JP5510643B2 - Water-based coating composition - Google Patents
Water-based coating composition Download PDFInfo
- Publication number
- JP5510643B2 JP5510643B2 JP2010044379A JP2010044379A JP5510643B2 JP 5510643 B2 JP5510643 B2 JP 5510643B2 JP 2010044379 A JP2010044379 A JP 2010044379A JP 2010044379 A JP2010044379 A JP 2010044379A JP 5510643 B2 JP5510643 B2 JP 5510643B2
- Authority
- JP
- Japan
- Prior art keywords
- meth
- acrylate
- parts
- component
- water
- 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.)
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 57
- 239000008199 coating composition Substances 0.000 title description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 109
- 239000000203 mixture Substances 0.000 claims description 82
- 239000011248 coating agent Substances 0.000 claims description 57
- 239000000178 monomer Substances 0.000 claims description 37
- 229920002554 vinyl polymer Polymers 0.000 claims description 18
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 16
- -1 2-ethylhexyl Chemical group 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims description 11
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 8
- 125000000524 functional group Chemical group 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 229920001521 polyalkylene glycol ether Polymers 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 31
- 239000000047 product Substances 0.000 description 26
- 239000011347 resin Substances 0.000 description 25
- 229920005989 resin Polymers 0.000 description 25
- 239000000463 material Substances 0.000 description 24
- 238000006116 polymerization reaction Methods 0.000 description 24
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 18
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 13
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 12
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 12
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 11
- 239000003112 inhibitor Substances 0.000 description 11
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 8
- 239000007809 chemical reaction catalyst Substances 0.000 description 8
- 229950000688 phenothiazine Drugs 0.000 description 8
- 229920001223 polyethylene glycol Polymers 0.000 description 8
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 7
- 230000002209 hydrophobic effect Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- 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 6
- 238000012360 testing method Methods 0.000 description 6
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 5
- 238000004945 emulsification Methods 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 229920000515 polycarbonate Polymers 0.000 description 5
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- CMVNWVONJDMTSH-UHFFFAOYSA-N 7-bromo-2-methyl-1h-quinazolin-4-one Chemical compound C1=CC(Br)=CC2=NC(C)=NC(O)=C21 CMVNWVONJDMTSH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZNAOFAIBVOMLPV-UHFFFAOYSA-N hexadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C(C)=C ZNAOFAIBVOMLPV-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- DWLAGFAYZCBIMG-UHFFFAOYSA-N 1-(3-hydroxyphenyl)-2-methylpropan-1-one Chemical compound CC(C)C(=O)C1=CC=CC(O)=C1 DWLAGFAYZCBIMG-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- AUFZRCJENRSRLY-UHFFFAOYSA-N 2,3,5-trimethylhydroquinone Chemical compound CC1=CC(O)=C(C)C(C)=C1O AUFZRCJENRSRLY-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-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
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- PGDIJTMOHORACQ-UHFFFAOYSA-N 9-prop-2-enoyloxynonyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCCCCOC(=O)C=C PGDIJTMOHORACQ-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- XVZXOLOFWKSDSR-UHFFFAOYSA-N Cc1cc(C)c([C]=O)c(C)c1 Chemical group Cc1cc(C)c([C]=O)c(C)c1 XVZXOLOFWKSDSR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- HZHWZZXJPIFIPG-UHFFFAOYSA-N benzene;butyl acetate Chemical compound C1=CC=CC=C1.CCCCOC(C)=O HZHWZZXJPIFIPG-UHFFFAOYSA-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
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- XNNQFQFUQLJSQT-UHFFFAOYSA-N bromo(trichloro)methane Chemical compound ClC(Cl)(Cl)Br XNNQFQFUQLJSQT-UHFFFAOYSA-N 0.000 description 1
- KQBTUOVABZLXGP-UHFFFAOYSA-N butane-1,4-diol;ethane-1,2-diol Chemical compound OCCO.OCCCCO KQBTUOVABZLXGP-UHFFFAOYSA-N 0.000 description 1
- DDPAAMHROJBRGE-UHFFFAOYSA-N butane-1,4-diol;propane-1,2-diol Chemical compound CC(O)CO.OCCCCO DDPAAMHROJBRGE-UHFFFAOYSA-N 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- BMFYCFSWWDXEPB-UHFFFAOYSA-N cyclohexyl(phenyl)methanone Chemical compound C=1C=CC=CC=1C(=O)C1CCCCC1 BMFYCFSWWDXEPB-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 150000002027 dodecanoic acid esters Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001227 electron beam curing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- ZIFBQDDDTRMSDJ-UHFFFAOYSA-N furan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CO1 ZIFBQDDDTRMSDJ-UHFFFAOYSA-N 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- IIRDTKBZINWQAW-UHFFFAOYSA-N hexaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCO IIRDTKBZINWQAW-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- DAHPIMYBWVSMKQ-UHFFFAOYSA-N n-hydroxy-n-phenylnitrous amide Chemical compound O=NN(O)C1=CC=CC=C1 DAHPIMYBWVSMKQ-UHFFFAOYSA-N 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
本発明は、各種プラスチック用の水系コーティング剤組成物に関する。 The present invention relates to an aqueous coating agent composition for various plastics.
近年、省エネルギー・環境への負荷低減の観点から各種プラスチック用コーティング剤の水系化が求められるようになってきている。コーティング剤を水系化する方法としては、コーティング剤の主成分である活性エネルギー線硬化型樹脂を水可溶化させる方法、乳化分散させる方法が考えられる。しかし、活性エネルギー線硬化型樹脂を水可溶化する場合には、水に溶解する性能を該樹脂に付与するために該樹脂構造が限定されてしまい、各種用途に広範囲に適用できないという不利があった。 In recent years, water-based coating agents for various plastics have been demanded from the viewpoint of energy saving and environmental load reduction. As a method of making the coating agent water-based, a method of solubilizing an active energy ray-curable resin, which is a main component of the coating agent, or a method of emulsifying and dispersing it is considered. However, when the active energy ray-curable resin is water-solubilized, the resin structure is limited to give the resin the ability to dissolve in water, and there is a disadvantage that it cannot be widely applied to various applications. It was.
一方、乳化分散する方法としては、活性エネルギー線硬化型樹脂に乳化性を付与する方法と、乳化剤を使用して活性エネルギー線硬化型樹脂を乳化する方法とがある。 On the other hand, the emulsifying and dispersing method includes a method of imparting emulsifiability to the active energy ray-curable resin and a method of emulsifying the active energy ray-curable resin using an emulsifier.
しかし、前者の方法では、樹脂中に親水性の官能基を多く導入しなければならないなど分子設計の自由度が制限され、希釈剤として水に不溶な疎水性モノマーを用いる場合には、乳化が困難となり、樹脂組成物としての安定性が低いという問題があった。また、後者の方法では、乳化剤を使用することによる硬化物の性能（密着性・硬度・耐擦傷性の低下、発泡など。）が低下してしまう場合があった。 However, in the former method, the degree of freedom in molecular design is limited, for example, a large number of hydrophilic functional groups must be introduced into the resin, and emulsification occurs when a water-insoluble hydrophobic monomer is used as a diluent. There was a problem that it became difficult and the stability as a resin composition was low. In the latter method, the performance of the cured product (decrease in adhesion, hardness, scratch resistance, foaming, etc.) due to the use of an emulsifier may be deteriorated.
なお、本出願人は、先に特定の（メタ）アクリル当量、水酸基価、重量平均分子量を有するポリマーと多官能イソシアネートを含有する活性エネルギー線硬化性樹脂組成物の熱架橋反応生成物からなる表面保護シートを提案している（特許文献１参照。）。しかし、このものの水系化に関しては何ら開示されていなかった。
本発明は、水に可溶または水に分散させることができ、硬度や耐擦傷性に優れた硬化膜を提供することができ、また、水に不溶な疎水性モノマーを併用する場合に、容易に疎水性モノマーを乳化により安定化でき、アクリロニトリル−ブタジエン−スチレン（ＡＢＳ）樹脂等のプラスチックに優れた密着性を発揮する水系コーティング剤組成物を提供することを目的とする。 INDUSTRIAL APPLICABILITY The present invention can provide a cured film that is soluble in water or can be dispersed in water, has excellent hardness and scratch resistance, and can be easily used in combination with a hydrophobic monomer that is insoluble in water. Another object of the present invention is to provide a water-based coating agent composition that can stabilize a hydrophobic monomer by emulsification and exhibits excellent adhesion to plastics such as acrylonitrile-butadiene-styrene (ABS) resin.
本発明者は、前記課題を解決すべく鋭意検討したところ、特定の構造を導入した反応物を用いることにより、前記課題を解決することができることを見出し、本発明を完成させた。 The present inventor has intensively studied to solve the above problems, and has found that the above problems can be solved by using a reactant into which a specific structure is introduced, and has completed the present invention.
すなわち、本発明１は、エポキシ基を有するラジカル重合性ビニル単量体（ａ１）、分子中にポリアルキレングリコールエーテル構造を有するラジカル重合性ビニル単量体（ａ２）、及び、炭素数２〜３０のアルキル（メタ）アクリレートを含有する単量体成分（ａ３）を重合することにより得られた重合体（Ａ）にカルボキシル基を有するラジカル重合性ビニル単量体（ｂ）を反応させて得られる反応物（Ｂ）、並びに、ペンタエリスリトールトリ（メタ）アクリレート（Ｃ）を含有する水系コーティング剤組成物である。 That is, the present invention 1 includes a radical polymerizable vinyl monomer (a1) having an epoxy group, a radical polymerizable vinyl monomer (a2) having a polyalkylene glycol ether structure in the molecule, and 2 to 30 carbon atoms. It is obtained by reacting a polymer (A) obtained by polymerizing a monomer component (a3) containing an alkyl (meth) acrylate with a radical polymerizable vinyl monomer (b) having a carboxyl group. It is a water-based coating agent composition containing the reactant (B) and pentaerythritol tri (meth) acrylate (C).
本発明２は、本発明１において、更に、１分子中の（メタ）アクリル基の数平均が１〜４であって、活性水素含有官能基を有しない炭化水素系（メタ）アクリレート、エーテル系（メタ）アクリレート、及び、エステル系（メタ）アクリレートから選ばれた１種以上の（メタ）アクリレート（Ｄ）を含む請求項１記載の水系コーティング剤組成物である。 The present invention 2 is the same as the present invention 1, wherein the number average of (meth) acrylic groups in one molecule is 1 to 4, and the hydrocarbon-based (meth) acrylate or ether-based compound having no active hydrogen-containing functional group The aqueous coating agent composition according to claim 1, comprising at least one (meth) acrylate (D) selected from (meth) acrylate and ester-based (meth) acrylate.
