JPWO2014003139A1 - Energy ray curable resin composition and weather-resistant hard coat film using the same - Google Patents
Energy ray curable resin composition and weather-resistant hard coat film using the same Download PDFInfo
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- JPWO2014003139A1 JPWO2014003139A1 JP2014522690A JP2014522690A JPWO2014003139A1 JP WO2014003139 A1 JPWO2014003139 A1 JP WO2014003139A1 JP 2014522690 A JP2014522690 A JP 2014522690A JP 2014522690 A JP2014522690 A JP 2014522690A JP WO2014003139 A1 JPWO2014003139 A1 JP WO2014003139A1
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- resin composition
- curable resin
- energy ray
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- 239000011342 resin composition Substances 0.000 title claims abstract description 37
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003999 initiator Substances 0.000 claims abstract description 18
- 239000006096 absorbing agent Substances 0.000 claims abstract description 11
- 238000002835 absorbance Methods 0.000 claims abstract description 10
- 239000004611 light stabiliser Substances 0.000 claims abstract description 9
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012964 benzotriazole Substances 0.000 claims abstract description 8
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001412 amines Chemical class 0.000 claims abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 12
- 125000000524 functional group Chemical group 0.000 claims description 9
- 238000004383 yellowing Methods 0.000 claims description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000576 coating method Methods 0.000 abstract description 30
- 239000011248 coating agent Substances 0.000 abstract description 29
- -1 acryl Chemical group 0.000 description 20
- 239000010410 layer Substances 0.000 description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 10
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 150000002222 fluorine compounds Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 210000002268 wool Anatomy 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 2
- 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 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-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
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000002519 antifouling agent Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 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 2
- TUKWPCXMNZAXLO-UHFFFAOYSA-N ethyl 2-nonylsulfanyl-4-oxo-1h-pyrimidine-6-carboxylate Chemical compound CCCCCCCCCSC1=NC(=O)C=C(C(=O)OCC)N1 TUKWPCXMNZAXLO-UHFFFAOYSA-N 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
- 239000003112 inhibitor Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- XOTQXTVSGIEPEA-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) hexanoate Chemical compound CCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XOTQXTVSGIEPEA-UHFFFAOYSA-N 0.000 description 1
- JMUOXOJMXILBTE-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 JMUOXOJMXILBTE-UHFFFAOYSA-N 0.000 description 1
- QYGBYAQGBVHMDD-XQRVVYSFSA-N (z)-2-cyano-3-thiophen-2-ylprop-2-enoic acid Chemical compound OC(=O)C(\C#N)=C/C1=CC=CS1 QYGBYAQGBVHMDD-XQRVVYSFSA-N 0.000 description 1
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-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
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 description 1
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
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- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- WFHIKGUIMORKSQ-UHFFFAOYSA-N 2,2-dimethoxy-1,2-diphenylethanone;2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1.C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 WFHIKGUIMORKSQ-UHFFFAOYSA-N 0.000 description 1
- PVLQFJVKPOVXNP-UHFFFAOYSA-N 2-(2,5-dimethylphenyl)-1,3,5-triazine Chemical compound CC1=CC=C(C)C(C=2N=CN=CN=2)=C1 PVLQFJVKPOVXNP-UHFFFAOYSA-N 0.000 description 1
- LEVFXWNQQSSNAC-UHFFFAOYSA-N 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexoxyphenol Chemical compound OC1=CC(OCCCCCC)=CC=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 LEVFXWNQQSSNAC-UHFFFAOYSA-N 0.000 description 1
- WXHVQMGINBSVAY-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 WXHVQMGINBSVAY-UHFFFAOYSA-N 0.000 description 1
- ITLDHFORLZTRJI-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-5-octoxyphenol Chemical compound OC1=CC(OCCCCCCCC)=CC=C1N1N=C2C=CC=CC2=N1 ITLDHFORLZTRJI-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
- 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
- KLIZOTJVECGYSJ-UHFFFAOYSA-N 2-[2-[3-(benzotriazol-2-yl)-5-(2-phenylpropan-2-yl)phenyl]propan-2-yl]phenol Chemical compound C=1C(N2N=C3C=CC=CC3=N2)=CC(C(C)(C)C=2C(=CC=CC=2)O)=CC=1C(C)(C)C1=CC=CC=C1 KLIZOTJVECGYSJ-UHFFFAOYSA-N 0.000 description 1
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- SITYOOWCYAYOKL-UHFFFAOYSA-N 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(3-dodecoxy-2-hydroxypropoxy)phenol Chemical compound OC1=CC(OCC(O)COCCCCCCCCCCCC)=CC=C1C1=NC(C=2C(=CC(C)=CC=2)C)=NC(C=2C(=CC(C)=CC=2)C)=N1 SITYOOWCYAYOKL-UHFFFAOYSA-N 0.000 description 1
- WYLMGXULBMHUDT-UHFFFAOYSA-N 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(2-ethylhexoxy)-2-hydroxypropoxy]phenol Chemical compound OC1=CC(OCC(O)COCC(CC)CCCC)=CC=C1C1=NC(C=2C(=CC(C)=CC=2)C)=NC(C=2C(=CC(C)=CC=2)C)=N1 WYLMGXULBMHUDT-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
- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 description 1
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- IPTNXMGXEGQYSY-UHFFFAOYSA-N acetic acid;1-methoxybutan-1-ol Chemical compound CC(O)=O.CCCC(O)OC IPTNXMGXEGQYSY-UHFFFAOYSA-N 0.000 description 1
- 229940081735 acetylcellulose Drugs 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
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- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
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- 239000002216 antistatic agent Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 1
- YICDLGHIRXZGFF-UHFFFAOYSA-N butanedioic acid;2,2,6,6-tetramethylpiperidine Chemical compound OC(=O)CCC(O)=O.CC1(C)CCCC(C)(C)N1.CC1(C)CCCC(C)(C)N1 YICDLGHIRXZGFF-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229920005994 diacetyl cellulose Polymers 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
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- 239000004210 ether based solvent Substances 0.000 description 1
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- 239000003063 flame retardant Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000007756 gravure coating Methods 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
- 230000002209 hydrophobic effect Effects 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride 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
- 150000003254 radicals Chemical class 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000004804 winding Methods 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
- 239000008096 xylene Substances 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
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
- C08F299/065—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes from polyurethanes with side or terminal unsaturations
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- 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
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
Abstract
硬化させた際に塗膜硬度、耐擦傷性、耐候性及び耐湿性に優れる塗膜を形成するエネルギー線硬化型樹脂組成物及びこれを利用した耐候性ハードコートフィルムを提供する。(A)エネルギー線硬化型オリゴマーと、(B)ベンゾトリアゾール系紫外線吸収剤及びトリアジン系紫外線吸収剤の中から選ばれる少なくとも１種と、(C)ヒンダードアミン系光安定剤と、(D)光重合開始剤と、を含有するエネルギー線硬化型樹脂組成物であって、前記(B)成分を前記(A)成分100質量部に対し、2〜12質量部添加するとともに、前記(D)成分が(D１)メタノール又はアセトニトリルに溶解させた0.01%質量溶液における340nm〜400nmの波長範囲における吸光度の最大値が0.1以上である光重合開始剤と、(D２)メタノール又はアセトニトリルに溶解させた0.001質量%溶液における220nm〜280nmの波長範囲における吸光度の最大値が0.1以上である光重合開始剤と、をそれぞれ少なくとも１種以上含有する。Provided are an energy ray-curable resin composition that forms a coating film having excellent coating film hardness, scratch resistance, weather resistance and moisture resistance when cured, and a weather resistant hard coat film using the same. (A) energy beam curable oligomer, (B) at least one selected from benzotriazole UV absorber and triazine UV absorber, (C) hindered amine light stabilizer, (D) photopolymerization An energy ray curable resin composition containing an initiator, wherein the component (B) is added in an amount of 2 to 12 parts by mass with respect to 100 parts by mass of the component (A), and the component (D) (D1) a photopolymerization initiator having a maximum absorbance of 0.1 or more in a wavelength range of 340 nm to 400 nm in a 0.01% mass solution dissolved in methanol or acetonitrile, and (D2) 0.001 mass% dissolved in methanol or acetonitrile. And at least one photopolymerization initiator having a maximum absorbance of 0.1 or more in a wavelength range of 220 nm to 280 nm in the solution.
Description
本発明は、エネルギー線硬化型樹脂組成物及びこれを利用した耐候性ハードコートフィルムに関する。 The present invention relates to an energy ray curable resin composition and a weather resistant hard coat film using the same.
ディスプレイ、タッチパネル、携帯電話等の表示画面等にハードコートフィルムは広く使用されているが、特に、携帯電話、スマートフォン等のモバイル製品は屋外で使用される機会が多くなっている。このような屋外用途のハードコートフィルムでは、紫外線に長時間曝露されても黄変せず、ハードコート層と基材フィルムとの剥れを生じない、優れた耐候性が必要とされる。このため、耐候性を付与する目的で、ハードコート層に紫外線吸収剤や光安定剤を添加することが提案されている（例えば、特許文献１参照）。 Hard coat films are widely used for display screens of displays, touch panels, mobile phones and the like, but in particular, mobile products such as mobile phones and smartphones are increasingly used outdoors. Such a hard coat film for outdoor use is required to have excellent weather resistance that does not turn yellow even when exposed to ultraviolet rays for a long period of time and does not peel off the hard coat layer and the base film. For this reason, it has been proposed to add an ultraviolet absorber or a light stabilizer to the hard coat layer for the purpose of imparting weather resistance (see, for example, Patent Document 1).
