CN109134816B - Urethane (meth) acrylate, active energy ray-curable resin composition, cured product, and film - Google Patents
Urethane (meth) acrylate, active energy ray-curable resin composition, cured product, and film Download PDFInfo
- Publication number
- CN109134816B CN109134816B CN201810606583.0A CN201810606583A CN109134816B CN 109134816 B CN109134816 B CN 109134816B CN 201810606583 A CN201810606583 A CN 201810606583A CN 109134816 B CN109134816 B CN 109134816B
- Authority
- CN
- China
- Prior art keywords
- meth
- acrylate
- mass
- parts
- urethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 154
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000011342 resin composition Substances 0.000 title claims abstract description 35
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 60
- 150000001875 compounds Chemical group 0.000 claims abstract description 39
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 34
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 34
- 239000000047 product Substances 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- 239000002216 antistatic agent Substances 0.000 claims description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 14
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 11
- 239000008096 xylene Substances 0.000 claims description 8
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 5
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 abstract description 8
- 239000010408 film Substances 0.000 description 62
- 229920000193 polymethacrylate Polymers 0.000 description 23
- -1 methacryloyl Chemical group 0.000 description 21
- 125000002947 alkylene group Chemical group 0.000 description 19
- 239000000203 mixture Substances 0.000 description 19
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 239000002904 solvent Substances 0.000 description 16
- 239000000178 monomer Substances 0.000 description 13
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 10
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 9
- 239000002585 base Substances 0.000 description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- 238000007865 diluting Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000012788 optical film Substances 0.000 description 4
- 229920001515 polyalkylene glycol Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 3
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 150000001925 cycloalkenes Chemical class 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 1
- ZODNDDPVCIAZIQ-UHFFFAOYSA-N (2-hydroxy-3-prop-2-enoyloxypropyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)COC(=O)C=C ZODNDDPVCIAZIQ-UHFFFAOYSA-N 0.000 description 1
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 102100040409 Ameloblastin Human genes 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 101000891247 Homo sapiens Ameloblastin Proteins 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical class CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 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 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DVQGYGDSAGBRSZ-UHFFFAOYSA-N bis(1-cyclohexylcyclohexa-2,4-dien-1-yl)methanone Chemical compound C1C=CC=CC1(C1CCCCC1)C(=O)C1(C2CCCCC2)CC=CC=C1 DVQGYGDSAGBRSZ-UHFFFAOYSA-N 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001227 electron beam curing Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000007760 metering rod coating Methods 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
-
- 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
- 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
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
- C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/794—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aromatic isocyanates or isothiocyanates
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
[ problem ] the present invention provides a urethane (meth) acrylate, an active energy ray-curable resin composition, a cured product, and a film. [ means of solution ] the present invention provides a urethane (meth) acrylate which is a reaction product of a compound group containing the following (A) and (B): a polyisocyanate (a) which is a polymer of xylylene diisocyanate; and a hydroxyl group-containing (meth) acrylate (B). The film of the cured product of the active energy ray-curable resin composition containing the urethane (meth) acrylate has a high refractive index, high hardness, low curling properties, and high light resistance.
Description
Technical Field
The present invention relates to a urethane (meth) acrylate, an active energy ray-curable resin composition, a cured product, and a film.
Background
Liquid crystal displays use a large number of optical films such as prism sheets, Index Matching (IM) films, and antireflection films. Among the above films, a high-refractive-index resin material is required from the viewpoints of high brightness, skeleton visibility prevention (resistance to viewing of the bone え), and adjustment of reflection prevention. The high refractive index resin material is, for example, a material using a polymerizable monomer having a fluorene skeleton (patent document 1).
Documents of the prior art
Patent document
[ patent document 1] Japanese patent application laid-open No. 2010-007004
Disclosure of Invention
Technical problem to be solved by the invention
The active energy ray-curable resin composition is required to have various physical properties depending on the use. The present invention aims to provide an active energy ray curable resin composition which forms a cured product layer having a high refractive index, high hardness, low curling properties and high light resistance on the surface of a base film.
Means for solving the problems
The present inventors have made extensive studies to solve the above-mentioned problems and have found that the above-mentioned problems can be solved by using a reaction product having a specific structure, thereby completing the present invention.
The following items are provided by the present invention.
(item 1)
A urethane (meth) acrylate which is a reaction product of a compound group containing the following (a) and (B):
a polyisocyanate (a) which is a polymer of xylylene diisocyanate; and
a hydroxyl group-containing (meth) acrylate (B).
(item 2)
The urethane (meth) acrylate according to the above item, wherein the polyisocyanate (A) is an isocyanurate polymer, a biuret polymer or an addition polymer of xylene diisocyanate.
(item 3)
An active energy ray-curable resin composition containing the urethane (meth) acrylate as defined in any one of the above items.
(item 4)
The active energy ray-curable resin composition according to the above item, which contains a photopolymerization initiator.
(item 5)
The active energy ray-curable resin composition according to any one of the above items, which contains a polymerizable monomer.
(item 6)
The active energy ray-curable resin composition according to any one of the above items, which contains an antistatic agent.
(item 7)
A cured product of the active energy ray-curable resin composition according to any one of the above items.
(item 8)
A film comprising the cured product as described above.
In the present invention, one or more of the above-described features may be provided in further combinations than those explicitly described.
Advantageous effects
By using the active energy ray-curable resin composition provided by the present invention, a cured product layer (cured film) having a high refractive index, high hardness, low curling properties, and high light resistance can be formed on the surface of the base film.
Detailed Description
The ranges of numerical values such as values and contents of the respective physical properties may be appropriately set (for example, selected from the upper and lower limits described in the following items) throughout the present invention. Specifically, the numerical value α is, for example, in the case where the upper limit of the numerical value α is, for example, a1, a2, A3 or the like, and the lower limit of the numerical value α is, for example, B1, B2, B3 or the like, the range of the numerical value α is, for example, a1 or less, a2 or less, A3 or less, B1 or more, B2 or more, B3 or more, a1 to B1, a1 to B2, a1 to B3, a2 to B1, a2 to B2, a2 to B3, A3 to B1, A3 to B2, A3 to B3 or the like.
[ urethane (meth) acrylate ]
The present invention provides a urethane (meth) acrylate which is a reaction product of a compound group containing the following (a) and (B):
a polyisocyanate (a) which is a polymer of xylylene diisocyanate; and
a hydroxyl group-containing (meth) acrylate (B).
In the present invention, "(meth) acrylic acid" means "at least one selected from the group consisting of acrylic acid and methacrylic acid". Likewise, "(meth) acrylate" means "at least one selected from the group consisting of acrylate and methacrylate". Further, "(meth) acryloyl" means "at least one selected from the group consisting of acryloyl and methacryloyl".