本発明３は、本発明１又は２において、炭素数２〜３０のアルキル（メタ）アクリレートを含有する単量体成分（ａ３）が、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート（ＬＭＡ）、セチル（メタ）アクリレート（ＣＭＡ）、ステアリル（メタ）アクリレート（ＳＭＡ）、ベヘニル（メタ）アクリレート（ＶＭＡ）から選ばれる少なくとも１種のアルキル（メタ）アクリレート及び/又はビニル化合物を含有する単量体成分である水系コーティング剤組成物。 Invention 3 is the invention 1 or 2, wherein the monomer component (a3) containing an alkyl (meth) acrylate having 2 to 30 carbon atoms is ethyl (meth) acrylate, butyl (meth) acrylate, or 2-ethylhexyl. At least selected from (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate (LMA), cetyl (meth) acrylate (CMA), stearyl (meth) acrylate (SMA), and behenyl (meth) acrylate (VMA) An aqueous coating composition which is a monomer component containing one kind of alkyl (meth) acrylate and / or vinyl compound.
本発明４は、本発明１〜３において、炭素数２〜３０のアルキル（メタ）アクリレートを含有する単量体成分（ａ３）の使用量（重量比）が、重合体（Ａ）を１００重量％とした場合に、１〜３０重量％である水系コーティング剤組成物である。 Invention 4 is the invention 1 to 3, wherein the amount (weight ratio) of the monomer component (a3) containing an alkyl (meth) acrylate having 2 to 30 carbon atoms is 100% by weight of the polymer (A). %, It is an aqueous coating agent composition that is 1 to 30% by weight.
本発明５は、本発明１〜４において、ポリアルキレングリコールエーテル構造が、一般式（１）：−（Ｘ−Ｏ）ｎ−（式中、Ｘは分岐構造を有していてもよい炭素数２〜４のアルキレン基であって、それぞれが異なっていてもよく、ｎは９〜９０の整数を表す。）で表される水系コーティング剤組成物である。 The present invention 5 is the present invention 1 to 4, wherein the polyalkylene glycol ether structure is represented by the general formula (1):-(XO) n- (wherein X may have a branched structure). 2 to 4 alkylene groups, each of which may be different, and n represents an integer of 9 to 90).
本発明によれば、水に可溶または水に安定に分散させることができ、硬度、耐擦傷性に優れた硬化膜を提供することができ、また、水に不溶な疎水性モノマーを併用する場合に、容易に疎水性モノマーを乳化により安定化でき、各種プラスチックに優れた密着性を発揮する水系コーティング剤組成物を提供することができる。本発明の水系コーティング剤組成物の硬化物は特にＡＢＳ樹脂に対する密着性、硬度、耐擦傷性に優れるため、特にハードコーティング剤として好適である。 According to the present invention, it is possible to provide a cured film that is soluble in water or can be stably dispersed in water, has excellent hardness and scratch resistance, and uses a hydrophobic monomer that is insoluble in water. In this case, it is possible to provide a water-based coating agent composition that can easily stabilize a hydrophobic monomer by emulsification and exhibits excellent adhesion to various plastics. The cured product of the aqueous coating agent composition of the present invention is particularly suitable as a hard coating agent because it is excellent in adhesion, hardness and scratch resistance to ABS resin.
本発明の水系コーティング剤組成物は、エポキシ基を有するラジカル重合性ビニル単量体（ａ１）（以下、（ａ１）成分という）、分子中にポリアルキレングリコールエーテル構造を有するラジカル重合性ビニル単量体（ａ２）（以下、（ａ２）成分という）、及び、炭素数２〜３０のアルキル（メタ）アクリレートを含有する単量体成分（ａ３）（以下、（ａ３）成分という）を重合することにより得られた重合体（Ａ）（以下、（Ａ）成分という）に、カルボキシル基を有するラジカル重合性ビニル単量体（ｂ）を反応させて得られる反応物（Ｂ）（以下、（Ｂ）成分という）、並びに、ペンタエリスリトールトリ（メタ）アクリレート（Ｃ）（以下、（Ｃ）成分という）を含有することを特徴とする。なお、本発明の水系コーティング剤組成物は、少なくとも上記（Ｂ）成分及び（Ｃ）成分を含むものであるが、（Ｂ）成分及び（Ｃ）成分が水に溶解したものであってもよく、（Ｂ）成分及び（Ｃ）成分が水に分散したものであってもよい。また、非ラジカル重合性有機溶媒を含有するものであってもよい。この場合には、非ラジカル重合性有機溶媒の使用量を、水よりも少なくする必要がある。 The aqueous coating agent composition of the present invention comprises a radical polymerizable vinyl monomer (a1) having an epoxy group (hereinafter referred to as component (a1)) and a radical polymerizable vinyl monomer having a polyalkylene glycol ether structure in the molecule. Polymerizing the body (a2) (hereinafter referred to as component (a2)) and the monomer component (a3) (hereinafter referred to as component (a3)) containing an alkyl (meth) acrylate having 2 to 30 carbon atoms A reaction product (B) (hereinafter referred to as (B) obtained by reacting the radically polymerizable vinyl monomer (b) having a carboxyl group with the polymer (A) (hereinafter referred to as component (A)) obtained by ) Component) and pentaerythritol tri (meth) acrylate (C) (hereinafter referred to as component (C)). In addition, although the water-based coating agent composition of this invention contains the said (B) component and (C) component at least, (B) component and (C) component may melt | dissolve in water, ( The component (B) and the component (C) may be dispersed in water. Further, it may contain a non-radically polymerizable organic solvent. In this case, it is necessary to use less non-radically polymerizable organic solvent than water.
本発明に用いられる（Ａ）成分は、（ａ１）成分、（ａ２）成分及び（ａ３）成分を含むものである。
上記（ａ１）成分は、ラジカル重合性ビニル単量体であってエポキシ基及びビニル基をそれぞれ１つ有するものであれば特に限定されず、公知のものを用いることができる。（ａ１）成分としては、例えば、グリシジル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレートグリシジルエーテル、などが挙げられる。これらは１種を単独で用いてもよく、２種以上を混合して用いてもよい。（ａ１）成分としては、得られる硬化膜のハードコート性の点からグリシジル（メタ）アクリレートが好ましい。
The component (A) used in the present invention includes the component (a1), the component (a2), and the component (a3).
The component (a1) is not particularly limited as long as it is a radical polymerizable vinyl monomer and has one epoxy group and one vinyl group, and a known one can be used. Examples of the component (a1) include glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether. These may be used alone or in combination of two or more. As the component (a1), glycidyl (meth) acrylate is preferable from the viewpoint of hard coat properties of the obtained cured film.
上記（ａ２）成分は、（ａ１）成分以外のビニル基を１つ有するラジカル重合性ビニル単量体であって分子中にポリアルキレングリコールエーテル構造を有するものであれば特に限定されず、公知のものを用いることができる。なお、ポリアルキレングリコール構造とは、一般式（１）：−（Ｘ−Ｏ）ｎ−で表される構造である。なお、一般式（１）中、Ｘは分岐構造を有していてもよいアルキレン基を表す。Ｘとしては、炭素数２〜４のアルキレン基が好ましく、特に、エチレン基が好ましい。また、ｎは、９〜９０の整数を表す。乳化安定性の観点から（ａ２）成分に含まれるｎの平均数は、２０〜９０とすることが好ましい。（ａ２）成分としては、例えば、ポリエチレングリコールモノ（メタ）アクリレート（繰り返し単位数が９〜９０のもの）、ポリプロピレングリコールモノ（メタ）アクリレート（繰り返し単位数が９〜９０のもの）、ポリエチレングリコール−ポリプロピレングリコールモノ（メタ）アクリレート（各繰り返し単位数の和が９〜９０のもの）、ポリ（エチレングリコール−テトラメチレングリコール）モノ（メタ）アクリレート（各繰り返し単位数の和が９〜９０のもの）、ポリ（プロピレングリコールーテトラメチレングリコール）モノ（メタ）アクリレート（各繰り返し単位数の和が９〜９０のもの）、メトキシポリエチレングリコールモノ（メタ）アクリレート（繰り返し単位数が９〜９０のもの）、オクトキシポリエチレングリコール−ポリプロピレングリコールモノ（メタ）アクリレート（各繰り返し単位数の和が９〜９０のもの）、ラウロキシポリエチレングリコールモノ（メタ）アクリレート（繰り返し単位が９〜９０のもの）、ステアロキシポリエチレングリコールモノ（メタ）アクリレート（繰り返し単位が９〜９０のもの）、ノニルフェノキシポリエチレングリコールモノ（メタ）アクリレート（繰り返し単位数が９〜９０のもの）、ノニルフェノキシポリプロピレングリコールポリエチレングリコールモノ（メタ）アクリレート（各繰り返し単位数の和が９〜９０のもの）などが挙げられる。なお、（ａ２）成分としては、市販のものをそのまま用いても良い。市販品としては、例えば、日油（株）製ブレンマーシリーズ、などが挙げられる。これらのなかでは、メトキシポリエチレングリコールモノメタクリレート、例えば、日油（株）製ブレンマーＰＭＥシリーズが、得られる硬化物のハードコート性、及び、水分散安定性の点で好ましい。（ａ２）成分は、上記のうち１種又は２種以上を混合して用いることができる。 The component (a2) is not particularly limited as long as it is a radical polymerizable vinyl monomer having one vinyl group other than the component (a1) and has a polyalkylene glycol ether structure in the molecule. Things can be used. The polyalkylene glycol structure is a structure represented by the general formula (1): — (X—O) n —. In general formula (1), X represents an alkylene group which may have a branched structure. X is preferably an alkylene group having 2 to 4 carbon atoms, and particularly preferably an ethylene group. N represents an integer of 9 to 90. From the viewpoint of emulsion stability, the average number of n contained in the component (a2) is preferably 20 to 90. Examples of the component (a2) include polyethylene glycol mono (meth) acrylate (having 9 to 90 repeating units), polypropylene glycol mono (meth) acrylate (having 9 to 90 repeating units), polyethylene glycol- Polypropylene glycol mono (meth) acrylate (with 9 to 90 sum of each repeating unit), poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate (with 9 to 90 sum of each repeating unit) , Poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate (the sum of the number of each repeating unit is 9 to 90), methoxypolyethylene glycol mono (meth) acrylate (the number of the repeating unit is 9 to 90), Octoxy polyethylene glycol Ru-polypropylene glycol mono (meth) acrylate (having a total number of repeating units of 9 to 90), lauroxy polyethylene glycol mono (meth) acrylate (having 9 to 90 repeating units), stearoxy polyethylene glycol mono ( (Meth) acrylate (having 9 to 90 repeating units), nonylphenoxypolyethylene glycol mono (meth) acrylate (having 9 to 90 repeating units), nonylphenoxypolypropylene glycol polyethylene glycol mono (meth) acrylate (repeating each repeating unit) The sum of the numbers is 9 to 90). In addition, as (a2) component, you may use a commercially available thing as it is. As a commercial item, NOF Corporation Blemmer series etc. are mentioned, for example. Among these, methoxypolyethylene glycol monomethacrylate, such as Bremer PME series manufactured by NOF Corporation, is preferable in terms of hard coat properties and water dispersion stability of the obtained cured product. (A2) A component can be used 1 type or in mixture of 2 or more types among the above.
