JP2019011419A - Active energy ray-curable resin composition and laminate - Google Patents
Active energy ray-curable resin composition and laminate Download PDFInfo
- Publication number
- JP2019011419A JP2019011419A JP2017128141A JP2017128141A JP2019011419A JP 2019011419 A JP2019011419 A JP 2019011419A JP 2017128141 A JP2017128141 A JP 2017128141A JP 2017128141 A JP2017128141 A JP 2017128141A JP 2019011419 A JP2019011419 A JP 2019011419A
- Authority
- JP
- Japan
- Prior art keywords
- component
- resin composition
- active energy
- energy ray
- curable resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000011342 resin composition Substances 0.000 title claims abstract description 48
- 239000000178 monomer Substances 0.000 claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- 239000010419 fine particle Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000011164 primary particle Substances 0.000 claims abstract description 11
- 125000003386 piperidinyl group Chemical group 0.000 claims abstract description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 6
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 6
- -1 polyethylene terephthalate Polymers 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 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
- 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
- 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
- 239000003513 alkali Substances 0.000 abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 46
- 239000007787 solid Substances 0.000 description 22
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- 238000004519 manufacturing process Methods 0.000 description 16
- 239000011248 coating agent Substances 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
- 238000006243 chemical reaction Methods 0.000 description 12
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- 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 8
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
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- 238000012360 testing method Methods 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 5
- 239000012964 benzotriazole Substances 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 5
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
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- 238000006116 polymerization reaction Methods 0.000 description 5
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-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
- 239000002253 acid Substances 0.000 description 4
- 239000008119 colloidal silica Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000000758 substrate 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
- 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
- 102100026735 Coagulation factor VIII Human genes 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 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
- 239000006096 absorbing agent Substances 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000002585 base Substances 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
- 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
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
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- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
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- 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
- 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
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 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
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- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 1
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- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 description 1
- PRKMQTLVLAHFAW-UHFFFAOYSA-N 3-[1-(3,5-ditert-butyl-4-hydroxyphenyl)-2-methyl-4,4-bis(1,2,2,6,6-pentamethylpiperidin-4-yl)butan-2-yl]oxy-3-oxopropanoic acid Chemical compound C1C(C)(C)N(C)C(C)(C)CC1C(C1CC(C)(C)N(C)C(C)(C)C1)CC(C)(OC(=O)CC(O)=O)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 PRKMQTLVLAHFAW-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 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
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- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
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- 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
- 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
- XNNQFQFUQLJSQT-UHFFFAOYSA-N bromo(trichloro)methane Chemical compound ClC(Cl)(Cl)Br XNNQFQFUQLJSQT-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
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- 235000005822 corn Nutrition 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- BMFYCFSWWDXEPB-UHFFFAOYSA-N cyclohexyl(phenyl)methanone Chemical compound C=1C=CC=CC=1C(=O)C1CCCCC1 BMFYCFSWWDXEPB-UHFFFAOYSA-N 0.000 description 1
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- 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
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 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
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- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 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
- 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
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement 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
- 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
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 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
- 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
- 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
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 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
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007767 slide coating Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 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
- 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
- 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
- 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
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- 239000004711 α-olefin Substances 0.000 description 1
Abstract
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, lighter and have excellent impact resistance. It is used in applications such as plastic covers for automobiles such as automobile covers and glazings, sunroofs, and building materials. In such applications, in addition to the weather resistance similar to that of glass, so-called abrasion resistance is required, in which a windshield wiper is applied to the windshield of an automobile or the side glass is not damaged when the side glass is raised or lowered. It is known that the material is not sufficient.
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。 To solve these drawbacks, for example, urethane acrylate having a specific number of acryloyl groups, acetophenone photopolymerization initiator, phosphine oxide photopolymerization initiator, ultraviolet absorber and light stabilizer each containing specific amounts. A curable coating composition and a coated article (Patent Document 1) obtained by coating the composition on a base material are known. As a component of the coating composition, nanocomposite urethane acrylate in which nanosilica is dispersed is used, but when it is used as a coated article, the wear resistance is insufficient. In addition, a reaction product obtained by reacting a monomer having a carboxyl group with a copolymer having a radical polymerizable vinyl monomer containing an epoxy group as an essential component, an activity containing a specific vinyl compound and silica fine particles. An energy ray curable resin composition (Patent Document 2) is also known. However, the resin composition does not have sufficient weather resistance, and in order to give abrasion resistance, silica fine particles are blended in the resin composition. However, the silica fine particles have high hydrophilicity and alkali resistance. It was something to lower.
