JP6311880B2 - Film-forming composition and film-forming method - Google Patents
Film-forming composition and film-forming method Download PDFInfo
- Publication number
- JP6311880B2 JP6311880B2 JP2014152512A JP2014152512A JP6311880B2 JP 6311880 B2 JP6311880 B2 JP 6311880B2 JP 2014152512 A JP2014152512 A JP 2014152512A JP 2014152512 A JP2014152512 A JP 2014152512A JP 6311880 B2 JP6311880 B2 JP 6311880B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- forming composition
- mass
- component
- glycol
- 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.)
- Active
Links
- 239000000203 mixture Substances 0.000 title claims description 68
- 238000000034 method Methods 0.000 title claims description 29
- 239000011248 coating agent Substances 0.000 claims description 27
- 238000000576 coating method Methods 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- -1 isobutyl glycol Chemical compound 0.000 claims description 20
- 238000005498 polishing Methods 0.000 claims description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 229920000058 polyacrylate Polymers 0.000 claims description 12
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- 239000012780 transparent material Substances 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000004925 Acrylic resin Substances 0.000 claims description 6
- 229920000178 Acrylic resin Polymers 0.000 claims description 6
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 5
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 229920005668 polycarbonate resin Polymers 0.000 claims description 3
- 239000004431 polycarbonate resin Substances 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 3
- XLYOFNOQVPJJNP-DYCDLGHISA-N deuterium hydrogen oxide Chemical compound [2H]O XLYOFNOQVPJJNP-DYCDLGHISA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 23
- 238000011156 evaluation Methods 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 238000012360 testing method Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004383 yellowing Methods 0.000 description 9
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 239000000443 aerosol Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000004417 polycarbonate Substances 0.000 description 6
- 229920000515 polycarbonate Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000000470 constituent Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000003380 propellant Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 229920006243 acrylic copolymer Polymers 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- CETWDUZRCINIHU-UHFFFAOYSA-N 2-heptanol Chemical compound CCCCCC(C)O CETWDUZRCINIHU-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- RZKSECIXORKHQS-UHFFFAOYSA-N Heptan-3-ol Chemical compound CCCCC(O)CC RZKSECIXORKHQS-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 125000006226 butoxyethyl group Chemical group 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 2
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- NDVWOBYBJYUSMF-RNFRBKRXSA-N (1r,2r)-2-methylcyclohexan-1-ol Chemical compound C[C@@H]1CCCC[C@H]1O NDVWOBYBJYUSMF-RNFRBKRXSA-N 0.000 description 1
- NDVWOBYBJYUSMF-NKWVEPMBSA-N (1r,2s)-2-methylcyclohexan-1-ol Chemical compound C[C@H]1CCCC[C@H]1O NDVWOBYBJYUSMF-NKWVEPMBSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 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
- MZQZXSHFWDHNOW-UHFFFAOYSA-N 1-phenylpropane-1,2-diol Chemical compound CC(O)C(O)C1=CC=CC=C1 MZQZXSHFWDHNOW-UHFFFAOYSA-N 0.000 description 1
- LXOFYPKXCSULTL-UHFFFAOYSA-N 2,4,7,9-tetramethyldec-5-yne-4,7-diol Chemical compound CC(C)CC(C)(O)C#CC(C)(O)CC(C)C LXOFYPKXCSULTL-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- HHAPGMVKBLELOE-UHFFFAOYSA-N 2-(2-methylpropoxy)ethanol Chemical compound CC(C)COCCO HHAPGMVKBLELOE-UHFFFAOYSA-N 0.000 description 1
- QNVRIHYSUZMSGM-LURJTMIESA-N 2-Hexanol Natural products CCCC[C@H](C)O QNVRIHYSUZMSGM-LURJTMIESA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- FKPLZJCSXGKJNK-UHFFFAOYSA-N 4,4-dimethylpentane-2,3-diol Chemical compound CC(O)C(O)C(C)(C)C FKPLZJCSXGKJNK-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- RNKURRDNOYXATR-UHFFFAOYSA-N 4-methylpentane-2,3-diol Chemical compound CC(C)C(O)C(C)O RNKURRDNOYXATR-UHFFFAOYSA-N 0.000 description 1
- GHMRLAGSBJPPDG-UHFFFAOYSA-N 5-ethyl-2-methylnon-2-enoic acid Chemical compound CCCCC(CC)CC=C(C)C(O)=O GHMRLAGSBJPPDG-UHFFFAOYSA-N 0.000 description 1
- TZTVPRXOBDHAMM-UHFFFAOYSA-N 5-methylhexane-2,3-diol Chemical compound CC(C)CC(O)C(C)O TZTVPRXOBDHAMM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CMKJZFRZWHSKMT-UHFFFAOYSA-N P(=O)(OCC(C)O)(O)O.C(C=C)(=O)O Chemical compound P(=O)(OCC(C)O)(O)O.C(C=C)(=O)O CMKJZFRZWHSKMT-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229940064004 antiseptic throat preparations Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012897 dilution medium Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- VUVZASHBYYMLRC-UHFFFAOYSA-N heptane-2,3-diol Chemical compound CCCCC(O)C(C)O VUVZASHBYYMLRC-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- QCIYAEYRVFUFAP-UHFFFAOYSA-N hexane-2,3-diol Chemical compound CCCC(O)C(C)O QCIYAEYRVFUFAP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- XZSNTZYKCRWZMS-UHFFFAOYSA-N nonane-2,3-diol Chemical compound CCCCCCC(O)C(C)O XZSNTZYKCRWZMS-UHFFFAOYSA-N 0.000 description 1
- XMTUJCWABCYSIV-UHFFFAOYSA-N octane-2,3-diol Chemical compound CCCCCC(O)C(C)O XMTUJCWABCYSIV-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- XLMFDCKSFJWJTP-UHFFFAOYSA-N pentane-2,3-diol Chemical compound CCC(O)C(C)O XLMFDCKSFJWJTP-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Description
本発明は、被膜形成に用いる組成物に関するもので、特に自動車のヘッドライト等の、透明性と耐候性が求められる部材に適用される、透明性被膜を形成するための組成物に関するものである。また当該被膜形成組成物を用いた、透明部材に対する被膜形成方法、特に黄変やくすみ等の生じたヘッドライト等の部材に対する、透明性を復元するための被膜形成方法に関する。 The present invention relates to a composition used for forming a film, and particularly to a composition for forming a transparent film, which is applied to a member that requires transparency and weather resistance, such as an automobile headlight. . The present invention also relates to a method of forming a film on a transparent member using the film-forming composition, and more particularly to a method of forming a film for restoring transparency to a member such as a headlight in which yellowing or dullness has occurred.
従来より、ポリカーボネートやアクリル樹脂といった、高分子素材から成る透明材料は、その加工性や軽量性、コスト優位性などから、自動車等の輸送機器のヘッドライト等の燈火類やリアウィンド、建築材料、水槽、照明カバー、ショーウィンドー等の産業材料として、身の回りで日常的に使用されている。 Conventionally, transparent materials made of polymer materials such as polycarbonate and acrylic resin are used for fireworks such as headlights for transportation equipment such as automobiles, rear windows, building materials, etc. It is used everyday as an industrial material such as water tanks, lighting covers, and show windows.
しかしながら、この様な透明な材料、特に屋外で使用されるものは、紫外線等の影響により高分子素材が劣化したり、添加剤等が分解することにより経時的に黄変する、という問題を生じる。さらに使用状況によっては、細かな擦過により表面が傷つけられ、徐々にくすみが生じ透明性を喪失してしまう、という問題も孕んでいる。 However, such transparent materials, particularly those used outdoors, have the problem that the polymer material deteriorates due to the influence of ultraviolet rays or the like, and the yellowing occurs over time due to the decomposition of additives and the like. . Furthermore, depending on the use situation, there is a problem that the surface is damaged by fine rubbing, and dullness is gradually generated and transparency is lost.
上記問題を解決するため、前記透明材料の透明性を復元されるための方策として引用文献1では、透明部材の表面を無機粒子等を含んで成る前処理剤で研磨処理した後、ここに湿気硬化性のシリコーンレジン等を含んで成るコーティング組成物を塗布するという、透明性回復の手法が提案されている。引用文献2には、損傷したプラスチック表面を予め、特定のグリッド粒度を有する艶出し研磨剤で研磨した後、これに異なるグリッド粒度を有した光沢付与研磨材で処理し、ここにさらにアクリルポリマー、エチレングリコールモノブチルエーテルなどを含んでなる紫外線防御コーティング組成物を塗布することによる、透明性と光透過性の回復手法について提案されている。 In order to solve the above problem, as a measure for restoring the transparency of the transparent material, in the cited document 1, the surface of the transparent member is polished with a pretreatment agent containing inorganic particles and the like, and then moisture is added thereto. A technique for restoring transparency has been proposed in which a coating composition containing a curable silicone resin or the like is applied. In the cited document 2, a damaged plastic surface is previously polished with a polishing abrasive having a specific grid particle size, and then treated with a glossing abrasive having a different grid particle size, and an acrylic polymer, A method for recovering transparency and light transmittance by applying an ultraviolet protective coating composition containing ethylene glycol monobutyl ether or the like has been proposed.
