JPH09143396A - Ultraviolet-curable resin composition for coating metallic can - Google Patents
Ultraviolet-curable resin composition for coating metallic canInfo
- Publication number
- JPH09143396A JPH09143396A JP7300845A JP30084595A JPH09143396A JP H09143396 A JPH09143396 A JP H09143396A JP 7300845 A JP7300845 A JP 7300845A JP 30084595 A JP30084595 A JP 30084595A JP H09143396 A JPH09143396 A JP H09143396A
- Authority
- JP
- Japan
- Prior art keywords
- coating
- resin composition
- ultraviolet
- curable resin
- metal
- 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.)
- Pending
Links
- 239000011248 coating agent Substances 0.000 title claims abstract description 62
- 238000000576 coating method Methods 0.000 title claims abstract description 56
- 239000011342 resin composition Substances 0.000 title claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 229920006267 polyester film Polymers 0.000 claims abstract description 11
- 230000009477 glass transition Effects 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims description 40
- 239000002184 metal Substances 0.000 claims description 40
- 229920005989 resin Polymers 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 23
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 21
- 150000002576 ketones Chemical class 0.000 claims description 7
- 239000000049 pigment Substances 0.000 claims description 6
- 239000007870 radical polymerization initiator Substances 0.000 claims description 2
- 239000003999 initiator Substances 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 28
- -1 4-t-butylcyclohexyl Chemical group 0.000 description 8
- 239000003973 paint Substances 0.000 description 8
- 229960000834 vinyl ether Drugs 0.000 description 8
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 238000010526 radical polymerization reaction Methods 0.000 description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000003085 diluting agent Substances 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 238000007865 diluting Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 229920003002 synthetic resin Polymers 0.000 description 5
- 239000000057 synthetic resin Substances 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920000193 polymethacrylate Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 150000003505 terpenes Chemical class 0.000 description 3
- 235000007586 terpenes Nutrition 0.000 description 3
- DNJRKFKAFWSXSE-UHFFFAOYSA-N 1-chloro-2-ethenoxyethane Chemical compound ClCCOC=C DNJRKFKAFWSXSE-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- OIAUFEASXQPCFE-UHFFFAOYSA-N formaldehyde;1,3-xylene Chemical compound O=C.CC1=CC=CC(C)=C1 OIAUFEASXQPCFE-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- 239000005029 tin-free steel Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 description 1
- GJZFGDYLJLCGHT-UHFFFAOYSA-N 1,2-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(CC)C(CC)=CC=C3SC2=C1 GJZFGDYLJLCGHT-UHFFFAOYSA-N 0.000 description 1
- DYUWIMGIHNMKSD-UHFFFAOYSA-N 1-(2-chloroethoxy)-2-ethenoxyethane Chemical compound ClCCOCCOC=C DYUWIMGIHNMKSD-UHFFFAOYSA-N 0.000 description 1
- OSNILPMOSNGHLC-UHFFFAOYSA-N 1-[4-methoxy-3-(piperidin-1-ylmethyl)phenyl]ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1CN1CCCCC1 OSNILPMOSNGHLC-UHFFFAOYSA-N 0.000 description 1
- PNEWSCXZLUPKET-UHFFFAOYSA-N 1-chloro-4-ethenoxybutane Chemical compound ClCCCCOC=C PNEWSCXZLUPKET-UHFFFAOYSA-N 0.000 description 1
- CZAVRNDQSIORTH-UHFFFAOYSA-N 1-ethenoxy-2,2-bis(ethenoxymethyl)butane Chemical compound C=COCC(CC)(COC=C)COC=C CZAVRNDQSIORTH-UHFFFAOYSA-N 0.000 description 1
- SAMJGBVVQUEMGC-UHFFFAOYSA-N 1-ethenoxy-2-(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOC=C SAMJGBVVQUEMGC-UHFFFAOYSA-N 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- WSQJNWOFGXRSML-UHFFFAOYSA-N 2-(3-ethenoxypropyl)oxirane Chemical compound C=COCCCC1CO1 WSQJNWOFGXRSML-UHFFFAOYSA-N 0.000 description 1
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 1
- OUELSYYMNDBLHV-UHFFFAOYSA-N 2-ethenoxyethylbenzene Chemical compound C=COCCC1=CC=CC=C1 OUELSYYMNDBLHV-UHFFFAOYSA-N 0.000 description 1
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- SKKHNUKNMQLBTJ-UHFFFAOYSA-N 3-bicyclo[2.2.1]heptanyl 2-methylprop-2-enoate Chemical compound C1CC2C(OC(=O)C(=C)C)CC1C2 SKKHNUKNMQLBTJ-UHFFFAOYSA-N 0.000 description 1
- OJXVWULQHYTXRF-UHFFFAOYSA-N 3-ethenoxypropan-1-ol Chemical compound OCCCOC=C OJXVWULQHYTXRF-UHFFFAOYSA-N 0.000 description 1
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000001293 FEMA 3089 Substances 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical group OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- MSYLJRIXVZCQHW-UHFFFAOYSA-N formaldehyde;6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound O=C.NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 MSYLJRIXVZCQHW-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、紫外線照射によっ
て硬化する樹脂組成物に関し、特に金属缶及びポリエス
テルフィルム被覆絞り金属缶用の被覆剤として有用な紫
外線硬化型樹脂組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition which is cured by ultraviolet irradiation, and more particularly to an ultraviolet curable resin composition which is useful as a coating agent for metal cans and polyester film-coated drawn metal cans.
【０００２】[0002]
【従来の技術】大気汚染の原因の一つとなる有機溶剤を
含有しない、硬化型樹脂組成物として従来より種々の樹
脂系が検討されている。その一つとして紫外線硬化型樹
脂がある。紫外線硬化型樹脂としては、ラジカル重合型
としてのアクリル系樹脂、不飽和ポリエステル系樹脂、
ポリエン−チオール系樹脂、カチオン重合型としてのエ
ポキシ樹脂、ビニルエーテル樹脂などが知られている。
ビニルエーテル樹脂はラジカル重合型としても知られて
いる。これらの樹脂組成物はコーティング剤、印刷イン
キ、接着剤などに用いられている。2. Description of the Related Art Various resin systems have been studied as a curable resin composition which does not contain an organic solvent which is one of the causes of air pollution. One of them is UV curable resin. As the ultraviolet curable resin, an acrylic resin as a radical polymerization type, an unsaturated polyester resin,
Polyene-thiol resin, cationic polymerization type epoxy resin, vinyl ether resin and the like are known.
