JP2008248014A - Energy radiation-curarble aqueous resin composition and paint using the same - Google Patents
Energy radiation-curarble aqueous resin composition and paint using the same Download PDFInfo
- Publication number
- JP2008248014A JP2008248014A JP2007088976A JP2007088976A JP2008248014A JP 2008248014 A JP2008248014 A JP 2008248014A JP 2007088976 A JP2007088976 A JP 2007088976A JP 2007088976 A JP2007088976 A JP 2007088976A JP 2008248014 A JP2008248014 A JP 2008248014A
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- Prior art keywords
- meth
- resin composition
- water
- compound
- acrylate
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 28
- 239000003973 paint Substances 0.000 title description 6
- -1 acrylate compound Chemical class 0.000 claims abstract description 45
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- 238000000576 coating method Methods 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 abstract description 8
- 230000003373 anti-fouling effect Effects 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 51
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 26
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 21
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 18
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 239000005056 polyisocyanate Substances 0.000 description 12
- 229920001228 polyisocyanate Polymers 0.000 description 12
- 229920005862 polyol Polymers 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- 230000001804 emulsifying effect Effects 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 9
- 229920005749 polyurethane resin Polymers 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 229920000768 polyamine Polymers 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 150000003077 polyols Chemical class 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 7
- 150000005846 sugar alcohols Polymers 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004945 emulsification Methods 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 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 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 2
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 241000047703 Nonion Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229930182556 Polyacetal Natural products 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 150000001261 hydroxy acids Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 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
- 239000007769 metal material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000005702 oxyalkylene group Chemical group 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920006289 polycarbonate film Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 229920006295 polythiol Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 1
- CTNICFBTUIFPOE-UHFFFAOYSA-N 2-(4-hydroxyphenoxy)ethane-1,1-diol Chemical compound OC(O)COC1=CC=C(O)C=C1 CTNICFBTUIFPOE-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-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
- MUBQKSBEWRYKES-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO MUBQKSBEWRYKES-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
- SPGHPHFQNQIZME-UHFFFAOYSA-N 2-n-ethylethane-1,1,2-triamine Chemical compound CCNCC(N)N SPGHPHFQNQIZME-UHFFFAOYSA-N 0.000 description 1
- YUZJZPMLAIYVGM-UHFFFAOYSA-N 2-n-methylethane-1,1,2-triamine Chemical compound CNCC(N)N YUZJZPMLAIYVGM-UHFFFAOYSA-N 0.000 description 1
- CKNCVRMXCLUOJI-UHFFFAOYSA-N 3,3'-dibromobisphenol A Chemical compound C=1C=C(O)C(Br)=CC=1C(C)(C)C1=CC=C(O)C(Br)=C1 CKNCVRMXCLUOJI-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- XRBXGZZMKCBTFP-UHFFFAOYSA-N 4-(2,2-dihydroxyethoxycarbonyl)benzoic acid Chemical compound OC(O)COC(=O)C1=CC=C(C(O)=O)C=C1 XRBXGZZMKCBTFP-UHFFFAOYSA-N 0.000 description 1
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
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- 230000005251 gamma ray Effects 0.000 description 1
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- 125000005843 halogen group Chemical group 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
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- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、特にプラスチック、金属材料、木工用等に対する密着性、耐薬品性、耐汚染性、耐屈曲性に優れたコーティング用途に適したエネルギー線硬化型水系樹脂組成物及びこれを用いた塗料に関する。また、無公害で安全性に優れた水系樹脂組成物及びこれを用いた塗料に関するものである。 The present invention particularly relates to an energy ray-curable water-based resin composition suitable for coating applications excellent in adhesion, chemical resistance, stain resistance, and bending resistance to plastics, metal materials, woodworking, and the like, and a paint using the same About. The present invention also relates to a water-based resin composition that is pollution-free and excellent in safety, and a paint using the same.
床や壁に代表される建材用途や、携帯電話、各種構造物、成型物等は、基材を保護し、美観を保つために、塗料でコーティングするのが一般的である。 For building materials such as floors and walls, mobile phones, various structures, molded products, etc., it is common to coat them with paints to protect the base material and maintain its beauty.
塗料としては、従来は合成樹脂を有機溶剤で溶解させた溶剤タイプが一般的であったが、作業環境の改善や、火気に対する危険防止等の点から、エネルギー線照射によって硬化可能な樹脂を用いたエネルギー線硬化型の塗料が種々開発され、化粧板やプラスチック用コーティング、木工用塗料、金属用塗料、紙コーティング、レジスト用材料、接着剤、電子機器の部品等の幅広い分野で実用化されている。 Conventionally, a solvent type in which a synthetic resin is dissolved in an organic solvent is generally used as a paint, but a resin that can be cured by irradiation with energy rays is used in order to improve the working environment and prevent danger to fire. Various types of energy ray curable coatings have been developed and put into practical use in a wide range of fields such as decorative panels, plastic coatings, wood coatings, metal coatings, paper coatings, resist materials, adhesives, and electronic device parts. Yes.
かかるコーティング用途ではプラスチック、金属材料、木工用等に対する密着性、耐薬品性、耐汚染性、耐屈曲性が要求され、塩素化されたポリヒドロキシ化合物とカルボキシ基及び（メタ）アクリロイル基を有する不飽和モノヒドロキシ化合物を塩基性化合物で中和し水に分散させて得られた水性ポリウレタン（メタ）アクリレート化合物であることを特徴とする密着性に優れた光硬化型水性樹脂組成物（特許文献１）や、分子中にメタクリロイル基とアクリロイル基を導入したエネルギー線硬化型水性ポリウレタン組成物（特許文献２）が提案されている。
しかしながら、特許文献１、２に記載の水性ポリウレタン組成物では、上記のように密着性、耐薬品性、耐汚染性、耐屈曲性を兼ね備えた性能は得られず、不十分でありより上記性能を向上させることが望まれているのが実状である。 However, in the aqueous polyurethane compositions described in Patent Documents 1 and 2, performances having adhesion, chemical resistance, stain resistance, and flex resistance as described above cannot be obtained, and the above performance is insufficient. It is the actual situation that it is desired to improve.