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 excellent in 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 has paid attention to the fact that the cause of the problem is the hydrophilicity of the silica fine particles, and as a result of extensive studies, incorporated a piperidinyl group that interacts with the hydrophilic functional group of silica into the polymer, and further unsaturated two The active energy ray-curable resin composition obtained by introducing a double bond and protecting the polar group of the silica fine particles, and further improving the binding force with other compounds via the polymer during photopolymerization The inventors have found that the alkalinity and weather resistance are excellent, and have completed the present invention. That is, the present invention relates to the following active energy ray-curable resin composition and laminate.
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. 10 to 60% by weight of polymer (A) having an unsaturated double bond and a piperidinyl group in one molecule,
10 to 60% by weight of compound (B) having two unsaturated double bonds in the molecule,
And 20-60 wt% of metal oxide fine particles (D) having an average primary particle diameter of 20-80 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. (A) component is
Polymer of monomer component (A1) containing monomer (a1) having at least one functional group selected from the group consisting of epoxy group, hydroxyl group and isocyanate group, and monomer (a2) having piperidinyl group )When,
(A1) The active energy ray-curable resin composition according to item 1 above, which is a reaction product of the functional group-containing monomer (a4) capable of reacting with the functional group of the component.
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. The active energy ray-curable resin composition according to item 2 above, wherein the monomer component constituting the component (A1) further includes a monomer (a3) copolymerizable 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 preceding 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). Furthermore, the active energy ray-curable resin composition according to any one of 1 to 5 above, which comprises 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). (D) The active energy ray-curable resin composition according to any one of 1 to 6 above, wherein the component is one or more 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). The laminated body which has the cured film of the active energy ray curable resin composition in any one of the preceding clauses 1-7 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. 9. The laminate according to item 8 above, wherein the substrate 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。 ADVANTAGE OF THE INVENTION According to this invention, the active energy ray-curable resin composition which forms the cured film excellent in alkali resistance and weather resistance is obtained. The resin composition can be applied to various plastic films and molded products, but is particularly suitable as a coating agent for hard coat, plastic materials for automobiles such as headlamp covers, resin glazing, sunroofs, building materials, 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 comprises 10 to 60% by weight of a polymer (A) having an unsaturated double bond and a piperidinyl group in one molecule (hereinafter referred to as “component (A)”). 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 referred to as ( It is characterized by containing 20 to 60% by weight of component D).