A polyisocyanate (a) which is a polymer of xylylene diisocyanate; also referred to as polyisocyanate (A) and (A) Components >
In the present invention, the "polyisocyanate" refers to a compound having two or more isocyanate groups (-N ═ C ═ O).
The polyisocyanate (a) may be used alone or in combination of two or more. In one embodiment, the polyisocyanate (a) is an isocyanurate, biuret or addition polymer of xylene diisocyanate.
An isocyanurate polymer of xylylene diisocyanate is exemplified by a compound represented by the following structural formula (A-1).
[ solution 1]
(in the formula, n1 is an integer of 0 or more, and n1 is preferably 0 to 3).
Examples of the biuret multimer of xylene diisocyanate include compounds represented by the following structural formula (A-2).
[ solution 2]
(in the formula, n2 is an integer of 0 or more, and n2 is preferably 0 to 3).
Addition polymers of xylylene diisocyanate such as addition products of trimethylolpropane and xylylene diisocyanate represented by the following formula (A-3),
[ solution 3]
(in the formula, n3 is an integer of 0 or more, and n3 is preferably 0 to 3).
An adduct of glycerin represented by the following structural formula (A-4) with xylene diisocyanate, and the like.
[ solution 4]
(in the formula, n4 is an integer of 0 or more, and n4 is preferably 0 to 3).
In addition, the above structural formula is only an example, and the present invention is not intended to be limited to the compound represented by the above structural formula.
The term "polymer of xylylene diisocyanate" as used herein means a compound having at least two dimers. The upper limit of the polymerization degree of the polymer of xylene diisocyanate is, for example, 12, 11, 10, 9, 8, 7, 6, 5, 4, etc., and the lower limit thereof is, for example, 11, 10, 9, 8, 7, 6, 5, 4, 3, etc. In one embodiment, the polymerization degree is preferably 3 to 12, and more preferably 3 to 9. Furthermore, multimers are usually available as a mixture of different multimers, the degree of polymerization of which is an average, i.e., expressed as the average degree of polymerization. Preferred values of the average polymerization degree are the same as those described above. In the present invention, the polymerization degree of the n-mer is n.
The weight average molecular weight (Mw) of the polyisocyanate (a) is not particularly limited. The upper limit of the weight average molecular weight (Mw) of the polyisocyanate (A) is, for example, 80000, 70000, 60000, 50000, 40000, 30000, 20000, 10000, 9000, 8000, 7000, 6000, 5000, 4000, 3000, 2000, 1500, 1000, 600 or the like, and the lower limit is, for example, 70000, 60000, 50000, 40000, 30000, 20000, 10000, 9000, 8000, 7000, 6000, 5000, 4000, 3000, 2000, 1500, 1000, 600, 500 or the like. In one embodiment, the weight average molecular weight (Mw) of the polyisocyanate (a) is preferably 500 to 50000, more preferably 600 to 50000, from the viewpoint of the productivity of the urethane (meth) acrylate.
The number average molecular weight (Mn) of the polyisocyanate (a) is not particularly limited. The upper limit of the number average molecular weight (Mn) of the polyisocyanate (A) is, for example, 60000, 50000, 40000, 30000, 20000, 10000, 9000, 8000, 7000, 6000, 5000, 4000, 3000, 2000, 1000, 600, 500, 300, etc., and the lower limit is, for example, 55000, 50000, 40000, 35000, 30000, 20000, 10000, 9000, 8000, 7000, 6000, 5000, 4000, 3000, 2000, 1000, 500, etc. In one embodiment, the number average molecular weight (Mn) of the polyisocyanate (a) is preferably 500 to 60000, more preferably 500 to 40000, from the viewpoint of the productivity of the urethane (meth) acrylate.
The upper limit of the molecular weight distribution (Mw/Mn) of the polyisocyanate (A) is, for example, 8.0, 7.0, 6.0, 5.0, 4.0, 3.0, 2.0, etc., and the lower limit is, for example, 7.0, 6.0, 5.0, 4.0, 3.0, 2.0, 1.0, etc. In one embodiment, the molecular weight distribution (Mw/Mn) of the polyisocyanate (A) is preferably 1.0 to 8.0 from the viewpoint of the productivity of the urethane (meth) acrylate.
The weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined as polystyrene equivalent values measured by Gel Permeation Chromatography (GPC) (the same applies hereinafter).
The proportion of the polyisocyanate (a) to 100 parts by mass of the compound group is not particularly limited as long as the desired effect can be obtained. The upper limit of the proportion of the polyisocyanate (a) is, for example, 70, 60, 50, 40, 30, 25, 20, 10 parts by mass and the lower limit is, for example, 60, 50, 45, 40, 30, 20, 10, 5 parts by mass with respect to 100 parts by mass of the compound group. In one embodiment, the proportion of the polyisocyanate (a) to 100 parts by mass of the compound group is preferably 5 to 70 parts by mass, and more preferably 20 to 70 parts by mass, from the viewpoint of achieving a combination of high hardness, low curling properties, and a high refractive index.
< hydroxyl group-containing (meth) acrylate (B), also referred to as component (B) >
In the present invention, the "hydroxyl group-containing (meth) acrylate" refers to a compound having a hydroxyl group and a (meth) acryloyl group.
The hydroxyl group-containing monofunctional (meth) acrylate may be used alone or in combination of two or more. Examples of the hydroxyl group-containing (meth) acrylate include hydroxyl group-containing (meth) acrylic acid glyceride (B-1), hydroxyl group-containing (poly) pentaerythritol poly (meth) acrylate (B-2), hydroxyl group-containing (poly) trimethylolpropane poly (meth) acrylate (B-3), and hydroxyl group-containing monofunctional (meth) acrylate (B-4).
(Glycerol (meth) acrylate (B-1) containing hydroxyl group)
The hydroxyl-containing glycerol (meth) acrylate is a compound represented by the structural formula (B-1).
[ solution 5]
(in the formula, Rb1～Rb3May each independently be a hydrogen atom, (meth) acryloyl, alkyl, aryl or
[ solution 6]
(wherein b is an integer of 1 or more),
Rb1～Rb3at least one is a hydrogen atom or
[ solution 7]
(wherein b is an integer of 1 or more) and at least one is a (meth) acryloyl group).