本発明は、上記に鑑みてなされたものであり、密着性、耐薬品性、耐汚染性、耐屈曲性に優れた水系ウレタン樹脂と（メタ）アクリレート化合物を含有するエネルギー線硬化型水系樹脂組成物を提供することを目的とする。 The present invention has been made in view of the above, and an energy ray-curable water-based resin composition containing a water-based urethane resin and a (meth) acrylate compound excellent in adhesion, chemical resistance, stain resistance, and flex resistance. The purpose is to provide goods.
本発明のエネルギー線硬化型水系樹脂組成物は、上記の課題を解決するために、水系ウレタン樹脂（Ａ）と（メタ）アクリレート系化合物（Ｂ）とを含有するエネルギー線硬化型水系樹脂組成物であって、前記水系ウレタン樹脂（Ａ）と（メタ）アクリレート系化合物（Ｂ）との配合比率（Ａ／Ｂ）が重量固形分比率で１００／３０〜３／１００であることを特徴とする。 The energy beam curable aqueous resin composition of the present invention contains an aqueous urethane resin (A) and a (meth) acrylate compound (B) in order to solve the above problems. The mixing ratio (A / B) of the water-based urethane resin (A) and the (meth) acrylate-based compound (B) is 100/30 to 3/100 in terms of weight solid content. .
本発明においては、前記（メタ）アクリレート系化合物（Ｂ）が分子中に２個以上のエネルギー線硬化性不飽和二重結合を含有していることが好ましい。 In the present invention, the (meth) acrylate compound (B) preferably contains two or more energy ray-curable unsaturated double bonds in the molecule.
また、光重合開始剤をさらに含有するものとすることができる。 Further, it may further contain a photopolymerization initiator.
本発明の塗料は、上記いずれかのエネルギー線硬化型水系樹脂組成物を用いてなるものとする。 The coating material of the present invention is formed using any one of the above energy beam curable water-based resin compositions.
本発明のエネルギー線硬化型水系樹脂組成物によれば、密着性、耐薬品性、耐汚染性、耐屈曲性に優れたエネルギー線硬化型水系樹脂組成物が得られる。従って、本発明の樹脂組成物を用いた塗料によれば、これらの性能を具備した塗膜が得られる。 According to the energy beam curable water-based resin composition of the present invention, an energy beam curable water-based resin composition excellent in adhesion, chemical resistance, stain resistance, and flex resistance can be obtained. Therefore, according to the paint using the resin composition of the present invention, a coating film having these performances can be obtained.
本発明のエネルギー線硬化型水系樹脂組成物は、上述の通り水系ウレタン樹脂（Ａ）と（メタ）アクリレート系化合物（Ｂ）とを含有するエネルギー線硬化型樹水系樹脂組成物であって、前記水系ウレタン樹脂（Ａ）と（メタ）アクリレート系化合物（Ｂ）の配合比率（Ａ／Ｂ）が重量固形分比率で１００／３０〜３／１００であることを特徴とするものである。 The energy beam curable aqueous resin composition of the present invention is an energy beam curable resinous resin composition containing the aqueous urethane resin (A) and the (meth) acrylate compound (B) as described above, The mixing ratio (A / B) of the water-based urethane resin (A) and the (meth) acrylate-based compound (B) is 100/30 to 3/100 by weight solid content ratio.
本発明の水系ウレタン樹脂の製造方法としては、２個以上の活性水素原子含有化合物と有機ポリイソシアネートとの反応により得られるＮＣＯ基含有ウレタンプレポリマーを、水中に乳化後、多価アミン化合物あるいは水との反応により高分子量化して得られる場合、或いは２個以上の活性水素原子含有化合物と有機ポリイソシアネートとの反応により得られるＯＨ基末端ウレタンポリマーを水中に乳化する方法が挙げられる。 As a method for producing the water-based urethane resin of the present invention, an NCO group-containing urethane prepolymer obtained by a reaction of two or more active hydrogen atom-containing compounds and an organic polyisocyanate is emulsified in water, and then a polyvalent amine compound or water. And a method of emulsifying an OH group-terminated urethane polymer obtained by the reaction of two or more active hydrogen atom-containing compounds and an organic polyisocyanate in water.
［ＮＣＯ基含有ウレタンプレポリマーの乳化方法］
（１）２個以上の活性水素原子含有化合物、有機ポリイソシアネート、ならびにＮＣＯ基と反応性の活性水素原子及び塩形成基を有する化合物から合成されるＮＣＯ基含有ウレタンプレポリマーに塩形成剤を添加し、水中に乳化後、多価アミン化合物や水で鎖伸長して得られるアニオン性、またはカチオン性ポリウレタン樹脂水分散体。
[Emulsification method of NCO group-containing urethane prepolymer]
(1) Adding a salt-forming agent to an NCO group-containing urethane prepolymer synthesized from two or more active hydrogen atom-containing compounds, an organic polyisocyanate, and a compound having an active hydrogen atom reactive with an NCO group and a salt-forming group An anionic or cationic polyurethane resin aqueous dispersion obtained by chain elongation with a polyamine compound or water after emulsification in water.
（２）２個以上の活性水素原子含有化合物、有機ポリイソシアネート、ならびにモノアルコールまたは多価アルコールのエチレンオキサイド単独もしくはエチレンオキサイド及びプロピレンオキサイド付加物から合成されるＮＣＯ基含有ウレタンプレポリマーに疎水性化合物を添加し、水中に乳化後、多価アミン化合物や水で鎖伸長して得られるノニオン性ポリウレタン樹脂水分散体。 (2) Hydrophobic compounds to NCO group-containing urethane prepolymers synthesized from two or more active hydrogen atom-containing compounds, organic polyisocyanates, and mono- or polyhydric alcohol ethylene oxide alone or ethylene oxide and propylene oxide adducts An aqueous dispersion of nonionic polyurethane resin obtained by adding a polymer, emulsifying in water, and then chain-extending with a polyamine compound or water.
