JPS6367809B2 - - Google Patents
Info
- Publication number
- JPS6367809B2 JPS6367809B2 JP59248933A JP24893384A JPS6367809B2 JP S6367809 B2 JPS6367809 B2 JP S6367809B2 JP 59248933 A JP59248933 A JP 59248933A JP 24893384 A JP24893384 A JP 24893384A JP S6367809 B2 JPS6367809 B2 JP S6367809B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- synthetic resin
- resin molded
- dipentaerythritol
- parts
- 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
- 229920003002 synthetic resin Polymers 0.000 claims description 64
- 239000000057 synthetic resin Substances 0.000 claims description 64
- 238000000576 coating method Methods 0.000 claims description 46
- 239000000178 monomer Substances 0.000 claims description 45
- 239000008199 coating composition Substances 0.000 claims description 44
- 239000011248 coating agent Substances 0.000 claims description 43
- 239000003960 organic solvent Substances 0.000 claims description 38
- 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 25
- 238000000034 method Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 19
- 229920005989 resin Polymers 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
- 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 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000000113 methacrylic resin Substances 0.000 claims description 11
- 239000003504 photosensitizing agent Substances 0.000 claims description 11
- 230000001588 bifunctional effect Effects 0.000 claims description 9
- 238000003618 dip coating Methods 0.000 claims description 9
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 8
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- JUDXBRVLWDGRBC-UHFFFAOYSA-N [2-(hydroxymethyl)-3-(2-methylprop-2-enoyloxy)-2-(2-methylprop-2-enoyloxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(COC(=O)C(C)=C)COC(=O)C(C)=C JUDXBRVLWDGRBC-UHFFFAOYSA-N 0.000 claims description 5
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012456 homogeneous solution Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000005299 abrasion Methods 0.000 description 32
- 238000012360 testing method Methods 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000003973 paint Substances 0.000 description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 16
- 239000012298 atmosphere Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 13
- 230000001678 irradiating effect Effects 0.000 description 13
- 239000000758 substrate Substances 0.000 description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 12
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000001723 curing Methods 0.000 description 12
- 230000008901 benefit Effects 0.000 description 11
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 11
- 229910052753 mercury Inorganic materials 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 10
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 239000010453 quartz Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 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 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- -1 acryloxyethoxyphenyl Chemical group 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 239000001294 propane Substances 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 210000002268 wool Anatomy 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 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 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 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 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 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
- VIYWVRIBDZTTMH-UHFFFAOYSA-N 2-[4-[2-[4-[2-(2-methylprop-2-enoyloxy)ethoxy]phenyl]propan-2-yl]phenoxy]ethyl 2-methylprop-2-enoate Chemical compound C1=CC(OCCOC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCCOC(=O)C(C)=C)C=C1 VIYWVRIBDZTTMH-UHFFFAOYSA-N 0.000 description 2
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PPAIPYKTXXJNAI-UHFFFAOYSA-N C(C=C)(=O)OC1C(C(C(C=C1)(C(C)(C)C1(C(C(C(C=C1)OC(C=C)=O)(OCC)OCC)(OCC)OCC)OCC)OCC)(OCC)OCC)(OCC)OCC Chemical compound C(C=C)(=O)OC1C(C(C(C=C1)(C(C)(C)C1(C(C(C(C=C1)OC(C=C)=O)(OCC)OCC)(OCC)OCC)OCC)OCC)(OCC)OCC)(OCC)OCC PPAIPYKTXXJNAI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 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 2
- UUQJMSSFMULZHR-UHFFFAOYSA-N [4,5,5,6,6-pentaethoxy-4-[2-[1,5,5,6,6-pentaethoxy-4-(2-methylprop-2-enoyloxy)cyclohex-2-en-1-yl]propan-2-yl]cyclohex-2-en-1-yl] 2-methylprop-2-enoate Chemical compound C(C(=C)C)(=O)OC1C(C(C(C=C1)(C(C)(C)C1(C(C(C(C=C1)OC(C(=C)C)=O)(OCC)OCC)(OCC)OCC)OCC)OCC)(OCC)OCC)(OCC)OCC UUQJMSSFMULZHR-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
- 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 2
- 229960002130 benzoin Drugs 0.000 description 2
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical compound C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001035 drying 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
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920005990 polystyrene resin Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- CSUUDNFYSFENAE-UHFFFAOYSA-N (2-methoxyphenyl)-phenylmethanone Chemical compound COC1=CC=CC=C1C(=O)C1=CC=CC=C1 CSUUDNFYSFENAE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 1
- UGVRJVHOJNYEHR-UHFFFAOYSA-N 4-chlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 UGVRJVHOJNYEHR-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
- 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
- SCDHUPXEFVDBOB-UHFFFAOYSA-N C(C(=C)C)(=O)O.C(C(=C)C)(=O)O.C(C(=C)C)(=O)O.OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO Chemical compound C(C(=C)C)(=O)O.C(C(=C)C)(=O)O.C(C(=C)C)(=O)O.OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO SCDHUPXEFVDBOB-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- XQAVYBWWWZMURF-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO 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)CO XQAVYBWWWZMURF-UHFFFAOYSA-N 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
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- SWHLOXLFJPTYTL-UHFFFAOYSA-N [2-methyl-3-(2-methylprop-2-enoyloxy)-2-(2-methylprop-2-enoyloxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(COC(=O)C(C)=C)COC(=O)C(C)=C SWHLOXLFJPTYTL-UHFFFAOYSA-N 0.000 description 1
- HSZUHSXXAOWGQY-UHFFFAOYSA-N [2-methyl-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(C)(COC(=O)C=C)COC(=O)C=C HSZUHSXXAOWGQY-UHFFFAOYSA-N 0.000 description 1
- LVPVKTANBAXGMA-UHFFFAOYSA-N [3-(2-hydroxypropoxy)-4-[2-[2-(2-hydroxypropoxy)-4-(2-methylprop-2-enoyloxy)phenyl]propan-2-yl]phenyl] 2-methylprop-2-enoate Chemical compound CC(O)COC1=CC(OC(=O)C(C)=C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1OCC(C)O LVPVKTANBAXGMA-UHFFFAOYSA-N 0.000 description 1
- FOLZXGNHMSXYOG-UHFFFAOYSA-N [3-[2-(2-hydroxypropoxy)ethoxy]-4-[2-[2-[2-(2-hydroxypropoxy)ethoxy]-4-(2-methylprop-2-enoyloxy)phenyl]propan-2-yl]phenyl] 2-methylprop-2-enoate Chemical compound CC(O)COCCOC1=CC(OC(=O)C(C)=C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1OCCOCC(C)O FOLZXGNHMSXYOG-UHFFFAOYSA-N 0.000 description 1
- SJSXBTSSSQCODU-UHFFFAOYSA-N [4-[2-[2,3-diethoxy-4-(2-methylprop-2-enoyloxy)phenyl]propan-2-yl]-2,3-diethoxyphenyl] 2-methylprop-2-enoate Chemical compound CCOC1=C(OC(=O)C(C)=C)C=CC(C(C)(C)C=2C(=C(OCC)C(OC(=O)C(C)=C)=CC=2)OCC)=C1OCC SJSXBTSSSQCODU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 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
- 238000004040 coloring Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002542 deteriorative effect 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
- 238000002845 discoloration Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- GFAZHVHNLUBROE-UHFFFAOYSA-N hydroxymethyl propionaldehyde Natural products CCC(=O)CO GFAZHVHNLUBROE-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000003754 machining Methods 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
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- 238000007639 printing Methods 0.000 description 1
