JPS6328095B2 - - Google Patents
Info
- Publication number
- JPS6328095B2 JPS6328095B2 JP55031017A JP3101780A JPS6328095B2 JP S6328095 B2 JPS6328095 B2 JP S6328095B2 JP 55031017 A JP55031017 A JP 55031017A JP 3101780 A JP3101780 A JP 3101780A JP S6328095 B2 JPS6328095 B2 JP S6328095B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- monomer
- synthetic resin
- monomer mixture
- 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.)
- Expired
Links
- 239000000178 monomer Substances 0.000 claims description 69
- 239000000203 mixture Substances 0.000 claims description 49
- 239000011248 coating agent Substances 0.000 claims description 37
- 238000000576 coating method Methods 0.000 claims description 37
- 229920003002 synthetic resin Polymers 0.000 claims description 34
- 239000000057 synthetic resin Substances 0.000 claims description 34
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 229920000058 polyacrylate Polymers 0.000 claims description 20
- 239000008199 coating composition Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- -1 acryloyloxy groups Chemical group 0.000 claims description 16
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 229920001296 polysiloxane Polymers 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 8
- 239000012965 benzophenone Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 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 claims description 7
- 238000009835 boiling Methods 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound 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 claims description 6
- 229920001519 homopolymer Polymers 0.000 claims description 6
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 229960000969 phenyl salicylate Drugs 0.000 claims description 5
- 239000003504 photosensitizing agent Substances 0.000 claims description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 230000002745 absorbent Effects 0.000 claims 2
- 239000002250 absorbent Substances 0.000 claims 2
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 claims 2
- 238000000465 moulding Methods 0.000 claims 1
- 238000005299 abrasion Methods 0.000 description 17
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 239000006096 absorbing agent Substances 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 229920005668 polycarbonate resin Polymers 0.000 description 7
- 239000004431 polycarbonate resin Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 5
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method 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
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000037048 polymerization activity Effects 0.000 description 4
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 3
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-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
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 125000005702 oxyalkylene group Chemical group 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- WTJWFFXZUSGGKB-UHFFFAOYSA-N (4-octoxyphenyl)-phenylmethanone Chemical compound C1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 WTJWFFXZUSGGKB-UHFFFAOYSA-N 0.000 description 2
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 2
- 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 2
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 2
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 description 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 2
- ROWKJAVDOGWPAT-UHFFFAOYSA-N Acetoin Chemical compound CC(O)C(C)=O ROWKJAVDOGWPAT-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- YSKCRYMJUCLQDG-UHFFFAOYSA-N [4-[2-(2,3-diethoxy-4-prop-2-enoyloxyphenyl)propan-2-yl]-2,3-diethoxyphenyl] prop-2-enoate Chemical compound CCOC1=C(OC(=O)C=C)C=CC(C(C)(C)C=2C(=C(OCC)C(OC(=O)C=C)=CC=2)OCC)=C1OCC YSKCRYMJUCLQDG-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229940035429 isobutyl alcohol Drugs 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920005990 polystyrene resin Polymers 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- POLSVAXEEHDBMJ-UHFFFAOYSA-N (2-hydroxy-4-octadecoxyphenyl)-phenylmethanone Chemical compound OC1=CC(OCCCCCCCCCCCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 POLSVAXEEHDBMJ-UHFFFAOYSA-N 0.000 description 1
- POTYORUTRLSAGZ-UHFFFAOYSA-N (3-chloro-2-hydroxypropyl) prop-2-enoate Chemical compound ClCC(O)COC(=O)C=C POTYORUTRLSAGZ-UHFFFAOYSA-N 0.000 description 1
- ARVUDIQYNJVQIW-UHFFFAOYSA-N (4-dodecoxy-2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC(OCCCCCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 ARVUDIQYNJVQIW-UHFFFAOYSA-N 0.000 description 1
- SWFHGTMLYIBPPA-UHFFFAOYSA-N (4-methoxyphenyl)-phenylmethanone Chemical compound C1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 SWFHGTMLYIBPPA-UHFFFAOYSA-N 0.000 description 1
- OMWSZDODENFLSV-UHFFFAOYSA-N (5-chloro-2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=C(Cl)C=C1C(=O)C1=CC=CC=C1 OMWSZDODENFLSV-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- WXHVQMGINBSVAY-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 WXHVQMGINBSVAY-UHFFFAOYSA-N 0.000 description 1
- ITLDHFORLZTRJI-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-5-octoxyphenol Chemical compound OC1=CC(OCCCCCCCC)=CC=C1N1N=C2C=CC=CC2=N1 ITLDHFORLZTRJI-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- PTJDGKYFJYEAOK-UHFFFAOYSA-N 2-butoxyethyl prop-2-enoate Chemical compound CCCCOCCOC(=O)C=C PTJDGKYFJYEAOK-UHFFFAOYSA-N 0.000 description 1
- JGRXEBOFWPLEAV-UHFFFAOYSA-N 2-ethylbutyl prop-2-enoate Chemical compound CCC(CC)COC(=O)C=C JGRXEBOFWPLEAV-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- LKJTVGPNIFDNOA-UHFFFAOYSA-N 3-[4-[2-[4-(3-prop-2-enoyloxypropoxy)phenyl]propan-2-yl]phenoxy]propyl prop-2-enoate Chemical compound C=1C=C(OCCCOC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OCCCOC(=O)C=C)C=C1 LKJTVGPNIFDNOA-UHFFFAOYSA-N 0.000 description 1
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 1
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-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
- BVEYJWQCMOVMAR-UHFFFAOYSA-N 5-Hydroxy-4-octanone Chemical compound CCCC(O)C(=O)CCC BVEYJWQCMOVMAR-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005711 Benzoic acid Substances 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
- XWUNIDGEMNBBAQ-UHFFFAOYSA-N Bisphenol A ethoxylate diacrylate Chemical compound C=1C=C(OCCOC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OCCOC(=O)C=C)C=C1 XWUNIDGEMNBBAQ-UHFFFAOYSA-N 0.000 description 1
- PTQAJIGNKQQAGE-UHFFFAOYSA-N C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.OCCC Chemical compound C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.OCCC PTQAJIGNKQQAGE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004420 Iupilon Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- RVWADWOERKNWRY-UHFFFAOYSA-N [2-(dimethylamino)phenyl]-phenylmethanone Chemical compound CN(C)C1=CC=CC=C1C(=O)C1=CC=CC=C1 RVWADWOERKNWRY-UHFFFAOYSA-N 0.000 description 1
- RVHZAEROAXRASX-UHFFFAOYSA-N [3-(2-hydroxypropoxy)-4-[2-[2-(2-hydroxypropoxy)-4-prop-2-enoyloxyphenyl]propan-2-yl]phenyl] prop-2-enoate Chemical compound CC(O)COC1=CC(OC(=O)C=C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1OCC(C)O RVHZAEROAXRASX-UHFFFAOYSA-N 0.000 description 1
