, therefore operation becomes miscellaneous or film marresistance drop
It is low.
On the other hand, in the public technology of patent document 3, available cure shrinkage is small and crimps suppressed solidification and applies
Film, but consider the viewpoint of hardness, it is insufficient.
In addition, the public technology of patent document 4, although the surface hardness of cured coating film is high, the curling occurred when solidifying
Greatly, and it is hard and crisp, so can be ruptured when being bent film.
The present invention be under such a background, provide containing when foring cured coating film because cure shrinkage is small so being not easy
Curling, and the activity of hardness and bendability also carbamate (methyl) acrylate composition of excellent film can be formed
Energy ray-curable resin combination and the smears for using this composition.
The solution to the problem
Inventors etc. make great efforts to study in view of the situation, as a result, it has been found that: by using carbamate (methyl)
It is small therefore be not easy curling and hardness and bendability are also excellent to obtain cure shrinkage as cure component for acrylate composition
Cured coating film；Carbamate (methyl) acrylate composition is at least one of pentaerythrite and dipentaerythritol
The hydroxyl of (methyl) acrylate in the hydroxyl value and the reaction product of particular range is shown with the reaction product of (methyl) acrylic acid
Base is reacted with polyisocyanates and is generated.
That is, the 1st purport of the invention is related to a kind of actinic energy ray curable resion composition, contain carbamic acid
Ester (methyl) acrylate composition [I] is (methyl) acrylate (a1)~(a3) and polyisocyanic acid in mixture (A)
Obtained from ester (CA) reaction, the mixture (A) is as the following of pentaerythrite and the reaction product of (methyl) acrylic acid
(methyl) acrylate (a1)~(a4) mixture,
The hydroxyl value of the mixture (A) is 200mgKOH/g or more；
Mixture (A)
(a1) single (methyl) acrylate, pentaerythritol
(a2) two (methyl) acrylate, pentaerythritol
(a3) three (methyl) acrylate, pentaerythritol
(a4) four (methyl) acrylate, pentaerythritol.
In addition, the 2nd purport of the invention is related to a kind of actinic energy ray curable resion composition, contain above-mentioned ammonia
Carbamate (methyl) acrylate composition [I] and carbamate (methyl) acrylate composition [II],
Carbamate (methyl) acrylate composition [II] is (methyl) acrylate in mixture (B)
(b1) obtained from~(b5) is reacted with polyisocyanates (CB), the mixture (B) is as dipentaerythritol and (methyl)
The mixture of following (methyl) acrylate (b1)~(b6) of the reaction product of acrylic acid,
The hydroxyl value of said mixture (B) is 40mgKOH/g or more；
Mixture (B)
(b1) single (methyl) acrylic acid dipentaerythritol ester
(b2) two (methyl) acrylic acid dipentaerythritol ester
(b3) three (methyl) acrylic acid dipentaerythritol ester
(b4) four (methyl) acrylic acid dipentaerythritol ester
(b5) five (methyl) acrylic acid dipentaerythritol ester
(b6) six (methyl) acrylic acid dipentaerythritol ester.
In turn, the 3rd purport of the invention is related to a kind of actinic energy ray curable resion composition, contains amino first
Acid esters (methyl) acrylate composition [III],
Carbamate (methyl) acrylate composition [III] is by (methyl) acrylic acid as following [α]
Ester (a1)~(a3), (methyl) acrylate (b1)~(b5) as following [β] and polyisocyanates (CC) reaction obtain
's；
Following (methyl) acrylate (a1)~(a4) of [α] as pentaerythrite and the reaction product of (methyl) acrylic acid
Mixture (A) in (methyl) acrylate (a1)~(a3), and the hydroxyl value of said mixture (A) be 200mgKOH/g with
On；
(a1) single (methyl) acrylate, pentaerythritol
(a2) two (methyl) acrylate, pentaerythritol
(a3) three (methyl) acrylate, pentaerythritol
(a4) four (methyl) acrylate, pentaerythritol
[β] as dipentaerythritol and the reaction product of (methyl) acrylic acid following (methyl) acrylate (b1)~
(b6) (methyl) acrylate (b1)~(b5) in mixture (B), and the hydroxyl value of said mixture (B) is 40mgKOH/g
More than；
(b1) single (methyl) acrylic acid dipentaerythritol ester
(b2) two (methyl) acrylic acid dipentaerythritol ester
(b3) three (methyl) acrylic acid dipentaerythritol ester
(b4) four (methyl) acrylic acid dipentaerythritol ester
(b5) five (methyl) acrylic acid dipentaerythritol ester
(b6) six (methyl) acrylic acid dipentaerythritol ester.
In addition, the present invention is also provided containing smears made of above-mentioned actinic energy ray curable resion composition.
The effect of invention
The actinic energy ray curable resion composition of 1st purport of the invention, cure shrinkage is small therefore is not easy to crimp, energy
Enough form hardness and the excellent cured coating film of bendability, even and film before curing can also form inviscid film table
Face is useful especially in the various uses such as the smears of hard coating.
In addition, the actinic energy ray curable resion composition of the 2nd purport of the invention, cure shrinkage is small therefore is not easy to roll up
Song, and then it is capable of forming hardness and the excellent cured coating film of bendability, especially have in various uses such as the smears of hard coating
With.
In turn, the actinic energy ray curable resion composition of the 3rd purport of the invention, cure shrinkage is small therefore is not easy to roll up
Song, and the cured coating film of hardness, bendability and excellent scratch resistance can be formed, it is especially various in the smears of hard coating etc.
Purposes is useful.
If two (methyl) acrylic acid pentaerythrites in the mixture (A) of above-mentioned (methyl) acrylate (a1)~(a4)
The containing ratio of ester (a2) is 10~50 weight %, then excellent in terms of taking into account hardness and bendability.
Two (methyl) acrylate, pentaerythritols (a2) are relative to above-mentioned (methyl) acrylate (a1)~(a3) total amount
Containing ratio if 15~55 weight %, it is more excellent in the viewpoint for taking into account hardness and bendability.
The weight average molecular weight of above-mentioned carbamate (methyl) acrylate composition [I] if 1000~20000,
It is excellent in terms of the handling easiness of actinic energy ray curable resion composition.
Five (methyl) acrylic acid dipentaerythritol esters in the mixture (B) of above-mentioned (methyl) acrylate (b1)~(b6)
(b5) containing ratio is more excellent in terms of taking into account hardness and bendability if 15~60 weight %.
Five (methyl) acrylic acid dipentaerythritol esters (b5) are amounted to relative to above-mentioned (methyl) acrylate (b1)~(b5)
The containing ratio of amount is more excellent in terms of simultaneous solid hardness is with bendability if 45~90 weight %.
Four (methyl) acrylic acid dipentaerythritol esters in the mixture (B) of above-mentioned (methyl) acrylate (b1)~(b6)
(b4) containing ratio is if 1~35 weight %, then bendability is excellent.
Four (methyl) acrylic acid dipentaerythritol esters (b4) are amounted to relative to above-mentioned (methyl) acrylate (b1)~(b5)
The containing ratio of amount is if 2~40 weight %, then bendability is more excellent.
The weight average molecular weight of above-mentioned carbamate (methyl) acrylate composition [II] if 1000~20000,
Then the handling easiness of actinic energy ray curable resion composition is excellent.
The weight average molecular weight of above-mentioned carbamate (methyl) acrylate composition [III] if 1000~20000,
Then the handling easiness of actinic energy ray curable resion composition is more excellent.
Specific embodiment
The present invention described further below.
It should be noted that (methyl) acrylic refers to acrylic or methacrylic acid group, (methyl) in the present invention
Acryloyl group refers to acryloyl group or methylacryloyl, and (methyl) acrylate refers to acrylate or methacrylate.
Actinic energy ray curable resion composition of the invention is characterized in that, containing selected from by following carbamic acid
Ester (methyl) acrylate composition [I], carbamate (methyl) acrylate composition [I] and [II] and amino
Any carbamate (methyl) acrylic ester group in group that formic acid esters (methyl) acrylate composition [III] is constituted
Object is closed, there are 3 kinds of forms.
Above-mentioned carbamate (methyl) acrylate composition [I] is (methyl) acrylate in mixture (A)
(a1) obtained from~(a3) is reacted with polyisocyanates (CA), the mixture (A) is as pentaerythrite and (methyl) third
The mixture of following (methyl) acrylate (a1)~(a4) of the reaction product of olefin(e) acid, and the hydroxyl value of said mixture (A) is
200mgKOH/g or more.
Mixture (A)
(a1) single (methyl) acrylate, pentaerythritol
(a2) two (methyl) acrylate, pentaerythritol
(a3) three (methyl) acrylate, pentaerythritol
(a4) four (methyl) acrylate, pentaerythritol.
Above-mentioned carbamate (methyl) acrylate composition [II] is (methyl) acrylate in mixture (B)
(b1) obtained from~(b5) is reacted with polyisocyanates (CB), the mixture (B) is as dipentaerythritol and (methyl)
The mixture of following (methyl) acrylate (b1)~(b6) of the reaction product of acrylic acid, and the hydroxyl value of said mixture (B)
For 40mgKOH/g or more.
Mixture (B)
(b1) single (methyl) acrylic acid dipentaerythritol ester
(b2) two (methyl) acrylic acid dipentaerythritol ester
(b3) three (methyl) acrylic acid dipentaerythritol ester
(b4) four (methyl) acrylic acid dipentaerythritol ester
(b5) five (methyl) acrylic acid dipentaerythritol ester
(b6) six (methyl) acrylic acid dipentaerythritol ester.
Above-mentioned carbamate (methyl) acrylate composition [III] is by (methyl) propylene as following [α]
Acid esters (a1)~(a3), as following [β] (methyl) acrylate (b1)~(b5), react and obtain with polyisocyanates (CC)
It arrives.
Following (methyl) acrylate (a1)~(a4) of [α] as pentaerythrite and the reaction product of (methyl) acrylic acid
Mixture (A) in (methyl) acrylate (a1)~(a3), and the hydroxyl value of said mixture (A) be 200mgKOH/g with
On.
(a1) single (methyl) acrylate, pentaerythritol
(a2) two (methyl) acrylate, pentaerythritol
(a3) three (methyl) acrylate, pentaerythritol
(a4) four (methyl) acrylate, pentaerythritol.
[β] as dipentaerythritol and the reaction product of (methyl) acrylic acid following (methyl) acrylate (b1)~
(b6) (methyl) acrylate (b1)~(b5) in mixture (B), and the hydroxyl value of said mixture (B) is 40mgKOH/g
More than.
(b1) single (methyl) acrylic acid dipentaerythritol ester
(b2) two (methyl) acrylic acid dipentaerythritol ester
(b3) three (methyl) acrylic acid dipentaerythritol ester
(b4) four (methyl) acrylic acid dipentaerythritol ester
(b5) five (methyl) acrylic acid dipentaerythritol ester
(b6) six (methyl) acrylic acid dipentaerythritol ester.
<carbamate (methyl) acrylate composition [I]>
Firstly, being illustrated for above-mentioned carbamate (methyl) acrylate composition [I].
In the present invention, above-mentioned pentaerythrite is reacted with (methyl) acrylic acid and above-mentioned (methyl) acrylate that obtains
(a1) for the hydroxyl value of~(a4) mixture (A), need to be 200mgKOH/g or more, more preferably 210~380mgKOH/g, into
One step is preferably 230~320mgKOH/g.
The mixture (A) if hydroxyl value it is too small, the weight of carbamate (methyl) acrylate composition [III] is equal
Molecular weight and molecular weight, thus cure shrinkage when solidifying increases, therefore have the tendency that easily crimping, and bendability has the tendency that reduction.It needs
If being noted that, usually above-mentioned hydroxyl value excessively increases, and there will be adjoint molecular weight to increase, and viscosity improves, therefore operates and become hardly possible
Tendency.
In the present invention, hydroxyl value is available to be acquired according to the method for JIS K 0,070 1992.
In addition, in the present invention, if two (methyl) in the mixture (A) of above-mentioned (methyl) acrylate (a1)~(a4)
The containing ratio of acrylate, pentaerythritol (a2) is 10~50 weight %, then considers that taking into account hardness and the viewpoint of bendability relatively manages
Think, further preferably 15~45 weight %, more preferably 20~40 weight %.Containing ratio bendability if too small has drop
Low tendency has the tendency that hardness decline or viscosity increase if excessive.
In addition, two (methyl) acrylate, pentaerythritols (a2) are total relative to above-mentioned (methyl) acrylate (a1)~(a3)
If the containing ratio of metering is 15~55 weight %, consideration takes into account hardness and the viewpoint of bendability is more satisfactory, further preferably
For 20~50 weight %, more preferably 25~45 weight %.The containing ratio has the tendency that bendability reduction if too small, if mistake
It is big then have the tendency that hardness decline or viscosity increase.
In the present invention, prepares (methyl) acrylic acid of pentaerythrite to react pentaerythrite with (methyl) acrylic acid and add
At object, but reacting for pentaerythrite and (methyl) acrylic acid, it can be according to known common method progress.In the reaction, meeting
It obtains relative to list (methyl) acrylate, pentaerythritol (a1) of pentaerythrite addition 1 (methyl) acrylic acid, addition 2
Two (methyl) acrylate, pentaerythritols (a2) of a (methyl) acrylic acid, addition three (methyl) of 3 (methyl) acrylic acid
Acrylate, pentaerythritol (a3), addition four (methyl) acrylate, pentaerythritols (a4) of 4 (methyl) acrylic acid it is mixed
It closes object (A), can get the mixture (A) for having above-mentioned hydroxyl value for all.
In addition, in said mixture (A), the side reaction product of Michael addition adducts containing acrylic acid etc. sometimes.
When adjusting hydroxyl value, for example, can come by adjusting (methyl) acrylate (a1)~(a4) containing ratio into
Row.
