TW201902971A - 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
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- TW201902971A TW201902971A TW107120075A TW107120075A TW201902971A TW 201902971 A TW201902971 A TW 201902971A TW 107120075 A TW107120075 A TW 107120075A TW 107120075 A TW107120075 A TW 107120075A TW 201902971 A TW201902971 A TW 201902971A
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- Prior art keywords
- meth
- acrylate
- mass
- urethane
- parts
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 152
- 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 40
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 64
- 150000001875 compounds Chemical group 0.000 claims abstract description 37
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 35
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 35
- 239000008096 xylene Substances 0.000 claims abstract description 18
- 239000002216 antistatic agent Substances 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 7
- 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
- 239000000376 reactant Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 abstract 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 66
- -1 acrylfluorenyl Chemical group 0.000 description 37
- 229920000193 polymethacrylate Polymers 0.000 description 24
- 125000002947 alkylene group Chemical group 0.000 description 19
- 239000004593 Epoxy Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 15
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 239000003999 initiator Substances 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 239000003085 diluting agent Substances 0.000 description 11
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 10
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 9
- 239000002585 base Substances 0.000 description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000006116 polymerization reaction Methods 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
- 238000000576 coating method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 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
- 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 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 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 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 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
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 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
- 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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000005227 gel permeation chromatography Methods 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
- 239000007787 solid Substances 0.000 description 3
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 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
- 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
- 230000001133 acceleration Effects 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 230000015572 biosynthetic process 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
- 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
- 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
- 238000005562 fading Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 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
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229960002446 octanoic acid Drugs 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
- 238000007639 printing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 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
- XHVSJCKGMZSWIN-UHFFFAOYSA-N (2-hydroxy-3-prop-1-enoxypropyl) 2-methylprop-2-enoate Chemical compound CC=COCC(O)COC(=O)C(C)=C XHVSJCKGMZSWIN-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
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- 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 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
- LESMLVDJJCWZAJ-UHFFFAOYSA-N 2-(diphenylphosphorylmethyl)-1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 LESMLVDJJCWZAJ-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
- 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
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 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
- 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
- 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
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- 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
- 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
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000005540 biological transmission 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
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 125000002091 cationic group Chemical group 0.000 description 1
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- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000000539 dimer Substances 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
- 239000002608 ionic liquid Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
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- 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
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- 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
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 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
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- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- YGSFNCRAZOCNDJ-UHFFFAOYSA-N propan-2-one Chemical compound CC(C)=O.CC(C)=O YGSFNCRAZOCNDJ-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 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
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 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
- 239000010409 thin film Substances 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
- 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
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Classifications
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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
- 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
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- 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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- 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
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- Chemical & Material Sciences (AREA)
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- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
- Polymerisation Methods In General (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
本發明係關於胺基甲酸酯(甲基)丙烯酸酯、活性能量射線硬化性樹脂組成物、硬化物及薄膜。 The present invention relates to a urethane (meth) acrylate, an active energy ray-curable resin composition, a cured product, and a film.
液晶顯示器中使用棱鏡片、折射率匹配(IM)薄膜、防反射薄膜等大量光學用薄膜。上述薄膜中,從高亮度、防骨架可見性、防反射性的調整的觀點出發,要求高折射率樹脂材料。高折射率樹脂材料例如是使用具有芴骨架的聚合性單體的物質等(專利文獻1)。 A large number of optical films such as prism sheets, refractive index matching (IM) films, and antireflection films are used in liquid crystal displays. Among the above-mentioned films, a high refractive index resin material is required from the viewpoint of adjustment of high brightness, anti-frame visibility, and anti-reflection properties. The high refractive index resin material is, for example, a substance using a polymerizable monomer having a fluorene skeleton (Patent Document 1).
[專利文獻1]日本特開2010-007004號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2010-007004
活性能量射線硬化性樹脂組成物中,根據用途不同,要 求各種不同的物理性質。本發明所欲解決的技術問題為提供一種在基膜的表面形成兼具高折射率、高硬度性、低捲曲性及高耐光性之硬化物層之活性能量射線硬化性樹脂組成物。 The active energy ray-curable resin composition requires various physical properties depending on the application. The technical problem to be solved by the present invention is to provide an active energy ray-curable resin composition for forming a hardened material layer having a high refractive index, high hardness, low curl, and high light resistance on the surface of a base film.
本發明者為了解決前述技術問題而深入研究,發現藉由使用具有特定結構的反應物,可以解決前述技術問題,從而完成了本發明。 The present inventors conducted intensive research in order to solve the aforementioned technical problems, and found that the aforementioned technical problems can be solved by using a reactant having a specific structure, thereby completing the present invention.
藉由本發明提供以下項目。 The following items are provided by the present invention.
(項目1) (Item 1)
一種胺基甲酸酯(甲基)丙烯酸酯,其特徵係含有下述(A)及(B)之化合物群之反應物:聚異氰酸酯(A),其為二甲苯二異氰酸酯的多聚體;以及含有羥基的(甲基)丙烯酸酯(B)。 A urethane (meth) acrylate, characterized in that it contains the reactants of the following compound groups (A) and (B): polyisocyanate (A), which is a polymer of xylene diisocyanate; And (meth) acrylate (B) containing a hydroxyl group.
(項目2) (Item 2)
如上述項目所記載之胺基甲酸酯(甲基)丙烯酸酯,其中,前述聚異氰酸酯(A)為二甲苯二異氰酸酯的異氰脲酸酯多聚體、縮二脲多聚體或加成多聚體。 The urethane (meth) acrylate according to the above item, wherein the polyisocyanate (A) is an isocyanurate polymer, a biuret polymer, or an addition of xylene diisocyanate Multimer.
(項目3) (Item 3)
一種活性能量射線硬化性樹脂組成物,其特徵係含有如上述項目中任一項所記載之胺基甲酸酯(甲基)丙烯酸酯。 An active-energy-ray-curable resin composition characterized by containing the urethane (meth) acrylate as described in any one of the above items.
(項目4) (Item 4)
如上述項目所記載之活性能量射線硬化性樹脂組成物,其中,其係含有光聚合引發劑。 The active energy ray-curable resin composition according to the above item, wherein the active energy ray-curable resin composition contains a photopolymerization initiator.
(項目5) (Item 5)
如上述項目中任一項所記載之活性能量射線硬化性樹脂組成物,其中,其係含有聚合性單體。 The active energy ray-curable resin composition according to any one of the above items, wherein the active energy ray-curable resin composition contains a polymerizable monomer.
(項目6) (Item 6)
如上述項目中任一項所記載之活性能量射線硬化性樹脂組成物,其中,其係含有抗靜電劑。 The active energy ray-curable resin composition according to any one of the above items, wherein the active energy ray-curable resin composition contains an antistatic agent.
(項目7) (Item 7)
一種如上述項目中任一項所記載之活性能量射線硬化性樹脂組成物之硬化物。 The hardened | cured material of the active-energy-ray-curable resin composition as described in any one of the said items.
(項目8) (Item 8)
一種薄膜,其特徵係含有如上述項目所記載之硬化物。 A film characterized by containing the hardened | cured material as described in the said item.
在本發明中,對於上述一個或多個特徵,除了明示的組合以外,還可以提供進一步的組合。 In the present invention, further combinations may be provided for one or more of the above features in addition to the combinations explicitly stated.
藉由使用由本發明提供的活性能量射線硬化性樹脂組成物,可以在基膜的表面形成兼具高折射率、高硬度性、低捲曲性及高耐光性的硬化物層(硬化皮膜)。 By using the active energy ray-curable resin composition provided by the present invention, it is possible to form a hardened material layer (hardened film) having a high refractive index, high hardness, low curl, and high light resistance on the surface of the base film.
在本發明全文之中,各物理性質的值及含量等數值的範圍可以適當設定(例如從下述各項目所記載的上限及下限的值中選擇)。具體而言,對於數值α,在數值α的上限例如是A1、A2、A3等、數值α的下限例如是B1、B2、B3等的情況下,數值α的範圍例如是A1以下、A2以下、A3以下、B1以上、B2以上、B3以上、A1~B1、A1~B2、A1~B3、A2~B1、A2~B2、A2~B3、A3~B1、A3~B2、A3~B3等。 Throughout the present invention, ranges of numerical values such as values and contents of physical properties can be appropriately set (for example, selected from the values of the upper and lower limits described in the following items). Specifically, for the numerical value α, when the upper limit of the numerical value α is, for example, A1, A2, A3, etc., and the lower limit of the numerical value α is, for example, B1, B2, B3, etc., the range of the numerical value α is, for example, A1 or lower, A2 or lower, Below A3, above B1, above B2, above B3, A1 ~ B1, A1 ~ B2, A1 ~ B3, A2 ~ B1, A2 ~ B2, A2 ~ B3, A3 ~ B1, A3 ~ B2, A3 ~ B3, etc.
[胺基甲酸酯(甲基)丙烯酸酯] [Urethane (meth) acrylate]
本發明提供一種胺基甲酸酯(甲基)丙烯酸酯,其係含有下述(A)及(B)的化合物群的反應物:聚異氰酸酯(A),其為二甲苯二異氰酸酯的多聚體;以及含有羥基的(甲基)丙烯酸酯(B)。 The present invention provides a urethane (meth) acrylate, which is a reactant containing the following compound groups (A) and (B): polyisocyanate (A), which is a polymer of xylene diisocyanate Body; and (meth) acrylate (B) containing a hydroxyl group.
在本發明中,「(甲基)丙烯酸」是指「選自丙烯酸及甲基丙烯酸所成群中的至少一種」。同樣地,「(甲基)丙烯酸酯」是指「選自丙烯酸酯及甲基丙烯酸酯所成群中的至少一種」。此外「(甲基)丙烯醯基」是指「選自丙烯醯基及甲基丙烯醯基所成群中的至少一種」。 In the present invention, "(meth) acrylic acid" means "at least one selected from the group consisting of acrylic acid and methacrylic acid". Similarly, "(meth) acrylate" means "at least one selected from the group consisting of acrylate and methacrylate". In addition, "(meth) acrylfluorenyl" means "at least one selected from the group consisting of acrylfluorenyl and methacrylfluorenyl".