しかしながら、特許文献１で提案されているハードコートフィルムは、紫外線吸収剤や光安定剤を添加することにより硬化阻害が生じ、塗膜硬度、耐擦傷性及び基材密着性が低下するという問題が生じている。この問題は、より高い耐候性のレベルに対応するため紫外線吸収剤や光安定剤を多量に添加した場合に顕著である。 However, the hard coat film proposed in Patent Document 1 has a problem in that curing inhibition occurs due to the addition of an ultraviolet absorber or a light stabilizer, and the coating film hardness, scratch resistance, and substrate adhesion deteriorate. Has occurred. This problem is remarkable when a large amount of an ultraviolet absorber or a light stabilizer is added to cope with a higher level of weather resistance.
一方、前記モバイル製品は生産コストを抑えるために各構成部品の生産拠点とモバイル製品の組み立て拠点が異なることが多く、各種構成部品の製造、輸送時における高温多湿の環境下やモバイル製品の長期保存性を考慮し、耐湿性や耐候性に関する促進試験が行われるのが通常である。このような場合においてもハードコート層と基材フィルムとの剥れを生じない優れた基材密着性を有することが必要とされる。 On the other hand, in order to reduce production costs, the production base of each component and the assembly base of the mobile product are often different in the mobile product. In consideration of the properties, accelerated tests on moisture resistance and weather resistance are usually performed. Even in such a case, it is necessary to have excellent substrate adhesion that does not cause peeling between the hard coat layer and the substrate film.
このため、紫外線吸収剤や光安定剤を多量に添加した場合や促進試験下においても塗膜硬度、耐擦傷性、耐候性及び耐湿性に優れたハードコートフィルムが産業界から強く要望されている。 For this reason, there is a strong demand from the industry for a hard coat film excellent in coating film hardness, scratch resistance, weather resistance and moisture resistance even when a large amount of ultraviolet absorber or light stabilizer is added or under accelerated tests. .
そこで、本発明の目的は、前記の欠点を改善し、硬化させた際に塗膜硬度、耐擦傷性、耐候性及び耐湿性に優れたエネルギー線硬化型樹脂組成物及びこれを利用した耐候性ハードコートフィルムを提供することにある。 Accordingly, an object of the present invention is to improve the above-mentioned drawbacks and when cured, an energy ray curable resin composition excellent in coating film hardness, scratch resistance, weather resistance and moisture resistance, and weather resistance using the same. It is to provide a hard coat film.
本発明者らは前記課題を解決するため鋭意検討を行った結果、特定の化合物を特定の割合で含有する樹脂組成物及びこれを利用したハードコートフィルムが前記課題を解決することを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that a resin composition containing a specific compound in a specific ratio and a hard coat film using the same solve the above problems, The invention has been completed.
即ち、本発明のエネルギー線硬化型樹脂組成物は、
［１］（Ａ）エネルギー線硬化型オリゴマーと、（Ｂ）ベンゾトリアゾール系紫外線吸収剤及びトリアジン系紫外線吸収剤の中から選ばれる少なくとも１種と、（Ｃ）ヒンダードアミン系光安定剤と、（Ｄ）光重合開始剤と、を含有するエネルギー線硬化型樹脂組成物であって、前記（Ｂ）成分を前記（Ａ）成分１００質量部に対し、２〜１２質量部添加するとともに、前記（Ｄ）成分が（Ｄ１）メタノール又はアセトニトリルに溶解させた０．０１％質量溶液における３４０ｎｍ〜４００ｎｍの波長範囲における吸光度の最大値が０．１以上である光重合開始剤と、（Ｄ２）メタノール又はアセトニトリルに溶解させた０．００１質量％溶液における２２０ｎｍ〜２８０ｎｍの波長範囲における吸光度の最大値が０．１以上である光重合開始剤と、をそれぞれ少なくとも１種以上含有することを特徴とするものである。That is, the energy beam curable resin composition of the present invention is
[1] (A) an energy ray curable oligomer, (B) at least one selected from benzotriazole ultraviolet absorbers and triazine ultraviolet absorbers, (C) a hindered amine light stabilizer, and (D ) A photopolymerization initiator, which is an energy ray curable resin composition, and the component (B) is added in an amount of 2 to 12 parts by mass with respect to 100 parts by mass of the component (A). And (D2) a photopolymerization initiator having a maximum absorbance of 0.1 or more in a wavelength range of 340 nm to 400 nm in a 0.01% mass solution dissolved in (D1) methanol or acetonitrile; and (D2) methanol or acetonitrile. The maximum absorbance in the wavelength range of 220 nm to 280 nm in a 0.001% by mass solution dissolved in 0.1 wt. It is characterized in that it contains more than at least one agent, respectively.
［２］前記（Ａ）成分が、エネルギー線硬化性官能基数が１０〜２０の範囲である多官能ウレタン（メタ）アクリレートオリゴマーからなるエネルギー線硬化型樹脂組成物である。 [2] The energy ray-curable resin composition comprising the polyfunctional urethane (meth) acrylate oligomer in which the component (A) has an energy ray-curable functional group number in the range of 10 to 20.
［３］（Ｅ）成分としてさらに、エネルギー線硬化型モノマーを用いる［１］記載のエネルギー線硬化型樹脂組成物である。 [3] The energy ray curable resin composition according to [1], wherein an energy ray curable monomer is further used as the component (E).
［４］前記（Ａ）成分１００質量部に対し、前記（Ｄ）成分を１〜１５質量部添加する［１］記載のエネルギー線硬化型樹脂組成物である。 [4] The energy ray-curable resin composition according to [1], wherein 1 to 15 parts by mass of the component (D) is added to 100 parts by mass of the component (A).
［５］前記（Ｄ１）の添加量が（Ｄ２）の添加量と同量又は少量である［１］記載のエネルギー線硬化型樹脂組成物である。 [5] The energy ray-curable resin composition according to [1], wherein the addition amount of (D1) is the same or a small amount as the addition amount of (D2).
［６］前記（Ｄ１）成分と前記（Ｄ２）成分の添加比が質量比で３：９７〜４５：５５の範囲である［１］記載のエネルギー線硬化型樹脂組成物である。 [6] The energy beam curable resin composition according to [1], wherein an addition ratio of the component (D1) and the component (D2) is in a range of 3:97 to 45:55 by mass ratio.
本発明のハードコートフィルムは、
［７］基材フィルム上の少なくとも片面に［１］記載のエネルギー線硬化型樹脂組成物を塗布硬化させ、ハードコート層として設けたことを特徴とするものである。The hard coat film of the present invention is
[7] The energy ray curable resin composition described in [1] is applied and cured on at least one surface of the base film, and is provided as a hard coat layer.
［８］ＡＳＴＭ Ｇ−１５４に準拠した耐候性試験１２サイクル後の黄変度（Δｂ）が１．０未満である［７］記載のハードコートフィルムである。 [8] The hard coat film according to [7], wherein the yellowing degree (Δb) after 12 cycles of a weather resistance test based on ASTM G-154 is less than 1.0.
［９］ＡＳＴＭ Ｇ−１５４に準拠した耐候性試験１２サイクル後のＪＩＳ Ｋ−５４００に規定の基材密着性が９０／１００以上である［７］記載のハードコートフィルムである。 [9] The hard coat film according to [7], wherein the base material adhesion specified in JIS K-5400 after 12 cycles of a weather resistance test based on ASTM G-154 is 90/100 or more.
［１０］温度６０℃、湿度９０％の環境下で５００時間後のＪＩＳ Ｋ−５４００に規定の基材密着性が９０／１００以上である［７］記載のハードコートフィルムである。 [10] The hard coat film according to [7], wherein the substrate adhesion specified in JIS K-5400 after 500 hours in an environment of a temperature of 60 ° C. and a humidity of 90% is 90/100 or more.
本発明により、硬化させた際には塗膜硬度、耐擦傷性、耐候性及び耐湿性に優れるエネルギー線硬化型樹脂組成物及びこれを利用した耐候性ハードコートフィルムを提供することができる。 According to the present invention, it is possible to provide an energy ray curable resin composition excellent in coating film hardness, scratch resistance, weather resistance and moisture resistance when cured, and a weather resistant hard coat film using the same.
以下、本発明のエネルギー線硬化型樹脂組成物、耐候性ハードコートフィルムの各形態について具体的に説明するが、本発明は以下の形態に限定されるものではなく、本発明の趣旨を逸脱しない範囲で、当業者の通常の知識に基づいて、以下の実施の形態に対し、適宜変更、改良等が加えられたものも本発明の範囲のものである。
［エネルギー線硬化型樹脂組成物］Hereinafter, although each form of the energy ray curable resin composition and the weather resistant hard coat film of the present invention will be specifically described, the present invention is not limited to the following forms and does not depart from the gist of the present invention. It is within the scope of the present invention to appropriately modify and improve the following embodiments based on the ordinary knowledge of those skilled in the art.