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical compound C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-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
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-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
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- QKLCQKPAECHXCQ-UHFFFAOYSA-N ethyl phenylglyoxylate Chemical compound CCOC(=O)C(=O)C1=CC=CC=C1 QKLCQKPAECHXCQ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- IQRVNLYKJBNWHE-UHFFFAOYSA-N heptan-2-yl prop-2-enoate Chemical compound CCCCCC(C)OC(=O)C=C IQRVNLYKJBNWHE-UHFFFAOYSA-N 0.000 description 1
- MDNFYIAABKQDML-UHFFFAOYSA-N heptyl 2-methylprop-2-enoate Chemical compound CCCCCCCOC(=O)C(C)=C MDNFYIAABKQDML-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- GFAZHVHNLUBROE-UHFFFAOYSA-N hydroxymethyl propionaldehyde Natural products CCC(=O)CO GFAZHVHNLUBROE-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- YNXCGLKMOXLBOD-UHFFFAOYSA-N oxolan-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CCCO1 YNXCGLKMOXLBOD-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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- QONHNMFEHWGACQ-UHFFFAOYSA-N pentan-3-yl prop-2-enoate Chemical compound CCC(CC)OC(=O)C=C QONHNMFEHWGACQ-UHFFFAOYSA-N 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000196 poly(lauryl methacrylate) Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- WREHAFOLOOKAOW-UHFFFAOYSA-N propane-1,2,3-triol prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO WREHAFOLOOKAOW-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- GDESWOTWNNGOMW-UHFFFAOYSA-N resorcinol monobenzoate Chemical compound OC1=CC=CC(OC(=O)C=2C=CC=CC=2)=C1 GDESWOTWNNGOMW-UHFFFAOYSA-N 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は空気雰囲気下で紫外線照射により、耐
摩耗性、可撓性、耐熱性、耐溶剤性、基材との密
着性および耐候性等に優れた架橋硬化被膜を形成
しうる被覆材組成物並びにこれを用いて耐摩耗性
および耐候性等に優れた合成樹脂成形品を製造す
る方法に関する。
ポリメチルメタクリレート樹脂、ポリカーボネ
ート樹脂、ポリスチレン樹脂、AS樹脂などから
製造された合成樹脂成形品は軽量で耐衝撃性にす
ぐれているばかりでなく、安価で成形加工が容易
であるなど種々の利点を有しており、多くの分野
でその用途開発が進められている。しかし反面こ
れらの合成樹脂成形品はその表面の耐摩耗性が不
足しているため、他の硬い物体との接触、摩擦、
ひつかきなどによつて表面に損傷を受けやすく、
表面に発生した損傷はその商品価値を著しく低下
させたり、短期間で使用不能となつたりするので
表面の耐摩耗性を改良することが強く要求されて
いる。また、これらの被覆材を用いて耐摩耗性の
改良された合成樹脂成形品はその使用用途によつ
ては屋外で使用される場合も有り、たとえば航空
機の風防板、屋外看板、交通標識、自動車部品な
どではその耐候性が強く要求されている。
このような合成樹脂成形品の欠点を改良する方
法については従来より種々検討されてきており、
例えばシリコン系、メラミン系等の樹脂組成物か
らなる被覆材を合成樹脂成形品表面に塗布し、加
熱縮合によつて架橋被膜を形成し合成樹脂成形品
の耐摩耗性を向上させる方法および１分子中に１
個以上の重合性基を有する多官能性単量体を合成
樹脂成形品表面上に塗布して、活性エネルギー線
を照射させ、ラジカル重合によつて合成樹脂成形
品表面に架橋硬化被膜を形成する耐摩耗性に優れ
た合成樹脂成形品を製造する方法等が提案されて
いる（特公昭48−42211号および同49−22951号）。
これらの方法による合成樹脂成形品表面の耐摩
耗性はある程度改善されるようになつたものの、
前者については熱シヨツク、熱水などに対する耐
久性とか、耐薬品性が不十分であつたり、後者に
ついては耐久性、耐薬品性等にはすぐれるものの
耐摩耗性合成樹脂成形品製造時に高価な不活性ガ
スを必要とするなど種々の欠点を有する上に、さ
らに耐候性に関しても満足すべきものではなかつ
た。
特に基材の合成樹脂成形品の耐候性が本質的に
不良なもの、例えばポリカーボネート樹脂等の場
合は、表面硬化被膜自身の耐候性は良好であつて
も、被膜を透過した紫外線等の活性エネルギー線
によつて基材自身が劣化を受け、成形品が強く黄
変したり、表面の硬化被膜にクラツクが生じた
り、ひどい場合には被膜が剥落したりする。
本発明者らはこのような状況に鑑み、耐摩耗性
の改善に対しては多くの提案を行なつてきている
が（特開昭53−102936号、同53−104638号および
特願昭53−4079号）、さらに耐候性にも優れた耐
摩耗性合成樹脂成形品を得るべく鋭意検討した結
果、ある特定の多官能アクリレートおよび１官能
性（メタ）アクリレートを特定の割合に配合し、
さらに特定の（メタ）アクリル酸アルキルの単独
重合または共重合体と、紫外線吸収剤、シリコン
系界面活性剤および光増感剤を特定の割合に配合
した被覆材組成物を合成樹脂成形品に塗布して硬
化させることにより、耐候性において非常にすぐ
れた合成樹脂成形品がえられることを見い出し本
発明を完成した。
すなわち本発明の要旨とするところは、
(a) 次の一般式
（式中X11，X12，X13，X22，X23…Xn2，
Xn3，X14の内少なくとも３個はCH2＝CH―
COO―基で残りは―OH基である。またｎは１
〜５の整数である。）で示される１分子中に３
個以上のアクリロイルオキシ基を有するモノ又
はポリペンタエリスリトールのポリアクリレー
トの１種以上40〜100重量％と、
次の一般式
（式中X1，X2…Xnは炭素数６以下の同じも
しくは異なるアルキレン基又はその水素原子１
個が水酸基で置換された構造のものであり、ｎ
は０〜５の整数を示す。）で示される２官能単
量体０〜50重量％と、
１分子中に１個のアクリロイルオキシ基を有
し、かつ常圧での沸点が150℃以上で、20℃に
おける粘度が20cps以下である１官能性単量体
０〜60重量％からなる単量体混合物、
(b) 該単量体混合物100重量部に対して少なくと
も１種の紫外線吸収剤５〜35重量部、
(c) 該単量体混合物100重量部に対して少なくと
も１種の（メタ）アクリル酸アルキル重合体
0.5〜８重量部、
(d) 該単量体混合物100重量部に対して光増感剤
0.01〜６重量部、および
(e) 好ましくは該単量体100重量部に対して
0.0001〜2.0重量部のポリオキシアルキレン基
で変性した少なくとも１種の界面活性剤
とからなる被覆材組成物並びに被覆材組成物を合
成樹脂成形品表面に塗布し、空気中で紫外線を照
射して膜厚１〜30μの架橋硬化被覆を有する耐摩
耗性および耐候性に優れた合成樹脂成形品を製造
する方法にある。
本発明において使用される一般式（）で示さ
れる１分子中に３個以上のアクリロイルオキシ基
を有するモノまたはポリペンタエリスリトールポ
リアクリレート単量体は紫外線の照射によつて非
常に良好な重合活性を有しており、また架橋硬化
して高度の耐摩耗性を示す高度の架橋硬化重合体
を形成するものである。本発明においては、上記
一般式（）で示される単量体を使用することに
より、充分その目的を達成しうるが、とりわけジ
ペンタエリスリトールテトラアクリレート、ジペ
ンタエリスリトールペンタアクリレート、ジペン
タエリスリトールヘキサアクリレートなどが空気
中で紫外線照射による重合活性の面で特に好まし
い。前記一般式（）で示される単量体は１種又
は２種以上混合して使用してもよい。
該単量体の使用割合は、単量体混合物中40〜
100重量％、好ましくは50〜90重量％であり、該
単量体の量が単量体混合物40重量％未満の場合に
は十分な耐摩耗性を有する硬化被膜が得られな
い。
また本発明においては、例え１分子中に３個以
上のアクリロイルオキシ基を有する単量体であつ
ても、前記一般式（）を満足しない多官能単量
体、例えばトリメチロールプロパントリアクリレ
ート、トリメチロールエタントリアクリレート、
ペンタグリセロールトリアクリレートなどの多官
能性アクリレートは空気中での紫外線照射による
重合活性が劣り、本発明の目的には用いられな
い。
また本発明において、前記一般式（）と併用
して用いる一般式（）の２官能単量体は空気中
での紫外線照射による硬化性が良好なものであつ
て、架橋硬化被膜の耐摩耗性を低下させることな
く架橋硬化被膜にすぐれた可撓性が要求される場
合に配合される。
この一般式（）で示される化合物においても
Xnの炭素数が７個以上になつたり、ｎの数が６
以上の場合には架橋硬化被膜の耐摩耗性が劣つた
り、あるいは基材との密着性が低下したりして好
ましくない。より好ましい単量体としては、Xn
の炭素数が３個以下で、かつｎの数が３以下のも
のである。
上記の一般式（）で示される２官能単量体の
具体例としては、例えば２，２―ビス（４アクリ
ロキシフエニル）プロパン、２，２―ビス（４ア
クリロキシエトキシフエニル）プロパン、２，２
―ビス（４アクリロキシジエトキシフエニル）プ
ロパン、２，２―ビス（４アクリロキシプロポキ
シフエニル）プロパン、２，２―ビス〔４アクリ
ロキシ（２ヒドロキシプロポキシ）フエニル〕プ
ロパン、２，２―ビス〔４アクリロキシ（２ヒド
ロキシプロポキシエトキシ）フエニル〕プロパン
などが挙げられる。これらの単量体は１種を単独
で使用することもでき、またその組成範囲内にお
いては２種以上混合して使用してもよい。
一般式（）で示されるこれら２官能単量体の
使用割合は、単量体混合物中０〜50重量％であ
り、好ましくは０〜30重量％である。２官能単量
体の量が単量体混合物中50重量％をこえる場合に
は架橋硬化被膜の耐摩耗性が低下するので好まし
くない。
また、前記の多官能単量体と併用して用いる１
分子中に１個のアクリロイルオキシ基を有し常圧
での沸点が150℃以上で、かつ20℃での粘度が20
センチポイズ以下の１官能単量体（以下、単に１
官能単量体と略称する）は成形品に被覆材組成物
を塗装した後、形成される塗装面に優れた平滑性
と共に硬化被膜に優れた可撓性並びに基材との密
着性が要求される場合に必要である。即ち、本発
明の被覆材組成物を成形品に塗布した後、平滑性
にすぐれた塗布被膜を形成させるためには、単量
体混合物の粘度が1000センチポイズ以下であるこ
とが望ましく、かつ硬化した後の硬化被膜に同様
な平滑性を与え、可撓性、基材との密着性を付与
するために上記の如き条件をみたす１官能単量体
を併用する必要がある。この１官能単量体の具体
的な例としては、ブチルアクリレート、イソブチ
ルアクリレート、ｔ―ブチルアクリレート、２―
エチルヘキシルアクリレート、ラウリルアクリレ
ート、トリデシルアクリレート、シクロヘキシル
アクリレート、２―ヒドロキシエチルアクリレー
ト、２―ヒドロキシプロピルアクリレート、グリ
シジルアクリレート、テトラヒドロフルフリルア
クリレート、ベンジルアクリレート、１，４―ブ
チレングリコールモノアクリレート、エトキシエ
チルアクリレート、エチルカルビトールアクリレ
ート、２―ヒドロキシ―３―クロロプロピルアク
リレートなどがあげられる。これらの単量体の中
でも本発明の場合には２―ヒドロキシエチルアク
リレート、２―ヒドロキシプロピルアクリレー
ト、グリシジルアクリレート、テトラヒドロフル
フリルアクリレート、エトキシエチルアクリレー
ト、エチルカルビトールアクリレート、ブトキシ
エチルアクリレート、１，４―ブチレングリコー
ルモノアクリレートなどのように単量体の側鎖に
水酸基および／または環状エーテル結合および／
または鎖状エーテル結合を有する単量体が空気中
での重合活性にすぐれているので特に好ましい。
これらの１官能単量体は１種を単独で使用する
こともでき、またその組成範囲内において２種以
上混合して使用してもよい。１官能単量体の使用
割合は、単量体混合物中０〜60重量％であり、好
ましくは10〜50重量％である。１官能単量体の量
が単量体混合物中10重量％未満の場合には、被覆
材組成物の粘度を充分低下させることができない
ため、若干面の平滑性が低下する場合がある。一
方１官能単量体60重量％をこえる場合には充分な
耐摩耗性を有する架橋硬化被膜が得られないので
好ましくない。１官能単量体を10〜50重量％の範
囲に用いた場合には、架橋硬化被膜の耐摩耗性を
低下させることなく後述する（メタ）アクリル酸
アルキル重合体との相乗効果により何ら架橋硬化
被膜に悪影響を与えることなく、さらに多量の紫
外線吸収剤を安定に多量に含有させることが可能
になる。さらに１官能単量体の沸点が常圧におい
て150℃よりも低い場合には、被覆材組成物を成
形品表面に塗布して硬化させる際、揮発逃散して
被覆材組成物の粘度上昇をもたらし、又単量体の
粘度が20℃で20センチポイズをこえる場合には、
単量体混合物の粘度を有効に下げることができな
いので好ましくない。
前記単量体混合物に添加して用いられる（メ
タ）アクリル酸アルキルの重合体は、架橋硬化被
膜の透明性および平滑性等の外観を低下させるこ
となく、硬化被膜の基材との密着性を改善し、多
量の紫外線吸収剤を架橋硬化被膜中に均一に分散
させうる分散助剤的な効果を有するものであり、
耐摩耗性に優れた合成樹脂成形品の耐候性を向上
させるためには必須の成分である。
塗料中に紫外線吸収剤を含有させ塗膜または塗
装品の耐候性を向上させる方法については公知で
あるが、本発明のように高度の架橋構造を有し、
表面硬度および耐摩耗性に優れる硬化被膜中に多
量の紫外線吸収剤を含有させることは不可能であ
つた。すなわち、被覆材組成物中に多量の紫外線
吸収剤を添加しておいても、その被覆材組成物の
硬化時に、多量の紫外線吸収剤が架橋結合被膜中
に十分均一に保持されず架橋被膜中に微小な島状
に集合するか、あるいは硬化被膜表面に浸出し
て、被膜全体が乳白色にくもつたり、硬化被膜の
表面硬度および耐摩耗性が極度に低下したりす
る。
事実、本発明のアクリル系単量体混合物からな
る架橋硬化被膜に対しても高々４重量部（単量体
混合物100重量部に対して）前後しか包含されな