In the present invention, above-mentioned polyisocyanates (CA) is and above-mentioned (methyl) acrylate (a1)~(a3) reactor, tool
It for body, can enumerate for example: toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate, polyphenyl methane polyisocyanates, modification
'-diphenylmethane diisocyanate, benzene dimethylene diisocyanate, tetramethylxylylene diisocyanate, phenylene two are different
The aromatic systems polyisocyanates such as cyanate, naphthalene diisocyanate；Hexamethylene diisocyanate, tri-methyl hexamethylene two are different
The fatty families polyisocyanates such as cyanate, lysine diisocyanate, lysine triisocyanate；Hydrogenated methylene diphenyld two is different
Cyanate, hydrogenation benzene dimethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate etc. are alicyclic
It is polyisocyanates；Or tripolymer compound or polymer compounds, the urea formic acid esters of these polyisocyanates
(allophanate) type polyisocyanates, biuret form polyisocyanates, water dispersive polyisocyanate (such as: Tosoh strain formula
" Aquanate 105 ", " Aquanate 120 ", " Aquanate 210 " etc. of commercial firm's manufacture) etc..They can be used alone
Or it is used in combination of two or more.
Among these, alicyclic ring family polyisocyanates, aromatic system polyisocyanates are more satisfactory from the viewpoint of the intensity, into
One step is preferably isophorone diisocyanate, hydrogenation benzene dimethylene diisocyanate, benzene dimethylene diisocyanate, first
Phenylene diisocyanate.
In the present invention, carbamate (methyl) acrylate composition [I] is to make above-mentioned (methyl) acrylate
(a1) (methyl) acrylate (a1)~(a3) hydroxyl and above-mentioned polyisocyanates (CA) in~(a4) mixture (A)
Obtained from isocyanate group reaction.In this case, in carbamate (methyl) acrylate composition [I], meeting
Winner, (methyl) acrylate (a2) and polyisocyanates are reacted with polyisocyanates (CA) containing (methyl) acrylate (a1)
(CA) it reacts winner, (methyl) acrylate (a3) and reacts winner with polyisocyanates (CA), in turn, can also contain in system
(methyl) acrylate (a1)~(a3) unreacted product, (methyl) acrylate (a4) for having neither part nor lot in reaction etc..
(methyl) acrylate (a1)~(a3) is reacted with polyisocyanates (CA's), can carry out hydroxyl and isocyanate group
Functional group's molar ratio adjustment, optionally aftermentioned catalysts can be used to carry out.
The polyisocyanates (CA) and the charging of (methyl) acrylate (a1)~(a4) mixture (A) are reacted mole
Than, when the isocyanate group of polyisocyanates (CA) has 2, polyisocyanates (CA): (methyl) acrylate mixture (A)
Preferably 1:1~1:5, further preferably 1:1~1:3, more preferably 1:1~1:2.
The ratio of the mixture (A) low molecular weight monomers if excessive can increase, and cure shrinkage increases, therefore curling has increase
Tendency, mixture (A) if ratio it is very few there will be unreacted polyisocyanates (CA) remaining, have the stabilization of cured coating film
Property, safety reduce tendency.
(methyl) acrylate (a1)~(a3) and polyisocyanates (CA) in (methyl) acrylate mixture (A)
Reaction usually by the primary whole of said mixture (A) and polyisocyanates (CA) or is fed separately into reactor and makes its reaction
?.
In above-mentioned reaction, in order to promote to react, it is also preferred that can be enumerated for example as the catalyst: two using catalyst
Dibutyl tin laurate, dibutyltin diacetate, trimethyl stannic hydroxide, tetra-n-butyl tin, bis-acetylacetonate zinc, three (acetyl
Acetone) organo-metallic compounds such as oacetic acid zirconium, four acetylacetone,2,4-pentanedione zirconiums；Tin octoate, octenoic acid tin, caproic acid zinc, octene
The metal salts such as sour zinc, zinc stearate, 2 ethyl hexanoic acid zirconium, cobalt naphthenate, stannous chloride (II), tin tetrachloride (IV), potassium acetate；
Triethylamine, triethylenediamine, benzyl diethylamine, 1,4- diazabicyclo [2,2,2] octane, 1,8- diazabicyclo [5,4,0] ten
One alkene, N, N, N ', the amine systems catalyst such as N '-tetramethyl -1,3- butanediamine, N-methylmorpholine, N-ethylmorpholine；Bismuth nitrate, bromine
Change except bismuth, bismuth iodide, bismuth sulfide etc. there are also the bismuth organic compounds such as di lauric dibutyl bismuth, tin dilaurate dioctyl bismuth,
2 ethyl hexanoic acid bismuth salt, aphthenic acids bismuth salt, isodecyl acid bismuth salt, neodecanoic acid bismuth salt, lauric acid bismuth salt, maleic acid bismuth salt, stearic acid
Bismuth salt, oleic acid bismuth salt, linolenic acid (linoleic acid) bismuth salt, acetic acid bismuth salt, bismuth neodecanoate, two salicylic acid bismuth salts, two do not have
Bismuths series catalysts such as the organic acids bismuth salt such as gallate-based bismuth salt etc., wherein preferred dibutyl tin dilaurate, 1,8- diazabicyclo
[5,4,0] hendecene.Can they be used alone or are used in combination of two or more.
In addition, it is more preferable to further use polymerization inhibitor in above-mentioned reaction.Above-mentioned polymerization inhibitor, which can be used, is commonly used as polymerization inhibitor
The known common product used, can enumerate for example: 1,4-benzoquinone, naphthoquinones, toluiquinone, 2,5- diphenyl -1,4-benzoquinone, quinhydrones,
The quinones such as DBH 2,5 di tert butylhydroquinone, methylnaphthohydroquinone, single tert-butyl hydroquinone；4- metoxyphenol, 2,6- di-tert-butyl cresol etc.
Aromatic；P-tert-butyl catechol etc..Wherein, aromatic is more satisfactory, further preferred 4- metoxyphenol, 2,6-, bis- uncle
Butyl cresols.Can they be used alone or are used in combination of two or more.
In addition, the organic solvent for not having the functional group reacted for isocyanate group, example can be used in above-mentioned reaction
Such as: ethyl acetate, butyl acetate esters；The ketones such as methyl ethyl ketone, methylisobutylketone；Aromatics such as toluene, dimethylbenzene etc. have
Solvent.Can they be used alone or are used in combination of two or more.
Reaction temperature is usually 30~90 DEG C, and more preferably 40~80 DEG C, the reaction time is usually 4~72 hours, more excellent
It is selected as 8~48 hours.
By this method, carbamate (methyl) acrylate composition [I] that the available present invention uses.
The weight average molecular weight preferably 1000~20000 of carbamate (methyl) acrylate composition [I], into one
Step preferably 2000~18000, more preferably 3000~16000.Weight average molecular weight cured coating film if too small, which has, to become fragile
Tendency, viscosity increases if excessive, there is not easy-operating tendency.
In addition, above-mentioned weight average molecular weight is the weight average molecular weight obtained by the conversion of standard polystyren molecular weight, height is utilized
Effect liquid phase chromatogram (water generation company manufacture, " ACQUITY APC system "), as pillar by 1 ACQUITY APC XT 450,
1 ACQUITY APC XT, 200,2 ACQUITY APC XT 45, total 4 root canal columns are used in series to measure.
Carbamate (methyl) acrylate in above-mentioned carbamate (methyl) acrylate composition [I]
Content is more preferably 50 weight % or more, further preferably 60 weight % or more, more preferably 70 weight % or more, especially excellent
It is selected as 80 weight % or more.It should be noted that the upper limit is usually 95 weight %.
<carbamate (methyl) acrylate composition [II]>
Then, it is illustrated for carbamate (methyl) acrylate composition [II].
In the present invention, above-mentioned dipentaerythritol reacts above-mentioned (methyl) acrylate (b1) obtained with (methyl) acrylic acid
The hydroxyl value of the mixture (B) of~(b6) need to be 40mgKOH/g or more, more preferably 43~130mgKOH/g, further preferably
45~125mgKOH/g, more preferably 70~120mgKOH/g.
The hydroxyl value of the mixture (B) if too small for low molecular weight and ethylenically unsaturated group number it is more, not with isocyanates
The content of six (methyl) acrylic acid dipentaerythritol esters (b6) of reaction increases, therefore cure shrinkage when solidify increases, therefore has easy
The tendency of curling, and then have the tendency that bendability reduction.In addition, if usually above-mentioned hydroxyl value becomes excessive, as molecular weight increases
Add, viscosity improves, and has not easy-operating tendency.
In the present invention, if five (methyl) propylene in the mixture (B) of above-mentioned (methyl) acrylate (b1)~(b6)
The containing ratio of sour dipentaerythritol ester (b5) is 15~60 weight %, and consideration takes into account hardness and the viewpoint of bendability is more satisfactory,
Further preferably 20~55 weight %, more preferably 25~55 weight %.Containing ratio bendability if too small has reduction
Tendency, have the tendency that if excessive hardness reduce or viscosity increase.
If five (methyl) acrylic acid dipentaerythritol esters (b5) are relative to above-mentioned (methyl) acrylate (b1)~(b5)
The containing ratio of total amount is 45~90 weight %, and consideration takes into account hardness and the viewpoint of bendability is more satisfactory, further preferably
50~90 weight %, more preferably 55~90 weight %.Containing ratio bendability if too small has the tendency that reduction, if excessive
Then have the tendency that hardness reduces or viscosity increases.
Four (methyl) acrylic acid dipentaerythritol esters in the mixture (B) of above-mentioned (methyl) acrylate (b1)~(b6)
(b4) containing ratio is 1~35 weight %, considers that the viewpoint of bendability is more satisfactory, further preferably 2~30 weight %, more
Preferably 3~25 weight %.The containing ratio has the tendency that bendability reduction if too small, if excessive have hardness to decline or glue
Spend the tendency increased.
If four (methyl) acrylic acid dipentaerythritol esters (b4) are relative to above-mentioned (methyl) acrylate (b1)~(b5)
The containing ratio of total amount is 2~40 weight %, considers that the viewpoint of bendability is more satisfactory, further preferably 3~35 weight %,
More preferably 4~30 weight %.The containing ratio have the tendency that if too small bendability reduction, if it is excessive have hardness reduce or
The tendency that viscosity increases.
In the present invention, (methyl) propylene of dipentaerythritol is prepared to react dipentaerythritol with (methyl) acrylic acid
Sour addition product can be carried out for dipentaerythritol with reacting for (methyl) acrylic acid according to known common method.In the reaction,
It can obtain containing for single (methyl) acrylic acid dipentaerythritol ester obtained by 1 (methyl) acrylic acid of dipentaerythritol addition
(b1), two (methyl) acrylic acid dipentaerythritol esters (b2), addition obtained by 2 (methyl) acrylic acid of addition, 3 (first
Base) four obtained by three (methyl) acrylic acid dipentaerythritol esters (b3), addition obtained by acrylic acid, 4 (methyl) acrylic acid
Two season penta of five (methyl) acrylic acid obtained by 5 (methyl) acrylic acid dipentaerythritol ester (b4), addition (methyl) acrylic acid
The mixture of six (methyl) acrylic acid dipentaerythritol esters (b6) obtained by 6 four alcohol esters (b5), addition (methyl) acrylic acid
(B), it can get the mixture (B) for meeting above-mentioned hydroxyl value for all.
In addition, in said mixture (B), side reaction products such as Michael addition adducts containing acrylic acid sometimes.
When carrying out the adjustment of hydroxyl value, such as: it can come by adjusting (methyl) acrylate (b1)~(b6) containing ratio
It carries out.
In the present invention, above-mentioned polyisocyanates (CB) is and above-mentioned (methyl) acrylate (b1)~(b5) reactor, tool
For body, person identical as above explained polyisocyanates (CA) can be enumerated.Above-mentioned polyisocyanates (CB) and above-mentioned polyisocyanate cyanogen
Acid esters (CA) may be the same or different.
In addition, polyisocyanates (CB) can be the reaction product of above-mentioned polyisocyanates and polyalcohol.It is such a polynary
Alcohol, such as: it is more can specifically to enumerate polyether system polyalcohol, Polyester for the polyalcohol of the polyalcohol of low molecular weight, high molecular weight
The polyene that the reactions such as first alcohol, polycarbonate-based polyalcohol, polybutadiene system polyalcohol, ethylene isoprene butadiene obtain
Hydrocarbon system polyalcohol or its hydride, polyolefin polyalcohol other than the above, (methyl) acrylic acid series multiple alcohol etc..
In these polyisocyanates (CB), alicyclic ring family polyisocyanates, aromatic system polyisocyanates with regard to weatherability with
The viewpoint of intensity is more satisfactory, further preferably isophorone diisocyanate, hydrogenation benzene dimethylene diisocyanate, benzene two
Methylene diisocyanate, toluene di-isocyanate(TDI).
In the present invention, carbamate (methyl) acrylate composition [II] is to make above-mentioned (methyl) acrylate
(b1) (methyl) acrylate (b1)~(b5) hydroxyl and above-mentioned polyisocyanates (CB) in~(b6) mixture (B)
Obtained from isocyanate group reaction.In this case, in carbamate (methyl) acrylate composition [II], meeting
It is reacted containing (methyl) acrylate (b1) with polyisocyanates (CB) and obtains person, (methyl) acrylate (b2) and polyisocyanic acid
Ester (CB) reacts and obtains person, (methyl) acrylate (b3) and react with polyisocyanates (CB) and obtain person, (methyl) acrylate
(b4) it is reacted with polyisocyanates (CB) and obtains person, (methyl) acrylate (b5) and reacted with polyisocyanates (CB) and obtain person,
In addition, (methyl) propylene that can contain (methyl) acrylate (b1)~(b5) unreacted product in system, have neither part nor lot in reaction
Acid esters (b6) etc..
The polyisocyanates (CB) and the charging of (methyl) acrylate (b1)~(b6) mixture (B) are reacted mole
Than, such as: when the isocyanate group of polyisocyanates (CB) is 2, polyisocyanates (CB): (methyl) acrylate mixture
(B) preferred 1:1~1:5, further preferably 1:1~1:4, more preferably 1:1~1:3.
The ratio of the mixture (B) low molecular weight monomers if excessive increase, and cure shrinkage increases, so curling has increase
Tendency, the ratio of mixture (B) unreacted polyisocyanates (CB) remaining if excessively few has the stabilization of cured coating film
Property, safety reduce tendency.
(methyl) acrylate (b1)~(b5) and polyisocyanates (CB) in (methyl) acrylate mixture (B) is anti-
It answers, usually make said mixture (B) and the primary whole of polyisocyanates (CB) or is fed separately into reactor and makes its reaction
?.
In above-mentioned reaction, in order to promote reaction it is also preferred that the catalyst can be enumerated and in above-mentioned amino first using catalyst
Acid esters (methyl) acrylate composition [I] illustrates identical substance.