Vinyl ether resins are also known as radical polymerization types. These resin compositions are used as coating agents, printing inks, adhesives and the like.
【０００３】アクリル系樹脂を用いたラジカル重合型と
しては例えば、反応性オリゴマーとノルボルニル（メ
タ）アクリレートを主体とした光硬化性樹脂組成物（特
開平７−２９６２号公報）や、反応性希釈モノマーとし
て４−ｔ−ブチルシクロヘキシル（メタ）アクリレート
を用いた光硬化性樹脂組成物（特開平７−１８０３７号
公報）、また、特開平７−１５７６６８号公報には不飽
和基含有化合物とビニルエーテル化合物を用いた放射線
硬化型樹脂組成物が開示されている。The radical polymerization type using an acrylic resin is, for example, a photocurable resin composition mainly composed of a reactive oligomer and norbornyl (meth) acrylate (JP-A-7-2962) and a reactive diluting monomer. As a photocurable resin composition using 4-t-butylcyclohexyl (meth) acrylate as a compound (JP-A-7-18037), JP-A-7-157668 discloses an unsaturated group-containing compound and a vinyl ether compound. The radiation curable resin composition used is disclosed.
【０００４】さらには、ペンタエリスリトール系アクリ
レートと軟化点３０℃以上の非ラジカル重合性樹脂を用
いた活性エネルギー線硬化性樹脂組成物（特開平７−１
１１６６号公報）などが開示されている。Furthermore, an active energy ray-curable resin composition using a pentaerythritol-based acrylate and a non-radical-polymerizable resin having a softening point of 30 ° C. or higher (JP-A-7-1)
1166) and the like are disclosed.
【０００５】アルミニウムやスチール製の金属缶やポリ
エステルフィルム被覆絞り金属缶（ポリエステルフィル
ム被覆絞り金属缶とは、アルミニウムやスチールの金属
板にポリエチレンテレフタレートフィルムを張り合わ
せ、２００ｃｃ〜５００ｃｃの容量の円筒型に絞り加工
したものである）は、被覆剤を塗装した後に、蓋巻き締
め部分へのネックイン加工や、缶胴部分へのダイヤカッ
ト加工（四角錘状の凹凸をいれる）が施されたり、内容
物が充填された後に内容物の殺菌のためのレトルト処理
（１３０℃−３０分の熱水処理）が施される。従って、
係る被覆剤には、それらに対する各種の高度な特性（硬
化塗膜の密着性、加工性、耐レトルト性など）や高速硬
化性が要求される。しかも、金属缶被覆用樹脂組成物は
毎分１００ｍ以上の高速で塗装され、かつ、美麗な塗装
表面が要求される為、金属缶被覆用樹脂組成物には高速
塗装に対応し得るフローやレベリングの良さが求められ
る。しかし、従来のアクリル系樹脂は、フローやレベリ
ング、密着性、加工性、耐レトルト性が不十分であり、
金属缶やポリエステルフィルム被覆絞り金属缶の被覆剤
としては満足できるものではなかった。フローやレベリ
ングを改良するために、非反応性の有機溶剤を添加する
ことも検討されてはいるが、有機溶剤を含有しないこと
を目指している紫外線硬化型樹脂組成物の流れには逆行
するものである。A metal can made of aluminum or steel or a polyester film-coated squeezed metal can (a polyester film-coated squeezed metal can is formed by laminating a polyethylene terephthalate film on a metal plate of aluminum or steel and squeezing it into a cylindrical type having a capacity of 200 cc to 500 cc After being coated with a coating agent, the neck-in processing for the lid winding part and the diamond cutting processing for the body of the can (the square pyramid-shaped irregularities are added) are applied. After being filled, the retort treatment (hot water treatment at 130 ° C. for 30 minutes) for sterilizing the contents is performed. Therefore,
Such coating materials are required to have various high-level properties (adhesion of cured coating film, workability, retort resistance, etc.) and high-speed curing properties. Moreover, since the resin composition for coating a metal can is coated at a high speed of 100 m / min or more and a beautiful coating surface is required, the resin composition for coating a metal can has a flow and leveling capable of supporting high-speed coating. Goodness is required. However, conventional acrylic resins have insufficient flow, leveling, adhesion, processability, and retort resistance,
It was not satisfactory as a coating agent for metal cans and polyester film coated drawn metal cans. In order to improve the flow and leveling, addition of a non-reactive organic solvent has been considered, but it is against the flow of the ultraviolet curable resin composition aiming not to contain the organic solvent. Is.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、金属
缶及びポリエステルフィルム被覆絞り金属缶に対する優
れた密着性、加工性、耐熱性、塗膜硬度を有し、かつ、
非反応性の有機溶剤等を含有することなく、高速塗装可
能な被覆剤として有用な、紫外線硬化型樹脂組成物を提
供することにある。The object of the present invention is to have excellent adhesion to metal cans and polyester film-coated drawn metal cans, workability, heat resistance, and coating hardness, and
An object of the present invention is to provide an ultraviolet-curable resin composition that does not contain a non-reactive organic solvent and is useful as a coating material that can be applied at high speed.
【０００７】[0007]
【課題を解決するための手段】すなわち、第１の発明
は、ラジカル重合性化合物（Ａ）、ガラス転移点が４０
℃以上１５０℃以下の非ラジカル重合性化合物（Ｂ）、
及び光ラジカル重合開始剤（Ｃ）を含有し、２５℃にお
ける粘度が５０〜１０００ｃｐｓであることを特徴とす
る金属缶被覆用紫外線硬化型樹脂組成物であり、第２の
発明は、非ラジカル重合性化合物（Ｂ）の数平均分子量
が５００以上５０００以下であることを特徴とする第１
の発明記載の金属缶被覆用紫外線硬化型樹脂組成物であ
り、さらに第３の発明は非ラジカル重合性化合物（Ｂ）
が、ケトンホルムアルデヒド樹脂であることを特徴とす
る第１の発明ないし第２の発明いずれか記載の金属缶被
覆用紫外線硬化型樹脂組成物である。さらに、第４の発
明は、顔料（Ｄ）を含有することを特徴とする第１の発
明ないし第３の発明いずれか記載の金属缶被覆用紫外線
硬化型樹脂組成物であり、第５の発明は、ポリエステル
フィルム被覆絞り金属缶を被覆することを特徴とする第
１の発明ないし第４の発明いずれか記載の金属缶被覆用
紫外線硬化型樹脂組成物である。That is, the first invention is a radically polymerizable compound (A) having a glass transition point of 40.