い。この量をこえて多量に紫外線吸収剤を配合す
ると上述したような種々の欠陥が生起するし、ま
た一方４重量部以下の場合は上述したような問題
点は少なくなるもののその耐候性改善効果は不十
分であつた。
しかし、ここで前記した（メタ）アクリル酸ア
ルキルの重合体を本発明の被覆材組成物中に少量
配合すると、前記問題点が一挙に解決されること
を見い出した。
本発明において用いる（メタ）アクリル酸アル
キルの重合体としては、重合体平均分子量の目安
となる極限粘度〔η〕（ｇ／）が0.01〜0.30の
範囲にあるもので、好ましくは炭素数１〜８のア
ルキル基を有する（メタ）アクリル酸アルキルよ
り選ばれる単量体の単独重合体、またはそれらの
共重合体から選ばれるものである。
（メタ）アクリル酸アルキル重合体の極限粘度
〔η〕が0.01未満の場合は（メタ）アクリル酸ア
ルキル重合体による紫外線吸収剤の架橋硬化被膜
中への分散効果が十分でなく、また一方0.3をこ
える場合は（メタ）アクリル酸アルキル重合体の
本発明被覆材中への溶解性が十分でなかつたり、
硬化被膜の平滑性および耐摩耗性が低下したりす
る。また、アルキル基の炭素数が９以上の場合
も、（メタ）アクリル酸アルキル重合体の被覆材
中への溶解性が悪くなつたり、硬化被膜の平滑性
および耐摩耗性が低下したりする。
（メタ）アクリル酸アルキル重合体の具体例と
しては、メチル（メタ）アクリレート、エチル
（メタ）アクリレート、プロピル（メタ）アクリ
レート、ブチル（メタ）アクリレート、イソブチ
ル（メタ）アクリレート、アミルメタクリレー
ト、ヘキシルメタクリレート、ヘプチルメタクリ
レート、オクチルメタクリレート、２―エチル―
１―ヘキシル（メタ）アクリレート、３―ペンチ
ルアクリレート、３―メチル―１―ブチルアクリ
レート、２―エチル―１―ブチルアクリレートま
たは２―ヘプチルアクリレートの単独重合体また
はそれらの共重合体等があげられる。これらの重
合体は１種を単独で使用することもでき、また２
種以上混合して使用してもよい。
（メタ）アクリル酸アルキル重合体の単量体混
合物100重量部に対する配合量は0.5〜8.0重量部
の範囲が望ましく、より好ましくは１〜５重量部
で、0.5重量部未満の場合は紫外線吸収剤を多量
に含有することができず、またその量が8.0重量
部をこえる場合には、架橋硬化被膜の平滑性およ
び耐摩耗性が低下するようになる。
また本発明において使用される紫外線吸収剤と
しては特に限定されず、広義には高分子用光安定
剤に類するものも含まれ、本発明の被覆材組成物
に均一に溶解し、かつその耐候性が良好なもので
あれば使用することが可能であるが、本発明組成
物に対する良好な溶解性および耐候性改善効果と
いう点から見た場合、ベンゾフエノン系、ベンズ
トリアゾール系、サリチル酸フエニル系または安
息香酸フエニル系から誘導された化合物で、それ
らの最大吸収波長が240〜380nmの範囲である紫
外線吸収剤が望ましく、特にベンゾフエノン系の
紫外線吸収剤が本発明組成物に多量に含有させる
ことが出来るという点においてより好ましい。
紫外線吸収剤の具体例として、２―ヒドロキシ
ベンゾフエノン、５―クロロ―２―ヒドロキシベ
ンゾフエノン、２，４―ジヒドロキシベンゾフエ
ノン、２―ヒドロキシ―４―メトキシベンゾフエ
ノン、２―ヒドロキシ―４―オクチロキシベンゾ
フエノン、４―ドデシロキシ―２―ヒドロキシベ
ンゾフエノン、２―ヒドロキシ―４―オクタデシ
ロキシベンゾフエノン、２，2′―ジヒドロキシ―
４―メトキシベンゾフエノン、２，2′―ジヒドロ
キシ―４，4′―ジメトキシベンゾフエノン、フエ
ニルサリシレート、ｐ―tert.―ブチルフエニルサ
リシレート、ｐ―（１，１，３，３，―テトラメ
チルブチル）フエニルサリシレート、３―ヒドロ
キシフエニルベンゾエート、フエニレン―１，３
―ジベンゾエート、２―（２―ヒドロキシ―5′―
メチルフエニル）ベンゾトリアゾール、２―（２
―ヒドロキシ―５―tert.―ブチルフエニル）―５
―クロロベンゾトリアゾール、２―（２―ヒドロ
キシ―３，５―ジ―tert.―ブチルフエニル）ベン
ゾトリアゾール、２―（２―ヒドロキシ―５―
tert―ブチルフエニル）ベンゾトリアゾール、２
―（２―ヒドロキシ―４―オクチロキシフエニ
ル）ベンゾトリアゾール等が挙げられるが、これ
らのうち、ベンゾフエノン系の２―ヒドロキシ―
４―オクチロキシベンゾフエノンおよび２，４―
ジヒドロキシベンゾフエノンがベンゾフエノン系
紫外線吸収剤の中でも、本発明組成物への溶解性
という面において最も好ましい。またこれらの紫
外線吸収剤は、（メタ）アクリル酸アルキル重合
体の中でもエチル（メタ）アクリレートの単独重
合体または共重合体と組み合わせた場合には本発
明の効果が最大限に発揮される。これらの紫外線
吸収剤は単独で用いてもよいし、２種以上を混合
して用いてもよい。
紫外線吸収剤の単量体混合物への配合量は、単
量体混合物100重量部に対して５〜35重量部の範
囲が望ましく、より好ましくは８〜30重量部であ
る。５重量部未満では前述したように合成樹脂成
形品の耐候性改善効果が十分でなく、また35重量
部をこえると架橋硬化被膜の耐摩耗性および平滑
性等の低下が著しくなる。
本発明において使用されるシリコン系界面活性
剤は架橋硬化被膜平滑性を改善し、さらに有機溶
剤との接触による白化が生ずる場合にはこの白化
を防止するのに必要な成分である。
その配合量は単量体混合物100重量部に対して
0.0001〜2.0重量部の範囲である。その使用量が
0.0001重量部未満の場合は効果が少なく、一方
2.0重量部をこえると被膜の平滑性を低下させる
ので好ましくない。
シリコン系界面活性剤としては特に限定されな
いが、好ましくは特願昭54−4569号に記載してな
るようなその分子構造がポリジメチルシロキサン
単位からなり、その一部がポリオキシアルキレン
基で変性されているものが好ましく、変性度とし
てはメチルシロキサン基１単位CH3（SiO）1/2−に
対して少なくとも１種のオキシアルキレン基（―
OCH2CH2―，
The present invention provides a coating material composition that can form a crosslinked cured film with excellent abrasion resistance, flexibility, heat resistance, solvent resistance, adhesion to a base material, weather resistance, etc. by irradiation with ultraviolet rays in an air atmosphere. The present invention also relates to a method of manufacturing synthetic resin molded articles having excellent wear resistance, weather resistance, etc. using the same. Synthetic resin molded products made from polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, AS resin, etc. are not only lightweight and have excellent impact resistance, but also have various advantages such as being inexpensive and easy to mold. The development of its applications is progressing in many fields. However, on the other hand, these synthetic resin molded products lack surface wear resistance, so they are susceptible to contact with other hard objects, friction,
The surface is easily damaged by scratches, etc.
Since damage to the surface significantly reduces its commercial value or renders it unusable in a short period of time, there is a strong need to improve the abrasion resistance of the surface. In addition, synthetic resin molded products with improved wear resistance using these coating materials may be used outdoors depending on the intended use, such as aircraft windshields, outdoor signboards, traffic signs, and automobiles. Weather resistance is strongly required for parts and the like. Various methods have been studied to improve these drawbacks of synthetic resin molded products.
For example, a method of applying a coating material made of a silicone-based, melamine-based, etc. resin composition to the surface of a synthetic resin molded product and forming a crosslinked film through heat condensation to improve the wear resistance of the synthetic resin molded product, and a single molecule Inside 1
A polyfunctional monomer having three or more polymerizable groups is applied onto the surface of a synthetic resin molded product, and active energy rays are irradiated to form a crosslinked cured film on the surface of the synthetic resin molded product through radical polymerization. Methods for manufacturing synthetic resin molded products with excellent wear resistance have been proposed (Japanese Patent Publications No. 48-42211 and No. 49-22951). Although these methods have improved the abrasion resistance of synthetic resin molded product surfaces to some extent,
For the former, durability against heat shocks, hot water, etc., and chemical resistance are insufficient, and for the latter, although they have excellent durability and chemical resistance, they are expensive when manufacturing wear-resistant synthetic resin molded products. In addition to having various drawbacks such as the need for an inert gas, the weather resistance was also unsatisfactory. In particular, if the weather resistance of the base synthetic resin molded product is inherently poor, such as polycarbonate resin, even if the surface hardening coating itself has good weather resistance, active energy such as ultraviolet rays that has passed through the coating may The base material itself is deteriorated by the wires, resulting in the molded product becoming strongly yellowed, cracks appearing in the hardened film on the surface, and in severe cases, the film peeling off. In view of this situation, the present inventors have made many proposals for improving wear resistance (Japanese Patent Laid-Open No. 53-102936, No. 53-104638, and Japanese Patent Application No. 53-104). -4079), and as a result of intensive studies to obtain a wear-resistant synthetic resin molded product with excellent weather resistance, a specific polyfunctional acrylate and a monofunctional (meth)acrylate were blended in a specific ratio,
Furthermore, a coating composition containing a specific alkyl (meth)acrylate homopolymer or copolymer, a UV absorber, a silicone surfactant, and a photosensitizer in a specific ratio is applied to the synthetic resin molded product. The present invention was completed based on the discovery that a synthetic resin molded article with excellent weather resistance could be obtained by curing the resin. In other words, the gist of the present invention is that (a) the following general formula (In the formula, X 11 , X 12 , X 13 , X 22 , X 23 ...Xn 2 ,
At least three of Xn 3 and X 14 are CH 2 = CH-
COO- group and the rest are -OH groups. Also, n is 1
It is an integer of ~5. ) is 3 in one molecule.