[Energy ray curable resin composition]
本発明のエネルギー線硬化型樹脂組成物は、（Ａ）エネルギー線硬化型オリゴマーと、（Ｂ）ベンゾトリアゾール系紫外線吸収剤及びトリアジン系紫外線吸収剤の中から選ばれる少なくとも１種と、（Ｃ）ヒンダードアミン系光安定剤と、（Ｄ）光重合開始剤と、を含有するものである。各成分について以下に詳細に説明する。 The energy beam curable resin composition of the present invention comprises (A) an energy beam curable oligomer, (B) at least one selected from benzotriazole ultraviolet absorbers and triazine ultraviolet absorbers, and (C) It contains a hindered amine light stabilizer and (D) a photopolymerization initiator. Each component will be described in detail below.
［（Ａ）成分］
本発明で使用される（Ａ）成分は、エネルギー線硬化型オリゴマーである。[(A) component]
The component (A) used in the present invention is an energy beam curable oligomer.
ここでエネルギー線硬化型オリゴマーとしては、１分子中に２個以上のアクリロイル基を有し、架橋硬化することにより３次元網目構造となる（メタ）アクリル系オリゴマーが特に好ましく使用される。この（メタ）アクリル系オリゴマーとしては、ウレタン（メタ）アクリレート、ポリエステル（メタ）アクリレート、エポキシ（メタ）アクリレート、メラミン（メタ）アクリレート等を挙げることができる。これらのものは１種単独で用いてもよいし、２種以上を併用して用いてもよい。なお、（メタ）アクリルとはアクリル又はメタクリルを、（メタ）アクリレートはアクリレート又はメタクリレートを指す。 Here, as the energy ray curable oligomer, a (meth) acrylic oligomer having two or more acryloyl groups in one molecule and having a three-dimensional network structure by crosslinking and curing is particularly preferably used. Examples of the (meth) acrylic oligomer include urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, and melamine (meth) acrylate. These may be used alone or in combination of two or more. In addition, (meth) acryl refers to acryl or methacryl, and (meth) acrylate refers to acrylate or methacrylate.
（Ａ）成分において使用されるエネルギー線硬化型オリゴマーは、質量平均分子量は１，０００〜２０，０００が好ましい。質量平均分子量が１，０００未満である場合には柔軟性が不足するからであり、２０，０００を超えた場合には塗膜硬度が不足するからである。柔軟性と塗膜硬度の観点から質量平均分子量は、１，０００〜１０，０００であることが更に好ましい。 The energy ray curable oligomer used in the component (A) preferably has a mass average molecular weight of 1,000 to 20,000. This is because the flexibility is insufficient when the mass average molecular weight is less than 1,000, and the coating film hardness is insufficient when it exceeds 20,000. From the viewpoints of flexibility and coating film hardness, the mass average molecular weight is more preferably 1,000 to 10,000.
（Ａ）成分において使用されるエネルギー線硬化型オリゴマーは、エネルギー線硬化性官能基数が１０〜２０である多官能ウレタン（メタ）アクリレートオリゴマーからなるものであることが好ましい。このオリゴマーを使用することにより、塗膜硬度を保ちながら柔軟性も保持する効果が奏される。エネルギー線硬化性官能基数が１０未満の場合には塗膜硬度が不足し、２０を超えた場合には柔軟性が不足するからである。エネルギー線硬化性官能基数は、塗膜硬度と柔軟性の観点から１０〜１６の範囲が更に好ましい。 The energy ray curable oligomer used in the component (A) is preferably a polyfunctional urethane (meth) acrylate oligomer having 10 to 20 energy ray curable functional groups. By using this oligomer, the effect of maintaining flexibility while maintaining the coating film hardness is exhibited. This is because when the number of energy ray-curable functional groups is less than 10, the coating film hardness is insufficient, and when it exceeds 20, the flexibility is insufficient. The number of energy ray-curable functional groups is more preferably in the range of 10 to 16 from the viewpoint of coating film hardness and flexibility.
［（Ｅ）成分］
本発明のエネルギー線硬化型樹脂組成物においては、（Ａ）成分に加えて、（Ｅ）成分として更にエネルギー線硬化型モノマーを用いることもできる。この場合、（Ｅ）成分の割合は、（Ａ）成分と（Ｅ）成分の合計に対して４０質量％未満となるようにするのが好ましい。このような範囲とすることにより、後述する耐湿性試験における基材密着性をより向上させることができるからである。（Ｅ）成分としては、ジペンタエリスリトールヘキサ（メタ）アクリレート、トリメチロールプロパン（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、エチレングルコールジ（メタ）アクリレート、トリエチレングリコールジビニルエーテル、テトラエチレングリコール（メタ）アクリレート、トリプロピレングリコール（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリメチロールプロパントリオキシエチル（メタ）アクリレート、トリス（２−ヒドロキシエチル）イソシアヌレートトリ（メタ）アクリレート等を好適に挙げることができる。これらのものは１種単独で用いてもよいし、２種以上を併用して用いてもよい。[(E) component]
In the energy beam curable resin composition of the present invention, in addition to the component (A), an energy beam curable monomer can also be used as the component (E). In this case, it is preferable that the ratio of the component (E) is less than 40% by mass with respect to the total of the components (A) and (E). It is because it can improve the base-material adhesiveness in the moisture resistance test mentioned later by setting it as such a range. As component (E), dipentaerythritol hexa (meth) acrylate, trimethylolpropane (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol divinyl ether, tetraethylene glycol (Meth) acrylate, tripropylene glycol (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri Preferable examples include oxyethyl (meth) acrylate and tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate. These may be used alone or in combination of two or more.
上記の（Ｅ）成分以外にも、（Ｅ）成分として、ジペンタエリスリトールポリアクリレート、ジペンタエリスリトールヘキサアクリレート、トリシクロデカンジメタノールジアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、トリメチロールプロパントリアクリレート、ジトリメチロールプロパンテトラアクリレートといった疎水性の２官能以上の（メタ）アクリレートモノマーを使用することも好ましい。これらのモノマーを使用することにより後述する耐湿性試験における基材密着性をより向上させることができるからである。 In addition to the above component (E), as component (E), dipentaerythritol polyacrylate, dipentaerythritol hexaacrylate, tricyclodecane dimethanol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane tri It is also preferable to use a hydrophobic bifunctional or higher functional (meth) acrylate monomer such as acrylate or ditrimethylolpropane tetraacrylate. This is because by using these monomers, the substrate adhesion in the moisture resistance test described later can be further improved.
［（Ｂ）成分］
本発明で使用される（Ｂ）成分は、ベンゾトリアゾール系紫外線吸収剤及びトリアジン系紫外線吸収剤の中から選ばれる少なくとも１種である。これらのものは、ＵＶＡ（波長３２０〜４００ｎｍ）領域に吸収を有するものであるため、後述するＵＶＡ３４０ランプを用いた耐候性試験で良好な結果を示すことができる。なお、ベンゾトリアゾール系紫外線吸収剤の方がＵＶＡ領域の吸収が大きいため、耐候性試験において良好な結果を得ることができる。なお、[Component (B)]
(B) component used by this invention is at least 1 sort (s) chosen from a benzotriazole type ultraviolet absorber and a triazine type ultraviolet absorber. Since these have absorption in the UVA (wavelength 320 to 400 nm) region, good results can be shown in a weather resistance test using a UVA340 lamp described later. In addition, since a benzotriazole type ultraviolet absorber has a larger absorption in the UVA region, good results can be obtained in a weather resistance test. In addition,
ベンゾトリアゾール系化合物としては、例えば、２−（２’−ヒドロキシ−５’−メチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−５’−ｔ−ブチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−３’−ｔ−ブチル−５’−メチルフェニル）−５−クロロベンゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ジ−ｔ−ブチルフェニル）−５−クロロベンゾトリアゾール、２−（２’−ヒドロキシ−３’−ｔ−ブチル−５’−（２−（オクチルオキシカルボニル）エチル）フェニル）−５−クロロベンゾトリアゾール、２−（２’−ヒドロキシ−３’−ドデシル−５’−メチルフェニル）−５−クロロベンゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ジ−ｔ−アミルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−５’−ｔ−オクチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ジ−（ジメチルベンジル）フェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−４’−オクチルオキシフェニル）ベンゾトリアゾール、２，２’−メチレン−ビス（２−（２’−ヒドロキシ−５’−ｔ−オクチルフェニル）ベンゾトリアゾール）２−（２’−ヒドロキシ−３’−（３，４，５，６−テトラヒドロフタルイミジルメチル）−５’−メチルベンジル）フェニル）ベンゾトリアゾール等を挙げることができる。これらのものは１種単独で用いてもよいし、２種以上を併用して用いてもよい。 Examples of the benzotriazole compounds include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2 ′ -Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole 2- (2′-hydroxy-3′-t-butyl-5 ′-(2- (octyloxycarbonyl) ethyl) phenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-dodecyl) -5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotria 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di- (dimethylbenzyl) phenyl) benzotriazole, 2- ( 2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2,2'-methylene-bis (2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole) 2- (2'-hydroxy -3 '-(3,4,5,6-tetrahydrophthalimidylmethyl) -5'-methylbenzyl) phenyl) benzotriazole and the like. These may be used alone or in combination of two or more.
トリアジン系化合物の代表例としては、２−（４−ヘキシロキシ−２−ヒドロキシフェニル）−４，６−ジフェニル−１，３，５−トリアジン、２−（４−オクチロキシ−２−ヒドロキシフェニル）−４，６−ジ（２，５−ジメチルフェニル）−１，３，５−トリアジン、２−（４−ブトキシ−２−ヒドロキシフェニル）−４，６−ジ（４−ブトキシフェニル）−１，３，５−トリアジン、２−（４−ブトキシ−２−ヒドロキシフェニル）−４，６−ジ（２，４−ジブトキシフェニル）−１，３，５−トリアジン、２−（４−（３−（２−エチルヘキシロキシ）−２−ヒドロキシプロポキシ）−２−ヒドロキシフェニル）−４，６−ジ（２，４−ジメチルフェニル）−１，３，５−トリアジン、２−（４−（３−ドデシロキシ−２−ヒドロキシプロポキシ）−２−ヒドロキシフェニル）−４，６−ジ（２，４−ジメチルフェニル）−１，３，５−トリアジン、２，４−ジ（４−ブトキシ−２−ヒドロキシフェニル）−６−（４−ブトキシフェニル）−１，３，５−トリアジン、２，４−ジ（４−ブトキシ−２−ヒドロキシフェニル）−６−（２，４−ジブトキシフェニル）−１，３，５−トリアジン等を挙げることができる。これらのものは１種単独で用いてもよいし、２種以上を併用して用いてもよい。 Representative examples of triazine compounds include 2- (4-hexyloxy-2-hydroxyphenyl) -4,6-diphenyl-1,3,5-triazine and 2- (4-octyloxy-2-hydroxyphenyl) -4. , 6-Di (2,5-dimethylphenyl) -1,3,5-triazine, 2- (4-butoxy-2-hydroxyphenyl) -4,6-di (4-butoxyphenyl) -1,3 5-triazine, 2- (4-butoxy-2-hydroxyphenyl) -4,6-di (2,4-dibutoxyphenyl) -1,3,5-triazine, 2- (4- (3- (2 -Ethylhexyloxy) -2-hydroxypropoxy) -2-hydroxyphenyl) -4,6-di (2,4-dimethylphenyl) -1,3,5-triazine, 2- (4- (3-dodecyloxy- 2-hydroxy Propoxy) -2-hydroxyphenyl) -4,6-di (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-di (4-butoxy-2-hydroxyphenyl) -6- ( 4-butoxyphenyl) -1,3,5-triazine, 2,4-di (4-butoxy-2-hydroxyphenyl) -6- (2,4-dibutoxyphenyl) -1,3,5-triazine, etc. Can be mentioned. These may be used alone or in combination of two or more.
（Ｂ）成分の添加量は、前記（Ａ）成分１００質量部に対して２〜１２質量部の範囲であることが必要である。２質量部未満では耐候性が劣ることとなるからであり、また、１２質量部を超える場合は、塗膜硬度及び基材密着性が劣ることとなるからである。耐候性、塗膜硬度と基材密着性の観点から２．５〜１０質量部の範囲であることが好ましく、３〜８質量部であることが更に好ましい。なお、前記（Ａ）成分の他、（Ｅ）成分としてエネルギー線硬化型モノマーを用いた場合には、前記（Ｂ）成分の配合量は、（Ａ）成分であるエネルギー線硬化型オリゴマーと（Ｅ）成分であるエネルギー線硬化型モノマーの合計量１００質量部あたりの添加量を指す。 (B) The addition amount of a component needs to be the range of 2-12 mass parts with respect to 100 mass parts of said (A) component. This is because if it is less than 2 parts by mass, the weather resistance will be inferior, and if it exceeds 12 parts by mass, the coating film hardness and the substrate adhesion will be inferior. From the viewpoint of weather resistance, coating film hardness, and substrate adhesion, the range is preferably 2.5 to 10 parts by mass, and more preferably 3 to 8 parts by mass. In addition to the component (A), when an energy ray curable monomer is used as the component (E), the blending amount of the component (B) is the energy ray curable oligomer (A) and ( E) The addition amount per 100 parts by mass of the total amount of the energy ray-curable monomer as the component.
［（Ｃ）成分］
本発明で使用される（Ｃ）成分は、ヒンダードアミン系化合物である。このものを添加することにより、紫外線照射により発生したラジカルを効率的に補足することができるので耐候性を向上させることができる。（Ｃ）成分としては、例えば、４−ペゾイルオキシ−２，２，６，６−テトラメチルピペリジン、４−ヘキサノイルオキシ−２，２，６，６−テトラメチルピペリジン、４−オクタノイルオキシ−２，２，６，６−テトラメチルピペリジン、４−ステアロイルオキシ−２，２，６，６−テトラメチルピペリジン、コハク酸−ビス（２，２，６，６−テトラメチルピペリジン）、サバシン酸−ビス（２，２，６，６−テトラメチルピペリジン）、サバシン酸−ビス（１，２，２，６，６−ペンタメチル−４−ピペリジン）、８−アセチル−３−ドデシル−７，７，９，９−テトラメチル−１，３，８−トリアザスピロ［４，５］デカン−２，４−ジオン、Ｎ−メチル−３−ドデシル−１−（２，２，６，６−テトラメチル−４−ピペリジニル）ピロリジン−２，５−ジオン、Ｎ−アセチル−３−ドデシル−１−（２，２，６，６−テトラメチル−４−ピペリジニル）ピロリジン−２，５−ジオン、フタル酸−ビス（１，２，２，６，６−ペンタメチル−４−ピペリジン）、トリメシン酸−トリス（２，２，６，６−テトラメチル−４−ピペリジル）等を挙げることができる。これらのものは１種単独で用いてもよいし、２種以上を併用して用いてもよい。[Component (C)]
The component (C) used in the present invention is a hindered amine compound. By adding this, it is possible to efficiently capture radicals generated by ultraviolet irradiation, so that the weather resistance can be improved. Examples of the component (C) include 4-pezoyloxy-2,2,6,6-tetramethylpiperidine, 4-hexanoyloxy-2,2,6,6-tetramethylpiperidine, 4-octanoyloxy-2. , 2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, succinic acid-bis (2,2,6,6-tetramethylpiperidine), sabasinic acid-bis (2,2,6,6-tetramethylpiperidine), sabasinic acid-bis (1,2,2,6,6-pentamethyl-4-piperidine), 8-acetyl-3-dodecyl-7,7,9, 9-tetramethyl-1,3,8-triazaspiro [4,5] decane-2,4-dione, N-methyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl ) Loridin-2,5-dione, N-acetyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione, phthalate-bis (1,2 , 2,6,6-pentamethyl-4-piperidine), trimesic acid-tris (2,2,6,6-tetramethyl-4-piperidyl) and the like. These may be used alone or in combination of two or more.
（Ｃ）成分の添加量は、前記（Ａ）成分１００質量部に対して０．０５〜５質量部の範囲であることが好ましい。０．０５質量部未満では耐候性が劣るからであり、また、５質量部を超える場合は、耐擦傷性が劣ることとなるからである。耐候性と耐擦傷性の観点から０．５〜３質量部の範囲であることが好ましい。なお、前記（Ａ）成分の他、（Ｅ）成分としてエネルギー線硬化型モノマーを用いた場合には、前記（Ｃ）成分の配合量は、（Ａ）成分であるエネルギー線硬化型オリゴマーと（Ｅ）成分であるエネルギー線硬化型モノマーの合計量１００質量部あたりの添加量を指す。 (C) It is preferable that the addition amount of a component is the range of 0.05-5 mass parts with respect to 100 mass parts of said (A) component. This is because the weather resistance is inferior if it is less than 0.05 parts by mass, and the scratch resistance is inferior if it exceeds 5 parts by mass. From the viewpoint of weather resistance and scratch resistance, it is preferably in the range of 0.5 to 3 parts by mass. In addition to the component (A), when an energy beam curable monomer is used as the component (E), the blending amount of the component (C) is the energy beam curable oligomer (A) and ( E) The addition amount per 100 parts by mass of the total amount of the energy ray-curable monomer as the component.
［（Ｄ）成分］
本発明で使用される（Ｄ）成分は（Ｄ１）メタノール又はアセトニトリルに溶解させた０．０１％質量溶液における３４０ｎｍ〜４００ｎｍの波長範囲における吸光度の最大値が０．１以上である光重合開始剤と、（Ｄ２）メタノール又はアセトニトリルに溶解させた０．００１質量％溶液における２２０ｎｍ〜２８０ｎｍの波長範囲における吸光度の最大値が０．１以上である光重合開始剤と、をそれぞれ少なくとも１種以上含有するものである。これら２種類の光重合吸収剤を添加することにより、各々単独で用いた場合よりも耐湿性に関して大幅な相乗効果が見られる点が本発明の特徴の一つである。[(D) component]
Component (D) used in the present invention is (D1) a photopolymerization initiator having a maximum absorbance of 0.1 or more in a wavelength range of 340 nm to 400 nm in a 0.01% mass solution dissolved in methanol or acetonitrile. And (D2) at least one photopolymerization initiator having a maximum absorbance of 0.1 or more in a wavelength range of 220 nm to 280 nm in a 0.001 mass% solution dissolved in methanol or acetonitrile, respectively. To do. It is one of the features of the present invention that by adding these two types of photopolymerization absorbents, a greater synergistic effect can be seen with respect to moisture resistance than when they are used alone.
本発明で使用される（Ｄ）成分の添加量は、前記（Ａ）成分の合計１００質量部あたり、１〜１５質量部の範囲であることが好ましい。１質量部未満では塗膜硬度及び基材密着性が不足するからであり、また、１５質量部を超える場合は、この成分同士の再結合による硬化阻害に伴い基材密着性が不足するからである。塗膜硬度、基材密着性の点から３〜１２質量部の範囲であることが更に好ましい。なお、前記（Ａ）成分の他（Ｅ）成分として更にエネルギー線硬化型モノマーを用いた場合には、前記（Ｄ）成分の配合量は、（Ａ）成分であるエネルギー線硬化型オリゴマーと（Ｅ）成分であるエネルギー線硬化型モノマーの合計量１００質量部あたりの添加量を指す。 It is preferable that the addition amount of (D) component used by this invention is the range of 1-15 mass parts per 100 mass parts of total of said (A) component. If the amount is less than 1 part by mass, the coating film hardness and the substrate adhesion are insufficient, and if it exceeds 15 parts by mass, the substrate adhesion is insufficient due to the inhibition of curing by recombination of these components. is there. The range of 3 to 12 parts by mass is more preferable from the viewpoints of coating film hardness and substrate adhesion. In addition, when an energy ray curable monomer is used as the component (E) in addition to the component (A), the blending amount of the component (D) is the energy ray curable oligomer (A) and ( E) The addition amount per 100 parts by mass of the total amount of the energy ray-curable monomer as the component.
［（Ｄ１）成分］
本発明で使用される（Ｄ１）成分は、メタノール又はアセトニトリルに溶解させた０．０１％質量溶液における３４０ｎｍ〜４００ｎｍの波長範囲における吸光度の最大値が０．１以上である光重合開始剤をいう。例えば、１−ヒドロキシ−シクロヘキシル−フェニル−ケトン、２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン、ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタノン−１、ビス（η５−２，４−シクロペンタジエン−１−イル）−ビス（２，６−ジフルオロ−３−（１Ｈ−ピロール−１−イル）−フェニル）チタニウム、２−ジメチルアミノ−２−（４−メチルベンジル）−１−（４−モルフォリノフェニル）ブタノン、ジフェニル（２，４，６−トリメチルベンゾイル）ホスフィンオキシド等を挙げることができる。これらのものは１種単独で用いてもよいし、２種以上を併用して用いてもよい。[(D1) component]
The component (D1) used in the present invention refers to a photopolymerization initiator having a maximum absorbance of 0.1 or more in a wavelength range of 340 nm to 400 nm in a 0.01% mass solution dissolved in methanol or acetonitrile. . For example, 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-benzyl- 2-Dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole) 1-yl) -phenyl) titanium, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinophenyl) butanone, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, etc. be able to. These may be used alone or in combination of two or more.
（Ｄ１）成分は市販品を使用することができ、例えばイルガキュア６５１、９０７、８１９、３６９、３７９、１８００、７８４、ダロキュア４２６５、ルシリンＴＰＯ（以上、ＢＡＳＦ社製）等を挙げることができる。 As the component (D1), commercially available products can be used, and examples thereof include Irgacure 651, 907, 819, 369, 379, 1800, 784, Darocur 4265, Lucillin TPO (above, manufactured by BASF).
［（Ｄ２）成分］
本発明で使用される（Ｄ２）成分は、メタノール又はアセトニトリルに溶解させた０．００１質量％溶液における２２０ｎｍ〜２８０ｎｍの波長範囲における吸光度の最大値が０．１以上である光重合開始剤をいう。例えば、２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オン２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン、１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン、２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オン、オキソフェニル酢酸メチル、オリゴ［２−ヒドロキシ−２−メチル−［１−（４−メチルビニル）フェニル］プロパノン等を挙げることができる。これらのものは１種単独で用いてもよいし、２種以上を併用して用いてもよい。[(D2) component]
The component (D2) used in the present invention refers to a photopolymerization initiator having a maximum absorbance of 0.1 or more in a wavelength range of 220 nm to 280 nm in a 0.001 mass% solution dissolved in methanol or acetonitrile. . For example, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one 2,2-dimethoxy-1,2-diphenylethane-1-one, 1- [4- (2 -Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, methyl oxophenylacetate, oligo [2 -Hydroxy-2-methyl- [1- (4-methylvinyl) phenyl] propanone and the like can be mentioned. These may be used alone or in combination of two or more.
（Ｄ２）成分は市販品を使用することができ、例えばイルガキュア１８４、６５１、５００、２９５９、１２７、７５４、９０７、１８００、ダロキュア１１７３、ＭＢＦ（以上、ＢＡＳＦ社製）、イサキュアＫＩＰ１５０、ＫＩＰ１００Ｆ、ＯＮＥ、（以上、ランベルティ社製）等を挙げることができる。 As the component (D2), a commercially available product can be used. (Above, manufactured by Lamberti).
このような（Ｄ）成分は、耐湿性向上の観点から、前記（Ｄ１）成分を有する光重合開始剤の添加量が前記（Ｄ２）成分を有する光重合開始剤の添加量と同量若しくは少量とすることが好ましい。（Ｄ１）成分と（Ｄ２）成分の添加割合は質量比で３：９７〜４５：５５の範囲であることが特に好ましい。なお、（Ｄ）成分は、１種類の光重合開始剤で、（Ｄ１）成分と（Ｄ２）成分の光重合開始波長領域を有するものもあるが、本発明においては少なくとも（Ｄ１）成分を有するものと（Ｄ２）成分を有するものの２種類を用いる必要がある。よって、このような（Ｄ１）成分と（Ｄ２）成分を有する１種類の光重合開始剤を用いる場合であっても、もう１種類別の光重合開始剤を用いらなければならない。このように２種類の光重合開始剤を含有することにより、紫外線吸収性能を有するエネルギー線硬化型樹脂組成物であっても、硬化させた際に耐擦傷性に優れ、耐湿性に優れた塗膜を得ることができる。 From the viewpoint of improving moisture resistance, the component (D) is added in the same amount or a small amount of the photopolymerization initiator having the component (D1) as the additive amount of the photopolymerization initiator having the component (D2). It is preferable that The addition ratio of the component (D1) and the component (D2) is particularly preferably in the range of 3:97 to 45:55 by mass ratio. In addition, although (D) component is one kind of photoinitiator and has what has the photoinitiation wavelength range of (D1) component and (D2) component, in this invention, it has at least (D1) component. It is necessary to use two types, one having a component and the component (D2). Therefore, even when one type of photopolymerization initiator having such components (D1) and (D2) is used, another type of photopolymerization initiator must be used. By containing two types of photopolymerization initiators as described above, even an energy ray curable resin composition having ultraviolet absorption performance has excellent scratch resistance and excellent moisture resistance when cured. A membrane can be obtained.
更に、本発明のエネルギー線硬化型樹脂組成物には、必要に応じて、他の樹脂、溶剤や光重合開始助剤、レベリング剤、消泡剤、酸化防止剤、重合禁止剤、架橋剤、顔料、防汚剤、微粒子、滑剤、蛍光増白剤、帯電防止剤、難燃剤、抗菌剤、防カビ剤、可塑剤、流動調整剤、分散剤、離型剤等の添加剤等を添加し、それぞれ目的とする機能を付与することも可能である。 Furthermore, in the energy beam curable resin composition of the present invention, if necessary, other resins, solvents, photopolymerization initiation assistants, leveling agents, antifoaming agents, antioxidants, polymerization inhibitors, crosslinking agents, Add additives such as pigments, antifouling agents, fine particles, lubricants, fluorescent brighteners, antistatic agents, flame retardants, antibacterial agents, antifungal agents, plasticizers, flow regulators, dispersants, release agents, etc. It is also possible to give each intended function.
光重合開始助剤としては、例えば、アミン化合物、カルボン酸化合物、多官能チオール化合物等を挙げることができる。これらのものは１種単独で用いてもよいし、２種以上を併用して用いてもよい。溶剤については特に限定はないが、前記（Ａ）成分と反応し得る官能基を含まないものであれば好適に用いることができる。 Examples of the photopolymerization initiation assistant include amine compounds, carboxylic acid compounds, and polyfunctional thiol compounds. These may be used alone or in combination of two or more. Although there is no limitation in particular about a solvent, if it does not contain the functional group which can react with the said (A) component, it can use suitably.
好ましい溶媒としてはトルエン、キシレン等の芳香族系溶媒；酢酸エチル、酢酸ブチル、メトキシブチルアセテート、メトキシプロピルアセテート等のエステル系溶媒；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶媒；ジエチルエーテル、ジブチルエーテル、テトラヒドロフラン、１，３−ジオキソラン、１，４−ジオキサン、プロピレングリコールモノメチルエーテルアセテート、ジエチレングリコールジメチルエーテル、ジエチレングリコールエチルメチルエーテル等のエーテル系溶媒：その他の公知の有機溶剤を挙げることができる。 Preferred solvents include aromatic solvents such as toluene and xylene; ester solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate and methoxypropyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; diethyl ether And ether solvents such as dibutyl ether, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and the like.
使用する有機溶媒の種類は同時に添加される前記（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）成分等との溶解性を考慮して決められるが、乾燥時の残存溶媒の残りにくさの点からメチルエチルケトン、メチルイソブチルケトン、テトラヒドロフラン等の沸点が１２０℃以下の有機溶媒が好ましい。これらのものは１種単独で用いてもよいし、２種以上を併用して用いてもよい。溶剤使用量は特に限定はないが、組成物粘度が採用する塗工方式に適した粘度になるように調整することが好ましい。好ましい使用量としては組成物全体の５〜９０質量％であり、より好ましくは１０〜８５質量％、更に好ましくは２０〜８０質量％である。 The type of organic solvent to be used is determined in consideration of the solubility with the components (A), (B), (C), (D) and the like added at the same time. In view of the above, an organic solvent having a boiling point of 120 ° C. or lower, such as methyl ethyl ketone, methyl isobutyl ketone, and tetrahydrofuran, is preferable. These may be used alone or in combination of two or more. The amount of solvent used is not particularly limited, but is preferably adjusted so that the viscosity of the composition is suitable for the coating method employed. The preferred amount is 5 to 90% by mass of the total composition, more preferably 10 to 85% by mass, and still more preferably 20 to 80% by mass.
レベリング剤としてはアクリル系化合物、高沸点溶剤、フッ素系化合物、シリコーン系化合物等を挙げることができるが、表面を鏡面に仕上げる点でフッ素系化合物、シリコーン系化合物が好ましい。酸化防止剤としてはフェノール系化合物等を、重合禁止剤としては、メトキノン、メチルハイドロキノン、ハイドロキノン等が挙げられ、架橋剤としては、前記イソシアネート類、メラミン化合物等を挙げることができる。微粒子は、シリカ、炭酸カルシウム等の無機微粒子及びポリメチルメタクリレートやポリスチレン等の有機微粒子等を挙げることできる。防汚剤はフッ素系化合物、ケイ素系化合物、またはこれらの混合物を挙げることができ、防汚性能よりフッ素系化合物が好ましい。 Examples of the leveling agent include acrylic compounds, high-boiling solvents, fluorine compounds, silicone compounds, and the like, but fluorine compounds and silicone compounds are preferred in terms of finishing the surface to a mirror surface. Examples of the antioxidant include phenolic compounds, examples of the polymerization inhibitor include methoquinone, methylhydroquinone, and hydroquinone. Examples of the crosslinking agent include the isocyanates and melamine compounds. Examples of the fine particles include inorganic fine particles such as silica and calcium carbonate, and organic fine particles such as polymethyl methacrylate and polystyrene. The antifouling agent can include a fluorine compound, a silicon compound, or a mixture thereof, and a fluorine compound is preferred from the antifouling performance.
本発明のエネルギー線硬化型樹脂組成物は上述した（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）成分、さらには必要に応じて、（Ｅ）成分、溶剤、並びに添加剤を任意の順序で添加することにより得ることができる。以下、本発明において前記各種成分を添加した液をハードコート液と呼ぶことがある。 The energy beam curable resin composition of the present invention may contain the components (A), (B), (C), and (D) described above, and optionally the component (E), the solvent, and the additives. It can be obtained by adding in order. Hereinafter, the liquid to which the various components are added in the present invention may be referred to as a hard coat liquid.
［ハードコートフィルム］
本発明のハードコートフィルムは本発明のエネルギー線硬化型樹脂組成物を基材フィルムの少なくとも片面に塗布する工程を含む製法で得ることが出来る。このため、本発明のハードコートフィルムには、ハードコート層を両面に塗布したもの、ハードコート層を塗布していない基材フィルム面に粘着剤層、印刷層を塗布したものも含まれることになる。[Hard coat film]
The hard coat film of this invention can be obtained with the manufacturing method including the process of apply | coating the energy-beam curable resin composition of this invention to the at least single side | surface of a base film. For this reason, the hard coat film of the present invention includes those obtained by applying a hard coat layer on both sides, and those obtained by applying a pressure-sensitive adhesive layer and a printing layer on a base film surface not applied with a hard coat layer. Become.
基材フィルムとしては、例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリエチレンフィルム、ポリプロピレンフィルム、セロファン、ジアセチルセルロースフィルム、トリアセチルセルロースフィルム、アセチルセルロースブチレートフィルム、ポリ塩化ビニルフィルム、ポリ塩化ビニリデンフィルム、ポリビニルアルコールフィルム、エチレン−酢酸ビニル共重合体フィルム、ポリスチレンフィルム、ポリカーボネートフィルム、ポリメチルペンテンフィルム、ポリスルホンフィルム、ポリエーテルエーテルケトンフィルム、ポリエーテルスルホンフィルム、ポリエーテルイミドフィルム、ポリイミドフィルム、フッソ樹脂フィルム、ナイロンフィルム、アクリル樹脂フィルム等を用いることが出来る。なお、エネルギー線硬化型樹脂組成物との密着性を向上させる目的で、易接着層の塗布による処理、サンドブラスト法や溶剤処理法等による表面の凹凸化処理、あるいはコロナ放電処理、クロム酸処理、火炎処理、熱風処理、プラズマ処理、オゾン・紫外線照射処理等の表面処理を施してもよい。基材フィルムにはエネルギー線硬化型樹脂組成物を塗布する前にあらかじめ片面又は両面に粘着剤層や意匠性付与のための印刷やコーティングが付与されていてもよい。 Examples of the base film include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film, polyvinyl chloride film, and polyvinylidene chloride. Film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyetheretherketone film, polyethersulfone film, polyetherimide film, polyimide film, fluorine resin For film, nylon film, acrylic resin film, etc. Rukoto can be. In addition, for the purpose of improving the adhesiveness with the energy beam curable resin composition, treatment by application of an easy-adhesion layer, surface roughening treatment by sandblasting or solvent treatment, or corona discharge treatment, chromic acid treatment, Surface treatments such as flame treatment, hot air treatment, plasma treatment, ozone / ultraviolet irradiation treatment, etc. may be applied. Before applying the energy ray curable resin composition to the base film, a pressure sensitive adhesive layer or printing or coating for imparting design properties may be provided on one side or both sides in advance.
塗布には公知の方法、例えば、グラビアコート法、バーコート法、ナイフコート法、ロールコート法、ブレードコート法、ダイコート法、スピンコート法、フローコート法、ディップコート法、スプレーコート法、スクリーン印刷法、刷毛塗り等を用いることができる。 For coating, known methods such as gravure coating, bar coating, knife coating, roll coating, blade coating, die coating, spin coating, flow coating, dip coating, spray coating, and screen printing. Method, brushing, etc. can be used.
エネルギー線硬化型樹脂組成物の粘度が塗布に適した粘度より高ければ溶剤を用いて粘度調整をしてもよい。使用可能な溶剤は上述のとおりである。 If the viscosity of the energy ray curable resin composition is higher than the viscosity suitable for coating, the viscosity may be adjusted using a solvent. Solvents that can be used are as described above.
エネルギー硬化型樹脂組成物で溶剤を含む場合には、塗布後に乾燥を行う必要がある。乾燥温度は乾燥ラインの長さ、ライン速度、塗布量、残存溶剤量、基材の種類等を考慮して決めればよい。基材がポリエチレンテレフタレートフィルムであれば、一般的な乾燥温度は５０〜１００℃である。１ラインに複数の乾燥機がある場合は、それぞれの乾燥機を異なる温度、風速に設定してもよい。塗工外観の良好な塗膜を得るためには、入り口側の乾燥条件をマイルドにするのが好ましい。塗布厚みに特に制限はないが乾燥後膜厚が１〜２０μｍになるように塗工するのが好ましい。より好ましくは１〜１５μｍ、更に好ましくは１〜１０μｍである。 When the energy curable resin composition contains a solvent, it is necessary to dry after application. The drying temperature may be determined in consideration of the length of the drying line, the line speed, the coating amount, the residual solvent amount, the type of substrate, and the like. If a base material is a polyethylene terephthalate film, a general drying temperature is 50-100 degreeC. When there are a plurality of dryers in one line, each dryer may be set to a different temperature and wind speed. In order to obtain a coating film having a good coating appearance, it is preferable that the drying condition on the inlet side is mild. Although there is no restriction | limiting in particular in coating thickness, It is preferable to apply so that a film thickness may become 1-20 micrometers after drying. More preferably, it is 1-15 micrometers, More preferably, it is 1-10 micrometers.
本発明のエネルギー線硬化型樹脂組成物を硬化させる活性エネルギー線としては、紫外線、電子線等を挙げることができる。紫外線により硬化させる場合、光源としてはキセノンランプ、高圧水銀灯、メタルハライドランプ等を有する紫外線照射装置が使用され、必要に応じて光量、光源の配置等が調整される。高圧水銀灯を使用する場合、８０〜１６０Ｗ／ｃｍ２のエネルギーを有するランプ１灯に対して搬送速度５〜６０ｍ／分で硬化させるのが好ましい。電子線により硬化させる場合、１００〜５００ｅＶのエネルギーを有する電子線加速装置を使用するのが好ましい。Examples of active energy rays for curing the energy ray curable resin composition of the present invention include ultraviolet rays and electron beams. In the case of curing with ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, a metal halide lamp or the like is used as a light source, and the amount of light, the arrangement of the light source, etc. are adjusted as necessary. When using a high-pressure mercury lamp, it is preferable to cure at a conveying speed of 5 to 60 m / min for one lamp having an energy of 80 to 160 W / cm 2 . When hardening with an electron beam, it is preferable to use an electron beam accelerator having an energy of 100 to 500 eV.
本発明のハードコートフィルムのハードコート層は、ＪＩＳ Ｋ−５４００に規定の鉛筆硬度が、２Ｈ以上、さらには、３Ｈ以上に調整されていることが好ましい。鉛筆硬度が所定値以上に調整されていることにより、ハードコート層の表面が傷つくことを効果的に防止することができる。 The hard coat layer of the hard coat film of the present invention preferably has a pencil hardness specified in JIS K-5400 of 2H or higher, more preferably 3H or higher. By adjusting the pencil hardness to a predetermined value or higher, it is possible to effectively prevent the surface of the hard coat layer from being damaged.
このようなハードコート層は＃００００のスチールウールを３ｃｍ２円柱治具へかぶせて巻いたものを、加重５００ｇをかけた状態で、３０往復、より好ましくは５０往復、特に好ましくは７０往復以上させたときに傷を生じることがないように調整されていることが好ましい。このように調整することで、必要な耐擦傷性を確保することができる。Such a hard coat layer is made by winding # 0000 steel wool on a 3 cm 2 cylindrical jig and applying 30 g, more preferably 50 reciprocations, particularly preferably 70 reciprocations or more with a weight of 500 g applied. It is preferable to adjust so as not to cause scratches. By adjusting in this way, necessary scratch resistance can be ensured.
本発明のハードコートフィルムは、ＡＳＴＭ Ｇ−１５４に規定の耐候性試験の１２サイクル経過後の黄変度（Δｂ）が１．０未満、より好ましくは、０．５未満であることが望ましい。黄変度（Δｂ）とは耐候性試験後のｂ値（ｂ１）から試験前のｂ値（ｂ０）を減じた値を示す。また、ＡＳＴＭ Ｇ−１５４に規定の耐候性試験の１２サイクル経過後の基材密着性がＪＩＳ Ｋ−５４００に基づき９０／１００以上であることが好ましい。黄変度（Δｂ）と基材密着性をこのように調整することにより耐候性の良好なハードコートフィルムを得ることができる。 The hard coat film of the present invention desirably has a degree of yellowing (Δb) of less than 1.0, more preferably less than 0.5, after 12 cycles of the weather resistance test specified in ASTM G-154. The yellowing degree (Δb) indicates a value obtained by subtracting the b value (b0) before the test from the b value (b1) after the weather resistance test. Moreover, it is preferable that the base-material adhesiveness after 12 cycles of a weather resistance test prescribed | regulated to ASTM G-154 is 90/100 or more based on JISK-5400. A hard coat film with good weather resistance can be obtained by adjusting the degree of yellowing (Δb) and the substrate adhesion in this manner.
本発明のハードコートフィルムは、温度６０℃、湿度９０％の環境下で５００時間後のＪＩＳ Ｋ−５４００に規定の基材密着性が９０／１００以上、より好ましくは１００／１００であることが好ましい。このように調整することにより耐湿性の良好なハードコートフィルムを得ることができる。 In the hard coat film of the present invention, the substrate adhesion specified in JIS K-5400 after 500 hours in an environment of temperature 60 ° C. and humidity 90% is 90/100 or more, more preferably 100/100. preferable. By adjusting in this way, a hard coat film with good moisture resistance can be obtained.
以下、本発明を実施例により更に詳細に説明するが、本発明はこれら実施例によって限定されるものではない。又、実施例中、特に断りがない限り部は質量部を示す。 EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited by these Examples. Moreover, unless otherwise indicated, in an Example, a part shows a mass part.
（塗膜硬度）
ＪＩＳ Ｋ−５４００に従い、鉛筆引っかき試験機を用いて、ハードコートフィルムの鉛筆硬度を測定した。詳しくは、測定する硬化皮膜を有するポリエステルフィルム上に、鉛筆を４５度の角度でセットし、上から１０００ｇの荷重をかけて５ｍｍ程度引っかき、５回中４回以上傷の付かなかった鉛筆の硬さで表した。(Coating hardness)
According to JIS K-5400, the pencil hardness of the hard coat film was measured using a pencil scratch tester. Specifically, a pencil is set on a polyester film having a cured film to be measured at an angle of 45 degrees, scratched about 5 mm by applying a load of 1000 g from above, and the hardness of the pencil that has not been damaged more than 4 times out of 5 times. I expressed it.
（耐擦傷性）
耐スチールウール試験として、＃００００のスチールウールを３ｃｍ２円柱治具へ被せて巻いたものを本発明のハードコート層上に載せ、加重５００ｇをかけた状態で往復させた。キズが最初に発生した直前の回数を記録した。(Abrasion resistance)
As a steel wool resistance test, a steel wool of # 0000 covered with a 3 cm 2 cylindrical jig was placed on the hard coat layer of the present invention and reciprocated in a state where a load of 500 g was applied. The number of times immediately before the first scratch was recorded.
（耐候性）
ＡＳＴＭ Ｇ−１５４に準拠し、ＱＵＶ紫外線蛍光促進機（Ｑ−ＬＡＢ社製）を使用して６０℃の環境下で８時間ＵＶＡ３４０ランプを用い紫外線を照射後、５０℃の環境下で４時間結露させる。これを１サイクルとして１２サイクル行った。１２サイクル後の黄変度（Δｂ）を分光測色計（商品名：ＣＭ−５、コニカミノルタセンシング社製）を用いて測定（後述する表１〜４において耐候性（Δｂ）と記載）すると共に、基材密着性（後述する表１〜４において耐候性（密着）と記載）をＪＩＳ Ｋ−５４００に基づき評価した。(Weatherability)
Conforms to ASTM G-154, uses UV irradiation with UVA340 lamp for 8 hours under 60 ° C environment using QUV ultraviolet fluorescence accelerator (Q-LAB), then condenses for 4 hours under 50 ° C environment Let This was regarded as one cycle and carried out 12 cycles. The yellowing degree (Δb) after 12 cycles is measured using a spectrocolorimeter (trade name: CM-5, manufactured by Konica Minolta Sensing) (described as weather resistance (Δb) in Tables 1 to 4 described later). At the same time, substrate adhesion (described as weather resistance (adhesion) in Tables 1 to 4 described later) was evaluated based on JIS K-5400.
（耐湿性）
温度６０℃、湿度９０％Ｒ．Ｈ．（相対湿度）の環境下で５００時間後の基材密着性をＪＩＳ Ｋ−５４００に基づき評価した。(Moisture resistance)
Temperature 60 ° C., humidity 90% H. The substrate adhesion after 500 hours in an environment of (relative humidity) was evaluated based on JIS K-5400.
各実施例、比較例で用いた（Ａ）成分〜（Ｅ）成分は以下のとおりである。 The components (A) to (E) used in each example and comparative example are as follows.
（Ａ１）成分：脂肪族ウレタンアクリレートオリゴマー（商品名：アートレジンＵＮ−９０４、根上工業社製、エネルギー線硬化性官能基数：１０、質量平均分子量４９００）である。 (A1) Component: Aliphatic urethane acrylate oligomer (trade name: Art Resin UN-904, manufactured by Negami Kogyo Co., Ltd., number of energy ray-curable functional groups: 10, mass average molecular weight 4900).
（Ａ２）成分：脂肪族ウレタンアクリレートオリゴマー（商品名：アートレジンＵＮ−３３２０ＨＳ、根上工業社製、エネルギー線硬化性官能基数：１５、質量平均分子量４９００）である。 (A2) Component: Aliphatic urethane acrylate oligomer (trade name: Art Resin UN-3320HS, manufactured by Negami Kogyo Co., Ltd., number of energy ray-curable functional groups: 15, mass average molecular weight 4900).
（Ｂ１）成分：ベンゾトリアゾール系紫外線吸収剤（商品名：ＵＬＳ−１９３３Ｄ、一方社油脂工業社製）である。 Component (B1): a benzotriazole-based ultraviolet absorber (trade name: ULS-1933D, manufactured by Otsuka Kogyo Co., Ltd.).
（Ｂ２）成分：トリアジン系紫外線吸収剤（商品名：チヌビン４７７、ＢＡＳＦ社製）である。 Component (B2): a triazine-based ultraviolet absorber (trade name: Tinuvin 477, manufactured by BASF).
（Ｃ）成分：ヒンダードアミン系光安定剤（商品名：チヌビン７６５、ＢＡＳＦ社製）である。 Component (C): a hindered amine light stabilizer (trade name: Tinuvin 765, manufactured by BASF).
（Ｄ１）成分：ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド（商品名：イルガキュア８１９、ＢＡＳＦ社製）である。 Component (D1): bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: Irgacure 819, manufactured by BASF).
（Ｄ２）成分：２−メチル−１−［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オン（商品名：イルガキュア９０７、ＢＡＳＦ社製）である。 (D2) Component: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name: Irgacure 907, manufactured by BASF).
（Ｅ）成分：ジペンタエリスリトールヘキサアクリレートモノマー（商品名：Ａ−ＤＰＨ、新中村化学工業社製、エネルギー線硬化性官能基数：６、質量平均分子量５７８）である。 (E) Component: Dipentaerythritol hexaacrylate monomer (trade name: A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd., number of energy ray-curable functional groups: 6, mass average molecular weight 578).
他の紫外線吸収剤：ベンゾフェノン系紫外線吸収剤（商品名：ＬＳ−９０７、一方社油脂工業社製）である。 Other ultraviolet absorbers: Benzophenone-based ultraviolet absorbers (trade name: LS-907, manufactured by Yushi Kogyo Co., Ltd.).
レベリング剤：ポリエーテル変性ポリジメチルシロキサン（商品名：ＢＹＫ−３３１、ビックケミー・ジャパン社製） Leveling agent: Polyether-modified polydimethylsiloxane (trade name: BYK-331, manufactured by Big Chemie Japan)
実施例１
（Ａ１）１００質量部、（Ｂ１）５質量部、（Ｃ）１質量部、（Ｄ１）３質量部、（Ｄ２）４質量部に、レベリング剤０．２５質量部、メチルエチルケトン（ＭＥＫ）７５質量部、プロピレングリコールモノメチルエーテル（ＰＧＭ）７５質量部を加え、撹拌、添加することにより固形分が４３％のハードコート液を調製した。次に、この塗工液を、厚さ１８８μｍのＰＥＴフィルム（商品名：コスモシャインＡ４３００、東洋紡社製）の表面に、ワイヤーバーを用いて塗布し、８０℃で２分乾燥、高圧水銀等を３００ｍＪ／ｃｍ２照射で硬化することにより膜厚６μｍのハードコート層を形成した。このものの物性を表１に示す。Example 1
(A1) 100 parts by mass, (B1) 5 parts by mass, (C) 1 part by mass, (D1) 3 parts by mass, (D2) 4 parts by mass, leveling agent 0.25 parts by mass, methyl ethyl ketone (MEK) 75 parts by mass And 75 parts by mass of propylene glycol monomethyl ether (PGM) were added, and the mixture was stirred and added to prepare a hard coat solution having a solid content of 43%. Next, this coating solution is applied to the surface of a 188 μm-thick PET film (trade name: Cosmo Shine A4300, manufactured by Toyobo Co., Ltd.) using a wire bar, dried at 80 ° C. for 2 minutes, and high-pressure mercury is applied. A hard coat layer having a film thickness of 6 μm was formed by curing with 300 mJ / cm 2 irradiation. The physical properties of this product are shown in Table 1.
実施例２〜１７
表１〜３に示す組成のエネルギー線硬化型樹脂組成物をそれぞれ用い、実施例１と同様にしてハードコートフィルムを作製した。これらのハードコートフィルムの物性を表１〜３に示す。Examples 2-17
A hard coat film was produced in the same manner as in Example 1 using the energy ray curable resin compositions having the compositions shown in Tables 1 to 3, respectively. The physical properties of these hard coat films are shown in Tables 1-3.
比較例１〜６
表４に示す組成のハードコート液をそれぞれ用い、実施例１と同様にしてハードコートフィルムを作製した。これらのハードコートフィルムの物性を表４に示す。Comparative Examples 1-6
A hard coat film was prepared in the same manner as in Example 1 using the hard coat liquid having the composition shown in Table 4. Table 4 shows the physical properties of these hard coat films.
（評価）
表１〜３を見ると、実施例１〜１７の何れにおいても鉛筆硬度は３Ｈであり、塗膜硬度に優れていることが理解できる。また、耐擦傷性の評価においても何れも３０回を超えており、耐擦傷性に優れていることが理解できる。実施例４を見ると、（Ｃ）成分の添加量が少量であるため他の実施例と比較して耐候性の点でやや不足する結果となった。実施例８においては、（Ｄ１）成分の配合量が（Ｄ２）成分の配合量よりも多いため耐湿性がやや不足していることが理解できる。実施例８と１７を見ると、（Ａ１）成分の一部を（Ｅ）成分に置き換えたことにより、耐湿性が向上していることが理解できる。(Evaluation)
When looking at Tables 1-3, in any of Examples 1-17, pencil hardness is 3H and it can be understood that it is excellent in coating-film hardness. In addition, in the evaluation of scratch resistance, all exceeded 30 times, and it can be understood that the scratch resistance is excellent. When Example 4 was seen, since the addition amount of the component (C) was small, the result was slightly insufficient in terms of weather resistance as compared with other examples. In Example 8, since the blending amount of the component (D1) is larger than the blending amount of the component (D2), it can be understood that the moisture resistance is slightly insufficient. When Example 8 and 17 is seen, it can be understood that moisture resistance is improved by replacing part of the component (A1) with the component (E).
一方、表４を見ると比較例１では（Ｂ１）成分の配合量が少ないため、耐候性に劣ることが理解できる。比較例２においては、（Ｂ１）成分の配合量が多いため、耐擦傷性、耐候性の基材密着性、耐湿性に劣ることが理解できる。比較例３においては、（Ｃ）成分を添加していないため耐候性の黄変度（Δｂ）の評価において劣ることが理解できる。比較例４、５において、（Ｄ１）成分と（Ｄ２）成分とを併用していないため、耐湿性、耐擦傷性が著しく劣ることが理解できる。なお、比較例４、５と実施例１とを比較すると、実施例１は（Ｄ１）成分と（Ｄ２）成分を併用することにより、耐擦傷性と耐湿性が著しく向上することも理解できる。比較例６を見ると他の紫外線吸収剤を使用したことにより、耐候性、耐湿性において劣っていることが理解できる。 On the other hand, it can be understood from Table 4 that in Comparative Example 1, since the blending amount of the component (B1) is small, the weather resistance is poor. In Comparative Example 2, it can be understood that since the blending amount of the component (B1) is large, it is inferior in scratch resistance, weather resistance substrate adhesion, and moisture resistance. In Comparative Example 3, since the component (C) is not added, it can be understood that the evaluation of weathering yellowing degree (Δb) is inferior. In Comparative Examples 4 and 5, since the component (D1) and the component (D2) are not used in combination, it can be understood that the moisture resistance and scratch resistance are remarkably inferior. In addition, comparing Comparative Examples 4 and 5 with Example 1, it can also be understood that in Example 1, the scratch resistance and moisture resistance are remarkably improved by using the component (D1) and the component (D2) in combination. When Comparative Example 6 is seen, it can be understood that the use of other ultraviolet absorbers is inferior in weather resistance and moisture resistance.
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| JP6533046B2 (en) * | 2013-09-24 | 2019-06-19 | ソマール株式会社 | Coating composition and hard coat film using the same |
| CN104819929A (en) * | 2015-04-16 | 2015-08-05 | 中国第一汽车股份有限公司 | Detection method for quickly evaluating weatherability of coating |
| WO2018070438A1 (en) * | 2016-10-12 | 2018-04-19 | 日産化学工業株式会社 | Light-fast hard coat material |
| JP6933460B2 (en) * | 2016-12-21 | 2021-09-08 | アイカ工業株式会社 | UV curable resin composition and weather resistant hard coat film |
| JP6531969B2 (en) * | 2017-04-27 | 2019-06-19 | Dic株式会社 | Active energy ray curable composition and hard coat film |
| EP3632978A4 (en) * | 2017-06-02 | 2020-06-03 | Toppan Printing Co., Ltd. | Resin molded body, laminate and decorative sheet |
| JP2020117586A (en) | 2019-01-22 | 2020-08-06 | 株式会社リコー | Curable composition, storage container, two-dimensional or three-dimensional image forming apparatus, two-dimensional or three-dimensional image forming method, and cured product |
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| JPH1060307A (en) * | 1996-08-27 | 1998-03-03 | Asahi Glass Co Ltd | Ultraviolet-curable coating composition and its use |
| JPH1177878A (en) * | 1997-07-11 | 1999-03-23 | Asahi Glass Co Ltd | Transparent coated molding |
| JP2007038150A (en) * | 2005-08-03 | 2007-02-15 | Toyoda Gosei Co Ltd | Method for forming multi-layer coating film, paint to be used therein, and coated article |
| JP2009533242A (en) * | 2006-04-08 | 2009-09-17 | バイエル・マテリアルサイエンス・アクチェンゲゼルシャフト | UV curable protective layer for thermoplastic substrates |
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| JPH09157315A (en) | 1995-12-06 | 1997-06-17 | Daicel U C B Kk | Ultraviolet-curable resin raw material composition, resin molding surface-modified therewith, and production of the molding |
| JP2003176454A (en) * | 2001-12-12 | 2003-06-24 | Gen Gijutsu Kenkyusho:Kk | Method for forming cured coating film |
| JP2010215754A (en) * | 2009-03-16 | 2010-09-30 | Dic Corp | Active energy ray-curable composition and coated article |
| JP2012081742A (en) * | 2010-09-16 | 2012-04-26 | Mitsubishi Chemicals Corp | Laminate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH1060307A (en) * | 1996-08-27 | 1998-03-03 | Asahi Glass Co Ltd | Ultraviolet-curable coating composition and its use |
| JPH1177878A (en) * | 1997-07-11 | 1999-03-23 | Asahi Glass Co Ltd | Transparent coated molding |
| JP2007038150A (en) * | 2005-08-03 | 2007-02-15 | Toyoda Gosei Co Ltd | Method for forming multi-layer coating film, paint to be used therein, and coated article |
| JP2009533242A (en) * | 2006-04-08 | 2009-09-17 | バイエル・マテリアルサイエンス・アクチェンゲゼルシャフト | UV curable protective layer for thermoplastic substrates |
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| KR20150035753A (en) | 2015-04-07 |
| TWI591138B (en) | 2017-07-11 |
| KR102097311B1 (en) | 2020-04-06 |
| JP6348840B2 (en) | 2018-06-27 |
| CN104395366A (en) | 2015-03-04 |
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