Examples of the hydroxyl group-containing glycerol (meth) acrylate include 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, 2-hydroxy-3-methoxypropyl (meth) acrylate, 1-hydroxy-2-phenoxypropyl (meth) acrylate, 1-hydroxy-2- (meth) acryloyloxypropyl (meth) acrylate, 1-hydroxy-2-methoxypropyl (meth) acrylate, and caprolactone adduct of 2-hydroxy-3-phenoxypropyl (meth) acrylate.
(hydroxyl group-containing (poly) pentaerythritol Poly (meth) acrylate (B-2))
A compound of which the structural formula (B-2) is shown in the specification, wherein the compound contains hydroxyl (poly) pentaerythritol multi (methyl) acrylate.
[ solution 8]
(wherein m is an integer of 0 or more, Rb4～Rb9May each independently be a hydrogen atom, a (meth) acryloyl group or
[ solution 9]
(wherein B is an integer of 1 or more), and in the structural formula (B-2), R is represented byb4～Rb9At least one selected is a hydrogen atom, or
[ solution 10]
(wherein b is an integer of 1 or more) and at least one is a (meth) acryloyl group. Furthermore, Rb7And Rb8The groups may be different for each structural unit).
In the present invention, "(poly) pentaerythritol poly (meth) acrylate" means "at least one selected from the group consisting of pentaerythritol poly (meth) acrylate and polypentaerythritol poly (meth) acrylate".
Further, the phrase "the groups may be different for each structural unit" means that, for example, in the structural formula (B-2), when m is 2,
[ solution 11]
Rb7AAnd Rb7BMay be different radicals Rb8AAnd Rb8BMay be different groups (the same applies hereinafter).
Examples of pentaerythritol poly (meth) acrylate are pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate and the like.
Examples of the polypentaerythritol poly (meth) acrylate are dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol di (meth) acrylate, tripentaerythritol tri (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, and the like.
(hydroxyl group-containing (poly) trimethylolpropane poly (meth) acrylate (B-3))
A compound of the structural formula (B-3) of (poly) trimethylolpropane poly (meth) acrylate containing hydroxyl groups.
[ solution 12]
(wherein p is an integer of 0 or more, Rb10～Rb13Is a hydrogen atom, a (meth) acryloyl group, or a compound of formula 13]
(wherein b is an integer of 1 or more), from Rb10～Rb13At least one selected from the group consisting of hydrogen atoms or
[ solution 14]
(wherein b is an integer of 1 or more) and at least one is a (meth) acryloyl group. Furthermore, Rb12The groups may be different for each structural unit).
In the present invention, "(poly) trimethylolpropane poly (meth) acrylate" means "at least one selected from the group consisting of trimethylolpropane poly (meth) acrylate and polytrimethylolpropane poly (meth) acrylate".
Examples of the trimethylolpropane poly (meth) acrylate include trimethylolpropane di (meth) acrylate and the like.
Examples of the poly (trimethylolpropane poly (meth) acrylate) include ditrimethylolpropane di (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and the like.
(hydroxyl-containing monofunctional (meth) acrylate (B-4))
The monofunctional (meth) acrylate having a hydroxyl group is a compound represented by the formula (B-4).
[ solution 15]
(in the formula, Rb14Is a hydrogen atom or a methyl group, Rb15Is straight-chain alkylene, branched-chain alkylene, cycloalkylene or
[ solution 16]
(in the formula, Rb15aIs a hydrogen atom or an alkyl group (e.g., methyl)),
Rb16is a hydrogen atom or
[ solution 17]
(wherein b is an integer of 1 or more)
Examples of the compound represented by the formula (B-4) include a hydroxyl group-containing linear alkyl (meth) acrylate, a hydroxyl group-containing linear alkyl (meth) acrylate caprolactone adduct, a hydroxyl group-containing branched alkyl (meth) acrylate caprolactone adduct, a hydroxyl group-containing cycloalkyl (meth) acrylate caprolactone adduct, a polyalkylene glycol mono (meth) acrylate, and a polyalkylene glycol mono (meth) acrylate caprolactone adduct.
Examples of the hydroxyl group-containing straight-chain alkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
Examples of the hydroxyl group-containing linear alkyl (meth) acrylate caprolactone adduct include 3-hydroxypropyl (meth) acrylate caprolactone adduct, 2-hydroxyethyl (meth) acrylate caprolactone adduct, and 4-hydroxybutyl (meth) acrylate caprolactone adduct.
Examples of the branched alkyl (meth) acrylate having a hydroxyl group include 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl (meth) acrylate.
Examples of the branched alkyl (meth) acrylate caprolactone adduct having a hydroxyl group include a 2-hydroxypropyl (meth) acrylate caprolactone adduct, a 2-hydroxybutyl (meth) acrylate caprolactone adduct, and a 3-hydroxybutyl (meth) acrylate caprolactone adduct.
Examples of the cycloalkyl (meth) acrylate having a hydroxyl group include hydroxycyclohexyl (meth) acrylate and the like.
Examples of the hydroxyl group-containing cycloalkyl (meth) acrylate caprolactone adduct include hydroxycyclohexyl (meth) acrylate caprolactone adduct.
Examples of the polyalkylene glycol mono (meth) acrylate include polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate.
Examples of the polyalkylene glycol mono (meth) acrylate caprolactone adduct include polyethylene glycol mono (meth) acrylate caprolactone adduct and polypropylene glycol mono (meth) acrylate caprolactone adduct.
The hydroxyl value of the hydroxyl group-containing (meth) acrylate (B) is not particularly limited as long as the desired effect can be obtained. The upper limit of the hydroxyl value of the hydroxyl group-containing (meth) acrylate (B) is, for example, 500, 490, 450, 400, 350, 300, 250, 200, 150, 100, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20mgKOH/g or the like, and the lower limit is, for example, 400, 350, 300, 250, 200, 150, 100, 80, 70, 65, 60, 55, 50, 45, 40, 35mgKOH/g or the like. In one embodiment, the hydroxyl value of the polypentaerythritol poly (meth) acrylate (B) is preferably 35 to 500mgKOH/g, more preferably 35 to 490mgKOH/g, from the viewpoint of combining high hardness, low curling properties, and high refractive index.
In the present invention, the hydroxyl value means a calculated value obtained by the following formula:
(hydroxyl value) ═ 1000 (molecular weight of potassium hydroxide: 56.1) × (hydroxyl equivalent);
(hydroxyl equivalent) — (molecular weight of 1 molecule)/(number of hydroxyl groups present in 1 molecule).