40 to 100% by weight of one or more mono- or polypentaerythritol polyacrylates having at least 2 acryloyloxy groups, and the following general formula: (In the formula, X 1 , X 2 ...Xn are the same or different alkylene groups having 6 or less carbon atoms, or 1 hydrogen atom thereof
It has a structure in which n are substituted with hydroxyl groups, and n
represents an integer from 0 to 5. ), and has one acryloyloxy group in one molecule, and has a boiling point of 150℃ or higher at normal pressure and a viscosity of 20cps or lower at 20℃. (b) 5 to 35 parts by weight of at least one UV absorber per 100 parts by weight of the monomer mixture; (c) 5 to 35 parts by weight of at least one UV absorber; At least one alkyl (meth)acrylate polymer per 100 parts by weight of the monomer mixture
0.5 to 8 parts by weight, (d) photosensitizer based on 100 parts by weight of the monomer mixture
0.01 to 6 parts by weight, and (e) preferably based on 100 parts by weight of said monomer.
A coating composition comprising 0.0001 to 2.0 parts by weight of at least one surfactant modified with a polyoxyalkylene group and a coating composition are applied to the surface of a synthetic resin molded article, and irradiated with ultraviolet rays in the air. The present invention provides a method for producing a synthetic resin molded article having a cross-linked cured coating having a thickness of 1 to 30 microns and having excellent wear resistance and weather resistance. The mono- or polypentaerythritol polyacrylate monomer having three or more acryloyloxy groups in one molecule represented by the general formula () used in the present invention exhibits very good polymerization activity when irradiated with ultraviolet rays. It also crosslinks and cures to form a highly crosslinked and cured polymer that exhibits a high degree of abrasion resistance. In the present invention, the purpose can be fully achieved by using the monomer represented by the above general formula (), but in particular dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, etc. is particularly preferable in terms of polymerization activity by ultraviolet irradiation in air. The monomers represented by the general formula () may be used alone or in combination of two or more. The proportion of the monomer used is 40 to 40% in the monomer mixture.
If the amount of the monomer is less than 40% by weight of the monomer mixture, a cured film with sufficient wear resistance cannot be obtained. In addition, in the present invention, even if the monomer has three or more acryloyloxy groups in one molecule, polyfunctional monomers that do not satisfy the general formula (), such as trimethylolpropane triacrylate, methylolethane triacrylate,
Polyfunctional acrylates such as pentaglycerol triacrylate have poor polymerization activity when irradiated with ultraviolet light in air and cannot be used for the purpose of the present invention. In addition, in the present invention, the bifunctional monomer of the general formula () used in combination with the general formula () has good curability by ultraviolet irradiation in the air, and has good abrasion resistance of the crosslinked cured film. It is blended when excellent flexibility is required in the crosslinked cured coating without reducing the properties. Also in the compound represented by this general formula ()
The number of carbons in Xn is 7 or more, or the number of n is 6
In the above cases, the abrasion resistance of the crosslinked cured coating may be poor, or the adhesion to the substrate may be reduced, which is not preferable. A more preferable monomer is Xn
The number of carbon atoms is 3 or less, and the number of n is 3 or less. Specific examples of the bifunctional monomer represented by the above general formula () include 2,2-bis(4acryloxyphenyl)propane, 2,2-bis(4acryloxyethoxyphenyl)propane, 2,2
-Bis(4acryloxydiethoxyphenyl)propane, 2,2-bis(4acryloxypropoxyphenyl)propane, 2,2-bis[4acryloxy(2hydroxypropoxy)phenyl]propane, 2,2-bis Examples include [4acryloxy(2hydroxypropoxyethoxy)phenyl]propane. These monomers can be used alone or in combination of two or more within the composition range. The proportion of these bifunctional monomers represented by the general formula () in the monomer mixture is 0 to 50% by weight, preferably 0 to 30% by weight. If the amount of the bifunctional monomer exceeds 50% by weight in the monomer mixture, it is not preferable because the abrasion resistance of the crosslinked cured coating decreases. In addition, 1 used in combination with the above-mentioned polyfunctional monomer
Contains one acryloyloxy group in the molecule, has a boiling point of 150°C or higher at normal pressure, and has a viscosity of 20°C at 20°C.
A monofunctional monomer of centipoise or less (hereinafter simply 1
After coating a molded article with a coating composition, functional monomers (abbreviated as functional monomers) are required to have excellent smoothness on the coated surface, as well as excellent flexibility and adhesion to the substrate in the cured film. It is necessary when That is, in order to form a coating film with excellent smoothness after applying the coating composition of the present invention to a molded article, it is desirable that the viscosity of the monomer mixture be 1000 centipoise or less, and In order to impart similar smoothness, flexibility, and adhesion to the substrate to the cured film afterward, it is necessary to use a monofunctional monomer that satisfies the above conditions. Specific examples of this monofunctional monomer include butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-
Ethylhexyl acrylate, lauryl acrylate, tridecyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, 1,4-butylene glycol monoacrylate, ethoxyethyl acrylate, ethyl Examples include carbitol acrylate and 2-hydroxy-3-chloropropyl acrylate. Among these monomers, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, ethoxyethyl acrylate, ethyl carbitol acrylate, butoxyethyl acrylate, 1,4- Hydroxyl groups and/or cyclic ether bonds and/or
A monomer having a chain ether bond is particularly preferred since it has excellent polymerization activity in air. These monofunctional monomers may be used alone or in combination of two or more within the composition range. The proportion of the monofunctional monomer used is 0 to 60% by weight, preferably 10 to 50% by weight in the monomer mixture. If the amount of the monofunctional monomer is less than 10% by weight in the monomer mixture, the viscosity of the coating composition cannot be sufficiently lowered, so that the surface smoothness may be slightly reduced. On the other hand, if the monofunctional monomer content exceeds 60% by weight, it is not preferable because a crosslinked cured coating having sufficient wear resistance cannot be obtained. When the monofunctional monomer is used in the range of 10 to 50% by weight, no crosslinking and curing occurs due to the synergistic effect with the alkyl (meth)acrylate polymer described below without reducing the abrasion resistance of the crosslinked cured film. It becomes possible to stably contain a larger amount of ultraviolet absorber without adversely affecting the film. Furthermore, if the boiling point of the monofunctional monomer is lower than 150°C at normal pressure, when the coating composition is applied to the surface of the molded product and cured, it will volatilize and escape, resulting in an increase in the viscosity of the coating composition. , and if the viscosity of the monomer exceeds 20 centipoise at 20℃,
This is not preferred because the viscosity of the monomer mixture cannot be effectively lowered. The alkyl (meth)acrylate polymer added to the monomer mixture improves the adhesion of the cured film to the substrate without reducing the appearance such as transparency and smoothness of the crosslinked cured film. It has the effect of a dispersion aid that can uniformly disperse a large amount of ultraviolet absorber in a crosslinked cured film.
It is an essential component in order to improve the weather resistance of synthetic resin molded products with excellent wear resistance. Methods for improving the weather resistance of paint films or coated products by incorporating ultraviolet absorbers into paints are known, but methods for improving the weather resistance of paint films or coated products by including UV absorbers in paints,
It has been impossible to incorporate a large amount of ultraviolet absorber into a cured film that has excellent surface hardness and abrasion resistance. In other words, even if a large amount of ultraviolet absorber is added to the coating composition, when the coating composition is cured, the large amount of ultraviolet absorber is not sufficiently uniformly retained in the crosslinked coating, and the coating composition is cured. They either aggregate into minute islands or ooze out onto the surface of the cured film, causing the entire film to become milky and cloudy, and the surface hardness and abrasion resistance of the cured film to be extremely reduced. In fact, the crosslinked cured coating made of the acrylic monomer mixture of the present invention contains only about 4 parts by weight (based on 100 parts by weight of the monomer mixture). If the amount of ultraviolet absorber exceeds this amount, the various defects mentioned above will occur, while if the amount is less than 4 parts by weight, the above-mentioned problems will be reduced, but the effect of improving weather resistance will be low. It was insufficient. However, it has been found that when a small amount of the above-mentioned alkyl (meth)acrylate polymer is blended into the coating material composition of the present invention, the above problems can be solved at once. The alkyl (meth)acrylate polymer used in the present invention has an intrinsic viscosity [η] (g/), which is a guideline for the average molecular weight of the polymer, in the range of 0.01 to 0.30, and preferably has 1 to 1 carbon atoms. It is selected from homopolymers of monomers selected from alkyl (meth)acrylates having 8 alkyl groups, or copolymers thereof. If the intrinsic viscosity [η] of the alkyl (meth)acrylate polymer is less than 0.01, the dispersion effect of the ultraviolet absorber into the crosslinked cured film by the alkyl (meth)acrylate polymer is insufficient; If it exceeds the level, the solubility of the alkyl (meth)acrylate polymer in the coating material of the present invention is insufficient, or
The smoothness and abrasion resistance of the cured film may deteriorate. Furthermore, when the number of carbon atoms in the alkyl group is 9 or more, the solubility of the alkyl (meth)acrylate polymer in the coating material deteriorates, and the smoothness and abrasion resistance of the cured film deteriorate. Specific examples of the alkyl (meth)acrylate polymer include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, amyl methacrylate, hexyl methacrylate, Heptyl methacrylate, octyl methacrylate, 2-ethyl-
Examples include homopolymers of 1-hexyl (meth)acrylate, 3-pentyl acrylate, 3-methyl-1-butyl acrylate, 2-ethyl-1-butyl acrylate, or 2-heptyl acrylate, or copolymers thereof. These polymers can be used alone or in combination.