（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 compounds 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 component (a1)), and a monomer having a piperidinyl group A functional group capable of reacting with the functional group of the polymer (A1) (hereinafter referred to as the (A1) component) containing (a2) (hereinafter referred to as the (a2) component) and the (A1) component. And a reaction product with the monomer (a4) (hereinafter referred to as “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. For example, glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, Examples include 3,4-epoxycyclohexylmethyl (meth) acrylate and 1,2-epoxy-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. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl acrylate, 3-hydroxy Examples 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。 Of the components (a1), the monomer having an isocyanate group is not particularly limited. For example, 2-isocyanatoethyl (meth) acrylate, 1,1- (bisacryloyloxymethyl) ethyl isocyanate, acrylic acid 2 -(2-isocyanatoethoxy) ethyl and the like. 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 contributes to alkali resistance and weather resistance by being incorporated as a skeleton of the component (A1). (A2) It does not specifically limit as a component, Various well-known things 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- , 2,6,6-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- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butyl malonate, and the like. These may be used alone or in combination of two or more. Among these, a 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。 (A2) The usage-amount of a component is not specifically limited, It adjusts suitably so that the amine equivalent of (A) component may be set to 450-3000eq / 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。 In order to increase the compatibility with the component (A) and the component (B), and / or the component (A) and the component (D), the monomer may be any component (a1) or (a2). ) Component (a3) that can be copolymerized with the component (hereinafter referred to as 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。 Although it does not specifically limit as (a3) component, For example, alkyl (meth) acrylates, such as methyl (meth) acrylate and ethyl (meth) acrylate; Cycloaliphatic (meth) acrylates, such as isobornyl (meth) acrylate; (Meth) acrylates containing heteroatoms such as phosphorus; aromatic monomers such as styrene, α-methylstyrene, vinyltoluene; vinyl acetate, vinyl propionate, (meth) acrylonitrile, (meth) acrylamide, α-olefin, etc. Is 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 wear resistance of the cured coating. 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 of wear resistance, alkali resistance and heat resistance of the cured film obtained. Is preferably about 1/9 to 7/3, and 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 radical polymerization of the components (a1) and (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 in which the above components are heated 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 initiators can be used. For example, inorganic peroxides such as hydrogen peroxide, ammonium persulfate, and potassium persulfate, benzoyl peroxide, dialkyl 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 not particularly limited, but the total amount of the components (a1) to (a4) in terms of the solid content is about 0.01 to 8 parts by weight with respect to 100 parts by weight. preferable. In addition, you may add a chain transfer agent etc. as needed. The chain transfer agent is not particularly limited, and examples thereof include lauryl mercaptan, dodecyl mercaptan, 2-mercaptobenzothiazole, bromotrichloromethane and the like. These may be used alone or in combination of two or more. The amount of chain transfer agent used is not particularly limited, but the total amount of the components (a1) to (a3) 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 the component constituting the component (A) of the present invention, is not particularly limited. For example, a monomer having a hydroxyl group or an isocyanate group exemplified as the aforementioned component (a1), (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. In addition, as a preferable monomer in (a4) component, it changes with kinds of monomer which belongs to (a1) component.
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, for a monomer having an epoxy group belonging to the component (a1), an unsaturated carboxylic acid is preferable, and the resulting active energy ray-curable resin composition has good photopolymerizability, and the resulting cured film Acrylic acid is more preferable from the viewpoint of excellent wear 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 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, the photopolymerizability of the generated active energy ray-curable resin composition is good, and the obtained cured film is excellent in wear resistance, so that 2-isocyanatoethyl acrylate, acrylic acid 2- (2-isocyanatoethoxy) ) 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。 For the monomer having an isocyanate group belonging to the component (a1), a monomer having a hydroxyl group is preferable, the photopolymerizability of the generated active energy ray-curable resin composition is good, and the obtained cured film However, 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate are more preferable from the viewpoint of excellent wear 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 to be equal to or less than the functional group (epoxy group, hydroxyl group, isocyanate group) in the component (a1). The resulting cured coating is excellent in 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。 (A) component of this invention is obtained by manufacturing by various well-known methods. Although it does not specifically limit as a manufacturing method, For example, heating said (A1) component and (a4) component in presence of a catalyst, etc. are mentioned. 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; and lauric acid esters such as dibutyltin laurate. 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 components (A1) and (a4) in terms of solid content. It 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 components (A1) and (a4), and various known solvents 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 such as diglyme, chloroform, dimethylformamide and the like. These may be used alone or in combination of two or more. Examples of the polymerization inhibitor include methoquinone, hydroquinone, trimethylhydroquinone, N-nitrosophenylhydroxylamine and the like. In addition, although the usage-amount of a polymerization inhibitor is not specifically limited, Since the polymerizability of the coating agent obtained may deteriorate, in solid content weight, the total amount of (A1) component and (a4) component is 100 weight part. On the other hand, it is usually preferable to be about 1 part by weight or less. 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。 Although it does not specifically limit as a physical property of the obtained (A) component, For example, a double bond equivalent is about 250-2000 g / eq normally, Preferably it is about 250-1200 g / eq. It is preferable that the double bond equivalent is 250 to 2000 g / eq because both the wear resistance and the heat resistance of the resulting cured film can be achieved. In addition, a double bond equivalent is represented by the weight of the polymer per 1 mol of unsaturated double bonds, and is calculated by the following (Formula 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） (Formula 1) Double bond equivalent (g / eq) = [{(a1) to (a4) component use weight (g)} + {initiator use weight (g)}] / (a4) component use Molar amount (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。 Moreover, the amine equivalent of (A) component is about 400-3000 g / eq normally, Preferably it is about 500-2500 g / eq. It is preferable to set the amine equivalent to 400 to 3000 g / eq since both the alkali resistance and the weather resistance of the resulting cured film can be achieved. In addition, an amine equivalent is defined by the weight of the polymer per 1 mol of amino groups, and is calculated by the following (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) used weight of component (g)} + {initiator used weight (g)}] / (a2) used molar amount of component (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中の合計量を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 usage-amount of a component is 10-60 weight% normally by making the total amount in an active energy ray-curable resin composition into 100 weight%. 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. In addition, when using the solution and dispersion of (A) component, the said usage-amount is represented by the solid content of (A) component.