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- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
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- 229960002447 thiram Drugs 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
Description
本発明は、耐摩耗性の改良された合成樹脂成形
品の製造方法に関する。
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、スチレン―アクリロニ
トリル共重合樹脂（AS樹脂）、ポリ塩化ビニル樹
脂、アセテート樹脂、アクリロニトリル―ブタジ
エン―スチレン共重合樹脂（ABS樹脂）、ポリエ
ステル樹脂などから製造された合成樹脂成形品は
ガラス製品に比較して軽量で耐衝撃性に優れてい
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、有機板ガラス、照明
器具カバー、光学用レンズ、眼鏡用レンズ、反射
鏡、鏡などの光学的用途、看板、デイスプレーな
どの装飾的用途あるいはネームプレート、ダスト
カバーケース、自動車部品など多くの分野でその
用途開発が進められている。
しかし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成形品の輸送中、部品
の取付時あるいは使用中に他の物体との接触、衝
突、引つかきなどの作用によつて表面が損傷を受
け製品歩留を低下させたり、美観がそこなわれた
りする。特に成形品の用途がカメラ、虫メガネな
どの光学用レンズ、フアツシヨングラス、サング
ラス、矯正用レンズなどの眼鏡用レンズあるいは
窓ガラス、装飾用のケース、カバー、時計用レン
ズ、反射鏡、鏡などの場合には、その表面に発生
する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。
このような合成樹脂成形品の欠点を改良する方
法が従来より種々検討されてきており、例えばそ
の１つとして合成樹脂成形品の表面にシリコン系
塗料あるいはメラミン系塗料を塗布し、加熱硬化
処理するいわゆる熱硬化型の架橋硬化被膜を合成
樹脂成形品の表面に形成させる方法がある。しか
しこれらの方法は熱硬化型であるために塗料の貯
蔵安定性が良くないばかりでなく、架橋硬化被膜
を形成させるのに高温で長時間加熱する必要があ
り、そのために作業性、生産性が悪く、更に架橋
硬化処理をした後においても、徐々に硬化反応が
進行するために製品化した後の架橋硬化膜にクラ
ツクが発生したり、基材との界面に亀裂を生じ基
材との密着性が低下したり、又耐水性、耐候性な
どの性能上の欠点がある。
もう１つの方法として１分子中に重合性のエチ
レン性不飽和基を２個以上を有する多官能のアク
リレートあるいはメタアクリレート単量体を架橋
硬化塗料として合成樹脂成形品の表面に塗布し、
活性エネルギー線を照射して合成樹脂成形品の表
面でラジカル重合によつて架橋硬化被膜を形成さ
せる方法がある。
従来このような多官能のアクリレート又はメタ
アクリレート単量体は活性エネルギー線照射によ
る重合活性が優れているので、速乾性のインキ用
素材として、米国特許第3661614号、同第3551311
号、同第3551246号、あるいは英国特許第1198259
号明細書などに提案されており、またこれら多官
能のアクリレート又はメタクリレート単量体を合
成樹脂成形品の表面改質材としての応用に関して
は、米国特許第3552986号、同第2413973号、ある
いは同第3770490号明細書などに提案されている。
一方、本出願人らも早くより多官能のアクリレ
ート又はメタクリレート単量体が活性エネルギー
線照射による架橋硬化重合性に優れ、かつそれが
合成樹脂成形品の表面の耐摩耗性を改良しうる架
橋硬化膜形成用素材として有効であることを見出
し多くの提案を行なつてきた（特公昭48―42211
号、同49―12886号、同49―22951号、同49―
14859号、同49―22952号公報）。
これらの多官能のアクリレート又はメタクリレ
ート単量体を架橋硬化性塗料として合成樹脂成形
品の表面に塗布し、活性エネルギー線を照射して
合成樹脂成形品の表面に架橋硬化被膜を形成させ
る方法は前記の熱硬化性の塗料を用いて、加熱処
理によつて架橋硬化被膜を形成させる方法に比
べ、塗料の貯蔵安定性も良く、活性エネルギー線
を照射して重合架橋硬化せしめるので、常温で分
あるいは秒オーダーの短時間で架橋硬化被膜を形
成させることができ、生産性の面でも優れてお
り、かつ性能的にも耐摩耗性に優れ、硬化膜の経
時変化もなく、耐水性、耐候性ならびに基材との
初期密着性に優れるなど多くの利点を有してい
る。
しかし反面次のような問題点があることも判明
している。先ずその第１点は合成樹脂成形品の表
面に塗料を塗布した後、これに活性エネルギー線
を照射して架橋硬化被膜を形成させる際、窒素ガ
ス、炭酸ガスなどの不活性ガス雰囲気下で行なわ
ないと、架橋硬化反応が空気中の酸素によつて抑
制されるため、十分な耐摩耗性を有する架橋硬化
被膜が形成されないことである。これは実用上極
めて重要な問題であり、工程作業が煩雑になるば
かりでなく、雰囲気中の酸素濃度を低い状態で常
時一定に保つことが困難なため、性能にバラツキ
を生じ製品歩留を低下させたり、コストアツプの
原因ともなる。第２点は多官能アクリレート又は
メタクリレート単量体は常温では高粘度のものが
多く、しかも耐摩耗性の改良に対して有効なもの
程高粘度となり、塗布作業性が悪く塗料の塗布方
法が限定されるばかりでなく、架橋硬化被膜の表
面平滑性が十分でなかつたり、膜厚の均一性に劣
つたり、膜厚コントロールが困難であるなどの作
業上問題があり、その他基材との密着性、耐摩耗
性、表面平滑性、膜厚均一性に優れた薄い架橋硬
化被膜の形成を行うことが極めて困難である。
以上述べた如く、多官能のアクリレート又はメ
タクリレート単量体を塗料として合成樹脂成形品
の表面に塗布し、活性エネルギー線を照射して得
られる表面に架橋硬化被膜を有する合成樹脂成形
品は改良すべき多くの問題点を残しており、有用
な利点があるにもかかわらず今だに実用化に至つ
ていないのが現状である。
本発明者らはこのような情況に鑑み、鋭意研究
を重ねた結果、特定の成分を特定の割合に配合さ
せた塗料組成物を用い、かつこれを合成樹脂成形
品の表面に塗布し、特定の条件下で活性エネルギ
ー線を照射して特定の厚み範囲を有する架橋硬化
被膜を形成させることにより、前述の点が一挙に
解決できることを見出し本発明を完成した。
すなわち、本発明は、ペンタエリスリトールト
リアクリレート、ペンタエリスリトールトリメタ
クリレート、ペンタエリスリトールテトラアクリ
レート、ペンタエリスリトールテトラメタクリレ
ート、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トリメタクリレー
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テトラメタクリレー
ト、ジペンタエリスリトルペンタアクリレート、
ジペンタエリスリトールペンタメタクリレート、
ジペンタエリスリトールヘキサアクリレート及び
ジペンタエリスリトールヘキサメタクリレートよ
りなる群から選ばれる少なくとも１種の多官能単
量体30〜98重量％と次の一般式
（式中、R1は水素又はメチル基であり、ｎは
０又は１〜５の整数であり、Ｘは炭素原子数６以
下のアルキレン基又はアルキレン基の水素原子１
個が水酸基で置換されたものであり、これらはｎ
が２以上の時同じもしくは異なつてもよい。）で
示される２官能単量体70〜２重量％からなる単量
体混合物〔Ａ〕100重量部と、光増感剤０〜10重
量部とよりなり、空気中で活性エネルギー線照射
により耐摩耗性に優れた架橋硬化被膜を形成し得
る塗料組成物を合成樹脂成形品の表面に塗布し、
これに活性エネルギー線を照射することによつて
膜１〜30μの架橋硬化被膜を形成させることを特
徴とする耐摩耗性の改良された合成樹脂成形品の
製造方法に関するものである。
本発明の最大の特徴は特定の多官能（メタ）ア
クリレート単量体と特定の２官能（メタ）アクリ
レート及び光増感剤を特定の割合に配合させた組
成物を塗料として使用することにあり、これによ
つて初めて本発明の目的である、空気雰囲気下で
活性エネルギー線を照射しても耐摩耗性、表面平
滑性、可撓性、耐水性、耐熱性、耐薬品性ならび
に基材との密着性に優れた透明な架橋硬化被膜を
有する合成樹脂成形品が得られるのであつて、本
発明に係る以外の多官能単量体あるいは２官能単
量体を使用したり、又はその配合組成割合が異な
る場合には、空気雰囲気下での架橋硬化反応が阻
害されたり、架橋硬化被膜の耐摩耗性や可撓性が
劣つたり、あるいは基材との密着性が低下したり
して上記の如き各種性能にバランスのとれた合成
樹脂成形品は得られず、本発明の目的も達成され
ない。
前記の多官能単量体は活性エネルギー線を照射
するに当つて、空気硬化性を有すると同時に形成
される架橋硬化被膜に高度の耐摩耗性を付与する
ような単量体であつて、具体例を示せばペンタエ
リスリトールトリアクリレート、ペンタエリスリ
トールトリメタクリレート、ペンタエリスリトー
ルテトラアクリレート、ペンタエリスリトールテ
トラメタクリレート、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トリメ
タクリレート、ジペンタエリスリトールテトラア
クリレート、ジペンタエリトールテトラメタクリ
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ペンタメタクリレ
ート、ジペンタエリスリトールヘキサアクリレー
ト、ジペンタエリスリトールヘキサメタクリレー
ト等があげられる。これらは１種もしくは２種以
上混合して用いることができる。
同じ多官能のアクリレート系単量体であつても
トリメチロールプロパントリアクリレート、トリ
メチロールプロパントリメタクリレート、トリメ
チロールエタントリアクリレート、トリメチロー
ルエタントリメタクリレート、ペンタグリセロー
ルトリアクリレート、ペンタグリセロールトリメ
タクリレートなどの多官能単量体は活性エネルギ
ー線による空気硬化性が劣り、したがつて空気雰
囲気下においては耐摩耗性に優れた架橋硬化被膜
を形成し難いので好ましくない。
塗料組成物中の多官能単量体の使用割合は30〜
98重量％の範囲にあることが必要であり、好まし
くは40〜96重量％である。使用割合が30重量％未
満の場合には十分な耐摩耗性を有する架橋硬化被
膜が形成されず、また98重量％をこえる場合には
耐摩耗性の面で問題ないが、架橋硬化被膜の可撓
性ならびに合成樹脂基材の密着性が低下するた
め、クラツクの発生あるいは膜剥げなど好ましく
ない現象を生ずる。
また多官能（メタ）アクリレート単量体を併用
して用いる２官能単量体は架橋硬化被膜の耐摩耗
性を低下させることなく、これに可撓性を与え、
基材に対する密着性を高めかつ活性エネルギーを
照射する場合、空気硬化性を付与する単量体であ
つて次の一般式で示される２官能アクリレート又
はメタクリレート単量体である。
（式中、R1は水素又はメチル基であり、ｎは
０又は１〜５の整数であり、Ｘは炭素原子数６以
下のアルキレン基又はそのアルキレン基の水素原
子１個が水酸基で置換されたものであり、これら
はｎが２以上の時同じもしくは異なつてもよい。）
この一般式で示される化合物においてもＸ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、Ｘ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メタクリロキ
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メタ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メタクリロキシジ
エトキシフエニル）プロパン、２，２ビス（４ア
クリロキシペンタエトキシフエニル）プロパン、
２，２ビス（４メタクリロキシペンタエトキシフ
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
メタ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メ
タクリロキシ（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、２，２ビス〔４メタクリロキシ（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官能アクリレート又
はメタクリレート単量体の塗料組成物中での使用
割合としては70〜２重量％の範囲にある必要があ
り、より好ましくは60〜４重量％の範囲である。
使用割合が70重量％をこえる場合には架橋硬化被
膜の耐摩耗性が低下し、逆に２重量％未満の場合
には架橋硬化被膜の可撓性が劣り、基材に変形歪
を加えたときに硬化被覆にクラツクが発生した
り、基材との密着性が低下するので好ましくな
い。本発明においては前記塗料組成物中にもし必
要があればこの構成条件を満たし、かつ空気中で
活性エネルギー線を照射した場合の空気硬化性を
大きく低下させない範囲内において、合成樹脂成
形品の表面に形成させ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他
の単量体を併用してもよい。
本発明で使用する塗料組成物はその必要性によ
つては特定の特性を有する有機溶剤と混合して使
用することができる。混合して使用する場合の有
機溶剤は塗料組成物を合成樹脂成形品の表面に塗
布する際の、塗布作業性、均一な塗布被覆形成性
あるいは貯蔵安定性に極めて好ましい効果を付与
するばかりでなく架橋硬化被膜の基材に対する密
着性を増大させる作用も有している。例えば架橋
硬化被膜を形成させて表面の耐摩耗性の改良され
た合成樹脂成形品を温水浸漬→冷水浸漬→高温乾
燥よりなる苛酷なくり返し試験を行なつた場合な
どのような硬化被膜の基材に対する密着性の経時
変化ないしは耐久性に大きい効果を有している。
これはおどろくべきことであり、その理由につい
て明確ではないが、有機溶剤の基材ならびに多官
能単量体に対する微妙な相互作用、均一でかつ表
面平滑性に極めて優れた架橋硬化被膜が形成され
たことあるいはこれらの相乗作用などがその理由
の一つとして推定される。
従来多官能のアクリレート又はメタクリレート
単量体を合成樹脂成形品その他の物体の表面に塗
布し活性エネルギー線を照射して架橋硬化被膜を
形成される方法においては、重合による架橋硬化
反応が非常に速いため、多官能のアクリレート又
はメタクリレート単量体に有機溶剤を併用するこ
とは、架橋硬化被膜中に有機溶剤が残存したり、
硬化膜の表面平滑性を損う可能性が強いため、む
しろ有機溶剤を使用しない方向でのみその検討が
進められてきた。
本発明者らは有機溶剤併用による塗布作業性の
利点を有効に生かすべくその点に関して詳細な検
討を重ねた結果、有機溶剤が次のような要件を満
足している場合に初めて使用可能となり、それば
かりかむしろ前記した如き架橋硬化被膜の密着性
ないしは耐久性に予想外の効果があることを見出
した。
すなわち本発明において塗料組成物と混合して
使用できる有機溶剤は
１ 塗料組成物と混合して均一な溶液を形成する
こと
２ 常圧での沸点が50℃以上200℃以下であるこ
と
の２つの条件を満足する必要がある。まず第１の
塗料組成物と混合して均一な溶液を形成すること
は、当然でかつ最も重要な条件であつて、例えば
ｎ―ヘキサン、ｎ―ヘプタン、シクロヘキサンな
どの飽和炭化水素系の有機溶剤は均一な溶液を形
成しないので使用できない。第２の常圧での沸点
50℃以上200℃以下の条件は合成樹脂成形品の表
面に塗布した際の均一な被膜形成性あるいは表面
平滑性の優れた架橋硬化被膜を形成させるために
必要な要件である。常圧での沸点が50℃未満の場
合には塗料組成物を塗布した後、塗膜から揮発す
る有機溶剤の潜熱で基材表面が冷却され、そこに
空気中の水分が凝結して塗膜の表面平滑性が失わ
れ、また200℃をこえる場合には、逆に塗膜から
の有機溶剤の揮発が非常に遅いため作業性に問題
があることと、活性エネルギー線照射工程で残存
有機溶剤の揮発逃散と重合による架橋硬化被膜の
形成とのバランスがとれないため架橋硬化被膜の
均一性、表面平滑性が失われたり、あるいは架橋
硬化被膜に有機溶剤が残存し被膜が白化するので
好ましくない。
したがつて使用する有機溶剤の沸点としては常
圧で50℃以上200℃以下のものである必要があり、
より好ましくは60〜150℃の沸点範囲のものであ
る。
有機溶剤の混合量としては使用目的によつても
異なるが、単量体混合物〔Ａ〕５〜90重量部に対
して95〜10重量部（合計100重量部）の範囲が好
ましい。10重量部未満の場合にはその効果が少な
く、95重量部をこえる場合は架橋硬化被膜の膜厚
コントロールが困難となつたり、耐摩耗性が劣つ
たりして好ましくない。
使用できる有機溶剤としては、前述の条件を満
足する必要があり、具体的にはエタノール、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―プ
ロピル、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挙げられる。これらの有
機溶剤は１種を単独で使用してもよいし、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種以上の混合溶媒を使用して
もよい。
また特定の目的がありかつ有機溶剤と同じよう
な条件を満たし同じ効果を有するものであればメ
チルアクリレート、エチルアクリレート、メチル
メタアクリレート、スチレンなどの重合性単量体
を有機溶剤の１種として使用することも可能であ
る。
これらの有機溶剤は基材となる合成樹脂の種類
によつては、透明な目的で使用するものを曇価さ
せたり、着色基材の染顔料を溶出して変色させた
り、あるいは基材そのものにクラツクを発生しや
すくする場合があるので、使用する有機溶剤の種
類は表面に架橋硬化被膜を形成させる基材の種類
あるいは目的に応じて適宜選択して使用する必要
がある。
本発明において塗料組成物あるいは有機溶剤と
混合した塗料組成物を目的とする合成樹脂成形品
の表面に塗布し、架橋硬化被膜を形成せしめるた
めには、これに紫外線、電子線あるいは放射線な
どの活性エネルギー線を照射する必要がある。こ
の中でも紫外線照射による方法は実用的にみて最
も好ましい架橋硬化方法である。紫外線を塗布被
膜の架橋硬化エネルギー線として利用する場合に
は前記の塗料組成物に対し、紫外線照射によつて
重合開始反応を開始しうる光増感剤を加えておく
必要がある。このような光増感剤の具体例として
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
ソブチルエーテル、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―クロルベンゾフエ
ノン、ｐ―メトキシベンゾフエノンなどのカルボ
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。これらの光増感剤は単
独で使用してもよいし２種以上組合せて用いても
よい。これら光増感剤の塗料組成物中への添加量
は単量体合物〔Ａ〕又は単量体混合物〔Ａ〕と有
機溶剤〔Ｂ〕との合計100重量部に対して０〜10
重量部、好ましくは0.01〜10重量部の範囲であ
る。あまり多量の添加は架橋硬化被膜を着色させ
たり、耐候性の低下などを引き起こすので好まし
くない。
また本発明で使用する塗料組成物中には必要に
応じて帯電防止剤、界面活性剤あるいは貯蔵安定
剤などの添加剤を適宜添加して使用することがで
きる。
本発明に使用さ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
成形品が用いられ、例えば具体例としてポリメチ
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、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挙げら
れる。
これらの成形品のうち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。
本発明に使用される各種成形品はそのままでも
使用することができるが、もし必要あれば洗浄、
エツチング、コロナ放電、活性エネルギー線照
射、染色、印刷などの前処理を施したものも使用
できる。
これらの合成樹脂成形品に対する前述した塗料
組成物の塗布方法としては、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
などの方法が採用される。それぞれの方法には一
長一短があり、合成樹脂成形品に対する要求性
能、あるいはその使用用途によつて適宜その塗布
方法も選択する必要がある。例えば目的とする合
成樹脂成形品の一部分のみに耐摩耗性を付与した
い場合には刷毛塗りあるいは流し塗りが適してお
り、成形品の表面形状が複雑な場合にはスプレー
塗布、成形品が比較的平たんで対称的な場合には
回転塗布、成形品の形状がロツドあるいはシート
状の場合には浸漬塗布がそれぞれ適している。
塗料組成物の合成樹脂成形品の表面に対する塗
布量としては、得られる成形品の使用用途又は塗
料組成物中の単量体の含有量によつて異なるが、
合成樹脂成形品の表面に形成される架橋硬化膜の
膜厚が１〜30μの範囲になるように塗布すること
が望ましい。膜厚が1μ未満の場合には耐摩耗性
が劣り、逆に30μをこえる場合には被膜の可撓性
が損なわれ、被膜にクラツクが発生しやすくなる
ためそれによつて成形品自体の強度が低下するこ
とがあるので好ましくない。
塗料組成物の塗布方法としては前記した如く
種々の方法があるが、それらの塗布方法の中でも
特に浸漬塗布方法は合成樹脂成形品の形状によつ
ては制約される面もあるが、塗布作業が簡単で生
産性にも優れている以外に、架橋硬化被膜の膜厚
が比較的自由に変えられるなどの利点がある。し
かし反面浸漬塗布が可能でかつその利点を生かす
ためには、これに使用する塗料には次のような
種々の条件が要求される。
すなわち、塗料の粘度が比較的自由にコントロ
ールできること、浸漬塗布によつて塗布被膜形成
性に優れていること、塗料の粘度の経時変化がな
く、貯蔵安定性に優れていることなどの条件が満
足されなければならない。
本発明で用いる塗料組成物、とりわけ有機溶剤
を混合した塗料組成物はこれらの要件を満足し、
かつ耐摩耗性、表面平滑性、、可撓性、耐久性、
耐水性、耐溶剤性ならびに基材との密着性に優れ
た透明な架橋硬化被膜を形成し得る浸漬塗布法に
優れた適応性を有する塗料である。
また表面に架橋硬化被膜を形成させた合成樹脂
成形品の用途によつては、表面平滑性の極めて優
れたものが要求されたり、更には架橋硬化被膜を
形成させた後に、適当な加熱下で曲げ加工を行な
つたり、切断ならびに穴あけなどの切削加工を行
なつたり、部品取付時あるいは使用中に大きい変
形歪みが加わつたりなどの苛酷な条件にも耐える
ことが要求される。このような場合には架橋硬化
被膜自体が可撓性ならびに基材樹脂との密着性な
どの特性に優れていることが当然必要であるが第
２の因子として硬化被膜の膜厚の問題がある。す
なわち膜厚としては薄いもの程これらの外的作用
に対する耐性があるが反面極度に薄くなると耐摩
耗性が低下するので架橋硬化被膜の膜厚としては
１〜9μの範囲が望ましい。
従来の多官能アクリレート又はメタクリレート
単量体あるいはその混合物を架橋硬化被膜形成材
として利用する技術レベルにおいては、耐摩耗性
に優れかつ表面平滑性、膜厚均一性ならびに透明
性、被膜外観などに優れた上記のような薄い架橋
硬化被膜を合成樹脂成形品の表面に形成させるこ
とは不可能であつた。
ところが本発明に用いられる有機溶剤を混合し
た塗料組成物の中で25℃の粘度が10センチポイズ
以下となるように調製した塗料組成物を浸漬塗布
法によつて合成樹脂成形品の表面に塗布し、架橋
硬化せしめることによつて耐摩耗性、表面平滑
性、膜厚均一性、被膜外観ならびに基材との密着
性などに優れた１〜9μという範囲の薄い透明な
架橋硬化被膜を形成させることが可能となつた。
これは本発明の重要な点の一つである。
つぎに合成樹脂成形品の形状もしくはその要求
性能に適した方法で塗布した合成樹脂成形品は活
性エネルギー線の照射により架橋硬化されるが、
塗料として有機溶剤を添加した塗料組成物を使用
する場合は、活性エネルギー線を照射して架橋硬
化被膜を形成させる前に特定の条件下に置いて、
合成樹脂成形品の表面に塗布した被膜中に含まれ
る有機溶剤の50重量％以上を揮発逃散させた後、
活性エネルギー線を照射した方がよい。塗布被膜
中に50重量％以上の有機溶剤を含有した状態でこ
れに活性エネルギー線を照射すると、有機溶剤の
種類によつては形成される架橋硬化被膜の表面平
滑性が損われたり、被膜に気泡が発生したり、あ
るいは架橋硬化被膜中に有機溶剤が残存し、被膜
が白化したりするなどの好ましくない現象を生ず
る。
架橋硬化被膜を形成せしめるには、キセノンラ
ンプ、低圧水銀灯、中圧水銀灯、高圧水銀灯又は
超高圧水銀灯などの光源から発せられる紫外線又
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塗布被膜に照射して架橋硬
化させなければならない。実用性あるいは作業性
からみた場合、照射線源としては紫外線が最も好
ましい。
活性エネルギー線を照射する雰囲気としては窒
素ガス、炭酸ガスなどの不活性ガス雰囲気下ある
いは酸素濃度を低下させた雰囲気下でも勿論さし
つかえないが、本発明で使用する塗料組成物は通
常の空気雰囲気下でも耐摩耗性その他の特性に優
れた架橋硬化被膜を形成させることが可能であ
る。照射雰囲気温度としては常温でもよく又基材
合成樹脂成形品に有害な変形などが生じない程度
に加温された雰囲気でもよい。
本発明の方法によつて製造される表面に架橋硬
化被膜を有する合成樹脂成形品は表面平滑性と美
観に優れ、かつ表面硬度ないしは耐摩耗性、耐擦
傷性に極めて優れたものである。更に表面に形成
された架橋硬化被膜は透明で可撓性を有する均一
な被膜であり、基材との密着性は極めて優れ、苛
酷な条件、環境下においても被膜の剥離、亀裂な
どを生じることがなく、有機窓ガラス、照明器具
カバー、反射鏡、鏡、眼鏡用レンズ、サングラス
用レンズ、光学用レンズ、時計用レンズ、などの
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更に詳細に
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
ａ 表面硬度……JISK5651―1966に準じた鉛筆
硬度
ｂ 擦傷テスト…＃000のスチールウールによる
擦傷テスト
〇……軽くこすつてもその表面にほとんど傷が
つかない
△……軽くこするとその表面に少し傷がつく
×……軽くこすつてもその表面にひどく傷がつ
く
（基材樹脂と同程度）
(2) 密着性
架橋硬化被膜に対するクロスカツト―セロテー
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、縦、横それぞれに11本入
れて１mm2の目数を100個つくり、その上にセロテ
ープを貼りつけ、急激にはがす。このセロテープ
の操作を同一個所で３回くり返す。
〇……３回くり返しても架橋硬化被膜の剥離目
なし
△……３回くり返した後の剥離目の数１〜50個
×……３回くり返した後の剥離目の数51〜100
個
(3) 可撓性（最大曲げ角度）
厚さ２〜３mmのシート状成形品の表面に架橋硬
化被膜を形成させ、これから巾６mm、長さ５cmの
短冊状の試験片を切り出し、この短冊の両端から
力を加えて曲げ変型歪を与え、被膜にクラツクが
発生したときの試験片の水平面からの角度を求め
る。これが“最大曲げ角度”でこの角度が大きい
程被膜の可撓性がよい。
(4) サーマル、サイクル試験
表面に架橋硬化被膜を形成させた成形品を65℃
の温水に１時間浸漬した後ただちに０℃の氷水に
10分間浸漬し、つづいて80℃で１時間熱風乾燥す
る。これを数回くり返した後で各種試験を行な
う。
実施例 １
回転駆動体を装備した石英筒内の回転板の上に
厚さ２mm、直径４cmの円板状のメタクリル樹脂射
出成形品を回転軸の中心に成形品の中心がくるよ
うに貼りつけ、筒内の温度が40℃になるように保
つた。この円筒状成形品の上面中央部に第１表に
示すつうな塗料組成物約1.0ｇを流し、ただちに
回転板を3000回転／分の速度で回転させ、成形品
の上部表面に塗布被膜を形成させた。次いで回転
数を５回転／分の速度におとし、ゆつくり回転さ
せながら空気雰囲気下で石英筒外ななめ上方より
100W高圧水銀灯（ウシオ電機製）を10分間照射
して、成形品の上部表面に架橋硬化被膜を形成さ
せた。
得られた成形品についての評価結果を第１表に
示した。
なお、第１表に示す塗料組成物はいずれも2.0
重量部のベンゾインイソブチルエーテルを含有す
る。
The present invention relates to a method for producing a synthetic resin molded article with improved wear resistance. Polymethyl methacrylate resin, polycarbonate resin, polyallyl diglycol carbonate resin, polystyrene resin, styrene-acrylonitrile copolymer resin (AS resin), polyvinyl chloride resin, acetate resin, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), Synthetic resin molded products made from polyester resin etc. are not only lighter and have better impact resistance than glass products, but also have various advantages such as being inexpensive and easy to mold. Its applications include optical applications such as plate glass, lighting equipment covers, optical lenses, eyeglass lenses, reflectors, and mirrors, decorative applications such as signboards and display displays, and many other fields such as name plates, dust cover cases, and automobile parts. Development is underway. However, these synthetic resin molded products lack surface wear resistance, so they are susceptible to contact with other objects, collisions, and scratches during transport, when installing parts, or during use. As a result, the surface is damaged, reducing product yield and deteriorating the aesthetic appearance. In particular, molded products are used for cameras, optical lenses such as magnifying glasses, optical lenses such as fashion glasses, sunglasses, corrective lenses, or window glass, decorative cases and covers, watch lenses, reflectors, and mirrors. In such cases, the damage that occurs to the surface may significantly reduce its commercial value, or
Since it becomes unusable in a short period of time, there is a strong need to improve the wear resistance of the surface. Various methods have been studied to improve these drawbacks of synthetic resin molded products. For example, one method is to apply a silicone-based paint or melamine-based paint to the surface of a synthetic resin molded product and heat-cure it. There is a method of forming a so-called thermosetting crosslinked cured film on the surface of a synthetic resin molded product. However, since these methods are thermosetting, the storage stability of the paint is not good, and it is necessary to heat the paint at high temperature for a long time to form a crosslinked cured film, which reduces workability and productivity. Unfortunately, even after cross-linking and curing treatment, the curing reaction proceeds gradually, resulting in cracks in the cross-linked cured film after it is commercialized, or cracks at the interface with the substrate, resulting in poor adhesion to the substrate. There are performance disadvantages such as decreased properties and water resistance and weather resistance. Another method is to apply a polyfunctional acrylate or methacrylate monomer having two or more polymerizable ethylenically unsaturated groups in one molecule to the surface of a synthetic resin molded product as a crosslinked and cured coating.