You may use a mixture of more than one species. The amount of the alkyl (meth)acrylate polymer to be added to 100 parts by weight of the monomer mixture is preferably in the range of 0.5 to 8.0 parts by weight, more preferably 1 to 5 parts by weight, and if it is less than 0.5 parts by weight, it is an ultraviolet absorber. If it cannot be contained in a large amount and the amount exceeds 8.0 parts by weight, the smoothness and abrasion resistance of the crosslinked cured coating will decrease. Further, the ultraviolet absorber used in the present invention is not particularly limited, and in a broad sense includes substances similar to light stabilizers for polymers, which are uniformly dissolved in the coating material composition of the present invention and have excellent weather resistance. However, from the viewpoint of good solubility and weather resistance improvement effect for the composition of the present invention, benzophenone, benztriazole, phenyl salicylate, or benzoic acid Ultraviolet absorbers that are compounds derived from phenyl compounds and have a maximum absorption wavelength in the range of 240 to 380 nm are desirable, and in particular benzophenone ultraviolet absorbers can be contained in large amounts in the composition of the present invention. More preferred. Specific examples of ultraviolet absorbers include 2-hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxybenzophenone. 4-octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-
4-Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, phenyl salicylate, p-tert.-butylphenyl salicylate, p-(1,1,3,3,- Tetramethylbutyl) phenyl salicylate, 3-hydroxyphenyl benzoate, phenylene-1,3
-dibenzoate, 2-(2-hydroxy-5'-
methylphenyl)benzotriazole, 2-(2
-Hydroxy-5-tert.-butylphenyl)-5
-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert.-butylphenyl)benzotriazole, 2-(2-hydroxy-5-
tert-butylphenyl)benzotriazole, 2
-(2-hydroxy-4-octyloxyphenyl)benzotriazole, etc. Among these, benzophenone-based 2-hydroxy-
4-octyloxybenzophenone and 2,4-
Dihydroxybenzophenone is the most preferred among benzophenone ultraviolet absorbers in terms of solubility in the composition of the present invention. Moreover, when these ultraviolet absorbers are combined with a homopolymer or copolymer of ethyl (meth)acrylate among alkyl (meth)acrylate polymers, the effects of the present invention are maximized. These ultraviolet absorbers may be used alone or in combination of two or more. The amount of the ultraviolet absorber added to the monomer mixture is preferably 5 to 35 parts by weight, more preferably 8 to 30 parts by weight, based on 100 parts by weight of the monomer mixture. If it is less than 5 parts by weight, the effect of improving the weather resistance of the synthetic resin molded article will not be sufficient as mentioned above, and if it exceeds 35 parts by weight, the abrasion resistance and smoothness of the crosslinked cured coating will be significantly reduced. The silicone surfactant used in the present invention is a necessary component to improve the smoothness of the crosslinked cured film and to prevent whitening if it occurs due to contact with an organic solvent. The amount is based on 100 parts by weight of the monomer mixture.
It ranges from 0.0001 to 2.0 parts by weight. Its usage is
If it is less than 0.0001 part by weight, the effect is small;
If it exceeds 2.0 parts by weight, the smoothness of the coating will decrease, which is not preferable. The silicone surfactant is not particularly limited, but preferably has a molecular structure consisting of polydimethylsiloxane units, as described in Japanese Patent Application No. 54-4569, a part of which is modified with a polyoxyalkylene group. The degree of modification is preferably such that at least one oxyalkylene group (-
OCH 2 CH 2 ―、
【式】等）が0.1〜10.0
単位の範囲内で結合しているものが好ましい。オ
キシアルキレン基による変性度が0.1未満の場合
は被膜の平滑性はシリコン系界面活性剤を添加し
ない場合よりもむしろ悪くなり、一方オキシアル
キレン基による変性度が10を越える場合には被膜
の平滑性が低下するので好ましくない。
また、本発明において使用する光増感剤として
は、たとえばベンゾイン、ベンゾインメチルエー
テル、ベンゾインエチルエーテル、ベンゾインイ
ソプロピルエーテル、アセトイン、ブチロイン、
トルオイン、ベンジル、ベンゾフエノン、ｐ―メ
トキシベンゾフエノン、ジエトキシアセトフエノ
ン、α，α―ジメトキシ―α―フエニルアセトフ
エノン、メチルフエニルグリオキシレート、エチ
ルフエニルグリオキシレート、４，4′―ビス（ジ
メチルアミノベンゾフエノン）、２―ヒドロキシ
―２―メチル―１―フエニルプロパン―１―オン
等のカルボニル化合物、テトラメチルチウラムモ
ノスルフイド、テトラメチルチウラムジスルフイ
ドなどの硫黄化合物、アゾビスイソブチロニトリ
ル、アゾビス―２，４―ジメチルバレロニトリル
などのアゾ化合物、ベンゾイルパーオキサイド、
ジターシヤリーブチルパーオキサイドなどのパー
オキサイド化合物などが挙げられる。単量体混合
物100重量部に対する配合量は0.01〜６重量部が
好ましく、多量に添加しすぎる場合は架橋硬化被
膜を着色させたり、耐候性の低下を招くので好ま
しくなく、またその添加量が少なすぎると紫外線
による硬化性が悪くなる。
以上が本発明を構成する必要不可欠な構成成分
であるが、もし必要があれば形成される架橋硬化
被膜に制電性、防曇性あるいはその他の機能を付
与する目的で紫外線で重合活性のある他のビニル
系単量体の少なくとも１種を併用してもよい。ま
た必要に応じて酸化防止剤、貯蔵安定剤等の安定
剤を適宜添加して使用することができる。
本発明組成物を塗布する方法としては刷毛塗
り、流し塗り、スプレー塗布、回転塗布あるいは
浸漬塗布までの方法が採用されるが、被覆材組成
物の塗布作業性、被膜の平滑性、均一性、硬化被
膜の基材に対する密着性向上の点からは適当な有
機溶剤を用いて浸漬法にて塗布するのが最も好ま
しい方法である。
浸漬塗布法に利用する有機溶剤としては、特開
昭53−102936号に記載してあるような前記被覆材
全組成物と混合して均一な溶液を形成し、常圧で
の沸点が50℃以上200℃以下であり、常温での粘
度が10センチポイズ以下であるような有機溶剤が
好ましい。
有機溶剤の使用量は前記被覆材組成物10〜80重
量部に対して90〜20重量部（合計100重量部）の
割合である。有機溶剤は使用量が20重量部未満の
場合には、特に被膜の平滑性ならびに均一性にす
ぐれたものがえられず、また一方90重量部をこえ
る場合には膜厚が薄くなりすぎて表面硬度が低下
する。
有機溶剤の具体例としてはエタノール、イソプ
ロパノール、ノルマルプロパノールイソブチルア
ルコール、ノルマルブチルアルコールなどのアル
コール類、ベンゼン、トルエン、キシレン、エチ
ルベンゼンなどの芳香族炭化水素類、アセトン、
メチルエチルケトンなどのケトン類、ジオキサン
などのエーテル類、酢酸エチル、酢酸ｎ―ブチ
ル、プロピオン酸エチルなどの酸エステル類など
がある。これらの有機溶剤は１種を単独で使用し
てもよく、また混合したものの沸点、成分割合が
前述の要件を満す範囲内であれば、２種以上を混
合して使用してもよい。
被覆材組成物の合成樹脂成形品表面に対する塗
布量としては硬化被膜の膜厚が１〜30μ、好まし
くは2.5μ〜20μの範囲になるように塗布する必要
がある。架橋硬化被膜の膜厚が1μ未満の場合に
は耐候性改善効果に劣り、30μを越える場合は基
材との密着性が低下したり、クラツク、ヘーズ等
が発生しやすくなつたり、あるいは被覆材組成物
の紫外線照射による硬化が不良となつたりする。
本発明の被覆材組成物を硬化する手段として
は、通常20〜2000KVの電子線加速器から取り出
される電子線、α線、β線、γ線などの放射線な
どの活性エネルギー線を照射しても可能である
が、本発明の特長である空気中で活性エネルギー
線を照射して高硬度の架橋硬化被膜を得るために
は紫外線を照射することが必須であつて他の活性
エネルギー線を用いては本発明の目的は達成され
ない。また、紫外線照射雰囲気としては窒素、炭
酸ガス、アルゴン等の不活性ガス中で照射しても
もちろん差しつかえないが本組成物は通常の空気
雰囲気下でも高硬度の架橋硬化被膜が得られるこ
とに最大の特徴があるのである。
本発明において耐摩耗性及び耐候性にすぐれた
合成樹脂成形品の製造に用いられる合成樹脂成形
品としては、熱可塑性樹脂、熱硬化性樹脂を問わ
ず各種合成樹脂成形品、例えばポリメチルメタア
クリレート樹脂、ポリカーボネート樹脂、ポリア
リルジグリコールカーボネート樹脂、ポリスチレ
ン樹脂、アクリロニトリル―スチレン共重合樹脂
（AS樹脂）、ポリ塩化ビニル樹脂、アセテート樹
脂、ABS樹脂、ポリエステル樹脂などから製造
されるシート状成形品、フイルム状成形品、ロツ
ド状成形品ならびに各種射出成形品などが具体例
として挙げられる。これらの成形品の内でもポリ
メチルメタアクリレート樹脂、ポリカーボネート
樹脂などから製造される成形品はその光学的性
質、耐熱性、耐衝撃性などの特性を生かして使用
される場合が多く、かつ耐摩耗性及び耐候性（特
に耐候性の不十分なポリカーボネート樹脂につい
ては）改良への要求も強いので、これらの成形品
は本発明に使用される合成樹脂成形品としては特
に好ましいものである。
以上本発明の被覆材組成物並びにこれを用いて
製造される耐摩耗性及び耐候性に優れた合成樹脂
成形品は、その他平滑性、耐水性、耐薬品性、耐
久性等にも優れた性能を有するものであり、酸
素、オゾン、雨水、熱、大気中の各種のガス等の
苛酷な条件、環境下におかれてもその性能はほと
んど低下することがなく、耐摩耗性及び耐候性が
要求される分野の用途に極めて有用である。
以下実施例によつて本発明の内容をさらに詳細
に説明する。なお実施例中の測定評価は次のよう
な方法で行なつた。
(1) 耐摩耗性
＃000のスチールウールを直径25mmの円筒先端
に装着し、水平に置かれたサンプル面に接触さ
せ、0.3Kg荷重で５回転（20rpm）し、傷の付着
程度を目視観察し、次の基準で評価した。
〇……サンプル表面にほとんど傷がついていな
い
△……サンプル表面に少し傷がつく
×……サンプル表面にひどく傷がつく
(2) 密着性
架橋硬化被膜に対するクロスカツト―セロハン
テープ剥離テスト。すなわち被膜に１mm間かくに
基材に達する被膜切断線を、たて、よこそれぞれ
に11本入れて１mm2の目数を100個つくり、その上
にセロハンテープを貼りつけ、急激にはがす。
〇……架橋硬化被膜の剥離目なし
△……剥離目の数１〜50個
×……剥離目の数51〜100個
(3) 面の平滑性
〇……被膜の面の平滑性は良好である
△……被膜の面に少し乱れがある
×……面の乱れが大きく平滑性に劣る
(4) 外観
ａ 変色またはヘーズ
〇……変色（黄変又は白化）又はヘーズなし
△……少し変色又はヘーズ有り
×……変色又はヘーズ目立つ
ｂ クラツク、膜はげ等
〇……無し
×……有り
なお耐候性テストはサンシヤインカーボンウエ
ザオメータ（東洋理化WE―SUN―HC型）耐候
試験機を用いて行なつた。試験条件はブラツクパ
ネル温度63±３℃、降雨120分、サイクルで18分
であつた。
実施例１〜４、比較例１〜８
表に示す硬化液を調整し、これに厚さ２mmの
ポリカーポネート樹脂板（三菱ガス化学製、商品
名ユーピロン）を浸漬して、引き上げ被膜を形成
させた。これを３分間放置後、空気中で2KWの
高圧水銀燈（オゾン型）を用いて、板の両面、
各々20cmの距離から紫外線を10秒間、２度照射し
た。得られた結果を表に示す。
なお表中の記号は次の物質を表わす。
2P5A：ジペンタエリスリトールペンタアクリレ
ート
THF―Ａ：テトラヒドロフルフリルアクリレー
ト
Bip：ベンゾインイソプロピルエーテル
Ｙ：２―ヒドロキシ―４―ｎ―オクトキシベンゾ
フエノン
MA2：メタクリン酸メチル／メタクリル酸ブチ
ル＝50／50（重量比）の共重合体（〔η〕〕
0.04）
MA7：ポリエチルメタクリレート（〔η〕＝0.09）
MA10：ポリ―iso―ブチルメタクリレート
（〔η〕＝0.03）
MA11：ポリスチレン（〔η〕＝0.10）
MA12：ポリドデシルメタクリレート（〔η〕＝
0.13）
MA13ポリ―iso―ブチルメタクリレート（〔η〕
＝0.002）
MA14ポリ―iso―ブチルメタクリレート（〔η〕
＝0.50）
iso―proHイソプロピルアルコール[Formula] etc.) are preferably bonded within a range of 0.1 to 10.0 units. If the degree of modification by oxyalkylene groups is less than 0.1, the smoothness of the film will be worse than when no silicone surfactant is added, whereas if the degree of modification by oxyalkylene groups is more than 10, the smoothness of the film will be worse. This is not preferable because it reduces the Examples of the photosensitizer used in the present invention include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetoin, butyroin,
Toluoine, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, α,α-dimethoxy-α-phenylacetophenone, methyl phenyl glyoxylate, ethyl phenyl glyoxylate, 4,4 '-Bis(dimethylaminobenzophenone), carbonyl compounds such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, and sulfur such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide. compounds, azo compounds such as azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, benzoyl peroxide,