<聚異氰酸酯(A),其為二甲苯二異氰酸酯的多聚體:亦稱為聚異氰酸酯(A)、(A)成分> <Polyisocyanate (A), which is a polymer of xylene diisocyanate: also known as polyisocyanate (A), (A) component>
在本發明中,「聚異氰酸酯」是指具有兩個以上的異氰酸酯基(-N=C=O)的化合物。 In the present invention, the "polyisocyanate" means a compound having two or more isocyanate groups (-N = C = O).
聚異氰酸酯(A)可以單獨使用,也可以將兩種以上合併使用。在一個實施方式中,聚異氰酸酯(A)為二甲苯二異氰酸酯的 異氰脲酸酯多聚體、縮二脲多聚體或加成多聚體。 The polyisocyanate (A) may be used alone or in combination of two or more kinds. In one embodiment, the polyisocyanate (A) is an isocyanurate polymer, a biuret polymer, or an addition polymer of xylene diisocyanate.
二甲苯二異氰酸酯的異氰脲酸酯多聚體例如下述結構式(A-1)所示的化合物等。 The isocyanurate polymer of xylene diisocyanate is, for example, a compound represented by the following structural formula (A-1).
(式中,n1是0以上的整數。n1較佳為0~3。) (In the formula, n1 is an integer of 0 or more. N1 is preferably 0 to 3.)
二甲苯二異氰酸酯的縮二脲多聚體例如下述結構式(A-2)所示的化合物等。 The biuret polymer of xylene diisocyanate is, for example, a compound represented by the following structural formula (A-2).
(式中,n2是0以上的整數。n2較佳為0~3。) (In the formula, n2 is an integer of 0 or more. N2 is preferably 0 to 3.)
二甲苯二異氰酸酯的加成多聚體例如下述結構式(A-3)所示的三羥甲基丙烷與二甲苯二異氰酸酯的加成產物;[化3]
(式中,n3是0以上的整數。n3較佳為0~3。) (In the formula, n3 is an integer of 0 or more. N3 is preferably 0 to 3.)
下述結構式(A-4)所示的甘油與二甲苯二異氰酸酯的加成產物等。 An addition product of glycerol and xylene diisocyanate, etc. represented by the following structural formula (A-4).
(式中,n4是0以上的整數。n4較佳為0~3。) (In the formula, n4 is an integer of 0 or more. N4 is preferably 0 to 3.)
另外,上述結構式僅是一個示例,本發明並非意在限定於由上述結構式表示的化合物。 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.
本發明中所謂「二甲苯二異氰酸酯的多聚體」表示二聚體以上的化合物。二甲苯二異氰酸酯的多聚體的聚合度上限例如是12、11、10、9、8、7、6、5、4等,下限例如是11、10、9、8、7、6、5、4、3等。在一個實施方式中,聚合度較佳為3~12,進一步較佳為3~9。此外,通常可購買的多聚體為不同多聚體的混合物,其聚合度為平均值,即以平均聚合度表示。平均聚合度的較佳值與上述聚合度的較佳值相同。此外,本發明中,n聚體的聚合度為n。 The "multimer of xylene diisocyanate" in the present invention means a compound having a dimer or higher. 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 is, for example, 11, 10, 9, 8, 7, 6, 5, 4, 3, etc. In one embodiment, the degree of polymerization is preferably 3-12, and more preferably 3-9. In addition, commonly available polymers are a mixture of different polymers, and the degree of polymerization is an average value, that is, expressed as the average degree of polymerization. The preferable value of the average polymerization degree is the same as the above-mentioned preferable value of the polymerization degree. In the present invention, the degree of polymerization of the n-mer is n.
對聚異氰酸酯(A)的重量平均分子量(Mw)的值並無特別限制。聚異氰酸酯(A)的重量平均分子量(Mw)的上限例如是80000、70000、60000、50000、40000、30000、20000、10000、9000、8000、7000、6000、5000、4000、3000、2000、1500、1000、600等,下限例如是70000、60000、50000、40000、30000、20000、10000、9000、8000、7000、6000、5000、4000、3000、2000、1500、1000、600、500等。在一個實施方式中,從胺基甲酸酯(甲基)丙烯酸酯的生產性的觀點來看,聚異氰酸酯(A)的重量平均分子量(Mw)較佳為500~50000,進一步較佳為600~50000。 The value of 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, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 9000, 8000, 7000, 6000, 5000, 4000, 3000, 2000, 1500, 1000, 600, etc. The lower limits are, for example, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10000, 9000, 8000, 7000, 6000, 5000, 4000, 3000, 2000, 1500, 1000, 600, 500, and so on. In one embodiment, from the viewpoint of the productivity of the urethane (meth) acrylate, the weight average molecular weight (Mw) of the polyisocyanate (A) is preferably 500 to 50,000, and more preferably 600. ~ 50000.
聚異氰酸酯(A)的數目平均分子量(Mn)的值並無特別限制。聚異氰酸酯(A)的數目平均分子量(Mn)的上限例如是60000、50000、40000、30000、20000、10000、9000、8000、7000、6000、5000、4000、3000、2000、1000、600、500、300等,下限例如是55000、50000、40000、35000、30000、20000、10000、9000、8000、7000、6000、5000、4000、3000、2000、1000、500等。在一個實施方式中,從胺基甲酸酯(甲基)丙烯酸酯的生產性的觀點來看,聚異氰酸酯(A)的數目平均分子量(Mn)較佳為500~60000,進一步較佳為500~40000。 The value of 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, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 9000, 8000, 7000, 6000, 5000, 4000, 3000, 2000, 1000, 600, 500, 500, 300, etc. The lower limit is, for example, 55,000, 50000, 40,000, 35000, 30,000, 20000, 10000, 9000, 8000, 7000, 6000, 5000, 4000, 3000, 2000, 1000, 500, and so on. In one embodiment, from the viewpoint of the productivity of the urethane (meth) acrylate, the number average molecular weight (Mn) of the polyisocyanate (A) is preferably 500 to 60,000, and more preferably 500. ~ 40000.
聚異氰酸酯(A)的分子量分佈(Mw/Mn)的上限例如是8.0、7.0、6.0、5.0、4.0、3.0、2.0等,下限例如是7.0、6.0、5.0、4.0、3.0、2.0、1.0等。在一個實施方式中,從胺基甲酸酯(甲基)丙烯酸酯的生產性的觀點來看,聚異氰酸酯(A)的分子量分佈(Mw/Mn) 較佳為1.0~8.0。 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, or the like, and the lower limit is, for example, 7.0, 6.0, 5.0, 4.0, 3.0, 2.0, 1.0, or the like. In one embodiment, from the viewpoint of the productivity of the urethane (meth) acrylate, the molecular weight distribution (Mw / Mn) of the polyisocyanate (A) is preferably 1.0 to 8.0.
重量平均分子量(Mw)及數目平均分子量(Mn)可以藉由凝膠滲透層析法(GPC)測定的聚苯乙烯換算值求出(以下同)。 The weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined from polystyrene conversion values measured by gel permeation chromatography (GPC) (the same applies hereinafter).
只要能得到所希望的效果,相對於化合物群100質量份的聚異氰酸酯(A)的比例並無特別限制。相對於化合物群100質量份,聚異氰酸酯(A)的比例的上限例如是70、60、50、40、30、25、20、10質量份等,下限例如是60、50、45、40、30、20、10、5質量份等。在一個實施方式中,從兼具高硬度、低捲曲性、高折射率的觀點來看,相對於化合物群100質量份的聚異氰酸酯(A)的比例較佳為5~70質量份,進一步較佳為20~70質量份。 The ratio of the polyisocyanate (A) to 100 parts by mass of the compound group is not particularly limited as long as a desired effect can be obtained. The upper limit of the proportion of the polyisocyanate (A) with respect to 100 parts by mass of the compound group is, for example, 70, 60, 50, 40, 30, 25, 20, 10 parts by mass, and the like, and the lower limit is, for example, 60, 50, 45, 40, 30. , 20, 10, 5 parts by mass. In one embodiment, from the viewpoint of both high hardness, low curlability, and high refractive index, the ratio of the polyisocyanate (A) to 100 parts by mass of the compound group is preferably 5 to 70 parts by mass, and more preferably It is preferably 20 to 70 parts by mass.
<含有羥基的(甲基)丙烯酸酯(B):亦稱為(B)成分> <Hydroxy-containing (meth) acrylate (B): also referred to as (B) component>
本發明中,所謂「含有羥基的(甲基)丙烯酸酯」表示具有羥基以及(甲基)丙烯醯基的化合物。 In the present invention, the "hydroxy-containing (meth) acrylate" means a compound having a hydroxyl group and a (meth) acrylfluorenyl group.
含有羥基的(甲基)丙烯酸酯可以單獨使用,也可以將兩種以上合併使用。含有羥基的(甲基)丙烯酸酯例如是含有羥基的甘油(甲基)丙烯酸酯(B-1)、含有羥基的(聚)季戊四醇聚(甲基)丙烯酸酯(B-2)、含有羥基的(聚)三羥甲基丙烷聚(甲基)丙烯酸酯(B-3)、含有羥基的單官能(甲基)丙烯酸酯(B-4)等。 The hydroxyl group-containing (meth) acrylate may be used alone or in combination of two or more. The hydroxyl-containing (meth) acrylate is, for example, glycerol (meth) acrylate (B-1) containing hydroxyl, (poly) pentaerythritol poly (meth) acrylate (B-2) containing hydroxyl, or hydroxyl-containing (meth) acrylate (Poly) trimethylolpropane poly (meth) acrylate (B-3), a hydroxyl-containing monofunctional (meth) acrylate (B-4), and the like.
(含有羥基的甘油(甲基)丙烯酸酯(B-1)) (Glycerol (meth) acrylate (B-1) containing hydroxyl group)
含有羥基的甘油(甲基)丙烯酸酯為如結構式(B-1)所示的化合物。 The glycerol (meth) acrylate containing a hydroxyl group is a compound represented by a structural formula (B-1).
(式中,Rb1~Rb3可各自獨立地為氫原子、(甲基)丙烯醯基、烷基、芳基或
(式中,b為1以上的整數。) (In the formula, b is an integer of 1 or more.)