（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 compounds can be used. For example, diacrylate having an alicyclic structure such as dimethylol tricyclodecane diacrylate; diacrylate having an isocyanuric ring structure such as bis (2-acryloxyethyl) -hydroxyethyl-isocyanurate; ethylene oxide (EO) of bisphenol A EO-modified diacrylate of modified diacrylate or bisphenol F; diacrylate having a fatty chain such as 1,6-hexanediol diacrylate; poly such as tetraethylene glycol diacrylate, tripropylene glycol diacrylate, polytetramethylene glycol diacrylate Examples include alkylene glycol diacrylate. Among these, diacrylates having an alicyclic structure are preferable from the viewpoint of wear resistance and weather resistance of the cured coating.
（Ｂ）成分の使用量は、活性エネルギー線硬化性樹脂組成物中の合計量を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。 (B) The usage-amount of a component is 10 to 60 weight% normally by making the total amount in an active energy ray-curable resin composition into 100 weight%. If the amount used is less than 10% by weight, the adhesion tends to be insufficient, and if it exceeds 60% by weight, the alkali resistance tends to be lowered. Moreover, from the point of balance of these physical properties, Preferably it is 10 to 30 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 one can be used. The average primary particle diameter is a value determined by a measuring method such as a dynamic light scattering method. When the particle diameter is 20 to 80 nm, curing excellent in alkali resistance, heat resistance and weather resistance is achieved. 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。 Although it does not specifically limit as (D) component, For example, a silica, a zirconia, an alumina, a titania, a zinc oxide etc. are mentioned. These may be used alone or in combination of two or more. Among these, at least one selected from the group consisting of silica, zirconia and alumina is preferable from the viewpoint of wear resistance, and silica is more preferable. In addition, (D) component may use a commercial item as it is, and it is not specifically limited, For example, as a silica, Snowtex (Nissan Chemical Industry Co., Ltd. product), Quartron (Fuso Chemical Industry Co., Ltd. product) ), Aerosil (manufactured by Nippon Aerosil Co., Ltd.), Sildex (manufactured by Asahi Glass Co., Ltd.), Silysia 470 (manufactured by Fuji Silysia Chemical Co., Ltd.); As zirconia, TZP-108 (manufactured by Taisei Kako Co., Ltd.); Examples of alumina include NANOBYK-3610 (manufactured by Big Chemie Japan Co., Ltd.), Nanoclear HC-A01 (manufactured by CIK Nanotech Co., Ltd.) and the like. In the present invention, it is preferable to use an organosilica sol previously dispersed in an organic solvent for the purpose of simplification of production. For example, PGM-AC4130Y (a propylene glycol monomethyl ether dispersion manufactured by Nissan Chemical Industries, Ltd.), IPA- ST-MS (isopropanol dispersion manufactured by Nissan Chemical Industries, Ltd.), MA-ST-M (methanol dispersion manufactured by Nissan Chemical Industries, Ltd.), Quattron PL-2-IPA (isopropanol dispersion manufactured by Fuso Chemical Industries, 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。 (D) The usage-amount of a component is 20 to 60 weight% normally by making an active energy ray-curable resin composition into 100 weight%. If the amount used is less than 20% by weight, the wear resistance tends to be insufficient, and if it exceeds 60% by weight, the transparency tends to decrease when cured by active energy rays. Moreover, from these points, it is preferably 20 to 60% by weight, more preferably 25 to 50% by weight. In addition, when (D) component is a dispersion, the said usage-amount is represented by the solid content of (D) component.