A non-radical-polymerizable compound (B) having a temperature of not less than 150 ° C and not more than 150 ° C,
And a photoradical polymerization initiator (C), and a viscosity at 25 ° C. of 50 to 1000 cps, which is an ultraviolet-curable resin composition for coating a metal can. The second invention is a non-radical polymerization. First, the number average molecular weight of the organic compound (B) is 500 or more and 5000 or less.
An ultraviolet-curable resin composition for coating a metal can according to the invention, further comprising a non-radical polymerizable compound (B).
Is a ketone formaldehyde resin, which is the ultraviolet-curable resin composition for coating a metal can according to any one of the first and second inventions. Further, a fourth invention is the ultraviolet-curable resin composition for coating a metal can according to any one of the first invention to the third invention, which contains a pigment (D), and a fifth invention. Is an ultraviolet-curable resin composition for coating a metal can according to any one of the first to fourth inventions, characterized in that it covers a polyester film-covered drawn metal can.
【０００８】[0008]
【発明の実施の形態】本発明において使用するラジカル
重合性化合物（Ａ）は、分子内にラジカル重合性の不飽
和二重結合を有する反応性オリゴマー及び反応性希釈モ
ノマーを表す。反応性オリゴマーの例としては、飽和ま
たは不飽和のポリカルボン酸とアルキルポリオール及び
（メタ）アクリル酸との反応で得られるポリエステル
（メタ）アクリレート、エポキシ樹脂と（メタ）アクリ
ル酸との反応で得られるエポキシポリ（メタ）アクリレ
ート、ポリオールとポリイソシアネートと水酸基含有
（メタ）アクリレートとの反応で得られるウレタンポリ
（メタ）アクリレート、ポリシロキサンと（メタ）アク
リル酸との反応によって得られるポリシロキサンポリ
（メタ）アクリレート、ポリアミドと（メタ）アクリル
酸との反応によって得られるポリアミドポリ（メタ）ア
クリレート等が挙げられる。この中で、金属缶用被覆剤
として特に好ましいオリゴマーは、ポリエステル（メ
タ）アクリレートとエポキシポリ（メタ）アクリレート
である。BEST MODE FOR CARRYING OUT THE INVENTION The radical-polymerizable compound (A) used in the present invention represents a reactive oligomer having a radical-polymerizable unsaturated double bond in the molecule and a reactive diluting monomer. Examples of the reactive oligomer include polyester (meth) acrylate obtained by reaction of saturated or unsaturated polycarboxylic acid with alkyl polyol and (meth) acrylic acid, and reaction of epoxy resin with (meth) acrylic acid. Epoxy poly (meth) acrylate, urethane poly (meth) acrylate obtained by the reaction of polyol, polyisocyanate and hydroxyl group-containing (meth) acrylate, and polysiloxane poly (poly (siloxane) obtained by the reaction of polysiloxane and (meth) acrylic acid. Examples thereof include (meth) acrylates and polyamide poly (meth) acrylates obtained by reacting polyamide with (meth) acrylic acid. Among them, particularly preferable oligomers as a coating agent for metal cans are polyester (meth) acrylate and epoxy poly (meth) acrylate.
【０００９】本発明の反応性希釈モノマーとしては、１
官能、２官能、３官能、４官能以上のものが適宜選択で
き、２５℃での粘度が５００ｃｐｓ以下の液状物質が好
ましい。反応性希釈モノマーのうち、１官能のものとし
ては、メチル（メタ）アクリレート、エチル（メタ）ア
クリレート、プロピル（メタ）アクリレート等のアルキ
ル（メタ）アクリレート、アルキルフェノールのアルキ
レンオキサイド付加物の（メタ）アクリレート、シクロ
ヘキシル（メタ）アクリレート、ベンジル（メタ）アク
リレート等の（メタ）アクリレート系の１官能希釈剤、The reactive diluent monomer of the present invention is 1
A functional substance, a bifunctional, a trifunctional, a tetrafunctional or higher can be appropriately selected, and a liquid substance having a viscosity at 25 ° C. of 500 cps or less is preferable. Among the reactive diluting monomers, monofunctional ones include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate and propyl (meth) acrylate, and (meth) acrylates of alkylene oxide adducts of alkylphenols. (Meth) acrylate-based monofunctional diluents such as, cyclohexyl (meth) acrylate, and benzyl (meth) acrylate,
【００１０】クロルエチルビニルエーテル、クロルブチ
ルビニルエーテル、クロルエトキシエチルビニルエーテ
ル、グリシジルビニルエーテル、グリシジルエチルビニ
ルエーテル、ヒドロキシエチルビニルエーテル、ヒドロ
キシプロピルビニルエーテル、ヒドロキシブチルビニル
エーテル、フェニルエチルビニルエーテル等の１官能ビ
ニルエーテル系希釈剤が挙げられる。Monofunctional vinyl ether type diluents such as chloroethyl vinyl ether, chlorobutyl vinyl ether, chloroethoxyethyl vinyl ether, glycidyl vinyl ether, glycidyl ethyl vinyl ether, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether and phenylethyl vinyl ether can be mentioned.
【００１１】２官能（メタ）アクリレート系希釈剤とし
ては、エチレングリコールジ（メタ）アクリレート、ジ
エチレングリコールジ（メタ）アクリレート、ポリエチ
レングリコールジ（メタ）アクリレート、プロピレング
リコールジ（メタ）アクリレート、ブチレングリコール
ジ（メタ）アクリレート、ビスフェノールＡアルキレン
オキサイドジ（メタ）アクリレート、ビスフェノールＦ
アルキレンオキサイドジ（メタ）アクリレート等が挙げ
られる。As the bifunctional (meth) acrylate diluent, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di ( (Meth) acrylate, bisphenol A alkylene oxide di (meth) acrylate, bisphenol F
Examples thereof include alkylene oxide di (meth) acrylate.