The (meth) acrylic acid equivalent of the hydroxyl group-containing (meth) acrylate (B) is not particularly limited as long as the desired effect can be obtained. The upper limit of the (meth) acrylic acid equivalent of the hydroxyl group-containing (meth) acrylate (B) is, for example, 500, 450, 400, 350, 300, 250, 200, 150, 140, 130, 120, 110g/eq and the like, and the lower limit is, for example, 140, 130, 120, 110, 100, 99, 95g/eq and the like. In one embodiment, the hydroxyl group-containing poly (meth) acrylate (B) has a (meth) acrylic acid equivalent of preferably 95 to 500g/eq, more preferably 99 to 150g/eq, from the viewpoint of combining high hardness, low curling properties, and high refractive index.
In the present invention, "(meth) acrylic acid equivalent" means a molecular weight per mole of (meth) acryloyl group, and is determined by the following formula:
((meth) acrylic acid group equivalent) — (molecular weight of 1 molecule)/(number of (meth) acrylic groups present in 1 molecule).
The upper limit of the proportion of the hydroxyl group-containing poly (meth) acrylate (B) is, for example, 80, 70, 60, 50, 40, 35 parts by mass and the lower limit is, for example, 70, 60, 55, 50, 40, 30 parts by mass with respect to 100 parts by mass of the compound group. In one embodiment, the proportion of the hydroxyl group-containing poly (meth) acrylate (B) is preferably 30 to 80 parts by mass with respect to 100 parts by mass of the compound group from the viewpoint of achieving both high hardness and high refractive index.
< Compounds other than either component (A) or component (B), also referred to as other Compounds >
In the production of the urethane (meth) acrylate, a compound other than the component (A) or the component (B) may be used. That is, the compound group may contain a compound that is not the component (a) or the component (B).
In one embodiment, the proportion of the other compounds relative to 100% by mass of the above-mentioned compound group is, for example: 0 to 50 mass%, less than 40 mass%, less than 25 mass%, less than 10 mass%, less than 5 mass%, less than 1 mass%, less than 0.1 mass%, less than 0.01 mass%, 0 mass%, and the like.
In one embodiment, the proportion of the other compounds, relative to 100 mol% of the above-mentioned compound group, is, for example: 0 to 50 mol%, less than 40 mol%, less than 25 mol%, less than 10 mol%, less than 5 mol%, less than 1 mol%, less than 0.1 mol%, less than 0.01 mol%, 0 mol%, etc.
The above-mentioned method for producing a urethane (meth) acrylate may be a known method, and the component (a) and the component (B) may be reacted in the absence of a solvent or in a suitable solvent (toluene or the like) in the presence of a suitable catalyst (tin octylate or the like) at a suitable reaction temperature (60 to 90 ℃ or the like).
< relative proportions of the respective ingredients >
The mass ratio of the polyisocyanate (a) to the hydroxyl group-containing (meth) acrylate (B) (polyisocyanate (a)/hydroxyl group-containing (meth) acrylate (B)) is not particularly limited as long as the desired effect can be obtained. The mass ratio of the polyisocyanate (a) to the hydroxyl group-containing (meth) acrylate (B) (polyisocyanate (a)/hydroxyl group-containing (meth) acrylate (B)) has an upper limit of, for example, 2.5, 2, 1.9, 1.5, 1.0, 0.9, 0.5, 0.4, 0.3, etc., and a lower limit of, for example, 2, 1.9, 1.5, 1.0, 0.9, 0.5, 0.4, 0.3, 0.25, etc. In one embodiment, the mass ratio of the polyisocyanate (a) to the hydroxyl group-containing (meth) acrylate (B) (polyisocyanate (a)/hydroxyl group-containing (meth) acrylate (B)) is preferably 0.25 to 2.5 from the viewpoint of achieving a combination of high hardness, low curling properties, and a high refractive index.
The mass ratio of the other compound to the polyisocyanate (A) (other compound/polyisocyanate (A)) has an upper limit of, for example, 10, 9, 7.5, 5, 2.5, 1, 0.5, etc., and a lower limit of, for example, 9, 7.5, 5, 2.5, 1, 0.5, 0, etc. In one embodiment, the mass ratio of the other compound to the polyisocyanate (a) (other compound/polyisocyanate (a)) is preferably 0 to 10.
The mass ratio of the other compound to the hydroxyl group-containing polypentaerythritol poly (meth) acrylate (B) (other compound/hydroxyl group-containing polypentaerythritol poly (meth) acrylate (B)) has an upper limit of, for example, 1, 0.9, 0.75, 0.5, 0.25, 0.1, 0.05, and a lower limit of, for example, 0.9, 0.75, 0.5, 0.25, 0.1, 0.05, 0, and the like. In one embodiment, the mass ratio of the other compound to the hydroxyl group-containing polypentaerythritol poly (meth) acrylate (B) (other compound/hydroxyl group-containing polypentaerythritol poly (meth) acrylate (B)) is preferably 0 to 1.
The ratio of the amount of the hydroxyl group-containing (meth) acrylate (B) to the isocyanate group of the polyisocyanate (A) [ (OH)/(NCO) ] is not particularly limited as long as the desired effect can be obtained. The upper limit of the ratio [ (OH)/(NCO) ] of the hydroxyl group-containing (meth) acrylate (B) to the amount of the isocyanate group of the polyisocyanate (A) is, for example, 3.0, 2.5, 2.0, 1.5, 1.0, etc., and the lower limit thereof is, for example, 2.4, 2.0, 1.5, 1.0, 0.95, etc. In one embodiment, the ratio [ (OH)/(NCO) ] of the amount of the hydroxyl group-containing (meth) acrylate (B) to the isocyanate group of the polyisocyanate (A) is preferably 0.95 to 3.0. < physical Properties of urethane (meth) acrylate, etc. >
The weight average molecular weight (Mw) of the urethane (meth) acrylate is not particularly limited. The upper limit of the weight average molecular weight (Mw) of the urethane (meth) acrylate is, for example, 80000, 70000, 60000, 50000, 40000, 30000, 20000, 10000, 9000, 8000, 7000, 6000, 5000, 4000, 3000, etc., and the lower limit is, for example, 70000, 60000, 50000, 40000, 30000, 20000, 10000, 9000, 8000, 7000, 6000, 5000, 4000, 3000, 2000, 1750, 1700, 1500, etc. In one embodiment, the weight average molecular weight (Mw) of the urethane (meth) acrylate is preferably 1500 to 80000, more preferably 1700 to 80000, from the viewpoint of productivity of the urethane (meth) acrylate and the film.