In addition, in above-mentioned reaction, for use polymerization inhibitor, without the organic of the functional group reacted for isocyanate group
The situation of solvent can also be enumerated and the identical object of explanation in above-mentioned carbamate (methyl) acrylate composition [I]
Matter.
In addition, the preparation of carbamate (methyl) acrylate composition [II] can be according to above-mentioned carbamate
The preparation of (methyl) acrylate composition [I] carries out.
Like this, carbamate (methyl) acrylate composition [II] that the present invention uses is obtained.
The weight average molecular weight of carbamate (methyl) acrylate composition [II] is preferably 1000~20000,
More preferably 1500~18000, further preferably 2000~16000.Weight average molecular weight cured coating film if too small has change
Crisp tendency, viscosity is got higher if excessive, there is not easy-operating tendency.
In addition, the measuring method of above-mentioned weight average molecular weight is identical as said determination method.
The viscosity at 60 DEG C of carbamate (methyl) acrylate composition [II] is preferably 1000~
300000mPas, further preferably 1500~200000mPas, more preferably 2000~100000mPas.The viscosity
When outside for above range, the tendency of coating reduction is had.
In addition, the measuring method of 60 DEG C of viscosity is carried out using E type viscosimeter.
Carbamate (methyl) acrylate in above-mentioned carbamate (methyl) acrylate composition [II]
Content be more preferably 35 weight % or more, further preferably 40 weight % or more, more preferably 45 weight % or more, especially
Preferably 50 weight % or more, more preferably 60 weight % or more.In addition, the upper limit is usually 95 weight %.
<carbamate (methyl) acrylate composition [III]>
In turn, it is illustrated for carbamate (methyl) acrylate composition [III].
<mixture (A)>
Firstly, for the (first containing the constituent material as carbamate (methyl) acrylate composition [III]
Base) acrylate (a1)~(a3) mixture (A) is illustrated.
Mixture (A) is that above-mentioned pentaerythrite reacts above-mentioned (methyl) acrylate (a1) obtained with (methyl) acrylic acid
The mixture of~(a4), hydroxyl value need to be 200mgKOH/g or more, more preferably 210~380mgKOH/g, further preferably
230~320mgKOH/g.
For said mixture (A), can enumerate and in above-mentioned carbamate (methyl) acrylate composition [I]
Illustrate identical substance.
In said mixture (A), (methyl) acrylate (a1)~(a3) with hydroxyl can be with aftermentioned polyisocyanates
(CC) it reacts.
<mixture (B)>
Then, for (the first containing the constituent material as carbamate (methyl) acrylate composition [III]
Base) acrylate (b1)~(b5) mixture (B) is illustrated.
Mixture (B) is that above-mentioned dipentaerythritol reacts above-mentioned (methyl) acrylate obtained with (methyl) acrylic acid
(b1)~(b6) mixture, hydroxyl value need to be 40mgKOH/g or more, more preferably 43~130mgKOH/g, further preferably
For 45~125mgKOH/g, more preferably 70~120mgKOH/g.
For said mixture (B), can enumerate and in above-mentioned carbamate (methyl) acrylate composition [II]
It is middle to illustrate identical substance.
In said mixture (B), (methyl) acrylate (b1)~(b5) with hydroxyl can be with following polyisocyanates
(CC) it reacts.
<polyisocyanates (CC)>
Then, for the polyisocyanate cyanogen of the constituent material as carbamate (methyl) acrylate composition [III]
Acid esters (CC) is illustrated.
In the present invention, above-mentioned polyisocyanates (CC) is and (methyl) acrylate containing hydroxyl namely above-mentioned (methyl)
Acrylate (a1)~(a3) and (methyl) acrylate (b1)~(b5) reactor, specifically, can enumerate and in above-mentioned ammonia
Polyisocyanates (CA) that carbamate (methyl) acrylate composition [I] illustrates and with above-mentioned carbamate (first
Base) the middle identical substance of polyisocyanates (CB) illustrated of acrylate composition [II].Above-mentioned polyisocyanates (CC) can
From above-mentioned polyisocyanates (CA) or polyisocyanates (CB) is identical can also be different.
In addition, above-mentioned polyisocyanates (CC), total with above-mentioned polyisocyanates (CA) and polyisocyanates (CB) sometimes
Referred to as " polyisocyanates (C) ".
It, can be by (methyl) acrylic acid in the mixture (A) of above-mentioned (methyl) acrylate (a1)~(a4) in the present invention
Ester (a1)~(a3) hydroxyl, above-mentioned (methyl) acrylate (b1)~(b6) mixture (B) in (methyl) acrylate
(b1)~(b5) hydroxyl reacts with the isocyanate group of above-mentioned polyisocyanates (CC) and obtains carbamate (methyl) third
Olefin(e) acid ester system: compositions [III].In this case, in carbamate (methyl) acrylate composition [III], can contain
There is (methyl) acrylate (a1) to react and winner, (methyl) acrylate (a2) and polyisocyanates with polyisocyanates (CC)
(CC) reaction and winner, (methyl) acrylate (a3) react and winner with polyisocyanates (CC), (methyl) acrylic acid in turn
Ester (b1) is reacted with polyisocyanates (CC) and winner, (methyl) acrylate (b2) are reacted with polyisocyanates (CC)
Person, (methyl) acrylate (b3) react and winner, (methyl) acrylate (b4) and polyisocyanic acid with polyisocyanates (CC)
Ester (CC) reacts and winner, (methyl) acrylate (b5) react and winner, (a1)~(a3) and (first with polyisocyanates (CC)
Base) acrylate (b1)~(b5) mixes and reacts and winner etc. with polyisocyanates (CC), and then can also contain in system
The unreacted product of (methyl) acrylate (a1)~(a3) and (b1)~(b5), (methyl) acrylate for having neither part nor lot in reaction
(a4) and (b6) etc..
(methyl) acrylate (a1)~(a3) and (methyl) acrylate (b1)~(b5) and polyisocyanates (CC)
In reaction, functional group's molar ratio of hydroxyl and isocyanate group can adjust, and optionally carried out using aftermentioned catalysts.
It should (methyl) acrylate (a1)~(a4) mixture (A), (methyl) acrylate (b1)~(b6) mixing
Object (B) reacts molar ratio with the charging of polyisocyanates (CC), when the isocyanate group of polyisocyanates (CC) is 2,
Polyisocyanates (CC): the total of (methyl) acrylate mixture (A) and (methyl) acrylate mixture (B) is preferably 1:
1~1:5, further preferably 1:1~1:3, more preferably 1:1~1:2.In addition, (methyl) acrylate mixture (A): (first
Base) acrylate mixture (B) by weight, be 90:10~10:90 it is further preferred that further preferably 70:30~15:85, more
Preferably 50:50~20:80.
The total amount of mixture (A) and mixture (B) relative to polyisocyanates (CC) if ratio it is excessive, low molecule
Amount monomer increases, and cure shrinkage increases, therefore curling has the tendency that increase, the ratio of mixture (A) and the total amount of mixture (B)
If very few, unreacted polyisocyanates (CC) remaining has the stability of cured coating film, the tendency that safety reduces.
Mixture (B) relative to mixture (A) if ratio it is excessive, low molecular weight monomers increase, and cure shrinkage increases,
Therefore curling has the tendency that increase, the ratio of mixture (B) hardness and scratch resistance has the tendency that reduction if excessively few.
(methyl) acrylate (a1)~(a3), (methyl) in (methyl) acrylate mixture (A) is acrylic ester mixed
It closes (methyl) acrylate (b1)~(b5) in object (B), reacted with polyisocyanates (CC), usually by said mixture
(A), the primary whole of mixture (B) and polyisocyanates (CC) or it is fed separately into reactor.
In above-mentioned reaction, in order to promote reaction it is also preferred that the catalyst can be enumerated and in above-mentioned amino first using catalyst
The identical substance of explanation in acid esters (methyl) acrylate composition [I].
In addition, in above-mentioned reaction, for use polymerization inhibitor, without the organic molten of the functional group reacted isocyanate group
The situation of agent can be enumerated and the same substance of explanation in above-mentioned carbamate (methyl) acrylate composition [I].
In addition, the preparation of carbamate (methyl) acrylate composition [III], it can be according to above-mentioned carbamic acid
The preparation of ester (methyl) acrylate composition [I] carries out.
In this manner, obtaining makes above-mentioned (methyl) acrylate (a1)~(a3) as [α], is above-mentioned as [β]
(methyl) acrylate (b1)~(b5), carbamate (methyl) acrylate for reacting and generating with polyisocyanates (CC)
System: compositions [III].
In the present invention, it can also react containing polyalcohol and with polyisocyanates (CC), obtain by (the first as [α]
Base) acrylate (a1)~(a3), (methyl) acrylate (b1)~(b5) as [β], polyisocyanates (CC) and polynary
Carbamate (methyl) acrylate composition [III] that alcohol is constituted.
Above-mentioned polyalcohol, such as: the polyalcohol of the polyalcohol of low molecular weight, high molecular weight can specifically enumerate polyethers
It is that polyalcohol, polyester-based polyols, polycarbonate-based polyalcohol, ethylene isoprene butadiene etc. are reacted and obtained poly-
The polyalcohols such as olefin-based polyalcohol or its hydride, polyolefin polyalcohol other than the above, (methyl) acrylic acid series multiple alcohol
Deng.
The weight average molecular weight of carbamate (methyl) acrylate composition [III] is more preferably 1000~
20000, more preferably 2000~15000, further preferably 3000~12000, particularly preferably 4000~10000.This is heavy
Average molecular weight cured coating film if too small has the tendency that becoming fragile, if excessive become high viscosity, has the tendency that operation is not easy.
In addition, above-mentioned weight average molecular weight is the weight average molecular weight obtained using the conversion of standard polystyren molecular weight, utilize
High performance liquid chromatography (water generation company manufacture, " ACQUITY APC system "), as pillar by 1 ACQUITY APC XT
450,1 ACQUITY APC XT, 200,2 ACQUITY APC XT 45, total 4 be used in series to measure.
Carbamate (methyl) acrylate in above-mentioned carbamate (methyl) acrylate composition [III]
Content be more preferably 50 weight % or more, further preferably 60 weight % or more, more preferably 70 weight % or more, especially
Preferably 80 weight % or more.In addition, the upper limit is usually 95 weight %.
<actinic energy ray curable resion composition>
Actinic energy ray curable resion composition of the invention includes: containing above-mentioned carbamate (methyl) propylene
The 1st form<invention of the 1st purport>of acid esters system: compositions [I]；Contain above-mentioned carbamate (methyl) acrylic ester group
Close the 2nd form (invention of the 2nd purport) of object [I] and carbamate (methyl) acrylate composition [II]；And contain
The 3rd form (invention of the 3rd purport) of above-mentioned carbamate (methyl) acrylate composition [III].
Above-mentioned 2nd form actinic energy ray curable resion composition, it is such as above-mentioned, contain carbamate (methyl) third
Olefin(e) acid ester system: compositions [I] and carbamate (methyl) acrylate composition [II] form.For the carbamate
The containing ratio of (methyl) acrylate composition [I] and carbamate (methyl) acrylate composition [II]
([I]/[II]), by weight preferably 90/10~10/90, further preferably 87/13~20/80, more preferably 85/15
~30/70, particularly preferably 80/20~55/45, more preferably 80/20~65/35.The containing ratio has bending if too small
Property reduce tendency, hardness has the tendency that becoming inadequate if excessive.
The actinic energy ray curable resion composition of the invention of above-mentioned 1st~3 form is (hereinafter sometimes referred to simply as
" resin combination ") in, preferably also contain Photoepolymerizationinitiater initiater (D).In addition, in the range for not undermining effect of the present invention, it can also
The olefinic added other than other carbamate (methyl) acrylate, carbamate (methyl) acrylate is unsaturated single
Body, acrylic resin, surface conditioner, levelling agent, polymerization inhibitor etc. can also further be compounded filler, dyestuff, pigment, oil, plasticising
Agent, wax class, desiccant, dispersing agent, wetting agent, gelling agent, stabilizer, defoaming agent, surfactant, levelling agent, thixotropy are assigned
Give agent, antioxidant, fire retardant, antistatic agent, filler, reinforcing agent, delustering agent, crosslinking agent, silica, through water dispersion or
Silica, zirconium compounds, the preservative etc. of solvent dispersion.
It as above-mentioned Photoepolymerizationinitiater initiater (D), can enumerate for example: diethoxy acetophenone, 2- hydroxy-2-methyl -1-
Phenyl-propane -1- ketone, benzil dimethyl ketal, 4- (2- hydroxyl-oxethyl) phenyl-(2- hydroxyl -2- propyl) ketone, 1- hydroxyl
Cyclohexyl benzophenone, 1- [4- (2- hydroxyl-oxethyl)-phenyl] -2- hydroxy-2-methyl -1- propane -1- ketone, 2- hydroxyl -1- { 4-
[4- (2- hydroxy-2-methyl-propiono)-benzyl]-phenyl } -2- methyl-propan, 2- methyl -2- morpholino (4- sulphomethyl
Phenyl) propane -1- ketone, 2- benzyl -2- dimethylamino -1- (4- morphlinophenyl) butanone, 2- hydroxy-2-methyl -1- [4- (1-
Methyl ethylene) phenyl] acetophenones such as acetone oligomer；Benzoin, benzoin methyl ether, benzoin ether, benzoin isopropyl
The benzoins classes such as ether, benzoin isobutyl ether；Benzophenone, o-benzoyl yl benzoic acid methyl esters, 4- phenyl benzophenone, 4- (4-
Anisyl) -2- butanone, 3,3 ', 4,4 '-four (t-butyl peroxy carbonyl) benzophenone, 2,4,6- tri-methyl benzophenone, 4-
Benzoyl-N, N- dimethyl-N-[2- (1- oxo -2- propenyloxy group) ethyl] bromination benzene methanamine, (4- benzoylbenzyl)
The benzophenones such as trimethyl ammonium chloride；2- isopropyl thioxanthone, 4- isopropyl thioxanthone, 2,4- diethyl thioxanthene
Ketone, bis- chlorothiaxanthenone of 2,4-, the chloro- 4- propoxyl group thioxanthone of 1-, 2- (3- dimethylamino -2- hydroxyl) -3,4- dimethyl -
The thioxanthones such as 9H- thioxanthone the meso of -9- ketone (meso) chloride；2,4,6- trimethylbenzoy-dipheny oxygen
Change phosphine, bis- (2,6- Dimethoxybenzoyl) -2,4,4- trimethyl-pentyl phosphine oxides, bis- (2,4,6- trimethylbenzoyls
Base) acylphosphine oxide class such as-phenyl phosphine oxide；1.2- acetyl caproyl, the oximes such as 1- [4- (thiophenyl)-, 2- (o-benzoyl base oxime)]
Esters etc..In addition, these Photoepolymerizationinitiater initiaters (D) can be used alone a kind, can also be used in combination of two or more.