また引用文献3では、当該透明材料と近似する屈折率、光線透過率を有する合成樹脂エマルジョン含有の透明性復元剤、具体的にはカルボキシル基変性アクリル樹脂エマルジョンを含んで成る水性の組成物を、研磨等の前処理をなされていない透明材料に塗布して塗膜を形成する、という透明性復元の手法が提案されている。 Further, in Cited Document 3, a water-based composition comprising a synthetic resin emulsion-containing transparency restoring agent having a refractive index similar to that of the transparent material and a light transmittance, specifically a carboxyl group-modified acrylic resin emulsion, There has been proposed a method for restoring transparency in which a coating film is formed by applying to a transparent material that has not been subjected to pretreatment such as polishing.
このように、高分子材料からなる透明部材の黄変、くすみを取り除き、透明性を復元するための手法については知られているが、いずれも課題を有している。例えば特許文献1、2の技術では、透明性の復元に際し、対象となる部材を予め特定の研磨材等で前処理を行う必要があり、これにより当該基材の表面を所定の状態、すなわちその粗度、あるいは化学状態を精密に調整された状態に変質させておく必要があった。他方で特許文献3の技術では、基材に何ら下処理がなされていないため、組成物の基材に対する密着性は十分ではなく、外部からの物理的刺激により容易に剥離するものである。また基材の透明性復元には当該組成物の塗布を行うのみの処理であるため、塗布後の透明性については十分なものとは言えない。 As described above, methods for removing yellowing and dullness of a transparent member made of a polymer material and restoring transparency are known, but both have problems. For example, in the techniques of Patent Documents 1 and 2, when restoring transparency, it is necessary to pre-treat the target member with a specific abrasive or the like in advance, and thereby the surface of the substrate is in a predetermined state, that is, It was necessary to change the roughness or chemical state to a precisely adjusted state. On the other hand, in the technique of Patent Document 3, since the base material is not subjected to any pretreatment, the adhesiveness of the composition to the base material is not sufficient, and is easily peeled off by physical stimulation from the outside. Moreover, since it is a process which only apply | coats the said composition for the transparency restoration of a base material, it cannot be said that the transparency after application | coating is enough.
本発明では、上記課題を解決するため鋭意検討を行った結果、基材の表面を精密に制御する必要なく塗布することができるものでありながら、優れた特性の被膜を形成することができる、被膜形成組成物を実現するに至った。即ち、以下(a)〜(d)の成分を含んで成る被膜形成組成物である。
(a)質量平均分子量が20000〜100000の水溶性アクリル重合体 100質量部
(b)以下の化学構造を有する有機化合物 40〜200質量部
R1−O−CH2−CR2R3−OH
(式中R1は炭素数が1〜6の、分岐構造を有しても良い炭化水素基であり、R2は水素または炭素数が1〜3の炭化水素基であり、R3は水素または炭素数が1〜3の炭化水素基であって、R2とR3は同一であっても異なっていても良い)
(c)水 25〜75質量部
(d)前記(b)以外の常温液状のアルコール 150〜500質量部
In the present invention, as a result of intensive studies to solve the above problems, it is possible to form a coating film with excellent characteristics while being able to be applied without the need to precisely control the surface of the substrate. It came to implement | achieve a film forming composition. That is, it is a film-forming composition comprising the following components (a) to (d).
(A) Water-soluble acrylic polymer having a mass average molecular weight of 20000 to 100000 100 parts by mass (b) Organic compound having a chemical structure of 40 to 200 parts by mass R 1 —O—CH 2 —CR 2 R 3 —OH
(Wherein R 1 is a hydrocarbon group having 1 to 6 carbon atoms which may have a branched structure, R 2 is hydrogen or a hydrocarbon group having 1 to 3 carbon atoms, and R 3 is hydrogen. Or a hydrocarbon group having 1 to 3 carbon atoms, and R 2 and R 3 may be the same or different.)
(C) Water 25 to 75 parts by mass (d) Room temperature liquid alcohol other than the above (b) 150 to 500 parts by mass
また本発明は、以下の実施態様も含む。
第二の実施態様は、前記(b)成分が、ブチルグリコール、またはイソブチルグリコールを含んでなるものである、前記第一の実施態様に記載の被膜形成組成物である。
第三の実施態様は、前記(b)成分がさらにメチルプロピレングリコールを含んでなるものである、前記第二の実施態様に記載の被膜形成組成物である。
第四の実施態様は、前記(a)成分を構成するアクリルモノマーが、(メタ)アクリル酸ブチルを含んでなるものである、前記第一乃至三のいずれかの実施態様に記載の被膜形成組成物である。
第五の実施態様は、前記(d)成分が、メタノール、エタノール、n−プロパノール、2−プロパノール、2−メチル−2−プロパノールを含むものである、前記実施態様一乃至四のいずれかの実施態様に記載の被膜形成組成物である。
第六の実施態様は、前記の被膜形成組成物が、透明な基材に適用するものである、前記実施態様一乃至五のいずれかの実施態様に記載の被膜形成組成物である。
The present invention also includes the following embodiments.
The second embodiment is the film-forming composition according to the first embodiment, wherein the component (b) comprises butyl glycol or isobutyl glycol.
A third embodiment is the film forming composition according to the second embodiment, wherein the component (b) further comprises methylpropylene glycol.
In the fourth embodiment, the film forming composition according to any one of the first to third embodiments, wherein the acrylic monomer constituting the component (a) comprises butyl (meth) acrylate. It is a thing.
In a fifth embodiment, the component (d) includes methanol, ethanol, n-propanol, 2-propanol, and 2-methyl-2-propanol. It is a film forming composition as described.
A sixth embodiment is the film forming composition according to any one of the first to fifth embodiments, wherein the film forming composition is applied to a transparent substrate.
また本発明は上記被膜形成組成物を用いた被膜形成方法にも関する。即ち、本発明の第七の実施態様は、基材表面に前記被膜形成組成物を塗布し、揮発成分を揮発させることにより被膜を形成する、被膜形成方法である。
第八の実施態様は、前記基材が、ポリカーボネート、アクリル樹脂から選ばれる透明材料である、前記第七の実施態様に記載の被膜形成方法である。
第九の実施態様は、前記透明材料表面を予め研磨した上で、前記被膜形成組成物を塗布するものである、前記第八の実施態様に記載の被膜形成方法である。
The present invention also relates to a film forming method using the above film forming composition. That is, the seventh embodiment of the present invention is a film forming method in which the film forming composition is applied to the surface of a substrate to form a film by volatilizing a volatile component.
The eighth embodiment is the film forming method according to the seventh embodiment, wherein the substrate is a transparent material selected from polycarbonate and acrylic resin.
The ninth embodiment is the film forming method according to the eighth embodiment, in which the surface of the transparent material is polished in advance, and then the film forming composition is applied.
本発明の被膜形成組成物は、自動車のヘッドライト等の燈火類、リアウィンド、店舗等のショーウィンド、ショーケース、水槽等の、特に高い透明性が求められる部材に塗布して用いることで、保護層となる被膜を形成する。ここで、黄変やくすみが生じている基材の表面を予め研磨しておくことで、被膜形成後に透明性を有した表面を復元することができ、またその透明性を長期間に渡って保持することができる。 The film-forming composition of the present invention is used by applying it to members that require particularly high transparency, such as fires such as automobile headlights, rear windows, shop windows, showcases, water tanks, etc. A film to be a protective layer is formed. Here, by polishing the surface of the base material in which yellowing or dullness has occurred in advance, the surface having transparency can be restored after the coating is formed, and the transparency can be maintained over a long period of time. Can be held.
本発明の被膜形成組成物は、前記構成を含むことにより好ましい特性を発揮することができるようになる。以下に各構成について説明する。 The film-forming composition of the present invention can exhibit desirable characteristics by including the above-described configuration. Each configuration will be described below.