Examples include peroxide compounds such as ditertiary butyl peroxide. The amount to be added is preferably 0.01 to 6 parts by weight per 100 parts by weight of the monomer mixture; if too much is added, it is undesirable because it will discolor the cross-linked cured film or cause a decrease in weather resistance. If it is too strong, the curing properties due to ultraviolet rays will deteriorate. The above are the essential components constituting the present invention. At least one other vinyl monomer may be used in combination. Further, stabilizers such as antioxidants and storage stabilizers may be appropriately added and used as necessary. The composition of the present invention can be applied by brush coating, flow coating, spray coating, spin coating, or dip coating, but the coating workability of the coating composition, the smoothness and uniformity of the coating, From the viewpoint of improving the adhesion of the cured film to the substrate, the most preferred method is to apply by dipping using a suitable organic solvent. The organic solvent used in the dip coating method is one that can be mixed with the entire coating composition as described in JP-A-53-102936 to form a uniform solution, and has a boiling point of 50°C at normal pressure. An organic solvent having a temperature of 200°C or less and a viscosity of 10 centipoise or less at room temperature is preferable. The amount of the organic solvent used is 90 to 20 parts by weight (total 100 parts by weight) based on 10 to 80 parts by weight of the coating material composition. If the amount of organic solvent used is less than 20 parts by weight, it will not be possible to obtain a film with excellent smoothness and uniformity, while if it exceeds 90 parts by weight, the film thickness will be too thin and the surface will be damaged. Hardness decreases. Specific examples of organic solvents include alcohols such as ethanol, isopropanol, normal propanol isobutyl alcohol, and normal butyl alcohol, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, acetone,
Examples include ketones such as methyl ethyl ketone, ethers such as dioxane, and acid esters such as ethyl acetate, n-butyl acetate, and ethyl propionate. One type of these organic solvents may be used alone, or two or more types may be used in combination as long as the boiling point and component ratio of the mixture are within the range that satisfies the above-mentioned requirements. The coating amount of the coating composition on the surface of the synthetic resin molded article must be such that the thickness of the cured film is in the range of 1 to 30 microns, preferably 2.5 to 20 microns. If the thickness of the cross-linked cured film is less than 1 μm, the weather resistance improvement effect will be poor, and if it exceeds 30 μm, the adhesion with the substrate will decrease, cracks, haze, etc. will be likely to occur, or the coating material will deteriorate. The curing of the composition by ultraviolet irradiation may become poor. As a means of curing the coating material composition of the present invention, irradiation with active energy rays such as electron beams, alpha rays, beta rays, and γ rays, which are usually taken out from an electron beam accelerator of 20 to 2000 KV, is also possible. However, in order to obtain a highly hard crosslinked cured film by irradiating active energy rays in air, which is a feature of the present invention, it is essential to irradiate ultraviolet rays, and it is not possible to use other active energy rays. The object of the invention is not achieved. Furthermore, although it is of course possible to irradiate ultraviolet rays in an inert gas such as nitrogen, carbon dioxide, or argon, it is possible to obtain a crosslinked cured film with high hardness even in a normal air atmosphere. It has the biggest feature. In the present invention, synthetic resin molded products used in the production of synthetic resin molded products with excellent wear resistance and weather resistance include various synthetic resin molded products, regardless of thermoplastic resin or thermosetting resin, such as polymethyl methacrylate. Sheet-like molded products and films manufactured from resins, polycarbonate resins, polyallyl diglycol carbonate resins, polystyrene resins, acrylonitrile-styrene copolymer resins (AS resins), polyvinyl chloride resins, acetate resins, ABS resins, polyester resins, etc. Specific examples include shaped molded products, rod-shaped molded products, and various injection molded products. Among these molded products, molded products made from polymethyl methacrylate resin, polycarbonate resin, etc. are often used to take advantage of their optical properties, heat resistance, impact resistance, etc., and are also wear resistant. Since there is a strong demand for improvement in properties and weather resistance (particularly for polycarbonate resins with insufficient weather resistance), these molded products are particularly preferred as synthetic resin molded products used in the present invention. As described above, the coating material composition of the present invention and the synthetic resin molded product manufactured using the same with excellent wear resistance and weather resistance also have excellent performance such as smoothness, water resistance, chemical resistance, and durability. Its performance hardly deteriorates even under harsh conditions and environments such as oxygen, ozone, rainwater, heat, and various gases in the atmosphere, and it has excellent wear and weather resistance. It is extremely useful for applications in the required fields. The contents of the present invention will be explained in more detail below with reference to Examples. In addition, the measurement evaluation in the examples was performed by the following method. (1) Abrasion resistance Attach #000 steel wool to the tip of a cylinder with a diameter of 25 mm, contact it with the sample surface placed horizontally, rotate it 5 times (20 rpm) with a load of 0.3 kg, and visually observe the extent of scratches. and evaluated based on the following criteria. 〇...Almost no scratches on the sample surface △...Slight scratches on the sample surface ×...Severe scratches on the sample surface (2) Adhesion Cross-cut cellophane tape peel test on cross-linked cured film. That is, make 100 1 mm 2 lines by inserting 11 film cutting lines vertically and horizontally into the film that reach the base material at 1 mm intervals, then stick cellophane tape on top of it and peel it off rapidly. 〇……No peeling marks of cross-linked cured coating △……Number of peeling lines 1 to 50 ×……Number of peeling lines 51 to 100 (3) Surface smoothness 〇……Smoothness of the surface of the coating is good △...The surface of the film is slightly disturbed ×...The surface is greatly disturbed and the smoothness is poor (4) Appearance a Discoloration or haze 〇...No discoloration (yellowing or whitening) or haze △...Slightly Discoloration or haze ×……Discoloration or haze is noticeable b Cracks, film peeling, etc. 〇……No ×……Yes The weather resistance test was performed using a Sunshine Carbon Weather-Ometer (Toyo Rika WE-SUN-HC model) weather resistance tester. This was done using The test conditions were a black panel temperature of 63±3°C, 120 minutes of rain, and an 18 minute cycle. Examples 1 to 4, Comparative Examples 1 to 8 The curing liquid shown in the table was prepared, and a 2 mm thick polycarbonate resin plate (manufactured by Mitsubishi Gas Chemical, trade name: Iupilon) was immersed in it to form a pulled film. I let it happen. After leaving this for 3 minutes, use a 2KW high pressure mercury lamp (ozone type) in the air to clean both sides of the board.
Ultraviolet light was irradiated twice for 10 seconds each from a distance of 20 cm. The results obtained are shown in the table. The symbols in the table represent the following substances. 2P5A: Dipentaerythritol pentaacrylate THF-A: Tetrahydrofurfuryl acrylate Bip: Benzoin isopropyl ether Y: 2-Hydroxy-4-n-octoxybenzophenone MA2: Methyl methacrylate/Butyl methacrylate = 50/50 (weight) copolymer ([η]]
0.04) MA7: Polyethyl methacrylate ([η] = 0.09) MA10: Poly-iso-butyl methacrylate ([η] = 0.03) MA11: Polystyrene ([η] = 0.10) MA12: Polydodecyl methacrylate ([η] =
0.13) MA13 poly-iso-butyl methacrylate ([η]
=0.002) MA14 poly-iso-butyl methacrylate ([η]
=0.50) iso-proH isopropyl alcohol
【表】
＊１） 樹脂板曲げ時にクラツク発生
実施例５、比較例９〜13
表に示す硬化液に、３mm厚のポリカーボネー
ト樹脂板を浸漬し、引き上げ被膜を形成させた。
これを空気中で2KWの高圧水銀燈（オゾン型）
から発せられる紫外線を20cmの距離から15秒間、
両面から照射した。得られた結果を表に示す。[Table] *1) Cracks occur when bending resin plate Example 5, Comparative Examples 9 to 13 A 3 mm thick polycarbonate resin plate was immersed in the curing liquid shown in the table to form a pulled film.