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 point of wear resistance of the cured film, the compound (C) having three or more unsaturated double bonds in the molecule (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。 (C) It does not specifically limit as a component, A well-known thing 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, ditrimethylolpropane tetra ( (Meth) acrylic esters such as (meth) acrylate; polyfunctional (meth) acrylate oligomers having a hydroxyl group such as dipentaerythritol pentaacrylate and pentaerythritol triacrylate and a compound having two or more isocyanate groups in one molecule Polyfunctional urethane (meth) acrylate obtained by reaction; dipentaerythritol, pentaerythritol, glycerin, diglycerin, trimethylo Polyether (meth) acrylate obtained by modifying polyfunctional alcohol such as rupropane with ethylene oxide or propylene oxide and acrylic acid added; oligomer such as polyester poly (meth) acrylate epoxy (meth) acrylate or polyol (meth) acrylate Etc. 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 further has excellent abrasion resistance and weather resistance of the cured coating. , 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。 Although the usage-amount of (C) component is not specifically limited, From an abrasion-resistant point of a cured film, an active energy ray curable resin composition is 100 weight% normally, and is about 10 to 50 weight% normally. From the same point, 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 not particularly limited as long as it is compatible with both the component (A) and the component (B), does not affect the dispersibility of the component (D), and has good volatility during drying. Various known materials can be used. For example, ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetylacetone; esters such as methyl acetate, ethyl acetate, butyl acetate; ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, isobutyl alcohol, tert-butyl alcohol, diacetone alcohol Alcohols such as toluene, aromatic hydrocarbons such as xylene, aliphatic hydrocarbons such as n-hexane, cyclohexane, methylcyclohexane, and n-heptane; isopropyl ether, methyl cellosolve, ethyl cellosolve, 1,4-dioxane, propylene glycol Examples 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. Moreover, it is although it does not specifically limit as solid content concentration, It is preferable to set it as 10 to 70 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 may further comprise various known additives such as photosensitizers, antioxidants, light stabilizers, leveling agents, pigments, photopolymerization initiators, ultraviolet rays, if necessary. An absorbent or the like may be included.
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. For example, 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-cyclohexyl phenyl ketone, 2-hydroxy- 2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1 -[4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6) -Trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 4-methylbenzo Enon, and the like. These may be used alone or in combination of two or more. In addition, although a photoinitiator is used when hardening with an active energy ray, it is not necessarily required when hardening with an electron beam among them. The amount of the photopolymerization initiator used is 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.
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, absorbs ultraviolet rays such as benzophenone ultraviolet absorbers, triazine ultraviolet absorbers, and benzotriazole ultraviolet absorbers, 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。 Although it does not specifically limit as a benzophenone series ultraviolet absorber, For example, a hydroxybenzophenone series ultraviolet absorber is used preferably. Although it does not specifically limit as a hydroxybenzophenone series ultraviolet absorber, For example, 2-hydroxybenzophenone, 2, 4- dihydroxy benzophenone, 2,2'- dihydroxy-4,4'- dimethoxy benzophenone, 2,2'-4, Examples thereof include 4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, hydroxymethoxybenzophenonesulfonic acid and its trihydrate, and hydroxymethoxybenzophenonesulfonic acid sodium.