(a)質量平均分子量が20000〜100000の水溶性アクリル重合体について
本発明で用いる水溶性アクリル重合体は、本発明の被膜形成組成物において被膜を形成する主要な要素である。本発明でいう水溶性とは、当該化合物と水、必要によりアルコールなどの媒介物質を混ぜ合わせた際において、質量比で当該化合物と水の割合が少なくとも10/1にて均一に混合でき、常温で静置しても10日以上は分離や沈降を示さないものである。当該化合物を得る方法としては、アクリル重合体の原料となる単量体中に水との親和性の高い官能基を有する化合物を用いる、または重合体を界面活性剤で修飾して水との親和性を高める、或いはこれらの手法を組み合わせることなどが挙げられる。当該化合物の質量平均分子量としては、20000〜100000の範囲にあるものであり、より好ましくは25000〜75000である。質量平均分子量が20000以上であることにより、形成した被膜は適切な強靱さを保持することができる。他方で質量平均分子量が100000以下であることにより、形成した被膜は適切な柔軟さを有することができ、同時に塗布に好適な粘性を確保することができ、また水中への好適な分散、溶解性を付与することができる。ここで、本発明において定義する質量平均分子量(Mw)の値は、ゲルパーミエーションクロマトグラフィー(GPC)を用いて以下条件の下ポリスチレン換算相対分子量分布を測定することにより得られるものである。
測定機種 TOSOH HLC−8120GPC
カラム TSKgel SuperMultipore HZ−M(4本)
溶離液 THF
温度 カラム恒温槽 40℃
流速 0.35mL/min
注入量 40μL
検出器 示差屈折計(RI)
(A) Water-soluble acrylic polymer having a mass average molecular weight of 20,000 to 100,000 The water-soluble acrylic polymer used in the present invention is a main element for forming a film in the film-forming composition of the present invention. The term “water-soluble” as used in the present invention means that when the compound and water, and if necessary, a mediator such as alcohol are mixed, the compound and water can be uniformly mixed at a mass ratio of at least 10/1. Even if it is left still, it does not show separation or sedimentation for more than 10 days. As a method for obtaining the compound, a compound having a functional group with high affinity for water is used in the monomer that is a raw material of the acrylic polymer, or the polymer is modified with a surfactant to have an affinity for water. For example, it is possible to improve the performance or to combine these methods. As a mass mean molecular weight of the said compound, it exists in the range of 20000-100,000, More preferably, it is 25000-75000. When the mass average molecular weight is 20000 or more, the formed film can maintain appropriate toughness. On the other hand, when the mass average molecular weight is 100000 or less, the formed film can have appropriate flexibility, and at the same time, it can ensure viscosity suitable for coating, and can be suitably dispersed and soluble in water. Can be granted. Here, the value of the mass average molecular weight (Mw) defined in the present invention is obtained by measuring the relative molecular weight distribution in terms of polystyrene under the following conditions using gel permeation chromatography (GPC).
Measurement model TOSOH HLC-8120GPC
Column TSKgel SuperMultipore HZ-M (four)
Eluent THF
Temperature Column temperature chamber 40 ℃
Flow rate 0.35mL / min
Injection volume 40μL
Detector Differential refractometer (RI)
本発明で用いる前記水溶性アクリル重合体は、(メタ)アクリルモノマーを重合してなる、水溶性の重合体である。当該重合体の骨格を構成する要素が(メタ)アクリルモノマーであれば、その種類を特定するものではなく、例えば(メタ)アクリル酸、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n−プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸n−ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸t−ブチル、(メタ)アクリル酸n−プロピル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸2−エチルヘキシル、(メタ)アクリル酸ラウリル、(メタ)アクリル酸ステアリル、(メタ)アクリル酸ベンジル、(メタ)アクリル酸2−トリフルオロエチル等の(メタ)アクリル酸の(フルオロ)アルキルエステル、(メタ)アクリル酸2−ヒドロキシエチル、(メタ)アクリル酸2−ヒドロキシプロピル、(メタ)アクリル酸4−ヒドロキシブチル、(メタ)アクリル酸グリシジル、(メタ)アクリル酸メチルグリシジル、3,4−エポキシシクロヘキシルメチル(メタ)アクリレート、(メタ)アクリロイルモルホリン、(メタ)アクリル酸アリル等から選ばれる一種以上の(メタ)アクリルモノマーを構成単位としてなるアクリル重合体から適宜選択できる。。なお本発明において(メタ)アクリルと表記しているものは、アクリルまたはメタクリルの意である。 The water-soluble acrylic polymer used in the present invention is a water-soluble polymer obtained by polymerizing a (meth) acryl monomer. If the element constituting the skeleton of the polymer is a (meth) acrylic monomer, the type is not specified. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, ( N-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-propyl (meth) acrylate, ( (Meth) acrylic acid cyclohexyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid lauryl, (meth) acrylic acid stearyl, (meth) acrylic acid benzyl, (meth) acrylic acid 2-trifluoroethyl etc. ) (Fluoro) alkyl esters of acrylic acid, 2-hydroxyethyl (meth) acrylate, (meth) acrylate 2-hydroxypropyl phosphate, 4-hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, (meth) acryloylmorpholine, One or more (meth) acrylic monomers selected from (meth) acrylic acid allyl and the like can be appropriately selected from acrylic polymers having as structural units. . In addition, what is described as (meth) acryl in this invention means acryl or methacryl.
本発明における前記水溶性アクリル重合体を構成する化合物として特に好適には、(メタ)アクリル酸n−ブチルを含んでなるものである。更には、当該化合物を構成モノマーとして50質量%以上含んでいることが好ましく、より好適には65質量%以上含むものである。当該化合物の構成モノマー比が50質量%以上であることで、重合体は塗膜にした際に良好な柔軟性、耐久性、透明性等を確保することができる。(メタ)アクリル酸ブチル以外の構成(メタ)アクリルモノマーは、これと共重合できる化合物から任意に選択することができるが、当該共重合性化合物としては、(メタ)アクリル酸2−ヒドロキシエチル等の水酸基含有アクリルモノマーが好適で、水分散性の観点から前記水酸基含有アクリルモノマーを1〜10質量%の割合で含んでいることが特に好ましい。また本発明のアクリル重合体としては上記アクリル化合物を構成モノマーに含むのであれば、スチレン、エチレン、プロピレン、ブタジエン、イソプレン、クロロプレン等のアクリル化合物でない化合物と共重合させてなる共重合体でも構わず、塗膜への強度付与等の観点から、スチレンを共重合化合物として含んでいることが好ましい As the compound constituting the water-soluble acrylic polymer in the present invention, n-butyl (meth) acrylate is particularly preferable. Further, the compound preferably contains 50% by mass or more, more preferably 65% by mass or more, as a constituent monomer. When the constituent monomer ratio of the compound is 50% by mass or more, the polymer can ensure good flexibility, durability, transparency and the like when formed into a coating film. The (meth) acrylic monomer other than (meth) butyl acrylate can be arbitrarily selected from compounds that can be copolymerized therewith, and examples of the copolymerizable compound include 2-hydroxyethyl (meth) acrylate and the like. The hydroxyl group-containing acrylic monomer is suitable, and it is particularly preferable that the hydroxyl group-containing acrylic monomer is contained in an amount of 1 to 10% by mass from the viewpoint of water dispersibility. Further, the acrylic polymer of the present invention may be a copolymer obtained by copolymerizing a compound that is not an acrylic compound such as styrene, ethylene, propylene, butadiene, isoprene, or chloroprene as long as the above-mentioned acrylic compound is included in the constituent monomer. From the viewpoint of imparting strength to the coating film, it is preferable to contain styrene as a copolymer compound.
(b)成分について
(b)成分は、以下の化学構造を有する有機化合物である。
R1−O−CH2−CR2R3−OH (化1)
ここで、式中R1は炭素数が1〜6の、分岐構造を有しても良い炭化水素基であり、R2は水素または炭素数が1〜3の炭化水素基であり、R3は水素または炭素数が1〜3の炭化水素基であって、R2とR3は同一であっても異なっていても良い。ここで、前記R1の中には酸素、窒素、硫黄等のヘテロ原子で連結された炭化水素構造、例えばエーテル構造を有しないものである。より好ましくは、R1は炭素数が1〜4の範囲にあるものであり、R2、R3はいずれか一方が水素で、他方は水素またはメチル基であることが好適である。本発明の(b)成分としては当該範囲内にあれば特にその構造を限定するものではなく、例えばメチルグリコール、メチルプロピレングリコール、エチルグリコール、エチルプロピレングリコール、プロピルグリコール、プロピルプロピレングリコール、イソプロピルグリコール、イソプロピルプロピレングリコール、ブチルグリコール、ブチルプロピレングリコール、イソブチルグリコール、イソブチルプロピレングリコール、t−ブチルグリコール、t−ブチルプロピレングリコール、ペンチルグリコール、ペンチルプロピレングリコール、ヘキシルグリコール、ヘキシルプロピレングリコール、フェニルグリコール、フェニルプロピレングリコール等から選ばれる一種以上の化合物を挙げることができる。本発明で特に好適に用いることができる化合物としては、ブチルグリコール、イソブチルグリコール、メチルプロピレングリコールから選ばれる一種以上であり、さらに好ましくはブチルグリコールまたはイソブチルグリコールとメチルプロピレングリコールの組み合わせである。
Component (b) The component (b) is an organic compound having the following chemical structure.