【００１２】２官能ビニルエーテル希釈剤としては、ジ
エチレングリコールジビニルエーテル、トリエチレング
リコールジビニルエーテル、シクロヘキサンジメチロー
ルジビニルエーテル、１，６−ヘキサンジビニルエーテ
ル等が挙げられる。Examples of the bifunctional vinyl ether diluent include diethylene glycol divinyl ether, triethylene glycol divinyl ether, cyclohexane dimethylol divinyl ether and 1,6-hexane divinyl ether.
【００１３】反応性希釈モノマーのうち、（メタ）アク
リレート系３官能のものとしては、トリメチロールエタ
ントリ（メタ）アクリレート、トリメチロールプロパン
トリ（メタ）アクリレート、グリセリントリ（メタ）ア
クリレート等が挙げられ、Among the reactive diluting monomers, (meth) acrylate-based trifunctional ones include trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate and glycerin tri (meth) acrylate. ,
【００１４】（メタ）アクリレート系４官能以上の希釈
モノマーとしては、ジトリメチロールプロパンテトラ
（メタ）アクリレート、ペンタエリスリトールテトラ
（メタ）アクリレート、ペンタエリスリトールアルキレ
ンオキサイドテトラ（メタ）アクリレート、ジペンタエ
リスリトールヘキサ（メタ）アクリレート等が挙げら
れ、Examples of the (meth) acrylate-based tetrafunctional or higher-functional diluent monomer include ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol alkylene oxide tetra (meth) acrylate, and dipentaerythritol hexa (meth). ) Acrylate and the like,
【００１５】３官能以上のビニルエーテル系希釈モノマ
ーとしては、トリメチロールプロパントリビニルエーテ
ル、ポリエステルポリビニルエーテル等を挙げることが
出来る。Examples of trifunctional or higher functional vinyl ether-based diluting monomers include trimethylolpropane trivinyl ether and polyester polyvinyl ether.
【００１６】本発明に用いられる非ラジカル重合性化合
物（Ｂ）とは、ラジカル重合に対して不活性な化合物で
あることを意味する。ラジカル重合に対して不活性であ
るため、ラジカル重合時の硬化歪を抑制・緩和し、塗膜
の密着性を維持・向上できる。これら、非ラジカル重合
性化合物（Ｂ）のガラス転移温度（以下Ｔｇと略す）は
４０℃以上１５０℃以下である。ガラス転移温度が４０
℃以下では塗膜の耐熱性が劣り、塗膜硬度が不十分で金
属缶用としての実用に供さない。ガラス転移温度が１５
０℃以上になると、塗膜が脆弱となり、加工性が劣る。
また、これら非ラジカル重合性化合物（Ｂ）の数平均分
子量（以下、Ｍｎと略す）は５００以上５０００以下で
あることが望ましい。数平均分子量が５００未満では金
属缶及びポリエステルフィルム被覆絞り金属缶に対する
密着性が不十分となり、５０００以上では被覆剤として
の粘度が増大し、塗装が困難となる。The non-radical-polymerizable compound (B) used in the present invention means a compound inactive to radical polymerization. Since it is inactive against radical polymerization, it can suppress or alleviate curing strain during radical polymerization and maintain or improve the adhesion of the coating film. The glass transition temperature (hereinafter abbreviated as Tg) of these non-radical polymerizable compounds (B) is 40 ° C. or higher and 150 ° C. or lower. Glass transition temperature 40
If the temperature is below ℃, the heat resistance of the coating film will be poor, and the hardness of the coating film will be insufficient, and it will not be put to practical use for metal cans. Glass transition temperature is 15
If the temperature is higher than 0 ° C, the coating becomes brittle and the workability is poor.
The number average molecular weight (hereinafter abbreviated as Mn) of these non-radical polymerizable compounds (B) is preferably 500 or more and 5000 or less. If the number average molecular weight is less than 500, the adhesion to the metal can and the polyester film-coated drawn metal can will be insufficient, and if the number average molecular weight is more than 5000, the viscosity as a coating agent will increase and coating will be difficult.
【００１７】本発明に用いられる非ラジカル重合性化合
物（Ｂ）の具体例としては、ケトンホルムアルデヒド樹
脂、キシレンホルムアルデヒド樹脂、エポキシ樹脂、ポ
リエステル樹脂、テルペン系樹脂等があげられる。Specific examples of the non-radical polymerizable compound (B) used in the present invention include ketone formaldehyde resin, xylene formaldehyde resin, epoxy resin, polyester resin and terpene resin.
【００１８】ケトンホルムアルデヒド樹脂は、芳香族及
び／叉は脂肪族ケトンとホルムアルデヒドとの付加縮合
により合成されるものであり、その水素付加体叉は、イ
ソシアネート変性体も用いることが出来る。例えば、ヒ
ュルス社製のＳｙｎｔｈｅｔｉｃ ｒｅｓｉｎ ＡＰ
（Ｔｇ：５１℃、Ｍｎ：７８０）、Ｓｙｎｔｈｅｔｉｃ
ｒｅｓｉｎ ＳＫ（Ｔｇ：８３℃、Ｍｎ：８００）、Ｓ
ｙｎｔｈｅｔｉｃ ｒｅｓｉｎ ＢＬ１２０１（Ｔｇ：
１２４℃、Ｍｎ：１８００）等があげられる。The ketone formaldehyde resin is synthesized by addition condensation of aromatic and / or aliphatic ketone and formaldehyde, and its hydrogenated product or isocyanate modified product can be used. For example, Synthetic resin AP manufactured by Huls
(Tg: 51 ° C., Mn: 780), Synthetic
resin SK (Tg: 83 ° C, Mn: 800), S
synthetic resin BL1201 (Tg:
124 ° C., Mn: 1800) and the like.