Rb1~Rb3至少一個為氫原子或
(式中,b為1以上的整數。),同時,至少一個為(甲基)丙烯醯基。) (In the formula, b is an integer of 1 or more.) At the same time, at least one is a (meth) acrylfluorenyl group. )
含有羥基的甘油(甲基)丙烯酸酯例如是2-羥基-3-苯氧基丙基(甲基)丙烯酸酯、2-羥基-3-(甲基)丙烯醯氧基丙基(甲基)丙烯酸酯、2-羥基-3-甲氧基丙基(甲基)丙烯酸酯、1-羥基-2-苯氧基丙基(甲基)丙烯酸酯、1-羥基-2-(甲基)丙烯醯氧基丙基(甲基)丙烯酸酯、1-羥基-2-甲氧基丙基(甲基)丙烯酸酯、2-羥基-3-苯氧基丙基(甲基)丙烯酸酯己內酯加成物等。 Glycerol (meth) acrylate containing a hydroxyl group is, for example, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropyl (meth) Acrylate, 2-hydroxy-3-methoxypropyl (meth) acrylate, 1-hydroxy-2-phenoxypropyl (meth) acrylate, 1-hydroxy-2- (meth) propylene Methoxypropyl (meth) acrylate, 1-hydroxy-2-methoxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate caprolactone Adducts, etc.
(含有羥基的(聚)季戊四醇聚(甲基)丙烯酸酯(B-2)) (Hydroxy-containing (poly) pentaerythritol poly (meth) acrylate (B-2))
含有羥基的(聚)季戊四醇聚(甲基)丙烯酸酯如結構式(B-2)所示的化合物。 The hydroxyl-containing (poly) pentaerythritol poly (meth) acrylate is a compound represented by the structural formula (B-2).
(式中,m為0以上的整數,Rb4~Rb9可各自獨立地為氫原子、(甲基)丙烯醯基或
(式中,b為1以上的整數。),結構式(B-2)中,從Rb4~Rb9選擇的至少一個為氫原子,或
(式中,b為1以上的整數。),同時至少一個為(甲基)丙烯醯 基。此外,Rb7及Rb8對於各結構單元而言基團亦可不同。) (In the formula, b is an integer of 1 or more.) At least one of them is a (meth) acrylfluorenyl group. In addition, R b7 and R b8 may have different groups for each structural unit. )
本發明中「(聚)季戊四醇聚(甲基)丙烯酸酯」表示「選自季戊四醇聚(甲基)丙烯酸酯及聚季戊四醇聚(甲基)丙烯酸酯所成群中的至少一種」。 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".
此外,所謂「對於各結構單元而言基團亦可不同」,表示例如在結構式(B-2)中,m為2時,
Rb7A與Rb7B可以為不同的基團,Rb8A與Rb8B可以為不同的基團(以下同)。 R b7A and R b7B may be different groups, and R b8A and R b8B may be different groups (hereinafter the same).
季戊四醇聚(甲基)丙烯酸酯例如是季戊四醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯等。 The pentaerythritol poly (meth) acrylate is, for example, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, or the like.
聚季戊四醇聚(甲基)丙烯酸酯例如是二季戊四醇二(甲基)丙烯酸酯、二季戊四醇三(甲基)丙烯酸酯、二季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、三季戊四醇二(甲基)丙烯酸酯、三季戊四醇三(甲基)丙烯酸酯、三季戊四醇四(甲基)丙烯酸酯、三季戊四醇五(甲基)丙烯酸酯、三季戊四醇六(甲基)丙烯酸酯、三季戊四醇七(甲基)丙烯酸酯等。 The polypentaerythritol poly (meth) acrylate is, for example, 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.
(含有羥基的(聚)三羥甲基丙烷聚(甲基)丙烯酸酯 (B-3)) (Hydroxy-containing (poly) trimethylolpropane poly (meth) acrylate (B-3))
含有羥基的(聚)三羥甲基丙烷聚(甲基)丙烯酸酯如結構式(B-3)所示的化合物。 The (poly) trimethylolpropane poly (meth) acrylate containing a hydroxyl group is a compound represented by a structural formula (B-3).
(式中,p為0以上的整數,Rb10~Rb13為氫原子、(甲基)丙烯醯基、或[化13]
(式中,b為1以上的整數。),從Rb10~Rb13選擇的至少一個為氫原子或
(式中,b為1以上的整數。),同時,至少一個為(甲基)丙烯醯基。此外,Rb12對於各結構單元而言基團亦可不同。) (In the formula, b is an integer of 1 or more.) At the same time, at least one is a (meth) acrylfluorenyl group. In addition, R b12 may have different groups for each structural unit. )
本發明中,「(聚)三羥甲基丙烷聚(甲基)丙烯酸酯」表示「選自三羥甲基丙烷聚(甲基)丙烯酸酯及聚三羥甲基丙烷聚(甲 基)丙烯酸酯所成群中的至少一種」。 In the present invention, "(poly) trimethylolpropane poly (meth) acrylate" means "selected from trimethylolpropane poly (meth) acrylate and polytrimethylolpropane poly (meth) acrylate At least one of the groups of esters. "
三羥甲基丙烷聚(甲基)丙烯酸酯例如是三羥甲基丙烷二(甲基)丙烯酸酯等。 Trimethylolpropane poly (meth) acrylate is, for example, trimethylolpropane di (meth) acrylate.
聚三羥甲基丙烷聚(甲基)丙烯酸酯例如是雙三羥甲基丙烷二(甲基)丙烯酸酯、雙三羥甲基丙烷三(甲基)丙烯酸酯、雙三羥甲基丙烷四(甲基)丙烯酸酯等。 The polytrimethylolpropane poly (meth) acrylate is, for example, bistrimethylolpropane di (meth) acrylate, bistrimethylolpropane tri (meth) acrylate, bistrimethylolpropane tetra (Meth) acrylates and the like.
(含有羥基的單官能(甲基)丙烯酸酯(B-4)) (Hydroxy-containing monofunctional (meth) acrylate (B-4))
含有羥基的單官能(甲基)丙烯酸酯為如結構式(B-4)所示的化合物。 The hydroxyl-containing monofunctional (meth) acrylate is a compound represented by the structural formula (B-4).
(式中,Rb14為氫原子或甲基,Rb15為直鏈亞烷基、支鏈亞烷基、環亞烷基、或
(式中,Rb15a為氫原子或烷基(例如甲基)。),Rb16為氫原子或[化17]
(式中,b為1以上的整數。)) (In the formula, b is an integer of 1 or more.)
結構式(B-4)所示的化合物例如是含有羥基的直鏈烷基(甲基)丙烯酸酯、含有羥基的直鏈烷基(甲基)丙烯酸酯己內酯加成物、含有羥基的支鏈烷基(甲基)丙烯酸酯、含有羥基的支鏈烷基(甲基)丙烯酸酯己內酯加成物、含有羥基的環烷基(甲基)丙烯酸酯、含有羥基的環烷基(甲基)丙烯酸酯己內酯加成物、聚亞烷基二醇單(甲基)丙烯酸酯、聚亞烷基二醇單(甲基)丙烯酸酯己內酯加成物等。 The compound represented by the structural formula (B-4) is, for example, a linear alkyl (meth) acrylate containing a hydroxyl group, a linear alkyl (meth) acrylate containing a hydroxyl group, a caprolactone adduct, or a hydroxyl group containing Branched alkyl (meth) acrylate, hydroxyl-containing branched alkyl (meth) acrylate caprolactone adduct, hydroxyl-containing cycloalkyl (meth) acrylate, hydroxyl-containing cycloalkyl (Meth) acrylate caprolactone adduct, polyalkylene glycol mono (meth) acrylate, polyalkylene glycol mono (meth) acrylate caprolactone adduct, and the like.
含有羥基的直鏈烷基(甲基)丙烯酸酯例如是2-羥基乙基(甲基)丙烯酸酯、3-羥基丙基(甲基)丙烯酸酯、4-羥基丁基(甲基)丙烯酸酯等。 The hydroxyl-containing linear alkyl (meth) acrylate is, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate Wait.
含有羥基的直鏈烷基(甲基)丙烯酸酯己內酯加成物例如是3-羥基丙基(甲基)丙烯酸酯己內酯加成物、2-羥基乙基(甲基)丙烯酸酯己內酯加成物、4-羥基丁基(甲基)丙烯酸酯己內酯加成物等。 Hydroxyl-containing linear alkyl (meth) acrylate caprolactone adducts are, for example, 3-hydroxypropyl (meth) acrylate caprolactone adducts, 2-hydroxyethyl (meth) acrylate Caprolactone adduct, 4-hydroxybutyl (meth) acrylate caprolactone adduct, and the like.
含有羥基的支鏈烷基(甲基)丙烯酸酯例如是2-羥基丙基(甲基)丙烯酸酯、2-羥基丁基(甲基)丙烯酸酯、3-羥基丁基(甲基)丙烯酸酯等。 The hydroxyl-containing branched alkyl (meth) acrylate is, for example, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate Wait.
含有羥基的支鏈烷基(甲基)丙烯酸酯己內酯加成物例 如是2-羥基丙基(甲基)丙烯酸酯己內酯加成物、2-羥基丁基(甲基)丙烯酸酯己內酯加成物、3-羥基丁基(甲基)丙烯酸酯己內酯加成物等。 The hydroxyl-containing branched chain alkyl (meth) acrylate caprolactone adduct is, for example, 2-hydroxypropyl (meth) acrylate caprolactone adduct, 2-hydroxybutyl (meth) acrylate Caprolactone adduct, 3-hydroxybutyl (meth) acrylate caprolactone adduct, and the like.
含有羥基的環烷基(甲基)丙烯酸酯例如是(甲基)丙烯酸羥基環己酯等。 The hydroxy-containing cycloalkyl (meth) acrylate is, for example, hydroxycyclohexyl (meth) acrylate and the like.
含有羥基的環烷基(甲基)丙烯酸酯己內酯加成物例如是(甲基)丙烯酸羥基環己酯己內酯加成物等。 The hydroxy-containing cycloalkyl (meth) acrylate caprolactone adduct is, for example, a hydroxycyclohexyl caprolactone (meth) acrylate adduct.
聚亞烷基二醇單(甲基)丙烯酸酯例如是聚乙二醇單(甲基)丙烯酸酯、聚丙二醇單(甲基)丙烯酸酯等。 The polyalkylene glycol mono (meth) acrylate is, for example, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, or the like.