The number average molecular weight (Mn) of the urethane (meth) acrylate is not particularly limited. The upper limit of the number average molecular weight (Mn) of the urethane (meth) acrylate is, for example, 80000, 70000, 60000, 50000, 40000, 30000, 20000, 12000, 10000, 9000, 8100, 8000, 7800, 7000, 6000, 5600, 5000, 4000, 3500, 3100, 3001, 3000, 2900, 2000, etc., and the lower limit is, for example, 70000, 60000, 50000, 40000, 30000, 20000, 12000, 10000, 9000, 8100, 8000, 7800, 7000, 6000, 5600, 5000, 4000, 3500, 3100, 3001, 3000, 2900, 2000, 1500, 1200, 1000, etc. In one embodiment, the number average molecular weight (Mn) of the urethane (meth) acrylate is preferably 1000 to 80000, and more preferably 1200 to 80000, from the viewpoint of productivity of the urethane (meth) acrylate and the film.
The molecular weight distribution (Mw/Mn) of the urethane (meth) acrylate is not particularly limited. The upper limit of the molecular weight distribution (Mw/Mn) of the urethane (meth) acrylate is, for example, 8.0, 7.0, 6.0, 5.0, 4.0, 3.0, 2.0, etc., and the lower limit is, for example, 8.0, 7.0, 6.0, 5.0, 4.0, 3.0, 2.0, 1.2, 1.0, etc. In one embodiment, the molecular weight distribution (Mw/Mn) of the urethane (meth) acrylate is preferably 1.0 to 8.0, and more preferably 1.2 to 6.0, from the viewpoint of productivity of the urethane (meth) acrylate and the film.
The (meth) acrylic acid equivalent of the urethane (meth) acrylate is not particularly limited as long as the desired effect can be obtained. The upper limit of the (meth) acrylic acid equivalent of the urethane (meth) acrylate is, for example, 400, 350, 300, 290, 150, 140, 130, 120, 110g/eq, etc., and the lower limit is, for example, 390, 350, 300, 290, 140, 130, 120, 110, 100g/eq, etc. In one embodiment, the urethane (meth) acrylate preferably has a (meth) acrylic acid equivalent of 100 to 400g/eq, more preferably 280 to 400g/eq, from the viewpoint of achieving both high hardness and low curling properties.
[ active energy ray-curable resin composition, also referred to as composition ]
The present invention provides an active energy ray-curable resin composition containing the urethane (meth) acrylate.
The content of the urethane (meth) acrylate is not particularly limited as long as the desired effect is obtained. The upper limit of the content of the urethane (meth) acrylate is, for example, 100, 90, 80, 70, 60, 51, 50, 40, 36, 35, 31, 30, 29, 20, 15 parts by mass and the lower limit is, for example, 90, 80, 70, 60, 51, 50, 40, 36, 35, 31, 30, 29, 20, 15, 10 parts by mass with respect to 100 parts by mass of the composition. In one embodiment, the content of the urethane (meth) acrylate is preferably about 10 to 100 parts by mass per 100 parts by mass of the composition, from the viewpoint of achieving a combination of high hardness, low curling properties, and a high refractive index.
< photopolymerization initiator >
In one embodiment, the active energy ray-curable resin composition contains a photopolymerization initiator. The photopolymerization initiator may be any of various known photopolymerization initiators used alone, or two or more of them may be used in combination. In addition, the photopolymerization initiator is used in the case of performing ultraviolet curing, however, in the case of performing electron beam curing, the photopolymerization initiator is not necessarily required.
Examples of the photopolymerization initiator are: 1-hydroxy-cyclohexyl-phenyl ketone, 2-dimethoxy-1, 2-diphenylethane-1-one, 1-cyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide, 4-methylbenzophenone, and the like.
The upper limit of the content of the photopolymerization initiator is, for example, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 parts by mass and the lower limit is, for example, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0 parts by mass, with respect to 100 parts by mass of the composition. In one embodiment, the content of the photopolymerization initiator is preferably 0 to 10 parts by mass with respect to 100 parts by mass of the composition, from the viewpoint of the progress of the reaction of the (meth) acryloyl group.
The upper limit of the content of the photopolymerization initiator is, for example, 66.7, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 parts by mass and the like, and the lower limit is, for example, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0 parts by mass and the like, with respect to 100 parts by mass of the urethane (meth) acrylate. In one embodiment, the content of the photopolymerization initiator is preferably about 0 to 30.0 parts by mass per 100 parts by mass of the urethane (meth) acrylate, from the viewpoint of the progress of the reaction of the (meth) acryloyl group.
< polymerizable monomer >
In one embodiment, the active energy ray-curable resin composition contains a polymerizable monomer. The polymerizable monomer may be used alone or in combination of two or more kinds thereof.
Examples of the polymerizable monomer are: isobornyl (alkylene oxide-modified or epoxy-modified) (meth) acrylate, tetrahydrofurfuryl (alkylene oxide-modified or epoxy-modified) (meth) acrylate, hydroxyethyl (alkylene oxide-modified or epoxy-modified) (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (alkylene oxide-modified or epoxy-modified) (meth) acrylate, lauryl (alkylene oxide-modified or epoxy-modified) (meth) acrylate, 1, 4-butanediol di (alkylene oxide-modified or epoxy-modified) (meth) acrylate, 1, 6-hexanediol di (alkylene oxide-modified or epoxy-modified) (meth) acrylate, tetraethylene glycol di (alkylene oxide-modified or epoxy-modified) (meth) acrylate, tripropylene glycol di (alkylene oxide-modified or epoxy-modified) (meth) acrylate, trimethylolpropane tri (alkylene oxide-modified or epoxy-modified) (meth) acrylate, and mixtures thereof, Pentaerythritol tri (alkylene oxide-modified or epoxy-modified) (meth) acrylate, pentaerythritol tetra (alkylene oxide-modified or epoxy-modified) (meth) acrylate, dipentaerythritol penta (alkylene oxide-modified or epoxy-modified) (meth) acrylate, dipentaerythritol hexa (alkylene oxide-modified or epoxy-modified) (meth) acrylate, tripentaerythritol octa (alkylene oxide-modified or epoxy-modified) (meth) acrylate, and the like.
In the present invention, "(alkylene oxide-modified or epoxy-modified) (meth) acrylate" means "at least one selected from the group consisting of a (meth) acrylate, an alkylene oxide-modified (meth) acrylate, and an epoxy-modified (meth) acrylate".
The content of the polymerizable monomer is not particularly limited. The upper limit of the content of the polymerizable monomer is, for example, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 36, 35, 30, 25, 20, 19, 15, 14, 10, 5 parts by mass and the like, and the lower limit is, for example, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 36, 35, 30, 25, 20, 19, 15, 14, 10, 5, 0 parts by mass and the like, with respect to 100 parts by mass of the composition. In one embodiment, the content of the polymerizable monomer is preferably about 0 to 85 parts by mass, and more preferably about 0 to 70 parts by mass, per 100 parts by mass of the composition, from the viewpoint of combining high hardness, low curling property, and high refractive index.