【００１９】メタキシレンとホルムアルデヒドの付加縮
合により合成されるキシレンホルムアルデヒド樹脂及び
メシチレン、フェノールなどにより変性されたその誘導
体も好適に用いられ、例えば三菱化成社製のニカノール
レジンＨＰ−１２０（Ｔｇ：７６．８℃、Ｍｎ：１３０
０）、ニカノールレジンＨＰ−１００（Ｔｇ：６７．５
℃、Ｍｎ：１２００）、ニカノールレジンＧＨＰ−１６
０（Ｔｇ：１１４℃、Ｍｎ：１５００）等があげられ
る。A xylene-formaldehyde resin synthesized by addition condensation of meta-xylene and formaldehyde and a derivative thereof modified with mesitylene or phenol are also suitably used. For example, Nikanol Resin HP-120 (Tg: 76. 8 ° C, Mn: 130
0), Nikanol Resin HP-100 (Tg: 67.5)
C, Mn: 1200), Nikanol Resin GHP-16
0 (Tg: 114 ° C., Mn: 1500) and the like.
【００２０】エポキシ樹脂としては、ビスフェノールＡ
及び／叉はビスフェノールＦとエピクロルヒドリンとの
付加重合によって得られるビスフェノール型エポキシ樹
脂が挙げられ、ビスフェノールＡ型樹脂としては油化シ
ェルエポキシ社製のエピコート１００４（Ｔｇ：５３
℃、Ｍｎ：１４００）、エピコート１００７（Ｔｇ：６
９℃、Ｍｎ：２９００）、エピコート１００９（Ｔｇ：
７９℃、Ｍｎ：３８００）、ビスフェノールＦ型として
はエピコート４００４Ｐ（Ｔｇ：４３℃、Ｍｎ：１６３
０）、エピコート４００７Ｐ（Ｔｇ：５９℃、Ｍｎ：３
１６６）、エピコート４００９Ｐ（Ｔｇ：６２℃、Ｍ
ｎ：４１００）、エピコート４０１０Ｐ（Ｔｇ：６３
℃、Ｍｎ：４６４０）等があげられる。As the epoxy resin, bisphenol A
And / or a bisphenol-type epoxy resin obtained by addition polymerization of bisphenol F and epichlorohydrin. Examples of the bisphenol A-type resin include Epicoat 1004 (Tg: 53) manufactured by Yuka Shell Epoxy Co., Ltd.
C, Mn: 1400), Epicoat 1007 (Tg: 6)
9 ° C., Mn: 2900), Epicoat 1009 (Tg:
79 ° C., Mn: 3800), as a bisphenol F type, Epicoat 4004P (Tg: 43 ° C., Mn: 163)
0), Epicoat 4007P (Tg: 59 ° C., Mn: 3)
166), Epicoat 4009P (Tg: 62 ° C., M
n: 4100), Epicoat 4010P (Tg: 63)
C., Mn: 4640) and the like.
【００２１】ポリエステル樹脂としては多塩基酸と多価
アルコールとの縮合反応により得られる、線状飽和ポリ
エステルが好ましい。例えば、東洋紡社製のバイロン２
２０（Ｔｇ：５３℃、Ｍｎ：２０００〜３０００）等が
あげられる。The polyester resin is preferably a linear saturated polyester obtained by a condensation reaction of a polybasic acid and a polyhydric alcohol. For example, Byron 2 made by Toyobo
20 (Tg: 53 ° C., Mn: 2000 to 3000) and the like.
【００２２】テルペン系樹脂は生松脂、クラフトパル
プ、松根チップから得られるテレピン油を原料とする樹
脂の総称であり、例えばヤスハラケミカル社製のＣＬＥ
ＡＲＯＮ Ｐ−１２５（Ｔｇ：６８℃、Ｍｎ：７００）
や、ＹＳ ＲＥＳＩＮ ＴＯ−１２５（Ｔｇ：６４℃、
Ｍｎ：８００）等があげられる。The terpene-based resin is a general term for resins made from turpentine oil obtained from raw pine resin, kraft pulp and pine chips, for example CLE manufactured by Yasuhara Chemical Co.
ARON P-125 (Tg: 68 ° C, Mn: 700)
Or YS RESIN TO-125 (Tg: 64 ° C,
Mn: 800) and the like.
【００２３】その他、Ｔｇ：４０〜１５０℃という条件
を満たすものであれば、メラミンホルムアルデヒド樹
脂、ベンゾグアナミンホルムアルデホド樹脂、フェノー
ルホルムアルデヒド樹脂、エポキシ樹脂、テルペン樹
脂、ロジン系樹脂、アクリル樹脂、ウレタン樹脂等を単
独もしくは適宜組み合わせて用いることが出来る。In addition, melamine formaldehyde resin, benzoguanamine formaldehyde resin, phenol formaldehyde resin, epoxy resin, terpene resin, rosin resin, acrylic resin, urethane resin, etc. can be used as long as the condition of Tg: 40 to 150 ° C. is satisfied. They can be used alone or in combination as appropriate.
【００２４】ラジカル重合性化合物（Ａ）と非ラジカル
重合性化合物（Ｂ）の配合割合は、Ａ／Ｂ＝９５／５〜
４０／６０が好ましく、更に好ましくは、Ａ／Ｂ＝８０
／２０〜６０／４０である。非ラジカル重合性化合物の
量が５部未満になると、密着性、耐熱性が悪くなり、６
０部を越えると硬化性が悪くなる傾向にある。The mixing ratio of the radical-polymerizable compound (A) and the non-radical-polymerizable compound (B) is A / B = 95/5 to
40/60 is preferable, and more preferably A / B = 80
/ 20 to 60/40. If the amount of the non-radical polymerizable compound is less than 5 parts, the adhesiveness and heat resistance will deteriorate, and
If it exceeds 0 parts, the curability tends to deteriorate.