上記（ａ３）成分は、例えば、炭素数２〜３０のアルキル基を有するアルコールと（メタ）アクリル酸から得られる（メタ）アクリレート、炭素数が２〜３０のビニル化合物を含有する単量体成分であれば特に限定されず、公知のものを用いることができる。炭素数２〜３０のアルキル（メタ）アクリレートとしては、例えば、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート（ＬＭＡ）、セチル（メタ）アクリレート（ＣＭＡ）、ステアリル（メタ）アクリレート（ＳＭＡ）、ベヘニル（メタ）アクリレート（ＶＭＡ）等のアルキル（メタ）アクリレート類が挙げられる。特に、疎水性モノマーを併用する場合に、容易に疎水性モノマーを乳化し、安定化させるためには、炭素数１２〜２２のアルキル（メタ）アクリレートを用いることが好ましい。炭素数１８のステアリル（メタ）アクリレートがより好ましい。上記ビニル化合物は、ビニル基を有する化合物であれば特に限定されず、例えば、スチレン、α−メチルスチレン、ビニルトルエン等の芳香族系ビニル化合物；酢酸ビニル、プロピオン酸ビニル等が挙げられる。（ａ３）成分として炭素数１２〜２２のアルキル（メタ）アクリレート及び/又はビニル化合物を含有する単量体成分を用い、（ａ１）成分と（ａ２）成分をともに重合することにより得られた重合体（Ａ）にカルボキシル基を有するラジカル重合性ビニル単量体（ｂ）を反応させて得られる反応物（Ｂ）、並びに、ペンタエリスリトールトリ（メタ）アクリレート（Ｃ）を水に溶解させ、又は、水に分散させて得られる水系コーティング剤組成物は、塗料の水系化が可能となるだけでなく、基材との密着性等の物性改良を行うことが可能となる。 The component (a3) is, for example, a monomer component containing (meth) acrylate obtained from an alcohol having an alkyl group having 2 to 30 carbon atoms and (meth) acrylic acid, and a vinyl compound having 2 to 30 carbon atoms. If it is, it will not specifically limit, A well-known thing can be used. Examples of the alkyl (meth) acrylate having 2 to 30 carbon atoms include ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, and lauryl (meth) acrylate (LMA). And alkyl (meth) acrylates such as cetyl (meth) acrylate (CMA), stearyl (meth) acrylate (SMA), and behenyl (meth) acrylate (VMA). In particular, when a hydrophobic monomer is used in combination, an alkyl (meth) acrylate having 12 to 22 carbon atoms is preferably used in order to easily emulsify and stabilize the hydrophobic monomer. More preferred is stearyl (meth) acrylate having 18 carbon atoms. The vinyl compound is not particularly limited as long as it is a compound having a vinyl group, and examples thereof include aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyl toluene; vinyl acetate and vinyl propionate. (A3) A monomer component containing an alkyl (meth) acrylate having 12 to 22 carbon atoms and / or a vinyl compound as the component, and the weight obtained by polymerizing the components (a1) and (a2) together. A reaction product (B) obtained by reacting the polymer (A) with a carboxyl group-containing radical polymerizable vinyl monomer (b), and pentaerythritol tri (meth) acrylate (C) in water, or In addition, the aqueous coating agent composition obtained by dispersing in water can not only make the paint aqueous, but also improve physical properties such as adhesion to the substrate.
上記（ａ３）成分の使用量（重量比）が、重合体（Ａ）を１００重量％とした場合に、１〜３０重量％であることが水分散安定性という観点から好ましい。
上記（Ａ）成分の組成は特に限定されないが、（ａ１）成分、（ａ２）成分及び（ａ３）成分の合計量を１００重量％とした場合に（ａ１）成分が８０〜３０重量％、（ａ２）成分が１９〜４０重量％、及び（ａ３）成分が１〜３０重量％とすることが、得られる水系コーティング剤組成物の水分散安定性の観点から好ましく、（ａ１）成分が５０〜７０重量％、（ａ２）成分が２５〜３５重量％、（ａ３）成分が１〜１０重量％とすることが水分散安定性の点で好ましい。
From the viewpoint of water dispersion stability, the amount (weight ratio) of component (a3) is preferably 1 to 30% by weight when the polymer (A) is 100% by weight.
The composition of the component (A) is not particularly limited, but when the total amount of the components (a1), (a2) and (a3) is 100% by weight, the component (a1) is 80 to 30% by weight, ( From the viewpoint of water dispersion stability of the resulting aqueous coating composition, it is preferable that the component a2) is 19 to 40% by weight and the component (a3) is 1 to 30% by weight, and the component (a1) is 50 to 50%. It is preferable from the viewpoint of water dispersion stability that the content is 70% by weight, the component (a2) is 25 to 35% by weight and the component (a3) is 1 to 10% by weight.
本発明に用いられる（Ａ）成分は、（ａ１）成分、（ａ２）成分及び（ａ３）成分を、例えば、ラジカル重合させることにより得られる。ラジカル重合は、公知の方法で行なうことができる。例えば、（ａ１）〜（ａ３）成分をラジカル重合開始剤の存在下、加熱することにより得られる。ラジカル重合開始剤としては、特に限定されず、公知のものを使用することができる。具体的には、例えば、過酸化水素、過硫酸アンモニウム、過硫酸カリウム等の無機過酸化物、ベンゾイルパーオキサイド、ジクミルパーオキサイド、ラウリルパーオキサイド等の有機過酸化物、２，２’−アゾビスイソブチロニトリル、ジメチル−２，２’−アゾビスイソブチレート等のアゾ系化合物等が挙げられる。これらは１種を単独で用いてもよく、２種以上を混合して用いてもよい。なお、ラジカル重合開始剤の使用量は、（ａ）成分１００重量部に対し、０．０１〜８重量部程度とすることが好ましい。なお、必要に応じ、連鎖移動剤などを用いてもよい。連鎖移動剤としては、例えば、ラウリルメルカプタン、ドデシルメルカプタン、２−メルカプトベンゾチアゾール、ブロムトリクロルメタン等が挙げられる。これらは１種を単独で用いてもよく、２種以上を混合して用いてもよい。連鎖移動剤の使用量は、（ａ１）成分、（ａ２）成分、及び（ａ３）成分の合計量１００重量部に対し、０．０１〜５重量部程度とすることが好ましい。 (A) component used for this invention is obtained by radical-polymerizing (a1) component, (a2) component, and (a3) component, for example. The radical polymerization can be performed by a known method. For example, it can be obtained by heating the components (a1) to (a3) in the presence of a radical polymerization initiator. It does not specifically limit as a radical polymerization initiator, A well-known thing can be used. Specifically, for example, inorganic peroxides such as hydrogen peroxide, ammonium persulfate and potassium persulfate, organic peroxides such as benzoyl peroxide, dicumyl peroxide and lauryl peroxide, 2,2′-azobis And azo compounds such as isobutyronitrile and dimethyl-2,2′-azobisisobutyrate. These may be used alone or in combination of two or more. In addition, it is preferable that the usage-amount of a radical polymerization initiator shall be about 0.01-8 weight part with respect to 100 weight part of (a) component. In addition, you may use a chain transfer agent etc. as needed. Examples of the chain transfer agent include lauryl mercaptan, dodecyl mercaptan, 2-mercaptobenzothiazole, bromotrichloromethane, and the like. These may be used alone or in combination of two or more. The amount of the chain transfer agent used is preferably about 0.01 to 5 parts by weight with respect to 100 parts by weight of the total amount of the components (a1), (a2) and (a3).
このようにして得られた（Ａ）成分は、重量平均分子量（ゲルパーメーションクロマトグラフィーによるポリスチレン換算値）を５，０００〜３０，０００程度、エポキシ当量を１００〜３５０ｇ／ｅｑ程度とすることが水系コーティング剤をタックフリーとする観点及びハードコート性能の面から好ましい。 The component (A) thus obtained may have a weight average molecular weight (polystyrene conversion value by gel permeation chromatography) of about 5,000 to 30,000 and an epoxy equivalent of about 100 to 350 g / eq. From the viewpoint of tack-free water-based coating agent and hard coat performance, it is preferable.
本発明の（Ｂ）成分は、（Ａ）成分に（ｂ）成分を反応させることにより得られる。（ｂ）成分としては、分子中にカルボキシル基を有するラジカル重合性ビニル単量体であれば特に限定されず公知のものを用いることができる。例えば、（メタ）アクリル酸、クロトン酸、などが挙げられる。これらのなかでは、アクリル酸を用いることが反応物の活性エネルギー線硬化性の点から好ましい。（ｂ）成分の使用量は、特に限定されないが、エポキシ基と等量とすることが反応後に（ｂ）成分が残存しにくくなるため水分散安定性及び得られる硬化物のハードコート性の点で好ましい。 The component (B) of the present invention can be obtained by reacting the component (A) with the component (b). The component (b) is not particularly limited as long as it is a radical polymerizable vinyl monomer having a carboxyl group in the molecule, and a known one can be used. For example, (meth) acrylic acid, crotonic acid, etc. are mentioned. Among these, it is preferable to use acrylic acid from the viewpoint of the active energy ray curability of the reaction product. The amount of the component (b) used is not particularly limited. However, since it is difficult for the component (b) to remain after the reaction to be equivalent to the epoxy group, water dispersion stability and the hard coat property of the resulting cured product Is preferable.