R 1 —O—CH 2 —CR 2 R 3 —OH (Chemical Formula 1)
Here, in the formula, R 1 is a hydrocarbon group having 1 to 6 carbon atoms which may have a branched structure, R 2 is hydrogen or a hydrocarbon group having 1 to 3 carbon atoms, and R 3 Is hydrogen or a hydrocarbon group having 1 to 3 carbon atoms, and R 2 and R 3 may be the same or different. Here, R 1 does not have a hydrocarbon structure connected by a heteroatom such as oxygen, nitrogen, or sulfur, such as an ether structure. More preferably, R 1 has 1 to 4 carbon atoms, and R 2 and R 3 are each preferably hydrogen and the other is hydrogen or a methyl group. The component (b) of the present invention is not particularly limited as long as it is within the above range. For example, methyl glycol, methyl propylene glycol, ethyl glycol, ethyl propylene glycol, propyl glycol, propyl propylene glycol, isopropyl glycol, Isopropylpropylene glycol, butyl glycol, butyl propylene glycol, isobutyl glycol, isobutyl propylene glycol, t-butyl glycol, t-butyl propylene glycol, pentyl glycol, pentyl propylene glycol, hexyl glycol, hexyl propylene glycol, phenyl glycol, phenyl propylene glycol, etc. One or more compounds selected from can be mentioned. The compound that can be particularly preferably used in the present invention is at least one selected from butyl glycol, isobutyl glycol, and methylpropylene glycol, and more preferably butyl glycol or a combination of isobutyl glycol and methylpropylene glycol.
当該(b)成分は、本発明の被膜形成組成物にて被膜を形成した際、好適な特性を付与するための成分である。具体的には、被膜に透明性、レベリング性、肉盛性、耐久性等を付与するために加えられるものである。またその組成量としては、前記(a)成分100質量部に対して40〜200質量部であることが好ましく、より好適には75〜170質量部である。当該成分が40質量部未満であると、被膜は十分にその特性を発現できず、透明性が低下する、均一な表明形成ができない、長期使用時に性能の低下が早まる、といった問題が生じうる。他方で200質量部を超えると、肉盛性の低下、密着性の低下、といった問題を惹起しうる。 The component (b) is a component for imparting suitable characteristics when a film is formed with the film-forming composition of the present invention. Specifically, it is added to impart transparency, leveling properties, build-up properties, durability, etc. to the coating. In addition, the composition amount is preferably 40 to 200 parts by mass, more preferably 75 to 170 parts by mass with respect to 100 parts by mass of the component (a). If the amount of the component is less than 40 parts by mass, the coating film cannot sufficiently exhibit its characteristics, and transparency may be deteriorated, uniform expression cannot be formed, and performance deterioration may be accelerated during long-term use. On the other hand, when it exceeds 200 parts by mass, problems such as poor build-up and low adhesion can be caused.
(c)水について
本発明では希釈、分散媒として水を用いている。当該成分を用いることで、人体や自然環境への悪影響を低減できることは勿論であるが、塗布時に基材への悪影響を最小限に抑え、また飛散あるいは垂れにより基材以外に付着した組成物が、塗装面等を冒す可能性を低減できる。当該成分の組成量は、前記(a)成分100質量部に対して25〜75質量部であることが好ましく、より好適には30〜70質量部である。当該成分が25質量部未満であると、組成物が十分な流動性を得ることができず、75質量部を超えると、組成物が十分に分散、溶解できず、また被膜に濁りが生じる可能性がある。
(C) Water In the present invention, water is used as a dilution and dispersion medium. By using this component, it is possible to reduce the adverse effects on the human body and the natural environment, but it is possible to minimize the adverse effects on the base material at the time of application, and the composition adhered to other than the base material by scattering or dripping. The possibility of affecting the painted surface can be reduced. The composition amount of the component is preferably 25 to 75 parts by mass, and more preferably 30 to 70 parts by mass with respect to 100 parts by mass of the component (a). If the component is less than 25 parts by mass, the composition cannot obtain sufficient fluidity, and if it exceeds 75 parts by mass, the composition cannot be sufficiently dispersed and dissolved, and the coating may become turbid. There is sex.
(d)前記(b)以外の常温液状のアルコールについて
本発明の(d)成分としては、常温で液状のアルコールである。当該成分は、前記(a)〜(c)成分をそれぞれ相溶させ、組成物を安定に保ち、また適度の揮発性を確保するために用いるものである。常温、すなわち25℃で液状のアルコールであれば特に構造を問うものではないが、前記(b)とは異なるものとして用いる必要がある。当該成分の化合物としては、例えばメタノール、エタノール、n−プロパノール、イソプロピルアルコール、n−ブチルアルコール、sec−ブチルアルコール、イソブチルアルコール、1−ペンタノール、2−ペンタノール、3−ペンタノール、3−イソアミルアコール、t−アミルアコール、シクロペンタノール、1−ヘキサノール、2−ヘキサノール、2−エチルヘキサノール、cis/trans−2−メチルシクロヘキサノール、1−ヘプタノール、2−ヘプタノール、3−ヘプタノール等から選ばれる一種以上の化合物を挙げることができる。本発明における当該成分としては、塗布後の揮発性等の観点から、メタノール、エタノール、n−プロパノール、イソプロピルアルコール、t−ブチルアルコール(2−メチル−2−プロパノール)等の、沸点が100℃未満のものを(d)成分全体のうち50%以上含んでなることが好ましく、入手容易性や人体、環境への負荷の小ささ、臭気の少なさと適切な揮散性の観点から、エタノール、n−プロピルアルコール、イソプロピルアルコールから選ばれる1種以上のアルコールであることが特に好適である。当該成分の組成量は、前記(a)成分100質量部に対して150〜500質量部であることが好ましく、より好適には200〜350質量部である。当該成分が150質量部未満であると、前記(a)〜(c)成分を系中に均一に分散させることが困難となり、沈殿や凝集等を起こして透明な塗膜を形成することが困難となってしまう。他方当該成分が500質量部を超えると、組成物の揮発性が低下し、平滑な塗膜の形成が困難となってしまう。
(D) About room temperature liquid alcohols other than (b) The component (d) of the present invention is a liquid alcohol at room temperature. The said component is used in order to make the said (a)-(c) component each compatible, keep a composition stable, and ensure moderate volatility. The structure is not particularly limited as long as it is a liquid alcohol at room temperature, that is, 25 ° C., but it must be used differently from the above (b). Examples of the compound of the component include methanol, ethanol, n-propanol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, isobutyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, and 3-isoamyl. A kind selected from acol, t-amylacol, cyclopentanol, 1-hexanol, 2-hexanol, 2-ethylhexanol, cis / trans-2-methylcyclohexanol, 1-heptanol, 2-heptanol, 3-heptanol and the like The above compounds can be mentioned. In the present invention, the component has a boiling point of less than 100 ° C. such as methanol, ethanol, n-propanol, isopropyl alcohol, t-butyl alcohol (2-methyl-2-propanol), etc. from the viewpoint of volatility after coating. It is preferable to contain 50% or more of the total amount of component (d), ethanol, n-, from the viewpoints of availability, small burden on human body and environment, low odor and appropriate volatility. Particularly preferred is one or more alcohols selected from propyl alcohol and isopropyl alcohol. The composition amount of the component is preferably 150 to 500 parts by mass, and more preferably 200 to 350 parts by mass with respect to 100 parts by mass of the component (a). When the component is less than 150 parts by mass, it is difficult to uniformly disperse the components (a) to (c) in the system, and it is difficult to form a transparent coating film by causing precipitation or aggregation. End up. On the other hand, when the said component exceeds 500 mass parts, the volatility of a composition will fall and formation of a smooth coating film will become difficult.