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。 Although it does not specifically limit as a triazine type ultraviolet absorber, A hydroxyphenyl triazine type ultraviolet absorber is used preferably. Although it does not specifically limit as a hydroxyphenyl triazine type ultraviolet absorber, 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。 Although it does not specifically limit as a benzotriazole type ultraviolet absorber, For example, 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl ] Propionate, 2- (2H-benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4-methylphenol, 2- [5-chloro (2H) -benzotriazol-2-yl]- 4-methyl-6- (tert-butyl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol, 2- (2'-hydroxy-5'-methylphenyl) ) Benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'- Droxy-3'-tert-butyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2 '-Hydroxy-3'-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole, 2,2-methylenebis (4- (1,1,3,3 -Tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol), 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2 -[2-hydroxy-5- (2- (meth) acryloyloxyethyl) phenyl] -2H-benzotriazole, and 2- [2-hydroxy-5 (2- (meth) acryloyloxyethyl) phenyl] -2H- benzotriazole copolymerized polymer and the like.
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。 Although the usage-amount of a ultraviolet absorber is not specifically limited, It is preferable to set it as about 1-20 weight part with respect to the total amount of 100 weight part of (A)-(D) component by 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 laminated body of this invention has the cured film of the said active energy ray curable resin composition on the surface of a 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 substrate 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, and examples thereof include spray coating, dip coating, bar coating, spin coating, slide coating, roll coating, and the like. Is mentioned. The thickness of the coating layer is preferably 3 to 60 μm after being cured with active energy rays. When it is less than 3 μm, weather resistance and wear resistance are not sufficient. When it exceeds 60 μm, there is a problem that the cured coating may be colored. Moreover, from the same point, More preferably, it is about 5-40 micrometers.
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。 In order to remove the organic solvent, the laminate of the present invention is preferably pre-dried with a heat source in advance. Although it does not specifically limit as a heat source, A circulating air dryer, an electric furnace, a gas furnace, etc. are mentioned. Although it does not specifically limit as drying conditions, Temperature is about 40-100 degreeC, Preferably it is about 50-80 degreeC, Time is about 1 to 30 minutes, Preferably it is 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。 Subsequently, an active energy ray is irradiated and a coating layer is hardened. Although it does not specifically limit as an active energy ray, For example, an ultraviolet-ray, visible light, an electron beam, ionizing radiation etc. are mentioned. 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 ultraviolet light source is not particularly limited, and examples thereof include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon lamp, and a metal halide lamp. In addition, the irradiation condition varies depending on the light source to be 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 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。 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, headlamp covers, plastic materials for automobiles such as resin glazing, sunroofs, building materials, transparent It can be used as a resin composition for exterior members.
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。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited only to this Example. 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.
(Formula 1) Double bond equivalent (g / eq) = [{(a1) to (a4) component use weight (g)} + {initiator use weight (g)}] / (a4) component use Molar amount (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 the following formula 2.
(Formula 2) Amine equivalent (g / eq) = [{(a1) to (a4) used weight of component (g)} + {initiator used weight (g)}] / (a2) used molar amount of component (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 “GAMA”). 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 Then, the system was heated to a temperature of about 95 ° C. over about 1 hour under a nitrogen stream, and kept warm for 1 hour. Next, a mixed solution in which 90 parts of GMA, 60 parts of HALS-1, 150 parts of MMA and 12 parts of AIBN were previously charged was dropped into the system from a dropping funnel in a nitrogen stream in about 2 hours. After keeping the same temperature for 3 hours, 1 part of AIBN was charged and kept for 1 hour. Then, it heated up at 120 degreeC and heat-retained for 2 hours. Thereafter, 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, and after adding 60 parts of acrylic acid (hereinafter referred to as AA), 1 part of methoquinone and 3 parts of triphenylphosphine, and mixing, under air bubbling, The temperature was raised to 110 ° C. Next, after keeping at the same temperature for 8 hours, 1 part of methoquinone was added and cooled, and butyl acetate was added so that the solid content concentration became 50%, and the polymer (A-1) (hereinafter referred to as (A-1)). Solution). The physical properties are shown in Table 1. (The same applies hereinafter)
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 2-6, Comparative Production Example 1 (Production of Polymers (A-2) to (A-6), (F-1))
The compositions as shown in Table 1 were produced in the same manner as in Production Example 1 to obtain polymers (A-2) to (A-6) and (F-1).