The upper limit of the content of the polymerizable monomer is, for example, 567, 550, 500, 450, 400, 350, 300, 250, 200, 150, 100, 50, 25, 10, 5, 1 part by mass and the like with respect to 100 parts by mass of the urethane (meth) acrylate, and the lower limit is, for example, 550, 500, 450, 400, 350, 300, 250, 200, 150, 100, 50, 25, 10, 5, 1, 0 part by mass and the like. In one embodiment, the content of the polymerizable monomer is preferably about 0 to 567 parts by mass, and more preferably about 0 to 300 parts by mass, based on 100 parts by mass of the urethane (meth) acrylate, from the viewpoint of achieving a combination of high hardness, low curling properties, and a high refractive index.
< antistatic agent >
In one embodiment, the composition may contain an antistatic agent. The antistatic agent may be used alone or in combination of two or more.
Antistatic agents are, for example: anionic antistatic agents such as alkyl phosphates; cationic antistatic agents such as quaternary ammonium salts; nonionic antistatic agents such as polyoxyethylene alkyl ethers; antistatic agents using alkali metal salts such as lithium, sodium, and potassium; ionic liquid antistatic agents, and the like.
The content of the antistatic agent is not particularly limited. The upper limit of the content of the antistatic agent is, for example, 100, 50, 40, 30, 20, 15, 10, 5 parts by mass and the like, and the lower limit is, for example, 50, 25, 20, 15, 10, 5, 2.5, 0 parts by mass and the like, with respect to 100 parts by mass of the composition. In one embodiment, the content of the antistatic agent is preferably about 0 to 100 parts by mass, and more preferably about 0 to 25 parts by mass, relative to 100 parts by mass of the composition, from the viewpoint of coatability.
The upper limit of the content of the antistatic agent is, for example, 500, 100, 50 parts by mass and the like, and the lower limit is, for example, 100, 50, 25, 10, 5, 1, 0.5, 0 parts by mass and the like, with respect to 100 parts by mass of the urethane (meth) acrylate. In one embodiment, the content of the antistatic agent is preferably about 0 to 500 parts by mass, and more preferably about 0 to 100 parts by mass, based on 100 parts by mass of the urethane (meth) acrylate, from the viewpoint of both coatability and antistatic property of the antistatic agent.
< dilution solvent >
In one embodiment, the composition comprises a diluent solvent. The diluent solvent may be any known diluent solvent used alone or two or more thereof may be used in combination. The diluting solvent is preferably a solvent that does not react (polymerize) even when irradiated with ultraviolet light, i.e., an ultraviolet-non-reactive solvent.
The dilution solvent is, for example: methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, diacetone alcohol, acetylacetone, toluene, xylene, n-hexane, cyclohexane, methylcyclohexane, n-heptane, isopropyl ether, methyl cellosolve, ethyl cellosolve, 1, 4-dioxane, propylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and the like.
The upper limit of the content of the diluting solvent is 1900, 1750, 1500, 1250, 1000, 750, 500, 250, 100, 50, 25 parts by mass, for example, and the lower limit is 1750, 1500, 1250, 1000, 750, 500, 250, 100, 50, 25, 0 parts by mass, for example, with respect to 100 parts by mass of the composition. In one embodiment, the content of the diluting solvent is, for example, 0 to 1900 parts by mass with respect to 100 parts by mass of the composition from the viewpoint of coatability.
The upper limit of the content of the diluting solvent is, for example, 1900, 1750, 1500, 1250, 1000, 750, 500, 250, 100, 50, 25 parts by mass and the like, and the lower limit is, for example, 1750, 1500, 1250, 1000, 750, 500, 250, 100, 50, 25, 0 parts by mass and the like, with respect to 100 parts by mass of the urethane (meth) acrylate. In one embodiment, the content of the diluting solvent is, for example, 0 to 1900 parts by mass with respect to 100 parts by mass of the urethane (meth) acrylate from the viewpoint of coatability.
< additives >
The active energy ray-curable resin composition may contain, as additives, agents other than the urethane (meth) acrylate, photopolymerization initiator, polymerizable monomer, antistatic agent, and diluting solvent.
Examples of additives are: antioxidants, ultraviolet absorbers, light stabilizers, antifoaming agents, surface control agents, antifouling agents, pigments, metal oxide fine particle dispersions, organic fine particle dispersions, and the like.
In one embodiment, the content of the additive is, for example, with respect to 100 parts by mass of the composition: 0.05 to 50 parts by mass, less than 40 parts by mass, less than 25 parts by mass, less than 10 parts by mass, less than 5 parts by mass, less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, and the like.
In another embodiment, the content of the additive with respect to 100 parts by mass of the urethane (meth) acrylate is, for example: 0.05 to 333 parts by mass, less than 300 parts by mass, less than 200 parts by mass, less than 100 parts by mass, less than 50 parts by mass, less than 25 parts by mass, less than 10 parts by mass, less than 5 parts by mass, less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, and the like.
The composition is obtained by mixing the urethane (meth) acrylate and, if necessary, a polymerization initiator, a polymerizable monomer, a diluting solvent, additives, and the like, by various known methods.
The active energy ray-curable resin composition can be used as a coating agent, a coating agent for films, a coating agent for plastic sheets, and the like. Coating agents for films are, for example: a coating agent for triacetyl cellulose film (TAC film), an acrylic film, a cycloolefin resin film (COP film), and the like. [ cured product ]
The present invention provides a cured product of the active energy ray-curable resin composition. The cured product is obtained by irradiating the active energy ray-curable resin composition with an active energy ray such as ultraviolet ray, electron beam, or radiation.
The active energy rays used in the curing reaction are, for example, ultraviolet rays and electron beams. The light source of the ultraviolet ray is, for example, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, or the like. The light quantity, light source arrangement, transport speed, etc. may be adjusted as necessary, and when a high-pressure mercury lamp is used, it is preferable to cure the lamp at a transport speed of about 5 to 50 m/min for each lamp having a light quantity of about 80 to 160W/cm. On the other hand, in the case of an electron beam, it is preferable that the electron beam is cured at a transport speed of about 5 to 50 m/min in an electron beam accelerator having an acceleration voltage of about 10 to 300 kV.
[ film ]
The present invention provides a film containing the cured product. The film is an article having the cured product and various base films as components.