【００２５】本発明に用いる光ラジカル重合開始剤
（Ｃ）は、公知のものから任意に選択し、単独もしくは
適宜組み合わせて使用できる。その具体例としては、ベ
ンゾフェノン、オルソベンゾイル安息香酸メチル、ジエ
チルチオキサントン、イソプロピルチオキサントン等の
水素引き抜き型光重合開始剤、ベンゾインエーテル、ベ
ンジルジメチルケタール、α−ヒドロキシアルキルフェ
ノン、α−アミノアルキルフェノン、アシルフォスフィ
ンオキサイド等の分子内開裂型光重合開始剤が挙げられ
る。The photo-radical polymerization initiator (C) used in the present invention can be arbitrarily selected from known ones and used alone or in appropriate combination. Specific examples thereof include hydrogen abstraction type photopolymerization initiators such as benzophenone, methyl orthobenzoylbenzoate, diethylthioxanthone, and isopropylthioxanthone, benzoin ether, benzyldimethylketal, α-hydroxyalkylphenone, α-aminoalkylphenone, and acylphosphine. Examples thereof include intramolecular cleavage type photopolymerization initiators such as fin oxide.
【００２６】本発明の金属缶被覆用紫外線硬化型樹脂組
成物は、その粘度は５０〜１０００ｃｐｓであることが
重要である。すなわち、粘度が５０ｃｐｓ未満になる
と、高速塗装時に、ミストが発生したり塗料のタレが生
じ、１０００ｃｐｓを越えるとフローやレベリングが悪
く、平滑で美麗な塗装表面にならない。従って、粘度は
５０〜１０００ｃｐｓであることが重要である。It is important that the viscosity of the ultraviolet curable resin composition for coating a metal can of the present invention is 50 to 1000 cps. That is, if the viscosity is less than 50 cps, mist is generated or paint sags during high-speed coating, and if it exceeds 1000 cps, flow and leveling are poor and a smooth and beautiful coated surface cannot be obtained. Therefore, it is important that the viscosity is 50 to 1000 cps.
【００２７】本発明の金属缶被覆用紫外線硬化型樹脂組
成物は、顔料（Ｄ）を配合せずに金属缶やポリエステル
フィルム被覆絞り金属缶の外面のクリヤートップコート
用塗料やサイズコート用塗料として使用したり、さらに
顔料（Ｄ）を配合することによって、ホワイトコート用
塗料として用いることもできる。顔料（Ｄ）としては、
酸化チタン、硫酸バリウム、フタロシアニンブルー、ベ
ンジジンイエロー、ウオッチングレッド、カーボンブラ
ック等が挙げられ、ホワイトコート用塗料として用いる
場合には二酸化チタンが好ましい。も使用できる。The ultraviolet-curable resin composition for coating a metal can of the present invention is used as a clear top coat paint or a size coat paint on the outer surface of a metal can or a polyester film-coated drawn metal can without adding a pigment (D). By using or by blending the pigment (D), it can be used as a white coat paint. As the pigment (D),
Examples thereof include titanium oxide, barium sulfate, phthalocyanine blue, benzidine yellow, watching red, carbon black, etc. When used as a white coat paint, titanium dioxide is preferable. Can also be used.
【００２８】本発明の金属缶被覆用紫外線硬化型樹脂組
成物には、さらに、目的に応じて、増感剤、熱重合触
媒、熱重合禁止剤、界面活性剤、滑り剤、消泡剤等を配
合することができる。The ultraviolet curable resin composition for coating a metal can of the present invention further comprises a sensitizer, a thermal polymerization catalyst, a thermal polymerization inhibitor, a surfactant, a slip agent, an antifoaming agent, etc., depending on the purpose. Can be blended.
【００２９】本発明の金属缶被覆用紫外線硬化型樹脂組
成物は、アルミニウムやスチール製の金属缶及びポリエ
ステルフィルム被覆絞り金属缶の表面に塗装される。塗
装方法としては、ロールコート、グラビアコート、グラ
ビアオフセットコート、カーテンフローコート、リバー
スコート、スクリーン印刷、スプレー塗装及び浸漬法等
で塗装することができる。The ultraviolet-curable resin composition for coating a metal can of the present invention is applied to the surface of a metal can made of aluminum or steel and a polyester film-coated drawn metal can. As a coating method, roll coating, gravure coating, gravure offset coating, curtain flow coating, reverse coating, screen printing, spray coating, dipping and the like can be used.
【００３０】本発明の金属缶被覆用紫外線硬化型樹脂組
成物を光硬化させるための光源としては、通常、２００
〜５００ｎｍの範囲の光を含む光源、例えば高圧水銀
灯、超高圧水銀灯、メタルハライド灯、ガリウム灯、キ
セノン灯、カーボンアーク灯等を使用することができ
る。また、これらの光源と、赤外線、遠赤外線、熱風、
高周波加熱等による熱の併用も可能である。A light source for photocuring the ultraviolet-curable resin composition for coating a metal can of the present invention is usually 200
A light source containing light in the range of up to 500 nm, for example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp or the like can be used. In addition, these light sources, infrared, far infrared, hot air,
It is also possible to use heat by high frequency heating or the like together.
【００３１】[0031]
【実施例】以下に、本発明について、実施例及び比較例
を用いて説明するが、本発明はこれに限定されるもので
はない。なお、実施例中で部及び％とあるのは、重量部
及び重量％をそれぞれ意味する。EXAMPLES The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited thereto. In the examples, parts and% mean parts by weight and% by weight, respectively.
【００３２】[0032]
【実施例１】 ビスフェノールＡ型エポキシアクリレート ６０部 （ダイセル・ユーシービー社製 エベクリルＥＢ６００） ケトンホルムアルデヒド樹脂（Ｔｇ：５１℃、ＭＷ：７８０） ２０部 （ヒュルス社製 Ｓｙｎｔｈｅｔｉｃ ｒｅｓｉｎ ＡＰ） １−ヒドロキシシクロヘキシルフェニルケトン ５部 （チバガイギー社製 イルガキュアー１８４） クロルエチルビニルエーテル ２０部 を混合して撹拌し、塗料１を作成した。この塗料を、厚
さ３００μｍのティンフリースチール板に１００μｍの
ＰＥＴフィルムをラミネートした素材（以下、「ＰＥＴ
／ＴＦＳ」と略す）のＰＥＴフィルム上、及び厚さ３０
０μｍのアルミニュウム板上に、それぞれ膜厚１０μｍ
となるように塗布し、８０Ｗ／ｃｍの高圧水銀灯下を１
０ｍ／ｍｉｎの速度で通過させ、硬化塗膜を得た。Example 1 Bisphenol A type epoxy acrylate 60 parts (Ebecryl EB600 manufactured by Daicel UCB) Ketone formaldehyde resin (Tg: 51 ° C., MW: 780) 20 parts (Synthetic resin AP manufactured by Huls) 1-Hydroxycyclohexylphenyl 5 parts of ketone (Irgacure 184 manufactured by Ciba-Geigy) 20 parts of chloroethyl vinyl ether were mixed and stirred to prepare a paint 1. A material obtained by laminating a 100 μm PET film on a tin-free steel plate with a thickness of 300 μm (hereinafter referred to as “PET
/ TFS ") PET film and thickness 30
A film thickness of 10 μm each on a 0 μm aluminum plate
And apply under high pressure mercury lamp of 80W / cm for 1
It was passed at a speed of 0 m / min to obtain a cured coating film.
【００３３】[0033]
【実施例２】実施例１のケトンホルムアルデヒド樹脂に
Ｔｇ：８３℃、ＭＷ：８００の樹脂（ヒュルス社製 Ｓ
ｙｎｔｈｅｔｉｃ ｒｅｓｉｎ ＳＫ）を用いた以外
は、実施例１と同様の方法で混合し、更に酸化チタン
（石原産業社製タイペークＣＲ−５８）１００部を加え
て顔料分散を行い塗料を作成した。この塗料を用いて実
施例１と同様の方法で硬化塗膜を得た。Example 2 A resin having Tg: 83 ° C. and MW: 800 (S manufactured by Hüls) was added to the ketone formaldehyde resin of Example 1.
The mixture was mixed in the same manner as in Example 1 except that the synthetic resin SK was used, and 100 parts of titanium oxide (Taipaque CR-58 manufactured by Ishihara Sangyo Co., Ltd.) was further added to disperse the pigment to prepare a paint. Using this paint, a cured coating film was obtained in the same manner as in Example 1.
【００３４】実施例３〜４、比較例１〜４ 実施例３〜４及び比較例１〜４は表−１及び表２に示す
配合割合で塗料を作成し、実施例１と同様の方法で塗装
して、硬化塗膜を得た。Examples 3 to 4 and Comparative Examples 1 to 4 In Examples 3 to 4 and Comparative Examples 1 to 4, coating materials were prepared with the compounding ratios shown in Tables 1 and 2, and the same method as in Example 1 was used. The coating was applied to obtain a cured coating film.
【００３５】実施例１〜４及び比較例１〜４で得られた
塗料の粘度、及び硬化塗膜の密着性、加工性、耐熱性、
塗膜硬度を以下に示す方法で評価した。結果を表１〜表
３に示す。The viscosities of the coating materials obtained in Examples 1 to 4 and Comparative Examples 1 to 4 and the adhesion, processability and heat resistance of the cured coating film,
The coating film hardness was evaluated by the method described below. The results are shown in Tables 1 to 3.
【００３６】・粘度：Ｂ型粘度計を用いて２５℃の粘度
を測定した。Viscosity: The viscosity at 25 ° C. was measured using a B type viscometer.
【００３７】・密着性：ＪＩＳ Ｋ５４００に基づいて
セロハンテープ剥離試験を行い、碁盤目１００個当たり
の塗膜が剥離しなかった碁盤目の数を表示した。Adhesion: A cellophane tape peeling test was conducted based on JIS K5400, and the number of crosses where the coating film did not peel off per 100 crosses was displayed.
【００３８】・加工性：デュポン衝撃試験機を用い、１
／２インチロッド、荷重５００ｇ、５０ｃｍの高さで試
験を行い、塗膜の状態を目視評価した。 ◎ 異常なし ○ 試験跡の１／４にクラックが認められる △ 試験跡の１／２にクラックが認められる × 全面にクラックが発生Workability: 1 using a DuPont impact tester
A test was performed with a 1/2 inch rod, a load of 500 g, and a height of 50 cm, and the state of the coating film was visually evaluated. ◎ No abnormality ○ Cracks were found in 1/4 of the test marks △ Cracks were found in 1/2 of the test marks × Cracks were generated on the entire surface
【００３９】・耐熱性：デュポン衝撃試験を行った塗膜
を２００℃で１分間熱処理し、塗膜の剥離程度を目視評
価した。 ◎ 異常なし ○ 試験跡の１／４に塗膜剥離が認められる △ 試験跡の１／２に塗膜剥離が認められる × 全面に塗膜剥離が発生Heat resistance: The coating film subjected to the DuPont impact test was heat-treated at 200 ° C. for 1 minute, and the degree of peeling of the coating film was visually evaluated. ◎ No abnormality ○ Peeling of coating film was observed in 1/4 of the test traces △ Peeling of coating film was observed in 1/2 of the test traces × Peeling of coating film occurred on the entire surface
【００４０】・塗膜硬度：ＪＩＳ Ｋ５４００に基づい
て鉛筆硬度を測定した。Coating hardness: Pencil hardness was measured according to JIS K5400.
【００４１】[0041]
【表１】 [Table 1]
【００４２】[0042]
【表２】 [Table 2]
【００４３】[0043]
【表３】 [Table 3]
【００４４】[0044]
【発明の効果】本発明により、大気汚染の元となる非反
応性の有機溶剤を含有することなく、高速塗装可能で、
さらに、紫外線照射によって硬化し、金属缶やポリエス
テルフィルム被覆絞り金属缶に対する密着性、加工性、
耐熱性、塗膜硬度に優れた金属缶被覆用紫外線硬化型樹
脂組成物が得られた。According to the present invention, high-speed coating is possible without containing a non-reactive organic solvent that causes air pollution,
Further, it is cured by irradiation with ultraviolet rays, and has good adhesion to metal cans and polyester film coated squeezed metal cans, workability,
An ultraviolet curable resin composition for coating a metal can having excellent heat resistance and coating film hardness was obtained.
Claims (5)
移点が４０℃以上１５０℃以下の非ラジカル重合性化合
物（Ｂ）、及び光ラジカル重合開始剤（Ｃ）を含有し、
２５℃における粘度が５０〜１０００ｃｐｓであること
を特徴とする金属缶被覆用紫外線硬化型樹脂組成物。1. A radical-polymerizable compound (A), a non-radical-polymerizable compound (B) having a glass transition point of 40 ° C. or higher and 150 ° C. or lower, and a photo-radical polymerization initiator (C),
An ultraviolet curable resin composition for coating a metal can, which has a viscosity at 25 ° C. of 50 to 1000 cps.
分子量が５００以上５０００以下であることを特徴とす
る請求項１記載の金属缶被覆用紫外線硬化型樹脂組成
物。2. The ultraviolet-curable resin composition for coating metal cans according to claim 1, wherein the number-average molecular weight of the non-radical-polymerizable compound (B) is 500 or more and 5000 or less.
ンホルムアルデヒド樹脂であることを特徴とする請求項
１ないし請求項２いずれか記載の金属缶被覆用紫外線硬
化型樹脂組成物。3. The ultraviolet-curable resin composition for coating a metal can according to claim 1, wherein the non-radical-polymerizable compound (B) is a ketone formaldehyde resin.
請求項１ないし請求項３いずれか記載の金属缶被覆用紫
外線硬化型樹脂組成物。4. The ultraviolet-curable resin composition for coating a metal can according to claim 1, which further comprises a pigment (D).
被覆することを特徴とする請求項１ないし請求項４いず
れか記載の金属缶被覆用紫外線硬化型樹脂組成物。5. The ultraviolet-curable resin composition for coating a metal can according to claim 1, which coats a polyester film-coated drawn metal can.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7300845A JPH09143396A (en) | 1995-11-20 | 1995-11-20 | Ultraviolet-curable resin composition for coating metallic can |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7300845A JPH09143396A (en) | 1995-11-20 | 1995-11-20 | Ultraviolet-curable resin composition for coating metallic can |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09143396A true JPH09143396A (en) | 1997-06-03 |
Family
ID=17889818
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7300845A Pending JPH09143396A (en) | 1995-11-20 | 1995-11-20 | Ultraviolet-curable resin composition for coating metallic can |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09143396A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003024812A1 (en) * | 2001-09-17 | 2003-03-27 | Takeuchi Press Industries Co., Ltd., | Metal container having coating applied to inner surface thereof and method for production thereof |
| DE102007045944A1 (en) | 2007-09-25 | 2009-04-09 | Evonik Degussa Gmbh | Production of urethane acrylates, useful as e.g. main component in radiation-hardenable coating materials, comprises reacting a carbonyl hydrogenated ketone-aldehyde resin with di- or polyisocyanate in presence of tin-free catalyst |
| JP2010536951A (en) * | 2007-08-17 | 2010-12-02 | ピーピージー インダストリーズ オハイオ， インコーポレイテッド | Package with radiation curable coating |
-
1995
- 1995-11-20 JP JP7300845A patent/JPH09143396A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003024812A1 (en) * | 2001-09-17 | 2003-03-27 | Takeuchi Press Industries Co., Ltd., | Metal container having coating applied to inner surface thereof and method for production thereof |
| EP1428762A1 (en) * | 2001-09-17 | 2004-06-16 | Takeuchi Press Industries Co., Ltd. | Metal container having coating applied to inner surface thereof and method for production thereof |
| EP1428762A4 (en) * | 2001-09-17 | 2008-05-07 | Takeuchi Press | Metal container having coating applied to inner surface thereof and method for production thereof |
| US7824750B2 (en) | 2001-09-17 | 2010-11-02 | Takeuchi Press Industries Co., Ltd. | Inside-coated metal container and its manufacturing method |
| JP2010536951A (en) * | 2007-08-17 | 2010-12-02 | ピーピージー インダストリーズ オハイオ， インコーポレイテッド | Package with radiation curable coating |
| DE102007045944A1 (en) | 2007-09-25 | 2009-04-09 | Evonik Degussa Gmbh | Production of urethane acrylates, useful as e.g. main component in radiation-hardenable coating materials, comprises reacting a carbonyl hydrogenated ketone-aldehyde resin with di- or polyisocyanate in presence of tin-free catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3726568B2 (en) | UV curable coating composition and use thereof | |
| JP3609128B2 (en) | Can exterior coating composition | |
| JPH06228251A (en) | Radiation-curable composition and its use | |
| US6069187A (en) | Radiation curable coating compositions | |
| JP2010100736A (en) | Ultraviolet-curable coating composition for can and its use | |
| JPH09506916A (en) | Radiation-curable protective lacquer, especially for metallized surfaces | |
| JPH08231938A (en) | Active energy ray curing type adhesive composition for laminate | |
| JP3273016B2 (en) | Photocurable coating composition for printable basecoat | |
| JPH09302269A (en) | Ultraviolet-curable resin composition and coating agent containing the same | |
| JPH09143396A (en) | Ultraviolet-curable resin composition for coating metallic can | |
| JPH11148037A (en) | Energy light-curable printing ink composition for printing can and coating using the same | |
| EP1232194A1 (en) | Radiation curable hot melt composition and a process for the application thereof | |
| JPH09143393A (en) | Ultraviolet-curable resin composition and coating agent containing the same | |
| JP2000144043A (en) | Ultraviolet curable coating material and its use | |
| JPH09143398A (en) | Ultraviolet-curable resin composition and coating agent containing the same | |
| JPH09143397A (en) | Ultraviolet-curable resin composition and coating agent containing the same | |
| JP2000072832A (en) | Active energy ray-curable type composition, formation of cured film and cured product using the same | |
| JP3475528B2 (en) | UV curable resin composition and coating agent containing the same | |
| JPH10219135A (en) | Solventless curable resin composition and its curing method | |
| JP3863162B2 (en) | Method for producing tubular or cylindrical aluminum laminate and tubular or cylindrical aluminum laminate | |
| JP7427853B1 (en) | Active energy ray-curable adhesive composition, printed matter and laminate using the same | |
| JP4310590B2 (en) | Rosin ester resin and active energy ray-curable resin composition | |
| WO2020226018A1 (en) | Method for manufacturing printed matter | |
| JPH09143395A (en) | Ultraviolet-curable resin composition and coating agent containing the same | |
| JP6160870B2 (en) | Hydroxyl group-containing polymerizable copolymer, method for producing the same, active energy ray-curable resin composition, and cured product |