This is heated in the air using a 2KW high-pressure mercury lamp (ozone type).
UV rays emitted from a distance of 20 cm for 15 seconds,
Irradiated from both sides. The results obtained are shown in the table.
【表】
実施例 ６
ジペンタエリスリトールヘキサアクリレート25
重量部、ジペンタエリスリトールペンタアクリレ
ート20重量部、ジペンタエリスリトールテトラア
クリレート10重量部、２，２―ビス（４―アクリ
ロキシジエトキシフエニル）プロパン５重量部、
テトラヒドロフルフリルアクリレート35重量部、
２―ヒドロキシエチルアクリレート５重量部、イ
ソブチルアルコール100重量部、トルエン100重量
部、ベンゾインイソブチルエーテル２重量部、ポ
リエチルメタクリレート（MA7）4.0重量部、シ
リコン系界面活性剤0.2重量部、２―ヒドロキシ
―４―ｎ―オクトキシベンゾフエノン16重量部、
２，４―ジヒドロキシベンゾフエノン８重量部か
らなる被覆材組成物中に厚さ３mmのメタクリル樹
脂板を浸漬し、引き上げ被膜を形成した。３分間
放置後板の両面、20cmの距離から2KWの高圧水
銀燈（オゾン型）で13秒間を２度照射した。
得られた製品の耐摩耗性、外観、密着性は良好
であり、耐候テスト1500時間後の外観および密着
性も良好であつた。
実施例 ７
ジペンタエリスリトールヘキサアクリレート25
重量部、ジペンタエリスリトールペンタアクリレ
ート25重量部、ジペンタエリスリトールテトラア
クリレート10重量部、エチルカルビトールアクリ
レート10重量部、テトラヒドロフルフリルアクリ
レート30重量部、シリコン系界面活性剤0.4重量
部、ベンゾインエチルエーテル２重量部、ベンゾ
フエノン２重量部、ポリｎ―ブチルメタクリレー
ト４重量部（〔η〕＝0.07）、２―ヒドロキシ―４
―ｎ―オクトキシベンゾフエノン８重量部、２，
４―ジヒドロキシベンゾフエノン４重量部からな
る被覆材組成物を、夫々ポリカーボネートおよび
AS樹脂からなる３mm厚の射出成形板上に厚さ5μ
になるようにバーコーターを用いて塗布した。
これを実施例６と同一の高圧水銀燈を用いて20
cmの距離から13秒間を２度照射した。
得られた製品の耐摩耗性、外観および密着性は
良好であり、耐候テスト1000時間後の外観および
密着性も良好であつた。[Table] Example 6 Dipentaerythritol hexaacrylate 25
Parts by weight, 20 parts by weight of dipentaerythritol pentaacrylate, 10 parts by weight of dipentaerythritol tetraacrylate, 5 parts by weight of 2,2-bis(4-acryloxydiethoxyphenyl)propane,
35 parts by weight of tetrahydrofurfuryl acrylate,
5 parts by weight of 2-hydroxyethyl acrylate, 100 parts by weight of isobutyl alcohol, 100 parts by weight of toluene, 2 parts by weight of benzoin isobutyl ether, 4.0 parts by weight of polyethyl methacrylate (MA7), 0.2 parts by weight of silicone surfactant, 2-hydroxy- 16 parts by weight of 4-n-octoxybenzophenone,
A 3 mm thick methacrylic resin plate was immersed in a coating composition containing 8 parts by weight of 2,4-dihydroxybenzophenone to form a coating. After leaving it for 3 minutes, both sides of the board were irradiated twice for 13 seconds with a 2KW high-pressure mercury lamp (ozone type) from a distance of 20cm. The abrasion resistance, appearance, and adhesion of the obtained product were good, and the appearance and adhesion after a 1500-hour weather test were also good. Example 7 Dipentaerythritol hexaacrylate 25
Parts by weight, dipentaerythritol pentaacrylate 25 parts by weight, dipentaerythritol tetraacrylate 10 parts by weight, ethyl carbitol acrylate 10 parts by weight, tetrahydrofurfuryl acrylate 30 parts by weight, silicone surfactant 0.4 parts by weight, benzoin ethyl ether 2 Parts by weight, 2 parts by weight of benzophenone, 4 parts by weight of poly n-butyl methacrylate ([η] = 0.07), 2-hydroxy-4
-n-octoxybenzophenone 8 parts by weight, 2,
A coating composition consisting of 4 parts by weight of 4-dihydroxybenzophenone was applied to polycarbonate and polycarbonate, respectively.
5μ thick on a 3mm thick injection molded plate made of AS resin.
It was coated using a bar coater so that This was carried out for 20 minutes using the same high pressure mercury lamp as in Example 6.
Irradiation was performed twice for 13 seconds from a distance of 1.5 cm. The abrasion resistance, appearance and adhesion of the obtained product were good, and the appearance and adhesion after a 1000 hour weather test were also good.
Claims (1)
Xn3，X14の内少なくとも３個はCH2＝CH―
COO―基で残りは―OH基である。またｎは１
〜５の整数である。）で示される１分子中に３
個以上のアクリロイルオキシ基を有するモノ又
はポリペンタエリスリトールのポリアクリレー
トの１種以上40〜100重量％と、次の一般式 （式中X1，X2…Xnは炭素数６以下の同じも
しくは異なるアルキレン基又はその水素原子１
個が水酸基で置換された構造のものであり、ｎ
は０〜５の整数である。）で示される２官能単
量体０〜50重量％と、１分子中に１個のアクリ
ロイルオキシ基を有し、かつ常圧での沸点が
150℃以上で20℃における粘度が20cps以下であ
る１官能性単量体０〜60重量％からなる単量体
混合物、 (b) 該単量体混合物100重量部に対して少なくと
も１種の紫外線吸収剤５〜35重量部、 (c) 該単量体混合物100重量部に対して少なくと
も１種の（メタ）アクリル酸アルキル重合体
0.5〜８重量部、および (d) 該単量体混合物100重量部に対して光増感剤
0.01〜６重量部 とからなる被覆材組成物。 ２ 単量体混合物100重量部に対してポリオキシ
アルキレン基で変性されたシリコン系界面活性剤
の少なくとも１種を0.0001〜2.0重量部添加して
なる特許請求の範囲第１項記載の被覆材組成物。 ３ 一般式（）で表わされる単量体がジペンタ
エリスリトールトリアクリレート、ジペンタエリ
スリトールテトラアクリレート、ジペンタエリス
リトールペンタアクリレート、ジペンタエリスリ
トールヘキサアクリレートであることを特徴とす
る特許請求の範囲第１項記載の被覆材組成物。 ４ １分子中に１個のアクリロイルオキシ基を有
する単量体が分子中の側鎖に水酸基および／また
はエーテル結合を有するものであることを特徴と
する特許請求の範囲第１項記載の被覆材組成物。 ５ （メタ）アクリル酸アルキル重合体が炭素原
子数１〜８個のアルキル基をもつ（メタ）アクリ
ル酸アルキルより選ばれた単量体の単独重合体ま
たは共重合体であつて、それの極限粘度〔η〕が
0.01〜0.30であることを特徴とする特許請求の範
囲第１項記載の被覆材組成物。 ６ 紫外線吸収剤がベンゾフエノン系、ベンズト
リアゾール系、サリチル酸フエニル系または安息
香酸フエニル系から誘導された化合物であり、そ
の最大吸収波長が240〜380nmの範囲にあるもの
であることを特徴とする特許請求の範囲第１項記
載の被覆材組成物。 ７ (a) 次の一般式 （式中X11，X12，X13，X22，X23…Xn2，
Xn3，X14の内少なくとも３個はCH2＝CH―
COO―基で残りは―OH基である。またｎは１
〜５の整数である。）で示される１分子中に３
個以上のアクリロイルオキシ基を有するモノ又
はポリペンタエリスリトールのポリアクリレー
トの１種以上40〜100重量％と、次の一般式 （式中X1，X2…Xnは炭素数６以下の同じも
しくは異なるアルキレン基又はその水素原子１
個が水酸基で置換された構造のものであり、ｎ
は０〜５の整数である。）で示される２官能単
量体０〜50重量％と、１分子中に１個のアクリ
ロイルオキシ基を有し、かつ常圧での沸点が
150℃以上で20℃における粘度が20cps以下であ
る１官能性単量体０〜60重量％からなる単量体
混合物、 (b) 該単量体混合物100重量部に対して少なくと
も１種の紫外線吸収剤５〜35重量部、 (c) 該単量体混合物100重量部に対して少なくと
も１種の（メタ）アクリル酸アルキル重合体
0.5〜８重量部、および (d) 該単量体混合物100重量部に対して光増感剤
0.01〜６重量部 とからなる被覆材組成物を合成樹脂成形品の表面
に塗布した後、空気中で紫外線を照射して合成樹
脂の表面に膜厚１〜30μの架橋硬化被膜を形成さ
せることを特徴とする合成樹脂成形品の製造方
法。 ８ 単量体混合物100重量部に対してポリオキシ
アルキレン基で変性されたシリコン系界面活性剤
の少なくとも１種を0.0001〜2.0重量部添加して
なる特許請求の範囲第７項記載の合成樹脂成形品
の製造方法。 ９ 一般式（）で表わされる単量体がジペンタ
エリスリトールトリアクリレート、ジペンタエリ
スリトールテトラアクリレート、ジペンタエリス
リトールペンタアクリレート、ジペンタエリスリ
トールヘキサアクリレートであることを特徴とす
る特許請求の範囲第７項記載の合成樹脂成形品の
製造方法。 １０ １分子中に１個のアクリロイルオキシ基を
有する単量体が分子中の側鎖に水酸基および／ま
たはエーテル結合を有するものであることを特徴
とする特許請求の範囲第７項記載の合成樹脂成形
品の製造方法。 １１ （メタ）アクリル酸アルキル重合体が炭素
原子数１〜８個のアルキル基をもつ（メタ）アク
リル酸アルキルより選ばれた単量体の単独重合体
または共重合体であつて、それの極限粘度〔η〕
が0.01〜0.30であることを特徴とする特許請求の
範囲第７項記載の合成樹脂成形品の製造方法。 １２ 紫外線吸収剤がベンゾフエノン系、ベンズ
トリアゾール系、サリチル酸フエニル系または安
息香酸フエニル系から誘導された化合物であり、
その最大吸収波長が240〜380nmの範囲にあるも
のであることを特徴とする特許請求の範囲第７項
記載の合成樹脂成形品の製造方法。[Claims] 1 (a) The following general formula (In the formula, X 11 , X 12 , X 13 , X 22 , X 23 ...Xn 2 ,
At least three of Xn 3 and X 14 are CH 2 = CH-
COO- group and the rest are -OH groups. Also, n is 1
It is an integer of ~5. ) is 3 in one molecule.