また本発明においては、発明の効果を妨げない範囲で上記の他に透明充填材、防錆剤、界面活性剤、可塑剤、分散剤、接着助剤、防腐剤、消泡剤、湿潤剤、着色剤、乳化剤、希釈剤、pH調整剤、粘弾性調整剤、レオロジー調整剤などの添加剤を含ませることができる。特に本発明ではレオロジー調整剤等を含んだ界面活性剤を添加することにより、塗膜の平滑性の向上や泡噛みの低減、硬化速度の調整等を図ることができる。 In the present invention, in addition to the above, transparent fillers, rust preventives, surfactants, plasticizers, dispersants, adhesion assistants, antiseptics, antifoaming agents, wetting agents, as long as the effects of the invention are not hindered. Additives such as colorants, emulsifiers, diluents, pH adjusters, viscoelasticity adjusters, rheology adjusters and the like can be included. In particular, in the present invention, by adding a surfactant containing a rheology adjusting agent or the like, it is possible to improve the smoothness of the coating film, reduce foam biting, adjust the curing speed, and the like.
さらに本発明は、前記の被膜形成組成物を用いた被膜形成方法にも関する。当該被膜形成方法は、基材表面に、前記被膜形成組成物を塗布し、揮発成分を揮発させることにより被膜を形成する、というものである。ここで、前記基材は特に限定するものでなく、各種材質からなる部材に適用することができるが、本発明における基材としてはポリカーボネート、アクリル樹脂等からなる透明性を有した高分子材質であることが特に好ましく、より好適にはポリカーボネートを含んでなる透明性樹脂である。また、前記揮発成分の揮発方法としては、常温での自然乾燥でも、加温しての促進乾燥でも構わないが、好適には30度乃至50度程度に加温することによる促進乾燥である。当該加温方法としては特に限定するものではなく、熱線照射、温風、暖房による環境温度上昇等を用いることができるが、平滑な塗膜を形成する観点から熱線照射がより好適である。 Furthermore, this invention relates also to the film formation method using the said film formation composition. The said film formation method is that the said film formation composition is apply | coated to the base-material surface, and a film is formed by volatilizing a volatile component. Here, the base material is not particularly limited and can be applied to members made of various materials. However, the base material in the present invention is a polymer material having transparency made of polycarbonate, acrylic resin, or the like. Particularly preferred is a transparent resin comprising polycarbonate. The volatile component may be volatilized by natural drying at room temperature or accelerated drying by heating, but accelerated drying by heating to about 30 to 50 degrees is preferable. The heating method is not particularly limited, and heat ray irradiation, warm air, an increase in environmental temperature due to heating, and the like can be used, but heat ray irradiation is more preferable from the viewpoint of forming a smooth coating film.
さらに本発明では、前記基材が透明性を有した材料である場合、当該透明材料の表面を予め研磨した上で、前記被膜形成組成物を塗布するものであることが好ましい。当該研磨により予め前記表明に微少な凹凸を設けることで、本発明の被膜形成組成物を基材表面に付着し易くすることができる。また当該研磨を行うことにより、基材表面に存在している擦過傷等を均すことで、被膜形成後の被膜形成組成物が平坦な表面を形成することができ、これにより前記傷に起因する基材表面のくすみを低減することができる。さらに基材表面に析出した透明性樹脂材料中に含まれる添加剤等や、劣化した高分子成分を研磨により除去することで、これらに起因した機材の黄変等を低減させることができる。前記透明材料としては、特に美観向上が求められる自動車のヘッドランプやテールランプ、各種ウィンドウ、また店舗に設置されたショウウィンドウ、自動販売機の表示部カバー、照明の保護部、水槽といった部材を挙げることができ、本発明ではこれら部材に対して好適に用いることができる。 Furthermore, in this invention, when the said base material is a material with transparency, it is preferable to apply | coat the said film formation composition, after grind | polishing the surface of the said transparent material previously. By providing fine irregularities in the expression in advance by the polishing, the film-forming composition of the present invention can be easily attached to the substrate surface. Further, by performing the polishing, it is possible to form a flat surface of the film-forming composition after the film is formed by leveling the scratches present on the surface of the base material, thereby causing the scratches. Dullness on the surface of the substrate can be reduced. Furthermore, by removing the additives contained in the transparent resin material deposited on the surface of the base material and the deteriorated polymer component by polishing, yellowing of the equipment caused by these can be reduced. Examples of the transparent material include automobile headlamps and taillights that are particularly required to improve aesthetics, various windows, show windows installed in stores, vending machine display covers, lighting protection units, and water tanks. In the present invention, it can be suitably used for these members.
本発明においては、前記研磨の方法としてその条件を厳密に制御する必要がないことを特徴とするものであり、一般的な研磨方法により行うことができる。例えば、耐水研磨紙、あるいは液状の研磨材等を用いた手作業による研磨、ポリッシャーを用いた機械研磨等を適宜選択することができる。研磨状態の目安としては、対象となる部材表面が一様に研磨され、当該箇所の擦過傷が目視にて概ね均一に曇った状態となっていることが好ましい。本発明における研磨方法の一例としては、予め清浄な状態にした基材表面を#1000〜5000番の耐水研磨紙等で均等に研磨するのみ、あるいは予め#100〜1000番の耐水研磨紙で均等に研磨した後、#1000〜5000番の耐水研磨紙等で仕上げの研磨を行う、という段階的な研磨を挙げることができる。当該研磨の後、基材表面に付着した研磨滓は、エアブローや高圧水流による除去、または清浄なウェスで拭き取ることによる除去を行うことが好ましい。 In the present invention, it is not necessary to strictly control the conditions as the polishing method, and it can be performed by a general polishing method. For example, manual polishing using water-resistant abrasive paper or liquid abrasive or mechanical polishing using a polisher can be selected as appropriate. As an indication of the polishing state, it is preferable that the surface of the target member is uniformly polished, and the scratches at the part are in a state of being almost uniformly clouded visually. As an example of the polishing method in the present invention, the surface of the substrate that has been cleaned in advance is uniformly polished with # 1000-5000 water-resistant abrasive paper or the like, or previously with # 100-1000 water-resistant abrasive paper. Stepwise polishing may be mentioned in which polishing is performed with # 1000-5000 water-resistant polishing paper or the like after polishing. After the polishing, it is preferable to remove the polishing rod adhering to the substrate surface by air blowing or high-pressure water flow or by wiping with a clean cloth.
また本発明の被膜形成組成物は、耐圧容器中に噴射剤と共に充填することで、エアゾールとして梱包されるものであっても良い。その場合、エアゾール噴射剤としては公知の物質を用いることができる。当該噴射剤としては、ジメチルエーテル(DME)、二酸化炭素、液化石油ガス(LPG)、窒素、亜酸化窒素、イソブタン、ハロアルキル等から選択することができるが、入手容易性、安全性、環境負荷等の観点から、DME、二酸化炭素、窒素が特に好適である。 Moreover, the film forming composition of this invention may be packed as an aerosol by filling with a propellant in a pressure-resistant container. In that case, a known substance can be used as the aerosol propellant. The propellant can be selected from dimethyl ether (DME), carbon dioxide, liquefied petroleum gas (LPG), nitrogen, nitrous oxide, isobutane, haloalkyl, etc., but availability, safety, environmental impact, etc. From the viewpoint, DME, carbon dioxide, and nitrogen are particularly suitable.
本発明の被膜形成組成物をエアゾールとして用いる場合、被膜形成組成物100質量部に対する前記噴射剤の充填量は、50〜150質量部であることが好ましく、70〜130質量部であることがさらに好適である。エアゾールとして用いることで、噴射のための設備等を準備する必要が無く、また作業時の取り回し性が向上するため、自動車等の大型機材の部品に対する塗布が容易に行えるようになる。 When the film-forming composition of the present invention is used as an aerosol, the amount of the propellant filled with respect to 100 parts by mass of the film-forming composition is preferably 50 to 150 parts by mass, and more preferably 70 to 130 parts by mass. Is preferred. By using it as an aerosol, it is not necessary to prepare facilities for injection and the like, and the handling property at the time of work is improved, so that it can be easily applied to parts of large equipment such as automobiles.
以下、実施例により本発明の効果を詳説するが、これら実施例は本発明の態様の限定を意図するものでは無い。 Hereinafter, the effects of the present invention will be described in detail by way of examples. However, these examples are not intended to limit the embodiments of the present invention.
本発明の被膜形成組成物の特性は、以下方法による実施例にて評価検討を行った。また本発明の実施例、比較例にて評価した被膜形成性組成物に含まれる構成成分は、以下に示す材料を用いた。またそれぞれの組成は、表1,2に記載の組成比に従い調製した。なお表中に記載の数値は、各成分の添加質量比である。 The characteristics of the film-forming composition of the present invention were evaluated and examined in the following examples. Moreover, the material shown below was used for the structural component contained in the film forming composition evaluated in the Example of this invention and the comparative example. Each composition was prepared in accordance with the composition ratio described in Tables 1 and 2. In addition, the numerical value described in a table | surface is the addition mass ratio of each component.