聚亞烷基二醇單(甲基)丙烯酸酯己內酯加成物例如是聚乙二醇單(甲基)丙烯酸酯己內酯加成物、聚丙二醇單(甲基)丙烯酸酯己內酯加成物等。 The polyalkylene glycol mono (meth) acrylate caprolactone adduct is, for example, polyethylene glycol mono (meth) acrylate caprolactone adduct, polypropylene glycol mono (meth) acrylate caprolactone Ester adducts, etc.
只要能得到所希望的效果,含有羥基的(甲基)丙烯酸酯(B)的羥值並無特別限制。含有羥基的(甲基)丙烯酸酯(B)的羥值的上限例如是500、490、450、400、350、300、250、200、150、100、80、75、70、65、60、55、50、45、40、35、30、25、20mgKOH/g等,下限例如是400、350、300、250、200、150、100、80、70、65、60、55、50、45、40、35mgKOH/g等。在一個實施方式中,從兼具高硬度、低捲曲性、高折射率的觀點來看,聚季戊四醇聚(甲基)丙烯酸酯(B)的羥值較佳為35~500mgKOH/g,進一步較佳為35~490mgKOH/g。 The hydroxyl value of the hydroxyl-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-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, 20 mgKOH / g, etc. The lower limit is, for example, 400, 350, 300, 250, 200, 150, 100, 80, 70, 65, 60, 55, 50, 45, 40 , 35mgKOH / g and so on. In one embodiment, from the viewpoints of both high hardness, low curlability, and high refractive index, the polypentaerythritol poly (meth) acrylate (B) preferably has a hydroxyl value of 35 to 500 mgKOH / g, and more preferably It is preferably 35 ~ 490mgKOH / g.
在本發明中,羥值是指由下式得出的計算值: (羥值)=(氫氧化鉀分子量:56.1)×1000/(羥基當量);(羥基當量)=(1個分子的分子量)/(1個分子中存在的羥基數)。 In the present invention, the hydroxyl value refers to a calculated value obtained by the following formula: (hydroxy value) = (potassium hydroxide molecular weight: 56.1) × 1000 / (hydroxyl equivalent); (hydroxyl equivalent) = (molecular weight of 1 molecule) ) / (Number of hydroxyl groups present in 1 molecule).
只要能得到所希望的效果,含有羥基的(甲基)丙烯酸酯(B)的(甲基)丙烯酸當量並無特別限制。含有羥基的(甲基)丙烯酸酯(B)的(甲基)丙烯酸當量的上限例如是500、450、400、350、300、250、200、150、140、130、120、110g/eq等,下限例如是140、130、120、110、100、99、95g/eq等。在一個實施方式中,從兼具高硬度、低捲曲性、高折射率的觀點來看,含有羥基的聚(甲基)丙烯酸酯(B)的(甲基)丙烯酸當量較佳為95~500g/eq,進一步較佳為99~150g/eq。 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 equivalent of the hydroxyl-containing (meth) acrylate (B) is, for example, 500, 450, 400, 350, 300, 250, 200, 150, 140, 130, 120, 110 g / eq, etc., The lower limit is, for example, 140, 130, 120, 110, 100, 99, 95 g / eq, and the like. In one embodiment, from the viewpoint of having both high hardness, low curlability, and high refractive index, the (meth) acrylic equivalent of the hydroxyl-containing poly (meth) acrylate (B) is preferably 95 to 500 g. / eq, more preferably 99 to 150 g / eq.
在本發明中,「(甲基)丙烯酸基當量」是指每1莫耳(甲基)丙烯酸基的分子量,藉由下式求出:((甲基)丙烯酸基當量)=(1個分子的分子量)/(1個分子中存在的(甲基)丙烯酸基數)。 In the present invention, the "(meth) acrylic group equivalent" refers to the molecular weight per 1 mol of the (meth) acrylic group, and is calculated by the following formula: ((meth) acrylic group equivalent) = (1 molecule Molecular weight) / (number of (meth) acrylic groups present in 1 molecule).
相對於化合物群100質量份,含有羥基的聚(甲基)丙烯酸酯(B)的比例的上限例如是80、70、60、50、40、35質量份等,下限例如是70、60、55、50、40、30質量份等。在一個實施方式中,從兼具高硬度及高折射率的觀點來看,相對於化合物群100質量份,含有羥基的聚(甲基)丙烯酸酯(B)的比例較佳為30~80質量份。 The upper limit of the ratio of the hydroxyl-containing poly (meth) acrylate (B) to 100 parts by mass of the compound group is, for example, 80, 70, 60, 50, 40, 35 parts by mass, and the like, and the lower limit is, for example, 70, 60, 55. , 50, 40, 30 parts by mass. In one embodiment, from the viewpoint of having both high hardness and high refractive index, the ratio of the poly (meth) acrylate (B) containing a hydroxyl group is preferably 30 to 80 masses with respect to 100 mass parts of the compound group. Serving.
<既非(A)成分、也非(B)成分的化合物:亦稱為其他化合物> <Compounds which are neither (A) component nor (B) component: also referred to as other compounds>
在製造上述胺基甲酸酯(甲基)丙烯酸酯時,可以使用既非(A)成分、也非(B)成分的化合物。即,在上述化合物群中,可以含有既非(A)成分、也非(B)成分的化合物。 When producing the said urethane (meth) acrylate, the compound which is neither (A) component nor (B) component can be used. That is, the compound group may contain a compound that is neither the (A) component nor the (B) component.
在一個實施方式中,相對於上述化合物群100質量%,其他化合物的比例例如是:0~50質量%、小於40質量%、小於25質量%、小於10質量%、小於5質量%、小於1質量%、小於0.1質量%、小於0.01質量%、0質量%等。 In one embodiment, with respect to 100% by mass of the compound group, the ratio of other compounds is, for example, 0-50% by mass, less than 40% by mass, less than 25% by mass, less than 10% by mass, less than 5% by mass, and less than 1 Mass%, less than 0.1% by mass, less than 0.01% by mass, 0% by mass, etc.
在一個實施方式中,相對於上述化合物群100莫耳%,其他化合物的比例例如是:0~50莫耳%、小於40莫耳%、小於25莫耳%、小於10莫耳%、小於5莫耳%、小於1莫耳%、小於0.1莫耳%、小於0.01莫耳%、0莫耳%等。 In one embodiment, with respect to 100 mole% of the compound group, the proportion of other compounds is, for example, 0 to 50 mole%, less than 40 mole%, less than 25 mole%, less than 10 mole%, and less than 5 Mole%, less than 1 mole%, less than 0.1 mole%, less than 0.01 mole%, 0 mole%, etc.
上述胺基甲酸酯(甲基)丙烯酸酯的製造方法可以採用習知的方法,可以使(A)成分及(B)成分在無溶劑或適當的溶劑(甲苯等)中,在適當的催化劑(辛酸錫等)的存在下,以適當的反應溫度(60~90℃等)進行反應即可。 The method for producing the urethane (meth) acrylate may be a conventional method, and the component (A) and the component (B) can be contained in a solvent-free or suitable solvent (such as toluene) in a suitable catalyst. In the presence of (tin octoate, etc.), the reaction may be performed at an appropriate reaction temperature (60 to 90 ° C, etc.).
<各成分的相對比例> <Relative ratio of each component>
只要能得到所希望的效果,聚異氰酸酯(A)與含有羥基的(甲基)丙烯酸酯(B)的質量比(聚異氰酸酯(A)/含有羥基的(甲基)丙烯酸酯(B))並無特別限制。聚異氰酸酯(A)與含有羥基的(甲基)丙烯酸酯(B)的質量比(聚異氰酸酯(A)/含有羥基的(甲基)丙烯酸酯(B))的上限例如是2.5、2、1.9、1.5、1.0、0.9、0.5、0.4、0.3等,下限例如是2、1.9、1.5、1.0、0.9、0.5、0.4、0.3、0.25等。在 一個實施方式中,從兼具高硬度、低捲曲性、高折射率的觀點來看,聚異氰酸酯(A)與含有羥基的(甲基)丙烯酸酯(B)的質量比(聚異氰酸酯(A)/含有羥基的(甲基)丙烯酸酯(B))較佳為0.25~2.5。 As long as the desired effect can be obtained, the mass ratio of polyisocyanate (A) to hydroxyl-containing (meth) acrylate (B) (polyisocyanate (A) / hydroxyl-containing (meth) acrylate (B)) and No special restrictions. The upper limit of the mass ratio of the polyisocyanate (A) to the hydroxyl-containing (meth) acrylate (B) (polyisocyanate (A) / hydroxyl-containing (meth) acrylate (B)) is, for example, 2.5, 2, 1.9 , 1.5, 1.0, 0.9, 0.5, 0.4, 0.3, and the like, and the lower limit is, for example, 2, 1.9, 1.5, 1.0, 0.9, 0.5, 0.4, 0.3, 0.25, and the like. In one embodiment, the mass ratio of polyisocyanate (A) to hydroxyl-containing (meth) acrylate (B) (polyisocyanate (A ) / (Meth) acrylate (B)) containing a hydroxyl group is preferably 0.25 to 2.5.
其他化合物與聚異氰酸酯(A)的質量比(其他化合物/聚異氰酸酯(A))的上限例如是10、9、7.5、5、2.5、1、0.5等,下限例如是9、7.5、5、2.5、1、0.5、0等。在一個實施方式中,其他化合物與聚異氰酸酯(A)的質量比(其他化合物/聚異氰酸酯(A))較佳為0~10。 The upper limit of the mass ratio of other compounds to the polyisocyanate (A) (other compounds / polyisocyanate (A)) is, for example, 10, 9, 7.5, 5, 2.5, 1, 0.5, etc., and the lower limit is, 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.
其他化合物與含有羥基的聚季戊四醇聚(甲基)丙烯酸酯(B)的質量比(其他化合物/含有羥基的聚季戊四醇聚(甲基)丙烯酸酯(B))的上限例如是1、0.9、0.75、0.5、0.25、0.1、0.05等,下限例如是0.9、0.75、0.5、0.25、0.1、0.05、0等。在一個實施方式中,其他化合物與含有羥基的聚季戊四醇聚(甲基)丙烯酸酯(B)的質量比(其他化合物/含有羥基的聚季戊四醇聚(甲基)丙烯酸酯(B))較佳為0~1。 The upper limit of the mass ratio of the other compound to the hydroxyl-containing polypentaerythritol poly (meth) acrylate (B) (other compounds / hydroxyl-containing polypentaerythritol poly (meth) acrylate (B)) is, for example, 1, 0.9, or 0.75. , 0.5, 0.25, 0.1, 0.05, and the like, and the lower limit is, 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-containing polypentaerythritol poly (meth) acrylate (B) (other compound / hydroxyl-containing polypentaerythritol poly (meth) acrylate (B)) is preferably 0 ~ 1.