There is a method in which a crosslinked cured film is formed by radical polymerization on the surface of a synthetic resin molded article by irradiating it with active energy rays. Conventionally, such polyfunctional acrylate or methacrylate monomers have excellent polymerization activity when irradiated with active energy rays, so they have been used as quick-drying ink materials as described in U.S. Pat. Nos. 3,661,614 and 3,551,311.
No. 3551246 or British Patent No. 1198259
Regarding the application of these polyfunctional acrylate or methacrylate monomers as surface modification materials for synthetic resin molded products, U.S. Pat. No. 3,552,986, U.S. Pat. This is proposed in Specification No. 3770490, etc. On the other hand, the present applicants have also discovered that polyfunctional acrylate or methacrylate monomers have excellent crosslinking and curing polymerizability upon irradiation with active energy rays, and that this crosslinking and curing can improve the surface abrasion resistance of synthetic resin molded articles. He discovered that it was effective as a film-forming material and made many proposals.
No. 49-12886, No. 49-22951, No. 49-
14859, Publication No. 49-22952). The method of applying these polyfunctional acrylate or methacrylate monomers as a crosslinked curable paint to the surface of a synthetic resin molded product and irradiating it with active energy rays to form a crosslinked cured film on the surface of the synthetic resin molded product is as described above. Compared to the method of forming a crosslinked cured film by heat treatment using a thermosetting paint, the storage stability of the paint is better, and since it is polymerized and crosslinked by irradiation with active energy rays, it can be cured in minutes or at room temperature. It is possible to form a cross-linked cured film in a short time on the order of seconds, and it is excellent in terms of productivity. It also has excellent wear resistance in terms of performance, and there is no change in the cured film over time, and it has excellent water resistance, weather resistance, and It has many advantages such as excellent initial adhesion to the base material. However, on the other hand, it has also been found that there are the following problems. The first point is that after applying paint to the surface of a synthetic resin molded product, when irradiating it with active energy rays to form a crosslinked cured film, it is done in an inert gas atmosphere such as nitrogen gas or carbon dioxide gas. Otherwise, the crosslinking and curing reaction will be inhibited by oxygen in the air, and a crosslinked and cured film with sufficient wear resistance will not be formed. This is an extremely important problem in practical terms; it not only complicates the process, but also makes it difficult to keep the oxygen concentration in the atmosphere constant and low, leading to variations in performance and lower product yields. It can also cause an increase in costs. The second point is that many polyfunctional acrylate or methacrylate monomers have high viscosity at room temperature, and the more effective they are for improving wear resistance, the higher the viscosity becomes, resulting in poor coating workability and limited coating methods. In addition, there are operational problems such as the surface smoothness of the cross-linked cured film being insufficient, poor uniformity of film thickness, and difficulty in controlling the film thickness, and other problems such as poor adhesion to the substrate. It is extremely difficult to form a thin crosslinked cured film with excellent properties such as hardness, abrasion resistance, surface smoothness, and film thickness uniformity. As mentioned above, it is possible to improve synthetic resin molded products having a cross-linked cured coating on the surface obtained by applying a polyfunctional acrylate or methacrylate monomer as a paint to the surface of a synthetic resin molded product and irradiating it with active energy rays. Currently, there are many problems that need to be addressed, and although there are useful advantages, it has not yet been put into practical use. In view of these circumstances, the inventors of the present invention have conducted extensive research, and have found that they use a coating composition containing specific ingredients in specific proportions, apply this to the surface of a synthetic resin molded product, and obtain specific results. The present invention has been completed by discovering that the above-mentioned problems can be solved at once by irradiating active energy rays under the following conditions to form a crosslinked cured film having a specific thickness range. That is, the present invention provides pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol triacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, dipentaerys little pentaacrylate,
dipentaerythritol pentamethacrylate,
30 to 98% by weight of at least one polyfunctional monomer selected from the group consisting of dipentaerythritol hexaacrylate and dipentaerythritol hexamethacrylate and the following general formula (In the formula, R 1 is hydrogen or a methyl group, n is 0 or an integer of 1 to 5, and X is an alkylene group having 6 or less carbon atoms or 1 hydrogen atom of the alkylene group.
are substituted with hydroxyl groups, and these are n
may be the same or different when is 2 or more. 100 parts by weight of a monomer mixture [A] consisting of 70 to 2% by weight of a bifunctional monomer represented by ) and 0 to 10 parts by weight of a photosensitizer. A coating composition capable of forming a crosslinked cured film with excellent abrasion resistance is applied to the surface of a synthetic resin molded product,
The present invention relates to a method for producing a synthetic resin molded article with improved abrasion resistance, characterized in that a crosslinked cured coating with a thickness of 1 to 30 microns is formed by irradiating the article with active energy rays. The greatest feature of the present invention is the use of a composition containing a specific polyfunctional (meth)acrylate monomer, a specific bifunctional (meth)acrylate, and a photosensitizer in a specific ratio as a paint. As a result, for the first time, the objects of the present invention can be achieved, including abrasion resistance, surface smoothness, flexibility, water resistance, heat resistance, chemical resistance, and substrate resistance even when irradiated with active energy rays in an air atmosphere. A synthetic resin molded product having a transparent crosslinked cured film with excellent adhesion can be obtained, and it is possible to obtain a synthetic resin molded article having a transparent crosslinked cured film with excellent adhesion, and it is possible to use polyfunctional monomers or bifunctional monomers other than those according to the present invention, or to use a blended composition thereof. If the ratios are different, the crosslinking and curing reaction in an air atmosphere may be inhibited, the abrasion resistance and flexibility of the crosslinked cured film may be poor, or the adhesion to the substrate may be reduced, resulting in the above-mentioned problems. A synthetic resin molded article with well-balanced various performances cannot be obtained, and the object of the present invention cannot be achieved. The above-mentioned polyfunctional monomer is a monomer that has air curability and at the same time imparts a high degree of abrasion resistance to the crosslinked cured film formed when irradiated with active energy rays. Examples include pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol triacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, Examples include pentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like. These can be used alone or in a mixture of two or more. Even if they are the same polyfunctional acrylate monomers, polyfunctional ones such as trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane triacrylate, trimethylolethane trimethacrylate, pentaglycerol triacrylate, pentaglycerol trimethacrylate, etc. Monomers are not preferred because they have poor air curability with active energy rays, and therefore it is difficult to form a crosslinked cured film with excellent abrasion resistance in an air atmosphere. The proportion of polyfunctional monomer used in the paint composition is 30~
It needs to be in the range of 98% by weight, preferably 40-96% by weight. If the usage rate is less than 30% by weight, a crosslinked cured coating with sufficient wear resistance will not be formed, and if it exceeds 98% by weight, there will be no problem in terms of wear resistance, but the crosslinked cured coating will not be formed. Since the flexibility and adhesion of the synthetic resin base material are reduced, undesirable phenomena such as cracking and film peeling occur. In addition, the bifunctional monomer used in combination with the polyfunctional (meth)acrylate monomer imparts flexibility to the crosslinked cured coating without reducing its abrasion resistance.
When irradiating active energy while increasing adhesion to a substrate, a bifunctional acrylate or methacrylate monomer is a monomer that imparts air curability and is represented by the following general formula. (In the formula, R 1 is hydrogen or a methyl group, n is 0 or an integer from 1 to 5, and X is an alkylene group having 6 or less carbon atoms, or one hydrogen atom of the alkylene group is substituted with a hydroxyl group. (These may be the same or different when n is 2 or more.) In the compound represented by this general formula, when the number of carbon atoms in X is 7 or more, or the number of n is 6 or more, This is undesirable because the abrasion resistance of the crosslinked cured coating may be poor or the adhesion to the substrate may be reduced. More preferred monomers include those in which X has 3 or less carbon atoms and n has 3 or less carbon atoms. Specific examples of the bifunctional monomer represented by the above general formula include 2,2bis(4acryloxyphenyl)propane, 2,2bis(4methacryloxyphenyl)propane, and 2,2bis(4methacryloxyphenyl)propane. 4 acryloxyethoxyphenyl)propane, 2,2bis(4methacryloxyethoxyphenyl)propane,
2,2bis(4acryloxydiethoxyphenyl)propane, 2,2bis(4methacryloxydiethoxyphenyl)propane, 2,2bis(4acryloxypentaethoxyphenyl)propane,
2,2bis(4methacryloxypentaethoxyphenyl)propane, 2,2bis(4acryloxypropoxyphenyl)propane, 2,2bis(4methacryloxypentaethoxyphenyl)propane
methacryloxypropoxyphenyl) propane,
2,2bis[4acryloxy(2hydroxypropoxy)phenyl]propane, 2,2bis[4methacryloxy(2hydroxypropoxy)phenyl]propane, 2,2bis[4acryloxy(2hydroxypropoxy)phenyl]propane
Examples include hydroxypropoxyethoxy)phenyl]propane, 2,2bis[4methacryloxy(2hydroxypropoxyethoxy)phenyl]propane, and the like. These monomers can be used alone or in combination of two or more within the composition range. The proportion of these bifunctional acrylate or methacrylate monomers represented by the general formula in the coating composition must be in the range of 70 to 2% by weight, more preferably in the range of 60 to 4% by weight. .
If the usage ratio exceeds 70% by weight, the abrasion resistance of the cross-linked cured film decreases, and conversely, if the usage ratio is less than 2% by weight, the flexibility of the cross-linked cured film becomes poor and deformation strain is applied to the base material. This is undesirable because cracks sometimes occur in the cured coating and the adhesion to the substrate decreases. In the present invention, the surface of the synthetic resin molded product may be added to the coating composition, if necessary, within a range that satisfies these constitutional conditions and does not significantly reduce the air curability when irradiated with active energy rays in the air. The cross-linked cured film formed on the film has antistatic properties,
Other monomers may be used in combination for the purpose of imparting antifogging properties or other functions. The coating composition used in the present invention can be mixed with an organic solvent having specific properties depending on the necessity. When used in combination, organic solvents not only have extremely favorable effects on coating workability, uniform coating formation, and storage stability when coating a coating composition on the surface of a synthetic resin molded article. It also has the effect of increasing the adhesion of the crosslinked cured coating to the substrate. For example, a synthetic resin molded product with improved surface abrasion resistance by forming a crosslinked cured coating is subjected to a severe repeated test consisting of hot water immersion, cold water immersion, and high temperature drying. It has a great effect on changes in adhesion over time and durability.