（３）２個以上の活性水素原子含有化合物、有機ポリイソシアネートから合成されるＮＣＯ基含有ウレタンプレポリマーをアニオン、カチオン、ノニオン性等の界面活性剤と疎水性化合物を添加し、水中に乳化後、多価アミン化合物や水で鎖伸長して得られるポリウレタン樹脂水分散体。 (3) An NCO group-containing urethane prepolymer synthesized from two or more active hydrogen atom-containing compounds and an organic polyisocyanate is added with an anion, cation, nonionic surfactant and a hydrophobic compound, and then emulsified in water. An aqueous polyurethane resin dispersion obtained by chain elongation with a polyamine compound or water.
（４）２個以上の活性水素原子含有化合物、有機ポリイソシアネート、ならびにＮＣＯ基と反応性の活性水素原子及び塩形成基を有する化合物から合成されるＮＣＯ基含有ウレタンプレポリマーに塩形成剤とアニオン、カチオン、ノニオン性等の界面活性剤を添加し、水中に乳化後、多価アミン化合物や水で鎖伸長して得られるアニオン性、またはカチオン性ポリウレタン樹脂水分散体が挙げられる。 (4) An NCO group-containing urethane prepolymer synthesized from two or more active hydrogen atom-containing compounds, an organic polyisocyanate, and a compound having an active hydrogen atom reactive with an NCO group and a salt-forming group. An anionic or cationic polyurethane resin aqueous dispersion obtained by adding a surfactant such as cation or nonionic, emulsifying in water, and then chain-extending with a polyamine compound or water.
［ＯＨ基末端ウレタンポリマーの乳化方法］
（１）２個以上の活性水素原子含有化合物、有機ポリイソシアネート、ならびにＮＣＯ基と反応性の活性水素原子及び塩形成基を有する化合物から合成されるＯＨ基末端ウレタンポリマーに塩形成剤と疎水性化合物を添加し、水中に乳化して得られるアニオン性、またはカチオン性ポリウレタン樹脂水分散体。
[Emulsification method of OH group-terminated urethane polymer]
(1) OH group-terminated urethane polymer synthesized from two or more active hydrogen atom-containing compounds, organic polyisocyanate, and a compound having an active hydrogen atom reactive with NCO group and a salt-forming group. An anionic or cationic polyurethane resin aqueous dispersion obtained by adding a compound and emulsifying in water.
（２）２個以上の活性水素原子含有化合物、有機ポリイソシアネート、ならびにモノアルコールまたは多価アルコールのエチレンオキサイド単独もしくはエチレンオキサイド及びプロピレンオキサイド付加物から合成されるＯＨ基末端ウレタンポリマーに疎水性化合物を添加し、水中に乳化して得られるノニオン性ポリウレタン樹脂水分散体。 (2) Hydrophobic compound to OH group-terminated urethane polymer synthesized from two or more active hydrogen atom-containing compounds, organic polyisocyanate, and mono- or polyhydric alcohol ethylene oxide alone or ethylene oxide and propylene oxide adduct A nonionic polyurethane resin aqueous dispersion obtained by adding and emulsifying in water.
（３）２個以上の活性水素原子含有化合物、有機ポリイソシアネートから合成されるＯＨ基末端ウレタンポリマーにアニオン、カチオン、ノニオン性等の界面活性剤と疎水性化合物を添加し、水中に乳化して得られるポリウレタン樹脂水分散体。 (3) An anion, cation, nonionic surfactant and hydrophobic compound are added to an OH group-terminated urethane polymer synthesized from two or more active hydrogen atom-containing compounds and organic polyisocyanate and emulsified in water. Obtained polyurethane resin aqueous dispersion.
（４）２個以上の活性水素原子含有化合物、有機ポリイソシアネート、ならびにＮＣＯ基と反応性の活性水素原子及び塩形成基を有する化合物から合成されるＯＨ基末端ウレタンポリマーに塩形成剤とアニオン、カチオン、ノニオン性等の界面活性剤と疎水性化合物を添加し、水中に乳化して得られるアニオン性、またはカチオン性ポリウレタン樹脂水分散体が挙げられる。 (4) an OH group-terminated urethane polymer synthesized from two or more active hydrogen atom-containing compounds, an organic polyisocyanate, and a compound having an active hydrogen atom reactive with an NCO group and a salt-forming group; a salt-forming agent and an anion; An anionic or cationic polyurethane resin aqueous dispersion obtained by adding a cationic and nonionic surfactant and a hydrophobic compound and emulsifying the mixture in water may be mentioned.
本発明に於ける上記２個以上の活性水素原子を有する化合物は、ウレタン工業の分野において周知のものを使用することが出来る。 As the compound having two or more active hydrogen atoms in the present invention, those known in the field of urethane industry can be used.
この化合物は、分子末端または分子内に２個以上のヒドロキシル基、アミノ基またはメルカプト基を有するもので、一般に公知のポリエーテル、ポリエステル、ポリエーテルエステル、ポリカーボネート、ポリチオエーテル、ポリアセタール、ポリオレフィン、ポリシロキサン、フッ素系、植物油系等を例示することが出来、好ましいのは、分子末端に２個以上のヒドロキシル基を有する化合物である。なお、これら活性水素基を２個以上有する化合物の分子量は、５０〜５，０００の範囲であることが好ましい。 This compound has two or more hydroxyl groups, amino groups or mercapto groups at the molecular end or in the molecule, and is generally known polyether, polyester, polyether ester, polycarbonate, polythioether, polyacetal, polyolefin, polysiloxane. , Fluorine-based, vegetable oil-based and the like can be exemplified, and a compound having two or more hydroxyl groups at the molecular end is preferable. The molecular weight of the compound having two or more active hydrogen groups is preferably in the range of 50 to 5,000.