只要能得到所希望的效果,含有羥基的(甲基)丙烯酸酯(B)的羥基與聚異氰酸酯(A)的異氰酸酯基的物量之比〔(OH)/(NCO)〕並無特別限制。含有羥基的(甲基)丙烯酸酯(B)的羥基與聚異氰酸酯(A)的異氰酸酯基的物量之比〔(OH)/(NCO)〕的上限例如是3.0、2.5、2.0、1.5、1.0等,下限例如是2.4、2.0、1.5、1.0、0.95等。在一個實施方式中,含有羥基的(甲基)丙烯酸酯(B)的羥基與聚異氰酸酯(A)的異氰酸酯基的物量之比〔(OH)/(NCO)〕較 佳為0.95~3.0。 The ratio [(OH) / (NCO)] of the amount of the hydroxyl group of the hydroxyl group-containing (meth) acrylate (B) to the isocyanate group of the polyisocyanate (A) 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 isocyanate group amount of the polyisocyanate (A) is, for example, 3.0, 2.5, 2.0, 1.5, 1.0, etc. The lower limit is, for example, 2.4, 2.0, 1.5, 1.0, 0.95, and the like. In one embodiment, the ratio [(OH) / (NCO)] of the amount of the hydroxyl group of the hydroxyl group-containing (meth) acrylate (B) to the isocyanate group of the polyisocyanate (A) is preferably 0.95 to 3.0.
<胺基甲酸酯(甲基)丙烯酸酯的物理性質等> <Physical properties of urethane (meth) acrylate, etc.>
胺基甲酸酯(甲基)丙烯酸酯的重量平均分子量(Mw)並無特別限制。胺基甲酸酯(甲基)丙烯酸酯的重量平均分子量(Mw)的上限例如是80000、70000、60000、50000、40000、30000、20000、10000、9000、8000、7000、6000、5000、4000、3000等,下限例如是70000、60000、50000、40000、30000、20000、10000、9000、8000、7000、6000、5000、4000、3000、2000、1750、1700、1500等。在一個實施方式中,從胺基甲酸酯(甲基)丙烯酸酯及薄膜的生產性的觀點來看,胺基甲酸酯(甲基)丙烯酸酯的重量平均分子量(Mw)較佳為1500~80000,進一步較佳為1700~80000。 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, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 9000, 8000, 7000, 6000, 5000, 4000, 3000, etc. The lower limits are, for example, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 9000, 8000, 7000, 6000, 5000, 4000, 3000, 2000, 1750, 1700, 1500, and the like. In one embodiment, the weight average molecular weight (Mw) of the urethane (meth) acrylate is preferably 1500 from the viewpoint of productivity of the urethane (meth) acrylate and the film. ~ 800,000, more preferably 1700 ~ 80,000.
胺基甲酸酯(甲基)丙烯酸酯的數目平均分子量(Mn)並無特別限制。胺基甲酸酯(甲基)丙烯酸酯的數目平均分子量(Mn)的上限例如是80000、70000、60000、50000、40000、30000、20000、12000、10000、9000、8100、8000、7800、7000、6000、5600、5000、4000、3500、3100、3001、3000、2900、2000等,下限例如是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等。在一個實施方式中,從胺基甲酸酯(甲基)丙烯酸酯及薄膜的生產性的觀點來看,胺基甲酸酯(甲基)丙烯酸酯的數目平均分子量(Mn)較佳為1000~80000,進一步較佳為1200~80000。 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, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 12000, 10,000, 9000, 8100, 8000, 7800, 7000, 6000, 5600, 5000, 4000, 3500, 3100, 3001, 3000, 2900, 2000, etc. The lower limit is, for example, 70,000, 60,000, 50000, 40,000, 30,000, 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, from the viewpoint of the productivity of the urethane (meth) acrylate and the film, the number average molecular weight (Mn) of the urethane (meth) acrylate is preferably 1,000. ~ 80000, more preferably 1200 ~ 80,000.
胺基甲酸酯(甲基)丙烯酸酯的分子量分佈(Mw/Mn)並無特別限制。胺基甲酸酯(甲基)丙烯酸酯的分子量分佈(Mw/Mn)的上限例如是8.0、7.0、6.0、5.0、4.0、3.0、2.0等,下限例如是8.0、7.0、6.0、5.0、4.0、3.0、2.0、1.2、1.0等。在一個實施方式中,從胺基甲酸酯(甲基)丙烯酸酯及薄膜的生產性的觀點來看,胺基甲酸酯(甲基)丙烯酸酯的分子量分佈(Mw/Mn)較佳為1.0~8.0,進一步較佳為1.2~6.0。 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, and the like, 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, from the viewpoint of the productivity of the urethane (meth) acrylate and the film, the molecular weight distribution (Mw / Mn) of the urethane (meth) acrylate is preferably 1.0 to 8.0, more preferably 1.2 to 6.0.
只要能得到所希望的效果,胺基甲酸酯(甲基)丙烯酸酯的(甲基)丙烯酸當量並無特別限制。胺基甲酸酯(甲基)丙烯酸酯的(甲基)丙烯酸當量的上限例如是400、350、300、290、150、140、130、120、110g/eq等,下限例如是390、350、300、290、140、130、120、110、100g/eq等。在一個實施方式中,從兼具高硬度、低捲曲性的觀點來看,胺基甲酸酯(甲基)丙烯酸酯的(甲基)丙烯酸當量較佳為100~400g/eq,進一步較佳為280~400g/eq。 The (meth) acrylic 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 equivalent of the urethane (meth) acrylate is, for example, 400, 350, 300, 290, 150, 140, 130, 120, 110 g / eq, etc., and the lower limit is, for example, 390, 350, 300, 290, 140, 130, 120, 110, 100g / eq, etc. In one embodiment, from the viewpoint of both high hardness and low curlability, the (meth) acrylic equivalent of the urethane (meth) acrylate is preferably 100 to 400 g / eq, and more preferably It is 280 ~ 400g / eq.
[活性能量射線硬化性樹脂組成物:亦稱為組成物] [Active energy ray-curable resin composition: also called composition]
本發明提供一種含有上述胺基甲酸酯(甲基)丙烯酸酯的活性能量射線硬化性樹脂組成物。 The present invention provides an active energy ray-curable resin composition containing the urethane (meth) acrylate.
只要能得到所希望的效果,胺基甲酸酯(甲基)丙烯酸酯的含量並無特別限制。相對於上述組成物100質量份,上述胺基甲酸酯(甲基)丙烯酸酯的含量的上限例如是100、90、80、70、60、51、50、40、36、35、31、30、29、20、15質量份等,下限例如是90、80、70、60、51、50、40、36、35、31、30、29、20、15、10質量份等。在 一個實施方式中,從兼具高硬度、低捲曲性、高折射率的觀點來看,相對於上述組成物100質量份,上述胺基甲酸酯(甲基)丙烯酸酯的含量較佳為約10~100質量份。 The content of the urethane (meth) acrylate is not particularly limited as long as the desired effect can be obtained. The upper limit of the content of the urethane (meth) acrylate relative to 100 parts by mass of the composition is, for example, 100, 90, 80, 70, 60, 51, 50, 40, 36, 35, 31, 30 , 29, 20, 15 parts by mass, and the like, and the lower limit is, for example, 90, 80, 70, 60, 51, 50, 40, 36, 35, 31, 30, 29, 20, 15, 10, and so on. In one embodiment, from the viewpoint of having both high hardness, low curlability, and high refractive index, the content of the urethane (meth) acrylate is preferably based on 100 parts by mass of the composition. About 10 to 100 parts by mass.
<光聚合引發劑> <Photopolymerization initiator>
在一個實施方式中,上述活性能量射線硬化性樹脂組成物含有光聚合引發劑。光聚合引發劑可以將各種習知的光聚合引發劑單獨使用,也可以將兩種以上合併使用。另外,光聚合引發劑係在進行紫外線硬化的情況下使用,然而,在進行電子束硬化的情況下,光聚合引發劑並非必需的。 In one embodiment, the active energy ray-curable resin composition contains a photopolymerization initiator. As the photopolymerization initiator, various conventional photopolymerization initiators may be used alone, or two or more of them may be used in combination. In addition, a photopolymerization initiator is used when ultraviolet curing is performed, but when an electron beam curing is performed, a photopolymerization initiator is not necessary.
光聚合引發劑例如是:1-羥基-環己基-苯基酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、1-環己基苯基酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮、1-[4-(2-羥基乙氧基)-苯基]-2-羥基-2-甲基-1-丙烷-1-酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉代丙烷-1-酮、2,4,6-三甲基苯甲醯基-二苯基-氧化膦、4-甲基二苯甲酮等。 The photopolymerization initiator is, for example, 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-cyclohexylphenyl ketone, 2 -Hydroxy-2-methyl-1-phenyl-propane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane- 1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2,4,6-trimethylbenzyl-diphenyl -Phosphine oxide, 4-methylbenzophenone and the like.
相對於上述組成物100質量份,光聚合引發劑的含量的上限例如是10、9、8、7、6、5、4、3、2、1質量份等,下限例如是9、8、7、6、5、4、3、2、1、0.5、0質量份等。在一個實施方式中,從(甲基)丙烯醯基的反應進行的觀點來看,相對於上述組成物100質量份,光聚合引發劑的含量較佳為0~10質量份。 The upper limit of the content of the photopolymerization initiator with respect to 100 parts by mass of the composition is, for example, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, and 1 part by mass, and the lower limit is, for example, 9, 8, 7 , 6, 5, 4, 3, 2, 1, 0.5, 0 parts by mass. In one embodiment, from the viewpoint of the reaction of the (meth) acrylfluorenyl group, the content of the photopolymerization initiator is preferably 0 to 10 parts by mass based on 100 parts by mass of the composition.