This is surprising, and the reason for this is not clear, but due to the delicate interaction of the organic solvent with the base material and the polyfunctional monomer, a crosslinked cured film was formed that was uniform and had extremely excellent surface smoothness. It is presumed that one of the reasons for this is the synergistic effect between these two factors. In the conventional method of applying a polyfunctional acrylate or methacrylate monomer to the surface of a synthetic resin molded article or other object and irradiating it with active energy rays to form a crosslinked cured film, the crosslinking and curing reaction by polymerization is extremely fast. Therefore, using an organic solvent together with a polyfunctional acrylate or methacrylate monomer may cause the organic solvent to remain in the crosslinked cured film,
Since there is a strong possibility that the surface smoothness of the cured film will be impaired, studies have been progressing only in the direction of not using organic solvents. The inventors of the present invention have conducted detailed studies on this point in order to effectively take advantage of the advantages of coating workability when combined with organic solvents, and as a result, it has become possible to use organic solvents only when they satisfy the following requirements. In addition, it has been found that the above-mentioned crosslinked cured coating has an unexpected effect on the adhesion and durability. In other words, in the present invention, the organic solvent that can be used in combination with the coating composition has two properties: 1. It must be mixed with the coating composition to form a homogeneous solution. 2. It must have a boiling point of 50°C or more and 200°C or less at normal pressure. conditions must be met. First, it is natural and the most important condition to mix with the first coating composition to form a uniform solution. cannot be used because it does not form a homogeneous solution. Second boiling point at normal pressure
The conditions of 50°C or more and 200°C or less are necessary for forming a crosslinked cured film with excellent uniform film formation properties or surface smoothness when applied to the surface of a synthetic resin molded product. If the boiling point at normal pressure is less than 50°C, after the coating composition is applied, the surface of the substrate is cooled by the latent heat of the organic solvent that evaporates from the coating, and moisture in the air condenses there, causing the coating to form. In addition, if the temperature exceeds 200°C, the organic solvent evaporates from the coating film very slowly, resulting in workability problems, and the residual organic solvent may be removed during the active energy ray irradiation process. This is undesirable because the uniformity and surface smoothness of the cross-linked cured film may be lost due to the imbalance between the volatilization and the formation of a cross-linked cured film through polymerization, or the organic solvent may remain in the cross-linked cured film, resulting in whitening of the film. . Therefore, the boiling point of the organic solvent used must be between 50°C and 200°C at normal pressure.
More preferably, it has a boiling point range of 60 to 150°C. The amount of the organic solvent to be mixed varies depending on the purpose of use, but is preferably in the range of 95 to 10 parts by weight (total 100 parts by weight) based on 5 to 90 parts by weight of the monomer mixture [A]. If it is less than 10 parts by weight, the effect will be small, and if it exceeds 95 parts by weight, it will be difficult to control the thickness of the crosslinked cured film and the abrasion resistance will be poor, which is not preferable. Organic solvents that can be used must satisfy the above conditions, and specifically include alcohols such as ethanol, isopropanol, normal propanol, isobutyl alcohol, and normal butyl alcohol, benzene, toluene, xylene,
Examples include aromatic hydrocarbons such as ethylbenzene, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane, and acid esters such as ethyl acetate, n-propyl acetate, n-butyl acetate, and ethyl propionate. One of these organic solvents may be used alone, or a mixed solvent of two or more may be used as long as the boiling point and component ratio of the mixture meet the above requirements. . In addition, polymerizable monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, and styrene can be used as a type of organic solvent if they have a specific purpose, meet the same conditions, and have the same effects as organic solvents. It is also possible to do so. Depending on the type of synthetic resin that is used as the base material, these organic solvents may cause haze in those used for transparent purposes, may discolor the dyes and pigments in the colored base material, or may cause discoloration on the base material itself. Since cracks may easily occur, the type of organic solvent to be used must be appropriately selected depending on the type of substrate on which a crosslinked cured film is to be formed or the purpose. In the present invention, in order to apply the coating composition or the coating composition mixed with an organic solvent to the surface of the intended synthetic resin molded product and form a crosslinked cured film, it is necessary to apply active irradiation such as ultraviolet rays, electron beams, or radiation. It is necessary to irradiate it with energy rays. Among these, the method using ultraviolet irradiation is the most preferred crosslinking and curing method from a practical standpoint. When ultraviolet rays are used as energy rays for crosslinking and curing coatings, it is necessary to add to the coating composition a photosensitizer that can initiate a polymerization reaction upon irradiation with ultraviolet rays. Specific examples of such photosensitizers include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p-chlorobenzophenone, p- - Carbonyl compounds such as methoxybenzophenone, sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide, azo compounds such as azobisisobutyronitrile and azobis-2,4-dimethylvaleronitrile, Examples include peroxide compounds such as benzoyl peroxide and ditertiary butyl peroxide. These photosensitizers may be used alone or in combination of two or more. The amount of these photosensitizers added to the coating composition is 0 to 10 parts by weight per 100 parts by weight of the monomer compound [A] or monomer mixture [A] and organic solvent [B].
parts by weight, preferably in the range from 0.01 to 10 parts by weight. Addition of too large a quantity is not preferable since it may cause coloring of the crosslinked cured film or a decrease in weather resistance. Furthermore, additives such as antistatic agents, surfactants, and storage stabilizers may be appropriately added to the coating composition used in the present invention, if necessary. As the synthetic resin molded product used in the present invention, various synthetic resin molded products are used regardless of whether it is a thermoplastic resin or a thermosetting resin. Specific examples include polymethyl methacrylate resin, polycarbonate resin, and polyallyl diglycol carbonate. resin,
Examples include sheet-shaped molded products, film-shaped molded products, rod-shaped molded products, and various injection molded products manufactured from polystyrene resin, acrylonitrile-styrene copolymer resin, polyvinyl chloride resin, acetate resin, ABS resin, polyester resin, etc. It will be done. Among these molded products, molded products manufactured from polymethyl methacrylate resin, polycarbonate resin, polyallyl diglycol carbonate resin, etc. are used to take advantage of their optical properties, heat resistance, impact resistance, etc. These molded products are particularly preferred as synthetic resin molded products used in the present invention, since there is a strong demand for improved wear resistance. The various molded products used in the present invention can be used as they are, but if necessary, they can be cleaned and
Materials that have undergone pretreatment such as etching, corona discharge, active energy ray irradiation, dyeing, and printing can also be used. As a method for applying the above-mentioned coating composition to these synthetic resin molded articles, methods such as brush coating, flow coating, spray coating, spin coating, or dip coating are employed. Each method has its advantages and disadvantages, and the application method must be selected appropriately depending on the required performance of the synthetic resin molded article or its intended use. For example, if you want to impart wear resistance to only a portion of the desired synthetic resin molded product, brush coating or flow coating is suitable, whereas if the surface shape of the molded product is complex, spray coating or molded product is more suitable. Spin coating is suitable for flat and symmetrical molded products, and dip coating is suitable for molded products that are rod-like or sheet-like. The amount of the coating composition to be applied to the surface of the synthetic resin molded article varies depending on the intended use of the obtained molded article or the content of monomers in the coating composition.
It is desirable that the coating be applied so that the thickness of the crosslinked cured film formed on the surface of the synthetic resin molded product is in the range of 1 to 30 μm. If the film thickness is less than 1μ, the wear resistance will be poor, and if it exceeds 30μ, the flexibility of the film will be impaired and cracks will easily occur in the film, which will reduce the strength of the molded product itself. This is not preferable as it may cause a decrease in As mentioned above, there are various methods for applying the coating composition, but among these methods, the dip coating method in particular has some limitations depending on the shape of the synthetic resin molded product, but the coating process is In addition to being simple and having excellent productivity, it also has the advantage that the thickness of the crosslinked cured film can be changed relatively freely. On the other hand, in order to make dip coating possible and to take advantage of its advantages, the following various conditions are required for the paint used. In other words, the following conditions are satisfied: the viscosity of the paint can be controlled relatively freely, it has excellent coating film formation properties through dip coating, the viscosity of the paint does not change over time, and it has excellent storage stability. It must be. The coating composition used in the present invention, especially the coating composition mixed with an organic solvent, satisfies these requirements,
and wear resistance, surface smoothness, flexibility, and durability.
It is a paint that has excellent adaptability to dip coating methods and can form a transparent crosslinked cured film with excellent water resistance, solvent resistance, and adhesion to substrates. Furthermore, depending on the use of synthetic resin molded products with a cross-linked cured film formed on the surface, extremely excellent surface smoothness may be required, or even after the cross-linked cured film has been formed, it may be necessary to It is required to withstand severe conditions such as bending, machining such as cutting and drilling, and the application of large deformation strains during parts installation or use. In such cases, it is naturally necessary that the crosslinked cured film itself has excellent properties such as flexibility and adhesion to the base resin, but the second factor is the problem of the thickness of the cured film. . That is, the thinner the film, the more resistant it is to these external effects, but on the other hand, if it becomes extremely thin, the abrasion resistance decreases, so the thickness of the crosslinked cured film is preferably in the range of 1 to 9 microns. At the technical level of using conventional polyfunctional acrylate or methacrylate monomers or mixtures thereof as cross-linked cured film forming materials, it has excellent abrasion resistance, surface smoothness, film thickness uniformity, transparency, and film appearance. However, it has been impossible to form such a thin crosslinked cured film on the surface of a synthetic resin molded product. However, among the coating compositions mixed with organic solvents used in the present invention, a coating composition prepared such that the viscosity at 25°C is 10 centipoise or less is applied to the surface of a synthetic resin molded article by dip coating. By cross-linking and curing, a thin transparent cross-linked cured film in the range of 1 to 9 μm is formed which has excellent wear resistance, surface smoothness, film thickness uniformity, film appearance, and adhesion to the substrate. became possible.
This is one of the important points of the present invention. Next, the synthetic resin molded product, which is coated using a method suitable for the shape of the synthetic resin molded product or its required performance, is crosslinked and cured by irradiation with active energy rays.
When using a coating composition containing an organic solvent as a coating, it is placed under specific conditions before being irradiated with active energy rays to form a crosslinked cured film.
After evaporating more than 50% by weight of the organic solvent contained in the coating applied to the surface of the synthetic resin molded product,
It is better to irradiate with active energy rays. If the applied film contains 50% by weight or more of an organic solvent and is irradiated with active energy rays, depending on the type of organic solvent, the surface smoothness of the crosslinked cured film formed may be impaired or the film may be damaged. Unfavorable phenomena such as generation of bubbles or residual organic solvent in the crosslinked cured film may occur, such as whitening of the film. In order to form a cross-linked cured film, ultraviolet rays emitted from a light source such as a xenon lamp, low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp or ultra-high pressure mercury lamp, or an electron beam extracted from an electron beam accelerator of usually 20 to 2000 KV, alpha rays, The applied film must be crosslinked and cured by irradiating active energy rays such as β rays and γ rays. From the point of view of practicality or workability, ultraviolet light is the most preferable irradiation source. Although the atmosphere for irradiating active energy rays may be an inert gas atmosphere such as nitrogen gas or carbon dioxide gas or an atmosphere with a reduced oxygen concentration, the coating composition used in the present invention can be irradiated with an ordinary air atmosphere. However, it is possible to form a crosslinked cured film with excellent wear resistance and other properties. The temperature of the irradiation atmosphere may be room temperature, or may be an atmosphere heated to such an extent that no harmful deformation occurs to the base synthetic resin molded article. A synthetic resin molded article having a crosslinked cured coating on its surface produced by the method of the present invention has excellent surface smoothness and aesthetic appearance, and has extremely excellent surface hardness, abrasion resistance, and scratch resistance. Furthermore, the cross-linked cured film formed on the surface is a transparent, flexible, and uniform film that has extremely good adhesion to the base material and does not cause peeling or cracking even under harsh conditions or environments. It is extremely useful for applications such as organic window glass, lighting equipment covers, reflectors, mirrors, eyeglass lenses, sunglass lenses, optical lenses, and watch lenses. 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 a Surface hardness... Pencil hardness according to JISK5651-1966 b Scratch test... Scratch test with #000 steel wool 〇... There is almost no scratch on the surface even if lightly rubbed △... Lightly If rubbed, the surface will be slightly scratched. ×... Even if rubbed lightly, the surface will be severely scratched (same level as the base resin) (2) Adhesion Cross-cut cellotape peel test on cross-linked cured film. That is, make 100 1 mm 2 cuts 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. Repeat this cellotape operation three times at the same location. 〇……No peeling marks of the cross-linked cured film even after repeating 3 times △……Number of peeling marks after repeating 3 times 1 to 50 ×……Number of peeling marks after repeating 3 times 51 to 100
(3) Flexibility (maximum bending angle) A cross-linked cured film is formed on the surface of a sheet-like molded product with a thickness of 2 to 3 mm, and a strip-shaped test piece with a width of 6 mm and a length of 5 cm is cut out from this. Apply force from both ends to give a bending deformation strain, and find the angle from the horizontal plane of the specimen when a crack occurs in the coating. This is the "maximum bending angle", and the larger this angle, the better the flexibility of the coating. (4) Thermal and cycle tests Molded products with a cross-linked cured film formed on the surface were heated at 65°C.
After soaking in warm water for 1 hour, immediately put it in ice water at 0℃.