具体的には、２個以上の活性水素原子を有する基を有する化合物としては、エチレングリコール、プロピレングリコール、プロパンジオール、ブタンジオール、ペンタンジオール、３−メチル−１，５−ペンタンジオール、ヘキサンジオール、ネオペチルグリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ポリエチレングリコール、ジプロピレングリコール、トリプロピレングリコール、１，４−シクロヘキサンジメタノール、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、水素添加ビスフェノールＡ、ジブロモビスフェノールＡ、１，４−シクロヘキサンジメタノール、ジヒドロキシエチルテレフタレート、ハイドロキノンジヒドロキシエチルエーテル、トリメチロールプロパン、グリセリン、ペンタエリスリトール等の多価アルコール、それらのオキシアルキレン誘導体又はそれらの多価アルコール及びオキシアルキレン誘導体と多価カルボン酸、多価カルボン酸無水物、若しくは多価カルボン酸エステルからのエステル化物、ポリカーボネートポリオール、ポリカプロラクトンポリオール、ポリエステルポリオール、ポリチオエーテルポリオール、ポリアセタールポリオール、ポリテトラメチレングリコール、ポリブタジエンポリオール、ヒマシ油ポリオール、大豆油ポリオール、フッ素ポリオール、シリコンポリオール等のポリオール化合物やその変性体が挙げられる。アルキレンオキサイドとしては、エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイドなどが挙げられる。これら２個以上の活性水素原子を有する基を有する化合物は、単独で使用してもよく、２種以上を併用してもよい。 Specifically, examples of the compound having a group having two or more active hydrogen atoms include ethylene glycol, propylene glycol, propanediol, butanediol, pentanediol, 3-methyl-1,5-pentanediol, hexanediol, Neopetyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, 1,4-cyclohexanedimethanol, bisphenol A, bisphenol F, bisphenol S, hydrogenated bisphenol A, dibromobisphenol A 1,4-cyclohexanedimethanol, dihydroxyethyl terephthalate, hydroquinone dihydroxyethyl ether, trimethylolpropane, Polyhydric alcohols such as serine and pentaerythritol, their oxyalkylene derivatives or their polyhydric alcohols and oxyalkylene derivatives and polycarboxylic acids, polycarboxylic anhydrides, or esterified products from polycarboxylic esters, polycarbonates Examples include polyol compounds such as polyol, polycaprolactone polyol, polyester polyol, polythioether polyol, polyacetal polyol, polytetramethylene glycol, polybutadiene polyol, castor oil polyol, soybean oil polyol, fluorine polyol, and silicon polyol, and modified products thereof. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide and the like. These compounds having a group having two or more active hydrogen atoms may be used alone or in combination of two or more.
本発明に於ける有機ポリイソシアネート化合物は、ウレタン工業会の分野において周知であり、任意のものを使用し得る。有機ポリイソシアネート化合物としては、トリレンジイソシアネート（ＴＤＩ）、ジフェニルメタンジイソシアネート（ＭＤＩ）ポリメリックＭＤＩ、ヘキサメチレンジイソシアネート（ＨＭＤＩ）、キシリレンジイソシアネート（ＸＤＩ）、テトラメチルキシリレンジイソシアネート（ＴＭＸＤＩ）、イソホロンジイソシアネート（ＩＰＤＩ）、水素添加ＭＤＩ（Ｈ１２ＭＤＩ）、リジンジイソシアネート、ナフタレンジイソシアネート、ノルボルナフタレンジイソシアネート、ビューレット化ヘキサメチレンジイソシアネート、イソシアヌレート化ヘキサメチレンジイソシアネート等の各種の芳香族、脂肪族、脂環族等のイソシアネート類を単独又は混合して使用することが出来る。 The organic polyisocyanate compound in the present invention is well known in the field of the urethane industry association, and any can be used. Organic polyisocyanate compounds include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) polymeric MDI, hexamethylene diisocyanate (HMDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), and isophorone diisocyanate (IPDI). Various aromatic, aliphatic and alicyclic isocyanates such as hydrogenated MDI (H12MDI), lysine diisocyanate, naphthalene diisocyanate, norbornaphthalene diisocyanate, buretted hexamethylene diisocyanate, isocyanurated hexamethylene diisocyanate It can be used alone or in combination.
本発明の水系ポリウレタン樹脂でＮＣＯ基を有するウレタンプレポリマーを乳化分散する場合は、多価アミン化合物あるいは水との反応により高分子量化するが、多価アミン化合物としては、例えばエチレンジアミン、トリメチレンジアミン、プロピレンジアミン、ジエチレントリアミン、トリエチレンテトラミンなどの脂肪族ポリアミン化合物、メタキシレンジアミン、トリレンジアミン、ジアミノジフェニルメタン等の芳香族ポリアミン化合物、ピペラジン、イソホロンジアミン等の脂環族ポリアミン化合物、ヒドラジン、アジピン酸ジヒドラジドのようなポリヒドラジド化合物等が挙げられる。これらのポリアミン化合物は単独で使用してもよく、２種以上を併用してもよい。また、ポリマー化を大きく阻害しない程度に反応停止剤としてジブチルアミンなどの１価のアミンやメチルエチルケトオキシムのような反応停止剤を使用してもよい。 When the urethane prepolymer having an NCO group is emulsified and dispersed in the water-based polyurethane resin of the present invention, the polymer is increased in molecular weight by reaction with a polyvalent amine compound or water. Examples of the polyvalent amine compound include ethylenediamine and trimethylenediamine. , Aliphatic polyamine compounds such as propylenediamine, diethylenetriamine and triethylenetetramine, aromatic polyamine compounds such as metaxylenediamine, tolylenediamine and diaminodiphenylmethane, alicyclic polyamine compounds such as piperazine and isophoronediamine, hydrazine and adipic acid dihydrazide And polyhydrazide compounds such as These polyamine compounds may be used alone or in combination of two or more. Further, a monovalent amine such as dibutylamine or a reaction terminator such as methyl ethyl ketoxime may be used as a reaction terminator to such an extent that the polymerization is not greatly inhibited.
本発明に使用されるＮＣＯ基と反応性の活性水素原子及び塩形成基を有する化合物及びそれに対応する塩形成剤としては、１）塩形成性のカルボン酸またはスルホン酸基を有する化合物及び対応する塩形成剤、２）酸で中和可能な第４級または第３級基になり得る基を有する化合物及び対応する塩形成剤が挙げられる。 The compound having an active hydrogen atom reactive with an NCO group and a salt-forming group and a corresponding salt-forming agent used in the present invention are as follows: 1) a compound having a salt-forming carboxylic acid or sulfonic acid group and the corresponding compound Salt-forming agents, 2) compounds having groups that can be quaternary or tertiary groups neutralizable with acids and the corresponding salt-forming agents.