Among these, benzil dimethyl ketal, 1- hydroxycyclohexyl phenyl ketone, benzoin isopropyl ether, 4- are more preferably used
(2- hydroxyl-oxethyl)-phenyl (2- hydroxyl -2- propyl) ketone, 2- hydroxy-2-methyl -1- phenyl propyl- 1- ketone.
In addition, as they auxiliary agent can and with for example: triethanolamine, triisopropanolamine, 4,4 '-bis- (dimethylaminos) two
Benzophenone (Michler's keton), 4,4 '-lignocaine benzophenone, 2- dimethylaminoethyl benzoic acid, 4- dimethyl ethyl aminobenzoate, 4-
Dimethylaminobenzoic acid (n-butoxy) ethyl ester, 4- dimethylaminobenzoic acid isopentyl ester, 4- dimethylaminobenzoic acid 2- ethyl hexyl
Ester, 2,4- diethyl thioxanthone, 2,4- diisopropyl thioxanthone etc..Can they be used alone or are used in combination of two or more.
The content of Photoepolymerizationinitiater initiater (D) is preferably relative to 100 parts by weight of cure component contained in resin combination
0.1~20 parts by weight, further preferably 0.5~10 parts by weight, more preferably 1~10 parts by weight.Photoepolymerizationinitiater initiater (D)
If content is very few, become to solidify bad, have the tendency for being not easy to be formed film, becomes the original of cured coating film xanthochromia if excessive
Cause has the tendency that the problem of easily colouring.
As the ethylenically unsaturated monomer other than carbamate (methyl) acrylate, can enumerate for example: simple function
Monomer, bifunctional monomer, polyfunctional monomer more than trifunctional.Can they be used alone or are used in combination of two or more.
As the monofunctional monomer, can enumerate for example: styrene, vinyltoluene, chlorostyrene, α-methylstyrene
Etc. styrenic monomers；(methyl) methyl acrylate, (methyl) ethyl acrylate, acrylonitrile, (methyl) acrylic acid 2- methoxyl group
Ethyl ester, (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 2- hydroxybutyl, (first
Base) phenoxyethyl acrylate, (methyl) acrylic acid 2- phenoxy group -2- hydroxy propyl ester, (methyl) acrylic acid 2- hydroxyl -3- benzene oxygen
Base propyl ester, (methyl) acrylic acid 3- chlorine-2-hydroxyl propyl ester, (methyl) acrylic acid monoglyceride, (methyl) glycidyl
Ester, (methyl) lauryl acrylate, (methyl) cyclohexyl acrylate, the different camphane ester of (methyl) acrylic acid, (methyl) acrylic acid tricyclic
Last of the ten Heavenly stems ester, (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid dicyclopentenyl oxygroup ethyl ester, two ring penta of (methyl) acrylic acid
Ester, (2- methyl -2- ethyl -1,3- dioxolanes -4- base)-(methyl) methyl acrylate, hexamethylene spiral shell -2- (1,3- dioxy penta
Ring -4- base)-(methyl) methyl acrylate, 3- ethyl -3- oxetanylmethyl (methyl) acrylate, gamma-butyrolacton
(methyl) acrylate, (methyl) n-butyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) third
Olefin(e) acid monooctyl ester, (methyl) nonyl acrylate, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) acrylic acid ten
Modified (n=2) (methyl) acrylic acid of diester, the positive stearyl ester of (methyl) acrylic acid, (methyl) benzyl acrylate, phenolethylene oxide
Ester, nonyl phenol epoxy pronane modification (n=2.5) (methyl) acrylate, acid phosphatase 2- (methyl) acryloyloxyethyl ester,
Half (methyl) acrylate of the phthalic acid derivatives such as 2- (methyl) acryloxy -2- hydroxypropyl phthalic acid,
(methyl) acrylic acid furfuryl group ester, (methyl) tetrahydrofurfuryl acrylate, (methyl) carbitol acrylate, (methyl) acrylic acid benzyl
Ester, (methyl) acrylate, butoxy ethyl, (methyl) allyl acrylate, (methyl) acryloyl morpholine, polyoxyethylene are secondary
Alkyl ether acrylate etc. (methyl) acrylate monomer；2- hydroxyethyl acrylamide, N- methylol (methyl) acryloyl
Amine, n-vinyl pyrrolidone, 2- vinylpyridine, vinyl acetate etc..
It as the bifunctional monomer, can enumerate for example: two (methyl) acrylic acid glycol esters, two (methyl) acrylic acid two
Glycol ester, two (methyl) acrylic acid tetraethylene glycol esters, two (methyl) polyalkylene glycol acrylate esters, two (methyl) acrylic acid the third two
Alcohol ester, two (methyl) acrylic acid dipropylene glycol esters, two (methyl) acrylic acid polypropylene glycol esters, two (methyl) acrylic acid butanediols
Ester, two (methyl) acrylic acid neopentyl glycol ester, ethylene-oxide-modified bisphenol A-type two (methyl) acrylate, epoxy pronane modification
Bisphenol A-type two (methyl) acrylate, epoxy pronane modification bisphenol A-type two (methyl) acrylate, two (first of cyclohexanedimethanol
Base) acrylate, ethoxylation cyclohexanedimethanol two (methyl) acrylate, dihydroxymethyl bicyclopentane two (methyl) propylene
Acid esters, Tricyclodecane Dimethanol two (methyl) acrylate, 1,6- hexane diol two (methyl) acrylate, glycerol two (methyl)
Acrylate, two (methyl) acrylate, pentaerythritols, ethylene glycol diglycidylether two (methyl) acrylate, diethylene glycol
Diglycidyl ether two (methyl) acrylate, o-phthalic acid diglycidyl ester two (methyl) acrylate, hydroxyl front three
Guanidine-acetic acid is modified two (methyl) acrylic acid neopentyl glycol ester, the ethylene-oxide-modified diacrylate of isocyanuric acid etc..
It as the monomer more than trifunctional, can enumerate for example: trimethylolpropane tris (methyl) acrylate, three
(methyl) acrylate, pentaerythritol, four (methyl) acrylate, pentaerythritols, dipentaerythritol five (methyl) acrylate, six
(methyl) acrylic acid dipentaerythritol ester, three (methyl) acryloyloxyethoxy trimethylolpropanes, glycerol poly epihydric alcohol
Poly- (methyl) acrylate of ether, the ethylene-oxide-modified triacrylate of isocyanuric acid, caprolactone modification five (methyl) acrylic acid two
Pentaerythritol ester, (methyl) acrylic acid of caprolactone modification six dipentaerythritol ester, caprolactone modification three (methyl) acrylic acid season penta
Four alcohol esters, caprolactone modification four (methyl) acrylate, pentaerythritol, ethylene-oxide-modified five (methyl) acrylic acid, two Ji Wusi
Alcohol ester, ethylene-oxide-modified six (methyl) acrylic acid dipentaerythritol ester, ethylene-oxide-modified three (methyl) acrylic acid Ji Wusi
Alcohol ester, ethylene-oxide-modified four (methyl) acrylate, pentaerythritol, 15 glycerol tri-acrylate of ethoxylation etc..
In addition, can also and with the Michael addition adducts of acrylic acid or 2- acryloyl-oxyethyl dicarboxylic acid monoesters, this third
The Michael addition adducts of olefin(e) acid can enumerate (methyl) acrylic acid dimer, (methyl) acrylic acid tripolymer, (methyl) acrylic acid
Tetramer etc..Above-mentioned 2- acryloyl-oxyethyl dicarboxylic acid monoesters are the carboxylic acid with specified substituent, such as: 2- acryloyl-oxy
Base ethylsuccinic acid monoesters, 2- methylacryoyloxyethyl monomester succinate, 2- acryloyl-oxyethyl phthalic monoester,
2- methylacryoyloxyethyl phthalic monoester, 2- acryloyl-oxyethyl hexahydrophthalic acid monoesters, 2- methyl-prop
Alkene acyloxyethyl hexahydrophthalic acid monoesters etc..Other few polyester acrylates etc. can also be enumerated.
The olefinic other than carbamate (methyl) acrylate in the invention of 1st purport and the 2nd purport of the invention
The content of unsaturated monomer, 60 in whole cure components preferably contained in actinic energy ray curable resion composition
Weight % hereinafter, further preferably 55 weight % hereinafter, more preferably 50 weight % or less.In addition, lower limit value is usually 5 weights
Measure %.
On the other hand, the olefinic other than carbamate (methyl) acrylate in the invention of the 3rd purport of the invention
The content of unsaturated monomer is preferably in whole cure components contained in actinic energy ray curable resion composition
50 weight % hereinafter, further preferably 40 weight % hereinafter, more preferably 30 weight % hereinafter, particularly preferably 20 weight %
Below.In addition, lower limit value is usually 5 weight %.
As above-mentioned surface conditioner, can enumerate for example: celluosic resin, alkyd resin etc..Celluosic resin tool
There is the surface smoothness for making film preferably to act on, makes film property when alkyd resin plays the role of assigning coating.It can be single by them
Solely uses or be used in combination of two or more.
As long as playing the role of assigning substrate masking liquid penetrability, surface tension reduction actor i.e. as above-mentioned levelling agent
Can, well known common levelling agent can be used, such as: organic-silicon-modified resin, fluorine modified resin, alkyl-modified resin etc..It can
They are used alone or are used in combination of two or more.
Substance identical with what is used when reacting can be used as above-mentioned polymerization inhibitor, can enumerate for example: 1,4-benzoquinone, naphthalene
Quinone, toluiquinone, 2,5- diphenyl -1,4-benzoquinone, quinhydrones, DBH 2,5 di tert butylhydroquinone, methylnaphthohydroquinone, hydroquinone monomethyl ether, Dan Shuding
The quinones such as base quinhydrones；The aromatics such as 4- metoxyphenol, 2,6- di-tert-butyl cresol；P-tert-butyl catechol etc..It can be by it
Be used alone or be used in combination of two or more.
In addition, in actinic energy ray curable resion composition of the invention, optionally in order to make viscosity when coating
To be appropriate, it is also preferred that using diluted organic solvent is used for.As the organic solvent, can enumerate for example: methanol, ethyl alcohol, third
The alcohols such as alcohol, n-butanol, isobutanol；The ketones such as acetone, methylisobutylketone, methyl ethyl ketone, cyclohexanone；Ethyl matches the match Luo Soviet Union such as Luo Soviet Union
Class；The aromatics such as toluene, dimethylbenzene；The glycol ethers such as propylene glycol monomethyl ether；Methyl acetate, ethyl acetate, butyl acetate etc.
Acetate esters；Diacetone alcohol etc..These above-mentioned organic solvents can be used alone and can also be used in combination of two or more.
When being used in combination of two or more, from the group of the alcohols such as the ketones such as the glycol ethers such as propylene glycol monomethyl ether and methyl ethyl ketone, methanol
Two or more is selected to be used in combination in the alcohols such as combination, the methanol of the alcohols such as the ketones such as conjunction, methyl ethyl ketone and methanol, from the sight of appearance of film
Point is more satisfactory.
Actinic energy ray curable resion composition of the invention, the usable face paint as various substrates,
Anchor coating agent etc., film formation the effective substance of solidification compound.Also, it can be by by active energy ray-curable tree
Oil/fat composition is coated on after substrate (when being coated with the resin combination through organic solvent diluting, after being further dried), and irradiation is lived
Property energy-ray so that its solidify.
The substrate of the object of actinic energy ray curable resion composition as coating aforementioned present invention, can enumerate
Such as: polyolefin-based resins, polycarbonate-based resin, acrylonitrile butadient styrene (ABS), gather polyester based resin
Phenylethylene resin series etc., they the plastic basis materials such as molded product (film, piece, cup etc.), there are also polyethylene terephthalates
The optical thin films such as film, triacetyl cellulose film, cycloolefin film, they composite base material or be mixed with glass fibre,
Composite base material of the above-mentioned material of inorganic matter etc., metal (aluminium, copper, iron, SUS, zinc, magnesium, their alloy etc.), glass or this
The substrate etc. of priming coat is provided on a little substrates.
The coating method of actinic energy ray curable resion composition of the invention can enumerate for example: as spraying, spray
Wet coating method as leaching, intaglio plate coating, dipping, roller coating, spin coating, silk-screen printing etc., is usually coated on substrate at normal temperature
?.
In addition, actinic energy ray curable resion composition of the invention can be directly coated with, organic solvent can also be used
It dilutes and is coated with.When dilution, being diluted into solid component concentration using above-mentioned organic solvent is usually 3~70 weight %, more
Preferably 5~60 weight %.
Above-mentioned drying condition when being diluted using organic solvent, temperature are usually 40~120 DEG C, more preferably 50~
100 DEG C, drying time is usually 1~20 minute, and more preferably 2~10 minutes.
When being coated with actinic energy ray curable resion composition of the invention, viscosity of the resin combination at 20 DEG C is excellent
It is selected as 5~50000mPas, further preferably 10~10000mPas, more preferably 50~5000mPas.If should
Viscosity is to have the tendency of coating reduction outside above range.
In addition, the measuring method of the above-mentioned viscosity at 20 DEG C is to be carried out using Brookfield viscometer.But due to not making
Viscosity is high in the state of being diluted with solvent, when can not be measured at 20 DEG C using Brookfield viscometer, then E is used at 60 DEG C
Type viscosimeter is measured.
As activity used when making to have been coated with actinic energy ray curable resion composition on base material solidification
Energy-ray, using for example: the electromagnetism such as the light such as far ultraviolet, ultraviolet light, near ultraviolet ray, infrared ray, X-ray, gamma-rays
Electron beam, proton line, neutron ray etc. can be used in wave in addition to this, but considers that curing rate, the acquirement of irradiation unit are easy
Property, the viewpoints such as price, irradiate carried out solidification using ultraviolet light and be advantageous.In addition, not used when carrying out electron beam irradiation
Photoepolymerizationinitiater initiater (D) can also solidify.