相對於胺基甲酸酯(甲基)丙烯酸酯100質量份,光聚合引發劑的含量的上限例如是66.7、65、60、55、50、45、40、35、30、25、20、15、10、9、8、7、6、5、4、3、2、1質量份等,下限例 如是65、60、55、50、45、40、35、30、25、20、15、10、9、8、7、6、5、4、3、2、1、0.5、0質量份等。在一個實施方式中,從(甲基)丙烯醯基的反應進行的觀點來看,相對於胺基甲酸酯(甲基)丙烯酸酯100質量份,光聚合引發劑的含量較佳為約0~30.0質量份。 The upper limit of the content of the photopolymerization initiator with respect to 100 parts by mass of the urethane (meth) acrylate 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 part by mass, etc., 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. In one embodiment, the content of the photopolymerization initiator is preferably about 0 with respect to 100 parts by mass of the urethane (meth) acrylate from the viewpoint of the progress of the (meth) acrylfluorenyl group. ~ 30.0 parts by mass.
<聚合性單體> <Polymerizable monomer>
在一個實施方式中,上述活性能量射線硬化性樹脂組成物含有聚合性單體。聚合性單體可以將各種習知的聚合性單體單獨使用,也可以將兩種以上合併使用。 In one embodiment, the active energy ray-curable resin composition contains a polymerizable monomer. As the polymerizable monomer, various conventional polymerizable monomers may be used alone, or two or more of them may be used in combination.
聚合性單體例如是:異冰片基(伸烷基氧改性或環氧改性)(甲基)丙烯酸酯、四氫糠基(伸烷基氧改性或環氧改性)(甲基)丙烯酸酯、羥乙基(伸烷基氧改性或環氧改性)(甲基)丙烯酸酯、羥丙基(甲基)丙烯酸酯、4-羥丁基(伸烷基氧改性或環氧改性)(甲基)丙烯酸酯、月桂基(伸烷基氧改性或環氧改性)(甲基)丙烯酸酯、1,4-丁二醇二(伸烷基氧改性或環氧改性)(甲基)丙烯酸酯、1,6-己二醇二(伸烷基氧改性或環氧改性)(甲基)丙烯酸酯、四乙二醇二(伸烷基氧改性或環氧改性)(甲基)丙烯酸酯、三丙二醇二(伸烷基氧改性或環氧改性)(甲基)丙烯酸酯、三羥甲基丙烷三(伸烷基氧改性或環氧改性)(甲基)丙烯酸酯、季戊四醇三(伸烷基氧改性或環氧改性)(甲基)丙烯酸酯、季戊四醇四(伸烷基氧改性或環氧改性)(甲基)丙烯酸酯、二季戊四醇五(伸烷基氧改性或環氧改性)(甲基)丙烯酸酯、二季戊四醇六(伸烷基氧改性或環氧改性)(甲基)丙烯酸酯、三季戊四醇八(伸烷基氧改性或環氧改性)(甲基)丙烯酸酯等。 The polymerizable monomer is, for example, isobornyl (alkylene oxide modified or epoxy modified) (meth) acrylate, tetrahydrofurfuryl (alkylene oxide modified or epoxy modified) (methyl ) 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) (Epoxy modified) (meth) acrylate, 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, two Pentaerythritol hexa (alkylene oxide modified or epoxy modified) (meth) acrylate, tripentaerythritol octa (alkylene oxide modified or epoxy modified) (meth) acrylate and the like.
在本發明中,「(伸烷基氧改性或環氧改性)(甲基)丙烯酸酯」是指「選自(甲基)丙烯酸酯、伸烷基氧改性(甲基)丙烯酸酯及環氧改性(甲基)丙烯酸酯所成群中的至少一種」。 In the present invention, "(alkylene oxide modified or epoxy modified) (meth) acrylate" means "selected from (meth) acrylate, alkylene oxide modified (meth) acrylate And at least one of the groups of epoxy-modified (meth) acrylates. "
聚合性單體的含量並無特別限制。相對於組成物100質量份,聚合性單體的含量的上限例如是85、80、75、70、65、60、55、50、45、40、36、35、30、25、20、19、15、14、10、5質量份等,下限例如是85、80、75、70、65、60、55、50、45、40、36、35、30、25、20、19、15、14、10、5、0質量份等。在一個實施方式中,從兼具高硬度、低捲曲性、高折射率的觀點來看,相對於組成物100質量份,聚合性單體的含量較佳為約0~85質量份,進一步較佳為約0~70質量份。 The content of the polymerizable monomer is not particularly limited. The upper limit of the content of the polymerizable monomer with respect to 100 parts by mass of the composition 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 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. In one embodiment, from the viewpoint of both high hardness, low curlability, and high refractive index, the content of the polymerizable monomer is preferably about 0 to 85 parts by mass relative to 100 parts by mass of the composition, and more preferably It is preferably about 0 to 70 parts by mass.
相對於胺基甲酸酯(甲基)丙烯酸酯100質量份,聚合性單體的含量的上限例如是567、550、500、450、400、350、300、250、200、150、100、50、25、10、5、1質量份等,下限例如是550、500、450、400、350、300、250、200、150、100、50、25、10、5、1、0質量份等。在一個實施方式中,從兼具高硬度、低捲曲性、高折射率的觀點來看,相對於胺基甲酸酯(甲基)丙烯酸酯100質量份,聚合性單體的含量較佳為約0~567質量份,進一步較佳為約0~300質量份。 The upper limit of the content of the polymerizable monomer with respect to 100 parts by mass of the urethane (meth) acrylate is, for example, 567, 550, 500, 450, 400, 350, 300, 250, 200, 150, 100, 50 , 25, 10, 5, 1 part by mass, etc., and the lower limit is, for example, 550, 500, 450, 400, 350, 300, 250, 200, 150, 100, 50, 25, 10, 5, 1, 0 parts by mass, and the like. In one embodiment, from the viewpoint of both high hardness, low curlability, and high refractive index, the content of the polymerizable monomer is preferably 100 parts by mass based on the urethane (meth) acrylate. About 0 to 567 parts by mass, more preferably about 0 to 300 parts by mass.
<抗靜電劑> <Antistatic agent>
在一個實施方式中,上述組成物中含有抗靜電劑。抗靜電劑可以單獨使用,也可以將兩種以上合併使用。 In one embodiment, the composition contains an antistatic agent. The antistatic agent may be used alone or in combination of two or more.
抗靜電劑例如是:烷基磷酸酯等陰離子型抗靜電劑;季 銨鹽等陽離子型抗靜電劑;聚氧乙烯烷基醚等非離子型抗靜電劑;使用鋰、鈉、鉀等鹼金屬鹽的抗靜電劑;離子液體類抗靜電劑等。 Examples of the antistatic agent include: anionic antistatic agents such as alkyl phosphate esters; cationic antistatic agents such as quaternary ammonium salts; nonionic antistatic agents such as polyoxyethylene alkyl ether; and alkali metals such as lithium, sodium, and potassium Antistatic agents for salts; antistatic agents for ionic liquids, etc.
抗靜電劑的含量並無特別限制。相對於組成物100質量份,抗靜電劑的含量的上限例如是100、50、40、30、20、15、10、5質量份等,下限例如是50、25、20、15、10、5、2.5、0質量份等。在一個實施方式中,從塗佈性的觀點來看,相對於組成物100質量份,抗靜電劑的含量較佳為約0~100質量份,進一步較佳為約0~25質量份。 The content of the antistatic agent is not particularly limited. The upper limit of the content of the antistatic agent with respect to 100 parts by mass of the composition 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. In one embodiment, from the viewpoint of coatability, 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, based on 100 parts by mass of the composition.
相對於胺基甲酸酯(甲基)丙烯酸酯100質量份,抗靜電劑的含量的上限例如是500、100、50質量份等,下限例如是100、50、25、10、5、1、0.5、0質量份等。在一個實施方式中,從兼具抗靜電劑的塗佈性及抗靜電性的觀點來看,相對於胺基甲酸酯(甲基)丙烯酸酯100質量份,抗靜電劑的含量較佳為約0~500質量份,進一步較佳為約0~100質量份。 The upper limit of the content of the antistatic agent with respect to 100 parts by mass of the urethane (meth) acrylate 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, etc. In one embodiment, the content of the antistatic agent is more preferably 100 parts by mass of the urethane (meth) acrylate from the viewpoint of having both the coatability and the antistatic property of the antistatic agent. About 0 to 500 parts by mass, more preferably about 0 to 100 parts by mass.
<稀釋溶劑> <Diluted solvent>
在一個實施方式中,上述組成物含有稀釋溶劑。稀釋溶劑可以將各種習知的稀釋溶劑單獨使用,也可以將兩種以上合併使用。另外,稀釋溶劑較佳為即使照射紫外線也不發生反應(聚合)的溶劑,即紫外線非反應性溶劑。 In one embodiment, the composition contains a diluent solvent. As the diluent, various conventional diluents may be used alone, or two or more of them may be used in combination. In addition, the diluent solvent is preferably a solvent that does not react (polymerize) even when irradiated with ultraviolet rays, that is, an ultraviolet non-reactive solvent.
稀釋溶劑例如是:甲基乙基酮、甲基異丁基酮、乙酸甲酯、乙酸乙酯、乙酸丁酯、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、叔丁醇、二丙酮醇、乙醯丙酮、甲苯、二甲苯、正己烷、環己烷、甲基環己烷、正庚烷、異丙醚、甲基溶纖劑、乙基溶纖劑、1,4-二噁烷、丙 二醇單甲醚、乙二醇單***乙酸酯、丙二醇單甲醚乙酸酯等。 Diluent solvents are, for example: methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butyl Alcohol, diacetone alcohol, acetone acetone, 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.
相對於上述組成物100質量份,稀釋溶劑的含量的上限例如是1900、1750、1500、1250、1000、750、500、250、100、50、25質量份等,下限例如是1750、1500、1250、1000、750、500、250、100、50、25、0質量份等。在一個實施方式中,從塗佈性的觀點來看,相對於組成物100質量份,稀釋溶劑的含量例如是0~1900質量份等。 With respect to 100 parts by mass of the above composition, the upper limit of the content of the diluent solvent is, for example, 1900, 1750, 1500, 1250, 1000, 750, 500, 250, 100, 50, and 25 parts by mass, and the lower limit is, for example, 1750, 1500, 1250 , 1000, 750, 500, 250, 100, 50, 25, 0 parts by mass. In one embodiment, from the viewpoint of coatability, the content of the diluent solvent is, for example, 0 to 1900 parts by mass based on 100 parts by mass of the composition.