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 a reaction vessel similar to Production Example 1. Then, the system was heated to a temperature of about 95 ° C. over about 1 hour under a nitrogen stream, and kept warm for 1 hour. Next, a mixed solution prepared in advance with 90 parts of HEMA, 120 parts of HALS-1, 90 parts of MMA, and 12 parts of AIBN was dropped from the dropping funnel into the system in a nitrogen stream in about 2 hours. After keeping the same temperature for 3 hours, 1 part of AIBN was charged and kept for 1 hour. Then, it heated up at 120 degreeC and heat-retained for 2 hours. Thereafter, the reaction system was cooled to obtain a polymer (A7-1) solution.
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 inlet tube of the reaction vessel was replaced with an air inlet tube, 99 parts of 2-isocyanatoethyl acrylate (trade name: Karenz AOI, manufactured by Showa Denko KK, hereinafter referred to as AOI), 1 part of methoquinone and octyl. After adding 0.5 parts of tin (II) acid and mixing, it heated up to 80 degreeC under air bubbling. Next, after keeping at the same temperature for 4 hours, after confirming the disappearance of the IR peak of the isocyanate group, 1 part of methoquinone was charged, cooled, and butyl acetate was added so that the solid content concentration became 50%. A solution of A-7) was obtained. (The same applies hereinafter)
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 a reaction vessel similar to 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 system was heated to a temperature of about 95 ° C. over about 1 hour in a nitrogen stream and kept for 1 hour. Next, a liquid mixture 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 in about 2 hours. After keeping the same temperature for 3 hours, 1 part of AIBN was charged and kept for 1 hour. Then, it heated up at 120 degreeC and heat-retained for 2 hours. Thereafter, the reaction system was cooled to obtain a polymer (A8-1) solution.
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） Subsequently, the nitrogen inlet tube of the reaction vessel was replaced with an air inlet tube, and 89 parts of 2-hydroxyethyl acrylate (hereinafter referred to as HEA), 1 part of methoquinone and 0.5 part of tin (II) octylate were added and mixed. Then, it heated up to 80 degreeC under air bubbling. Next, after keeping at the same temperature for 4 hours, after confirming the disappearance of the IR peak of the isocyanate group, 1 part of methoquinone was charged, cooled, and butyl acetate was added so that the solid content concentration became 50%. A solution of A-8) was obtained. (The same applies hereinafter)
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
About the symbol of the component in Table 1, the following compounds are represented.
(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 weight: 20 parts), 20 parts of dimethylol tricyclodecane diacrylate (trade name: Light acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.) as component (B) As component (C), dimethylolpropane triacrylate (trade name: Beamset 730, manufactured by Arakawa Chemical Industries, Ltd.) 10 parts, as component (D), propylene glycol monomethyl ether dispersed colloidal silica (SiO 2 , average primary particles) Diameter: 40-60 nm, solid content concentration: 30%, trade name: PGM-AC4130Y, manufactured by Nissan Chemical Industries, Ltd.) 167 parts (solid content weight: 50 parts), and 1-hydroxy-cyclohexyl as a photopolymerization initiator -5 parts of phenyl ketone (trade name: Irgacure 184, manufactured by Ciba Japan Co., Ltd.) and as a surface conditioner Add 0.2 parts of BYK-310 (Bic Chemie) which is a corn surface conditioner, dilute with propylene glycol monomethyl ether (hereinafter referred to as PM) so that the solid content concentration is 33%, and active energy ray curability. A resin composition was prepared.
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 2-13, Comparative Examples 1-9
Active energy ray-curable resin compositions having the compositions shown in Table 2 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。
[Production of laminate (evaluation with 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 is passed under a high-pressure mercury lamp (integrated light quantity: 1000 mJ / cm 2 , irradiation intensity: 200 mW / cm 2 ) in the air (conveying speed: 10 m / min) and cured. A laminate was obtained. Moreover, the laminated body was obtained similarly about each resin composition of Examples 2-13 and Comparative Examples 1-9, respectively.
［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 substrate at 1 mm intervals, and a 100-cell grid cellophane tape peel test was performed to evaluate initial adhesion.