上記１）の場合の塩形成性のカルボン酸またはスルホン酸基を有する化合物としては、例えばグリコール酸、リンゴ酸、グリシン、アミノ安息香酸、アラニン、ジメチロールプロピオン酸、ジメチロールブタン酸等のヒドロキシ酸、アミノカルボン酸、多価ヒドロキシ酸類やアミノエチルスルホン酸、２−ヒドロキシエタンスルホン酸等のアミノスルホン酸、ヒドロキシスルホン酸類等が挙げられる。また、それに対応する塩形成剤としては、例えば水酸化カリウム、水酸化ナトリウム、水酸化カルシウム等の１価の金属水酸化物やアンモニア、トリメチルアミン、トリエチルアミン等の３級アミン化合物等が挙げられる。 Examples of the compound having a salt-forming carboxylic acid or sulfonic acid group in the case of 1) above are hydroxy acids such as glycolic acid, malic acid, glycine, aminobenzoic acid, alanine, dimethylolpropionic acid, dimethylolbutanoic acid and the like. Aminocarboxylic acids, polyvalent hydroxy acids, aminoethylsulfonic acids, aminosulfonic acids such as 2-hydroxyethanesulfonic acid, hydroxysulfonic acids, and the like. Examples of the corresponding salt forming agent include monovalent metal hydroxides such as potassium hydroxide, sodium hydroxide and calcium hydroxide, and tertiary amine compounds such as ammonia, trimethylamine and triethylamine.
上記２）の酸で中和可能な第４級または第３級基になり得る基を有する化合物としては、例えばＮ，Ｎ−ジメチルエタノールアミン、Ｎ−メチルジエタノールアミン、Ｎ−エチルジエタノールアミン等のＮ−アルキルジアルカノールアミン、Ｎ−メチルジアミノエチルアミン、Ｎ−エチルジアミノエチルアミン等のＮ−アルキルジアミノアルキルアミン等が挙げられる。これらの化合物は単独で使用してもよく、２種以上を併用してもよい。また、それらに対応する塩形成剤として、例えば蟻酸、酢酸、プロピオン酸、酪酸、乳酸、リンゴ酸、マロン酸、アジピン酸、硫酸ジメチル、硫酸ジエチル、メチルクロライド、ベンジルクロライド等の有機酸類、ギ酸、塩酸、燐酸、硝酸等の無機酸類、反応性ハロゲン原子を有する化合物が挙げられる。 Examples of the compound having a group capable of becoming a quaternary or tertiary group that can be neutralized with an acid of 2) above include N-N such as N, N-dimethylethanolamine, N-methyldiethanolamine, and N-ethyldiethanolamine. Examples thereof include N-alkyldiaminoalkylamines such as alkyl dialkanolamine, N-methyldiaminoethylamine, and N-ethyldiaminoethylamine. These compounds may be used alone or in combination of two or more. Further, as salt forming agents corresponding thereto, for example, formic acid, acetic acid, propionic acid, butyric acid, lactic acid, malic acid, malonic acid, adipic acid, dimethyl sulfate, diethyl sulfate, methyl chloride, benzyl chloride and other organic acids, formic acid, Examples thereof include inorganic acids such as hydrochloric acid, phosphoric acid, and nitric acid, and compounds having a reactive halogen atom.
本発明に使用されるモノアルコール又は多価アルコールのエチレンオキサイド単独もしくはエチレンオキサイド及びプロピレンオキサイド付加物におけるモノアルコールとしては、メタノール、エタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール、ヘプタノール、オクタノール、ラウリルアルコール等が、多価アルコールとしては前記多価アルコール等がそれぞれ挙げられる。 Examples of monoalcohols used in the present invention include monoalcohol or polyalcohol ethylene oxide alone or ethylene oxide and propylene oxide adducts such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, lauryl alcohol, etc. However, examples of the polyhydric alcohol include the polyhydric alcohols.
本発明の水系ウレタン樹脂の製造に使用されるアニオン、カチオン、ノニオン、両性等の乳化用界面活性剤として通常、界面活性剤の分野で使用されているもの全てが単独または併用が挙げられる。 As the surfactant for emulsification such as anion, cation, nonion and amphoteric used in the production of the water-based urethane resin of the present invention, all those usually used in the field of surfactants may be used alone or in combination.
上記エネルギー線硬化水系樹脂組成物において、水系ウレタン樹脂（Ａ）と（メタ）アクリレート系化合物（Ｂ）との配合比率（Ａ／Ｂ）は重量固形分比率で１００／３０〜３／１００の範囲で用いられる。 In the energy ray-curable water-based resin composition, the blending ratio (A / B) of the water-based urethane resin (A) and the (meth) acrylate-based compound (B) is in the range of 100/30 to 3/100 in terms of weight solid content. Used in
（メタ）アクリレート系化合物（Ｂ）の配合比率が水系ウレタン樹脂（Ａ）対して３０重量％未満では、架橋性が不十分となり、耐薬品性、耐汚染性が不十分となる。また、水系ウレタン樹脂（Ａ）が水系樹脂組成物の３重量％未満になると密着性、耐屈曲性が不十分となる。 When the blending ratio of the (meth) acrylate compound (B) is less than 30% by weight with respect to the water-based urethane resin (A), the crosslinkability is insufficient, and the chemical resistance and stain resistance are insufficient. On the other hand, when the water-based urethane resin (A) is less than 3% by weight of the water-based resin composition, the adhesion and the bending resistance are insufficient.