相對於上述胺基甲酸酯(甲基)丙烯酸酯100質量份,稀釋溶劑的含量的上限例如是1900、1750、1500、1250、1000、750、500、250、100、50、25質量份等,下限例如是1750、1500、1250、1000、750、500、250、100、50、25、0質量份等。在一個實施方式中,從塗佈性的觀點來看,相對於上述胺基甲酸酯(甲基)丙烯酸酯100質量份,稀釋溶劑的含量例如是0~1900質量份等。 The upper limit of the content of the diluent solvent with respect to 100 parts by mass of the urethane (meth) acrylate is, for example, 1900, 1750, 1500, 1250, 1000, 750, 500, 250, 100, 50, 25 parts by mass, etc. The lower limit is, for example, 1750, 1500, 1250, 1000, 750, 500, 250, 100, 50, 25, 0 parts by mass, and the like. In one embodiment, from the viewpoint of coatability, the content of the diluent solvent is, for example, 0 to 1900 parts by mass, based on 100 parts by mass of the urethane (meth) acrylate.
<添加劑> <Additives>
上述活性能量射線硬化性樹脂組成物可以含有除上述胺基甲酸酯(甲基)丙烯酸酯、光聚合引發劑、聚合性單體、抗靜電劑、稀釋溶劑以外的試劑作為添加劑。 The active energy ray-curable resin composition may contain, as additives, agents other than the urethane (meth) acrylate, a photopolymerization initiator, a polymerizable monomer, an antistatic agent, and a diluent.
添加劑例如是:抗氧化劑、紫外線吸收劑、光穩定劑、消泡劑、表面調整劑、防污染劑、顏料、金屬氧化物微粒子分散體、有機微粒子分散體等。 Additives are, for example, antioxidants, ultraviolet absorbers, light stabilizers, defoamers, surface modifiers, antifouling agents, pigments, metal oxide fine particle dispersions, organic fine particle dispersions, and the like.
在一個實施方式中,相對於組成物100質量份,添加劑的含量例如是:0.05~50質量份、小於40質量份、小於25質量份、小於10質量份、小於5質量份、小於1質量份、小於0.1質量份、小於0.01質量 份、0質量份等。 In one embodiment, with respect to 100 parts by mass of the composition, the content of the additive is, for example, 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, and less than 1 part by mass. , Less than 0.1 parts by mass, less than 0.01 parts by mass, 0 parts by mass, and the like.
在另一個實施方式中,相對於胺基甲酸酯(甲基)丙烯酸酯100質量份,添加劑的含量例如是:0.05~333質量份、小於300質量份、小於200質量份、小於100質量份、小於50質量份、小於25質量份、小於10質量份、小於5質量份、小於1質量份、小於0.1質量份、小於0.01質量份、0質量份等。 In another embodiment, the content of the additive is, for example, 0.05 to 333 parts by mass, less than 300 parts by mass, less than 200 parts by mass, and less than 100 parts by mass relative to 100 parts by mass of the urethane (meth) acrylate. , 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.
上述組成物藉由將上述胺基甲酸酯(甲基)丙烯酸酯以及根據需要的聚合引發劑、聚合性單體、稀釋溶劑及添加劑等使用各種習知的方法進行混合而得到。 The composition is obtained by mixing the urethane (meth) acrylate and, if necessary, a polymerization initiator, a polymerizable monomer, a diluent solvent, an additive, and the like using various conventional methods.
上述活性能量射線硬化性樹脂組成物可以作為塗佈劑、薄膜用塗佈劑、塑膠片用塗佈劑等使用。薄膜用塗佈劑例如是:三醋酸纖維素薄膜(TAC薄膜)用塗佈劑、丙烯酸薄膜用塗佈劑、環烯烴樹脂薄膜(COP薄膜)用塗佈劑等。 The active energy ray-curable resin composition can be used as a coating agent, a coating agent for a film, a coating agent for a plastic sheet, and the like. Coating agents for films are, for example, coating agents for cellulose triacetate films (TAC films), coating agents for acrylic films, coating agents for cycloolefin resin films (COP films), and the like.
[硬化物] [Hardened matter]
本發明提供一種上述活性能量射線硬化性樹脂組成物的硬化物。上述硬化物透過向上述活性能量射線硬化性樹脂組成物照射紫外線、電子束、放射線等活性能量射線而得到。 The present invention provides a cured product of the active energy ray-curable resin composition. The hardened material is obtained by irradiating the active energy ray-curable resin composition with active energy rays such as ultraviolet rays, electron beams, and radiation.
在硬化反應中使用的活性能量射線例如是紫外線或電子束。紫外線的光源例如是具有氙燈、高壓汞燈、金屬鹵化物燈的紫外線照射裝置等。另外,光量、光源配置、輸送速度等可以根據需要進行調整,在使用高壓汞燈的情況下,相對於每盞具有約80~160W/cm光量的燈,較佳以輸送速度約5~50m/分鐘使之硬化。另一方面,在電子束的 情況下,在具有約10~300kV的加速電壓的電子束加速裝置中,較佳以輸送速度約5~50m/分鐘使之硬化。 The active energy rays used in the hardening reaction are, for example, ultraviolet rays or electron beams. The ultraviolet light source is, for example, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, or a metal halide lamp. In addition, the light quantity, light source configuration, and conveying speed can be adjusted as required. In the case of using a high-pressure mercury lamp, it is preferable to use a conveying speed of about 5 to 50 m / relative to each lamp having a light quantity of about 80 to 160 W / cm. It hardens in minutes. On the other hand, in the case of an electron beam, in an electron beam acceleration device having an acceleration voltage of about 10 to 300 kV, it is preferably hardened at a conveying speed of about 5 to 50 m / min.
[薄膜] [Film]
本發明提供一種含有上述硬化物的薄膜。上述薄膜是以上述硬化物及各種基膜作為構成要素的物品。 The present invention provides a film containing the cured product. The said thin film is an article which consists of the said hardened | cured material and various base films as a component.
基膜可以使用各種習知的基膜,例如是:聚碳酸酯薄膜、丙烯酸薄膜(聚甲基丙烯酸甲酯薄膜等)、聚苯乙烯薄膜、聚酯薄膜、聚烯烴薄膜、環氧樹脂薄膜、三聚氰胺樹脂薄膜、三醋酸纖維素薄膜、ABS薄膜、AS薄膜、降冰片烯系樹脂薄膜、環烯烴薄膜、聚乙烯醇薄膜等。基膜的厚度不受特別限定,較佳為約15~100μm。 Various conventional base films can be used for the base film, for example: polycarbonate film, acrylic film (polymethyl methacrylate film, etc.), polystyrene film, polyester film, polyolefin film, epoxy resin film, Melamine resin film, cellulose triacetate film, ABS film, AS film, norbornene-based resin film, cycloolefin film, polyvinyl alcohol film, etc. The thickness of the base film is not particularly limited, but is preferably about 15 to 100 μm.
上述薄膜可以使用各種習知的方法製造。具體而言,將上述活性能量射線硬化性樹脂組成物塗佈在上述基膜的至少單面上,根據需要進行乾燥,接著照射活性能量射線即可。另外,也可以在所得到的基膜的非塗佈面上塗佈本實施方式之樹脂組成物,在其上貼合其他基膜,照射活性能量射線,由此製造積層膜。此等薄膜皆可以作為光學用薄膜使用。 The above-mentioned film can be produced using various conventional methods. Specifically, the active energy ray-curable resin composition may be coated on at least one surface of the base film, dried if necessary, and then irradiated with active energy rays. Further, the non-coated surface of the obtained base film may be coated with the resin composition of the present embodiment, another base film may be laminated thereon, and active energy rays may be irradiated to produce a laminated film. These films can be used as optical films.
塗佈方法例如是:刮棒塗佈機塗佈、繞線棒塗佈、邁耶棒涂布、氣刀塗佈、凹版塗佈、反向凹版塗佈、膠版印刷、柔版印刷、網版印刷法等。 The coating methods are, for example, bar coater coating, wire rod coating, Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing. Printing method, etc.
塗佈量不受特別限定,乾燥後的質量較佳為0.1~30g/m2,進一步較佳為1~20g/m2。 The coating amount is not particularly limited, and the mass after drying is preferably 0.1 to 30 g / m 2 , and more preferably 1 to 20 g / m 2 .
以下,透過實施例及比較例對本發明具體地進行說明。惟,上述較佳實施方式中的說明以及以下實施例僅是為了舉例的目的而提供,並非是為了限定本發明的目的而提供。因此,本發明的範圍係不受本說明書中具體記載的實施方式及實施例限定,而僅受申請專利範圍限定。此外,只要沒有特別說明,在各實施例及比較例中,份、%等的數值為質量基準。 Hereinafter, the present invention will be specifically described by way of examples and comparative examples. However, the description in the above preferred embodiments and the following examples are provided for the purpose of illustration only, and are not provided for the purpose of limiting the present invention. Therefore, the scope of the present invention is not limited by the embodiments and examples specifically described in this specification, but only by the scope of patent applications. In addition, unless otherwise stated, in each Example and a comparative example, numerical values, such as a part and%, are a mass basis.
(重量平均分子量) (Weight average molecular weight)
藉由凝膠滲透層析儀(TOSOH(股份有限公司)製造,商品名「HLC-8220」;管柱:TOSOH(股份有限公司)製造,商品名「TSKgel superHZM-M」而得的測定值。 Measured values were obtained by gel permeation chromatography (TOSOH (Co., Ltd.), trade name "HLC-8220"; column: manufactured by TOSOH (Co., Ltd.), trade name "TSKgel superHZM-M".