Evaluation criteria ○: no peeling ×: peeling occurred
［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]
According to JIS K 7361-1, the haze value of each laminated body was measured with the haze meter.
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]
In accordance with ASTM-D-1044, the cured film in each laminate was worn under the conditions of a wear wheel CS-10F, a load of 500 g, a rotation speed of 60 rpm, and a wear frequency of 500 cycles. 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 standard ◎: △ HAZE <5%
○: △ HAZE <10%
×: ΔHAZE ≧ 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 0.1N sodium hydroxide (NaOH) aqueous solution set at 55 ° C. for 4 hours. Thereafter, the surface was washed with pure water and dried, and then IR measurement was performed by the ATR method to evaluate changes in the peak derived from silica.
Evaluation criteria ○: IR peak area change amount is 20% or less ×: IR peak area change amount 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 laminated body was put in a hot air circulating dryer having a temperature of 140 ° C., left for 200 hours, cooled to room temperature, and then the surface state of the laminated body 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
[Weather resistance]
Using an i-super UV tester (Iwasaki Electric Co., Ltd.), after carrying out a weather resistance test under the following test conditions, the appearance (cracks, peeling) of the cured film in each laminate was visually observed. In accordance with JIS K 7373, ΔYI was measured by a transmission method using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd.) and evaluated based on the following criteria.
(Test conditions)
Each laminate was irradiated at 80 mW / cm 2 and tested for 360 hours at a black panel temperature of 63 ° C., and ion-exchanged water was sprayed on the surface of the cured coating every 10 hours for 10 seconds.
Evaluation criteria A: No visual change and ΔYI is less than 2.0 ○: No visual change and ΔYI is 2.0 or more and less than 4.0 ×: There is a visual change or ΔYI is 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）
About the symbol of the component in Table 2, the following compounds are represented.
(B) component B-1: dimethylol tricyclodecane diacrylate (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.)
Component (C) : C-1: dimethylolpropane triacrylate (DMPTA) (trade name: Beam Set 730, manufactured by Arakawa Chemical Industries, Ltd.)
C-2: EO-modified dipentaerythritol hexaacrylate (DPH-12E) (trade name: NK ester A-DPH-12E, manufactured by Shin-Nakamura Chemical Co., Ltd.)
Metal oxide particles · D-1: Propylene glycol monomethyl ether-dispersed colloidal silica (SiO 2, average primary particle diameter: 40 to 50 nm, solid concentration: 30%, trade name: PGM-AC4130Y, manufactured by Nissan Chemical Industries, Ltd. )
D-2: propylene glycol monomethyl ether acetate dispersed zirconium oxide (ZrO 2 , average primary particle size: 30 to 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 diameter: 10 to 15 nm, solid concentration: 40%, trade name: PGM-AC2140Y, manufactured by Nissan Chemical Industries, Ltd.)
H-1: Propylene glycol monomethyl ether-dispersed colloidal silica (SiO 2 , average primary particle size: 100 nm, solid content concentration: 50%, trade name: Admanano Slurry YA100C-LFG, manufactured by Admatechs)
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 laminate using a polyacrylic plate)
The active energy ray-curable resin composition of Example 1 was applied to the surface of a 2 mm thick polyacrylic plate 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 is passed under a high-pressure mercury lamp (integrated light quantity: 1000 mJ / cm 2 , irradiation intensity: 200 mW / cm 2 ) in the air (conveying speed: 10 m / min) and cured. A laminate was obtained. When the same evaluation was performed using the laminate, all showed good effects. The results are shown in Table 3.
Claims (9)
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。 10 to 60% by weight of polymer (A) having an unsaturated double bond and a piperidinyl group in one molecule,
10 to 60% by weight of compound (B) having two unsaturated double bonds in the molecule,
And 20-60 wt% of metal oxide fine particles (D) having an average primary particle diameter of 20-80 nm
An active energy ray-curable resin composition containing
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る、請求項１の活性エネルギー線硬化性樹脂組成物。 (A) component is
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 claim 1, which is a reaction product with a monomer (a4) having a functional group that can react with the functional group of the component (A1).
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