（メタ）アクリレート化合物としてモノマー類、ウレタン（メタ）アクリレート化合物、ポリエステル（メタ）アクリレート系化合物、エポキシ（メタ）アクリレート等が挙げられる。その中でも特にモノマー類が望ましい。更に分子中に２個以上のエネルギー線硬化性の不飽和二重結合を含有するモノマー類が好ましい。モノマー類としては、公知慣用のものが使用可能であるが、中でも代表的なものとして、アクリロイルモルホリン、２−エチルヘキシル（メタ）アクリレート、スチレン、メチルメタクリレート、テトラヒドロフルフリル（メタ）アクリレート、ドデシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、Ｎ−ビニル−２−ピロリドン、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、ネオペンチルグリコールジ（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、１，４−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、エチレンオキサイド変性ビスフェノールジ（メタ）アクリレート、プロピレンオキサイド変性ビスフェノールジ（メタ）アクリレート、エチレンオキサイド変性トリメチロールプロパントリ（メタ）アクリレート、プロピレンオキサイド変性トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、トリス（メタ）アクリロキシエチル）イソシアヌレート、ジペンタエリスリトールペンタ（メタ）アクリレート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る。これらは１種を単独で用いてもよく、複数種を併用してもよい。 Examples of the (meth) acrylate compound include monomers, urethane (meth) acrylate compounds, polyester (meth) acrylate compounds, and epoxy (meth) acrylates. Of these, monomers are particularly desirable. Furthermore, monomers containing two or more energy ray-curable unsaturated double bonds in the molecule are preferred. As the monomers, known and commonly used monomers can be used. Among them, typical examples include acryloylmorpholine, 2-ethylhexyl (meth) acrylate, styrene, methyl methacrylate, tetrahydrofurfuryl (meth) acrylate, dodecyl (meth) ) Acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, N-vinyl-2-pyrrolidone, ethylene glycol Di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene Glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene oxide modified bisphenol di (meth) acrylate, propylene oxide modified bisphenol di (meth) Acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tris (meth) acryloxyethyl) Examples include isocyanurate and dipentaerythritol penta (meth) acrylate dipentaerythritol hexa (meth) acrylate. These may be used individually by 1 type and may use multiple types together.
この中でも特にペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレートが好ましい。 Among these, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are particularly preferable.
前記（メタ）アクリレート化合物の添加方法は、水系ウレタン樹脂合成時に前記（メタ）アクリレート化合物を添加した後に、ウレタン樹脂と共に水に乳化分散してもよいし、前記（メタ）アクリレート化合物にアニオン、カチオン、ノニオン、両性等の乳化用界面活性剤を添加して乳化、分散して得られた乳化物を前記ウレタン樹脂に添加してもよい。 The (meth) acrylate compound may be added by emulsifying and dispersing in water together with the urethane resin after adding the (meth) acrylate compound during the synthesis of the aqueous urethane resin. An emulsion obtained by adding and emulsifying a surfactant for emulsification, such as nonionic and amphoteric, may be added to the urethane resin.
本発明のエネルギー線硬化型水系樹脂組成物には、必要に応じて光重合開始剤を添加する。光重合開始剤の種類は特に限定されず、公知のものが使用可能であるが、代表的な例としては、１−ヒドロキシ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、ベンジルジメチルケタール、ベンゾインイソプロピルエーテル、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、複数種を併用してもよい。 If necessary, a photopolymerization initiator is added to the energy beam curable aqueous resin composition of the present invention. The type of the photopolymerization initiator is not particularly limited, and known ones can be used. Typical examples include 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenylpropane-1. -One, benzyl dimethyl ketal, benzoin isopropyl ether, benzophenone and the like. These may be used individually by 1 type and may use multiple types together.
また、光重合開始剤を使用する場合のその添加量は、（メタ）アクリレート化合物に対し、１〜１０重量％程度であり、約３〜５重量％が好ましい。 Moreover, the addition amount in the case of using a photoinitiator is about 1 to 10 weight% with respect to a (meth) acrylate compound, and about 3 to 5 weight% is preferable.
光重合開始剤の添加方法は、水溶性タイプはそのまま添加してもよいが、非水溶性タイプは、光重合開始剤にアニオン、カチオン、ノニオン、両性等の乳化用界面活性剤を添加後、水を添加して乳化して得られた乳化物を添加してもよい。また、キサンタンガム、ポリビニルアルコール、カルボキシメチルセルロースナトリウム塩等の保護コロイド剤を併用してもよい。 As for the method of adding the photopolymerization initiator, the water-soluble type may be added as it is, but the water-insoluble type may be added after adding a surfactant for emulsification such as anion, cation, nonion, amphoteric to the photopolymerization initiator, You may add the emulsion obtained by adding water and emulsifying. Moreover, you may use together protective colloid agents, such as a xanthan gum, polyvinyl alcohol, and carboxymethylcellulose sodium salt.
さらに、本発明のエネルギー線硬化水系樹脂組成物には、必要に応じて、光安定剤、紫外線吸収剤、触媒、着色剤、帯電防止剤、滑剤、レベリング剤、消泡剤、重合促進剤、酸化防止剤、難燃剤、赤外線吸収剤、界面活性剤、表面改質剤等を添加することができる。 Furthermore, the energy ray curable water-based resin composition of the present invention includes a light stabilizer, an ultraviolet absorber, a catalyst, a colorant, an antistatic agent, a lubricant, a leveling agent, an antifoaming agent, a polymerization accelerator, if necessary. Antioxidants, flame retardants, infrared absorbers, surfactants, surface modifiers, and the like can be added.
なお、本発明のエネルギー線硬化型水系樹脂組成物を硬化させるエネルギー線源は特に限定されないが、例としては、高圧水銀灯、電子線、γ線、カーボンアーク灯、キセノン灯、メタルハライド灯等が挙げられる。 The energy ray source for curing the energy ray curable aqueous resin composition of the present invention is not particularly limited, and examples include high pressure mercury lamp, electron beam, γ ray, carbon arc lamp, xenon lamp, metal halide lamp and the like. It is done.
以下、本発明を実施例および比較例によりさらに具体的に説明するが、本発明はこれらの実施例に何ら限定されるものではない。なお、以下において、配合比率及び「％」は、特に断らないかぎり、全て重量基準であるものとする。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples at all. In the following, the blending ratio and “%” are all based on weight unless otherwise specified.