實施例1-1 Example 1-1
在具備攪拌裝置、冷卻管的反應容器中加入二甲苯二異氰酸酯的異氰脲酸酯改性物(TAKENATE D-131N,三井化學(股份有限公司)製造)300份(固體成分225份)、辛酸錫0.6份、2-羥基-3-苯氧基丙基丙烯酸酯(環氧酯M-600A,共榮社化學社製造)240份後,經過約1小時,將體系內的溫度升溫至約80℃。接着,將反應體系在相同溫度下保持2小時後,冷卻,得到胺基甲酸酯丙烯酸酯((1)-1)。重量平均分子量為2900。相對於該混合物100份,按照固體成分比例,配合1-羥基-環己基-苯基酮(BASF日本(股份有限公司)製造,商品名「IRGACURE184」,以下稱為HCPK)5份,使用甲基異丁基酮進行稀釋,製備不揮發成分40%的活性能量射線硬化性樹脂組成物。 A reaction vessel equipped with a stirring device and a cooling tube was charged with 300 parts (225 parts solids) of octanoic acid modified product of xylene diisocyanate (TAKENATE D-131N, manufactured by Mitsui Chemicals, Inc.), and caprylic acid. After 0.6 parts of tin and 240 parts of 2-hydroxy-3-phenoxypropyl acrylate (epoxy ester M-600A, manufactured by Kyoeisha Chemical Co., Ltd.), the temperature in the system was raised to about 80 after about 1 hour. ℃. Next, 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. 5 parts of 1-hydroxy-cyclohexyl-phenyl ketone (manufactured by BASF Japan (trade name "IRGACURE184", hereinafter referred to as HCPK)) was blended with 100 parts of the mixture in accordance with the solid content ratio, using methyl Isobutyl ketone was diluted to prepare an active energy ray-curable resin composition with a non-volatile content of 40%.
對於實施例1-1以外的實施例以及比較例,除了將表1中所記載的成分進行變更以外,與實施例1-1同樣地操作實施。 Examples and comparative examples other than Example 1-1 were implemented in the same manner as in Example 1-1 except that the components described in Table 1 were changed.
(薄膜的製造) (Manufacture of film)
在膜厚100μm的PET薄膜(東麗(股份有限公司)製造,lumirror 100U483)上,用# 14棒式塗佈機塗佈各活性能量射線硬化性樹脂組成物,使硬化後的塗膜的膜厚度為7μm,在80℃下乾燥1分鐘,從而製造薄膜。接著將得到的薄膜使用紫外線硬化裝置(產品名:UBT-080-7A/BM,MULTIPLY(股份有限公司)製造,高壓汞燈600mJ/cm2),得到提供硬化塗膜的薄膜。對於製造的薄膜的評價結果如表1以及表2所示。 On a PET film (lumirror 100U483, manufactured by Toray Industries, Ltd.) with a film thickness of 100 μm, each active energy ray-curable resin composition was coated with a # 14 bar coater to make a cured coating film film. The thickness was 7 μm, and the film was dried at 80 ° C. for 1 minute. Next, the obtained film was subjected to an ultraviolet curing device (product name: UBT-080-7A / BM, manufactured by MULTIPLY (Co., Ltd.), high-pressure mercury lamp 600 mJ / cm 2 ) to obtain a film providing a cured coating film. The evaluation results of the produced film are shown in Tables 1 and 2.
硬度(鉛筆硬度) Hardness (pencil hardness)
按照JIS K5600-5-4,藉由荷重500g的鉛筆劃痕試驗來評價硬化物的硬度。 In accordance with JIS K5600-5-4, the hardness of the cured product was evaluated by a pencil scratch test with a load of 500 g.
低捲曲性 Low curl
將薄膜切下10cm×10cm,薄膜不成為筒狀(薄膜的端部互相重疊的狀況)的情況分類為「○」;成為筒狀的情況分類為「×」。 When the film was cut out by 10 cm × 10 cm, the film was classified as “○” when the film did not become cylindrical (the end portions of the film overlapped with each other); when the film was cylindrical, it was classified as “×”.
耐光性 Lightfastness
在紫外線自動褪色測試儀(商品名:紫外線自動褪色測試儀U48AU,日本SUGA試驗機(股份有限公司)製造)中,將薄膜以碳弧燈曝光100小時。試驗後的薄膜藉由色差計(商品名:ZE 6000,日本電色工業(股份有限公司)製造)的透過法進行測量,如果曝光後的黃色指數值小於2,則分類為「○」;如果在2以上,則分類為「×」。 The film was exposed to a carbon arc lamp for 100 hours in an ultraviolet automatic fading tester (trade name: UV automatic fading tester U48AU, manufactured by Japan's SUGA Tester (Co., Ltd.)). The film after the test was measured by a transmission method of a color difference meter (trade name: ZE 6000, manufactured by Nippon Denshoku Industries Co., Ltd.). If the yellow index value after the exposure is less than 2, it is classified as "○"; if If it is 2 or more, it is classified as "×".
折射率 Refractive index
對於薄膜,藉由1-溴萘附著於阿貝折射儀的棱鏡上,在20℃下進行折射率(589nm的D線)的測定。如果折射率為1.550以上,分類為「○」;如果不到1.550,則分類為「×」。 For the film, 1-bromonaphthalene was attached to a prism of an Abbe refractometer, and the refractive index (D-line at 589 nm) was measured at 20 ° C. If the refractive index is 1.550 or more, it is classified as "○"; if it is less than 1.550, it is classified as "×".
實施例2 Example 2
對於本實施方式中的活性能量射線硬化性樹脂組成物進行進一步深入研究時,發現上述活性能量射線硬化性樹脂組成物的硬化物(硬化膜)具有優異的抗靜電性。 When the active energy ray-curable resin composition in the present embodiment is further studied, it is found that the cured product (cured film) of the active energy ray-curable resin composition has excellent antistatic properties.
合成例1(抗靜電劑(4a)) Synthesis example 1 (antistatic agent (4a))
在具備攪拌裝置、冷卻管、滴液漏斗及氮氣導入管的反應容器中加入含有季銨鹽結構的甲基丙烯醯氧基乙基三甲基氯化銨(以下,稱為DMC。)100份、ε-己內酯10mol改性的羥乙基甲基丙烯酸酯60份、甲基丙烯酸叔丁酯(以下,稱為t-BMA。)40份以及丙二醇單甲醚(PGME)800份,升溫至90℃。接著,加入2,2'-偶氮二(甲基丁腈)(AMBN)8份及PGME 32份,開始聚合反應,在100℃下保持6小時 後冷卻,得到含有季銨鹽結構的共聚物溶液(不揮發成分20%)(「(4a)成分」)。 100 parts of a methacryloxyethyl trimethylammonium chloride (hereinafter referred to as DMC) containing a quaternary ammonium salt structure was added to a reaction vessel including a stirring device, a cooling tube, a dropping funnel, and a nitrogen introduction tube. , 60 parts of ε-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). To 90 ° C. Next, was added 2,2 '- azobis (methylbutyronitrile) (AMBN) 8 parts and PGME 32 parts, the polymerization reaction was cooled after 6 hours maintained at 100 deg.] C, to obtain a copolymer containing a quaternary ammonium salt structure Solution (non-volatile content 20%) ("(4a) component").
實施例2-1 Example 2-1
相對於胺基甲酸酯丙烯酸酯((1)-1)100份,按照固體成分比例,配合抗靜電劑(4a)5份、HCPK 5份,用PGME進行稀釋,製備不揮發成分40%的活性能量射線硬化性樹脂組成物。 With respect to 100 parts of urethane acrylate ((1) -1), 5 parts of antistatic agent (4a) and 5 parts of HCPK were blended in accordance with the solid content ratio, and diluted with PGME to prepare 40% non-volatile components. Active energy ray-curable resin composition.
實施例2-2、比較例1-1 Example 2-2, Comparative Example 1-1
除了將表3中所記載的成分進行變更以外,與實施例2-1同樣地操作實施。 Except having changed the component shown in Table 3, it carried out similarly to Example 2-1.
抗靜電性 Antistatic
對於薄膜,在100μm厚的聚酯薄膜(東洋紡(股份有限公司)製造,商品名「COSMOSHINE A-4100」)上,將實施例1的活性能量射線硬化性樹脂組成物(剛製備)使用# 4棒式塗佈機進行塗佈(膜厚的計算值:2~3μm),在80℃下乾燥1分鐘。接著,將得到的薄膜在大氣中2次通過高壓汞燈(200mJ/cm2),由此製造具有硬化皮膜的抗靜電處理光學薄膜。對於其他的實施例以及比較例的活性能量射線硬化性樹脂組成物同樣製造抗靜電處理光學薄膜。接著,使用市售的電阻率儀(三菱化學(股份有限公司)製造,產品名「HIRESTA UP MCP-HT450」),根據JIS K 6911,在外加電壓500V下,測量該薄膜之硬化物(硬化膜)之表面電阻。 For the film, the active energy ray-curable resin composition (just prepared) of Example 1 was used on a 100 μm thick polyester film (manufactured by Toyobo Co., Ltd. under the trade name “COSMOSHINE A-4100”) # 4 The coating was performed with a bar coater (calculated film thickness: 2 to 3 μm), and dried at 80 ° C. for 1 minute. Next, the obtained film was passed through a high-pressure mercury lamp (200 mJ / cm 2 ) twice in the atmosphere, thereby producing an antistatic-treated optical film having a cured film. For the active energy ray-curable resin compositions of the other examples and comparative examples, an antistatic-treated optical film was produced in the same manner. Next, a commercially available resistivity meter (manufactured by Mitsubishi Chemical Corporation, product name "HIRESTA UP MCP-HT450") was used to measure the cured product (cured film) of the film at an applied voltage of 500 V in accordance with JIS K 6911. ) Surface resistance.
季戊四醇三丙烯酸酯:Viscoat # 260(大阪有機化學工業(股份有限公司)) Pentaerythritol triacrylate: Viscoat # 260 (Osaka Organic Chemical Industry Co., Ltd.)
2-羥基-3-丙烯醯氧基丙基甲基丙烯酸酯:NK酯701A(新中村化學工業(股份有限公司)) 2-hydroxy-3-propenyloxypropyl methacrylate: NK ester 701A (Shin Nakamura Chemical Industry Co., Ltd.)
二甲苯二異氰酸酯縮二脲體:Takenate 114N(三井化學(股份有限公司)) Xylene diisocyanate biuret: Takenate 114N (Mitsui Chemical Co., Ltd.)
季戊四醇四丙烯酸酯:ARONIX M-450(東亞合成(股份有限公司)) Pentaerythritol tetraacrylate: ARONIX M-450 (East Asia Synthesis Co., Ltd.)
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