Soak for 10 minutes, then dry with hot air at 80℃ for 1 hour. After repeating this several times, various tests are performed. Example 1 A disc-shaped methacrylic resin injection molded product with a thickness of 2 mm and a diameter of 4 cm was pasted on a rotating plate in a quartz cylinder equipped with a rotation drive body so that the center of the molded product was centered on the rotating shaft. The temperature inside the cylinder was maintained at 40℃. Approximately 1.0 g of the coating composition shown in Table 1 is poured onto the center of the upper surface of this cylindrical molded product, and the rotating plate is immediately rotated at a speed of 3000 revolutions per minute to form a coating film on the upper surface of the molded product. I let it happen. Next, the rotation speed was reduced to 5 rotations/minute, and the quartz cylinder was rotated slowly from above diagonally outside the quartz cylinder in an air atmosphere.
A 100W high-pressure mercury lamp (manufactured by Ushio Inc.) was irradiated for 10 minutes to form a crosslinked cured film on the upper surface of the molded product. Table 1 shows the evaluation results for the molded products obtained. The coating compositions shown in Table 1 are all 2.0
Contains parts by weight of benzoin isobutyl ether.
【表】【table】
【表】
この結果から明らかな如く、本発明によつて得
られた成形品（実験番号１）は表面平滑性、耐摩
耗性ならびに密着性に優れた架橋硬化被膜を有す
るものであるが、本発明以外の塗料組成物を使用
したものは、密着性が劣つたり（実験番号２）、
耐摩耗性が劣つたり（実験番号３）、あるいは架
橋硬化反応が充分に進まなかつたり（実験番号４
及び５）してバランスのとれた性能を有する成形
品は得られない。
実施例 ２
ジペンタエリスリトールペンタアクリレート90
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10重量部及びペンゾインエチ
ルエーテル２重量部を撹拌混合し、得られた塗料
組成物を厚さ２mmのメタクリル樹脂キヤスト成形
板の片面にバーコーターを用いて架橋硬化被膜の
膜厚が第２表になるように均一に塗布した。これ
に被膜面より約30cmはなれた距離から2kwの高圧
水銀灯を空気雰囲気下で15秒間照射して成形品の
表面に透明な架橋硬化被膜を形成させた。得られ
た結果を第２表に示した。[Table] As is clear from the results, the molded product obtained by the present invention (Experiment No. 1) has a crosslinked cured film with excellent surface smoothness, abrasion resistance, and adhesion. Paints using paint compositions other than those of the invention had poor adhesion (Experiment No. 2);
The abrasion resistance may be poor (Experiment No. 3) or the crosslinking curing reaction may not proceed sufficiently (Experiment No. 4).
and 5) a molded article with balanced performance cannot be obtained. Example 2 Dipentaerythritol pentaacrylate 90
10 parts by weight of 2,2-bis(4-acryloxydiethoxyphenyl)propane and 2 parts by weight of penzoin ethyl ether were stirred and mixed, and the resulting coating composition was applied to a methacrylic resin cast molded plate with a thickness of 2 mm. A cross-linked cured film was uniformly coated on one side of the film using a bar coater so that the film thickness was as shown in Table 2. This was irradiated with a 2 kW high-pressure mercury lamp for 15 seconds in an air atmosphere from a distance of approximately 30 cm from the coating surface to form a transparent crosslinked cured coating on the surface of the molded product. The results obtained are shown in Table 2.
【表】
この結果からわかるように架橋硬化被膜の膜厚
が35μと厚くなるにしたがい、硬化被膜の可撓性
ならびに密着性が悪くなり、また成形品の衝撃強
度も低下することがわかる。なおダインシユタツ
ト衝撃強度は得られた成形品から１cm×２cmの試
験片を切り出し、硬化被膜を有する面から衝撃を
加え、BS―1330に準じて測定した。
実施例 ３
ジペンタエリスリトールペンタアクリレート70
重量部、ペンタエリスリトールトリメタアクリレ
ート５重量部、２，２ビス（４アクリロキシプロ
ポキシフエニル）プロパン25重量部、ベンゾイン
イソブチルエーテル0.5重量部、ベンゾインエチ
ルエーテル0.5重量部及びベンゾフエノン1.0重量
部を60℃の加温下で撹拌混合して得られた塗料組
成物を第３表に示すような各種合成樹脂より得ら
れた厚さ３mmの射出成形板の片面にパーコーター
を用いて、塗布被膜の膜厚が12μになるように塗
布した。これに実施例２で行なつたと全く同じよ
うにして紫外線を照射し、各成形品の表面に架橋
硬化被膜を形成させた。
各成形品は優れた表面光沢を有するものであ
り、耐摩耗性ならびに密着性も良好であつた。評
価した結果を第３表に示す。[Table] As can be seen from this result, as the thickness of the cross-linked cured film increases to 35 μm, the flexibility and adhesion of the cured film deteriorates, and the impact strength of the molded product also decreases. Incidentally, the impact strength was measured in accordance with BS-1330 by cutting out a 1 cm x 2 cm test piece from the obtained molded product and applying an impact from the side having the cured film. Example 3 Dipentaerythritol pentaacrylate 70
parts by weight, 5 parts by weight of pentaerythritol trimethacrylate, 25 parts by weight of 2,2-bis(4-acryloxypropoxyphenyl)propane, 0.5 parts by weight of benzoin isobutyl ether, 0.5 parts by weight of benzoin ethyl ether, and 1.0 parts by weight of benzophenone at 60°C. The coating composition obtained by stirring and mixing under heating of It was applied so that the thickness was 12μ. This was irradiated with ultraviolet rays in exactly the same manner as in Example 2 to form a crosslinked cured film on the surface of each molded product. Each molded article had excellent surface gloss, and had good abrasion resistance and adhesion. The evaluation results are shown in Table 3.
【表】
実施例 ４
ジペンタエリスリトールペンタアクリレート25
重量部、ペンタエリスリトールトリアクリレート
25重量部、２，２ビス（４アクリロキシエトキシ
フエニル）プロパン50重量部及びベンゾインイソ
ブチルエーテル２重量部よりなる塗料組成物を歯
科用メタクリル樹脂で成形されたプラスチツク製
義歯の表面に塗布被膜の厚さが14〜16μになるよ
うに刷毛塗りした。
これを回転駆動体を装備した石英筒内の回転軸
に固定した後、この回転軸を５回転／分の速度で
回転し、筒内に空気を流通させながら、300Wの
遠赤外線を２分間続いて100Wの高圧水銀灯を10
分間石英筒外ななめ上方より照射し、プラスチツ
ク製義歯の表面に架橋硬化被膜を形成させた。得
られた成形品はスチールウール擦傷テストならび
に硬化被膜の密着性も優れたものであつた。
実施例 ５
ジペンタエリスリトールペンタアクリレート
360重量部、22ビス（４アクリロキシジエトキシ
フエニル）プロパン40重量部及びベンゾインエチ
ルエーテル20重量部を60℃の加温下で混合撹拌し
て単量体混合物を得た。この単量体混合物とイソ
プロピルアルコール340重量部、キシレン60重量
部を混合した有機溶剤を第４表に示したような割
合に混合して、均一な塗料組成物を得た。
これらの塗料組成物中に厚さ３mmのメタクリル
樹脂製キヤスト成形板を浸漬した後、0.5cm／秒
の速度でゆつくりと引き上げ成形板の表面に前記
塗料組成物の塗布被膜を形成せしめた。
これを25℃の室温に30分間放置した後、2kwの
高圧水銀灯２本を対向させ空気を流通させた高出
力対向紫外線照射ボツクス内に搬送できる駆動体
にとりつけた。次いでボツクス内での紫外線照射
時間が15秒間となるようにセツトし、駆動体を動
かし照射ボツクス内を通過させて、成形板の表面
に架橋硬化被膜を形成させた。得られた成形品の
性能を評価した結果を第４表に示した。[Table] Example 4 Dipentaerythritol pentaacrylate 25
Parts by weight, pentaerythritol triacrylate
A coating composition consisting of 25 parts by weight, 50 parts by weight of 2,2-bis(4-acryloxyethoxyphenyl)propane, and 2 parts by weight of benzoin isobutyl ether was applied to the surface of a plastic denture made of dental methacrylic resin. It was applied with a brush to a thickness of 14 to 16 μm. After fixing this to a rotating shaft inside a quartz cylinder equipped with a rotary drive body, this rotating shaft was rotated at a speed of 5 revolutions per minute, and while air was circulating inside the cylinder, 300 W of far infrared rays was applied for 2 minutes. 100W high pressure mercury lamp
The quartz cylinder was irradiated from diagonally above the outside to form a cross-linked hardened film on the surface of the plastic denture. The molded product obtained was excellent in the steel wool abrasion test and the adhesion of the cured film. Example 5 Dipentaerythritol pentaacrylate
360 parts by weight of 22bis(4-acryloxydiethoxyphenyl)propane and 20 parts by weight of benzoin ethyl ether were mixed and stirred at 60°C to obtain a monomer mixture. This monomer mixture was mixed with an organic solvent containing 340 parts by weight of isopropyl alcohol and 60 parts by weight of xylene in the proportions shown in Table 4 to obtain a uniform coating composition. A cast molded plate made of methacrylic resin having a thickness of 3 mm was immersed in these coating compositions, and then slowly pulled up at a speed of 0.5 cm/sec to form a coating film of the coating composition on the surface of the molded plate. After leaving it at a room temperature of 25°C for 30 minutes, it was attached to a drive body that could transport it into a high-power opposing ultraviolet irradiation box with two 2 kW high-pressure mercury lamps facing each other and air circulating through it. Next, the ultraviolet irradiation time in the box was set to 15 seconds, and the driver was moved to pass through the irradiation box to form a crosslinked cured film on the surface of the molded plate. Table 4 shows the results of evaluating the performance of the obtained molded products.
【表】
この結果から明らかな如く、浸漬塗布法は塗料
組成物の粘度調整により架橋硬化被膜の膜厚コン
トロールが比較的容易でかつ表面平滑性、均一性
にも優れている。特に塗料組成物の25℃での粘度
が10センチポイズ以下の場合には膜厚も薄くかつ
均一性にも優れる他可撓性にも優れている。
また実施例２の実験番号１と第４表の実験番号
７とを比較から明らかな如く、架橋硬化被膜の構
成成分は全く同じで、膜厚も大体同程度である
が、サーマルサイクル後の密着性に差を生じ、有
機溶剤使用による有利性が認められる。
本発明のものはすぐれた性能を示すが、実施例
５実験番号９の如く架橋硬化被膜の膜厚が極度に
薄い場合は被膜の可撓性、密着性は優れているが
耐摩耗性が低下する。
実施例 ６
ジペンタエリスリトールペンタアクリレート40
重量部、ペンタエリスリトールテトラアクリレー
ト40重量部、ペンタエリスリトールトリアクリレ
ート12重量部、２，２ビス（４アクリロキシプロ
ポキシフエニル）プロパン８重量部、ベンゾイン
エチルエーテル４重量部及び第５表に示したよう
な種類の有機溶剤を300重量部添加混合して、均
一な塗料組成物を得た。これらの組成物中に厚さ
２mmのメタクリル樹脂製キヤスト成形板を浸漬
し、ゆつくりと引き上げて成形板の表面に塗布被
膜を形成させた。これを40℃の温風を流通させた
ボツクス内に10分間放置した後、実施例５に使用
したと同じ高出力対向紫外線照射装置を用いて15
秒間紫外線を照射して成形品の表面に架橋硬化被
膜を形成させた。
得られた成形品の各種性能を測定しその評価し
た結果を第５表に示した。
第５表の結果から明らかな如く、本発明に使用
する以外の有機溶剤を用いた場合には塗布被膜形
成性、硬化被膜の密着性あるいは架橋硬化被膜の
外観が劣つたりする。[Table] As is clear from the results, the dip coating method allows relatively easy control of the thickness of the crosslinked cured film by adjusting the viscosity of the coating composition, and also has excellent surface smoothness and uniformity. In particular, when the viscosity of the coating composition at 25° C. is 10 centipoise or less, the film thickness is thin and has excellent uniformity, as well as excellent flexibility. Furthermore, as is clear from a comparison between Experiment No. 1 of Example 2 and Experiment No. 7 of Table 4, the constituent components of the cross-linked cured film are exactly the same and the film thickness is approximately the same, but the adhesion after thermal cycling is There is a difference in the properties and advantages of using an organic solvent are recognized. The product of the present invention shows excellent performance, but when the thickness of the cross-linked cured film is extremely thin as in Example 5 Experiment No. 9, the film has excellent flexibility and adhesion but deteriorates abrasion resistance. do. Example 6 Dipentaerythritol pentaacrylate 40
parts by weight, 40 parts by weight of pentaerythritol tetraacrylate, 12 parts by weight of pentaerythritol triacrylate, 8 parts by weight of 2,2-bis(4-acryloxypropoxyphenyl)propane, 4 parts by weight of benzoin ethyl ether, and as shown in Table 5. A uniform coating composition was obtained by adding and mixing 300 parts by weight of various types of organic solvents. A cast molded plate made of methacrylic resin having a thickness of 2 mm was immersed in these compositions and slowly pulled up to form a coating film on the surface of the molded plate. After leaving this for 10 minutes in a box that circulated hot air at 40°C, it was heated for 15 minutes using the same high-output opposite ultraviolet irradiation device as used in Example 5.
A crosslinked cured film was formed on the surface of the molded article by irradiating it with ultraviolet rays for seconds. Various performances of the obtained molded product were measured and the evaluation results are shown in Table 5. As is clear from the results in Table 5, when organic solvents other than those used in the present invention are used, the coating film forming properties, the adhesion of the cured film, or the appearance of the crosslinked cured film may be deteriorated.
【表】
＊ 主溶剤であるアルコールの沸点
実施例 ７
ジペンタエリスリトールヘキサアクリレート10
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、ペンタエリスリトールテトラメタ
アクリレート10重量部、２，２ビス（４メタクリ
ロキシエトキシフエニル）プロパン10重量部、イ
ソプロピルアルコール40重量部及びトルエン10重
量部を混合して均一な溶液とした。更にこれに光
増感剤としてベンゾインイソブチルエーテル0.4
重量部、ベンゾインエチルエーテル0.4重量部な
らびにベンゾフエノン1.2重量部よりなる増感剤
混合物を溶解させて塗料組成物を得た。これを厚
さ３mm、半径６cm、高さ５cmの円錐状メタクリル
樹脂射出成形品の外面にスプレー塗布し、塗布被
膜の平均膜厚が20μ程度になるような被膜を形成
させた。これを25℃の室温に30分間放置した後、
空気雰囲気下で被覆面から約30cmの距離から2kw
の高圧水銀灯からの光線を20秒間照射して、該成
形品の外面に平均膜厚11μの架橋硬化被膜を形成
させた。
得られた成形品外面の耐摩耗性は鉛筆硬度で
8H、スチールウール擦傷テストでも優れた性能
を有していた。また硬化被膜の密着性もクロスカ
ツトセロテープテストで剥離する個所がなくサー
マルサイクルテスト５回後も変化は認められなか
つた。
実施例 ８
ジペンタエリスリトールペンタアクリレート20
重量部、２，２ビス（４アクリロキシエトキシフ
エニル）プロパン10重量部、２，２ビス〔４―
（２ヒドロキシ―３アクリロキシプロポキシ）フ
エニル〕プロパン10重量部、ｎ―ブチルアルコー
ル55重量部、トルエン15重量部及びベンゾインイ
ソブチルエーテル1.5重量部からなる塗料組成物
に厚さ２mmのポリカーボネート板状成形品を浸漬
して塗布被膜を形成させた。
これを実施例５と全く同様にして高圧水銀灯か
らの光源を照射して成形品の表面に架橋硬化被膜
を形成させた。得られた成形品の表面は平滑性に
極めて優れ、硬化被膜の膜厚は5.0μであつた。表
面の鉛筆硬度は6Hで、被膜の密着性はクロスカ
ツトセロテープテストで剥離生せず、またサーマ
ルサイクルテストを５回くり返した後も耐摩耗性
ならびに被膜の密着性とも変化は認められなかつ
た。
実施例 ９
ペンタエリスリトールテトラアクリレート10重
量部、ペンタエリスリトールトリアクリレート10
重量部、２，２ビス（４アクリロキシエトキシフ
エニル）プロパン４重量部、２，２ビス（４アク
リロキシフエニル）プロパン１重量部、ｎ―ブチ
ルアルコール55重量部、キシレン15重量部及びベ
ンゾインイソブチルエーテル1.5重量部よりなる
塗料組成物にポリアリルジグリコールカーボネー
ト製レンズ（CR―39製レンズ）を浸漬し、ゆつ
くりと引き上げ該レンズの表面に塗布被膜を形成
させた。
これを40℃の熱風を流通させた石英筒内に入
れ、３分間保持した後、そのままの状態で成形品
表面より20cmの距離から100W高圧水銀灯の光線
を両面より10分間照射した。この際、最初の２分
間は300Wの遠赤外線を石英筒外ななめ上方の両
面から紫外線を同時に照射した。得られた成形品
の表面は平滑性に極めて優れ、硬化被膜の膜厚は
5.2μであつた。また表面の鉛筆硬度は8Hでスチ
ールウール擦傷テストも優れ、硬化膜の密着性も
クロスカツトセロテープテストで剥離する個所が
なかつた。
実施例 10
ジペンタエリスリトールペンタアクリレート５
重量部、ペンタエリスリトールテトラアクリレー
ト10重量部、ペンタエリスリトールトリアクリレ
ート10重量部、２，２ビス（４メタクロキシプロ
ポキシフエニル）プロパン５重量部、ベンゾイン
イソブチルエーテル２重量部及びメタクリル酸メ
チル／イソプロピルアルコール／トルエン＝40／
40／20重量％よりなる混合溶剤70重量部を混合し
て均一な塗料組成物を得た。これに厚さ４mmのメ
タクリル樹脂キヤスト成形板を浸漬し、ゆつくり
と引き上げて成形品の表面に塗布被膜を形成させ
た。
実施例５で行なつたのと全く同様の方法で硬化
処理を行ない、膜厚5.5μの架橋硬化被膜を有する
成形品を得た。
成形品の表面外観は極めて良好で、鉛筆硬度も
8Hを示し、またスチールウール擦傷テスト及び
被膜の密着性とも優れ、サーマルサイクルテスト
５回くり返しても耐摩耗性ならびに被膜密着性の
変化は認められなかつた。
実施例 11
ジペンタエリスリトールペンタアクリレート60
重量部、ペンタエリスリトールテトラアクリレー
ト15重量部、２，２ビス（４アクリロキシエトキ
シフエニル）プロパン10重量部、トルエン10重量
部、エタノール５重量部及びベンゾインイソブチ
ルエーテル２重量部を混合して均一な塗料組成物
を得た。これを実施例１と全く同様にして、厚さ
２mm、直径４cmの円板状メタクリル樹脂射出成形
板に回転塗布した後紫外線を照射して片面に膜厚
13μの架橋硬化被膜を形成させた。
成形品の表面外観は良好で、鉛筆硬度も8Hを
示し、またスチールウール擦傷テスト、被膜の密
着性とも優れ、サーマルサイクルテスト５回後も
耐摩耗性、密着性の変化は認められなかつた。
実施例 12
ジペンタエリスリトールヘキサアクリレート30
重量部、ジペンタエリスリトールペンタアクリレ
ート30重量部、ジペンタエリスリトールテトラア
クリレート30重量部、２，２ビス（４アクリロキ
シペンタエトキシフエニル）プロパン10重量部、
イソプロピルアルコール150重量部、トルエン150
重量部、ベンゾインエチルエーテル２重量部及び
ベンゾフエノン２重量部からなる組成物に、厚さ
２mmのメタクリル樹脂キヤスト成形板を浸漬し、
0.5cm／sec.の速度でゆつくりと引き上げて成形板
の表面に前記組成物の塗布被膜を形成せしめた。
これを５分間放置した後、実施例５で使用した
と同じ照射装置を用いて10秒間紫外線照射して成
形品の表面に膜厚4μの架橋硬化被膜を形成させ
た。得られた成形品の表面は平滑性にすぐれ、鉛
筆硬度も7Hを示し、またステール擦傷テスト及
び被膜の密着性とも優れ、サーマルサイクルテス
ト５回くり返しても耐摩耗性ならびに被膜の密着
性の変化は認められなかつた。[Table] * Boiling point example of main solvent alcohol 7 Dipentaerythritol hexaacrylate 10
parts by weight, 20 parts by weight of dipentaerythritol pentaacrylate, 10 parts by weight of pentaerythritol tetramethacrylate, 10 parts by weight of 2,2-bis(4-methacryloxyethoxyphenyl)propane, 40 parts by weight of isopropyl alcohol, and 10 parts by weight of toluene. to make a homogeneous solution. Furthermore, benzoin isobutyl ether 0.4 is added as a photosensitizer to this.
A coating composition was obtained by dissolving a sensitizer mixture consisting of 0.4 parts by weight of benzoin ethyl ether and 1.2 parts by weight of benzophenone. This was spray coated on the outer surface of a conical methacrylic resin injection molded product with a thickness of 3 mm, a radius of 6 cm, and a height of 5 cm to form a film having an average thickness of about 20 μm. After leaving this at room temperature of 25℃ for 30 minutes,
2kw from a distance of approximately 30cm from the covered surface in an air atmosphere
A cross-linked cured film with an average thickness of 11 μm was formed on the outer surface of the molded product by irradiating it with light from a high-pressure mercury lamp for 20 seconds. The abrasion resistance of the outer surface of the molded product is measured by pencil hardness.
It also had excellent performance in the 8H and steel wool abrasion tests. In addition, the adhesion of the cured film showed no peeling in the cross-cut Sellotape test, and no change was observed even after 5 thermal cycle tests. Example 8 Dipentaerythritol pentaacrylate 20
Parts by weight, 10 parts by weight of 2,2-bis(4-acryloxyethoxyphenyl)propane, 2,2-bis[4-
(2-hydroxy-3-acryloxypropoxy)phenyl] Polycarbonate plate-shaped molded product with a thickness of 2 mm coated with a coating composition consisting of 10 parts by weight of propane, 55 parts by weight of n-butyl alcohol, 15 parts by weight of toluene, and 1.5 parts by weight of benzoin isobutyl ether. was immersed to form a coating film. This was done in exactly the same manner as in Example 5, and a crosslinked cured film was formed on the surface of the molded product by irradiating it with a light source from a high-pressure mercury lamp. The surface of the obtained molded article was extremely smooth, and the thickness of the cured film was 5.0 μm. The pencil hardness of the surface was 6H, and the adhesion of the coating did not peel off in the cross-cut Sellotape test, and no change was observed in the abrasion resistance or adhesion of the coating even after the thermal cycle test was repeated five times. Example 9 10 parts by weight of pentaerythritol tetraacrylate, 10 parts by weight of pentaerythritol triacrylate
Parts by weight, 4 parts by weight of 2,2-bis(4-acryloxyethoxyphenyl)propane, 1 part by weight of 2,2-bis(4-acryloxyphenyl)propane, 55 parts by weight of n-butyl alcohol, 15 parts by weight of xylene, and benzoin. A polyallyl diglycol carbonate lens (CR-39 lens) was immersed in a coating composition containing 1.5 parts by weight of isobutyl ether and slowly pulled up to form a coating film on the surface of the lens. This was placed in a quartz cylinder through which hot air at 40°C was circulated, and after being held for 3 minutes, both sides of the molded product were irradiated with light from a 100W high-pressure mercury lamp for 10 minutes from a distance of 20cm from the surface of the molded product. At this time, for the first two minutes, 300 W of far infrared rays and ultraviolet rays were simultaneously irradiated from both sides of the quartz cylinder diagonally above. The surface of the molded product obtained is extremely smooth, and the thickness of the cured film is
It was 5.2μ. In addition, the pencil hardness of the surface was 8H and the steel wool abrasion test was excellent, and the adhesion of the cured film showed no peeling in the cross-cut Sellotape test. Example 10 Dipentaerythritol pentaacrylate 5
Parts by weight, 10 parts by weight of pentaerythritol tetraacrylate, 10 parts by weight of pentaerythritol triacrylate, 5 parts by weight of 2,2-bis(4-methacroxypropoxyphenyl)propane, 2 parts by weight of benzoin isobutyl ether, and methyl methacrylate/isopropyl alcohol/ Toluene = 40/
A uniform coating composition was obtained by mixing 70 parts by weight of a mixed solvent of 40/20% by weight. A methacrylic resin cast molded plate with a thickness of 4 mm was immersed in this and slowly pulled up to form a coating film on the surface of the molded product. A curing treatment was carried out in exactly the same manner as in Example 5 to obtain a molded article having a crosslinked cured film with a thickness of 5.5 μm. The surface appearance of the molded product is extremely good, and the pencil hardness is also low.
8H, and was also excellent in the steel wool abrasion test and film adhesion, and no change in abrasion resistance or film adhesion was observed even after the thermal cycle test was repeated 5 times. Example 11 Dipentaerythritol pentaacrylate 60
Parts by weight, 15 parts by weight of pentaerythritol tetraacrylate, 10 parts by weight of 2,2-bis(4-acryloxyethoxyphenyl)propane, 10 parts by weight of toluene, 5 parts by weight of ethanol and 2 parts by weight of benzoin isobutyl ether were mixed to form a homogeneous mixture. A coating composition was obtained. In exactly the same manner as in Example 1, this was spin-coated onto a disk-shaped methacrylic resin injection molded plate with a thickness of 2 mm and a diameter of 4 cm, and then ultraviolet rays were irradiated to form a film on one side.
A cross-linked cured film of 13μ was formed. The surface appearance of the molded product was good, the pencil hardness was 8H, and the steel wool abrasion test and film adhesion were excellent, and no change in abrasion resistance or adhesion was observed even after 5 thermal cycle tests. Example 12 Dipentaerythritol hexaacrylate 30
Parts by weight, 30 parts by weight of dipentaerythritol pentaacrylate, 30 parts by weight of dipentaerythritol tetraacrylate, 10 parts by weight of 2,2-bis(4-acryloxypentaethoxyphenyl)propane,
Isopropyl alcohol 150 parts by weight, toluene 150 parts
2 parts by weight of benzoin ethyl ether and 2 parts by weight of benzophenone, a methacrylic resin cast molded plate with a thickness of 2 mm is immersed,
The molded plate was slowly pulled up at a speed of 0.5 cm/sec. to form a coating film of the composition on the surface of the molded plate. After this was left for 5 minutes, ultraviolet rays were irradiated for 10 seconds using the same irradiation device used in Example 5 to form a crosslinked cured film with a thickness of 4 μm on the surface of the molded product. The surface of the molded product obtained was excellent in smoothness, with a pencil hardness of 7H, and was also excellent in the Stale abrasion test and film adhesion.Even after repeated thermal cycle tests 5 times, there were no changes in abrasion resistance and film adhesion. was not recognized.
Claims (1)
ンタエリスリトールトリメタクリレート、ペンタ
エリスリトールテトラアクリレート、ペンタエリ
スリトールテトラメタクリレート、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
トールトリメタクリレート、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
ルテトラメタクリレート、ジペンタエリスリトル
ペンタアクリレート、ジペンタエリスリトールペ
ンタメタクリレート、ジペンタエリスリトールヘ
キサアクリレート及びジペンタエリスリトールヘ
キサメタクリレートよりなる群から選ばれる少な
くとも１種の多官能単量体30〜98重量％と次の一
般式 （式中、R1は水素又はメチル基であり、ｎは
０又は１〜５の整数であり、Ｘは炭素原子数６以
下のアルキレン基又はそのアルキレン基の水素原
子１個が水酸基で置換されたものであり、これら
はｎが２以上の時同じもしくは異なつてもよい。）
で示される２官能単量体70〜２重量％からなる単
量体混合物〔Ａ〕100重量部と、光増感剤０〜10
重量部とよりなり、空気中で活性エネルギー線照
射により耐摩耗性に優れた架橋硬化被膜を形成し
得る塗料組成物を合成樹脂成形品の表面に塗布
し、これに活性エネルギー線を照射することによ
つて膜厚１〜30μの架橋硬化被膜を形成させるこ
とを特徴とする耐摩耗性合成樹脂成形品の製造方
法。 ２ 光増感剤の添加量が0.01〜10重量部であり、
活性エネルギー線が紫外線であることを特徴とす
る特許請求の範囲第１項記載の耐摩耗性合成樹脂
成形品の製造方法。 ３ 合成樹脂成形品がメタクリル樹脂、ポリカー
ボネート樹脂あるいはポリアリルジグリコールカ
ーボネート樹脂成形品であることを特徴とする特
許請求の範囲第１項記載の耐摩耗性合成樹脂成形
品の製造方法。 ４ ペンタエリスリトールトリアクリレート、ペ
ンタエリスリトールトリメタクリレート、ペンタ
エリスリトールテトラアクリレート、ペンタエリ
スリトールテトラメタクリレート、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
トールトリメタクリレート、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
ルテトラメタクリレート、ジペンタエリスリトル
ペンタアクリレート、ジペンタエリスリトールペ
ンタメタクリレート、ジペンタエリスリトールヘ
キサアクリレート及びジペンタエリスリトールヘ
キサメタクリレートよりなる群から選ばれる少な
くとも１種の多官能単量体30〜98重量％と次の一
般式 （式中、R1は水素又はメチル基であり、ｎは
０又は１〜５の整数であり、Ｘは炭素原子数６以
下のアルキレン基又はそのアルキレン基の水素原
子１個が水酸基で置換されたものであり、これら
はｎが２以上の時同じもしくは異なつてもよい。）
で示される２官能単量体70〜２重量％からなる単
量体混合物〔Ａ〕100重量部とこれと混合して均
一な溶液を形成する少なくとも１種の有機溶剤
〔Ｂ〕95〜10重量部と光増感剤（前記単量体混合
物〔Ａ〕と有機溶剤〔Ｂ〕との合計100重量部に
対し）０〜10重量部とよりなり、空気中で活性エ
ネルギー線照射により耐摩耗性に優れた架橋硬化
被膜を形成し得る塗料組成物を合成樹脂成形品の
表面に塗布した後、これに活性エネルギー線を照
射して合成樹脂成形品の表面に膜厚１〜30μの架
橋硬化被膜を形成させることを特徴とする耐摩耗
性合成樹脂成形品の製造方法。 ５ 有機溶剤が常圧での沸点が50℃以上200℃以
下である特許請求の範囲第４項記載の耐摩耗性合
成樹脂成形品の製造方法。 ６ 光増感剤の添加量が0.01〜10重量部であり、
活性エネルギー線が紫外線であることを特徴とす
る特許請求の範囲第４項記載の耐摩耗性合成樹脂
成形品の製造方法。 ７ 塗料組成物を合成樹脂の表面に塗布し、塗布
した被膜中に含まれる有機溶剤の50重量％以上を
揮発逃散させた後活性エネルギー線を照射して合
成樹脂成形品の表面に膜厚１〜30μの架橋被膜を
形成させることを特徴とする特許請求の範囲第４
項記載の耐摩耗性合成樹脂成形品の製造方法。 ８ 塗料組成物が25℃で10センチポイズ以下の粘
度を有するものであり、これを浸漬塗布法によつ
て合成樹脂成形品の表面に塗布し、架橋硬化被膜
の膜厚が１〜9μであることを特徴とする特許請
求の範囲第４又は７項記載の耐摩耗性合成樹脂成
形品の製造方法。 ９ 合成樹脂成形品がメタクリル樹脂、ポリカー
ボネート樹脂あるいはポリアリルジグリコールカ
ーボネート樹脂成形品であることを特徴とする特
許請求の範囲第４，７又は８項記載の耐摩耗性合
成樹脂成形品の製造方法。[Claims] 1. Pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol triacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate , 30 to 98% by weight of at least one polyfunctional monomer selected from the group consisting of dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate, and the following general formula: (In the formula, R 1 is hydrogen or a methyl group, n is 0 or an integer from 1 to 5, and X is an alkylene group having 6 or less carbon atoms, or one hydrogen atom of the alkylene group is substituted with a hydroxyl group. (These may be the same or different when n is 2 or more.)
100 parts by weight of a monomer mixture [A] consisting of 70 to 2% by weight of a bifunctional monomer represented by: and 0 to 10 parts by weight of a photosensitizer.
parts by weight, which can form a crosslinked cured film with excellent wear resistance when irradiated with active energy rays in air, is applied to the surface of a synthetic resin molded product, and then irradiated with active energy rays. 1. A method for producing a wear-resistant synthetic resin molded article, which comprises forming a cross-linked cured film with a thickness of 1 to 30 μm. 2. The amount of photosensitizer added is 0.01 to 10 parts by weight,
2. The method for producing a wear-resistant synthetic resin molded article according to claim 1, wherein the active energy ray is an ultraviolet ray. 3. The method for producing a wear-resistant synthetic resin molded article according to claim 1, wherein the synthetic resin molded article is a methacrylic resin, polycarbonate resin, or polyallyl diglycol carbonate resin molded article. 4 Pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol triacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol penta acrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate in an amount of 30 to 98% by weight of at least one polyfunctional monomer and the following general formula: (In the formula, R 1 is hydrogen or a methyl group, n is 0 or an integer from 1 to 5, and X is an alkylene group having 6 or less carbon atoms, or one hydrogen atom of the alkylene group is substituted with a hydroxyl group. (These may be the same or different when n is 2 or more.)
100 parts by weight of a monomer mixture [A] consisting of 70 to 2% by weight of a bifunctional monomer represented by: and 95 to 10 parts by weight of at least one organic solvent [B] which is mixed with this to form a homogeneous solution. 0 to 10 parts by weight of photosensitizer (total of 100 parts by weight of the monomer mixture [A] and organic solvent [B]), and has wear resistance by irradiation with active energy rays in air. After coating the surface of a synthetic resin molded product with a coating composition capable of forming a crosslinked cured film with excellent properties, active energy rays are irradiated to form a crosslinked cured film with a thickness of 1 to 30 μm on the surface of the synthetic resin molded product. 1. A method for producing a wear-resistant synthetic resin molded product, which comprises forming a wear-resistant synthetic resin molded product. 5. The method for producing a wear-resistant synthetic resin molded article according to claim 4, wherein the organic solvent has a boiling point of 50°C or more and 200°C or less at normal pressure. 6 The amount of photosensitizer added is 0.01 to 10 parts by weight,
5. The method for producing a wear-resistant synthetic resin molded article according to claim 4, wherein the active energy ray is an ultraviolet ray. 7 The coating composition is applied to the surface of the synthetic resin, and after evaporating and evaporating 50% or more of the organic solvent contained in the applied film, active energy rays are irradiated to form a film thickness of 1 on the surface of the synthetic resin molded product. Claim 4, characterized in that a crosslinked film of ~30μ is formed.
A method for manufacturing a wear-resistant synthetic resin molded product as described in . 8. The coating composition has a viscosity of 10 centipoise or less at 25°C, and when applied to the surface of a synthetic resin molded product by dip coating, the thickness of the crosslinked cured film is 1 to 9 μm. A method for manufacturing a wear-resistant synthetic resin molded article according to claim 4 or 7, characterized in that: 9. A method for manufacturing a wear-resistant synthetic resin molded article according to claim 4, 7, or 8, characterized in that the synthetic resin molded article is a methacrylic resin, polycarbonate resin, or polyallyl diglycol carbonate resin molded article. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59248933A JPS60149634A (en) | 1984-11-26 | 1984-11-26 | Production of abrasion-resistant synthetic resin molding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59248933A JPS60149634A (en) | 1984-11-26 | 1984-11-26 | Production of abrasion-resistant synthetic resin molding |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP52019038A Division JPS6052183B2 (en) | 1977-02-23 | 1977-02-23 | paint composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60149634A JPS60149634A (en) | 1985-08-07 |
| JPS6367809B2 true JPS6367809B2 (en) | 1988-12-27 |
Family
ID=17185571
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59248933A Granted JPS60149634A (en) | 1984-11-26 | 1984-11-26 | Production of abrasion-resistant synthetic resin molding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60149634A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63183904A (en) * | 1987-01-27 | 1988-07-29 | Kanebo Ltd | Visible light polymerization-curable composition |
| JP5393939B2 (en) * | 2005-10-14 | 2014-01-22 | 三菱レイヨン株式会社 | Floor coating composition and floor covering coated with the coating |
-
1984
- 1984-11-26 JP JP59248933A patent/JPS60149634A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60149634A (en) | 1985-08-07 |
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