When making its solidification using ultraviolet light irradiation, the high-pressure sodium lamp of the light of usable transmitting 150~450nm wave-length coverage,
Ultrahigh pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon lamp, chemical lamp, electrodeless discharge lamp, LED light etc., it can usually irradiate 30~
3000mJ/cm2, more preferably 100~1500mJ/cm2Ultraviolet light.
It can also optionally heat after ultraviolet light irradiation and reach and be fully cured.
For coating film thickness (film thickness after solidification), generally for the film as active energy ray-curable, light
Polymerization initiator (D) wants homogeneous reaction and considers that light penetrates, preferably 1~1000 μm, more preferably 2~500 μm, further
Preferably 3~200 μm.
Actinic energy ray curable resion composition of the invention uses preferably in the form of smears, particularly preferably with
The form use of hard coating smears, optical thin film smears.
In addition, actinic energy ray curable resion composition is coated on size 15cm × 15cm and thickness in the present invention
Polyethylene terephthalate (PET) film of 100 μm of degree makes the film after solidifying become 10 μm of thickness, in temperature 60
After carrying out drying in 3 minutes at DEG C, prepare the high-pressure sodium lamp of 80W in position of the height away from PET film face 18cm, with 5.1m/ minutes
Speed, irradiate ultraviolet light, make cumulative exposure become 500mJ/cm2, to obtain cured coating film.It is applied it is preferred that becoming following solidification
The smears of film: cutting out into 10cm × 10cm for the cured coating film, the height of jumping at four angles of the cured coating film cut out
Average value is 40mm hereinafter, especially 30mm is hereinafter, further 25mm or less.
In turn, in the present invention, actinic energy ray curable resion composition is coated on size 15cm × 15cm and thickness
The easy bonding PET film of 125 μm of degree, the film after solidification become 10 μm of thickness, drying in 3 minutes are carried out under temperature 60 C,
Prepare the high-pressure sodium lamp of 80W away from the position of easy bonding PET film face 18cm in height, it is ultraviolet with speed irradiation in 5.1m/ minutes
Line makes cumulative exposure become 500mJ/cm2, thus to obtain cured coating film.It is preferably made as following smears: the cured coating film
The evaluation for being carried out bendability using cylindrical mandrel Apparatus for Bending at low-temp according to JIS K 5600-5-1, evaluation is rolled up with cured coating film
When being wound on test bar, occur cracked or lifted off maximum diameter (integer value, mm) be 20mm hereinafter, especially preferably 15mm hereinafter,
More preferably 10mm is hereinafter, particularly preferably 8mm or less.
In the present invention, actinic energy ray curable resion composition is coated on size 15cm × 15cm and 125 μ of thickness
The easy bonding PET film of m makes the film after solidifying become 10 μm of thickness, after carrying out drying in 3 minutes under temperature 60 C,
Height prepares the high-pressure sodium lamp of 80W away from the position of easy bonding PET film face 18cm, irradiates ultraviolet light with 5.1m/ minutes speed,
Cumulative exposure is set to become 500mJ/cm2, to obtain cured coating film.For this cured coating film, steel wool (Japanese steel wool is used
Co., Ltd.'s manufacture, BON STAR#0000), in the state of applying the load of 500g behind cured coating film surface back and forth 10 times,
Visually to observe surface injury degree, in such a situation it is preferred to which film coated surface is without scar.
The invention of 1st purport of the invention is a kind of actinic energy ray curable resion composition, contains amino first
Acid esters (methyl) acrylate composition [I], carbamate (methyl) acrylate composition [I] are mixture
(A) (methyl) acrylate (a1)~(a3) in is reacted with polyisocyanates (CA) and is generated, and the mixture (A) is to make
It is above-mentioned for the mixture of pentaerythrite and above-mentioned (methyl) acrylate (a1)~(a4) of the reaction product of (methyl) acrylic acid
The hydroxyl value of mixture (A) is 200mgKOH/g or more.This actinic energy ray curable resion composition, because of cure shrinkage
It is small, it is not easy to crimp, is capable of forming hardness and the excellent cured coating film of bendability, even and then uncured state before curing
Film, film coated surface still will not stickness, have the effect that can form inviscid film coated surface, (in turn especially as smears
Hard coating smears, optical thin film smears) it is useful, in addition, being useful as coating, printing ink etc..
The invention of 2nd purport of the invention is a kind of actinic energy ray curable resion composition, contains amino first
Acid esters (methyl) acrylate composition [I] and carbamate (methyl) acrylate composition [II], the amino first
Acid esters (methyl) acrylate composition [I] is (methyl) acrylate (a1)~(a3) and polyisocyanate cyanogen in mixture (A)
Made of acid esters (CA) reaction, the mixture (A) is the above-mentioned (first as pentaerythrite and (methyl) acrylic acid reaction product
Base) acrylate (a1)~(a4) mixture；Carbamate (methyl) acrylate composition [II] is mixture
(B) made of (methyl) acrylate (b1)~(b5) in is reacted with polyisocyanates (CB), the mixture (B) is conduct
The mixture of dipentaerythritol and following (methyl) acrylate (b1)~(b6) of (methyl) acrylic acid reaction product；It is above-mentioned mixed
The hydroxyl value for closing object (A) is 200mgKOH/g or more, and the hydroxyl value of said mixture (B) is 40mgKOH/g or more.This active-energy
Ray-curable resin combination, cure shrinkage is small therefore is not easy to crimp, and hardness can be formed and the excellent solidification of bendability applies by having
The effect of film is useful especially as smears (and then being coated with firmly with smears, optical thin film smears), in addition, making
It is also useful for coating, printing ink etc..
The invention of 3rd purport of the invention is a kind of actinic energy ray curable resion composition, contains amino first
Acid esters (methyl) acrylate composition [III], which is by making
(methyl) acrylate (a1)~(a3) for above-mentioned [α], (methyl) acrylate (b1)~(b5) as above-mentioned [β], with
Polyisocyanates (CC) reaction and generate.This actinic energy ray curable resion composition, cure shrinkage is small, therefore is not easy to roll up
Song has the effect for the cured coating film that can form hardness, bendability and excellent scratch resistance, (and then applies firmly especially as smears
Cloth smears, optical thin film smears) it is useful.In addition, being also useful as coating, printing ink etc..
Embodiment
The present invention is more particularly described by the following examples, as long as but it is of the invention no more than its purport, it is not limited to following
Embodiment.In addition, " part ", " % " refer to weight basis in example.
<<embodiment for having used carbamate (methyl) acrylate composition [I]>>
As described below, prepare urethane acrylate system: compositions [I] ([I-1]~[I-4]), and prepare to than
Compared with urethane acrylate system: compositions [I '] ([I ' -1]~[I ' -4]).
(manufactures of urethane acrylate system: compositions [I-1])
Be equipped with thermometer, blender, water-cooled condenser, nitrogen mouth blown 4 mouthfuls of flasks in, be packed into isophorone two it is different
The acrylate mixture (A-1) (acrylic acid adduct of pentaerythrite) of cyanate (C-1) 36g, hydroxyl value 288mgKOH/g
64g, the ethyl acetate 100g as solvent, the 4- metoxyphenol 0.08g as polymerization inhibitor, as the February of catalysts
Dilaurylate 0.05g makes its reaction at 60 DEG C, and when remaining isocyanate group becomes 0.1%, reaction was completed, obtains ammonia
Urethane acrylate system: compositions [I-1] (resin component concentration 50%).
The weight average molecular weight of the urethane acrylate system: compositions [I-1] of acquisition is 4700, viscous at 20 DEG C
Degree is 80mPas.In addition, the measurement of the viscosity at 20 DEG C is implemented using Brookfield viscometer.Viscosimetric analysis at 20 DEG C with
Under it is identical.
In addition, in acrylate mixture (A-1), each ingredient relative to following ingredients (a1)~(a4) total amount
Containing ratio is as follows.
In addition, the containing ratio of each ingredient in mixture using liquid chromatography (agilent company manufacture,
" Technology HP 1100 ") it is carried out using tubing string (Imtakt company manufactures, 3 μm of 100 × 3mm of Cadenza CD-C18)
Measurement.
(manufactures of urethane acrylate system: compositions [I-2])
Be equipped with thermometer, blender, water-cooled condenser, nitrogen mouth blown 4 mouthfuls of flasks in be packed into two methylene of hydrogenation of benzene
Acrylate mixture (A-1) (the acrylic acid addition of pentaerythrite of group diisocyanate (C-2) 33g, hydroxyl value 288mgKOH/g
Object) 67g, the ethyl acetate 100g as solvent, the 4- metoxyphenol 0.08g as polymerization inhibitor, as catalysts
Dibutyl tin dilaurate 0.05g makes its reaction at 60 DEG C, and when remaining isocyanate group becomes 0.1%, reaction was completed, obtains
It obtains urethane acrylate system: compositions [I-2] (resin component concentration 50%).
The weight average molecular weight of the urethane acrylate system: compositions [I-2] of acquisition is 6200, viscous at 20 DEG C
Degree is 65mPas.
(manufactures of urethane acrylate system: compositions [I-3])
Be equipped with thermometer, blender, water-cooled condenser, nitrogen mouth blown 4 mouthfuls of flasks in, be packed into toluene diisocynate
Acrylate mixture (A-1) (acrylic acid adduct of pentaerythrite) 97g, work of ester (C-3) 43g, hydroxyl value 288mgKOH/g
Ethyl acetate 60g for solvent, the 4- metoxyphenol 0.08g as polymerization inhibitor, the tin dilaurate two as catalysts
Butyl tin 0.05g makes its reaction at 60 DEG C, and when remaining isocyanate group becomes 0.1%, reaction was completed, obtains carbamic acid
Ester acrylate composition [I-3] (resin component concentration 70%).
The weight average molecular weight of the urethane acrylate system: compositions [I-3] of acquisition is 7300, viscous at 20 DEG C
Degree is 161000mPas.
(manufactures of urethane acrylate system: compositions [I-4])
Be equipped with thermometer, blender, water-cooled condenser, nitrogen mouth blown 4 mouthfuls of flasks in, be packed into phenylenedimethylidyne two
The acrylate mixture (A-1) (acrylic acid adduct of pentaerythrite) of isocyanates (C-4) 48g, hydroxyl value 288mgKOH/g
90g, the ethyl acetate 60g as solvent, the 4- metoxyphenol 0.08g as polymerization inhibitor, as the February of catalysts
Dilaurylate 0.05g makes its reaction at 60 DEG C, and when remaining isocyanate group becomes 0.1%, reaction was completed, obtains ammonia
Urethane acrylate system: compositions [I-4] (resin component concentration 70%).
The weight average molecular weight of the urethane acrylate system: compositions [I-4] of acquisition is 12000, viscous at 20 DEG C
Measurement is not carried out because viscosity is high in degree.
(manufactures of urethane acrylate system: compositions [I ' -1])
Be equipped with thermometer, blender, water-cooled condenser, nitrogen mouth blown flask in, be packed into two isocyanide of isophorone
The acrylate mixture (A ' -1) (acrylic acid adduct of pentaerythrite) of acid esters (C-1) 38.4g, hydroxyl value 120mgKOH/g
161.6g, and the quinhydrones methyl ether 0.01g as polymerization inhibitor is added, as the dibutyl tin dilaurate 0.01g of catalysts,
React it 8 hours, reaction was completed when remaining isocyanate group becomes 0.3% or less, obtains carbamate
Acrylate composition [I ' -1] (resin component concentration 100%).
The weight average molecular weight of the urethane acrylate system: compositions [I ' -1] of acquisition is 1400, viscous at 60 DEG C
Degree is 3000mPas.But viscosity is high, therefore E type viscosimeter is used to implement measurement.
In addition, each ingredient is relative to following ingredients (a1)~(a4) total amount in acrylate mixture (A ' -1)
Containing ratio is as follows.
(a2) diacrylate pentaerythritol ester 5%
(a3) pentaerythritol triacrylate 50%
(a4) pentaerythritol tetracrylate 45%
But about (a1) single acrylate, pentaerythritol, content be determination limit hereinafter, therefore display (a2)~(a4) at
The containing ratio divided.
(manufactures of urethane acrylate system: compositions [I ' -2])
Be equipped with thermometer, blender, water-cooled condenser, nitrogen mouth blown 4 mouthfuls of flasks in, be packed into isophorone two it is different
The acrylate mixture (A-1) (acrylic acid adduct of pentaerythrite) of cyanate (C-1) 37g, hydroxyl value 288mgKOH/g
14g, the polyester polyol being made of adipic acid and neopentyl glycol (Dainippon Ink Chemicals manufactures, " ODX-2044 ", number-average molecular weight:
About 2000) 114g, as the 4- metoxyphenol 0.08g of polymerization inhibitor, as the dibutyl tin dilaurate of catalysts
0.05g makes its reaction at 60 DEG C, and the acrylic acid of hydroxyl value 288mgKOH/g is added when remaining isocyanate group becomes 3.9%
Ester admixture (A-1) (acrylic acid adduct of pentaerythrite) 35g, and then make its reaction at 60 DEG C.In remaining isocyanates
Reaction was completed when base is as 0.1%, obtains urethane acrylate system: compositions [I ' -2] (resin component concentration
100%).
In addition, there is no only (A-1) in the urethane acrylate system: compositions [I ' -2] of acquisition according to above procedure
And the reaction product of (C-1).
The weight average molecular weight of the urethane acrylate system: compositions [I ' -2] of acquisition is 18000, at 60 DEG C
Viscosity is 700000mPas.But viscosity is high, therefore E type viscosimeter is used to implement measurement.
(manufactures of urethane acrylate system: compositions [I ' -3])
Be equipped with thermometer, blender, water-cooled condenser, nitrogen mouth blown 4 mouthfuls of flasks in, be packed into isophorone two it is different
Acrylate mixture (A ' -2) (the acrylic acid addition of pentaerythrite of cyanate (C-1) 25.8g, hydroxyl value 184.2mgKOH/g
Object) 74.2g, the ethyl acetate 100g as solvent, the 4- metoxyphenol 0.08g as polymerization inhibitor, as catalysts
Dibutyl tin dilaurate 0.05g, its reaction is made at 60 DEG C, remaining isocyanate group become 0.1% when reaction was completed,
It obtains urethane acrylate system: compositions [I ' -3] (resin component concentration 50%).