[被膜形成組成物検体の材料]
・(a):質量平均分子量が20000〜100000の水溶性アクリル樹脂、及びその比較成分
(a−1):アクリセットARL−468 日本触媒社製品 構成モノマーとして、メタクリル酸ブチルを80〜90質量%、スチレンを1〜20質量%、2−ヒドロキシエチル(メタ)アクリル酸を1〜10質量%、その他共重合性成分を残余としてなる質量平均分子量(Mw)約36000のアクリル系共重合体、固形分質量が約45%の水溶液
(a−2):アクリセットARL−469 日本触媒社製品 質量平均分子量(Mw)約60000のアクリル系重合体、固形分質量が約45%の水溶液
(a’−1):ポリゾールTKK−1020 昭和電工社製品 アクリルモノマー、メタクリルモノマー、スチレンからなる、アクリル系共重合体、固形分質量比が約44%のエマルジョン
(a’−2):コーガムHW−600 昭和電工社製品 構成モノマーとして、メチルメタクリレートを90〜99質量%、2−エチルヘキシルメタクリル酸を1〜10質量%、その他共重合性成分を残余としてなる質量平均分子量(Mw)約18000のアクリル系共重合体、固形分質量比が約40%の水溶液
なお上記(a)及びその比較成分は、表中では樹脂固形分の質量のみ記載しており、当該製品中の溶剤その他の揮発性成分は、表中にそれぞれ別記した。
・(b):以下の化学構造を有する有機化合物、及びその比較成分
R1−O−CH2−CR2R3−OH
(b−1):エチレングリコールモノイソブチルエーテル(イソブチルグリコール、IBG) 化1中、R1がイソブチル基、R2、R3が共に水素である構造の化合物
(b−2):エチレングリコールモノブチルエーテル(ブチルグリコール、BG) 化1中、R1がブチル基、R2、R3が共に水素である構造の化合物
(b−3):プロピレングリコールモノメチルエーテル(メチルプロピレングリコール、MFG) 化1中、R1がメチル基、R2が水素、R3がメチル基である構造の化合物
(b’−1):ジエチレングリコールモノブチルエーテル(ブチルジグリコール、BDG) 化1中、R1がブトキシエチル基、R2、R3が共に水素である構造の化合物
(b’−2):ジプロピレングリコールモノメチルエーテル(メチルプロピレンジグリコール、MFDG) 化1中、R1がメトキシイソプロピル基、R2が水素、R3がメチル基である構造の化合物
(b’−3):ジエチレングリコールジエチルエーテル(ジエチルジグリコール、DEDG) 化1中、R1がエトキシエチル基、R2、R3が共に水素であり、かつ水酸基がエトキシ基に置換した構造の化合物
(b’−4):ジエチレングリコールジブチルエーテル(ジブチルジグリコール、DBDG) 化1中、R1がブトキシエチル基、R2、R3が共に水素であり、かつ水酸基がブトキシ基に置換した構造の化合物
・(c):イオン交換水
・(d):常温液状のアルコール
(d−1):エタノール
(d−2):n−プロパノール
[Material for film-forming composition specimen]
-(A): Water-soluble acrylic resin having a mass average molecular weight of 20000-100,000 and its comparative component (a-1): Acryset ARL-468 Nippon Shokubai Co., Ltd. 80-90% by mass of butyl methacrylate as a constituent monomer , 1-20% by mass of styrene, 1-10% by mass of 2-hydroxyethyl (meth) acrylic acid, and an acrylic copolymer having a mass average molecular weight (Mw) of about 36000, with the remaining copolymerizable component as the residue, solid Aqueous solution (a-2) having a mass of about 45%: Acryset ARL-469 A product of Nippon Shokubai Co., Ltd. Acrylic polymer having a mass average molecular weight (Mw) of about 60000, an aqueous solution having a solid mass of about 45% (a′− 1): Polysol TKK-1020 Showa Denko Co., Ltd. Acrylic monomer, methacrylic monomer, acrylic copolymer consisting of styrene, solid Emulsion (a′-2) having a mass ratio of about 44%: Cogham HW-600 Showa Denko Co., Ltd. Products As constituent monomers, methyl methacrylate is 90 to 99% by mass, 2-ethylhexyl methacrylic acid is 1 to 10% by mass, Other acrylic copolymer having a weight average molecular weight (Mw) of about 18000, and an aqueous solution having a solids mass ratio of about 40%, with the remaining copolymerizable component as the residue.
In addition, in the table | surface, the said (a) and its comparison component have described only the mass of resin solid content, and the solvent and other volatile components in the said product were each described separately in the table | surface.
(B): Organic compound having the following chemical structure, and its comparative component R 1 —O—CH 2 —CR 2 R 3 —OH
(B-1): ethylene glycol monoisobutyl ether (isobutyl glycol, IBG) Compound (b-2): ethylene glycol monobutyl ether in which R 1 is an isobutyl group and R 2 and R 3 are both hydrogen (Butyl glycol, BG) Compound (b-3): propylene glycol monomethyl ether (methylpropylene glycol, MFG) in formula 1 , wherein R 1 is a butyl group and R 2 and R 3 are both hydrogen Compound (b′-1) having a structure in which R 1 is a methyl group, R 2 is hydrogen, and R 3 is a methyl group: diethylene glycol monobutyl ether (butyl diglycol, BDG) In the formula 1, R 1 is a butoxyethyl group, R 2, R 3 are both compounds of structure is hydrogen (b'-2): dipropylene glycol monomethyl ether (methyl Ropi range glycol, MFDG) in of 1, R 1 is methoxy isopropyl group, R 2 is hydrogen, compounds of structure R 3 is a methyl group (b'-3): diethylene glycol diethyl ether (diethyl diglycol, DEDG) of 1 in which R 1 is an ethoxyethyl group, R 2 and R 3 are both hydrogen, and the hydroxyl group is substituted with an ethoxy group (b′-4): diethylene glycol dibutyl ether (dibutyl diglycol, DBDG) 1, a compound having a structure in which R 1 is a butoxyethyl group, R 2 and R 3 are both hydrogen, and a hydroxyl group is substituted with a butoxy group. (C): ion-exchanged water. (D): alcohol at room temperature ( d-1): ethanol (d-2): n-propanol
上記の各材料を用いて、次の処方により実施例、比較例にて特性評価に用いた被膜形成組成物検体を製造した。 Using each of the above materials, a film-forming composition specimen used for property evaluation in Examples and Comparative Examples was produced according to the following formulation.
[被膜形成組成物の製造方法]
(a)、(b)、(c)、(d)及びそれぞれの比較成分と、造膜助剤としてのミネラルターペンを、表1,2に示した組成質量比にて投入し、均一になるよう混合攪拌を行った。然る後、湿潤剤(日信化学工業社製品、サーフィノール104)を組成物全体の0.1質量%となるよう添加し、混合攪拌を行った。
[Method for producing film-forming composition]
(A), (b), (c), (d) and their respective comparative components and mineral terpenes as film-forming aids are charged at the compositional mass ratios shown in Tables 1 and 2, and become uniform. The mixture was stirred. Thereafter, a wetting agent (Nissin Chemical Industry Co., Ltd., Surfynol 104) was added so as to be 0.1% by mass of the total composition, followed by mixing and stirring.
上記方法により調製した被膜形成組成物は、以下の方法によりその特性の評価を行った。
[液外観評価]
前記の被膜形成組成物の検体を透明な試験管に封入し、液の濁り、沈殿、分離の発生等を目視で確認することにより評価した。評価基準は以下の通り。
○:濁り、沈殿、分離等の発生が認められなかったものを合格として表記
×:濁り、沈殿、分離等の発生が認められたものを不合格として表記
The film forming composition prepared by the above method was evaluated for its characteristics by the following method.
[Liquid appearance evaluation]
The specimen of the film-forming composition was sealed in a transparent test tube and evaluated by visually confirming the occurrence of turbidity, precipitation, separation, and the like. The evaluation criteria are as follows.