（Ａ）成分と（ｂ）成分の反応は、エポキシ開環反応であり、公知の反応条件を採用することができる。例えば、触媒の存在下、加熱することにより得られる。触媒としては、例えば、トリフェニルホスフィン、トリシクロヘキシルホスフィン等のホスフィン類；テトラメチルアンモニウムクロライド、トリメチルベンジルアンモニウムクロライド、テトラメチルアンモニウムブロマイド等の４級アンモニウム塩、トリメチルアミン、トリエチルアミン、ベンジルメチルアミン、トリブチルアミン等のアミン類；２−メチルイミダゾール等のイミダゾール類；ジブチル錫ジラウレート等のラウリン酸エステル類などが挙げられる。触媒の使用量は、特に限定されないが、（Ａ）成分と（ｂ）成分の合計重量１００重量部に対して、通常、０．０１〜５重量部程度とすることが好ましい。なお、必要に応じ、有機溶媒や重合禁止剤を用いてもよい。有機溶媒としては、（Ａ）成分、（ｂ）成分と反応しないものであれば、特に限定されず公知のものを用いることができる。具体的には、例えば、エチルアルコール、プロパノール等のアルコール類；アセトン、メチルエチルケトン等の低級ケトン類；トルエン、ベンゼン等の芳香族炭化水素類；酢酸ブチル、酢酸エチル、クロロホルム、ジメチルホルムアミド等が挙げられる、これらは１種を単独で用いてもよく、２種以上を混合して用いてもよい。重合禁止剤としては、メトキノン、ハイドロキノン、トリメチルハイドロキノン、Ｎ‐ニトロソフェニルヒドロキシルアミン等が挙げられる。なお、重合禁止剤の使用量は特に限定されないが、得られる（Ｂ）成分の重合性が悪化する場合があるため、（Ａ）成分と（ｂ）成分の合計重量１００重量部に対して、通常、１重量部程度以下とすることが好ましい。また、重合を防止するために、反応系中に空気を吹き込む等してもよい。 The reaction between the component (A) and the component (b) is an epoxy ring-opening reaction, and known reaction conditions can be employed. For example, it can be obtained by heating in the presence of a catalyst. Examples of the catalyst include phosphines such as triphenylphosphine and tricyclohexylphosphine; quaternary ammonium salts such as tetramethylammonium chloride, trimethylbenzylammonium chloride and tetramethylammonium bromide, trimethylamine, triethylamine, benzylmethylamine, tributylamine and the like. Amines; imidazoles such as 2-methylimidazole; and lauric acid esters such as dibutyltin dilaurate. Although the usage-amount of a catalyst is not specifically limited, Usually, it is preferable to set it as about 0.01-5 weight part with respect to 100 weight part of total weight of (A) component and (b) component. In addition, you may use an organic solvent and a polymerization inhibitor as needed. As an organic solvent, if it does not react with (A) component and (b) component, it will not specifically limit and a well-known thing can be used. Specific examples include alcohols such as ethyl alcohol and propanol; lower ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as toluene and benzene; butyl acetate, ethyl acetate, chloroform, dimethylformamide and the like. These may be used individually by 1 type, and may mix and use 2 or more types. Examples of the polymerization inhibitor include methoquinone, hydroquinone, trimethylhydroquinone, N-nitrosophenylhydroxylamine and the like. In addition, although the usage-amount of a polymerization inhibitor is not specifically limited, Since the polymerizability of the (B) component obtained may deteriorate, with respect to 100 weight part of total weight of (A) component and (b) component, Usually, it is preferably about 1 part by weight or less. In order to prevent polymerization, air may be blown into the reaction system.
このようにして得られた（Ｂ）成分は、重量平均分子量を５，５００〜６０，０００程度、アクリル当量を１５０〜４５０ｇ／ｅｑ程度、酸価を５ｍｇＫＯＨ／ｇ程度以下とすることが、得られる硬化膜のハードコート特性の点から好ましい。なお、重量平均分子量の測定はゲルパーメーションクロマトグラフィー法（東ソー（株）製 高速ＧＰＣ装置ＨＬＣ-８２２０ＧＰＣにて測定）によるポリスチレン換算値である。 The component (B) thus obtained has a weight average molecular weight of about 5,500 to 60,000, an acrylic equivalent of about 150 to 450 g / eq, and an acid value of about 5 mgKOH / g or less. From the point of the hard coat characteristic of the cured film obtained. In addition, the measurement of a weight average molecular weight is a polystyrene conversion value by a gel permeation chromatography method (measured with Tosoh Corporation high speed GPC apparatus HLC-8220GPC).
上記（Ｃ）成分は、ペンタエリスリトールトリ（メタ）アクリレート（ＰＥ３Ａ）である。（Ｃ）成分は、（ｂ）成分と（Ａ）成分を反応させる際に、あらかじめ添加しておいても良く、（ｂ）成分と（Ａ）成分を反応させて得られた（Ｂ）成分に添加しても良く、（ｂ）成分と（Ａ）成分との反応前後に分割して添加しても良い。（Ｃ）成分の使用量は特に限定されないが、（Ｂ）成分１００重量部に対し、１０〜４００重量部程度とすることが好ましく、５０〜２００重量部とすることが特に好ましい。１０重量部以上とすると、高粘度とならず取扱い容易となり、４００重量部以下であると、水分散時の乳化安定性が低下しにくい。 The component (C) is pentaerythritol tri (meth) acrylate (PE3A). The component (C) may be added in advance when the component (b) and the component (A) are reacted, and the component (B) obtained by reacting the component (b) and the component (A). Or may be added separately before and after the reaction between the component (b) and the component (A). Although the usage-amount of (C) component is not specifically limited, It is preferable to set it as about 10-400 weight part with respect to 100 weight part of (B) component, and it is especially preferable to set it as 50-200 weight part. When it is 10 parts by weight or more, it becomes easy to handle without high viscosity, and when it is 400 parts by weight or less, the emulsion stability at the time of water dispersion is hardly lowered.
本発明の水系コーティング剤組成物は、上記（Ｂ）成分及び（Ｃ）成分を含有するものである。この組成とすることにより、硬度及び耐擦傷性に優れ、ＡＢＳ樹脂（アクリロニトリル−ブタジエン−スチレン樹脂）への密着性に優れた硬化膜を得ることができる。 The aqueous coating agent composition of the present invention contains the above component (B) and component (C). By setting it as this composition, the cured film excellent in hardness and abrasion resistance, and excellent in adhesiveness to ABS resin (acrylonitrile-butadiene-styrene resin) can be obtained.
本発明の水系コーティング剤組成物は、上記（Ｂ）成分及び（Ｃ）成分の他に、更に（Ｄ）成分を含むものであることが好ましい。
上記（Ｄ）成分は、１分子中の（メタ）アクリル基の数平均が１〜４であって、活性水素含有官能基を有しない炭化水素系（メタ）アクリレート、エーテル系（メタ）アクリレート及びエステル系アクリレートから選ばれた１種以上の（メタ）アクリレートであれば、特に限定されない。好ましくは、エーテル系（メタ）アクリレートである。これにより、ＡＢＳ樹脂だけでなく、ポリカーボネートへの密着性にも優れた硬化膜を形成する水系コーティング剤組成物を得ることができる。
It is preferable that the aqueous coating agent composition of the present invention further comprises (D) component in addition to the (B) component and (C) component.
The component (D) has a number average of (meth) acrylic groups in one molecule of 1 to 4 and has no hydrocarbon (meth) acrylate, ether (meth) acrylate, and no active hydrogen-containing functional group. Any one or more (meth) acrylates selected from ester-based acrylates are not particularly limited. Ether-based (meth) acrylate is preferable. Thereby, not only ABS resin but the water-system coating agent composition which forms the cured film excellent also in the adhesiveness to a polycarbonate can be obtained.
上記活性水素含有官能基は、活性水素を含有する官能基であれば特に限定されず、カボキシル基、ヒドロキシル基、チオール基、第一級アミノ基、第二級アミノ基等が挙げられる。 The active hydrogen-containing functional group is not particularly limited as long as it is a functional group containing active hydrogen, and examples thereof include a carboxyl group, a hydroxyl group, a thiol group, a primary amino group, and a secondary amino group.
上記炭化水素系（メタ）アクリレートとは、炭化水素以外の炭素間の不飽和結合を実質的に含有しないものを指すが、炭化水素系基に（メタ）アクリル基が付加したものも含むことは当然であり、また炭化水素系基の水素の一部がフッ素等のハロゲン、ケイ素等の非金属元素、金属元素で置換されたものは含まない。
上記活性水素含有官能基を有しない炭化水素系（メタ）アクリレートとしては、例えば２−エチルヘキシル（メタ）アクリレート、ステアリル（メタ）アクリレート、ラウリル（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１官能（メタ）アクリレート類；エチレングリコールジ（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、ネオペンチルグリコールジ（メタ）アクリレート、１，３−ブタンジオールジ（メタ）アクリレート、１，４ーブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、１，９−ノナンジオールジ（メタ）アクリレート、ビスフェノールＡテトラエチレングリコールジ（メタ）アクリレート等の２官能（メタ）アクリレート類；トリメチロールプロパントリ（メタ）アクリレート等の３官能（メタ）アクリレート類；ペンタエリスリトールテトラ（メタ）アクリレート等の４官能（メタ）アクリレート類が挙げられる。
The hydrocarbon-based (meth) acrylate refers to a material that does not substantially contain unsaturated bonds between carbons other than hydrocarbons, but also includes those in which a (meth) acryl group is added to a hydrocarbon-based group. Naturally, it does not include those in which a part of hydrogen of the hydrocarbon group is substituted with halogen such as fluorine, nonmetallic element such as silicon, or metallic element.
Examples of the hydrocarbon-based (meth) acrylate having no active hydrogen-containing functional group include 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, and benzyl (meth). Monofunctional (meth) acrylates such as acrylate; ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1, Bifunctional such as 4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, bisphenol A tetraethylene glycol di (meth) acrylate, etc. Meth) acrylate; trifunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate; tetrafunctional (meth) acrylates such as pentaerythritol tetra (meth) acrylate.
上記エーテル系（メタ）アクリレートとは、炭化水素系（メタ）アクリレート、および後述するエステル系（メタ）アクリレートを除いたエーテル結合を含有する（メタ）アクリレートであれば特に限定されず、例えばテトラヒドロフルフリルアクリレート等の１官能（メタ）アクリレート類；ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ヘキサ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、ポリプロピレングリコールジ（メタ）アクリレート等の２官能（メタ）アクリレート類；エチレンオキシド変性トリメチロールプロパントリ（メタ）アクリレート、プロピレンオキシド変性トリメチロールプロパントリ（メタ）アクリレート、エチレンオキシド変性グリセロールトリ（メタ）アクリレート、プロピレンオキシド変性グリセロールトリ（メタ）アクリレート等の３官能（メタ）アクリレート類；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エトキシテトラ（メタ）アクリレート等の４官能（メタ）アクリレート類が挙げられる。 The ether-based (meth) acrylate is not particularly limited as long as it is a hydrocarbon-based (meth) acrylate and a (meth) acrylate containing an ether bond excluding an ester-based (meth) acrylate described later. Monofunctional (meth) acrylates such as furyl acrylate; diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, polyethylene glycol di ( Bifunctional (meth) acrylates such as (meth) acrylate and polypropylene glycol di (meth) acrylate; ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified Trifunctional (meth) acrylates such as dimethylolpropane tri (meth) acrylate, ethylene oxide modified glycerol tri (meth) acrylate, propylene oxide modified glycerol tri (meth) acrylate; ditrimethylolpropane tetra (meth) acrylate, pentaerythritol ethoxytetra Examples include tetrafunctional (meth) acrylates such as (meth) acrylate.
上記エステル系（メタ）アクリレートとは、炭化水素系（メタ）アクリレート、および上述のエーテル系（メタ）アクリレートを除いたエステル結合を含有する（メタ）アクリレートであれば特に限定されず、例えば、各種ポリエステルジオールの末端を（メタ）アクリル酸変性したもの等が挙げられる。 The ester-based (meth) acrylate is not particularly limited as long as it is a hydrocarbon-based (meth) acrylate and a (meth) acrylate containing an ester bond excluding the ether-based (meth) acrylate described above. Examples include those obtained by modifying the terminal of the polyester diol with (meth) acrylic acid.