The weight average molecular weight of the urethane acrylate system: compositions [I ' -3] of acquisition is 2100, viscous at 20 DEG C
Degree is 73mPas.
In addition, each ingredient is relative to following ingredients (a1)~(a4) total amount in acrylate mixture (A ' -2)
Containing ratio is as follows.
(manufactures of urethane acrylate system: compositions [I ' -4])
Be equipped with thermometer, blender, water-cooled condenser, nitrogen mouth blown 4 mouthfuls of flasks in, be packed into two methylene of hydrogenation of benzene
Acrylate mixture (A ' -2) (propylene of pentaerythrite of group diisocyanate (C-2) 23.3g, hydroxyl value 184.2mgKOH/g
Sour addition product) 76.7g, the ethyl acetate 100g as solvent, the 4- metoxyphenol 0.08g as polymerization inhibitor, as reaction
The dibutyl tin dilaurate 0.05g of catalyst makes its reaction, the knot when remaining isocyanate group becomes 0.1% at 60 DEG C
Shu Fanying is obtained urethane acrylate system: compositions [I ' -4] (resin component concentration 50%).
The weight average molecular weight of the urethane acrylate system: compositions [I ' -4] of acquisition is 2200, viscous at 20 DEG C
Degree is 85mPas.
<Examples 1 to 4, comparative example 1~4>
(manufacture of actinic energy ray curable resion composition)
In the urethane acrylate system: compositions ([I], [I ']) of above-mentioned acquisition, relative to cure component 100
1- hydroxycyclohexyl phenyl ketone (IGM company manufacture, " Omnirad 184 ") 4 part of part compounding as Photoepolymerizationinitiater initiater (D), is obtained
Obtain actinic energy ray curable resion composition.
In addition, in embodiment 3,4, comparative example 1,2, by the urethane acrylate system: compositions of acquisition ([I],
[I ']) it is diluted with ethyl acetate and resin component is made to become 50%, in addition to this as described above, obtain active energy beam
Hardening resin composition.
For the actinic energy ray curable resion composition of acquisition, as follows, it is (dry to form film before curing
Film) and evaluate the viscosity of film.And cured coating film is formed as follows, evaluate hardness, the bendability of cured coating film.Evaluation knot
Fruit table 1 as be described hereinafter.
(viscosity of dry coating)
The actinic energy ray curable resion composition of above-mentioned acquisition is coated on easily bonding PET film using spreading rod
(Co., Ltd.'s manufacture, 125 μm of " A4300 ", size 15cm × 15cm, thickness spin in Japan) on substrate, make the film after solidifying at
It is 3 minutes dry at 60 DEG C for 10 μm of thickness.The film before curing of acquisition is used into tack meter (RHESCA company
Manufacture, " TAC-II "), to be pushed into speed 120mm/ minutes, draw speed-raising degree 600mm/ minutes, pressure 20.4gf, pressing time 1.0
The condition of second carries out probe tack test.
(hardness of cured coating film)
The actinic energy ray curable resion composition of above-mentioned acquisition is coated on easily bonding PET film using spreading rod
(Co., Ltd.'s manufacture is spun by Japan, " A4300 ", size 15cm × 15cm, 125 μm of thickness) on substrate, make the film after solidifying at
For 10 μm of thickness, after carrying out drying in 3 minutes at 60 DEG C, using high-pressure sodium lamp 80W, 1 lamp, from the height of 18cm with 5.1m/
The ultraviolet light that the conveying tape speed of minute implements 2 tunnels irradiates (cumulative exposure 500mJ/cm2), form cured coating film.
For the above-mentioned cured coating film being coated in easily bonding PET film, is tested according to JIS K-5600, measure lead
Hardness.
(bendability of cured coating film)
Same progress is evaluated with above-mentioned hardness, forms cured coating film, and for the solidification being coated in easily bonding PET film
Film implements the evaluation of bendability according to JIS K 5600-5-1 using cylindrical mandrel Apparatus for Bending at low-temp.For use will be evaluated
Cured coating film by coated surface become outside in a manner of wound on test bar when there is cracked or lifted off maximum diameter (integer value, mm)
It is measured.Mean to be worth the smaller film higher for bendability.
[table 1]
From above-mentioned evaluation result: the work by amido-containing acid ester acrylate composition [I] of Examples 1 to 4
Property energy ray-curable resin combination obtain cured coating film, hardness and bendability are excellent, even and it is before curing not
The film of solid state is also inviscid.
On the other hand, the carbamate third other than specific urethane acrylate system: compositions [I] has been used
In each comparative example of olefin(e) acid ester system: compositions, the bendability of the cured coating film of comparative example 1 is bad, and film before curing have it is viscous
Property.In addition, comparative example 2, the hardness of cured coating film is bad, and film toughness before curing.Comparative example 3 and 4, cured coating film
Bendability is bad.
It can thus be appreciated that: the actinic energy ray curable resion composition of above-described embodiment 1~4 is inviscid, hardness and curved
Song is good, and the use in smears etc., particularly hard coating smears, optical thin film smears is on the way useful.
<<embodiment for having used carbamate (methyl) acrylate composition [I] and [II]>>
It is as follows, prepare urethane acrylate system: compositions [I] ([I-5]~[I-7]), [II] ([II-1]~
[II-2]), and prepare the urethane acrylate system: compositions [I '] ([I ' -5]~[I ' -7]) for comparing.
(urethane acrylate system: compositions [I-5])
Be equipped with thermometer, blender, water-cooled condenser, nitrogen mouth blown 4 mouthfuls of flasks in, be packed into isophorone two it is different
The acrylate mixture (A-1) (acrylic acid adduct of pentaerythrite) of cyanate (C-1) 36g, hydroxyl value 288mgKOH/g
64g, the ethyl acetate 100g as solvent, the 4- metoxyphenol 0.08g as polymerization inhibitor, as the February of catalysts
Dilaurylate 0.05g makes its reaction at 60 DEG C, and when remaining isocyanate group becomes 0.1%, reaction was completed, obtains ammonia
Urethane acrylate system: compositions [I-5] (resin component concentration 50%).
The weight average molecular weight of the urethane acrylate system: compositions [I-5] of acquisition is 4700, viscous at 20 DEG C
Degree is 80mPas.In addition, the measurement of the viscosity at 20 DEG C is implemented using Brookfield viscometer.Viscosimetric analysis at 20 DEG C, with
Under it is identical.
In addition, each ingredient contains relative to following ingredients (a1)~(a4) total amount in acrylate mixture (A-1)
There is ratio as follows.
(manufactures of urethane acrylate system: compositions [I-6])
Be equipped with thermometer, blender, water-cooled condenser, nitrogen mouth blown 4 mouthfuls of flasks in, be packed into two methylene of hydrogenation of benzene
Acrylate mixture (A-1) (the acrylic acid addition of pentaerythrite of group diisocyanate (C-2) 33g, hydroxyl value 288mgKOH/g
Object) 67g, the ethyl acetate 100g as solvent, the 4- metoxyphenol 0.08g as polymerization inhibitor, as catalysts
Dibutyl tin dilaurate 0.05g makes its reaction at 60 DEG C, and when remaining isocyanate group becomes 0.1%, reaction was completed, obtains
It obtains urethane acrylate system: compositions [I-6] (resin component concentration 50%).
The weight average molecular weight of the urethane acrylate system: compositions [I-6] of acquisition is 6200, viscous at 20 DEG C
Degree is 65mPas.
(manufactures of urethane acrylate system: compositions [I-7])
Be equipped with thermometer, blender, water-cooled condenser, nitrogen mouth blown 4 mouthfuls of flasks in, be packed into phenylenedimethylidyne two
The acrylate mixture (A-1) (acrylic acid adduct of pentaerythrite) of isocyanates (C-4) 32g, hydroxyl value 288mgKOH/g
68g, the ethyl acetate 100g as solvent, the 4- metoxyphenol 0.08g as polymerization inhibitor, as the February of catalysts
Dilaurylate 0.05g makes its reaction at 60 DEG C, and when remaining isocyanate group becomes 0.1%, reaction was completed, obtains ammonia
Urethane acrylate system: compositions [I-7] (resin component concentration 50%).
The weight average molecular weight of the urethane acrylate system: compositions [I-7] of acquisition is 5900, viscous at 20 DEG C
Degree is 50mPas.
(manufactures of urethane acrylate system: compositions [II-1])
Be equipped with thermometer, blender, water-cooled condenser, nitrogen mouth blown 4 mouthfuls of flasks in, be packed into two methylene of hydrogenation of benzene
Acrylate mixture (B-1) (acrylic acid of dipentaerythritol of group diisocyanate (C-2) 27.9g, hydroxyl value 96mgKOH/g
Addition product) 172.1g, as the 4- metoxyphenol 0.08g of polymerization inhibitor, as the dibutyl tin dilaurate of catalysts
0.1g makes its reaction at 60 DEG C, and when remaining isocyanate group becomes 0.1%, reaction was completed, obtains carbamate propylene
Acid esters system: compositions [II-1] (resin component concentration 100%).
The weight average molecular weight of the urethane acrylate system: compositions [II-1] of acquisition is 5500, viscous at 60 DEG C
Degree is 39400mPas.In addition, the measurement of the viscosity at 60 DEG C is implemented using E type viscosimeter.Viscosimetric analysis at 60 DEG C
It is same as below.
In addition, each ingredient contains relative to following ingredients (b1)~(b6) total amount in acrylate mixture (B-1)
There is ratio as follows.
(b4) dipentaerythritoltetraacrylate 18%
(b5) five acrylic acid dipentaerythritol ester 51%
(b6) six acrylic acid dipentaerythritol ester 31%
But for (b1) acrylic acid dipentaerythritol ester, (b2) diacrylate dipentaerythritol ester, (b3) three propylene
Sour dipentaerythritol ester, content are determination limit value hereinafter, therefore the containing ratio of display (b4)~(b6) ingredient.
(manufactures of urethane acrylate system: compositions [II-2])
Be equipped with thermometer, blender, water-cooled condenser, nitrogen mouth blown 4 mouthfuls of flasks in, be packed into isophorone two it is different
The acrylate mixture (B-1) (acrylic acid adduct of dipentaerythritol) of cyanate (C-1) 31.3g, hydroxyl value 96mgKOH/g
168.7g, as the 4- metoxyphenol 0.08g of polymerization inhibitor, as the dibutyl tin dilaurate 0.1g of catalysts,
Make its reaction at 60 DEG C, reaction was completed when remaining isocyanate group becomes 0.1%, obtains urethane acrylate system group
It closes object [II-2] (resin component concentration 100%).
The weight average molecular weight of the urethane acrylate system: compositions [II-2] of acquisition is 67000, at 60 DEG C
Viscosity is 65000mPas.
(manufactures of urethane acrylate system: compositions [II-3])
Be equipped with thermometer, blender, water-cooled condenser, nitrogen mouth blown 4 mouthfuls of flasks in, be packed into isophorone two it is different
The acrylate mixture (B-2) (acrylic acid adduct of dipentaerythritol) of cyanate (C-1) 13.2g, hydroxyl value 50mgKOH/g
186.8g, as the 4- metoxyphenol 0.08g of polymerization inhibitor, as the dibutyl tin dilaurate 0.1g of catalysts,
Make its reaction at 60 DEG C, reaction was completed when remaining isocyanate group becomes 0.1%, obtains urethane acrylate system group
It closes object [II-3] (resin component concentration 100%).
The weight average molecular weight of the urethane acrylate system: compositions [II-3] of acquisition is 2000, viscous at 60 DEG C
Degree is 1700mPas.
In addition, each ingredient contains relative to following ingredients (b1)~(b6) total amount in acrylate mixture (B-2)
There is ratio as follows.
(b4) dipentaerythritoltetraacrylate 6%
(b5) five acrylic acid dipentaerythritol ester 54%
(b6) six acrylic acid dipentaerythritol ester 40%
But for (b1) single acrylic acid dipentaerythritol ester, (b2) diacrylate dipentaerythritol ester, (b3) three propylene
Sour dipentaerythritol ester, content are determination limit value hereinafter, therefore the containing ratio of display (b4)~(b6) ingredient.
(manufactures of urethane acrylate system: compositions [I ' -5])
Be equipped with thermometer, blender, water-cooled condenser, nitrogen mouth blown flask in, be packed into two isocyanide of isophorone
The acrylate mixture (A ' -1) (acrylic acid adduct of pentaerythrite) of acid esters (C-1) 38.4g, hydroxyl value 118mgKOH/g
161.6g, and it is loaded as the quinhydrones methyl ether 0.01g of polymerization inhibitor, the dibutyl tin dilaurate 0.01g as catalysts,
React it 8 hours, reaction was completed when remaining isocyanate group becomes 0.3% or less, obtains carbamate
Acrylate composition [I ' -5] (resin component concentration 100%).
The weight average molecular weight of the urethane acrylate system: compositions [I ' -5] of acquisition is 1400, viscous at 60 DEG C
Degree is 3000mPas.
In addition, each ingredient is relative to following ingredients (a1)~(a4) total amount in acrylate mixture (A ' -1)
Containing ratio is as follows.
(a2) diacrylate pentaerythritol ester 5%
(a3) pentaerythritol triacrylate 50%
(a4) pentaerythritol tetracrylate 45%
But for (a1) single acrylate, pentaerythritol, content is determination limit value hereinafter, therefore display (a2)~(a4)
The containing ratio of ingredient.
(manufactures of urethane acrylate system: compositions [I ' -6])
Be equipped with thermometer, blender, water-cooled condenser, nitrogen mouth blown 4 mouthfuls of flasks in, be packed into two methylene of hydrogenation of benzene
Acrylate mixture (A ' -2) (propylene of pentaerythrite of group diisocyanate (C-2) 23.3g, hydroxyl value 184.2mgKOH/g
Sour addition product) 76.7g, the ethyl acetate 100g as solvent, the 4- metoxyphenol 0.08g as polymerization inhibitor, as reaction
The dibutyl tin dilaurate 0.05g of catalyst, makes its reaction at 60 DEG C, ties when remaining isocyanate group becomes 0.1%
Shu Fanying is obtained urethane acrylate system: compositions [I ' -6] (resin component concentration 50%).
The weight average molecular weight of the urethane acrylate system: compositions [I ' -6] of acquisition is 2200, viscous at 20 DEG C
Degree is 85mPas.
In addition, each ingredient is relative to following ingredients (a1)~(a4) total amount in acrylate mixture (A ' -2)
Containing ratio is as follows.
(manufactures of urethane acrylate system: compositions [I ' -7])
Be equipped with thermometer, blender, water-cooled condenser, nitrogen mouth blown 4 mouthfuls of flasks in, be packed into isophorone two it is different
Acrylate mixture (A ' -2) (the acrylic acid addition of pentaerythrite of cyanate (C-1) 25.8g, hydroxyl value 184.2mgKOH/g
Object) 74.2g, the ethyl acetate 100g as solvent, the 4- metoxyphenol 0.08g as polymerization inhibitor, as catalysts
Dibutyl tin dilaurate 0.05g, its reaction is made at 60 DEG C, remaining isocyanate group become 0.1% when reaction was completed,
It obtains urethane acrylate system: compositions [I ' -7] (resin component concentration 50%).
The weight average molecular weight of the urethane acrylate system: compositions [I ' -7] of acquisition is 2100, viscous at 20 DEG C
Degree is 73mPas.
<embodiment 5~12, comparative example 5~9>
(manufacture of actinic energy ray curable resion composition)
Making the urethane acrylate system: compositions ([I], [II], [I ']) of above-mentioned acquisition becomes following 2 institute of table
The compounding composition shown, and relative to 100 parts of cure component, add the 1- hydroxycyclohexyl phenyl ketone as Photoepolymerizationinitiater initiater (D)
4 parts of (manufacture of IGM company, " Omnirad184 "), obtains actinic energy ray curable resion composition.
For the actinic energy ray curable resion composition of acquisition, cured coating film, evaluation solidification are formed as follows
The hardness of film, bendability.Evaluation result such as following table 2.
(hardness of cured coating film)
The actinic energy ray curable resion composition of above-mentioned acquisition is coated on easily bonding PET film using spreading rod
(Co., Ltd.'s manufacture, 125 μm of " A4300 ", size 15cm × 15cm, thickness spin in Japan) on substrate, make the film after solidifying at
For 10 μm of thickness, after carrying out drying in 3 minutes at 60 DEG C, using high-pressure sodium lamp 80W, 1 lamp, from the height of 18cm with 5.1m/
The ultraviolet light that the conveying tape speed of minute implements 2 tunnels irradiates (cumulative exposure 500mJ/cm2), form cured coating film.
For the above-mentioned cured coating film being coated in easily bonding PET film, is tested according to JIS K-5600, measure lead
Hardness.
(bendability of cured coating film)
It is identically formed cured coating film with the evaluation of above-mentioned hardness, and is applied for the solidification being coated in easily bonding PET film
Film implements the evaluation of bendability according to JIS K 5600-5-1 using cylindrical mandrel Apparatus for Bending at low-temp.For that will evaluate with solid
Change film by coated surface become outside in a manner of wound on test bar when occur cracked or lifted off maximum diameter (integer value, mm) into
Row measurement.It is worth the smaller film higher for bendability.
[table 2]
From above-mentioned evaluation result: by the urethane acrylate system: compositions [I] containing embodiment 5~12 and
The cured coating film that the actinic energy ray curable resion composition of [II] obtains, hardness and bendability are all excellent.
On the other hand, urethane acrylate is used only without urethane acrylate system: compositions [I]
The comparative example 5 of system: compositions [II], the bendability of cured coating film are bad.And contain the acrylate mixture system low using hydroxyl value
The comparative example 6 and 7 of standby urethane acrylate system: compositions, the bendability of cured coating film are bad.
In addition, containing the urethane acrylate system: compositions using the slightly higher acrylate mixture preparation of hydroxyl value
Comparative example 8 and 9, the bendability of cured coating film is also bad.
It can thus be appreciated that: the actinic energy ray curable resion composition of above-described embodiment 5~12, hardness and bendability are good
Good, the use in the especially hard coating smears such as smears, optical thin film smears is on the way useful.
<<embodiment for having used carbamate (methyl) acrylate composition [III]>>
Before the manufacture of carbamate (methyl) acrylate composition, first prepare mixture (A), mixture as follows
(A ') (comparative example use), mixture (B), polyisocyanates (C), Photoepolymerizationinitiater initiater (D).
(mixture (A))
A-1: for the acrylic acid adduct of the pentaerythrite of hydroxyl value 288mgKOH/g, each ingredient is relative to following ingredients
(a1) containing ratio of~(a4) total amount is as follows.
(mixture (A ') (comparative example use))
A ' -1: for the acrylic acid adduct of the pentaerythrite of hydroxyl value 118mgKOH/g, each ingredient is relative to following ingredients
(a1) containing ratio of~(a4) total amount is as follows.
(a2) diacrylate pentaerythritol ester 5%
(a3) pentaerythritol triacrylate 50%
(a4) pentaerythritol tetracrylate 45%
But for (a1) single acrylate, pentaerythritol, content is determination limit value hereinafter, therefore display (a2)~(a4)
The containing ratio of ingredient.
A ' -2: for the acrylic acid adduct of the pentaerythrite of hydroxyl value 184.2mgKOH/g, each ingredient relative to it is following at
Divide the containing ratio of the total amount of (a1)~(a4) as follows.
(mixture (B))
B-1: for the acrylic acid adduct of the dipentaerythritol of hydroxyl value 96mgKOH/g, each ingredient is relative to following ingredients
(b1) containing ratio of~(b6) total amount is as follows.
(b4) dipentaerythritoltetraacrylate 18%
(b5) five acrylic acid dipentaerythritol ester 51%
(b6) six acrylic acid dipentaerythritol ester 31%
But for (b1) single acrylic acid dipentaerythritol ester, (b2) diacrylate dipentaerythritol ester, (b3) three propylene
Sour dipentaerythritol ester, content are determination limit value hereinafter, therefore the containing ratio of display (b4)~(b6) ingredient.
B-2: for the acrylic acid adduct of the dipentaerythritol of hydroxyl value 54mgKOH/g, each ingredient is relative to following ingredients
(b1) containing ratio of~(b6) total amount is as follows.
(b4) dipentaerythritoltetraacrylate 6%
(b5) five acrylic acid dipentaerythritol ester 54%
(b6) six acrylic acid dipentaerythritol ester 40%
But for (b1) single acrylic acid dipentaerythritol ester, (b2) diacrylate dipentaerythritol ester, (b3) three propylene
Sour dipentaerythritol ester, content are determination limit value hereinafter, therefore the containing ratio of display (b4)~(b6) ingredient.
(polyisocyanates (C))
C-1: isophorone diisocyanate
C-2: hydrogenation benzene dimethylene diisocyanate
C-4: benzene dimethylene diisocyanate
(Photoepolymerizationinitiater initiater (D))
D-1:1- hydroxycyclohexyl phenyl ketone (manufacture of IGM company, " Omnirad184 ")
(synthesis example 1: urethane acrylate system: compositions (III-1))
Be equipped with thermometer, blender, water-cooled condenser, nitrogen mouth blown 4 mouthfuls of flasks in, be packed into two methylene of hydrogenation of benzene
Acrylate mixture (A-1) (the acrylic acid addition of pentaerythrite of group diisocyanate (C-2) 24g, hydroxyl value 288mgKOH/g
Object) 33g, acrylate mixture (B-1) (acrylic acid adduct of dipentaerythritol) 43g of hydroxyl value 96mgKOH/g, as molten
The ethyl acetate 100g of agent, as the 4- metoxyphenol 0.08g of polymerization inhibitor, as the di lauric dibutyl of catalysts
Tin 0.05g makes its reaction at 60 DEG C, and when remaining isocyanate group becomes 0.1%, reaction was completed, obtains carbamate third
Olefin(e) acid ester system: compositions (III-1) (resin component concentration 50%).
The weight average molecular weight of the urethane acrylate system: compositions (III-1) of acquisition is 4900, at 20 DEG C
Viscosity is 40mPas.In addition, being measured as viscosity at 20 DEG C is implemented using Brookfield viscometer.Viscosity at 20 DEG C is surveyed
It is fixed, it is same as below.
(synthesis example 2: urethane acrylate system: compositions (III-2))
Be equipped with thermometer, blender, water-cooled condenser, nitrogen mouth blown 4 mouthfuls of flasks in, be packed into phenylenedimethylidyne two
The acrylate mixture (A-1) (acrylic acid adduct of pentaerythrite) of isocyanates (C-4) 23g, hydroxyl value 288mgKOH/g
33g, acrylate mixture (B-1) (acrylic acid adduct of dipentaerythritol) 44g of hydroxyl value 96mgKOH/g, as solvent
Ethyl acetate 100g, as the 4- metoxyphenol 0.08g of polymerization inhibitor, as the dibutyl tin dilaurate of catalysts
0.05g makes its reaction at 60 DEG C, and when remaining isocyanate group becomes 0.1%, reaction was completed, obtains carbamate propylene
Acid esters system: compositions (III-2) (resin component concentration 50%).
The weight average molecular weight of the urethane acrylate system: compositions (III-2) of acquisition is 4600, at 20 DEG C
Viscosity is 30mPas.
(synthesis example 3: urethane acrylate system: compositions (III-3))
Be equipped with thermometer, blender, water-cooled condenser, nitrogen mouth blown 4 mouthfuls of flasks in, be packed into two methylene of hydrogenation of benzene
Acrylate mixture (A-1) (the acrylic acid addition of pentaerythrite of group diisocyanate (C-2) 24g, hydroxyl value 288mgKOH/g
Object) 35g, acrylate mixture (B-2) (acrylic acid adduct of dipentaerythritol) 81g of hydroxyl value 54mgKOH/g, as molten
The ethyl acetate 60g of agent, as the 4- metoxyphenol 0.08g of polymerization inhibitor, as the di lauric dibutyl of catalysts
Tin 0.05g makes its reaction at 60 DEG C, and when remaining isocyanate group becomes 0.1%, reaction was completed, obtains carbamate third
Olefin(e) acid ester system: compositions (III-3) (resin component concentration 70%).
The weight average molecular weight of the urethane acrylate system: compositions (III-3) of acquisition is 3300, at 20 DEG C
Viscosity is 460mPas.
(synthesis example 4: urethane acrylate system: compositions (III-4))
Be equipped with thermometer, blender, water-cooled condenser, nitrogen mouth blown 4 mouthfuls of flasks in, be packed into isophorone two it is different
The acrylate mixture (A-1) (acrylic acid adduct of pentaerythrite) of cyanate (C-1) 39g, hydroxyl value 288mgKOH/g
49g, acrylate mixture (B-2) (acrylic acid adduct of dipentaerythritol) 112g of hydroxyl value 54mgKOH/g, as polymerization inhibitor
4- metoxyphenol 0.08g, the dibutyl tin dilaurate 0.05g as catalysts of agent, make its reaction at 60 DEG C,
When remaining isocyanate group becomes 0.1%, reaction was completed, obtains urethane acrylate system: compositions (III-3) (tree
Rouge constituent concentration 100%).
The weight average molecular weight of the urethane acrylate system: compositions (III-4) of acquisition is 3800.Very because of viscosity
Height, therefore viscosity can not be measured.
(synthesis example 5: urethane acrylate system: compositions (III ' -1))
Be equipped with thermometer, blender, water-cooled condenser, nitrogen mouth blown 4 mouthfuls of flasks in, be packed into two methylene of hydrogenation of benzene
Group diisocyanate (C-2) 22g, hydroxyl value 118mgKOH/g acrylate mixture (A ' -1) (acrylic acid of pentaerythrite adds
At object) 78g, hydroxyl value 96mgKOH/g acrylate mixture (B-1) (acrylic acid adduct of dipentaerythritol) 40g, conduct
The ethyl acetate 60g of solvent, the 4- metoxyphenol 0.08g as polymerization inhibitor, two fourth of tin dilaurate as catalysts
Base tin 0.05g, makes its reaction at 60 DEG C, and when remaining isocyanate group becomes 0.1%, reaction was completed, obtains carbamate
Acrylate composition (III ' -1) (resin component concentration 70%).
The weight average molecular weight of the urethane acrylate system: compositions (III ' -1) of acquisition is 1700, at 20 DEG C
Viscosity is 140mPas.
(synthesis example 6: urethane acrylate system: compositions (III ' -2))
Be equipped with thermometer, blender, water-cooled condenser, nitrogen mouth blown 4 mouthfuls of flasks in, be packed into two methylene of hydrogenation of benzene
Acrylate mixture (A ' -2) (propylene of pentaerythrite of group diisocyanate (C-2) 21.3g, hydroxyl value 184.2mgKOH/g
Sour addition product) 61.0g, hydroxyl value 96mgKOH/g acrylate mixture (B-1) (acrylic acid adduct of dipentaerythritol)
17.6g, the ethyl acetate 100g as solvent, the 4- metoxyphenol 0.08g as polymerization inhibitor, as the two of catalysts
Dibutyl tin laurate 0.05g makes its reaction at 60 DEG C, and when remaining isocyanate group becomes 0.1%, reaction was completed, obtains
Urethane acrylate system: compositions (III ' -2) (resin component concentration 50%).
The weight average molecular weight of the urethane acrylate system: compositions (III ' -2) of acquisition is 2300, at 20 DEG C
Viscosity is 65mPas.
(synthesis example 7: urethane acrylate system: compositions (III ' -3))
Be equipped with thermometer, blender, water-cooled condenser, nitrogen mouth blown 4 mouthfuls of flasks in, be packed into phenylenedimethylidyne two
The acrylate mixture (A-1) (acrylic acid adduct of pentaerythrite) of isocyanates (C-4) 32g, hydroxyl value 288mgKOH/g
68g, the ethyl acetate 100g as solvent, the 4- metoxyphenol 0.08g as polymerization inhibitor, as the February of catalysts
Dilaurylate 0.05g makes its reaction at 60 DEG C, and when remaining isocyanate group becomes 0.1%, reaction was completed, obtains ammonia
Urethane acrylate system: compositions (III ' -3) (resin component concentration 50%).
The weight average molecular weight of the urethane acrylate system: compositions (III ' -3) of acquisition is 5900, at 20 DEG C
Viscosity is 50mPas.
(synthesis example 8: the manufacture of urethane acrylate system: compositions (III ' -4))
Be equipped with thermometer, blender, water-cooled condenser, nitrogen mouth blown 4 mouthfuls of flasks in, be packed into two methylene of hydrogenation of benzene
Group diisocyanate (C-2) 28g, hydroxyl value 96mgKOH/g acrylate mixture (B-1) (acrylic acid of dipentaerythritol adds
At object) 172g, as the 4- metoxyphenol 0.08g of polymerization inhibitor, as the dibutyl tin dilaurate 0.1g of catalysts,
Make its reaction at 60 DEG C, reaction was completed when remaining isocyanate group becomes 0.1%, obtains urethane acrylate system
Composition (III ' -4) (resin component concentration 100%).
The weight average molecular weight of the urethane acrylate system: compositions (III ' -4) of acquisition is 5500, at 60 DEG C
Viscosity is 39400mPas.In addition, being measured as viscosity at 60 DEG C is implemented using E type viscosimeter.
<embodiment 13~16, comparative example 10~13>
(actinic energy ray curable resion composition)
In the urethane acrylate system: compositions (III-1~4, III ' -1~4) of above-mentioned acquisition, relative to solidification
1- hydroxycyclohexyl phenyl ketone (IGM company manufacture, " Omnirad184 ") 4 of 100 parts of the ingredient compoundings as Photoepolymerizationinitiater initiater (D)
Part, obtain actinic energy ray curable resion composition.
For the actinic energy ray curable resion composition of acquisition, as follows, cured coating film, evaluation solidification are formed
Hardness, bendability, the marresistance of film.Evaluation result such as following table 3.
(hardness of cured coating film)
The actinic energy ray curable resion composition of above-mentioned acquisition is coated on easily bonding PET film using spreading rod
(Co., Ltd.'s manufacture, 125 μm of " A4300 ", size 15cm × 15cm, thickness spin in Japan) on substrate, make the film after solidifying at
For 10 μm of thickness, after carrying out drying in 3 minutes at 60 DEG C, using high-pressure sodium lamp 80W, 1 lamp, from the height of 18cm with 5.1m/
The ultraviolet light that the conveying tape speed of minute implements 2 tunnels irradiates (cumulative exposure 500mJ/cm2), form cured coating film.
For the above-mentioned cured coating film being coated in easily bonding PET film, implements to test according to JIS K-5600, measure lead
Hardness.
(bendability of cured coating film)
Same progress is evaluated with above-mentioned hardness, forms cured coating film, and for the solidification being coated in easily bonding PET film
Film implements the evaluation of bendability according to JIS K 5600-5-1 using cylindrical mandrel Apparatus for Bending at low-temp.For use will be evaluated
Cured coating film by coated surface become outside in a manner of wound on test bar when there is cracked or lifted off maximum diameter (integer value, mm)
It is measured.It is worth the smaller film higher for bendability.
(marresistance of cured coating film)
It is identically formed cured coating film with the evaluation of above-mentioned hardness, and is applied for the solidification being coated in easily bonding PET film
Film is existed using steel wool (Japanese steel wool Co., Ltd. manufactures, BON STAR#0000) in the state for the load for applying 500g
The surface of cured coating film is back and forth after 10 times, visually to observe the injured degree on surface.
(evaluation)
Zero not can confirm that injury
× it can confirm that injury
[table 3]
From above-mentioned evaluation result: embodiment 13~16 by amido-containing acid ester acrylate composition [III]
Actinic energy ray curable resion composition obtain cured coating film, not only hardness and bendability are good, marresistance
It is excellent.
On the other hand, the acrylic acid adduct (A ' -1) of the pentaerythrite of the low hydroxyl value of 200mgKOH/g is not reached using hydroxyl value
Comparative example 10 when, the comparative example 13 of acrylic acid adduct (B-1) in mixture (A) and (B), using only dipentaerythritol
When, the bendability of cured coating film is bad.In addition, using hydroxyl value it is low a little pentaerythrite acrylic acid adduct (A ' -2)
Comparative example 11, hardness is slightly poor, and marresistance is bad.In addition, the pentaerythrite of high hydroxyl value is used only in mixture (A) and (B)
Acrylic acid adduct (A-1) comparative example 12 in the case where, the marresistance of cured coating film is bad.
It can thus be appreciated that: not only hardness, bendability are good for the actinic energy ray curable resion composition of embodiment 13~16
Good, marresistance is also good, the especially hard coating smears such as smears, optical thin film smears with being useful on the way
's.
It is to be disclosed for the specific form in the present invention, but above-described embodiment only simply illustrates in above-described embodiment, not
As limited explanation.It is believed that miscellaneous deformation known to a person skilled in the art, is included in of the invention
In range.
Industrial availability
Actinic energy ray curable resion composition of the invention, cure shrinkage is small when forming cured coating film, therefore is not easy
Curling can form hardness and the excellent film of bendability, as smears, especially hard coating smears, optical thin film painting
Cloth agent is useful.In addition, being also useful as coating, printing ink etc..In turn, active energy beam will have been formed on film to consolidate
After the resin combination side of the laminate film of the uncured state of the property changed resin composition layer is attached at molding, active energy is carried out
Actinic radiation-curable is measured, cured film can be formed as into various moldings easily.
Claims (15)
1. a kind of actinic energy ray curable resion composition, which is characterized in that it contains carbamate (methyl) propylene
Acid esters system: compositions [I],
Carbamate (methyl) acrylate composition [I] is (methyl) acrylate (a1) in mixture (A)
Obtained from~(a3) is reacted with polyisocyanates (CA), the mixture (A) is as pentaerythrite and (methyl) acrylic acid
Reaction product following (methyl) acrylate (a1)~(a4) mixture,
The hydroxyl value of the mixture (A) is 200mgKOH/g or more；
(a1) single (methyl) acrylate, pentaerythritol
(a2) two (methyl) acrylate, pentaerythritol
(a3) three (methyl) acrylate, pentaerythritol
(a4) four (methyl) acrylate, pentaerythritol.
2. a kind of actinic energy ray curable resion composition, which is characterized in that it contains carbamate (methyl) propylene
Acid esters system: compositions [I] and carbamate (methyl) acrylate composition [II],
Carbamate (methyl) acrylate composition [I] is (methyl) acrylate (a1) in mixture (A)
Obtained from~(a3) is reacted with polyisocyanates (CA), the mixture (A) is as pentaerythrite and (methyl) acrylic acid
Reaction product following (methyl) acrylate (a1)~(a4) mixture,
Carbamate (methyl) acrylate composition [II] is (methyl) acrylate (b1) in mixture (B)
Obtained from~(b5) is reacted with polyisocyanates (CB), the mixture (B) is as dipentaerythritol and (methyl) propylene
The mixture of following (methyl) acrylate (b1)~(b6) of the reaction product of acid,
The hydroxyl value of the mixture (A) is 200mgKOH/g or more and the hydroxyl value of said mixture (B) is 40mgKOH/g or more；
Mixture (A)
(a1) single (methyl) acrylate, pentaerythritol
(a2) two (methyl) acrylate, pentaerythritol
(a3) three (methyl) acrylate, pentaerythritol
(a4) four (methyl) acrylate, pentaerythritol
Mixture (B)
(b1) single (methyl) acrylic acid dipentaerythritol ester
(b2) two (methyl) acrylic acid dipentaerythritol ester
(b3) three (methyl) acrylic acid dipentaerythritol ester
(b4) four (methyl) acrylic acid dipentaerythritol ester
(b5) five (methyl) acrylic acid dipentaerythritol ester
(b6) six (methyl) acrylic acid dipentaerythritol ester.
3. a kind of actinic energy ray curable resion composition, which is characterized in that it contains carbamate (methyl) propylene
Acid esters system: compositions [III],
Carbamate (methyl) acrylate composition [III] is by (methyl) acrylate as following [α]
(a1)~(a3), (methyl) acrylate (b1)~(b5) as following [β] and polyisocyanates (CC) reaction obtain
's；
[α] as pentaerythrite and the reaction product of (methyl) acrylic acid following (methyl) acrylate (a1)~(a4) it is mixed
(methyl) acrylate (a1)~(a3) in object (A) is closed, and the hydroxyl value of the mixture (A) is 200mgKOH/g or more；
(a1) single (methyl) acrylate, pentaerythritol
(a2) two (methyl) acrylate, pentaerythritol
(a3) three (methyl) acrylate, pentaerythritol
(a4) four (methyl) acrylate, pentaerythritol
[β] is as dipentaerythritol with following (methyl) acrylate (b1)~(b6's) of the reaction product of (methyl) acrylic acid
(methyl) acrylate (b1)~(b5) in mixture (B), and the hydroxyl value of the mixture (B) is 40mgKOH/g or more；
(b1) single (methyl) acrylic acid dipentaerythritol ester
(b2) two (methyl) acrylic acid dipentaerythritol ester
(b3) three (methyl) acrylic acid dipentaerythritol ester
(b4) four (methyl) acrylic acid dipentaerythritol ester
(b5) five (methyl) acrylic acid dipentaerythritol ester
(b6) six (methyl) acrylic acid dipentaerythritol ester.
4. actinic energy ray curable resion composition described in any one of claim 1 to 3, wherein (the first
Base) containing ratio of two (methyl) acrylate, pentaerythritols (a2) in acrylate (a1)~(a4) mixture (A) is
10~50 weight %.
5. actinic energy ray curable resion composition according to any one of claims 1 to 4, wherein two (first
Base) acrylate, pentaerythritol (a2) relative to the containing ratio of the total amount of (methyl) acrylate (a1)~(a3) is
15~55 weight %.
6. according to claim 1, actinic energy ray curable resion composition described in any one of 2,4 or 5, wherein institute
The weight average molecular weight for stating carbamate (methyl) acrylate composition [I] is 1000~20000.
7. the actinic energy ray curable resion composition according to any one of claim 2~6, wherein (the first
Base) five (methyl) acrylic acid dipentaerythritol esters (b5) in acrylate (b1)~(b6) mixture (B) containing ratio
For 15~60 weight %.
8. the actinic energy ray curable resion composition according to any one of claim 2~7, wherein five (first
Base) containing ratio of the acrylic acid dipentaerythritol ester (b5) relative to the total amount of (methyl) acrylate (b1)~(b5)
For 45~90 weight %.
9. the actinic energy ray curable resion composition according to any one of claim 2~8, wherein (the first
Base) four (methyl) acrylic acid dipentaerythritol esters (b4) in acrylate (b1)~(b6) mixture (B) containing ratio
For 1~35 weight %.
10. the actinic energy ray curable resion composition according to any one of claim 2~9, wherein described four
(methyl) acrylic acid dipentaerythritol ester (b4) relative to (methyl) acrylate (b1)~(b5) total amount contain than
Rate is 2~40 weight %.
11. the actinic energy ray curable resion composition according to any one of claim 2,4~10, wherein institute
The weight average molecular weight for stating carbamate (methyl) acrylate composition [II] is 1000~20000.
12. the actinic energy ray curable resion composition according to any one of claim 3~5,7~10, wherein
The weight average molecular weight of carbamate (methyl) acrylate composition [III] is 1000~20000.
13. a kind of smears, which is characterized in that it is solid that it contains active energy beam described in any one of claim 1~12
The property changed resin combination.
14. smears according to claim 13, which is characterized in that used as hard coating with smears.
15. smears according to claim 13, which is characterized in that used as optical thin film with smears.
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| JP2017-070381 | 2017-03-31 | ||
| JP2017070381 | 2017-03-31 | ||
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| JP2017-074718 | 2017-04-04 | ||
| JP2017-082548 | 2017-04-19 | ||
| JP2017082548 | 2017-04-19 | ||
| PCT/JP2018/013806 WO2018181972A1 (en) | 2017-03-31 | 2018-03-30 | Active energy ray-curable resin composition and coating agent |
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| CN115362222A (en) * | 2020-04-07 | 2022-11-18 | 东洋油墨Sc控股株式会社 | Active energy ray-curable hard coating agent, laminated film, transparent conductive film, optical member, and electronic device |
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| CN113811555B (en) * | 2019-08-02 | 2023-03-10 | 根上工业株式会社 | Urethane (meth) acrylate, neutralized product thereof, photocurable resin composition, and liquid composition |
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| JP2012229412A (en) * | 2011-04-13 | 2012-11-22 | Nippon Synthetic Chem Ind Co Ltd:The | Resin composition and coating agent |
| CN103380157A (en) * | 2011-03-08 | 2013-10-30 | 日本合成化学工业株式会社 | Active-energy-curable resin composition and coating agent |
| WO2016194765A1 (en) * | 2015-06-04 | 2016-12-08 | Dic株式会社 | Urethane (meth)acrylate resin and laminated film |
| CN106459329A (en) * | 2014-06-13 | 2017-02-22 | 东亚合成株式会社 | Curable composition |
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| JP2009286924A (en) | 2008-05-30 | 2009-12-10 | Jsr Corp | Curable composition |
| JP5374997B2 (en) | 2008-09-26 | 2013-12-25 | Ｄｉｃ株式会社 | Active energy ray-curable resin composition for coating and film substrate |
| JP5497303B2 (en) | 2009-02-05 | 2014-05-21 | 共栄社化学株式会社 | Anti-curl coating agent |
| CN102803332B (en) * | 2009-06-17 | 2015-05-06 | 日本化药株式会社 | Urethane (meth) acrylate compound and resin composition containing same |
| JP2016104859A (en) * | 2014-11-25 | 2016-06-09 | 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103380157A (en) * | 2011-03-08 | 2013-10-30 | 日本合成化学工业株式会社 | Active-energy-curable resin composition and coating agent |
| JP2012229412A (en) * | 2011-04-13 | 2012-11-22 | Nippon Synthetic Chem Ind Co Ltd:The | Resin composition and coating agent |
| CN106459329A (en) * | 2014-06-13 | 2017-02-22 | 东亚合成株式会社 | Curable composition |
| WO2016194765A1 (en) * | 2015-06-04 | 2016-12-08 | Dic株式会社 | Urethane (meth)acrylate resin and laminated film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115362222A (en) * | 2020-04-07 | 2022-11-18 | 东洋油墨Sc控股株式会社 | Active energy ray-curable hard coating agent, laminated film, transparent conductive film, optical member, and electronic device |
| CN115362222B (en) * | 2020-04-07 | 2024-03-15 | 东洋油墨Sc控股株式会社 | Laminated film, transparent conductive film, optical member, and electronic device |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102445218B1 (en) | 2022-09-20 |
| CN110382575B (en) | 2022-11-22 |
| WO2018181972A1 (en) | 2018-10-04 |
| KR20190129848A (en) | 2019-11-20 |
| TW201841964A (en) | 2018-12-01 |
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