○: Not observed turbidity, precipitation, separation, etc. as acceptable x: Remarked turbidity, precipitation, separation, etc. as rejected
[被膜外観評価]
ポリカーボネート製のテストピース(NF−2000、2.0×70×150mm、三菱エンジニアリングプラスチック社製品)の表面をアルコールにて脱脂洗浄した後、3000番の耐水研磨紙にて均一に表面を研磨し、くすみの生じた透明な樹脂材料として調製した。ここに、前記の被膜形成組成物の検体を約1ml滴下し、70番のバーコーターを用いることにより一様な被膜を形成した。これを25℃、55%RH環境下で24時間静置、乾燥させることで膜厚が20〜40μmの被膜形成試験片を作成した。当該試験片の外観を目視にて確認し、塗膜の外観について評価した。評価基準は以下の通り。
○:くすみが無くなり、透明な表面が形成できているものを合格として表記
×:くすみの残存等の外観不良が認められたものを不合格として表記
[Film appearance evaluation]
The surface of a polycarbonate test piece (NF-2000, 2.0 × 70 × 150 mm, manufactured by Mitsubishi Engineering Plastics) was degreased and washed with alcohol, and then the surface was evenly polished with a No. 3000 water-resistant abrasive paper. It was prepared as a transparent resin material with dullness. About 1 ml of the specimen of the above-mentioned film-forming composition was dropped here, and a uniform film was formed by using a No. 70 bar coater. This was left to stand for 24 hours in an environment of 25 ° C. and 55% RH and dried to prepare a film-forming test piece having a film thickness of 20 to 40 μm. The appearance of the test piece was visually confirmed, and the appearance of the coating film was evaluated. The evaluation criteria are as follows.
○: Marked as a pass if no dullness and a transparent surface can be formed ×: Marked as rejected if a dull appearance or other appearance defects were observed
[乾燥性評価]
JIS−G−3303で規定されるSPTEテストピース上に前記の被膜形成組成物の検体を約1ml滴下し、70番のバーコーターを用いることにより膜厚が20〜40μmとなる一様な被膜を形成した。これを25℃55%RH環境下に静置し、30分経過後に脱脂した指で触れ、指先への付着の有無にて乾燥性の評価を行った。評価基準は以下の通り。
○:指先への付着が認められなかったものを合格として表記
×:指先への付着が認められたものを不合格として表記
[Dryability evaluation]
About 1 ml of the specimen of the above-mentioned film-forming composition is dropped on an SPTE test piece defined in JIS-G-3303, and a uniform film with a thickness of 20 to 40 μm is formed by using a # 70 bar coater. Formed. This was left to stand at 25 ° C. and 55% RH, touched with a degreased finger after 30 minutes, and the drying property was evaluated by the presence or absence of adhesion to the fingertip. The evaluation criteria are as follows.
○: A case where adhesion to the fingertip was not recognized is indicated as a pass. X: A case where adhesion to the fingertip was recognized is indicated as a failure.
[密着性評価]
前記乾燥性評価と同様の方法にてポリカーボネート製テストピース(NF−2000、2.0×70×150mm、三菱エンジニアリングプラスチック社製品)上に被膜形成組成物の検体を塗布し、これを25℃、55%RH環境下で24時間静置、乾燥させることで膜厚が20〜40μmの被膜を形成した試験片を作成した。当該試験片を、JIS−K−5400−5−6に規定される、クロスカット法、所謂碁盤目試験により付着性の評価を行った。評価基準は以下の通り。
○:残存する被膜が、100/100であるものを合格として表記
×:残存する被膜が、100/100未満であるものを不合格として表記
[Adhesion evaluation]
A sample of the film-forming composition was applied to a polycarbonate test piece (NF-2000, 2.0 × 70 × 150 mm, manufactured by Mitsubishi Engineering Plastics) in the same manner as the dryness evaluation, and this was treated at 25 ° C. The test piece which formed the film with a film thickness of 20-40 micrometers by making it stand still in a 55% RH environment for 24 hours, and making it dry was created. The adhesion of the test piece was evaluated by a cross-cut method, a so-called cross-cut test defined in JIS-K-5400-5-6. The evaluation criteria are as follows.
○: Remaining film is expressed as 100/100 as acceptable x: Remaining film is expressed as less than 100/100 as unacceptable
[耐久性評価]
前記密着性評価と同様の方法にてポリカーボネート製テストピース上に膜厚が20〜40μmの被膜を形成した試験片を作成した。当該試験片を、キセノンアークランプ式促進耐候性試験機中に300時間静置したものを目視にて確認し、黄変の発生、または被膜の剥離脱落等の外観不良について評価を行った。評価基準は以下の通り。
○:黄変等の外観不良の発生、または被膜の剥がれが認められなかったものを合格として表記
×:黄変等の外観不良の発生、または被膜の剥がれが認められたものを不合格として表記
[Durability evaluation]
The test piece which formed the film with a film thickness of 20-40 micrometers on the test piece made from a polycarbonate by the method similar to the said adhesive evaluation was created. The test piece was allowed to stand in a xenon arc lamp type accelerated weathering tester for 300 hours and visually confirmed, and evaluated for appearance defects such as occurrence of yellowing or peeling off of the coating. The evaluation criteria are as follows.
○: Appearance that the appearance failure such as yellowing or peeling of the coating was not recognized is indicated as acceptable. ×: The appearance failure such as yellowing or peeling of the coating was indicated as rejection.
[噴射性評価]
被膜形成組成物の各検体をそれぞれエアゾール耐圧容器に入れ、これを等量の噴射剤(ジメチルエーテル)と共に密封充填することでエアゾール試料として準備した。エアゾールとして噴射した際の、噴射の均一性、詰まりの有無について評価を行った。評価基準は以下の通り。
○:噴射口の詰まりが生じず、均一な噴射ができたものを合格として表記
×:噴射口に詰まりが生じ、または詰まりが無くとも均一な噴射を行えなかったものを不合格として表記
[Ejection evaluation]
Each specimen of the film-forming composition was placed in an aerosol pressure-resistant container and sealed with an equal amount of propellant (dimethyl ether) to prepare an aerosol sample. Evaluation was made on the uniformity of injection and the presence or absence of clogging when sprayed as an aerosol. The evaluation criteria are as follows.
○: Notation that clogging of the injection port did not occur and uniform injection was indicated as acceptable x: Indication that the injection port was clogged or even injection could not be performed even if there was no clogging was indicated as rejection
[厚膜性評価]
ポリカーボネート製のテストピース(NF−2000、2.0×70×150mm、三菱エンジニアリングプラスチック社製品)の表面をアルコールにて脱脂洗浄した後、前記の噴射性評価にて作成したエアゾール試料を、20cmの距離からテストピース表面に対し10秒かけて、均等な膜厚となるよう噴射塗布を行った。然る後、これを25℃、55%RH環境下で24時間静置、乾燥することにより、厚膜評価のための試験片を作成した。当該試験片の中央部5箇所についてダイヤルゲージにて計測し、それぞれの計測値から試験片の厚さを減じたものの平均値を被膜の膜厚として記録し、評価を行った。評価基準は以下の通り。
○:被膜の膜厚が0.2mm以上で平滑に形成されているものを合格として表記
×:被膜の膜厚が0.2mm未満である、または平滑な塗膜が形成されていないものを不合格として表記
[Thick film evaluation]
After degreasing and cleaning the surface of a polycarbonate test piece (NF-2000, 2.0 × 70 × 150 mm, manufactured by Mitsubishi Engineering Plastics) with alcohol, Spray coating was carried out over a period of 10 seconds from the distance so as to obtain a uniform film thickness. Thereafter, this was left to stand for 24 hours in an environment of 25 ° C. and 55% RH and dried to prepare a test piece for thick film evaluation. Measurement was performed with a dial gauge at five central portions of the test piece, and an average value obtained by subtracting the thickness of the test piece from each measured value was recorded as the film thickness of the coating for evaluation. The evaluation criteria are as follows.
○: A film having a film thickness of 0.2 mm or more and formed smoothly is expressed as acceptable. ×: A film having a film thickness of less than 0.2 mm or a film having a smooth film is not formed. Expressed as passing
(a)成分の構造等の影響の検証
(b)成分の構造、添加量の影響の検証
上記実施例に記載の通り、本発明に含まれる被膜形成組成物は、その特性において極めて良好な結果を示すことが確認できた。即ち各実施例に記載した通り、塗布前の液状態においては分離や沈殿を生じておらず、塗布する際に於いては、迅速に乾燥し、十分な厚さの被膜を形成することができる。さらにその被膜は、基材のくすみを無くさせることができ、さらに基材への密着性、また長期使用時の耐久性においても問題を生じないものである。 As described in the above examples, it was confirmed that the film-forming composition included in the present invention showed extremely good results in its characteristics. That is, as described in each example, separation and precipitation did not occur in the liquid state before coating, and when coating, it was possible to quickly dry and form a sufficiently thick film. . Furthermore, the coating can eliminate the dullness of the base material, and does not cause any problems in adhesion to the base material and durability during long-term use.