上記（Ｄ）成分は、炭化水素系（メタ）アクリレート、上記エーテル系（メタ）アクリレート及び上記エステル系（メタ）アクリレートから選ばれた１種以上の（メタ）アクリレートから選ばれた１種以上の（メタ）アクリレートである。 The component (D) is one or more selected from one or more (meth) acrylates selected from hydrocarbon (meth) acrylates, ether (meth) acrylates and ester (meth) acrylates. (Meth) acrylate.
上記（Ｄ）成分は、（Ａ）成分、（ｂ）成分及び（Ｃ）成分を反応させる際に、あらかじめ添加しておいても良いし、得られた（Ｂ）成分に添加してもよい。あらかじめ添加する場合は、（Ｃ）成分を添加した後に、（Ｄ）成分を添加してもよく、（Ｄ）成分を（Ｃ）成分より先に添加してもよく、（Ｃ）成分と（Ｄ）成分を同時に添加してもよい。 The component (D) may be added in advance when reacting the component (A), the component (b) and the component (C), or may be added to the component (B) obtained. . When adding beforehand, (D) component may be added after adding (C) component, (D) component may be added before (C) component, (C) component and ( Component D) may be added simultaneously.
上記（Ｄ）成分の使用量は、（Ｂ）成分と（Ｃ）成分の合計重量１００重量部に対して、１０〜３０重量部とすることが好ましい。１０重量％以上とすることで得られる水系コーティング剤組成物を用いたコーティング剤の密着性が低下しにくくなり、また３０重量％以下とすることで水分散時の安定性を向上させることができる。 It is preferable that the usage-amount of said (D) component shall be 10-30 weight part with respect to 100 weight part of total weight of (B) component and (C) component. Adhesiveness of a coating agent using an aqueous coating agent composition obtained by setting it to 10% by weight or more is unlikely to decrease, and by setting it to 30% by weight or less, stability during water dispersion can be improved. .
上記（Ｂ）成分及び（Ｃ）成分、必要に応じて更に（Ｄ）成分を水に溶解させるまたは水に分散させることにより本発明の水系コーティング剤組成物となる。水に分散させる場合には、高圧乳化法、転相乳化法等、公知の方法を採用すればよい。また、本発明の効果を損なわない範囲で、必要に応じて各種公知の乳化剤、分散剤を用いてもよい。本発明の水系コーティング剤組成物は、（Ｂ）成分および（Ｃ）成分を必須成分とするものであるが、さらに表面調整剤、消泡剤、光増感剤、酸化防止剤、光安定剤、レベリング剤、顔料等の各種公知の添加剤、光重合開始剤などを含有させてもよい。 The above-mentioned component (B) and component (C) and, if necessary, the component (D) are further dissolved in water or dispersed in water to obtain the aqueous coating composition of the present invention. In the case of dispersing in water, a known method such as a high pressure emulsification method or a phase inversion emulsification method may be employed. Moreover, you may use various well-known emulsifiers and a dispersing agent as needed in the range which does not impair the effect of this invention. The water-based coating agent composition of the present invention comprises components (B) and (C) as essential components, and further includes a surface conditioner, an antifoaming agent, a photosensitizer, an antioxidant, and a light stabilizer. Further, various known additives such as a leveling agent and a pigment, a photopolymerization initiator, and the like may be contained.
上記光重合開始剤としては、特に限定されず公知のものを用いることができる。具体的には、例えば、１−ヒドロキシ−シクロヘキシル−フェニルケトン、２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン、１−シクロヘキシルフェニルケトン、２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オン、１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノプロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタノン−１、ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド、２，４，６−トリメチルベンゾイル−ジフェニル−フォスフィンオキサイド、４−メチルベンゾフェノン等が挙げられる。これらは１種を単独で用いてもよく、２種以上を混合して用いてもよい。なお、光重合開始剤は、紫外線硬化を行なう場合に使用するが、電子線硬化をする場合には、必ずしも必要ではない。光重合開始剤を使用する場合の使用量は特に限定されないが、通常、（Ｂ）成分及び（Ｃ）成分、必要に応じて（Ｄ）成分の合計量１００重量部に対し、１〜１０重量部程度とすることが好ましい。 As said photoinitiator, it does not specifically limit and can use a well-known thing. Specifically, for example, 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl -Propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphos Examples include fin oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and 4-methylbenzophenone. That. These may be used alone or in combination of two or more. In addition, although a photoinitiator is used when performing ultraviolet curing, it is not necessarily required when performing electron beam curing. Although the usage-amount in the case of using a photoinitiator is not specifically limited, Usually, it is 1-10 weight with respect to 100 weight part of (B) component and (C) component and the total amount of (D) component as needed. It is preferable to be about a part.
本発明の水系コーティング剤組成物は、少なくとも（ａ１）成分、（ａ２）成分及び（ａ３）成分を重合して（Ａ）成分を得る工程（１）、得られた（Ａ）成分に（ｂ）成分を反応させて（Ｂ）成分を得る工程（２）及び（Ｂ）成分に（Ｃ）成分を加えて、更に水を加え水中に分散させる工程（３）にて製造することにより、安定した水系コーティング剤組成物を得ることができる。工程（３）において、更に（Ｄ）成分を添加することが好ましい。なお、（Ｄ）成分は工程（２）で添加することもできる。 The aqueous coating agent composition of the present invention comprises a step (1) in which at least (a1) component, (a2) component and (a3) component are polymerized to obtain (A) component, and (b) Stable production by adding (C) component to step (2) and (B) component obtained by reacting component) and (B), and then adding water and dispersing in water (3). Water-based coating agent composition can be obtained. In step (3), it is preferable to further add component (D). In addition, (D) component can also be added at a process (2).
以下、実施例及び比較例をあげて本発明方法を更に詳しく説明するが、本発明がこれらに限定されないことはもとよりである。なお、実施例中、部または％は重量基準である。 Hereinafter, the method of the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these. In the examples, parts or% is based on weight.
（活性エネルギー線硬化型樹脂の製造）
実施例１
窒素ガス導入管、温度計、還流冷却器及び攪拌装置を備えた四つ口フラスコに、グリシジルメタクリレート６０部、メトキシポリエチレングリコールモノメタクリレート（製品名「ブレンマーＰＭＥ１０００」日油（株）製）３０部、ステアリルメタクリレート１０部、メチルイソブチルケトン４００部、２、２´−アゾビス（２−メチルブチロニトリル）（ＡＢＮ−Ｅ）４部を仕込み、反応系を８７℃に昇温し、３０分間保温して重合を行った後、当該温度において、反応系内にモノマー混合物（グリシジルメタクリレート１８０部、メトキシポリエチレングリコールモノメタクリレート（製品名「ブレンマーＰＭＥ１０００」日油（株）製）９０部、ステアリルメタクリレート３０部、ＡＢＮ−Ｅ１２部）を２時間かけて滴下することにより、重合反応を行った。次いで、同温度において反応系を３時間保温し、その後ＡＢＮ−Ｅ２部を加え、さらに３０分保温し、１１６℃において反応系を２．５時間保温した。その後１６０℃において減圧下に該メチルイソブチルケトンを除去し、６０℃まで冷却し、反応物（Ａ−１）を得た。反応系にペンタエリスリトールトリアクリレート５２１．７部、アクリル酸１２１．７部、重合禁止剤であるメトキノン１．５６部、フェノチアジン０．５２部、反応触媒であるトリフェニルホスフィン１０．４部とを加え、１００℃に昇温、５時間保温することで活性エネルギー線硬化型樹脂（Ｂ−１）を含有する水系コーティング剤組成物を得た。当該活性エネルギー線硬化型樹脂（Ｂ−１）の重量平均分子量は１５０００、酸価は４．４ｍｇＫＯＨ／ｇであった。
(Manufacture of active energy ray-curable resin)
Example 1
In a four-necked flask equipped with a nitrogen gas introduction tube, a thermometer, a reflux condenser and a stirring device, 60 parts of glycidyl methacrylate, 30 parts of methoxypolyethylene glycol monomethacrylate (product name “Blenmer PME1000” manufactured by NOF Corporation), 10 parts of stearyl methacrylate, 400 parts of methyl isobutyl ketone, 4 parts of 2,2′-azobis (2-methylbutyronitrile) (ABN-E) are charged, the reaction system is heated to 87 ° C., and kept warm for 30 minutes. After the polymerization, at this temperature, the monomer mixture (180 parts of glycidyl methacrylate, 90 parts of methoxypolyethylene glycol monomethacrylate (product name “Blenmer PME1000” manufactured by NOF Corporation)), 30 parts of stearyl methacrylate, ABN -E12 parts) is dropped over 2 hours. Ri, the polymerization reaction was carried out. Next, the reaction system was kept at the same temperature for 3 hours, then 2 parts of ABN-E was added, and the mixture was further kept for 30 minutes, and the reaction system was kept at 116 ° C. for 2.5 hours. Thereafter, the methyl isobutyl ketone was removed under reduced pressure at 160 ° C., and the mixture was cooled to 60 ° C. to obtain a reaction product (A-1). To the reaction system, 521.7 parts of pentaerythritol triacrylate, 121.7 parts of acrylic acid, 1.56 parts of methoquinone as a polymerization inhibitor, 0.52 parts of phenothiazine, and 10.4 parts of triphenylphosphine as a reaction catalyst were added. The aqueous coating agent composition containing the active energy ray-curable resin (B-1) was obtained by raising the temperature to 100 ° C. and keeping the temperature for 5 hours. The active energy ray-curable resin (B-1) had a weight average molecular weight of 15000 and an acid value of 4.4 mgKOH / g.