［合成例１］（Ａ−１）
攪拌機、還流冷却管、温度計および窒素吹き込み管を備えた４つ口フラスコにポリカーボネートポリオール（日本ポリウレタン工業（株）製、ニッポラン９８１、活性水素原子数２）２３４重量部、トリメチロールプロパン１１．７重量部、ジメチロールプロピオン酸２３．４重量部、ジシクロヘキシルメタンジイソシアネート１８７重量部、メチルエチルケトン５００重量部を加え、７５℃で４時間反応させ、不揮発分に対する遊離のイソシアネート基含有量３．１％であるウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液を４５℃まで冷却し、トリエチルアミンを１４．２重量部加え中和後、水９７０重量部を徐々に加えてホモジナイザーを使用し乳化分散させた。その後、エチレンジアンミンを８．２重量部添加してアミン伸長した。これを減圧、５０℃下、脱溶剤を行い、不揮発分約３２％のポリウレタン水分散体を得た。
[Synthesis Example 1] (A-1)
A four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube is provided with 234 parts by weight of polycarbonate polyol (manufactured by Nippon Polyurethane Industry Co., Ltd., Nipponran 981, number of active hydrogen atoms 2), trimethylolpropane 11.7. Parts by weight, 23.4 parts by weight of dimethylolpropionic acid, 187 parts by weight of dicyclohexylmethane diisocyanate, and 500 parts by weight of methyl ethyl ketone are added and reacted at 75 ° C. for 4 hours to have a free isocyanate group content of 3.1% based on the nonvolatile content. A methyl ethyl ketone solution of urethane prepolymer was obtained. The solution was cooled to 45 ° C., neutralized by adding 14.2 parts by weight of triethylamine, 970 parts by weight of water was gradually added, and the mixture was emulsified and dispersed using a homogenizer. Thereafter, 8.2 parts by weight of ethylenediamine was added to extend the amine. The solvent was removed under reduced pressure at 50 ° C. to obtain a polyurethane water dispersion having a nonvolatile content of about 32%.
［合成例２］（Ａ−２）
攪拌機、還流冷却管、温度計および窒素吹き込み管を備えた４つ口フラスコにポリエステルポリオール（日立化成ポリマー（株）製、テスラック２５０８−７０、活性水素原子数２）４３７重量部、トリメチロールプロパン７．６重量部、ジメチロールプロピオン酸５５重量部、イソホロンジイソシアネート１５８重量部、メチルエチルケトン２８４重量部を加え、７５℃で４時間反応させ、不揮発分に対する遊離のイソシアネート基含有量０．８％であるウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液を４５℃まで冷却し、トリエチルアミンを２４．８重量部加え中和後、水１１１８重量部を徐々に加えてホモジナイザーを使用し乳化分散させた。これを減圧、５０℃下、脱溶剤を行い、不揮発分３５％のポリウレタン水分散体を得た。
[Synthesis Example 2] (A-2)
A four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube was charged with 437 parts by weight of polyester polyol (manufactured by Hitachi Chemical Co., Ltd., Teslac 2508-70, number of active hydrogen atoms 2), trimethylolpropane 7 .6 parts by weight, 55 parts by weight of dimethylolpropionic acid, 158 parts by weight of isophorone diisocyanate, and 284 parts by weight of methyl ethyl ketone were reacted at 75 ° C. for 4 hours, and the urethane having a free isocyanate group content of 0.8% relative to the nonvolatile content A methyl ethyl ketone solution of the prepolymer was obtained. The solution was cooled to 45 ° C., neutralized by adding 24.8 parts by weight of triethylamine, and gradually added 1118 parts by weight of water and emulsified and dispersed using a homogenizer. The solvent was removed under reduced pressure at 50 ° C. to obtain a polyurethane water dispersion having a nonvolatile content of 35%.
［アクリレート化合物の乳化物］（Ｂ−１）
ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物(日本化薬（株）製、ＫＡＹＡＲＡＤ ＤＰＨＡ)１００ｇにポリビニルアルコール（クラレ（株）製、ＰＶＡ−２１７Ｅ）の１０％水溶液を１１１ｇ、ポリオキシエチレンジスチリルフェニルエーテル硫酸エステルアンモニウム塩（第一工業製薬（株）製、ハイテノールＮＦ−１３）６ｇを添加し、水を徐々に添加しながらミキサーで乳化して乳化物を得た。
[Emulsion of acrylate compound] (B-1)
A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA) and 111 g of a 10% aqueous solution of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-217E), polyoxyethylene 6 g of distyrylphenyl ether sulfate ammonium salt (Daiichi Kogyo Seiyaku Co., Ltd., Haitenol NF-13) was added, and the mixture was emulsified with a mixer while gradually adding water to obtain an emulsion.
［アクリレート化合物の乳化方法］（Ｂ−２）
ペンタエリスリトールトリアクリレートとペンタエリスリトールテトラアクリレートの混合物（第一工業製薬（株）製、ニューフロンティアＰＥＴ−３）１００ｇにポリビニルアルコール（クラレ（株）製、ＰＶＡ２１７Ｅ）の１０％水溶液を１１１ｇ、ポリオキシエチレンジスチリルフェニルエーテル硫酸エステルアンモニウム塩（第一工業製薬（株）製、ハイテノールＮＦ−１３）６ｇを添加し、水を徐々に添加しながらミキサーで乳化して乳化物を得た。
[Method of emulsifying acrylate compound] (B-2)
A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (Daiichi Kogyo Seiyaku Co., Ltd., New Frontier PET-3) 100 g and polyvinyl alcohol (Kuraray Co., Ltd., PVA217E) 10% aqueous solution 111 g, polyoxyethylene 6 g of distyrylphenyl ether sulfate ammonium salt (Daiichi Kogyo Seiyaku Co., Ltd., Haitenol NF-13) was added, and the mixture was emulsified with a mixer while gradually adding water to obtain an emulsion.