As the base film, various known base films can be used, for example: polycarbonate film, acrylic film (polymethyl methacrylate film and the like), polystyrene film, polyester film, polyolefin film, epoxy resin film, melamine resin film, triacetyl cellulose film, ABS film, AS film, norbornene resin film, cycloolefin film, polyvinyl alcohol film and the like. The thickness of the base film is not particularly limited, but is preferably about 15 to 100 μm.
The film can be produced by various known methods. Specifically, the active energy ray-curable resin composition may be applied to at least one surface of the base film, dried as needed, and then irradiated with active energy rays. Alternatively, a laminate film may be produced by coating the resin composition according to the present embodiment on the non-coated surface of the obtained base film, laminating another base film thereon, and then irradiating with an active energy ray. These films are all useful as optical films.
The coating method is, for example: bar coater coating, wire bar coating (ワイヤーバー coater), Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing (フレキソ printing), screen printing, and the like.
The coating amount is not particularly limited, and the mass after drying is preferably 0.1 to 30g/m2More preferably 1 to 20g/m2。
Examples
The present invention is specifically illustrated by the following examples and comparative examples. However, the description of the preferred embodiments and the following examples are provided for illustrative purposes only and are not intended to limit the present invention. Therefore, the scope of the present invention is not limited to the embodiments specifically described in the present specification, nor to the examples specifically described in the present specification, but is limited only by the scope of the claims. Meanwhile, in each of examples and comparative examples, numerical values of parts,% and the like are based on mass unless otherwise specified.
(weight average molecular weight)
Measured by gel permeation chromatography (trade name "HLC-8220" manufactured by Nippon Tokyo ソー (K.K.); column: Nippon Tokyo ソー (K.K.); trade name "TSKgel SuperHZM-M").
Examples 1 to 1
300 parts (225 parts as a solid content), 0.6 part of tin octylate, and 240 parts of 2-hydroxy-3-phenoxypropyl acrylate (エポキシエステル M-600A, product of Eiken chemical Co., Ltd.) were charged into a reaction vessel equipped with a stirrer and a cooling tube, and the temperature in the system was raised to about 80 ℃ over about 1 hour. Subsequently, the reaction system was kept at the same temperature for 2 hours, and then cooled to obtain a urethane acrylate ((1) -1). The weight average molecular weight was 2900. To 100 parts of the mixture, 5 parts of 1-hydroxy-cyclohexyl-phenyl ketone (product name "IRGACURE 184(イルガキュアー 184)", hereinafter referred to as HCPK, manufactured by BASF japan) was mixed in a solid content ratio, and the mixture was diluted with methyl isobutyl ketone to prepare an active energy ray curable resin composition having a nonvolatile content of 40%.
The same operations as in example 1-1 were carried out except that the components shown in Table 1 were changed for examples and comparative examples other than example 1-1.
(production of film)
Each of the actinic-energy-ray-curable resin compositions was applied to a 100 μm-thick PET film (product name "ルミラー 100U 483" made by imperial レ (manufactured by imperial corporation)) by means of a #14 bar coater so that the film thickness of the cured coating film was 7 μm, and the film was dried at 80 ℃ for 1 minute to produce a film. The obtained film was then subjected to UV curing using a high-pressure mercury lamp 600mJ/cm (manufactured by Kogyo Co., Ltd.) under a name of UBT-080-7A/BM, マルチプライ (manufactured by Kabushiki Kaisha)2) To obtain a film providing a cured coating film. The evaluation results of the produced films are shown in tables 1 and 2。
Hardness (Pencil hardness)
The hardness of the cured product was evaluated by a pencil scratch test with a load of 500g in accordance with JIS K5600-5-4.
Low curling property
The membrane was cut out by 10cm × 10cm, and classified into "o" when the membrane was not cylindrical (in a state where the ends of the membrane were overlapped with each other) and "x" when the membrane was cylindrical.
Light resistance
The film was exposed to light for 100 hours using a carbon arc lamp in an ultraviolet autofadeometer (trade name: ultraviolet autofadeometer U48AU, manufactured by Japanese スガ testing machine). The film after the test was measured by a transmission method using a color difference meter (trade name: ZE 6000, manufactured by japan electro-chromic industry, ltd.), and if the yellow index value (イエローインデックス value) after exposure was less than 2, it was classified as "o"; if it is 2 or more, it is classified as "x".
Refractive index
For the film, the refractive index (D line of 589 nm) was measured at 20 ℃ by attaching 1-bromonaphthalene to the prism of an Abbe refractometer. When the refractive index is 1.550 or more, ". smallcircle"; if it is less than 1.550, it is classified as "x".
[ Table 1]
[ Table 2]
[ Table 3]
Example 2
As a result of further intensive studies on the active energy ray-curable resin composition in the present embodiment, it was found that a cured product (cured film) of the active energy ray-curable resin composition has excellent antistatic properties.
Synthesis example 1 (antistatic agent (4a))
100 parts of methacryloyloxyethyltrimethyl ammonium chloride (hereinafter, referred to as DMC) having a quaternary ammonium salt structure, 60 parts of [ epsilon ] -caprolactone 10 mol-modified hydroxyethyl methacrylate, 40 parts of t-butyl methacrylate (hereinafter, referred to as t-BMA) and 800 parts of Propylene Glycol Monomethyl Ether (PGME) were charged into a reaction vessel equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introduction tube, and the temperature was raised to 90 ℃. Then, 8 parts of 2, 2' -azobis (methylbutyronitrile) (AMBN) and 32 parts of PGME were added to start the polymerization reaction, and after 6 hours at 100 ℃, the reaction mixture was cooled to obtain a copolymer solution having a quaternary ammonium salt structure (nonvolatile fraction 20%) ("(4 a) fraction").
Example 2-1
An active energy ray-curable resin composition containing 40% nonvolatile content was prepared by mixing 5 parts of antistatic agent (4a) and 5 parts of HCPK in a solid content ratio with 100 parts of urethane acrylate ((1) -1) and diluting with PGME.
Example 2-2 and comparative example 1-1
The procedure of example 2-1 was repeated except that the components shown in Table 3 were changed.
Antistatic properties
The film was coated with the active energy ray-curable resin composition of example 1 (prepared just before) on a polyester film (product name: コスモシャイン A-4100, manufactured by DONGYANG , Inc.) 100 μm thick (calculated film thickness: 2 to 3 μm) using a #4 bar coater, and dried at 80 ℃ for 1 minute. The resulting film was then passed 2 times through a high pressure mercury lamp (200 mJ/cm) in air2) Thereby producing an antistatic-treated optical film having a cured film. Antistatic optical films were produced in the same manner as for the active energy ray-curable resin compositions of the other examples and comparative examples. Then, a commercially available resistivity meter (manufactured by Mitsubishi chemical corporation, product name "ハイレスタ UP MCP-HT450 ") and the surface resistance of the cured product (cured film) of the film was measured at an applied voltage of 500V in accordance with JIS K6911.