実施例２
実施例１と同様の四つ口フラスコに、グリシジルメタクリレート４０部、メトキシポリエチレングリコールモノメタクリレート（製品名「ブレンマーＰＭＥ１０００」日油（株）製）３０部、ステアリルメタクリレート３０部、メチルイソブチルケトン４００部、ＡＢＮ−Ｅ４部を仕込み、反応系を８７℃に昇温し、３０分間保温して重合を行った後、当該温度において、反応系内にモノマー混合物（グリシジルメタクリレート１２０部、メトキシポリエチレングリコールモノメタクリレート（製品名「ブレンマーＰＭＥ１０００」日油（株）製）９０部、ステアリルメタクリレート９０部、ＡＢＮ−Ｅ１２部）を２時間かけて滴下することにより、重合反応を行った。次いで、同温度において反応系を３時間保温し、その後ＡＢＮ−Ｅ２部を加え、さらに３０分保温し、１１６℃において反応系を２．５時間保温した。次いで、その後１６０℃において減圧下に該メチルイソブチルケトンを除去し、６０℃まで冷却し、反応物（Ａ−２）を得た。反応系にペンタエリスリトールトリアクリレート４８１．１部、アクリル酸８１．１部、重合禁止剤であるメトキノン１．４４部、フェノチアジン０．４８部、反応触媒であるトリフェニルホスフィン９．６４部とを加え、１００℃に昇温、６時間保温することで活性エネルギー線硬化型樹脂（Ｂ−２）を含有する水系コーティング剤組成物を得た。当該活性エネルギー線硬化型樹脂（Ｂ−２）の重量平均分子量は１５０００、酸価は３．２ｍｇＫＯＨ／ｇであった。
Example 2
In the same four-necked flask as in Example 1, 40 parts of glycidyl methacrylate, 30 parts of methoxypolyethylene glycol monomethacrylate (product name “Blenmer PME1000” manufactured by NOF Corporation), 30 parts of stearyl methacrylate, 400 parts of methyl isobutyl ketone, ABN-E (4 parts) was charged, the reaction system was heated to 87 ° C., and the polymerization was carried out by incubating for 30 minutes. At that temperature, the monomer mixture (120 parts of glycidyl methacrylate, methoxypolyethylene glycol monomethacrylate ( The product name "Blemmer PME1000" (manufactured by NOF Corporation) 90 parts, stearyl methacrylate 90 parts, ABN-E 12 parts) was added dropwise over 2 hours to carry out the polymerization reaction. Next, the reaction system was kept at the same temperature for 3 hours, then 2 parts of ABN-E was added, and the mixture was further kept for 30 minutes, and the reaction system was kept at 116 ° C. for 2.5 hours. Subsequently, the methyl isobutyl ketone was removed under reduced pressure at 160 ° C. and cooled to 60 ° C. to obtain a reaction product (A-2). Add 481.1 parts of pentaerythritol triacrylate, 81.1 parts of acrylic acid, 1.44 parts of methoquinone as a polymerization inhibitor, 0.48 parts of phenothiazine, and 9.64 parts of triphenylphosphine as a reaction catalyst to the reaction system. The aqueous coating agent composition containing the active energy ray-curable resin (B-2) was obtained by raising the temperature to 100 ° C. and keeping the temperature for 6 hours. The active energy ray-curable resin (B-2) had a weight average molecular weight of 15000 and an acid value of 3.2 mgKOH / g.
実施例３
実施例１と同様の四つ口フラスコに、グリシジルメタクリレート６０部、メトキシポリエチレングリコールモノメタクリレート（製品名「ブレンマーＰＭＥ１０００」日油（株）製）３０部、ラウリルメタクリレート１０部、メチルイソブチルケトン４００部、ＡＢＮ−Ｅ４部を仕込み、反応系を８７℃に昇温し、３０分間保温して重合を行った後、当該温度において、反応系内にモノマー混合物（グリシジルメタクリレート１８０部、メトキシポリエチレングリコールモノメタクリレート（製品名「ブレンマーＰＭＥ１０００」日油（株）製）９０部、ラウリルメタクリレート３０部、ＡＢＮ−Ｅ１２部）を２時間かけて滴下することにより、重合反応を行った。次いで、同温度において反応系を３時間保温し、その後ＡＢＮ−Ｅ２部を加え、さらに３０分保温し、１１６℃において反応系を２．５時間保温した。次いで、その後１６０℃において減圧下に該メチルイソブチルケトンを除去し、６０℃まで冷却し、反応物（Ａ−３）を得た。反応系にペンタエリスリトールトリアクリレート５２１．７部、アクリル酸１２１．７部、重合禁止剤であるメトキノン１．５６部、フェノチアジン０．５２部、反応触媒であるトリフェニルホスフィン１０．４部とを加え、１００℃に昇温、５時間保温することで活性エネルギー線硬化型樹脂（Ｂ−３）を含有する水系コーティング剤組成物を得た。当該活性エネルギー線硬化型樹脂（Ｂ−３）の重量平均分子量は１５０００、酸価は４．５ｍｇＫＯＨ／ｇであった。
Example 3
In a four-necked flask similar to that in Example 1, 60 parts of glycidyl methacrylate, 30 parts of methoxypolyethylene glycol monomethacrylate (product name “Blenmer PME1000” manufactured by NOF Corporation), 10 parts of lauryl methacrylate, 400 parts of methyl isobutyl ketone, ABN-E (4 parts) was charged, the reaction system was heated to 87 ° C., and the polymerization was carried out by incubating for 30 minutes. At that temperature, the monomer mixture (180 parts of glycidyl methacrylate, methoxypolyethylene glycol monomethacrylate ( The product name “Blenmer PME1000” (manufactured by NOF Corporation) 90 parts, 30 parts lauryl methacrylate, 12 parts ABN-E) was added dropwise over 2 hours to carry out the polymerization reaction. Next, the reaction system was kept at the same temperature for 3 hours, then 2 parts of ABN-E was added, and the mixture was further kept for 30 minutes, and the reaction system was kept at 116 ° C. for 2.5 hours. Subsequently, the methyl isobutyl ketone was removed under reduced pressure at 160 ° C. and cooled to 60 ° C. to obtain a reaction product (A-3). To the reaction system, 521.7 parts of pentaerythritol triacrylate, 121.7 parts of acrylic acid, 1.56 parts of methoquinone as a polymerization inhibitor, 0.52 parts of phenothiazine, and 10.4 parts of triphenylphosphine as a reaction catalyst were added. The aqueous coating agent composition containing the active energy ray-curable resin (B-3) was obtained by raising the temperature to 100 ° C. and keeping the temperature for 5 hours. The active energy ray-curable resin (B-3) had a weight average molecular weight of 15000 and an acid value of 4.5 mgKOH / g.
実施例４
実施例１と同様の四つ口フラスコに、グリシジルメタクリレート６０部、メトキシポリエチレングリコールモノメタクリレート（製品名「ブレンマーＰＭＥ１０００」日油（株）製）３０部、セチルメタクリレート１０部、メチルイソブチルケトン４００部、ＡＢＮ−Ｅ４部を仕込み、反応系を８７℃に昇温し、３０分間保温して重合を行った後、当該温度において、反応系内にモノマー混合物（グリシジルメタクリレート１８０部、メトキシポリエチレングリコールモノメタクリレート（製品名「ブレンマーＰＭＥ１０００」日油（株）製）９０部、セチルメタクリレート３０部、ＡＢＮ−Ｅ１２部）を２時間かけて滴下することにより、重合反応を行った。次いで、同温度において反応系を３時間保温し、その後ＡＢＮ−Ｅ２部を加え、さらに３０分保温し、１１６℃において反応系を２．５時間保温した。次いで、その後１６０℃において減圧下に該メチルイソブチルケトンを除去し、６０℃まで冷却し、反応物（Ａ−４）を得た。反応系にペンタエリスリトールトリアクリレート５２１．７部、アクリル酸１２１．７部、重合禁止剤であるメトキノン１．５６部、フェノチアジン０．５２部、反応触媒であるトリフェニルホスフィン１０．４部とを加え、１００℃に昇温、５時間保温することで活性エネルギー線硬化型樹脂（Ｂ−４）を含有する水系コーティング剤組成物を得た。当該活性エネルギー線硬化型樹脂（Ｂ−４）の重量平均分子量は１５０００、酸価は３．９ｍｇＫＯＨ／ｇであった。
Example 4
In the same four-necked flask as in Example 1, 60 parts of glycidyl methacrylate, 30 parts of methoxypolyethylene glycol monomethacrylate (product name “Blenmer PME1000” manufactured by NOF Corporation), 10 parts of cetyl methacrylate, 400 parts of methyl isobutyl ketone, ABN-E (4 parts) was charged, the reaction system was heated to 87 ° C., and the polymerization was carried out by incubating for 30 minutes. At that temperature, the monomer mixture (180 parts of glycidyl methacrylate, methoxypolyethylene glycol monomethacrylate ( The product name “Blenmer PME1000” (manufactured by NOF Corporation) 90 parts, 30 parts of cetyl methacrylate, 12 parts of ABN-E) was added dropwise over 2 hours to carry out the polymerization reaction. Next, the reaction system was kept at the same temperature for 3 hours, then 2 parts of ABN-E was added, and the mixture was further kept for 30 minutes, and the reaction system was kept at 116 ° C. for 2.5 hours. Subsequently, the methyl isobutyl ketone was removed under reduced pressure at 160 ° C. and cooled to 60 ° C. to obtain a reaction product (A-4). To the reaction system, 521.7 parts of pentaerythritol triacrylate, 121.7 parts of acrylic acid, 1.56 parts of methoquinone as a polymerization inhibitor, 0.52 parts of phenothiazine, and 10.4 parts of triphenylphosphine as a reaction catalyst were added. The aqueous coating agent composition containing the active energy ray-curable resin (B-4) was obtained by raising the temperature to 100 ° C. and keeping the temperature for 5 hours. The active energy ray-curable resin (B-4) had a weight average molecular weight of 15000 and an acid value of 3.9 mgKOH / g.
実施例５
実施例１と同様の四つ口フラスコに、グリシジルメタクリレート６０部、メトキシポリエチレングリコールモノメタクリレート（製品名「ブレンマーＰＭＥ１０００」日油（株）製）３０部、ベヘニルメタクリレート１０部、メチルイソブチルケトン４００部、ＡＢＮ−Ｅ４部を仕込み、反応系を８７℃に昇温し、３０分間保温して重合を行った後、当該温度において、反応系内にモノマー混合物（グリシジルメタクリレート１８０部、メトキシポリエチレングリコールモノメタクリレート（製品名「ブレンマーＰＭＥ１０００」日油（株）製）９０部、ベヘニルメタクリレート３０部、ＡＢＮ−Ｅ１２部）を２時間かけて滴下することにより、重合反応を行った。次いで、同温度において反応系を３時間保温し、その後ＡＢＮ−Ｅ２部を加え、さらに３０分保温し、１１６℃において反応系を２．５時間保温した。次いで、その後１６０℃において減圧下に該メチルイソブチルケトンを除去し、６０℃まで冷却し、反応物（Ａ−５）を得た。反応系にペンタエリスリトールトリアクリレート５２１．７部、アクリル酸１２１．７部、重合禁止剤であるメトキノン１．５６部、フェノチアジン０．５２部、反応触媒であるトリフェニルホスフィン１０．４部とを加え、１００℃に昇温、５時間保温することで活性エネルギー線硬化型樹脂（Ｂ−５）を含有する水系コーティング剤組成物を得た。当該活性エネルギー線硬化型樹脂（Ｂ−５）の重量平均分子量は１５０００、酸価は３．１ｍｇＫＯＨ／ｇであった。
Example 5
In the same four-necked flask as in Example 1, 60 parts of glycidyl methacrylate, 30 parts of methoxypolyethylene glycol monomethacrylate (product name “Blenmer PME1000” manufactured by NOF Corporation), 10 parts of behenyl methacrylate, 400 parts of methyl isobutyl ketone, ABN-E (4 parts) was charged, the reaction system was heated to 87 ° C., and the polymerization was carried out by incubating for 30 minutes. At that temperature, the monomer mixture (180 parts of glycidyl methacrylate, methoxypolyethylene glycol monomethacrylate ( The product name “Blenmer PME1000” (manufactured by NOF Corporation) 90 parts, 30 parts of behenyl methacrylate, 12 parts of ABN-E) was added dropwise over 2 hours to carry out the polymerization reaction. Next, the reaction system was kept at the same temperature for 3 hours, then 2 parts of ABN-E was added, and the mixture was further kept for 30 minutes, and the reaction system was kept at 116 ° C. for 2.5 hours. Subsequently, the methyl isobutyl ketone was removed under reduced pressure at 160 ° C. and cooled to 60 ° C. to obtain a reaction product (A-5). To the reaction system, 521.7 parts of pentaerythritol triacrylate, 121.7 parts of acrylic acid, 1.56 parts of methoquinone as a polymerization inhibitor, 0.52 parts of phenothiazine, and 10.4 parts of triphenylphosphine as a reaction catalyst were added. The aqueous coating agent composition containing the active energy ray-curable resin (B-5) was obtained by raising the temperature to 100 ° C. and keeping the temperature for 5 hours. The active energy ray-curable resin (B-5) had a weight average molecular weight of 15000 and an acid value of 3.1 mgKOH / g.