［光重合開始剤の乳化物］
２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン（チバ・スペシャリティケミカルズ（株）製、イルガキュア５００）１００ｇにポリオキシエチレンジスチリルフェニルエーテル硫酸エステルアンモニウム塩（第一工業製薬（株）製、ハイテノールＮＦ−１３）を２０ｇ添加し、水１００ｇを攪拌しながら加え、乳化して乳化物を得た。
[Emulsion of photopolymerization initiator]
Polyhydroxyethylene distyryl phenyl ether sulfate ammonium salt (Daiichi Kogyo Seiyaku Co., Ltd.) to 100 g of 2-hydroxy-2-methyl-1-phenylpropan-1-one (Ciba Specialty Chemicals Co., Ltd., Irgacure 500) 20 g of Hytenol NF-13) was added, and 100 g of water was added with stirring and emulsified to obtain an emulsion.
［実施例１〜８及び比較例１〜３］
上記合成例で得られた水系ウレタン樹脂、アクリレート化合物の乳化物、光重合開始剤の乳化物を配合して表１に記載の実施例、比較例の水系樹脂組成物を得た。
[Examples 1-8 and Comparative Examples 1-3]
The aqueous urethane resin obtained in the above synthesis example, an emulsion of an acrylate compound, and an emulsion of a photopolymerization initiator were blended to obtain aqueous resin compositions of Examples and Comparative Examples shown in Table 1.
実施例１〜８は水分散性樹脂（Ａ）と（メタ）アクリレート系化合物（Ｂ）との配合比率が重量固形分比率で１００／３０〜３／１００の範囲であり、比較例１〜３はそれ以外の範囲である。 In Examples 1 to 8, the mixing ratio of the water-dispersible resin (A) and the (meth) acrylate-based compound (B) is in the range of 100/30 to 3/100 in terms of weight solid content, and Comparative Examples 1 to 3 are used. Is the other range.
得られた水系樹脂組成物について、以下の要領で、密着性、耐アルカリ性、耐汚染性、耐屈曲性を測定した。結果を表２に示す。 The obtained aqueous resin composition was measured for adhesion, alkali resistance, stain resistance, and flex resistance in the following manner. The results are shown in Table 2.
・硬化条件
各樹脂組成物を各種基板に乾燥膜厚が３０μｍになるようにスピンコーターで塗布し、１００℃のオーブンで１０分間乾燥させたものに、８０Ｗ／ｃｍの高圧水銀灯を用いて積算照度１７０ｍＪ／ｃｍ２の紫外線を照射した。
Curing conditions Each resin composition was applied to various substrates with a spin coater so that the dry film thickness was 30 μm, and dried for 10 minutes in an oven at 100 ° C., and integrated illuminance using an 80 W / cm high-pressure mercury lamp Irradiation with ultraviolet rays of 170 mJ / cm 2 was performed.
・基材の種類
基材の種類としてはコロナ放電処理ポリエチレンテレフタレートフィルム（ＰＥＴ）、ポリカーボネートフィルム（ＰＣ）、亜鉛メッキ鋼鈑を使用した。
-Types of base materials As the types of base materials, corona discharge-treated polyethylene terephthalate film (PET), polycarbonate film (PC), and galvanized steel sheet were used.
・密着性
上記条件で各種基材上に硬化させた塗膜を碁盤目セロテープ剥離試験で密着性を評価した。（〇；９０／１００以上 △；５０〜９０／１００、×；５０／１００未満）
・耐アルカリ性
上記条件で各種基材上に硬化させた塗膜に５％水酸化ナトリウム水溶液を１滴落とし、１０分間静置する。ティッシュで拭き取り、フィルムに変化がないか目視にて確認する。（◎；全く変化なし、○；殆ど変化なし、△；多少変化あり）
・耐汚染性
上記条件で各種基材上に硬化させた塗膜を油性の赤、黒、青のマーキングペンで約２０ｍｍの線で線を描き、１８時間静置する。エタノールで拭き取り、塗膜が汚染されているか目視にて観察する。（◎；全く汚染なし、〇；殆ど汚染なし、△；多少変色あり）
・耐屈曲性
上記条件で各種基材上に硬化させた試験片を１８０°折り曲げた後の塗膜外観を観察した。（○；変化なし、×；割れ発生）
-Adhesiveness Adhesiveness was evaluated by the cross cut cell tape peeling test for the coating film hardened | cured on various base materials on the said conditions. (◯; 90/100 or more Δ; 50 to 90/100, ×; less than 50/100)
Alkali resistance One drop of 5% aqueous sodium hydroxide solution is dropped on the coating film cured on various substrates under the above conditions and left to stand for 10 minutes. Wipe with a tissue and check visually for any changes in the film. (◎: No change, ○: Almost no change, △: Some change)
-Contamination resistance The coating film cured on various substrates under the above conditions is drawn with an oil-based red, black, and blue marking pen with a line of about 20 mm, and left for 18 hours. Wipe off with ethanol and visually observe if the coating is contaminated. (◎: No contamination, ○: Almost no contamination, △: Some discoloration)
-Flexibility The appearance of the coating film was observed after bending the test pieces cured on various substrates under the above conditions by 180 °. (○: No change, ×: Crack generation)
表２から分かるように、実施例１〜８は、比較例１〜３に比べて密着性、耐薬品性、耐汚染性、耐屈曲性に優れている。 As can be seen from Table 2, Examples 1 to 8 are superior in adhesion, chemical resistance, contamination resistance, and flex resistance compared to Comparative Examples 1 to 3.
本発明の樹脂組成物は、塗料として各種建材、構造物、成型物等のコーティングに用いられるほか、紙コーティング、レジスト用材料、接着剤、電子機器の部品等にも用いることができる。 The resin composition of the present invention can be used as a coating material for coating various building materials, structures, molded articles and the like, as well as paper coatings, resist materials, adhesives, electronic device parts, and the like.
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| JP2012149141A (en) * | 2011-01-18 | 2012-08-09 | Jsr Corp | Active energy ray-curing aqueous emulsion composition, method for manufacturing the same, method for forming cured film, and hard coat forming agent |
| US8552109B2 (en) | 2008-05-29 | 2013-10-08 | Ube Industries, Ltd. | Aqueous polyurethane resin dispersion, preparation method of the same, and coating composition containing the same |
| JP2013237835A (en) * | 2012-04-20 | 2013-11-28 | Jsr Corp | Activation energy curable water-based emulsion composition, production method thereof, cured coating film forming method, and hard coat forming agent |
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