40 to 100% by weight of one or more mono- or polypentaerythritol polyacrylates having at least 2 acryloyloxy groups, and the following general formula: (In the formula, X 1 , X 2 ...Xn are the same or different alkylene groups having 6 or less carbon atoms, or 1 hydrogen atom thereof
It has a structure in which n are substituted with hydroxyl groups, and n
is an integer from 0 to 5. ) and one acryloyloxy group in one molecule, and the boiling point at normal pressure is 0 to 50% by weight.
A monomer mixture comprising 0 to 60% by weight of a monofunctional monomer having a viscosity of 20 cps or less at 20°C or higher at 150°C or higher; (b) at least one type of ultraviolet light per 100 parts by weight of the monomer mixture; 5 to 35 parts by weight of absorbent; (c) at least one alkyl (meth)acrylate polymer per 100 parts by weight of the monomer mixture;
0.5 to 8 parts by weight, and (d) a photosensitizer based on 100 parts by weight of the monomer mixture.
A coating composition comprising 0.01 to 6 parts by weight. 2. The coating material composition according to claim 1, wherein 0.0001 to 2.0 parts by weight of at least one silicone surfactant modified with a polyoxyalkylene group is added to 100 parts by weight of the monomer mixture. thing. 3. Claim 1, characterized in that the monomer represented by the general formula () is dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, or dipentaerythritol hexaacrylate. dressing composition. 4. The coating material according to claim 1, wherein the monomer having one acryloyloxy group in one molecule has a hydroxyl group and/or an ether bond in a side chain in the molecule. Composition. 5 The alkyl (meth)acrylate polymer is a homopolymer or copolymer of monomers selected from alkyl (meth)acrylates having an alkyl group having 1 to 8 carbon atoms, and the maximum Viscosity [η]
The coating material composition according to claim 1, characterized in that it has a molecular weight of 0.01 to 0.30. 6. A patent claim characterized in that the ultraviolet absorber is a compound derived from a benzophenone type, a benztriazole type, a phenyl salicylate type, or a phenyl benzoate type, and its maximum absorption wavelength is in the range of 240 to 380 nm. The coating composition according to item 1. 7 (a) The following general formula (In the formula, X 11 , X 12 , X 13 , X 22 , X 23 ...Xn 2 ,
At least three of Xn 3 and X 14 are CH 2 = CH-
COO- group and the rest are -OH groups. Also, n is 1
It is an integer of ~5. ) is 3 in one molecule.
40 to 100% by weight of one or more mono- or polypentaerythritol polyacrylates having at least 2 acryloyloxy groups, and the following general formula: (In the formula, X 1 , X 2 ...Xn are the same or different alkylene groups having 6 or less carbon atoms, or 1 hydrogen atom thereof
It has a structure in which n are substituted with hydroxyl groups, and n
is an integer from 0 to 5. ) and one acryloyloxy group in one molecule, and the boiling point at normal pressure is 0 to 50% by weight.
A monomer mixture comprising 0 to 60% by weight of a monofunctional monomer having a viscosity of 20 cps or less at 20°C or higher at 150°C or higher; (b) at least one type of ultraviolet light per 100 parts by weight of the monomer mixture; 5 to 35 parts by weight of absorbent; (c) at least one alkyl (meth)acrylate polymer per 100 parts by weight of the monomer mixture;
0.5 to 8 parts by weight, and (d) a photosensitizer based on 100 parts by weight of the monomer mixture.
After applying a coating material composition consisting of 0.01 to 6 parts by weight to the surface of a synthetic resin molded article, irradiation with ultraviolet rays in the air to form a crosslinked cured film with a thickness of 1 to 30 μm on the surface of the synthetic resin. A method for producing a synthetic resin molded product characterized by: 8. The synthetic resin molding according to claim 7, wherein 0.0001 to 2.0 parts by weight of at least one silicone surfactant modified with a polyoxyalkylene group is added to 100 parts by weight of the monomer mixture. method of manufacturing the product. 9 Claim 7, characterized in that the monomer represented by the general formula () is dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, or dipentaerythritol hexaacrylate. A method for manufacturing synthetic resin molded products. 10. The synthetic resin according to claim 7, wherein the monomer having one acryloyloxy group in one molecule has a hydroxyl group and/or an ether bond in a side chain in the molecule. Method of manufacturing molded products. 11 The alkyl (meth)acrylate polymer is a homopolymer or copolymer of a monomer selected from alkyl (meth)acrylates having an alkyl group having 1 to 8 carbon atoms, and the maximum Viscosity [η]
8. The method for producing a synthetic resin molded article according to claim 7, characterized in that: 0.01 to 0.30. 12 The ultraviolet absorber is a compound derived from a benzophenone type, benztriazole type, phenyl salicylate type or phenyl benzoate type,
8. The method for producing a synthetic resin molded article according to claim 7, wherein the maximum absorption wavelength is in the range of 240 to 380 nm.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3101780A JPS56127635A (en) | 1980-03-12 | 1980-03-12 | Coating material composition and preparation of molded synthetic resin article made therefrom |
| AU68030/81A AU542212B2 (en) | 1980-03-04 | 1981-03-03 | Photopolymerisable acrylic coating compositons |
| US06/239,202 US4339474A (en) | 1980-03-04 | 1981-03-03 | Coating composition and process for preparing synthetic resin shaped articles by using same |
| CA000372212A CA1149987A (en) | 1980-03-04 | 1981-03-03 | Coating composition and process for preparing synthetic resin shaped articles by using same |
| EP81101516A EP0035272B1 (en) | 1980-03-04 | 1981-03-03 | Coating composition and process for preparing synthetic resin shaped articles by using same |
| DE8181101516T DE3164954D1 (en) | 1980-03-04 | 1981-03-03 | Coating composition and process for preparing synthetic resin shaped articles by using same |
| MX186230A MX157398A (en) | 1980-03-04 | 1981-03-04 | IMPROVED COATING COMPOSITION |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3101780A JPS56127635A (en) | 1980-03-12 | 1980-03-12 | Coating material composition and preparation of molded synthetic resin article made therefrom |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56127635A JPS56127635A (en) | 1981-10-06 |
| JPS6328095B2 true JPS6328095B2 (en) | 1988-06-07 |
Family
ID=12319760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3101780A Granted JPS56127635A (en) | 1980-03-04 | 1980-03-12 | Coating material composition and preparation of molded synthetic resin article made therefrom |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56127635A (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5971335A (en) * | 1982-10-19 | 1984-04-23 | Mitsui Petrochem Ind Ltd | Curable resin composition for coating |
| JPS5978242A (en) * | 1982-10-27 | 1984-05-07 | Mitsui Petrochem Ind Ltd | Curable resin composition for coating |
| JPS59108038A (en) * | 1982-12-11 | 1984-06-22 | Toto Ltd | Artificial marble and method for finishing its surface |
| JPS6049036A (en) * | 1983-08-29 | 1985-03-18 | Mitsubishi Chem Ind Ltd | Film-forming composition and improvement in surface of synthetic resin molded article using the same |
| JPS60190428A (en) * | 1984-03-12 | 1985-09-27 | Mitsubishi Rayon Co Ltd | Molded article of heat-resistant resin having improved abrasion resistance and production thereof |
| JPS60177034A (en) * | 1984-02-21 | 1985-09-11 | Mitsubishi Rayon Co Ltd | Molded article of heat-resistant resin having improved abrasion resistance and production thereof |
| JPS61136529A (en) * | 1984-12-07 | 1986-06-24 | Mitsui Petrochem Ind Ltd | Curable resin composition for coating |
| JPH02261831A (en) * | 1989-03-31 | 1990-10-24 | Mitsubishi Rayon Co Ltd | Coated plastic sheet with excellent weather resistance |
| KR100561603B1 (en) | 1998-07-10 | 2006-03-16 | 오츠카 가가쿠 홀딩스 가부시키가이샤 | Weather-resistant composition, coating materials and molded articles |
| JP5430095B2 (en) * | 2008-08-11 | 2014-02-26 | 日本カーバイド工業株式会社 | Curable resin composition |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3407156A (en) * | 1964-06-03 | 1968-10-22 | Du Pont | Weatherable transparent coating composition for wood substrates |
| DE1694253A1 (en) * | 1968-03-09 | 1971-05-13 | Bayer Ag | Polyester molding and coating compounds which can be hardened by UV radiation |
| JPS53102936A (en) * | 1977-02-22 | 1978-09-07 | Mitsubishi Rayon Co Ltd | Coating composition and preparation of abrasion resistant synthetic resin molded article using the same |
| JPS53104638A (en) * | 1977-02-23 | 1978-09-12 | Mitsubishi Rayon Co Ltd | Coating composition and preparation of abrasion resistant synthetic resin molded artticle using the same |
-
1980
- 1980-03-12 JP JP3101780A patent/JPS56127635A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3407156A (en) * | 1964-06-03 | 1968-10-22 | Du Pont | Weatherable transparent coating composition for wood substrates |
| DE1694253A1 (en) * | 1968-03-09 | 1971-05-13 | Bayer Ag | Polyester molding and coating compounds which can be hardened by UV radiation |
| JPS53102936A (en) * | 1977-02-22 | 1978-09-07 | Mitsubishi Rayon Co Ltd | Coating composition and preparation of abrasion resistant synthetic resin molded article using the same |
| JPS53104638A (en) * | 1977-02-23 | 1978-09-12 | Mitsubishi Rayon Co Ltd | Coating composition and preparation of abrasion resistant synthetic resin molded artticle using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56127635A (en) | 1981-10-06 |
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