（紫外線硬化型水系コーティング剤組成物の製造）
実施例６
実施例１と同様の四つ口フラスコに、実施例１で調製した組成物１００部を十分に攪拌し、次いで水１５０部を徐々に添加し、４０℃で１時間強攪拌し水性物を得た。次いで、２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オン（製品名「ダロキュア１１７３」、チバ・ジャパン（株）製）５部、及びレベリング剤（製品名「ＢＹＫ３４８」、ビックケミー・ジャパン（株）製）０．７５部を加えてよく攪拌し、水系コーティング剤組成物（１）を得た。
(Production of UV-curable aqueous coating agent composition)
Example 6
In a four-necked flask similar to that in Example 1, 100 parts of the composition prepared in Example 1 was sufficiently stirred, and then 150 parts of water was gradually added, followed by strong stirring at 40 ° C. for 1 hour to obtain an aqueous material. It was. Subsequently, 5-hydroxy-2-methyl-1-phenyl-propan-1-one (product name “Darocur 1173”, manufactured by Ciba Japan Co., Ltd.) and a leveling agent (product name “BYK348”, Big Chemie 0.75 part of Japan Co., Ltd.) was added and stirred well to obtain an aqueous coating composition (1).
実施例７
実施例１と同様の四つ口フラスコに、実施例２で調製した組成物１００部を十分に攪拌し、次いで水１５０部を徐々に添加し、４０℃で１時間強攪拌し水性物を得た。次いで当該水性物に実施例６と同様の操作を行い、水系コーティング剤組成物（２）を得た。
Example 7
In a four-necked flask similar to that in Example 1, 100 parts of the composition prepared in Example 2 was sufficiently stirred, and then 150 parts of water was gradually added, followed by strong stirring at 40 ° C. for 1 hour to obtain an aqueous material. It was. Next, the same operation as in Example 6 was performed on the aqueous material to obtain an aqueous coating agent composition (2).
実施例８
実施例１と同様の四つ口フラスコに、実施例３で調製した組成物１００部を十分に攪拌し、次いで水１５０部を徐々に添加し、４０℃で１時間強攪拌し水性物を得た。次いで当該水性物に実施例６と同様の操作を行い、水系コーティング剤組成物（３）を得た。
Example 8
In a four-necked flask similar to Example 1, 100 parts of the composition prepared in Example 3 was sufficiently stirred, and then 150 parts of water was gradually added, followed by strong stirring at 40 ° C. for 1 hour to obtain an aqueous material. It was. Subsequently, the same operation as in Example 6 was performed on the aqueous material, to obtain an aqueous coating agent composition (3).
実施例９
実施例１と同様の四つ口フラスコに、実施例４で調製した組成物１００部を十分に攪拌し、次いで水１５０部を徐々に添加し、４０℃で１時間強攪拌し水性物を得た。次いで当該水性物に実施例６と同様の操作を行い、水系コーティング剤組成物（４）を得た。
Example 9
In a four-necked flask similar to Example 1, 100 parts of the composition prepared in Example 4 was sufficiently stirred, then 150 parts of water was gradually added, and the mixture was vigorously stirred at 40 ° C. for 1 hour to obtain an aqueous material. It was. Next, the same operation as in Example 6 was performed on the aqueous material to obtain an aqueous coating agent composition (4).
実施例１０
実施例１と同様の四つ口フラスコに、実施例５で調製した組成物１００部を十分に攪拌し、次いで水１５０部を徐々に添加し、４０℃で１時間強攪拌し水性物を得た。次いで当該水性物に実施例６と同様の操作を行い、水系コーティング剤組成物（５）を得た。
Example 10
In a four-necked flask similar to that in Example 1, 100 parts of the composition prepared in Example 5 were sufficiently stirred, and then 150 parts of water was gradually added, followed by strong stirring at 40 ° C. for 1 hour to obtain an aqueous material. It was. Subsequently, the same operation as in Example 6 was performed on the aqueous material, to obtain an aqueous coating agent composition (5).
実施例１１
実施例１と同様の四つ口フラスコに、実施例１で調製した組成物６０部、ＰＥ３Ａ１０部、ジトリメチロールプロパンテトラアクリレート（製品名「アロニックスＭ−４０８」東亞合成（株）製（ＤＴＭＰＴＡ））（Ｄ）３０部を十分に攪拌し、次いで水１５０部を徐々に添加し、４０℃で１時間強攪拌し水性物を得た。次いで当該水性物に実施例６と同様の操作を行い、水系コーティング剤組成物（６）を得た。
Example 11
In the same four-necked flask as in Example 1, 60 parts of the composition prepared in Example 1, 10 parts of PE3A, ditrimethylolpropane tetraacrylate (product name “Aronix M-408” manufactured by Toagosei Co., Ltd. (DTMPTA)) (D) 30 parts was sufficiently stirred, and then 150 parts of water was gradually added, followed by strong stirring at 40 ° C. for 1 hour to obtain an aqueous material. Next, the same operation as in Example 6 was performed on the aqueous material to obtain an aqueous coating agent composition (6).
実施例１２
実施例１と同様の四つ口フラスコに、実施例１で調製した組成物６０部、ＰＥ３Ａ（Ｃ）１５部、ＤＴＭＰＴＡ（Ｄ）２５部を十分に攪拌し、次いで水１５０部を徐々に添加し、４０℃で１時間強攪拌し水性物を得た。次いで当該水性物に実施例６と同様の操作を行い、水系コーティング剤組成物（７）を得た。
Example 12
In a four-necked flask similar to Example 1, 60 parts of the composition prepared in Example 1, 15 parts of PE3A (C), and 25 parts of DTMPTA (D) were sufficiently stirred, and then 150 parts of water was gradually added. And stirred vigorously at 40 ° C. for 1 hour to obtain an aqueous product. Subsequently, the same operation as in Example 6 was performed on the aqueous material, to obtain an aqueous coating agent composition (7).
実施例１３
実施例１と同様の四つ口フラスコに、実施例１で調製した組成物６０部、ＰＥ３Ａ（Ｃ）１５部、１，９−ノナンジオールジアクリレート（製品名「ビスコート２６０」大阪有機化学工業（株）製）（Ｄ）２５部を十分に攪拌し、次いで水１５０部を徐々に添加し、４０℃で１時間強攪拌し水性物を得た。次いで当該水性物に実施例６と同様の操作を行い、水系コーティング剤組成物（８）を得た。
Example 13
In a four-necked flask similar to that in Example 1, 60 parts of the composition prepared in Example 1, 15 parts of PE3A (C), 1,9-nonanediol diacrylate (product name “Biscoat 260” Osaka Organic Chemical Industry ( (D) 25 parts of (D) were sufficiently stirred, and then 150 parts of water was gradually added and stirred vigorously at 40 ° C. for 1 hour to obtain an aqueous product. Next, the same operation as in Example 6 was performed on the aqueous material, to obtain an aqueous coating agent composition (8).
実施例１４
実施例１と同様の四つ口フラスコに、実施例１で調製した組成物６０部、ＰＥ３Ａ（Ｃ）１５部、テトラヒドロフルフリルアクリレート（製品名「ビスコート１５０」大阪有機化学工業（株）製）（Ｄ）２５部を十分に攪拌し、次いで水１５０部を徐々に添加し、４０℃で１時間強攪拌し水性物を得た。次いで当該水性物に実施例６と同様の操作を行い、水系コーティング剤組成物（９）を得た。
Example 14
In the same four-necked flask as in Example 1, 60 parts of the composition prepared in Example 1, 15 parts of PE3A (C), tetrahydrofurfuryl acrylate (product name “Biscoat 150” manufactured by Osaka Organic Chemical Industry Co., Ltd.) (D) 25 parts was sufficiently stirred, and then 150 parts of water was gradually added and stirred vigorously at 40 ° C. for 1 hour to obtain an aqueous material. Subsequently, the same operation as in Example 6 was performed on the aqueous material, to obtain an aqueous coating agent composition (9).
実施例１５
実施例１と同様の四つ口フラスコに、実施例１で調製した組成物６０部、ＰＥ３Ａ（Ｃ）１５部、ポリエステルアクリレート（製品名「アロニックスＭ９０５０」東亞合成（株）製）（Ｄ）２５部を十分に攪拌し、次いで水１５０部を徐々に添加し、４０℃で１時間強攪拌し水性物を得た。次いで当該水性物に実施例６と同様の操作を行い、水系コーティング剤組成物（１０）を得た。
Example 15
In a four-necked flask similar to Example 1, 60 parts of the composition prepared in Example 1, 15 parts of PE3A (C), polyester acrylate (product name “Aronix M9050” manufactured by Toagosei Co., Ltd.) (D) 25 Then, 150 parts of water was gradually added and stirred vigorously at 40 ° C. for 1 hour to obtain an aqueous product. Next, the same operation as in Example 6 was performed on the aqueous material to obtain an aqueous coating agent composition (10).