[ Table 4]
Pentaerythritol triacrylate: ビスコート #260 (Osaka organic chemical industry (Ore))
2-hydroxy-3-acryloyloxypropyl methacrylate: NK エステル 701A (New Zhongcun chemical industry Co., Ltd.)
Xylene diisocyanate biuret body: タケネート 114N (Mitsui chemical (strain))
Pentaerythritol tetraacrylate: アロニックス M-450 (Toyo Seisaku-sho Co., Ltd.).
Claims (5)
1. An active energy ray-curable resin composition containing a urethane (meth) acrylate which is a reaction product of a compound group containing the following (a) and (B):
a polyisocyanate (a) which is an isocyanurate polymer, a biuret polymer, a trimethylolpropane addition polymer or a glycerol addition polymer of xylene diisocyanate; and
a hydroxyl group-containing (meth) acrylate (B),
the content of the urethane (meth) acrylate is 51 parts by mass or more per 100 parts by mass of the solid content of the active energy ray-curable resin composition.
2. The active energy ray-curable resin composition according to claim 1, which contains a photopolymerization initiator.
3. The active energy ray-curable resin composition according to claim 1 or 2, which contains an antistatic agent.
4. A cured product of the active energy ray-curable resin composition according to any one of claims 1 to 3.
5. A film comprising the cured product according to claim 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017-115556 | 2017-06-13 | ||
| JP2017115556 | 2017-06-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109134816A CN109134816A (en) | 2019-01-04 |
| CN109134816B true CN109134816B (en) | 2021-08-31 |
Family
ID=64801968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810606583.0A Active CN109134816B (en) | 2017-06-13 | 2018-06-13 | Urethane (meth) acrylate, active energy ray-curable resin composition, cured product, and film |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6885372B2 (en) |
| KR (1) | KR102314750B1 (en) |
| CN (1) | CN109134816B (en) |
| TW (1) | TWI736777B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112239599B (en) * | 2019-07-16 | 2023-04-07 | 荒川化学工业株式会社 | Active energy ray-curable resin composition, aqueous resin composition, coating agent composition, cured film, and film |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014142555A (en) * | 2013-01-25 | 2014-08-07 | Dainippon Printing Co Ltd | Hard coat film, polarizing plate, and image display device |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3058751B2 (en) * | 1992-03-11 | 2000-07-04 | 日本化薬株式会社 | Resin composition, ultraviolet curable resin composition for transmission screen and cured product thereof |
| JP3676260B2 (en) * | 2000-12-28 | 2005-07-27 | ナトコ株式会社 | Active energy ray curable urethane (meth) acrylate, active energy ray curable composition and use thereof |
| KR101013149B1 (en) | 2008-07-11 | 2011-02-10 | 정원옥 | sticker and method for manufacturing thereof |
| JP5255464B2 (en) | 2009-01-27 | 2013-08-07 | 株式会社日本総合研究所 | CONFERENCE SUPPORT DEVICE, CONFERENCE SUPPORT METHOD, AND COMPUTER PROGRAM |
| WO2010146801A1 (en) * | 2009-06-17 | 2010-12-23 | 日本化薬株式会社 | Urethane (meth)acrylate compound and resin composition containing same |
| KR102195015B1 (en) * | 2013-04-26 | 2020-12-28 | 다이셀올넥스 주식회사 | Urethane (meth)acrylate and active energy ray-curable resin composition |
| JP6371728B2 (en) * | 2015-03-24 | 2018-08-08 | 三井化学株式会社 | Primer composition and laminate |
| JP6364393B2 (en) * | 2015-09-30 | 2018-07-25 | 富士フイルム株式会社 | Planographic printing plate dummy plate, manufacturing method thereof, and printing method using the same |
-
2018
- 2018-06-11 TW TW107120075A patent/TWI736777B/en active
- 2018-06-12 KR KR1020180067206A patent/KR102314750B1/en active IP Right Grant
- 2018-06-12 JP JP2018111860A patent/JP6885372B2/en active Active
- 2018-06-13 CN CN201810606583.0A patent/CN109134816B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014142555A (en) * | 2013-01-25 | 2014-08-07 | Dainippon Printing Co Ltd | Hard coat film, polarizing plate, and image display device |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102314750B1 (en) | 2021-10-18 |
| TWI736777B (en) | 2021-08-21 |
| JP6885372B2 (en) | 2021-06-16 |
| JP2019002006A (en) | 2019-01-10 |
| TW201902971A (en) | 2019-01-16 |
| CN109134816A (en) | 2019-01-04 |
| KR20180135813A (en) | 2018-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10000655B2 (en) | Hard coating composition | |
| US9926461B2 (en) | Hard coating film | |
| US9884977B2 (en) | Hard coating composition | |
| US9777186B2 (en) | Hard coating film | |
| US8927098B2 (en) | Hard coating film | |
| US9783698B2 (en) | Hard coating film | |
| TWI510569B (en) | Plastic film | |
| EP2940088B1 (en) | Coating composition, and plastic film prepared therefrom | |
| JP2013173871A (en) | Composition, antistatic coating agent, and antistatic laminate | |
| CN109134816B (en) | Urethane (meth) acrylate, active energy ray-curable resin composition, cured product, and film | |
| JP2003306619A (en) | Photosensitive resin composition for hard-coating agent and film having cured skin comprising the same | |
| KR20180034267A (en) | Active energy ray curable resin compositon, cured coating film, optical film | |
| JP6652738B2 (en) | Photocurable resin composition and optical film using the same | |
| CN108727556B (en) | Urethane (meth) acrylate, active energy ray-curable resin composition, cured product, and film | |
| KR102409048B1 (en) | Photocurable resin composition, cured film, base material with coating film and method for producing the same, and anti-fogging treatment method for base material | |
| CN107189642B (en) | Photocurable resin composition, cured coating film, coated substrate and method for producing same, and method for anti-fogging treatment of substrate | |
| JP2010001399A (en) | Antistatic coating composition and film obtained by curing the same | |
| CN110117338B (en) | Polymer, composition, cured product, and protective film | |
| JP2023173047A (en) | Active energy ray curable hard coat agent, hard coat layer, optical member, and electronic device | |
| JP2022085047A (en) | Active energy ray-curable hard coat agent, hard coat layer, optical member, and electronic device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |