JP6859874B2 - Active energy ray-curable resin composition and laminate - Google Patents
Active energy ray-curable resin composition and laminate Download PDFInfo
- Publication number
- JP6859874B2 JP6859874B2 JP2017128141A JP2017128141A JP6859874B2 JP 6859874 B2 JP6859874 B2 JP 6859874B2 JP 2017128141 A JP2017128141 A JP 2017128141A JP 2017128141 A JP2017128141 A JP 2017128141A JP 6859874 B2 JP6859874 B2 JP 6859874B2
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- Prior art keywords
- component
- active energy
- energy ray
- resin composition
- curable resin
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims description 45
- -1 polyethylene terephthalate Polymers 0.000 claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
- 239000000178 monomer Substances 0.000 claims description 33
- 229920000642 polymer Polymers 0.000 claims description 23
- 239000010419 fine particle Substances 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- 150000001412 amines Chemical class 0.000 claims description 11
- 125000000524 functional group Chemical group 0.000 claims description 11
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000011164 primary particle Substances 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 125000003386 piperidinyl group Chemical group 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 229920005668 polycarbonate resin Polymers 0.000 claims description 5
- 239000004431 polycarbonate resin Substances 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 51
- 239000007787 solid Substances 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 14
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 13
- 238000005299 abrasion Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 11
- 239000003513 alkali Substances 0.000 description 11
- 239000003999 initiator Substances 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 7
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 125000004386 diacrylate group Chemical group 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 239000012964 benzotriazole Substances 0.000 description 4
- 239000008119 colloidal silica Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- NWPIOULNZLJZHU-UHFFFAOYSA-N (1,2,2,6,6-pentamethylpiperidin-4-yl) 2-methylprop-2-enoate Chemical compound CN1C(C)(C)CC(OC(=O)C(C)=C)CC1(C)C NWPIOULNZLJZHU-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- DPNXHTDWGGVXID-UHFFFAOYSA-N 2-isocyanatoethyl prop-2-enoate Chemical compound C=CC(=O)OCCN=C=O DPNXHTDWGGVXID-UHFFFAOYSA-N 0.000 description 3
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- FDUFQLNPPGRIKX-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CC(C)(CO)CO FDUFQLNPPGRIKX-UHFFFAOYSA-N 0.000 description 2
- ONTODYXHFBKCDK-UHFFFAOYSA-N 2-(2,4-dimethylphenyl)-1,3,5-triazine Chemical compound CC1=CC(C)=CC=C1C1=NC=NC=N1 ONTODYXHFBKCDK-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- VMRIVYANZGSGRV-UHFFFAOYSA-N 4-phenyl-2h-triazin-5-one Chemical compound OC1=CN=NN=C1C1=CC=CC=C1 VMRIVYANZGSGRV-UHFFFAOYSA-N 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 102100026735 Coagulation factor VIII Human genes 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 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 class 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
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
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- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000008199 coating composition Substances 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
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- 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
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- 238000010438 heat treatment Methods 0.000 description 2
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- 239000004615 ingredient Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- 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
- 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
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
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- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 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
- AUFZRCJENRSRLY-UHFFFAOYSA-N 2,3,5-trimethylhydroquinone Chemical compound CC1=CC(O)=C(C)C(C)=C1O AUFZRCJENRSRLY-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- ZMWRRFHBXARRRT-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(N2N=C3C=CC=CC3=N2)=C1O ZMWRRFHBXARRRT-UHFFFAOYSA-N 0.000 description 1
- LHPPDQUVECZQSW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-ditert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=CC=CC3=N2)=C1O LHPPDQUVECZQSW-UHFFFAOYSA-N 0.000 description 1
- AQROEYPMNFCJCK-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-6-tert-butyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=CC=CC3=N2)=C1O AQROEYPMNFCJCK-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- JCGAFSOOJHZRCB-UHFFFAOYSA-N 2-[(3,5-ditert-butyl-4-hydroxyphenyl)methoxycarbonyl]hexanoic acid Chemical compound CCCCC(C(O)=O)C(=O)OCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 JCGAFSOOJHZRCB-UHFFFAOYSA-N 0.000 description 1
- 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
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical group OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-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
- 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
- BSMGLVDZZMBWQB-UHFFFAOYSA-N 2-methyl-1-phenylpropan-1-one Chemical compound CC(C)C(=O)C1=CC=CC=C1 BSMGLVDZZMBWQB-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 1
- DRXGKQPTFWTTJW-UHFFFAOYSA-N 5-butoxy-2-[4-(4-butoxy-2-hydroxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazin-2-yl]phenol Chemical compound OC1=CC(OCCCC)=CC=C1C1=NC(C=2C(=CC(OCCCC)=CC=2)O)=NC(C=2C(=CC(OCCCC)=CC=2)OCCCC)=N1 DRXGKQPTFWTTJW-UHFFFAOYSA-N 0.000 description 1
- OCIFJWVZZUDMRL-UHFFFAOYSA-N 6-hydroxyhexyl prop-2-enoate Chemical compound OCCCCCCOC(=O)C=C OCIFJWVZZUDMRL-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 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
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- YRXGUZPUZBCGST-UHFFFAOYSA-N [2-(hydroxymethoxy)phenyl]-phenylmethanone Chemical compound OCOC1=CC=CC=C1C(=O)C1=CC=CC=C1 YRXGUZPUZBCGST-UHFFFAOYSA-N 0.000 description 1
- GLLSGHWYBGERSE-UHFFFAOYSA-N [2-(hydroxymethoxy)phenyl]-phenylmethanone;sodium Chemical compound [Na].OCOC1=CC=CC=C1C(=O)C1=CC=CC=C1 GLLSGHWYBGERSE-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 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
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 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
- SODJJEXAWOSSON-UHFFFAOYSA-N bis(2-hydroxy-4-methoxyphenyl)methanone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=C(OC)C=C1O SODJJEXAWOSSON-UHFFFAOYSA-N 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
- AEQPIBDYEXHEKN-UHFFFAOYSA-N butyl acetate;ethanol Chemical compound CCO.CCCCOC(C)=O AEQPIBDYEXHEKN-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 150000002027 dodecanoic acid esters Chemical class 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
- 238000002296 dynamic light scattering Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- DAHPIMYBWVSMKQ-UHFFFAOYSA-N n-hydroxy-n-phenylnitrous amide Chemical compound O=NN(O)C1=CC=CC=C1 DAHPIMYBWVSMKQ-UHFFFAOYSA-N 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007767 slide coating Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Description
本発明は、活性エネルギー線硬化性樹脂組成物及び積層体に関する。 The present invention relates to an active energy ray-curable resin composition and a laminate.
熱可塑性樹脂であるポリカーボネート樹脂、ポリアクリル樹脂、ポリエステル樹脂、ポリエチレン樹脂、ポリスチレン樹脂等は透明性が高く、更に軽量で優れた耐衝撃性を有することから、ガラス代替基材として、例えば、ヘッドランプ用カバー、グレージング等の自動車用プラスチック材料、サンルーフ、建築材料等の用途に利用されている。このような用途では、ガラス並みの耐侯性に加えて、自動車のフロントガラスにワイパーをかける、又はサイドガラスを昇降させる際に傷が付かない、いわゆる耐磨耗性が要求されているが、前記基材では充分でないことが知られている。 Polycarbonate resin, polyacrylic resin, polyester resin, polyethylene resin, polystyrene resin, etc., which are thermoplastic resins, are highly transparent, lightweight, and have excellent impact resistance. Therefore, as a glass substitute base material, for example, a head lamp It is used for automobile covers, plastic materials for automobiles such as glazing, sun roofs, building materials, etc. In such applications, in addition to the weather resistance comparable to that of glass, so-called wear resistance is required so that the windshield of an automobile is not scratched when the wiper is applied or the side glass is raised and lowered. It is known that wood is not enough.
これらの欠点を解決するために、例えば、特定数のアクリロイル基を有するウレタンアクリレート、アセトフェノン系光重合開始剤、ホスフィンオキサイド系光重合開始剤、紫外線吸収剤及び光安定剤をそれぞれ特定量含有する紫外線硬化性塗料組成物と、当該組成物を基材に塗装した塗装物品（特許文献１）が公知である。当該塗料組成物の成分には、ナノシリカを分散させたナノコンポジット型ウレタンアクリレートが用いられているが、塗装物品とした際に、耐磨耗性が不充分であった。また、エポキシ基を含有するラジカル重合性ビニル単量体を必須成分とした共重合体に、カルボキシル基を有する単量体を反応させた反応物に、特定のビニル化合物とシリカ微粒子を含有した活性エネルギー線硬化型樹脂組成物（特許文献２）も公知である。しかしながら、当該樹脂組成物の耐侯性が充分でなく、また耐磨耗性を持たせるために、シリカ微粒子を樹脂組成物中に配合させているが、シリカ微粒子は親水性が高く、耐アルカリ性を低下させるものであった。 In order to solve these drawbacks, for example, ultraviolet rays containing a specific amount of urethane acrylate having a specific number of acryloyl groups, an acetophenone-based photopolymerization initiator, a phosphine oxide-based photopolymerization initiator, an ultraviolet absorber, and a light stabilizer. A curable coating composition and a coated article (Patent Document 1) in which the composition is coated on a base material are known. A nanocomposite type urethane acrylate in which nanosilica is dispersed is used as a component of the coating composition, but the abrasion resistance is insufficient when it is used as a painted article. Further, the activity of containing a specific vinyl compound and silica fine particles in a reaction product obtained by reacting a copolymer having a radically polymerizable vinyl monomer containing an epoxy group as an essential component with a monomer having a carboxyl group. An energy ray-curable resin composition (Patent Document 2) is also known. However, the weather resistance of the resin composition is not sufficient, and silica fine particles are blended in the resin composition in order to have abrasion resistance. However, the silica fine particles are highly hydrophilic and have alkali resistance. It was something to reduce.
本発明は、耐アルカリ性及び耐侯性に優れた硬化被膜を形成する活性エネルギー線硬化型樹脂組成物を提供することを目的とする。 An object of the present invention is to provide an active energy ray-curable resin composition that forms a cured film having excellent alkali resistance and weather resistance.
本発明者は、前記課題の要因がシリカ微粒子の親水性にあることに着目し、鋭意検討したところ、重合体中にシリカの親水性官能基と相互作用するピペリジニル基を組み込み、更に不飽和二重結合を導入し、シリカ微粒子の極性基を保護しつつ、更に光重合時に重合体を介して他の化合物との結合力を向上させることで得られた活性エネルギー線硬化型樹脂組成物が耐アルカリ性及び耐侯性に優れることを見出し、本発明を完成させるに至った。すなわち、本発明は以下の活性エネルギー線硬化性樹脂組成物及び積層体に関する。 The present inventor paid attention to the fact that the cause of the problem was the hydrophilicity of the silica fine particles, and as a result of diligent studies, incorporated a piperidinyl group that interacts with the hydrophilic functional group of silica in the polymer, and further unsaturated double bonds. The active energy ray-curable resin composition obtained by introducing a double bond to protect the polar groups of the silica fine particles and further improving the bonding force with other compounds via a polymer during photopolymerization is resistant. We have found that it is excellent in alkalinity and weather resistance, and have completed the present invention. That is, the present invention relates to the following active energy ray-curable resin compositions and laminates.
１．一分子中に不飽和二重結合及びピペリジニル基を有する重合体（Ａ）１０〜６０重量％、
分子中に不飽和二重結合を２つ有する化合物（Ｂ）１０〜６０重量％、
及び
平均一次粒子径が２０〜８０ｎｍである金属酸化物微粒子（Ｄ）２０〜６０重量％
を含有する活性エネルギー線硬化性樹脂組成物。
1. 1. Polymer (A) having an unsaturated double bond and a piperidinyl group in one molecule, 10 to 60% by weight,
Compound (B) having two unsaturated double bonds in the molecule (B) 10-60% by weight,
And 20 to 60% by weight of the metal oxide fine particles (D) having an average primary particle size of 20 to 80 nm.
An active energy ray-curable resin composition containing.
２．（Ａ）成分が、
エポキシ基、水酸基及びイソシアネート基からなる群より選ばれる少なくとも１種の官能基を有する単量体（ａ１）、並びにピペリジニル基を有する単量体（ａ２）を含む単量体成分の重合体（Ａ１）と、
（Ａ１）成分が有する官能基と反応し得る、官能基を有する単量体（ａ４）との反応生成物である、前項１の活性エネルギー線硬化性樹脂組成物。
2. The component (A) is
A polymer (A1) of a monomer component containing a monomer (a1) having at least one functional group selected from the group consisting of an epoxy group, a hydroxyl group and an isocyanate group, and a monomer (a2) having a piperidinyl group. )When,
The active energy ray-curable resin composition according to item 1 above, which is a reaction product with a monomer (a4) having a functional group, which can react with the functional group of the component (A1).
３．（Ａ１）成分をなす単量体成分に、更に（ａ１）成分又は（ａ２）成分と共重合しうる単量体（ａ３）が含まれる、前項２の活性エネルギー線硬化性樹脂組成物。 3. 3. The active energy ray-curable resin composition according to item 2 above, wherein the monomer component forming the component (A1) further contains a monomer (a3) capable of copolymerizing with the component (a1) or the component (a2).
４．（ａ２）成分が、一般式（１）で表される前項１〜３のいずれかの活性エネルギー線硬化性樹脂組成物。
５．（Ａ）成分の二重結合当量が、２５０〜２０００ｅｑ／ｇであり、かつアミン当量が４００〜３０００ｅｑ／ｇである、前項１〜４のいずれかの活性エネルギー線硬化性樹脂組成物。 5. The active energy ray-curable resin composition according to any one of the above items 1 to 4, wherein the double bond equivalent of the component (A) is 250 to 2000 eq / g, and the amine equivalent is 400 to 3000 eq / g.
６．更に、分子中に不飽和二重結合を３つ以上有する化合物（Ｃ）を含有する前項１〜５のいずれかの活性エネルギー線硬化性樹脂組成物。 6. Further, the active energy ray-curable resin composition according to any one of the above items 1 to 5, which contains a compound (C) having three or more unsaturated double bonds in the molecule.
７．（Ｄ）成分が、シリカ、ジルコニア及びアルミナからなる群より選ばれる１種以上である、前項１〜６のいずれかの活性エネルギー線硬化性樹脂組成物。 7. The active energy ray-curable resin composition according to any one of the above items 1 to 6, wherein the component (D) is at least one selected from the group consisting of silica, zirconia and alumina.
８．前項１〜７のいずれかの活性エネルギー線硬化性樹脂組成物の硬化被膜を基材の表面に有する積層体。 8. A laminate having a cured film of the active energy ray-curable resin composition according to any one of the above items 1 to 7 on the surface of a base material.
９．基材が、ポリカーボネート樹脂、ポリアクリル樹脂及びポリエチレンテレフタレートからなる群より選ばれる少なくとも１種である前項８の積層体。 9. The laminate according to item 8 above, wherein the base material is at least one selected from the group consisting of polycarbonate resin, polyacrylic resin and polyethylene terephthalate.
本発明によれば、耐アルカリ性及び耐侯性に優れた硬化被膜を形成する活性エネルギー線硬化性樹脂組成物が得られる。また前記樹脂組成物は、各種プラスチックフィルムや成形体に適用可能であるが、特にハードコート用コーティング剤として好適であり、ヘッドランプ用カバー、樹脂グレージング等の自動車用プラスチック材料、サンルーフ、建築材料、透明エクステリア部材等の用途に有用である。 According to the present invention, an active energy ray-curable resin composition that forms a cured film having excellent alkali resistance and weather resistance can be obtained. Further, the resin composition can be applied to various plastic films and molded products, but is particularly suitable as a coating agent for hard coats, such as headlamp covers, resin glazing and other automobile plastic materials, sunroofs, building materials, etc. It is useful for applications such as transparent exterior members.
本発明の活性エネルギー線硬化性樹脂組成物は、一分子中に不飽和二重結合及びピペリジニル基を有する重合体（Ａ）（以下、（Ａ）成分という）１０〜６０重量％、分子中に不飽和二重結合を２つ有する化合物（Ｂ）（以下、（Ｂ）成分という）１０〜６０重量％、及び平均一次粒子径が２０〜８０ｎｍである金属酸化物微粒子（Ｄ）（以下、（Ｄ）成分という）２０〜６０重量％を含有することを特徴とする。 The active energy ray-curable resin composition of the present invention contains 10 to 60% by weight of a polymer (A) (hereinafter referred to as component (A)) having an unsaturated double bond and a piperidinyl group in one molecule. Compound (B) having two unsaturated double bonds (hereinafter referred to as component (B)) 10 to 60% by weight, and metal oxide fine particles (D) having an average primary particle size of 20 to 80 nm (hereinafter, (hereinafter referred to as (B) component). D) It is characterized by containing 20 to 60% by weight (referred to as a component).
（Ａ）成分としては、一分子中に不飽和二重結合及びピペリジニル基を有するものであれば、特に限定されず、各種公知のものを使用できる。具体的には、エポキシ基、水酸基及びイソシアネート基からなる群より選ばれる少なくとも１種の官能基を有する単量体（ａ１）（以下、（ａ１）成分という）、並びにピペリジニル基を有する単量体（ａ２）（以下、（ａ２）成分という）を含む単量体成分の重合体（Ａ１）（以下、（Ａ１）成分という）と、（Ａ１）成分が有する官能基と反応し得る、官能基を有する単量体（ａ４）（以下、（ａ４）成分という）との反応生成物等が挙げられる。 The component (A) is not particularly limited as long as it has an unsaturated double bond and a piperidinyl group in one molecule, and various known components can be used. Specifically, a monomer (a1) having at least one functional group selected from the group consisting of an epoxy group, a hydroxyl group and an isocyanate group (hereinafter, referred to as a component (a1)), and a monomer having a piperidinyl group. A polymer (A1) (hereinafter referred to as (A1) component) of a monomer component containing (a2) (hereinafter referred to as (a2) component) and a functional group capable of reacting with the functional group of the (A1) component. Examples thereof include reaction products with the monomer (a4) having (a4) (hereinafter, referred to as the component (a4)).
（ａ１）成分の内、エポキシ基を有する単量体としては、特に限定されないが、例えば、グリシジル（メタ）アクリレート、β−メチルグリシジル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレートグリシジルエーテル、３，４−エポキシシクロヘキシルメチル（メタ）アクリレート、１，２−エポキシー４−ビニルシクロヘキサン等が挙げられる。これらは単独でも２種以上を組み合わせても良い。これらの中でも、グリシジル（メタ）アクリレートが好ましい。 Among the components (a1), the monomer having an epoxy group is not particularly limited, and for example, glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and the like. Examples thereof include 3,4-epoxycyclohexylmethyl (meth) acrylate and 1,2-epoxide-4-vinylcyclohexane. These may be used alone or in combination of two or more. Among these, glycidyl (meth) acrylate is preferable.
（ａ１）成分の内、水酸基を有する単量体としては、特に限定されないが、例えば、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、３−ヒドロキシプロピルアクリレート、３−ヒドロキシブチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、６−ヒドロキシヘキシルアクリレート、グリセリンモノ（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート等が挙げられる。これらは単独でも２種以上を組み合わせても良い。これらの中でも、２−ヒドロキシエチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレートが好ましい。 Among the components (a1), the monomer having a hydroxyl group is not particularly limited, and is, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl acrylate, 3-hydroxy. Examples thereof include butyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl acrylate, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) acrylate. These may be used alone or in combination of two or more. Among these, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable.
（ａ１）成分の内、イソシアネート基を有する単量体としては、特に限定されないが、例えば、２−イソシアナトエチル（メタ）アクリレート、１，１−（ビスアクリロイルオキシメチル）エチルイソシアネート、アクリル酸２−（２−イソシアネートエトキシ）エチル等が挙げられる。これらは単独でも２種以上を組み合わせても良い。これらの中でも、２−イソシアナトエチル（メタ）アクリレートが好ましい。 Among the components (a1), the monomer having an isocyanate group is not particularly limited, and for example, 2-isocyanatoethyl (meth) acrylate, 1,1- (bisacryloyloxymethyl) ethyl isocyanate, acrylic acid 2 -(2-Isocyanateethoxy) ethyl and the like can be mentioned. These may be used alone or in combination of two or more. Among these, 2-isocyanatoethyl (meth) acrylate is preferable.
（ａ２）成分は、ピペリジニル基を有するものであり、（Ａ１）成分の骨格として組み込まれることで、耐アルカリ性及び耐侯性に寄与する。（ａ２）成分としては、特に限定されず、各種公知のものを使用できる。例えば、２，２，６，６−テトラメチル−４−ピペリジル（メタ）アクリレート、１，２，２，６、６−ペンタメチル−４−ピペリジル（メタ）アクリレート、１−エチル−２，２，６，６−テトラメチル−４−ピペリジル（メタ）アクリレート、１−プロピル−２，２，６，６−テトラメチル−４−ピペリジル（メタ）アクリレート、１−ｔ−ブチル−２，２，６，６−テトラメチル−４−ピペリジル（メタ）アクリレート、１−シクロヘキシル−２，２，６，６−テトラメチル−４−ピペリジル（メタ）アクリレート、１−（４−メチルシクロヘキシル）−２，２，６，６−テトラメチル−４−ピペリジル（メタ）アクリレート、１−ｔ−オクチル−２，２，６，６−テトラメチル−４−ピペリジル（メタ）アクリレート、１−デシル−２，２，６，６−テトラメチル−４−ピペリジル（メタ）アクリレート、１−ドデシル−２，２，６，６−テトラメチル−４−ピペリジル（メタ）アクリレート、ビス−（２，２，６，６−テトラメチル−４−ピペリジニル）セバケート、ビス−（ｎ−メチル−２，２，６，６−テトラメチル−４−ピペリジニル）セバケート、ビス−（１，２，２，６，６−ペンタメチル−４−ピペリジル）−２−（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）−２−ｎ−ブチルマロネート、等が挙げられる。これらは単独でも２種以上を組み合わせても良い。これらの中でも、下記式（１）で表される単量体が好ましく、１，２，２，６、６−ペンタメチル−４−ピペリジル（メタ）アクリレートがより好ましい。 The component (a2) has a piperidinyl group, and by incorporating it as the skeleton of the component (A1), it contributes to alkali resistance and weather resistance. The component (a2) is not particularly limited, and various known components can be used. For example, 2,2,6,6-tetramethyl-4-piperidyl (meth) acrylate, 1,2,2,6,6-pentamethyl-4-piperidyl (meth) acrylate, 1-ethyl-2,2,6 , 6-Tetramethyl-4-piperidyl (meth) acrylate, 1-propyl-2,2,6,6-tetramethyl-4-piperidyl (meth) acrylate, 1-t-butyl-2,2,6,6 -Tetramethyl-4-piperidyl (meth) acrylate, 1-cyclohexyl-2,2,6,6-tetramethyl-4-piperidyl (meth) acrylate, 1- (4-methylcyclohexyl) -2,2,6 6-Tetramethyl-4-piperidyl (meth) acrylate, 1-t-octyl-2,2,6,6-tetramethyl-4-piperidyl (meth) acrylate, 1-decyl-2,2,6,6- Tetramethyl-4-piperidyl (meth) acrylate, 1-dodecyl-2,2,6,6-tetramethyl-4-piperidyl (meth) acrylate, bis- (2,2,6,6-tetramethyl-4- Piperidinyl) sebacate, bis- (n-methyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis- (1,2,2,6,6-pentamethyl-4-piperidyl) -2- Examples thereof include (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate. These may be used alone or in combination of two or more. Among these, the monomer represented by the following formula (1) is preferable, and 1,2,2,6,6-pentamethyl-4-piperidyl (meth) acrylate is more preferable.
（ａ２）成分の使用量としては、特に限定されず、（Ａ）成分のアミン当量が４５０〜３０００ｅｑ／ｇとなるように、適宜調整されるものである。 The amount of the component (a2) used is not particularly limited, and is appropriately adjusted so that the amine equivalent of the component (A) is 450 to 3000 eq / g.
前記単量体には、任意ではあるが、（Ａ）成分及び（Ｂ）成分、並びに／又は(Ａ)成分及び（Ｄ）成分との相溶性を高めるために、（ａ１）成分又は（ａ２）成分と共重合しうる単量体（ａ３）（以下、（ａ３）成分という）を含有しても良い。 The monomer contains, although optional, the component (a1) or the component (a2) in order to enhance the compatibility with the components (A) and (B) and / or the components (A) and (D). ) May contain a monomer (a3) that can be copolymerized with the component (hereinafter, referred to as the component (a3)).
（ａ３）成分としては、特に限定されないが、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート等のアルキル（メタ）アクリレート；イソボルニル（メタ）アクリレート等の脂環式（メタ）アクリレート；アクリロイルモルフォリン等のヘテロ原子を含む（メタ）アクリレート；スチレン、α−メチルスチレン、ビニルトルエン等の芳香族単量体；酢酸ビニル、プロピオン酸ビニル、（メタ）アクリロニトリル、（メタ）アクリルアミド、α−オレフィン等が挙げられる。これらは単独でも２種以上を組み合わせても良い。これらの中では、硬化被膜の耐磨耗性の点から、スチレン、メチルメタクリレート、イソボルニルメタクリレートが好ましい。また、（ａ３）成分の使用量としては、特に限定されないが、得られる硬化被膜の耐摩耗性、耐アルカリ性と耐熱性のバランスから、（ａ１）成分と（ａ３）成分との固形分重量比で１／９〜７／３程度が好ましく、１／５〜５／３程度がより好ましい。 The component (a3) is not particularly limited, but for example, an alkyl (meth) acrylate such as methyl (meth) acrylate and ethyl (meth) acrylate; an alicyclic (meth) acrylate such as isobornyl (meth) acrylate; and acryloylmorpho. (Meta) acrylate containing heteroatoms such as phosphorus; aromatic monomers such as styrene, α-methylstyrene, vinyltoluene; vinyl acetate, vinyl propionate, (meth) acrylonitrile, (meth) acrylamide, α-olefin, etc. Can be mentioned. These may be used alone or in combination of two or more. Among these, styrene, methyl methacrylate, and isobornyl methacrylate are preferable from the viewpoint of abrasion resistance of the cured film. The amount of the component (a3) used is not particularly limited, but the solid content weight ratio of the component (a1) and the component (a3) is determined from the balance between the abrasion resistance, the alkali resistance and the heat resistance of the obtained cured film. It is preferably about 1/9 to 7/3, more preferably about 1/5 to 5/3.
本発明における（Ａ）成分は、（Ａ１）成分としては、（ａ１）成分及び（ａ２）成分、並びに必要に応じて、（ａ３）成分をラジカル重合させることにより得られる。ラジカル重合としては、特に限定されず、公知の方法を適宜選択できるが、例えば、前記成分を重合開始剤の存在下、加熱する方法等が挙げられる。重合条件としては、特に限定されず、通常、温度が４０〜１５０℃程度、好ましくは６０〜１２０℃程度であり、時間が４〜４８時間程度、好ましくは６〜２４時間程度で行われる。 The component (A) in the present invention can be obtained by radically polymerizing the component (a1), the component (a2), and, if necessary, the component (a3) as the component (A1). The radical polymerization is not particularly limited, and a known method can be appropriately selected. Examples thereof include a method of heating the component in the presence of a polymerization initiator. The polymerization conditions are not particularly limited, and the temperature is usually about 40 to 150 ° C., preferably about 60 to 120 ° C., and the time is about 4 to 48 hours, preferably about 6 to 24 hours.
ラジカル重合に用いる重合開始剤としては、特に限定されず、各種公知のものを使用することができ、例えば、過酸化水素、過硫酸アンモニウム、過硫酸カリウム等の無機過酸化物、ベンゾイルパーオキサイド、ジクミルパーオキサイド、ラウリルパーオキサイド等の有機過酸化物、２，２’−アゾビスイソブチロニトリル、ジメチル−２，２’−アゾビスイソブチレート等のアゾ系化合物等が挙げられる。これらは単独でも２種以上を組み合わせてもよい。また、重合開始剤の使用量も特に限定されないが、（ａ１）〜（ａ４）成分の固形分重量での合計量が１００重量部に対して、０．０１〜８重量部程度とすることが好ましい。なお、必要に応じて、連鎖移動剤等を添加してもよい。連鎖移動剤としては、特に限定されず、例えば、ラウリルメルカプタン、ドデシルメルカプタン、２−メルカプトベンゾチアゾール、ブロムトリクロルメタン等が挙げられる。これらは単独でも２種以上を組み合わせてもよい。また、連鎖移動剤の使用量も特に限定されないが、（ａ１）〜（ａ３）成分の合計使用量が１００重量部に対して、０．０１〜５重量部程度とすることが好ましい。 The polymerization initiator used for radical polymerization is not particularly limited, and various known ones can be used. For example, inorganic peroxides such as hydrogen peroxide, ammonium persulfate, and potassium persulfate, benzoyl peroxide, and diku. Examples thereof include organic peroxides such as mill peroxide and lauryl peroxide, and azo compounds such as 2,2'-azobisisobutyronitrile and dimethyl-2,2'-azobisisobutyrate. These may be used alone or in combination of two or more. The amount of the polymerization initiator used is also not particularly limited, but the total amount of the components (a1) to (a4) in terms of solid content may be about 0.01 to 8 parts by weight with respect to 100 parts by weight. preferable. If necessary, a chain transfer agent or the like may be added. The chain transfer agent is not particularly limited, and examples thereof include lauryl mercaptan, dodecyl mercaptan, 2-mercaptobenzothiazole, bromtrichloromethane and the like. These may be used alone or in combination of two or more. The amount of the chain transfer agent used is also not particularly limited, but the total amount of the components (a1) to (a3) used is preferably about 0.01 to 5 parts by weight with respect to 100 parts by weight.
本発明の（Ａ）成分をなす成分である、（ａ４）成分としては、特に限定されず、例えば、前述の（ａ１）成分として例示した水酸基又はイソシアネート基を有する単量体、（メタ）アクリル酸、クロトン酸等の不飽和カルボン酸等が挙げられる。これらは単独でも２種以上を組み合わせても良い。なお、（ａ４）成分の中で好ましい単量体としては、（ａ１）成分に属する単量体の種類によって異なる。 The component (a4), which is a component constituting the component (A) of the present invention, is not particularly limited, and for example, a monomer having a hydroxyl group or an isocyanate group exemplified as the component (a1) described above, (meth) acrylic. Examples thereof include unsaturated carboxylic acids such as acid and crotonic acid. These may be used alone or in combination of two or more. The preferred monomer among the components (a4) differs depending on the type of the monomer belonging to the component (a1).
例えば、（ａ１）成分に属するエポキシ基を有する単量体に対しては、不飽和カルボン酸が好ましく、生成する活性エネルギー線硬化性樹脂組成物の光重合性が良好で、得られた硬化被膜が耐磨耗性に優れる点から、アクリル酸がより好ましい。 For example, an unsaturated carboxylic acid is preferable for a monomer having an epoxy group belonging to the component (a1), and the produced active energy ray-curable resin composition has good photopolymerizability, and the obtained cured film is obtained. Acrylic acid is more preferable because it has excellent abrasion resistance.
（ａ１）成分に属する水酸基を有する単量体に対しては、先述のイソシアネート基を有する単量体であれば特に限定されず、単独でも２種以上を組み合わせても良い。中でも生成する活性エネルギー線硬化性樹脂組成物の光重合性が良好で、得られた硬化被膜が耐磨耗性に優れる点から、２−イソシアナトエチルアクリレート、アクリル酸２−（２−イソシアネートエトキシ）エチルがより好ましい。 The monomer having a hydroxyl group belonging to the component (a1) is not particularly limited as long as it is a monomer having an isocyanate group as described above, and may be used alone or in combination of two or more. Among them, 2-isocyanatoethyl acrylate and 2- (2-isocyanateethoxy) acrylate are excellent in photopolymerizability of the active energy ray-curable resin composition to be produced and the obtained cured film is excellent in abrasion resistance. ) Ethyl is more preferred.
（ａ１）成分に属するイソシアネート基を有する単量体に対しては、水酸基を有する単量体が好ましく、生成する活性エネルギー線硬化性樹脂組成物の光重合性が良好で、得られた硬化被膜が耐磨耗性に優れる点から、２−ヒドロキシエチルアクリレート、４−ヒドロキシブチルアクリレートがより好ましい。 As for the monomer having an isocyanate group belonging to the component (a1), the monomer having a hydroxyl group is preferable, and the active energy ray-curable resin composition to be produced has good photopolymerizability, and the obtained cured film is obtained. 2-Hydroxyethyl acrylate and 4-hydroxybutyl acrylate are more preferable because they are excellent in abrasion resistance.
（ａ４）成分の使用量は、特に限定されないが、（ａ１）成分中の官能基（エポキシ基、水酸基、イソシアネート基）と等モル以下とすることが反応後に（ａ４）成分が残らないため、得られる硬化被膜の耐磨耗性に優れる。 The amount of the component (a4) used is not particularly limited, but the component (a4) does not remain after the reaction if the molar amount is equal to or less than that of the functional group (epoxy group, hydroxyl group, isocyanate group) in the component (a1). The obtained cured film has excellent wear resistance.
本発明の（Ａ）成分としては、各種公知の方法により製造することで得られる。製造方法としては、特に限定されないが、例えば、触媒の存在下、前記（Ａ１）成分及び（ａ４）成分を加熱すること等が挙げられる。触媒としては、例えば、トリフェニルホスフィン、トリシクロヘキシルホスフィン等のホスフィン類；テトラメチルアンモニウムクロライド、トリメチルベンジルアンモニウムクロライド、テトラメチルアンモニウムブロマイド等の４級アンモニウム塩、トリメチルアミン、トリエチルアミン、ベンジルメチルアミン、トリブチルアミン等のアミン類；２−メチルイミダゾール等のイミダゾール類；ジブチル錫ラウレート等のラウリン酸エステル類等が挙げられる。また、触媒の使用量は、特に限定されないが、固形分重量で、（Ａ１）成分と（ａ４）成分との合計量１００重量部に対して、通常、０．０１〜５重量部程度とすることが好ましい。 The component (A) of the present invention can be obtained by producing it by various known methods. The production method is not particularly limited, and examples thereof include heating the components (A1) and (a4) in the presence of a catalyst. Examples of the catalyst include phosphines such as triphenylphosphine and tricyclohexylphosphine; quaternary ammonium salts such as tetramethylammonium chloride, trimethylbenzylammonium chloride and tetramethylammonium bromide, trimethylamine, triethylamine, benzylmethylamine, tributylamine and the like. Amines; imidazoles such as 2-methylimidazole; lauric acid esters such as dibutyltin laurate and the like. The amount of the catalyst used is not particularly limited, but is usually about 0.01 to 5 parts by weight with respect to 100 parts by weight of the total amount of the component (A1) and the component (a4) in terms of solid content weight. Is preferable.
なお、必要に応じて、有機溶媒や重合禁止剤を使用しても良い。有機溶媒としては、（Ａ１）成分、（ａ４）成分と反応しないものであれば、特に限定されず各種公知のものを使用できる。例えば、メチルエチルケトン、メチルイソブチルケトン等のケトン；トルエン、ベンゼン等の芳香族炭化水素；酢酸ブチル、酢酸プロピル、酢酸エチル、プロピレングリコールモノメチルエーテルアセテート等のエステル；エタノール、２−プロパノール、プロピレングリコールモノメチルエーテル等のアルコール；ジグライム、クロロホルム、ジメチルホルムアミド等が挙げられる、これらは単独でも２種以上を組み合わせても良い。重合禁止剤としては、メトキノン、ハイドロキノン、トリメチルハイドロキノン、Ｎ−ニトロソフェニルヒドロキシルアミン等が挙げられる。なお、重合禁止剤の使用量は特に限定されないが、得られるコーティング剤の重合性が悪化する場合があるため、固形分重量で、（Ａ１）成分と（ａ４）成分の合計量１００重量部に対して、通常、１重量部程度以下とすることが好ましい。また、重合を防止するために、反応系中に空気を吹き込む等しても良い。 If necessary, an organic solvent or a polymerization inhibitor may be used. The organic solvent is not particularly limited as long as it does not react with the component (A1) and the component (a4), and various known ones can be used. For example, ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and benzene; esters such as butyl acetate, propyl acetate, ethyl acetate and propylene glycol monomethyl ether acetate; ethanol, 2-propanol, propylene glycol monomethyl ether and the like. Alcohols: Diglime, chloroform, dimethylformamide and the like, which may be used alone or in combination of two or more. Examples of the polymerization inhibitor include methquinone, hydroquinone, trimethylhydroquinone, N-nitrosophenylhydroxylamine and the like. The amount of the polymerization inhibitor used is not particularly limited, but the polymerizable property of the obtained coating agent may deteriorate. Therefore, the total amount of the components (A1) and (a4) is 100 parts by weight in terms of solid content weight. On the other hand, it is usually preferably about 1 part by weight or less. Further, in order to prevent polymerization, air may be blown into the reaction system.
得られた（Ａ）成分の物性としては、特に限定されないが、例えば、二重結合当量が、通常２５０〜２０００ｇ／ｅｑ程度、好ましくは２５０〜１２００ｇ／ｅｑ程度である。二重結合当量を２５０〜２０００ｇ／ｅｑとすることで、得られる硬化被膜の耐磨耗性及び耐熱性が両立できるため好ましい。なお、二重結合当量は、不飽和二重結合１ｍｏｌあたりの重合体の重量で表され、本発明では以下の（式１）で算出される。 The physical properties of the obtained component (A) are not particularly limited, but for example, the double bond equivalent is usually about 250 to 2000 g / eq, preferably about 250 to 1200 g / eq. By setting the double bond equivalent to 250 to 2000 g / eq, it is preferable because both wear resistance and heat resistance of the obtained cured film can be achieved. The double bond equivalent is represented by the weight of the polymer per 1 mol of unsaturated double bond, and is calculated by the following formula (Equation 1) in the present invention.
（式１）二重結合当量（ｇ／ｅｑ）＝［｛（ａ１）〜（ａ４）成分の使用重量（ｇ）｝＋｛開始剤の使用重量（ｇ）｝］／（ａ４）成分の使用モル量（ｍｏｌ） (Equation 1) Double bond equivalent (g / eq) = [{(a1) to (a4) component working weight (g)} + {initiator working weight (g)}] / (a4) component use Amount of mole (mol)
また、（Ａ）成分のアミン当量が、通常４００〜３０００ｇ／ｅｑ程度、好ましくは５００〜２５００ｇ／ｅｑ程度である。アミン当量を４００〜３０００ｇ／ｅｑとすることで、得られる硬化被膜の耐アルカリ性及び耐候性が両立できるため好ましい。なお、アミン当量は、アミノ基１ｍｏｌあたりの重合体の重量で定義され、本発明では以下の（式２）で算出される。 The amine equivalent of the component (A) is usually about 400 to 3000 g / eq, preferably about 500 to 2500 g / eq. By setting the amine equivalent to 400 to 3000 g / eq, it is preferable because both alkali resistance and weather resistance of the obtained cured film can be achieved. The amine equivalent is defined by the weight of the polymer per 1 mol of amino group, and is calculated by the following formula (Formula 2) in the present invention.
（式２）アミン当量（ｇ／ｅｑ）＝［｛（ａ１）〜（ａ４）成分の使用重量（ｇ）｝＋｛開始剤の使用重量（ｇ）｝］／（ａ２）成分の使用モル量（ｍｏｌ） (Formula 2) Amine equivalent (g / eq) = [{(a1) to (a4) component used weight (g)} + {initiator used weight (g)}] / (a2) component used molar amount (Mol)
また、（Ａ）成分の粘度は、固形分濃度５０重量％、温度２５℃において、１００〜３０，０００ｍＰａ・ｓ程度であることが好ましく、１，０００〜１０，０００ｍＰａ・ｓ程度であることがより好ましい。 The viscosity of the component (A) is preferably about 100 to 30,000 mPa · s, preferably about 1,000 to 10,000 mPa · s, at a solid content concentration of 50% by weight and a temperature of 25 ° C. More preferred.
（Ａ）成分の使用量は、活性エネルギー線硬化性樹脂組成物を１００重量％として、通常、１０〜６０重量％である。（Ａ）成分の使用量が１０重量％未満の場合、耐アルカリ性が不充分となりやすく、６０重量％を超える場合、初期密着性が低下しやすい。なお、（Ａ）成分の溶液や分散体を使用する場合、当該使用量は（Ａ）成分の固形分量で表される。
(A) The amount of the component, an active energy ray curable resin composition as 100 wt%, usually 10 to 60 wt%. When the amount of the component (A) used is less than 10% by weight, the alkali resistance tends to be insufficient, and when it exceeds 60% by weight, the initial adhesion tends to decrease. When a solution or dispersion of the component (A) is used, the amount used is represented by the solid content of the component (A).
（Ｂ）成分としては、分子中に不飽和二重結合を２つ有するものであれば、特に限定されず各種公知のものを使用できる。例えば、ジメチロールトリシクロデカンジアクリレート等の脂環構造を有するジアクリレート；ビス（２−アクリロキシエチル）−ヒドロキシエチル−イソシアヌレート等のイソシアヌル環構造を有するジアクリレート；ビスフェノールＡのエチレンオキシド（ＥＯ）変性ジアクリレートやビスフェノールＦのＥＯ変性ジアクリレート；１，６-ヘキサンジオールジアクリレート等の脂肪鎖を有するジアクリレート；テトラエチレングリコールジアクリレート、トリプロピレングリコールジアクリレート、ポリテトラメチレングリコールジアクリレート等のポリアルキレングリコール系ジアクリレート等が挙げられる。これらの中では、硬化被膜の耐磨耗性及び耐侯性の点から、脂環構造を有するジアクリレートが好ましい。 The component (B) is not particularly limited as long as it has two unsaturated double bonds in the molecule, and various known components can be used. For example, a diacrylate having an alicyclic structure such as dimethylol tricyclodecanediacrylate; a diacrylate having an isocyanul ring structure such as bis (2-acryloxyethyl) -hydroxyethyl-isocyanurate; an ethylene oxide (EO) of bisphenol A. EO-modified diacrylate of modified diacrylate and bisphenol F; diacrylate having a fat chain such as 1,6-hexanediol diacrylate; poly such as tetraethylene glycol diacrylate, tripropylene glycol diacrylate and polytetramethylene glycol diacrylate. Examples thereof include alkylene glycol-based diacrylates. Among these, a diacrylate having an alicyclic structure is preferable from the viewpoint of abrasion resistance and weather resistance of the cured film.
（Ｂ）成分の使用量は、活性エネルギー線硬化性樹脂組成物を１００重量％として、通常１０〜６０重量％である。使用量が１０重量％未満であると、密着性が不充分となりやすく、６０重量％を超えると、耐アルカリ性が低下しやすい。また、これらの物性のバランスの点から、好ましくは１０〜３０重量％である。
The amount of the component (B) used is usually 10 to 60% by weight, assuming that the active energy ray-curable resin composition is 100% by weight. If the amount used is less than 10% by weight, the adhesiveness tends to be insufficient, and if it exceeds 60% by weight, the alkali resistance tends to decrease. Further, from the viewpoint of the balance of these physical properties, it is preferably 10 to 30% by weight.
（Ｄ）成分としては、平均一次粒子径が２０〜８０ｎｍの金属酸化物微粒子であれば特に限定されず、公知のものを使用することができる。なお、平均一次粒子径は、動的光散乱法等の測定法により決定された値であり、当該粒子径が、２０〜８０ｎｍであることにより、耐アルカリ性、耐熱性及び耐侯性に優れた硬化被膜となる。 The component (D) is not particularly limited as long as it is a metal oxide fine particle having an average primary particle diameter of 20 to 80 nm, and a known component can be used. The average primary particle size is a value determined by a measurement method such as a dynamic light scattering method, and since the particle size is 20 to 80 nm, curing is excellent in alkali resistance, heat resistance, and weather resistance. It becomes a film.
（Ｄ）成分としては、特に限定されないが、例えば、シリカ、ジルコニア、アルミナ、チタニア、酸化亜鉛等が挙げられる。これらは単独でも２種以上を組み合わせても良い。これらの中でも、耐摩耗性の点から、シリカ、ジルコニア及びアルミナからなる群より選ばれる１種以上が好ましく、シリカがより好ましい。なお、（Ｄ）成分は、市販品をそのまま使用しても良く、特に限定されないが、例えば、シリカとしては、スノーテックス（日産化学工業（株）製）、クォートロン（扶桑化学工業（株）製）、アエロジル（日本アエロジル（株）製）、シルデックス（旭硝子（株）製）、シリシア４７０（富士シリシア化学（株）製）；ジルコニアとしては、ＴＺＰ−１０８（大成化工（株）製）；アルミナとしては、ＮＡＮＯＢＹＫ−３６１０（ビックケミー・ジャパン（株）製）、ＮａｎｏｃｌｅａｒＨＣ−Ａ０１（ＣＩＫ ナノテック（株）製）等が挙げられる。また、本発明では製造の簡便化のため、予め有機溶媒に分散されたオルガノシリカゾルを用いることが好ましく、例えば、ＰＧＭ−ＡＣ４１３０Ｙ（日産化学工業（株）製 プロピレングリコールモノメチルエーテル分散体）、ＩＰＡ−ＳＴ−ＭＳ（日産化学工業（株）製 イソプロパノール分散体）、ＭＡ−ＳＴ−Ｍ（日産化学工業（株）製 メタノール分散体）、クォートロンＰＬ−２−ＩＰＡ（扶桑化学工業（株）製 イソプロパノール分散体）等が挙げられる。 The component (D) is not particularly limited, and examples thereof include silica, zirconia, alumina, titania, and zinc oxide. These may be used alone or in combination of two or more. Among these, from the viewpoint of wear resistance, one or more selected from the group consisting of silica, zirconia and alumina is preferable, and silica is more preferable. The component (D) may be a commercially available product as it is, and is not particularly limited. For example, silica is manufactured by Snowtex (manufactured by Nissan Chemical Industry Co., Ltd.) or Quattron (manufactured by Fuso Chemical Industry Co., Ltd.). ), Aerosil (manufactured by Nippon Aerosil Co., Ltd.), Syldex (manufactured by Asahi Glass Co., Ltd.), Silica 470 (manufactured by Fuji Silicia Chemical Co., Ltd.); Examples of alumina include NANOBYK-3610 (manufactured by Big Chemie Japan Co., Ltd.) and Nanoclear HC-A01 (manufactured by CIK Nanotech Co., Ltd.). Further, in the present invention, it is preferable to use an organosilica sol dispersed in an organic solvent in advance for simplification of production. For example, PGM-AC4130Y (propylene glycol monomethyl ether dispersion manufactured by Nissan Chemical Industries, Ltd.), IPA- ST-MS (isopropanol dispersion manufactured by Nissan Chemical Industry Co., Ltd.), MA-ST-M (methanol dispersion manufactured by Nissan Chemical Industry Co., Ltd.), Quartron PL-2-IPA (isopropanol dispersion manufactured by Fuso Chemical Industry Co., Ltd.) Body) and the like.
（Ｄ）成分の使用量は、活性エネルギー線硬化性樹脂組成物を１００重量％として、通常２０〜６０重量％である。使用量が２０重量％未満であると、耐摩耗性が不充分となりやすく、６０重量％を超えると、活性エネルギー線により硬化した際に、透明性が低下しやすい。また、これらの点から、好ましくは２０〜６０重量％、より好ましくは２５〜５０重量％である。なお、（Ｄ）成分が分散体の場合には、当該使用量は（Ｄ）成分の固形分量で表される。 The amount of the component (D) used is usually 20 to 60% by weight, assuming that the active energy ray-curable resin composition is 100% by weight. If the amount used is less than 20% by weight, the abrasion resistance tends to be insufficient, and if it exceeds 60% by weight, the transparency tends to decrease when cured by active energy rays. From these points, it is preferably 20 to 60% by weight, more preferably 25 to 50% by weight. When the component (D) is a dispersion, the amount used is represented by the solid content of the component (D).
本発明の活性エネルギー線硬化性樹脂組成物は、任意ではあるが、硬化被膜の耐磨耗性の点から、分子中に３つ以上の不飽和二重結合を有する化合物（Ｃ）（以下、（Ｃ）成分という）を含有することが好ましい。 The active energy ray-curable resin composition of the present invention is optional, but from the viewpoint of abrasion resistance of the cured film, the compound (C) having three or more unsaturated double bonds in the molecule (hereinafter, hereinafter, (C) component) is preferably contained.
（Ｃ）成分としては、特に限定されず、公知のものを使用できる。例えば、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ペンタエリスリトールテトラ（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、トリメチロールプロパントリ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート等の（メタ）アクリルエステル類；ジペンタエリスリトールペンタアクリレート、ペンタエリスリトールトリアクリレート等の水酸基を有する多官能（メタ）アクリレートオリゴマーと１分子中に２個以上のイソシアネート基を有する化合物とを反応させることにより得られる多官能ウレタン（メタ）アクリレート；ジペンタエリスリトール、ペンタエリスリトール、グリセリン、ジグリセリン、トリメチロールプロパン等の多官能アルコールをエチレンオキシド又はプロピレンオキシドで変性したものに、アクリル酸を付加させたポリエーテル（メタ）アクリレート；ポリエステルポリ（メタ）アクリレートエポキシ（メタ）アクリレート又はポリオール（メタ）アクリレート等のオリゴマー等が挙げられる。これらは、単独でも２種以上を組み合わせても良い。これらの中でも、（Ａ）成分及び（Ｂ）成分のいずれとも相溶し、かつ（Ｄ）成分の分散性にも影響を与えず、更に硬化被膜の耐磨耗性、耐候性が優れる点から、ジトリメチロールプロパンテトラアクリレート、多官能ウレタン（メタ）アクリレート、ポリエーテル（メタ）アクリレートが好ましい。 The component (C) is not particularly limited, and known components can be used. For example, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tetra (meth) acrylate. (Meta) acrylic esters such as meta) acrylates; polyfunctional (meth) acrylate oligomers having hydroxyl groups such as dipentaerythritol pentaacrylate and pentaerythritol triacrylate and compounds having two or more isocyanate groups in one molecule. Polyfunctional urethane (meth) acrylate obtained by reaction; Acrylate is added to a polyfunctional alcohol such as dipentaerythritol, pentaerythritol, glycerin, diglycerin, trimethylolpropane modified with ethylene oxide or propylene oxide. Polyether (meth) acrylate; Polyester poly (meth) acrylate Examples thereof include oligomers such as epoxy (meth) acrylate and polyol (meth) acrylate. These may be used alone or in combination of two or more. Among these, it is compatible with both the component (A) and the component (B), does not affect the dispersibility of the component (D), and has excellent wear resistance and weather resistance of the cured film. , Ditrimethylolpropane tetraacrylate, polyfunctional urethane (meth) acrylate, and polyether (meth) acrylate are preferable.
（Ｃ）成分の使用量は、特に限定されないが、硬化被膜の耐磨耗性の点から、活性エネルギー線硬化性樹脂組成物を１００重量％として、通常１０〜５０重量％程度である。また同様の点から、好ましくは１０〜４０重量％程度、より好ましくは１０〜３０重量％程度である。 The amount of the component (C) used is not particularly limited, but is usually about 10 to 50% by weight, assuming that the active energy ray-curable resin composition is 100% by weight, from the viewpoint of abrasion resistance of the cured film. From the same point of view, it is preferably about 10 to 40% by weight, more preferably about 10 to 30% by weight.
本発明の活性エネルギー線硬化性樹脂組成物は、必要に応じて、有機溶剤を含有しても良い。有機溶剤としては、（Ａ）成分及び（Ｂ）成分のいずれとも相溶し、かつ（Ｄ）成分の分散性にも影響を与えず、更に乾燥の際に揮発性が良ければ、特に限定されず各種公知のものを使用できる。例えば、メチルエチルケトン、メチルイソブチルケトン、アセチルアセトン等のケトン；酢酸メチル、酢酸エチル、酢酸ブチル等のエステル；エタノール、ｎ−プロピルアルコール、イソプロピルアルコール、ｎ−ブタノール、イソブチルアルコール、ｔｅｒｔ−ブチルアルコール、ジアセトンアルコール等のアルコール；トルエン、キシレン等の芳香族炭化水素、ｎ−ヘキサン、シクロヘキサン、メチルシクロヘキサン、ｎ−ヘプタン等の脂肪族炭化水素；イソプロピルエーテル、メチルセロソルブ、エチルセロソルブ、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、エチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート等のエーテル等が挙げられる。これらは単独でも２種以上を組み合わせても良い。また、固形分濃度としては、特に限定されないが、１０〜７０重量％とすることが好ましい。 The active energy ray-curable resin composition of the present invention may contain an organic solvent, if necessary. The organic solvent is particularly limited as long as it is compatible with both the components (A) and (B), does not affect the dispersibility of the component (D), and has good volatility during drying. Various known substances can be used. For example, ketones such as methyl ethyl ketone, methyl isobutyl ketone and acetyl acetone; esters such as methyl acetate, ethyl acetate and butyl acetate; ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, isobutyl alcohol, tert-butyl alcohol and diacetone alcohol. Alcohols such as; aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as n-hexane, cyclohexane, methylcyclohexane, n-heptane; isopropyl ether, methyl cellosolve, ethyl cellosolve, 1,4-dioxane, propylene glycol. Examples thereof include ethers such as monomethyl ether, ethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. These may be used alone or in combination of two or more. The solid content concentration is not particularly limited, but is preferably 10 to 70% by weight.
本発明の活性エネルギー線硬化性樹脂組成物は、必要に応じて、更に光増感剤、酸化防止剤、光安定剤、レベリング剤、顔料等の各種公知の添加剤、光重合開始剤、紫外線吸収剤等を含有させてもよい。 The active energy ray-curable resin composition of the present invention further comprises various known additives such as a photosensitizer, an antioxidant, a light stabilizer, a leveling agent, a pigment, a photopolymerization initiator, and ultraviolet rays, if necessary. It may contain an absorbent or the like.
光重合開始剤としては、特に限定されず、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、１−シクロヘキシルフェニルケトン、２−ヒドロキシ−２−メチル−１−フェニル−プロパン−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−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノプロパン−１−オン、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（２，４，６−トリメチルベンゾイル）−フェニルホスフィンオキサイド、２，４，６−トリメチルベンゾイル−ジフェニルホスフィンオキサイド、４−メチルベンゾフェノン等が挙げられる。これらは単独でも２種以上を組み合わせてもよい。なお、光重合開始剤は、活性エネルギー線で硬化する場合に使用するが、その内、電子線で硬化する場合には、必ずしも必要ではない。また光重合開始剤の使用量も特に限定されないが、固形分重量で、（Ａ）〜（Ｄ）成分の合計量１００重量部に対して、１〜２０重量部程度とすることが好ましい。 The photopolymerization initiator is not particularly limited, and is, for example, 1-hydroxy-cyclohexyl-phenylketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-cyclohexylphenylketone, 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-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6) -Trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 4-methylbenzophenone and the like can be mentioned. These may be used alone or in combination of two or more. The photopolymerization initiator is used when it is cured by an active energy ray, but it is not always necessary when it is cured by an electron beam. The amount of the photopolymerization initiator used is also not particularly limited, but the solid content weight is preferably about 1 to 20 parts by weight with respect to 100 parts by weight of the total amount of the components (A) to (D).
紫外線吸収剤としては、特に限定されず、例えば、ベンゾフェノン系紫外線吸収剤、トリアジン系紫外線吸収剤、およびベンゾトリアゾール系紫外線吸収剤、酸化チタン微粒子、酸化亜鉛微粒子、酸化錫微粒子等の紫外線を吸収する無機微粒子等が挙げられる。これらは単独でも２種以上を組み合わせてもよい。 The ultraviolet absorber is not particularly limited, and for example, it absorbs ultraviolet rays such as a benzophenone-based ultraviolet absorber, a triazine-based ultraviolet absorber, and a benzotriazole-based ultraviolet absorber, titanium oxide fine particles, zinc oxide fine particles, and tin oxide fine particles. Examples include inorganic fine particles. These may be used alone or in combination of two or more.
ベンゾフェノン系紫外線吸収剤としては、特に限定されないが、例えば、ヒドロキシベンゾフェノン系紫外線吸収剤が好ましく用いられる。ヒドロキシベンゾフェノン系紫外線吸収剤としては、特に限定されないが、例えば、２−ヒドロキシベンゾフェノン、２，４−ジヒドロキシベンゾフェノン、２，２’−ジヒドロキシ−４，４’−ジメトキシベンゾフェノン、２，２’−４，４’−テトラヒドロキシベンゾフェノン、２−ヒドロキシ−４−メトキシベンゾフェノン、ヒドロキシメトキシベンゾフェノンスルホン酸及びその三水塩、ならびにヒドロキシメトキシベンゾフェノンスルホン酸ナトリウム等が挙げられる。 The benzophenone-based ultraviolet absorber is not particularly limited, but for example, a hydroxybenzophenone-based ultraviolet absorber is preferably used. The hydroxybenzophenone-based ultraviolet absorber is not particularly limited, and for example, 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-4, Examples thereof include 4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, hydroxymethoxybenzophenone sulfonic acid and its trihydrate, and sodium hydroxymethoxybenzophenone sulfonate.
トリアジン系紫外線吸収剤としては、特に限定されないが、ヒドロキシフェニルトリアジン系紫外線吸収剤が好ましく用いられる。ヒドロキシフェニルトリアジン系紫外線吸収剤としては、特に限定されないが、例えば、２−（２−ヒドロキシ−４−［１−オクチルオキシカルボニルエトキシ］フェニル）−４，６−ビス（４−フェニルフェニル）−１，３，５−トリアジン、２−［４−［（２−ヒドロキシ−３−ドデシルオキシプロピル）オキシ］−２−ヒドロキシフェニル］−４，６−ビス（２，４−ジメチルフェニル）−１，３，５−トリアジン、２，４−ビス［２−ヒドロキシ−４−ブトキシフェニル］−６−（２，４−ジブトキシフェニル）−１，３，５−トリアジン、２−［４−［（２−ヒドロキシ−３−トリデシルオキシプロピル）オキシ］−２−ヒドロキシフェニル］−４，６−ビス（２，４−ジメチルフェニル）−１，３，５−トリアジン、および２−［４−［（２−ヒドロキシ−３−（２'−エチル）ヘキシル）オキシ］−２−ヒドロキシフェニル］−４，６−ビス（２，４−ジメチルフェニル）−１，３，５−トリアジン等が挙げられる。 The triazine-based ultraviolet absorber is not particularly limited, but a hydroxyphenyl triazine-based ultraviolet absorber is preferably used. The hydroxyphenyltriazine-based ultraviolet absorber is not particularly limited, and is, for example, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1. , 3,5-Triazine, 2- [4-[(2-Hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3 , 5-Triazine, 2,4-Bis [2-Hydroxy-4-butoxyphenyl] -6- (2,4-Dibutoxyphenyl) -1,3,5-Triazine, 2- [4-[(2-] Hydroxy-3-tridecyloxypropyl) Oxy] -2-Hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, and 2- [4-[(2-] Hydroxy-3- (2'-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and the like can be mentioned.
ベンゾトリアゾール系紫外線吸収剤としては、特に限定されないが、例えば、２−エチルヘキシル−３−〔３−ｔｅｒｔ−ブチル−４−ヒドロキシ−５−（５−クロロ−２Ｈ−ベンゾトリアゾール−２−イル）フェニル〕プロピオネート、２−（２Ｈ−ベンゾトリアゾール−２−イル）−６−（直鎖及び側鎖ドデシル）−４−メチルフェノール、２−〔５−クロロ（２Ｈ）−ベンゾトリアゾール−２−イル〕−４−メチル−６−（ｔｅｒｔ−ブチル）フェノール、２−（２Ｈ−ベンゾトリアゾール−２−イル）−４，６−ジ−ｔｅｒｔ−ペンチルフェノール、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−３′，５′−ジ−ｔｅｒｔ−ブチルフェニル）ベンゾトリアゾール、２−（２′−ヒドロキシ−３′−ｔｅｒｔ−ブチル−５′−メチルフェニル）ベンゾトリアゾール、２−（２′−ヒドロキシ−３′，５′−ジ−ｔｅｒｔ−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′−（３″，４″，５″，６″−テトラヒドロフタルイミドメチル）−５′−メチルフェニル）ベンゾトリアゾール、２，２−メチレンビス（４−（１，１，３，３−テトラメチルブチル）−６−（２Ｈ−ベンゾトリアゾール−２−イル）フェノール）、２−（２′−ヒドロキシ−３′−ｔｅｒｔ−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−５−（２−（メタ）アクリロイルオキシエチル）フェニル］−２Ｈ−ベンゾトリアゾール、および２−［２−ヒドロキシ−５−（２−（メタ）アクリロイルオキシエチル）フェニル］−２Ｈ−ベンゾトリアゾールを共重合したポリマー等が挙げられる。 The benzotriazole-based ultraviolet absorber is not particularly limited, and is, for example, 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazole-2-yl) phenyl. ] Propionate, 2- (2H-benzotriazole-2-yl) -6- (straight and side chain dodecyl) -4-methylphenol, 2- [5-chloro (2H) -benzotriazole-2-yl]- 4-Methyl-6- (tert-butyl) phenol, 2- (2H-benzotriazole-2-yl) -4,6-di-tert-pentylphenol, 2- (2'-hydroxy-5'-methylphenyl) ) Benzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzo Triazole, 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-(3 ", 4", 5 "" , 6 ″ -tetrahydrophthalimidemethyl) -5'-methylphenyl) benzotriazole, 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazole-2-) Il) phenol), 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- [2-hydroxy-5-(2- (meth) acryloyloxy) Examples thereof include polymers obtained by copolymerizing 2- [2-hydroxy-5-(2- (meth) acryloyloxyethyl) phenyl] -2H-benzotriazole with ethyl) phenyl] -2H-benzotriazole.
紫外線吸収剤の使用量も、特に限定されないが、固形分重量で、（Ａ）〜（Ｄ）成分の合計量１００重量部に対して、１〜２０重量部程度とすることが好ましい。 The amount of the ultraviolet absorber used is also not particularly limited, but is preferably about 1 to 20 parts by weight with respect to 100 parts by weight of the total amount of the components (A) to (D) in terms of solid content weight.
本発明の積層体は、前記活性エネルギー線硬化性樹脂組成物の硬化被膜を基材の表面に有するものである。 The laminate of the present invention has a cured film of the active energy ray-curable resin composition on the surface of the base material.
基材としては、特に限定されず、例えば、ポリエチレンテレフタレート、ポリエチレンナフタレート等のポリエステル、ポリカーボネート樹脂、ポリスチレン樹脂、ＡＳ樹脂、ＡＢＳ樹脂、ポリアクリル樹脂等が挙げられる。これらの中でも、透明性、強度及び耐衝撃性の点から、ポリカーボネート樹脂、ポリアクリル樹脂及びポリエチレンテレフタレートからなる群より選ばれる少なくとも１種が好ましい。 The base material is not particularly limited, and examples thereof include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate resins, polystyrene resins, AS resins, ABS resins, and polyacrylic resins. Among these, at least one selected from the group consisting of polycarbonate resin, polyacrylic resin and polyethylene terephthalate is preferable from the viewpoint of transparency, strength and impact resistance.
本発明の積層体において、活性エネルギー線硬化性樹脂組成物を基材に塗装する方法としては、特に限定されないが、例えば、スプレー塗装、ディップ塗装、バーコート、スピンコート、スライドコート、ロールコート等が挙げられる。また、塗工層の厚さとしては、活性エネルギー線で硬化した後で３〜６０μｍとなることが好ましい。３μｍ未満であると、耐候性および耐摩耗性が充分でない。６０μｍを超えると、硬化被膜が着色しうる問題がある。また、同様の点から、より好ましくは５〜４０μｍ程度である。 In the laminate of the present invention, the method for coating the active energy ray-curable resin composition on the substrate is not particularly limited, but for example, spray coating, dip coating, bar coating, spin coating, slide coating, roll coating and the like. Can be mentioned. The thickness of the coating layer is preferably 3 to 60 μm after being cured with active energy rays. If it is less than 3 μm, the weather resistance and wear resistance are not sufficient. If it exceeds 60 μm, there is a problem that the cured film may be colored. From the same point of view, it is more preferably about 5 to 40 μm.
本発明の積層体は、有機溶剤を除去するために、予め熱源でプレ乾燥させることが好ましい。熱源としては、特に限定されないが、循風乾燥機、電気炉、ガス炉等が挙げられる。乾燥条件としては、特に限定されないが、温度が４０〜１００℃程度、好ましくは５０〜８０℃程度であり、時間が１〜３０分間程度、好ましくは１〜１０分程度である。 The laminate of the present invention is preferably pre-dried with a heat source in order to remove the organic solvent. The heat source is not particularly limited, and examples thereof include a circulation dryer, an electric furnace, and a gas furnace. The drying conditions are not particularly limited, but the temperature is about 40 to 100 ° C., preferably about 50 to 80 ° C., and the time is about 1 to 30 minutes, preferably about 1 to 10 minutes.
次いで、活性エネルギー線を照射して塗工層を硬化させる。活性エネルギー線としては、特に限定されないが、例えば、紫外線、可視光、電子線、電離放射線等が挙げられる。本発明では、塗工層の硬化性の点から、紫外線を用いることが好ましい。 Next, the coating layer is cured by irradiating it with active energy rays. The active energy ray is not particularly limited, and examples thereof include ultraviolet rays, visible light, electron beams, and ionizing radiation. In the present invention, it is preferable to use ultraviolet rays from the viewpoint of curability of the coating layer.
紫外線の光源としては、特に限定されないが、例えば、超高圧水銀灯、高圧水銀灯、低圧水銀灯、カーボンアーク、キセノンランプ、メタルハライドランプ等が挙げられる。また、照射条件としては、使用する光源によって異なるが、通常は、積算光量が３００〜５，０００ｍＪ／ｃｍ２程度、好ましくは５００〜３，０００ｍＪ／ｃｍ２程度であり、また照射強度が１００〜５００ｍＷ／ｃｍ２程度、好ましくは１００〜３００ｍＷ／ｃｍ２程度である。 The light source of ultraviolet rays is not particularly limited, and examples thereof include an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon lamp, and a metal halide lamp. The irradiation conditions vary depending on the light source used, but usually, the integrated light amount is about 300 to 5,000 mJ / cm 2 , preferably about 500 to 3,000 mJ / cm 2 , and the irradiation intensity is 100 to 100. 500 mW / cm 2 or so, preferably 100~300mW / cm 2 approximately.
本発明の活性エネルギー線硬化性樹脂組成物は、硬化被膜にした際に耐アルカリ性及び耐侯性に優れるため、例えば、ヘッドランプ用カバー、樹脂グレージング等の自動車用プラスチック材料、サンルーフ、建築材料、透明エクステリア部材等の樹脂組成物として利用できる。 Since the active energy ray-curable resin composition of the present invention is excellent in alkali resistance and weather resistance when formed into a cured film, for example, a cover for a head lamp, a plastic material for automobiles such as resin glazing, a sunroof, a building material, and a transparent material. It can be used as a resin composition for exterior members and the like.
以下、実施例および比較例をあげて本発明を具体的に説明するが、本発明はかかる実施例のみに限定されるものではない。なお、各例中、部及び％は重量基準である。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In each example, parts and% are based on weight.
［二重結合当量］
二重結合当量は、以下の式１から算出した。
（式１）二重結合当量（ｇ／ｅｑ）＝［｛（ａ１）〜（ａ４）成分の使用重量（ｇ）｝＋｛開始剤の使用重量（ｇ）｝］／（ａ４）成分の使用モル量（ｍｏｌ）
[Double bond equivalent]
The double bond equivalent was calculated from Equation 1 below.
(Equation 1) Double bond equivalent (g / eq) = [{(a1) to (a4) component working weight (g)} + {initiator working weight (g)}] / (a4) component use Amount of mole (mol)
［アミン当量］
アミン当量は、以下の式２から算出した。
（式２）アミン当量（ｇ／ｅｑ）＝［｛（ａ１）〜（ａ４）成分の使用重量（ｇ）｝＋｛開始剤の使用重量（ｇ）｝］／（ａ２）成分の使用モル量（ｍｏｌ）
[Amine equivalent]
The amine equivalent was calculated from Equation 2 below.
(Formula 2) Amine equivalent (g / eq) = [{(a1) to (a4) component used weight (g)} + {initiator used weight (g)}] / (a2) component used molar amount (Mol)
製造例１（重合体（Ａ―１）の製造）
撹拌装置、冷却管、滴下ロート及び窒素導入管を備えた反応容器に、グリシジルメタクリレート（以下、ＧＭＡという）を３０部、１，２，２，６、６−ペンタメチル−４−ピペリジルメタクリレート（以下、ＨＡＬＳ―１という）を２０部、メチルメタクリレート（以下、ＭＭＡという）を５０部、２，２´−アゾビスイソブチロニトリル（以下、ＡＩＢＮという）を４部および酢酸ブチルを４００部仕込んだ後、窒素気流下に約１時間かけて系内温度が約９５℃になるまで昇温し、１時間保温した。次いで、あらかじめＧＭＡを９０部、ＨＡＬＳ−１を６０部、ＭＭＡを１５０部、およびＡＩＢＮを１２部仕込んだ混合液を滴下ロートより、窒素気流下に約２時間を要して系内へ滴下し、同温度で３時間保温後、ＡＩＢＮを１部仕込み、１時間保温した。その後、１２０℃に昇温し、２時間保温した。その後、反応系を冷却し、重合体（Ａ１―１）の溶液を得た。
Production Example 1 (Production of polymer (A-1))
In a reaction vessel equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introduction tube, 30 parts of glycidyl methacrylate (hereinafter referred to as GMA), 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (hereinafter referred to as GMA). After charging 20 parts of HALS-1), 50 parts of methyl methacrylate (hereinafter referred to as MMA), 4 parts of 2,2'-azobisisobutyronitrile (hereinafter referred to as AIBN) and 400 parts of butyl acetate. The temperature inside the system was raised to about 95 ° C. over about 1 hour under a nitrogen stream, and the temperature was kept for 1 hour. Next, a mixed solution containing 90 parts of GMA, 60 parts of HALS-1, 150 parts of MMA, and 12 parts of AIBN was dropped into the system from a dropping funnel in a nitrogen stream for about 2 hours. After keeping the temperature at the same temperature for 3 hours, a part of AIBN was charged and kept warm for 1 hour. Then, the temperature was raised to 120 ° C. and kept warm for 2 hours. Then, the reaction system was cooled to obtain a solution of the polymer (A1-1).
次いで、反応容器の窒素導入管を空気導入管につけ替え、アクリル酸（以下、ＡＡという）を６０部、メトキノンを１部及びトリフェニルホスフィンを３部加えて混合した後、空気バブリング下にて、１１０℃まで昇温した。次いで、同温度にて８時間保温後、メトキノンを１部仕込み、冷却して、固形分濃度が５０％となるよう酢酸ブチルを加え、重合体（Ａ−１）（以下、（Ａ−１）成分という）の溶液を得た。物性を表１に示す。（以下同様） Next, the nitrogen introduction tube of the reaction vessel was replaced with an air introduction tube, 60 parts of acrylic acid (hereinafter referred to as AA), 1 part of methquinone and 3 parts of triphenylphosphine were added and mixed, and then under air bubbling. The temperature was raised to 110 ° C. Next, after keeping the temperature at the same temperature for 8 hours, a part of methquinone was charged, cooled, and butyl acetate was added so that the solid content concentration became 50%, and the polymer (A-1) (hereinafter, (A-1)) was added. A solution of (called component) was obtained. The physical characteristics are shown in Table 1. (Same below)
製造例２〜６、比較製造例１（重合体（Ａ−２）〜（Ａ−６）、（Ｆ−１）の製造）
表１に示すような組成で、製造例１と同様の方法で製造し、重合体（Ａ−２）〜（Ａ−６）及び（Ｆ−１）をそれぞれ得た。
Production Examples 2 to 6 and Comparative Production Examples 1 (Production of Polymers (A-2) to (A-6) and (F-1))
Polymers (A-2) to (A-6) and (F-1) were obtained by the same method as in Production Example 1 with the compositions shown in Table 1, respectively.
製造例７（重合体（Ａ−７）の製造）
製造例１と同様の反応容器に、２−ヒドロキシエチルメタクリレート（以下、ＨＥＭＡという）を３０部、ＨＡＬＳ−１を４０部、ＭＭＡを３０部、ＡＩＢＮを４部および酢酸ブチルを４００部仕込んだ後、窒素気流下に約１時間かけて系内温度が約９５℃になるまで昇温し、１時間保温した。次いで、あらかじめＨＥＭＡを９０部、ＨＡＬＳ−１を１２０部、ＭＭＡを９０部、およびＡＩＢＮを１２部仕込んだ混合液を滴下ロートより、窒素気流下に約２時間を要して系内へ滴下し、同温度で３時間保温後、ＡＩＢＮを１部仕込み、１時間保温した。その後、１２０℃に昇温し、２時間保温した。その後、反応系を冷却し、重合体（Ａ７−１）の溶液を得た。
Production Example 7 (Production of polymer (A-7))
After charging 30 parts of 2-hydroxyethyl methacrylate (hereinafter referred to as HEMA), 40 parts of HALS-1, 30 parts of MMA, 4 parts of AIBN and 400 parts of butyl acetate in the same reaction vessel as in Production Example 1. The temperature in the system was raised to about 95 ° C. over about 1 hour under a nitrogen stream, and the temperature was kept for 1 hour. Next, a mixed solution containing 90 parts of HEMA, 120 parts of HALS-1, 90 parts of MMA, and 12 parts of AIBN was dropped into the system from the dropping funnel in a nitrogen stream for about 2 hours. After keeping the temperature at the same temperature for 3 hours, a part of AIBN was charged and kept warm for 1 hour. Then, the temperature was raised to 120 ° C. and kept warm for 2 hours. Then, the reaction system was cooled to obtain a solution of the polymer (A7-1).
次いで、反応容器の窒素導入管を空気導入管につけ替え、２−イソシアナトエチルアクリレート（商品名：カレンズＡＯＩ、昭和電工（株）製、以下、ＡＯＩという）を９９部、メトキノンを１部及びオクチル酸スズ（ＩＩ）を０．５部加えて混合した後、空気バブリング下にて、８０℃まで昇温した。次いで、同温度にて４時間保温後、イソシアネート基のＩＲピークの消失を確認した後、メトキノンを１部仕込み、冷却して、固形分濃度が５０％となるよう酢酸ブチルを加え、重合体（Ａ−７）の溶液を得た。（以下同様） Next, the nitrogen introduction tube of the reaction vessel was replaced with an air introduction tube, and 99 parts of 2-isocyanatoethyl acrylate (trade name: Karenz AOI, manufactured by Showa Denko KK, hereinafter referred to as AOI), 1 part of methquinone and octyl. After adding 0.5 part of tin (II) acid and mixing, the temperature was raised to 80 ° C. under air bubbling. Then, after keeping the temperature at the same temperature for 4 hours and confirming the disappearance of the IR peak of the isocyanate group, a part of methquinone was charged, cooled, and butyl acetate was added so that the solid content concentration became 50%, and the polymer ( A solution of A-7) was obtained. (Same below)
製造例８（重合体（Ａ−８）の製造）
製造例１と同様の反応容器に、２−イソシアナトエチルメタクリレート（商品名：カレンズＭＯＩ、昭和電工（株）製、以下、ＭＯＩという）を３０部、ＨＡＬＳ−１を４０部、ＭＭＡを３０部、ＡＩＢＮを４部および酢酸ブチルを４００部仕込んだ後、窒素気流下に約１時間かけて系内温度が約９５℃になるまで昇温し、１時間保温した。次いで、あらかじめＭＯＩを９０部、ＨＡＬＳ−１を１２０部、ＭＭＡを９０部、およびＡＩＢＮを１２部仕込んだ混合液を滴下ロートより、窒素気流下に約２時間を要して系内へ滴下し、同温度で３時間保温後、ＡＩＢＮを１部仕込み、１時間保温した。その後、１２０℃に昇温し、２時間保温した。その後、反応系を冷却し、重合体（Ａ８−１）の溶液を得た。
Production Example 8 (Production of Polymer (A-8))
In the same reaction vessel as in Production Example 1, 30 parts of 2-isocyanatoethyl methacrylate (trade name: Karenz MOI, manufactured by Showa Denko KK, hereinafter referred to as MOI), 40 parts of HALS-1, and 30 parts of MMA. After charging 4 parts of AIBN and 400 parts of butyl acetate, the temperature was raised in a nitrogen stream for about 1 hour until the temperature inside the system reached about 95 ° C., and the temperature was kept for 1 hour. Next, a mixed solution containing 90 parts of MOI, 120 parts of HALS-1, 90 parts of MMA, and 12 parts of AIBN was dropped into the system from a dropping funnel in a nitrogen stream for about 2 hours. After keeping the temperature at the same temperature for 3 hours, a part of AIBN was charged and kept warm for 1 hour. Then, the temperature was raised to 120 ° C. and kept warm for 2 hours. Then, the reaction system was cooled to obtain a solution of the polymer (A8-1).
次いで、反応容器の窒素導入管を空気導入管につけ替え、２−ヒドロキシエチルアクリレート（以下、ＨＥＡという）を８９部、メトキノンを１部及びオクチル酸スズ（ＩＩ）を０．５部加えて混合した後、空気バブリング下にて、８０℃まで昇温した。次いで、同温度にて４時間保温後、イソシアネート基のＩＲピークの消失を確認した後、メトキノンを１部仕込み、冷却して、固形分濃度が５０％となるよう酢酸ブチルを加え、重合体（Ａ−８）の溶液を得た。（以下同様） Next, the nitrogen introduction tube of the reaction vessel was replaced with an air introduction tube, and 89 parts of 2-hydroxyethyl acrylate (hereinafter referred to as HEA), 1 part of methquinone and 0.5 part of tin octylate (II) were added and mixed. After that, the temperature was raised to 80 ° C. under air bubbling. Then, after keeping the temperature at the same temperature for 4 hours and confirming the disappearance of the IR peak of the isocyanate group, a part of methquinone was charged, cooled, and butyl acetate was added so that the solid content concentration became 50%, and the polymer ( A solution of A-8) was obtained. (Same below)
表１における成分の略号については、以下の化合物を表している。
（ａ１）成分
・ＧＭＡ：グリシジルメタクリレート
・ＨＥＭＡ：２−ヒドロキシエチルメタクリレート
・ＭＯＩ：２−イソシアナトエチルメタクリレート
（ａ２）成分
・ＨＡＬＳ−１：１，２，２，６、６−ペンタメチル−４−ピペリジルメタクリレート
（ａ３）成分
・ＭＭＡ：メチルメタクリレート
（ａ４）成分
・ＡＡ：アクリル酸
・ＡＯＩ：２−イソシアナトエチルアクリレート
・ＨＥＡ：２−ヒドロキシエチルアクリレート
The abbreviations of the components in Table 1 represent the following compounds.
(A1) component-GMA: glycidyl methacrylate-HEMA: 2-hydroxyethyl methacrylate-MOI: 2-isocyanatoethyl methacrylate (a2) component-HALS-1: 1,2,2,6,6-pentamethyl-4-piperidyl Methacrylate (a3) component ・ MMA: Methyl methacrylate (a4) component ・ AA: Acrylic acid ・ AOI: 2-Isocyanatoethyl acrylate ・ HEA: 2-Hydroxyethyl acrylate
実施例１
重合体（Ａ−１）４０部（固形分重量：２０部）、（Ｂ）成分として、ジメチロールトリシクロデカンジアクリレート（商品名：ライトアクリレートＤＣＰ−Ａ、共栄社化学（株）製）２０部、（Ｃ）成分として、ジメチロールプロパントリアクリレート（商品名：ビームセット７３０、荒川化学工業（株）製）１０部、（Ｄ）成分としてプロピレングリコールモノメチルエーテル分散コロイダルシリカ（ＳｉＯ２、平均一次粒子径：４０〜６０ｎｍ、固形分濃度：３０％、商品名：ＰＧＭ−ＡＣ４１３０Ｙ、日産化学工業（株）製）１６７部（固形分重量：５０部）、また光重合開始剤として１−ヒドロキシ−シクロヘキシル−フェニルケトン（商品名：イルガキュア１８４、チバ・ジャパン（株）製）を５部および、表面調整剤としてシリコーン表面調整剤であるＢＹＫ−３１０（ビックケミー社製）を０．２部加え、固形分濃度が３３％となるようにプロピレングリコールモノメチルエーテル（以下、ＰＭという）で希釈し、活性エネルギー線硬化性樹脂組成物を調製した。
Example 1
40 parts of polymer (A-1) (solid content weight: 20 parts), 20 parts of dimethyloltricyclodecanediacrylate (trade name: light acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.) as a component (B) , (C) component: Dimethylolpropane triacrylate (trade name: Beamset 730, manufactured by Arakawa Chemical Industry Co., Ltd.) 10 parts, (D) component: propylene glycol monomethyl ether-dispersed colloidal silica (SiO 2 , average primary particles) Diameter: 40 to 60 nm, solid content concentration: 30%, trade name: PGM-AC4130Y, manufactured by Nissan Chemical Industry Co., Ltd., 167 parts (solid content weight: 50 parts), and 1-hydroxy-cyclohexyl as a photopolymerization initiator. -Add 5 parts of phenylketone (trade name: Irgacure 184, manufactured by Ciba Japan Co., Ltd.) and 0.2 part of BYK-310 (manufactured by Big Chemie), which is a silicone surface conditioner, as a surface conditioner, and add solid content. An active energy ray-curable resin composition was prepared by diluting with propylene glycol monomethyl ether (hereinafter referred to as PM) so as to have a concentration of 33%.
実施例２〜１３、比較例１〜９
表２に示す組成で、実施例１と同様にして、活性エネルギー線硬化性樹脂組成物をそれぞれ調製した。
Examples 2 to 13, Comparative Examples 1 to 9
With the compositions shown in Table 2, active energy ray-curable resin compositions were prepared in the same manner as in Example 1.
［積層体の作製（ポリカーボネート板を用いた積層体での評価）］
厚さ２ｍｍのポリカーボネート板の表面に、実施例１で得られた活性エネルギー線硬化性樹脂組成物をバーコーターで塗工層の厚さが１０μｍとなるように塗布し、８０℃で２分乾燥させた。次いで、得られた塗工フィルムを大気中で、高圧水銀灯（積算光量：１０００ｍＪ／ｃｍ２、照射強度：２００ｍＷ／ｃｍ２）の下を通過させて（搬送速度１０ｍ／分）、硬化させることにより、積層体を得た。また、実施例２〜１３及び比較例１〜９の各樹脂組成物についても同様にして積層体をそれぞれ得た。
[Preparation of laminate (evaluation of laminate using polycarbonate plate)]
The active energy ray-curable resin composition obtained in Example 1 was applied to the surface of a 2 mm-thick polycarbonate plate with a bar coater so that the thickness of the coating layer was 10 μm, and dried at 80 ° C. for 2 minutes. I let you. Next, the obtained coating film was passed under a high-pressure mercury lamp (integrated light intensity: 1000 mJ / cm 2 , irradiation intensity: 200 mW / cm 2 ) in the air (conveyance speed: 10 m / min) and cured. , A laminate was obtained. Further, laminated bodies were obtained in the same manner for each of the resin compositions of Examples 2 to 13 and Comparative Examples 1 to 9.
［初期密着性］
各積層体の表面につきＪＩＳ Ｋ ５４００に従って、１ｍｍ間隔で基材まで達する切り込みを入れ、１００マスの碁盤目セロハンテープ剥離試験を行い、初期密着性を評価した。
評価基準
○：剥がれがない ×：剥がれが発生
[Initial adhesion]
According to JIS K 5400, the surface of each laminate was cut to reach the base material at 1 mm intervals, and a 100-square grid cellophane tape peeling test was performed to evaluate the initial adhesion.
Evaluation criteria ○: No peeling ×: Peeling occurs
［初期外観］
ＪＩＳ Ｋ ７３６１−１に従って、各積層体のヘイズ値をヘイズメーターにて測定した。
評価基準
○：ＨＡＺＥ≦１．０％ ×：ＨＡＺＥ＞１．０％
[Initial appearance]
The haze value of each laminate was measured with a haze meter according to JIS K 7361-1.
Evaluation Criteria ◯: HAZE ≤ 1.0% ×: HAZE> 1.0%
［耐摩耗性］
ＡＳＴＭ−Ｄ−１０４４に従い、摩耗輪ＣＳ−１０Ｆ、荷重５００ｇ、回転速度６０ｒｐｍ、摩耗回数５００サイクルの条件で各積層体中の硬化被膜を摩耗させた後、ＪＩＳ Ｋ ７３６１−１に従って、ヘイズメーターを用いて、ヘイズ値を測定し、変化量を算出した。耐摩耗性は下記の△ＨＡＺＥで求め、値が小さいほど耐磨耗性に優れることを示す。
△ＨＡＺＥ（％）＝（摩耗試験後のヘイズ値）−（摩耗試験前のヘイズ値）
評価基準
◎：△ＨＡＺＥ＜５％
○：△ＨＡＺＥ＜１０％
×：△ＨＡＺＥ≧１０％
[Abrasion resistance]
According to ASTM-D-1044, the cured coating in each laminate is worn under the conditions of wear wheel CS-10F, load 500 g, rotation speed 60 rpm, and number of wear times 500 cycles, and then the haze meter is set according to JIS K 7361-1. The haze value was measured and the amount of change was calculated. The wear resistance is determined by the following ΔHAZE, and the smaller the value, the better the wear resistance.
ΔHAZE (%) = (haze value after wear test)-(haze value before wear test)
Evaluation criteria ◎: △ HAZE <5%
◯: △ HAZE <10%
×: △ HAZE ≧ 10%
［耐アルカリ性］
５５℃に設定した０．１Ｎの水酸化ナトリウム（ＮａＯＨ）水溶液に、各積層体を４時間接触させた。その後、表面を純水で洗い流して乾燥させた後に、ＡＴＲ法によるＩＲ測定を行いシリカに由来するピークの変化を評価した。
評価基準
○：ＩＲのピーク面積の変化量が２０％以下
×：ＩＲのピーク面積の変化量が２０％を超える
[Alkali resistance]
Each laminate was brought into contact with a 0.1 N aqueous sodium hydroxide (NaOH) solution set at 55 ° C. for 4 hours. Then, after the surface was rinsed with pure water and dried, IR measurement by the ATR method was performed to evaluate the change in the peak derived from silica.
Evaluation Criteria ○: The amount of change in the peak area of IR is 20% or less ×: The amount of change in the peak area of IR exceeds 20%
［耐熱性］
温度１４０℃の熱風循環式乾燥器の中に、各積層体を入れて、２００時間放置し、室温まで冷却した後、積層体の表面状態を目視で確認した。
○：変化なし
×：クラックがある
[Heat-resistant]
Each laminate was placed in a hot air circulation type dryer having a temperature of 140 ° C., left to stand for 200 hours, cooled to room temperature, and then the surface condition of the laminate was visually confirmed.
○: No change ×: There is a crack
［耐侯性］
アイスーパーＵＶテスター（岩崎電気（株）製）を用いて、以下の試験条件で耐候性試験を実施した後、各積層体における硬化被膜の外観（クラック、剥離）を目視にて観察し、更にＪＩＳ Ｋ ７３７３に準拠して、色の変化を色差計（日本電色工業（株）製）を用いた透過法にて△ＹＩを測定して、以下の基準で評価した。
（試験条件）
各積層体を８０ｍＷ/ｃｍ２で照射、ブラックパネル温度６３℃にて３６０時間試験を行い、６時間毎に硬化被膜の表面にイオン交換水を１０秒間スプレーした。
評価基準
◎：目視変化なし、かつ△ＹＩが２．０未満
○：目視変化なし、かつ△ＹＩが２．０以上４．０未満
×：目視変化あり、または△ＹＩが４．０以上
[Hou resistance]
After conducting a weather resistance test under the following test conditions using an eye super UV tester (manufactured by Iwasaki Electric Co., Ltd.), visually observe the appearance (cracks, peeling) of the cured film in each laminate, and further. In accordance with JIS K 7373, the change in color was measured by the transmission method using a color difference meter (manufactured by Nippon Denshoku Kogyo Co., Ltd.), and evaluated according to the following criteria.
(Test condition)
Each laminate was irradiated at 80 mW / cm 2 , tested at a black panel temperature of 63 ° C. for 360 hours, and ion-exchanged water was sprayed on the surface of the cured film every 6 hours for 10 seconds.
Evaluation Criteria ⊚: No visual change and ΔYI less than 2.0 ◯: No visual change and ΔYI 2.0 or more and less than 4.0 ×: Visual change or ΔYI 4.0 or more
表２における成分の記号については、以下の化合物を表している。
（Ｂ）成分
・Ｂ−１：ジメチロールトリシクロデカンジアクリレート（ＤＣＰ−Ａ）（商品名：ライトアクリレートＤＣＰ−Ａ、共栄社化学（株）製）
・Ｂ−２：１，６−ヘキサンジオールジアクリレート（ＨＤＤＡ）（商品名：ライトアクリレート１．６ＨＸ−Ａ、共栄社化学（株）製）
（Ｃ）成分
・Ｃ−１：ジメチロールプロパントリアクリレート（ＤＭＰＴＡ）（商品名：ビームセット７３０、荒川化学工業（株）製）
・Ｃ−２：ＥＯ変性ジペンタエリスリトールヘキサアクリレート（ＤＰＨ−１２Ｅ）（商品名：ＮＫエステルＡ−ＤＰＨ−１２Ｅ、新中村化学工（株）製）
金属酸化物微粒子
・Ｄ−１：プロピレングリコールモノメチルエーテル分散コロイダルシリカ（ＳｉＯ２、平均一次粒子径：４０〜５０ｎｍ、固形分濃度：３０％、商品名：ＰＧＭ−ＡＣ４１３０Ｙ、日産化学工業（株）製）
・Ｄ−２：プロピレングリコールモノメチルエーテルアセテート分散酸化ジルコニウム（ＺｒＯ２、平均一次粒子径：３０〜４０ｎｍ、固形分濃度：３０％、商品名：ＴＺＰ−１０８、大成化工（株）製）
・Ｇ−１：プロピレングリコールモノメチルエーテル分散コロイダルシリカ（ＳｉＯ２、平均一次粒子径：１０〜１５ｎｍ、固形分濃度：４０％、商品名：ＰＧＭ−ＡＣ２１４０Ｙ、日産化学工業（株）製）
・Ｈ−１：プロピレングリコールモノメチルエーテル分散コロイダルシリカ（ＳｉＯ２、平均一次粒子径：１００ｎｍ、固形分濃度：５０％、商品名：アドマナノスラリーＹＡ１００Ｃ−ＬＦＧ、（株）アドマテックス製）
The component symbols in Table 2 represent the following compounds.
(B) Ingredients -B-1: Dimethylol tricyclodecanediacrylate (DCP-A) (trade name: light acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.)
B-2: 1,6-hexanediol diacrylate (HDDA) (trade name: light acrylate 1.6HX-A, manufactured by Kyoeisha Chemical Co., Ltd.)
(C) Ingredients -C-1: Dimethylolpropane triacrylate (DMPTA) (Product name: Beamset 730, manufactured by Arakawa Chemical Industry Co., Ltd.)
C-2: EO-modified dipentaerythritol hexaacrylate (DPH-12E) (trade name: NK ester A-DPH-12E, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
Metal oxide fine particles D-1: Propylene glycol monomethyl ether dispersed colloidal silica (SiO 2 , average primary particle size: 40 to 50 nm, solid content concentration: 30%, trade name: PGM-AC4130Y, manufactured by Nissan Chemical Industry Co., Ltd. )
D-2: Propylene glycol monomethyl ether acetate dispersed zirconium oxide (ZrO 2 , average primary particle size: 30-40 nm, solid content concentration: 30%, trade name: TZP-108, manufactured by Taisei Kako Co., Ltd.)
G-1: Propylene glycol monomethyl ether dispersed colloidal silica (SiO 2 , average primary particle size: 10 to 15 nm, solid content concentration: 40%, trade name: PGM-AC2140Y, manufactured by Nissan Chemical Industry Co., Ltd.)
H-1: Propylene glycol monomethyl ether dispersed colloidal silica (SiO 2 , average primary particle size: 100 nm, solid content concentration: 50%, trade name: Admananoslurry YA100C-LFG, manufactured by Admatex Co., Ltd.)
評価例１（ポリアクリル板を用いた積層体での評価）
厚さ２ｍｍのポリアクリル板の表面に、実施例１の活性エネルギー線硬化性樹脂組成物をバーコーターで塗工層の厚さが１０μｍとなるように塗布し、８０℃で２分乾燥させた。次いで、得られた塗工フィルムを大気中で、高圧水銀灯（積算光量：１０００ｍＪ／ｃｍ２、照射強度：２００ｍＷ／ｃｍ２）の下を通過させて（搬送速度１０ｍ／分）、硬化させることにより、積層体を得た。前記積層体を用いて、同様の評価を行ったところ、いずれも良好な効果を示した。結果を表３に示す。
Evaluation Example 1 (Evaluation with a laminated body using a polyacrylic plate)
The active energy ray-curable resin composition of Example 1 was applied to the surface of a polyacrylic plate having a thickness of 2 mm with a bar coater so that the thickness of the coating layer was 10 μm, and dried at 80 ° C. for 2 minutes. .. Next, the obtained coating film was passed under a high-pressure mercury lamp (integrated light intensity: 1000 mJ / cm 2 , irradiation intensity: 200 mW / cm 2 ) in the air (conveyance speed: 10 m / min) and cured. , A laminate was obtained. When the same evaluation was performed using the laminated body, all showed good effects. The results are shown in Table 3.
Claims (7)
分子中に不飽和二重結合を２つ有する化合物（Ｂ）、
及び
平均一次粒子径が２０〜８０ｎｍである金属酸化物微粒子（Ｄ）を含有する活性エネルギー線硬化性組成物であって、
前記活性エネルギー線硬化性樹脂組成物を１００重量％として、
前記（Ａ）成分１０〜６０重量％、前記（Ｂ）成分１０〜６０重量％、及び前記（Ｄ）成分２０〜６０重量％を含有し、
（Ａ）成分が、
エポキシ基、水酸基及びイソシアネート基からなる群より選ばれる少なくとも１種の官能基を有する単量体（ａ１）、及びピペリジニル基を有する単量体（ａ２）を含む単量体成分の重合体（Ａ１）と、
（Ａ１）成分が有する官能基と反応し得る、官能基を有する単量体（ａ４）との反応生成物であり、
（ａ２）成分が、一般式（１）で表されるものである活性エネルギー線硬化性樹脂組成物。
Compound (B) having two unsaturated double bonds in the molecule ,
And an average primary particle diameter of a active energy ray-curable composition containing the metal oxide fine particles (D) is 20 to 80 nm,
With the active energy ray-curable resin composition as 100% by weight,
It contains 10 to 60% by weight of the component (A), 10 to 60% by weight of the component (B), and 20 to 60% by weight of the component (D).
The component (A) is
A polymer (A1) of a monomer component containing a monomer (a1) having at least one functional group selected from the group consisting of an epoxy group, a hydroxyl group and an isocyanate group, and a monomer (a2) having a piperidinyl group. )When,
(A1) is a reaction product with a functional group-containing monomer (a4) capable of reacting with a functional group contained in the component.
An active energy ray-curable resin composition in which the component (a2) is represented by the general formula (1).
The laminate according to claim 6 , wherein the base material is at least one selected from the group consisting of a polycarbonate resin, a polyacrylic resin, and polyethylene terephthalate.
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