（活性エネルギー線硬化型樹脂の製造）
比較例１
実施例１と同様の四つ口フラスコに、グリシジルメタクリレート（ａ１）７０部、メトキシポリエチレングリコールモノメタクリレート（製品名「ブレンマーＰＭＥ１０００」日油（株）製）（ａ２）３０部、メチルイソブチルケトン４００部、ＡＢＮ−Ｅ４部を仕込み、反応系を８７℃に昇温、３０分保温して重合を行った後、当該温度において、反応系内にモノマー混合物（グリシジルメタクリレート１９５部、メトキシポリエチレングリコールモノメタクリレート１０５部、ＡＢＮ−Ｅ１２部）を２時間かけて滴下することにより、重合反応を行った。次いで、同温度において反応系を３時間保温し、その後ＡＢＮ−Ｅ２部を加え、さらに３０分保温し、１１６℃において反応系を２．５時間保温した。次いで、その後１６０℃において減圧下に該メチルイソブチルケトンを除去し、６０℃まで冷却し、反応物（Ａ−６）を得た。反応系にＰＥ３Ａ（Ｃ）５３１．８部、アクリル酸（ｂ）１３１．８部、重合禁止剤であるメトキノン１．６部、フェノチアジン０．５２部、反応触媒であるトリフェニルホスフィン１０．６部を加え、１００℃に昇温し、３時間保温することで活性エネルギー線硬化型樹脂（Ｂ−６）を含有する水性コーティング剤組成物を得た。当該反応物（Ｂ−６）の重量平均分子量は１４０００、酸価は４．７ｍｇＫＯＨ／ｇであった。
(Manufacture of active energy ray-curable resin)
Comparative Example 1
In a four-necked flask similar to that in Example 1, 70 parts of glycidyl methacrylate (a1), methoxypolyethylene glycol monomethacrylate (product name “Blenmer PME1000” manufactured by NOF Corporation) (a2), 400 parts of methyl isobutyl ketone , 4 parts of ABN-E were added, the reaction system was heated to 87 ° C. and kept for 30 minutes for polymerization, and at that temperature, the monomer mixture (195 parts of glycidyl methacrylate, methoxypolyethylene glycol monomethacrylate 105 Part, ABN-E 12 parts) was added dropwise over 2 hours to carry out the polymerization reaction. Next, the reaction system was kept at the same temperature for 3 hours, then 2 parts of ABN-E was added, and the mixture was further kept for 30 minutes, and the reaction system was kept at 116 ° C. for 2.5 hours. Subsequently, the methyl isobutyl ketone was removed under reduced pressure at 160 ° C. and cooled to 60 ° C. to obtain a reaction product (A-6). In the reaction system, 531.8 parts of PE3A (C), 131.8 parts of acrylic acid (b), 1.6 parts of methoquinone as a polymerization inhibitor, 0.52 parts of phenothiazine, 10.6 parts of triphenylphosphine as a reaction catalyst Was added, and the temperature was raised to 100 ° C. and kept for 3 hours to obtain an aqueous coating agent composition containing the active energy ray-curable resin (B-6). The reaction product (B-6) had a weight average molecular weight of 14,000 and an acid value of 4.7 mgKOH / g.
比較例２
実施例１と同様の四つ口フラスコに、実施例１で得た組成物４００部、ＤＴＭＰＴＡ５２１．７部、アクリル酸１２１．７部、重合禁止剤であるメトキノン１．５６部、フェノチアジン０．５２部、反応触媒であるトリフェニルホスフィン１０．４部とを加え、１００℃に昇温、５時間保温することで活性エネルギー線硬化型樹脂（Ｂ−７）を含有する水性コーティング剤組成物を得た。当該活性エネルギー線硬化型樹脂（Ｂ−７）の重量平均分子量は１５０００、酸価は４．２ｍｇＫＯＨ／ｇであった。
Comparative Example 2
In the same four-necked flask as in Example 1, 400 parts of the composition obtained in Example 1, 521.7 parts of DTMPTA, 121.7 parts of acrylic acid, 1.56 parts of methoquinone which is a polymerization inhibitor, 0.52 of phenothiazine. Part and triphenylphosphine (10.4 parts) as a reaction catalyst are added, and heated to 100 ° C. and kept for 5 hours to obtain an aqueous coating agent composition containing an active energy ray-curable resin (B-7). It was. The active energy ray-curable resin (B-7) had a weight average molecular weight of 15000 and an acid value of 4.2 mgKOH / g.
比較例３
実施例１と同様の四つ口フラスコに、比較例２で得た組成物４００部、ＤＴＭＰＴＡ５３１．８部、アクリル酸１３１．８部、重合禁止剤であるメトキノン１．６部、フェノチアジン０．５２部、反応触媒であるトリフェニルホスフィン１０．６部とを加え、１００℃に昇温、５時間保温することで活性エネルギー線硬化型樹脂（Ｂ−８）を含有する水性コーティング剤組成物を得た。当該活性エネルギー線硬化型樹脂（Ｂ−８）の重量平均分子量は１４０００、酸価は４．５ｍｇＫＯＨ／ｇであった。
Comparative Example 3
In the same four-necked flask as in Example 1, 400 parts of the composition obtained in Comparative Example 2, 531.8 parts of DTMPTA, 131.8 parts of acrylic acid, 1.6 parts of methoquinone which is a polymerization inhibitor, 0.52 of phenothiazine. Part and triphenylphosphine (10.6 parts) as a reaction catalyst are added and heated to 100 ° C. and kept for 5 hours to obtain an aqueous coating agent composition containing an active energy ray-curable resin (B-8). It was. The active energy ray-curable resin (B-8) had a weight average molecular weight of 14,000 and an acid value of 4.5 mgKOH / g.
（水系コーティング剤組成物の製造）
比較例４
実施例１と同様の四つ口フラスコに、比較例１で調製した組成物１００部を十分に攪拌し、次いで水１５０部を徐々に添加し、４０℃で１時間強攪拌し水性物を得た。次いで当該水性物に実施例６と同様の操作を行い水系コーティング剤組成物（１１）を得た。
(Manufacture of aqueous coating agent composition)
Comparative Example 4
To the same four-necked flask as in Example 1, 100 parts of the composition prepared in Comparative Example 1 was sufficiently stirred, and then 150 parts of water was gradually added, followed by strong stirring at 40 ° C. for 1 hour to obtain an aqueous material. It was. Next, the same operation as in Example 6 was performed on the aqueous material to obtain an aqueous coating agent composition (11).
比較例５
実施例１と同様の四つ口フラスコに、比較例２で調製した組成物１００部を十分に攪拌し、次いで水１５０部を徐々に添加し、４０℃で１時間強攪拌し水性物を得た。次いで当該水性物に実施例６と同様の操作を行い、水系コーティング剤組成物（１２）を得た。
Comparative Example 5
To the same four-necked flask as in Example 1, 100 parts of the composition prepared in Comparative Example 2 was sufficiently stirred, and then 150 parts of water was gradually added, followed by strong stirring at 40 ° C. for 1 hour to obtain an aqueous material. It was. Next, the same operation as in Example 6 was performed on the aqueous material, to obtain an aqueous coating agent composition (12).
比較例６
実施例１と同様の四つ口フラスコに、比較例３で調製した組成物１００部を十分に攪拌し、次いで水１５０部を徐々に添加し、４０℃で１時間強攪拌し水性物を得た。次いで当該水性物に実施例６と同様の操作を行い、水系コーティング剤組成物（１３）を得た。
Comparative Example 6
To the same four-necked flask as in Example 1, 100 parts of the composition prepared in Comparative Example 3 was sufficiently stirred, and then 150 parts of water was gradually added, followed by strong stirring at 40 ° C. for 1 hour to obtain an aqueous material. It was. Next, the same operation as in Example 6 was performed on the aqueous material to obtain an aqueous coating agent composition (13).
比較例７
実施例１と同様の四つ口フラスコに、比較例１で調製した組成物６０部、ＰＥ３Ａ（Ｃ）１０部、ＤＴＭＰＴＡ（Ｄ）３０部を十分に攪拌し、次いで水１５０部を徐々に添加し、４０℃で１時間強攪拌し水性物を得た。次いで当該水性物に実施例６と同様の操作を行い、コーティング剤組成物（１４）を得た。
Comparative Example 7
In the same four-necked flask as in Example 1, 60 parts of the composition prepared in Comparative Example 1, 10 parts of PE3A (C) and 30 parts of DTMPTA (D) were sufficiently stirred, and then 150 parts of water was gradually added. And stirred vigorously at 40 ° C. for 1 hour to obtain an aqueous product. Subsequently, operation similar to Example 6 was performed to the said aqueous material, and the coating agent composition (14) was obtained.
＜乳化安定性の確認＞
水系コーティング剤組成物の状態を、水分散直後、１日後、７日後に、分離、沈降等の異常の有無を目視にて確認した。結果を表１〜３に示す。
０：水分散不可能
１：水分散直後に分離
２：１日後に分離
３：１週間後も分離なし
<Confirmation of emulsion stability>
The state of the aqueous coating agent composition was visually confirmed immediately after water dispersion for 1 day and 7 days after the presence of abnormality such as separation and sedimentation. The results are shown in Tables 1-3.
0: Water dispersible 1: Separation immediately after water dispersion 2: Separation after 1 day: No separation after 3: 1 week
＜コーティング被膜の作製＞
水系コーティング剤組成物（１）を、＃２０バーコーターを用いて膜厚が約１８μｍ（計算値）となるように、２ｍｍ厚のポリカーボネート（ＰＣ）フィルム（商品名「標準試験板ポリカーボネート」、日本テストパネル（株）製（ＰＣ））および２ｍｍ厚のＡＢＳフィルム（商品名「標準試験板ＡＢＳ（Ｎ）」、日本テストパネル（株）製（ＡＢＳ））に塗工し、８０℃で３分乾燥させた。次いで、得られた塗工フィルムを大気中で、８０Ｗ高圧水銀灯の下に通過させて（水銀灯高さ２０ｃｍ、搬送速度８ｍ／分、５回照射、紫外線照射量６００ｍＪ／ｃｍ２）、塗工面を硬化させることにより被覆ポリカーボネートフィルム及び被覆ＡＢＳフィルムを得た。また、水系コーティング剤組成物（２）〜（５）のそれぞれについても同様にして被覆ポリカーボネート（ＰＣ）フィルムおよび被覆ＡＢＳフィルムを得た。
<Production of coating film>
Using a # 20 bar coater, the water-based coating agent composition (1) is 2 mm thick polycarbonate (PC) film (trade name “Standard Test Panel Polycarbonate”, Japan) so that the film thickness is about 18 μm (calculated value). Test Panel Co., Ltd. (PC)) and 2 mm thick ABS film (trade name “Standard Test Board ABS (N)”, Nippon Test Panel Co., Ltd. (ABS)), coated at 80 ° C. for 3 minutes Dried. Then, the obtained coating film is passed under 80 W high-pressure mercury lamp in the atmosphere (mercury lamp height 20 cm, conveyance speed 8 m / min, five times irradiation, ultraviolet ray irradiation amount 600 mJ / cm 2 ), and the coated surface is A coated polycarbonate film and a coated ABS film were obtained by curing. Moreover, the coated polycarbonate (PC) film and the coated ABS film were obtained in the same manner for each of the aqueous coating agent compositions (2) to (5).
＜密着性試験＞
上記各被覆フィルムについて、ＪＩＳ−Ｋ−５６００に準拠して碁盤目試験を実施し、以下の基準に基づいて、被膜の密着性を評価した。結果を表１〜３に示す。
○：１００マス中１００マス残存
△：１００マス中３０〜９９マス残存
×：１００マス中０〜２９マス残存
<Adhesion test>
About each said coating film, the cross-cut test was implemented based on JIS-K-5600, and the adhesiveness of the film was evaluated based on the following references | standards. The results are shown in Tables 1-3.
○: 100 cells remaining in 100 cells Δ: 30-99 cells remaining in 100 cells x: 0-29 cells remaining in 100 cells
Claims (5)
The polyalkylene glycol ether structure has the general formula (1): — (X—O) n — (wherein X is an alkylene group having 2 to 4 carbon atoms which may have a branched structure, The water-based coating agent composition according to any one of claims 1 to 4, which may be different, and n represents an integer of 9 to 90.
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