一方で本発明に含まれない被膜形成着組成物は、被膜形成時に求められる特性を十分に備えていないことが認められる。ここで、(a)成分が所定の性質を備えていないもの、例えば比較例1〜3のように水溶液でなくエマルジョンとなっているものでは、被膜の厚膜性が不十分となるばかりでなく、組成物の相溶性に問題が生じるため、液外観も不良となり、また塗膜の外観にも濁りやくすみを生じる結果となっている。また比較例4〜5のように、水溶性樹脂化合物の分子量が所定の範囲にないアクリル系重合体を用いたものであると、基材への密着性が不十分で、また被膜の耐久性も足りず、被膜形成に必要な特性を備えていない。一方、比較例6に示したように(b)成分の組成量が所定範囲を超過したものでは、乾燥性に問題があるのみならず、形成された被膜が十分な厚さを確保することができないため、施工性に問題を生じるものである。また比較例7〜10に示した通り、(b)成分の組成量が所定範囲未満であり、当該成分の替わりの成分として本発明で特定した化学構造でない化合物を含ませた場合、いずれも乾燥性、厚膜性に問題が生じており、塗膜の外観や耐久性についても問題が生じうるものであった。 On the other hand, it is recognized that the film-forming composition not included in the present invention does not have sufficient characteristics required at the time of film formation. Here, in the case where the component (a) does not have a predetermined property, for example, in the case of an emulsion rather than an aqueous solution as in Comparative Examples 1 to 3, not only the film thickness is insufficient, Since the compatibility of the composition is problematic, the liquid appearance is also poor, and the appearance of the coating film is also turbid and dull. Further, as in Comparative Examples 4 to 5, if an acrylic polymer having a molecular weight of the water-soluble resin compound not in a predetermined range is used, the adhesion to the substrate is insufficient, and the durability of the coating film However, it does not have the characteristics necessary for film formation. On the other hand, as shown in Comparative Example 6, when the amount of the component (b) exceeds the predetermined range, there is not only a problem with the drying property, but also the formed film can ensure a sufficient thickness. Since it is not possible, it causes a problem in workability. In addition, as shown in Comparative Examples 7 to 10, when the amount of the component (b) is less than the predetermined range and a compound that does not have the chemical structure specified in the present invention is included as an alternative component, the component is dried. There has been a problem in the properties and the thick film properties, and there may be problems in the appearance and durability of the coating film.
本発明の被膜形成組成物は、被膜形成に必要な特性を備えたものであり、特に基材として透明な樹脂材料を選んだ場合、当該基材に対して適切な処理が施されている場合には、くすみや黄変といった外観の不良を改善することができ、美感の向上に寄与することができる有用なものである。 The film-forming composition of the present invention has characteristics necessary for film formation, and particularly when a transparent resin material is selected as the base material, the base material is appropriately treated. It is useful that it can improve appearance defects such as dullness and yellowing, and can contribute to the improvement of aesthetics.
Claims (9)
(a)質量平均分子量が20000〜100000の水溶性アクリル重合体 100質量部
(b)以下の化学構造を有する有機化合物 40〜200質量部
R1−O−CH2−CR2R3−OH
(式中R1は炭素数が1〜6の、分岐構造を有しても良い炭化水素基であり、R2は水素または炭素数が1〜3の炭化水素基であり、R3は水素または炭素数が1〜3の炭化水素基であって、R2とR3は同一であっても異なっていても良い)
(c)水 25〜75質量部
(d)前記(b)以外の常温で液状のアルコール 150〜500質量部 A film-forming composition comprising the following components (a) to (d):
(A) Water-soluble acrylic polymer having a mass average molecular weight of 20000 to 100000 100 parts by mass (b) Organic compound having a chemical structure of 40 to 200 parts by mass R 1 —O—CH 2 —CR 2 R 3 —OH
(Wherein R 1 is a hydrocarbon group having 1 to 6 carbon atoms which may have a branched structure, R 2 is hydrogen or a hydrocarbon group having 1 to 3 carbon atoms, and R 3 is hydrogen. Or a hydrocarbon group having 1 to 3 carbon atoms, and R 2 and R 3 may be the same or different.)
(C) 25 to 75 parts by mass of water (d) 150 to 500 parts by mass of liquid alcohol at room temperature other than (b) above
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014152512A JP6311880B2 (en) | 2014-07-28 | 2014-07-28 | Film-forming composition and film-forming method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014152512A JP6311880B2 (en) | 2014-07-28 | 2014-07-28 | Film-forming composition and film-forming method |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2016030770A JP2016030770A (en) | 2016-03-07 |
JP6311880B2 true JP6311880B2 (en) | 2018-04-18 |
Family
ID=55441360
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2014152512A Active JP6311880B2 (en) | 2014-07-28 | 2014-07-28 | Film-forming composition and film-forming method |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP6311880B2 (en) |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5266406A (en) * | 1989-11-08 | 1993-11-30 | E. I. Du Pont De Nemours And Company | Waterbased methylol (meth)acrylamide acrylic polymer and an acrylic hydrosol coating composition |
US5166255A (en) * | 1990-09-10 | 1992-11-24 | Basf Corporation | Metallic water borne base coat composition based on acrylic latex resins using an acrylic resin having acid and nonionic functionality for aluminum storage and a pregelled hetorite clay for rheology control--water base 4 |
JP3635682B2 (en) * | 1994-07-25 | 2005-04-06 | 大日本インキ化学工業株式会社 | Aqueous coating composition |
JP4280137B2 (en) * | 2003-09-17 | 2009-06-17 | 関西ペイント株式会社 | Repair painting method |
JP4920251B2 (en) * | 2005-12-22 | 2012-04-18 | 日本ペイント株式会社 | Bluring liquid composition and automotive exterior coating film repair method |
JP5315829B2 (en) * | 2008-07-22 | 2013-10-16 | 東亞合成株式会社 | Curable hard coat agent composition |
JP2010083940A (en) * | 2008-09-30 | 2010-04-15 | Nagase Chemtex Corp | Method for preventing electrification of polyamide film, antistatic film and manufacturing method of the same |
-
2014
- 2014-07-28 JP JP2014152512A patent/JP6311880B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
JP2016030770A (en) | 2016-03-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6567673B2 (en) | Aqueous dispersion containing multistage polymer and coating composition containing the same | |
CN106459299B (en) | Aqueous liquid dispersion and coating composition comprising it | |
TWI664251B (en) | Uv curable coating composition, method of applying the same and substrate coated therewith | |
TWI662089B (en) | Multi-layer coating system, method of applying the same and substrate coated therewith | |
CN103725245A (en) | Solvent-free UV (ultraviolet) curing glue for optical transparent adhesive tape and preparation method and application thereof | |
TW201831610A (en) | Anti-dazzling uv curable coating composition, method of applying the same and substrate coated therewith | |
KR20200027998A (en) | Low volatility organic compound water based UV curable single-layer coating composition, method of application thereof and substrate coated therewith | |
TWI616494B (en) | Topcoat composition, method of coating substrates with the same, and substrate | |
CN107430213A (en) | Hydrophilic optical feature monofilm and its layered product | |
BR112019011202B1 (en) | AQUEOUS DISPERSION, AND, PROCESS OF PREPARING AN AQUEOUS DISPERSION | |
BR112021005370A2 (en) | aqueous dispersion, and aqueous coating composition | |
EP1829926A2 (en) | Aqueous emulsion polymer | |
JP6637950B2 (en) | Coating composition and decorative sheet using the same | |
CN104558661A (en) | Antifogging resin optical lens and preparation method thereof | |
CN102559023A (en) | Scratch resistance waterborne polyurethane coating and preparation method thereof | |
WO2015178248A1 (en) | Hydrophilic single-layer film | |
TWI483985B (en) | Resin composition for the orientation of metal powder | |
JP6311880B2 (en) | Film-forming composition and film-forming method | |
BR112020005533B1 (en) | AQUEOUS AND AQUEOUS POLYMER COMPOSITIONS FOR COATING. | |
JPH08224538A (en) | Method for providing maximum luster of coating film | |
CN106947383B (en) | UV curable paint compositions | |
JP2007332174A (en) | Anti-fogging coating composition and method for producing anti-fogging film using the same | |
CN110903436B (en) | Solution containing self-extinction acrylic polymer particles and preparation method thereof | |
CN107502112A (en) | Aqueous industrial coating and its production method | |
KR101869203B1 (en) | Uv-curable coating composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160204 |
|
A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20160204 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20170705 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20180215 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20180221 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20180306 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6311880 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |