JP4940463B2 - Water-removable beauty nail - Google Patents
Water-removable beauty nail Download PDFInfo
- Publication number
- JP4940463B2 JP4940463B2 JP2005207862A JP2005207862A JP4940463B2 JP 4940463 B2 JP4940463 B2 JP 4940463B2 JP 2005207862 A JP2005207862 A JP 2005207862A JP 2005207862 A JP2005207862 A JP 2005207862A JP 4940463 B2 JP4940463 B2 JP 4940463B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- water
- nail
- acrylic resin
- 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
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- 230000003796 beauty Effects 0.000 title claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 113
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 87
- 239000000049 pigment Substances 0.000 claims description 56
- 229920000178 Acrylic resin Polymers 0.000 claims description 44
- 239000004925 Acrylic resin Substances 0.000 claims description 44
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 30
- 229920001577 copolymer Polymers 0.000 claims description 30
- 239000002562 thickening agent Substances 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000002270 dispersing agent Substances 0.000 claims description 22
- 239000003086 colorant Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000000230 xanthan gum Substances 0.000 claims description 6
- 229920001285 xanthan gum Polymers 0.000 claims description 6
- 235000010493 xanthan gum Nutrition 0.000 claims description 6
- 229940082509 xanthan gum Drugs 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 5
- 239000004927 clay Substances 0.000 claims description 5
- 239000011976 maleic acid Substances 0.000 claims description 5
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 4
- 229920000800 acrylic rubber Polymers 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 229920003146 methacrylic ester copolymer Polymers 0.000 claims description 2
- 210000003298 dental enamel Anatomy 0.000 claims 1
- 230000001568 sexual effect Effects 0.000 claims 1
- 239000000243 solution Substances 0.000 description 44
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 33
- -1 methacryloyl group Chemical group 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 29
- 239000003505 polymerization initiator Substances 0.000 description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 23
- 239000006185 dispersion Substances 0.000 description 22
- 239000011248 coating agent Substances 0.000 description 21
- 238000000576 coating method Methods 0.000 description 21
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 17
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 16
- 238000001035 drying Methods 0.000 description 16
- 238000005342 ion exchange Methods 0.000 description 14
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000004793 Polystyrene Substances 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 9
- 230000009477 glass transition Effects 0.000 description 9
- 229920002223 polystyrene Polymers 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 229920001567 vinyl ester resin Polymers 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229920002310 Welan gum Polymers 0.000 description 3
- 239000000980 acid dye Substances 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- 239000000440 bentonite Substances 0.000 description 3
- 229910000278 bentonite Inorganic materials 0.000 description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000004815 dispersion polymer Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 3
- 229940001584 sodium metabisulfite Drugs 0.000 description 3
- 235000010262 sodium metabisulphite Nutrition 0.000 description 3
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 229920002907 Guar gum Polymers 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000000665 guar gum Substances 0.000 description 2
- 235000010417 guar gum Nutrition 0.000 description 2
- 229960002154 guar gum Drugs 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
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- 239000000377 silicon dioxide Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
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- 239000011882 ultra-fine particle Substances 0.000 description 2
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- 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
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- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
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- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 1
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- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 description 1
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 description 1
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- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
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- QQILFGKZUJYXGS-UHFFFAOYSA-N Indigo dye Chemical compound C1=CC=C2C(=O)C(C3=C(C4=CC=CC=C4N3)O)=NC2=C1 QQILFGKZUJYXGS-UHFFFAOYSA-N 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UJMBCXLDXJUMFB-UHFFFAOYSA-K trisodium;5-oxo-1-(4-sulfonatophenyl)-4-[(4-sulfonatophenyl)diazenyl]-4h-pyrazole-3-carboxylate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-UHFFFAOYSA-K 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、水で除去できる美爪料に関し、詳しくは乾燥性にも優れる美爪料に関し、より詳しくは顔料の経時的な分散安定性にも優れる美爪料に関する。 The present invention relates to a beauty nail that can be removed with water, specifically relates to a beauty nail that is also excellent in drying properties, and more particularly relates to a beauty nail that is also excellent in dispersion stability of a pigment over time.
従来の美爪料は、トルエン、キシレンなどの炭化水素類や酢酸エチル、酢酸ブチルなどのケトン類などの有機溶剤中に樹脂を溶解し、顔料を分散した物が多い。これらは人体に対し必ずしも安全な溶剤とは言えず、常用すると爪の光沢が無くなったり、黄ばみを生じたりする事がある。 Many conventional nail polishes are obtained by dissolving a resin in an organic solvent such as hydrocarbons such as toluene and xylene and ketones such as ethyl acetate and butyl acetate and dispersing the pigment. These are not necessarily safe solvents for the human body. If they are used regularly, the gloss of the nails may be lost or yellowing may occur.
このため、特許文献１〜１９にあるように水やアルコールを主溶剤とした美爪料が提案されてきた。例えば、特開平９−２０２７１５（特許文献１９）には、水と低級アルコールとの混合物を主溶剤とする美爪料が開示されている。
しかしながら、これら水やアルコールを主溶剤とする美爪料は、爪上に塗布して塗膜とした場合に、有機溶剤を主溶剤とした美爪料と比べると、光沢性もしくは塗膜強度で著しく劣っており、日常生活での使用に耐えられるものではなかった。
For this reason, as described in Patent Documents 1 to 19, beauty nails having water or alcohol as a main solvent have been proposed. For example, Japanese Patent Application Laid-Open No. 9-202715 (Patent Document 19) discloses a nail polish containing a mixture of water and a lower alcohol as a main solvent.
However, these nail polishes that use water or alcohol as the main solvent have a glossiness or coating strength that is higher when applied to nails than a nail polish that uses an organic solvent as the main solvent. It was extremely inferior and could not withstand use in daily life.
ところで、美爪料は、一般に乾燥後、日常生活における耐水性を具備することが求められる。従って、有機溶剤を主溶剤とした美爪料と同様に、水やアルコールを主溶剤としたこれまでの美爪料にも、乾燥後は水で除去されないことが求められている。それゆえ、美爪料を取り除く際にはアセトンや酢酸エチルなどの有機溶剤を含有する除光液が必要されてきた。 By the way, the nail polish is generally required to have water resistance in daily life after drying. Therefore, as in the case of a nail polish using an organic solvent as a main solvent, the conventional nail polish using water or alcohol as a main solvent is required not to be removed with water after drying. Therefore, a light removing solution containing an organic solvent such as acetone or ethyl acetate has been required to remove the nail polish.
しかし、近年は様々な場面で美爪料が使用されようになり、時には日常生活における耐水性は必要とはされず、むしろ水で除去できる（以下、水除去性という。）ことが求められる場合がある。また、爪を痛めないためにも除光液を使用しない水除去性の美爪料が求められている。
しかしながら、このような水除去性に関する要求に対し、上記した水やアルコールを主溶剤とする美爪料のうち耐水性の悪いものを単純に転用するだけでは、各種要求を満たす美爪料は得られなかった。即ち、耐水性が悪いために水で比較的除去しやすくなるような美爪料は、水を主溶剤とするので、乾燥に要する時間が長く使用勝手が極めて悪かった。また、このような美爪料は、塗膜強度や保存安定性も悪かった。
However, in recent years, beauty nails have been used in various situations, and sometimes water resistance in daily life is not required, but rather it is required to be removed with water (hereinafter referred to as water removability). There is. In addition, there is a need for a water-removable beauty nail material that does not use a light removing solution so as not to damage the nail.
However, in response to such demands for water removability, a simple nail that has poor water resistance among the above-mentioned nail polishes that use water or alcohol as the main solvent can be used to obtain a nail polish that satisfies various requirements. I couldn't. In other words, the nail polish that is relatively easy to remove with water because of its poor water resistance has water as the main solvent, and thus has a long time to dry and is extremely poor in use. Further, such a beautiful nail material was also poor in coating film strength and storage stability.
特開平１０−２９８０２４号公報（特許文献２０）には、水で除去可能な膜を形成し得る水性化粧品組成物であって、水中で乳濁状態にあるポリマーの分散液を含有する水性化粧品組成物が開示されている。しかし、水中で乳濁状態にあるポリマーの分散液は、ポリマーの均一な溶液に比して一般に乾燥に要する時間が長く、顔料分散性、光沢、保存安定性、刷毛塗り性の点で劣る。
本発明は、水で除去し得る美爪料であって、乾燥性、顔料分散性にも優れ、機械物性もバランスよく高度なレベルにおいて満足し得る、常用しても爪を痛めない美爪料を提供することを目的とする。 The present invention is a beauty nail that can be removed with water, has excellent drying properties and pigment dispersibility, and can satisfy mechanical properties in a well-balanced and high level. The purpose is to provide.
本発明者らは、前記課題を解決するため鋭意研究を行った結果、特定の分子量と酸価を有するアクリル樹脂、着色剤、アルカリ性化合物、炭素数４以下のアルコールを含有する美爪料が、乾燥性、顔料分散性、機械物性に優れ、水除去性に優れる事を見出し、本発明を完成した。 As a result of intensive studies to solve the above problems, the present inventors have found that a nail polish containing an acrylic resin having a specific molecular weight and an acid value, a colorant, an alkaline compound, and an alcohol having 4 or less carbon atoms, The present invention was completed by finding that it has excellent drying properties, pigment dispersibility, mechanical properties, and excellent water removability.
即ち、本発明は、重量平均分子量が７０,０００〜２００,０００であって酸価が７０〜２００(mgＫＯＨ／g)のアクリル樹脂（Ａ）、炭素数４以下の低級アルコール（Ｂ）及びアルカリ性化合物（Ｃ）を含有するアクリル樹脂溶液と、着色剤（Ｄ）とを含有する、水で除去できる美爪料に関する。 That is, the present invention relates to an acrylic resin (A) having a weight average molecular weight of 70,000 to 200,000 and an acid value of 70 to 200 (mg KOH / g), a lower alcohol (B) having 4 or less carbon atoms, and an alkaline property. The present invention relates to a nail polish containing an acrylic resin solution containing a compound (C) and a colorant (D), which can be removed with water.
また、アクリル樹脂（Ａ）は、アクリル酸エステル−メタクリル酸エステル共重合体であることが好ましい。 The acrylic resin (A) is preferably an acrylic ester-methacrylic ester copolymer.
さらに、アルカリ性化合物（Ｃ）は、揮発性のものであり、その沸点が０℃以上であることが好ましい。 Furthermore, the alkaline compound (C) is volatile and preferably has a boiling point of 0 ° C. or higher.
さらに、着色剤（Ｄ）が顔料であり、さらに顔料分散剤（Ｅ）を含有することが好ましい。 Furthermore, it is preferable that the colorant (D) is a pigment and further contains a pigment dispersant (E).
さらに、顔料分散剤（Ｅ）は、スチレン・アクリル酸共重合体、スチレン・マレイン酸共重合体、スチレン・アクリル酸アルキル共重合体及びスチレン・マレイン酸アルキル共重合体からなる群より選ばれる、重量平均分子量が５,０００〜２０,０００であって酸価が１５０〜２５０の少なくとも１種の樹脂であることが好ましい。 Furthermore, the pigment dispersant (E) is selected from the group consisting of a styrene / acrylic acid copolymer, a styrene / maleic acid copolymer, a styrene / alkyl acrylate copolymer, and a styrene / alkyl maleate copolymer, It is preferably at least one resin having a weight average molecular weight of 5,000 to 20,000 and an acid value of 150 to 250.
さらに、美爪料は、増粘剤（Ｆ）を含有することが好ましい。 Furthermore, it is preferable that the nail polish contains a thickener (F).
さらに、増粘剤（Ｆ）は、粘土系増粘剤、キサンタンガム系増粘剤及びアクリル系増粘剤からなる群より選ばれる少なくとも１種であることが好ましい。 Furthermore, the thickener (F) is preferably at least one selected from the group consisting of a clay thickener, a xanthan gum thickener and an acrylic thickener.
さらに、アクリル樹脂溶液は水を含有し、下記（Ａ）〜（Ｆ）及び水の合計１００重量％中に、アクリル樹脂（Ａ）：３〜５０重量％、炭素数４以下の低級アルコール（Ｂ）と水の混合物：４０〜９０重量％、アルカリ性化合物（Ｃ）：０．１〜２０重量％、着色剤（Ｄ）：０．０１〜２０重量％、顔料分散剤（Ｅ）：０．０００１〜２０重量％、及び増粘剤（Ｆ）：０．０１〜１０重量％を含有することが好ましい。 Further, the acrylic resin solution contains water, and the acrylic resin (A): 3 to 50% by weight and a lower alcohol having 4 or less carbon atoms (B) in the following (A) to (F) and a total of 100% by weight of water. ) And water mixture: 40 to 90% by weight, alkaline compound (C): 0.1 to 20% by weight, colorant (D): 0.01 to 20% by weight, pigment dispersant (E): 0.0001 It is preferable to contain-20weight% and a thickener (F): 0.01-10weight%.
本発明により、水で除去し得る美爪料であって、乾燥性、顔料分散性にも優れ、機械物性もバランスよく高度なレベルにおいて満足し得る、常用しても爪を痛めない美爪料を提供することができるようになった。 According to the present invention, a nail polish that can be removed with water, has excellent drying properties and pigment dispersibility, can be satisfied at a high level with a good balance of mechanical properties, and does not damage nails even if it is used regularly. Can now be provided.
＜アクリル樹脂（Ａ）＞
本発明で用いられるアクリル樹脂（Ａ）は、重量平均分子量（以下、Ｍｗという）が７０,０００〜２００,０００であり、かつ酸価が７０〜２００（mgＫＯＨ／g）であることが重要であり、Ｍｗは７０,０００〜１５０,０００であることが好ましく、酸価は９０〜１５０（mgＫＯＨ／g）であることが好ましい。
<Acrylic resin (A)>
It is important that the acrylic resin (A) used in the present invention has a weight average molecular weight (hereinafter referred to as Mw) of 70,000 to 200,000 and an acid value of 70 to 200 (mgKOH / g). And Mw is preferably 70,000 to 150,000, and the acid value is preferably 90 to 150 (mg KOH / g).
Ｍｗが７０,０００より小さいと経時安定性や皮膜の機械物性が劣る傾向にある。他方、Ｍｗが２００,０００より大きいと刷毛塗り時に糸を引いたり、光沢が低下する傾向にある。
酸価が７０より小さいと水で除去できなくなったり、経時安定性が悪化したりする傾向にある。他方、酸価が２００より大きいと乾燥性が劣る傾向にある。
即ち、上記したような特定のＭｗ、特定の酸価のアクリル樹脂（Ａ）を使用することにより、水除去性、乾燥性、経時安定性、刷毛塗り性、光沢や機械物性に優れた皮膜を形成することができる。
When Mw is less than 70,000, the stability over time and the mechanical properties of the film tend to be inferior. On the other hand, if Mw is larger than 200,000, the yarn tends to be pulled or the gloss tends to be lowered when brushing.
If the acid value is less than 70, it tends to be impossible to remove with water, or the stability over time tends to deteriorate. On the other hand, when the acid value is larger than 200, the drying property tends to be inferior.
That is, by using the acrylic resin (A) having a specific Mw and a specific acid value as described above, a film excellent in water removal property, drying property, stability over time, brush coating property, gloss and mechanical properties is obtained. Can be formed.
上記アクリル樹脂（Ａ）を構成する単量体としては、従来公知であるアクリロイル基又はメタクリロイル基を有する種々のエチレン系不飽和化合物や、芳香族ビニル化合物が挙げられる。
アクリロイル基又はメタクリロイル基を有する種々のエチレン系不飽和化合物としては、以下の例には限定されないが、例えば、エチレン系不飽和カルボン酸、エチレン系不飽和カルボン酸アルキルアミド、エチレン系不飽和カルボン酸アミノアルキルエステル、シアン化ビニル系単量体、不飽和脂肪族グリシジルエステル、水酸基含有カルボン酸エステル、カルボン酸ビニルエステルが挙げられ、これらは１種又は２種以上を適宜選択することができる。アクリル樹脂（Ａ）は、これら各種単量体のうち、アクリロイル基を有するカルボン酸ビニルエステルとメタクリロイル基を有するカルボン酸ビニルエステルとを主成分とする共重合体が好ましく、特に、アクリル酸エステル−メタクリル酸エステル共重合体であることが好ましい。
Examples of the monomer constituting the acrylic resin (A) include conventionally known various ethylenically unsaturated compounds having an acryloyl group or a methacryloyl group, and aromatic vinyl compounds.
Examples of the various ethylenically unsaturated compounds having an acryloyl group or a methacryloyl group are not limited to the following examples. For example, an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid alkylamide, and an ethylenically unsaturated carboxylic acid Examples thereof include aminoalkyl esters, vinyl cyanide monomers, unsaturated aliphatic glycidyl esters, hydroxyl group-containing carboxylic acid esters, and carboxylic acid vinyl esters, and one or more of these can be appropriately selected. Among these various monomers, the acrylic resin (A) is preferably a copolymer mainly composed of a carboxylic acid vinyl ester having an acryloyl group and a carboxylic acid vinyl ester having a methacryloyl group. A methacrylic acid ester copolymer is preferred.
エチレン系不飽和カルボン酸としては、以下の例には限定されないが、（メタ）アクリル酸、イタコン酸、フマル酸、マレイン酸、クロトン酸などを例としてあげることができる。 The ethylenically unsaturated carboxylic acid is not limited to the following examples, but (meth) acrylic acid, itaconic acid, fumaric acid, maleic acid, crotonic acid and the like can be exemplified.
エチレン系不飽和カルボン酸アルキルアミドとしては、以下の例には限定されないが、アミノエチルアクリルアミド、ジメチルアミノメチルメタクリルアミド、メチルアミノプロピルメタクリルアミド、アミノアルキルアミド、（メタ）アクリルアミド、Ｎ−メチロールアクリルアミドなどを例としてあげることができる。 Examples of ethylenically unsaturated carboxylic acid alkylamides include, but are not limited to, aminoethylacrylamide, dimethylaminomethylmethacrylamide, methylaminopropylmethacrylamide, aminoalkylamide, (meth) acrylamide, N-methylolacrylamide, and the like. Can be given as an example.
エチレン系不飽和カルボン酸アミノアルキルエステルとしては、以下の例には限定されないが、アミノエチルアクリレート、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、ブチルアミノエチルアクリレートなどを例としてあげることができる。 Examples of ethylenically unsaturated carboxylic acid aminoalkyl esters include, but are not limited to, aminoethyl acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, butylaminoethyl acrylate, and the like. Can do.
シアン化ビニル系単量体としては、以下の例には限定されないが、（メタ）アクリロニトリル、α−クロルアクリロニトリルなどを例としてあげることができる。 The vinyl cyanide monomer is not limited to the following examples, but (meth) acrylonitrile, α-chloroacrylonitrile and the like can be given as examples.
不飽和脂肪族グリシジルエステルとしては、以下の例には限定されないが、グリシジル(メタ)アクリレート、３，４−エポキシシクロヘキシルメチル(メタ)アクレート、グリシジルビニルエーテル、３，４−エポキシシクロヘキシルビニルエーテル、グリシジル(メタ)アリルエーテル、３，４−エポキシシクロヘキシル(メタ)アリルエーテルなどを例としてあげることができる。 Examples of unsaturated aliphatic glycidyl esters include, but are not limited to, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl vinyl ether, 3,4-epoxycyclohexyl vinyl ether, glycidyl (meta Examples thereof include allyl ether and 3,4-epoxycyclohexyl (meth) allyl ether.
水酸基含有カルボン酸エステルとしては、以下の例には限定されないが、（メタ）アクリル酸ハイドロキシエチル、（メタ）アクリル酸ハイドロキシプロピル、（メタ）アクリル酸ヒドロキシブチルなどを例としてあげることができる。 Examples of the hydroxyl group-containing carboxylic acid ester include, but are not limited to, the following examples: hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and the like.
カルボン酸ビニルエステルとしては、以下の例には限定されないが、（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n-ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸tert-ブチル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸オクチル、（メタ）アクリル酸イソオクチル、（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）アクリル酸イソデシル、（メタ）アクリル酸トリデシル、（メタ）アルキル酸アルキレングリコール、（メタ）アクリル酸テトラヒドロフルフリル、（メタ）アクリル酸フェノキシエチル、（メタ）アクリル酸イソボニルなどを例としてあげることができる。 Examples of the carboxylic acid vinyl ester include, but are not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, (meth ) Isobutyl acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Lauryl (meth) acrylate, stearyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, alkylene glycol (meth) alkylate, tetrahydrofurfuryl (meth) acrylate, (meth) acrylic Examples of acid phenoxyethyl and isobornyl (meth) acrylate I can do it.
芳香族ビニル化合物としては、以下の例には限定されないが、スチレン、α−メチルスチレン、ビニルトルエンなどを例としてあげることができる。ただし、これら芳香族ビニル化合物を使用すると水除去性と美爪料の透明性の点で劣る傾向にあるので、その使用量は全単量体量を１００重量％とした場合５．０重量％以下が好ましい。 Examples of the aromatic vinyl compound include, but are not limited to, styrene, α-methylstyrene, vinyltoluene, and the like. However, since these aromatic vinyl compounds tend to be inferior in terms of water removability and transparency of the nail polish, the amount used is 5.0% by weight when the total monomer amount is 100% by weight. The following is preferred.
本発明で用いられるアクリル樹脂（Ａ）は、後述する炭素数４以下の低級アルコール（Ｂ）もしくは炭素数４以下の低級アルコール（Ｂ）と水との混合物及びアルカリ性化合物（Ｃ）の存在下に、アクリル樹脂溶液となり得るものであることが重要である。ここで、アクリル樹脂溶液とは、透明な溶液であって、アクリル樹脂（Ａ）が溶液中で均一な状態にある。アクリル樹脂（Ａ）が溶液に不均一に分散している場合は、不透明または半透明であり、アクリル樹脂溶液ではなく、アクリル樹脂の水性分散体である。水性分散体を用いて美爪料を作成した場合には、乾燥性、保存安定性、刷毛塗り性の点で難がある。また、水性分散体に着色剤（Ｄ）として顔料を加えて美爪料とする場合には、顔料の分散性が劣ることから、美爪料の乾燥後の光沢が低下する。 The acrylic resin (A) used in the present invention is in the presence of a lower alcohol (B) having 4 or less carbon atoms, a mixture of lower alcohol (B) having 4 or less carbon atoms and water, and an alkaline compound (C) described later. It is important that it can be an acrylic resin solution. Here, the acrylic resin solution is a transparent solution, and the acrylic resin (A) is in a uniform state in the solution. When the acrylic resin (A) is dispersed unevenly in the solution, it is opaque or translucent, and is not an acrylic resin solution but an aqueous dispersion of acrylic resin. When a nail polish is prepared using an aqueous dispersion, there are difficulties in terms of drying properties, storage stability, and brush coating properties. Further, when a pigment is added as a colorant (D) to an aqueous dispersion to make a nail polish, the dispersibility of the pigment is inferior, so that the gloss after drying the nail polish is lowered.
アクリル樹脂（Ａ）は、乳化重合、溶液重合等種々の方法で適宜得ることができるが、本発明においては、溶液重合で得ることが好ましい。溶液重合としては、例えば、美爪料を構成する後述の炭素数４以下の低級アルコール（Ｂ）もしくは炭素数４以下の低級アルコール（Ｂ）と水との混合物を用いて溶液重合することが、美爪料を作成する際の作業性の点で好ましい。なお、アクリル樹脂（Ａ）を乳化重合した場合には、その後の工程において、後述するアルカリ性化合物（Ｃ）により中和して均一化し、アクリル樹脂溶液としてもよい。 The acrylic resin (A) can be appropriately obtained by various methods such as emulsion polymerization and solution polymerization, but in the present invention, it is preferably obtained by solution polymerization. As solution polymerization, for example, solution polymerization may be performed using a lower alcohol (B) having 4 or less carbon atoms or a mixture of lower alcohol (B) having 4 or less carbon atoms and water, which constitutes the nail polish, It is preferable in terms of workability when creating a nail polish. In addition, when an acrylic resin (A) is emulsion-polymerized, it may be neutralized and neutralized with an alkaline compound (C), which will be described later, to obtain an acrylic resin solution.
本発明のアクリル樹脂（Ａ）を得るに際して用いられる重合開始剤としては、油溶性及び水溶性開始剤が挙げられ、ラジカル重合を開始する能力を有するものであれば特に制限はない。 The polymerization initiator used for obtaining the acrylic resin (A) of the present invention includes oil-soluble and water-soluble initiators, and is not particularly limited as long as it has the ability to initiate radical polymerization.
本発明において用いられる油溶性重合開始剤としては、以下の例には限定されないが、例えば、ベンゾイルパーオキサイド、ｔｅｒｔ−ブチルパーオキシベンゾエート、ｔｅｒｔ−ブチルハイドロパーオキサイド、ｔｅｒｔ−ブチルパーオキシ（２−エチルヘキサノエート）、ｔｅｒｔ−ブチルパーオキシ−３，５，５−トリメチルヘキサノエート、ジ−ｔｅｒｔ−ブチルパーオキサイド等の有機過酸化物、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス−２，４−ジメチルバレロニトリル、２，２’−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）、１，１’−アゾビス−シクロヘキサン−１−カルボニトリル、２,２’−アゾビス（２−メチルブチロニトリル）、ジメチル２，２’−アゾビス（２−メチルプロピオネート）、１,[（シアノ−１−メチルエチル）アゾ]ホルムアミド、２，２’−アゾビス[N−（２−プロペニル）−２−メチルプロピオンアミド]、２，２’−アゾビス（N−ブチル−２−メチルプロピオンアミド）、２，２’−アゾビス（N−シクロヘキシル−２−メチルプロピオンアミド）等のアゾビス化合物等を挙げることができる。
これらは１種類又は２種類以上を混合して使用することができる。これら重合開始剤は、アクリル樹脂（Ａ）の重合に使用される全ラジカル重合性不飽和単量体１００重量部に対して、０．１〜１０．０重量部程度の量を用いるのが好ましい。
The oil-soluble polymerization initiator used in the present invention is not limited to the following examples. For example, benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl hydroperoxide, tert-butyl peroxy (2- Ethyl hexanoate), organic peroxides such as tert-butylperoxy-3,5,5-trimethylhexanoate, di-tert-butyl peroxide, 2,2′-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis-cyclohexane-1-carbonitrile, 2'-azobis (2-methylbutyronitrile), dimethyl 2,2'-azobis (2-methylpropione) ), 1, [(cyano-1-methylethyl) azo] formamide, 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2′-azobis (N— And azobis compounds such as 2,2′-azobis (N-cyclohexyl-2-methylpropionamide).
These may be used alone or in combination of two or more. These polymerization initiators are preferably used in an amount of about 0.1 to 10.0 parts by weight with respect to 100 parts by weight of all radical polymerizable unsaturated monomers used for the polymerization of the acrylic resin (A). .
水溶性重合開始剤としては、従来既知のものを使用することができ、例えば、過硫酸アンモニウム、過硫酸カリウムなどが挙げられる。 As the water-soluble polymerization initiator, conventionally known ones can be used, and examples thereof include ammonium persulfate and potassium persulfate.
またアクリル樹脂（Ａ）を乳化重合で得るには、所望により上記水溶性重合開始剤とともに還元剤を併用することができる。これにより、乳化重合速度を促進したり、低温における乳化重合をしたりすることが容易になる。このような還元剤としては、例えば、アスコルビン酸、酒石酸、クエン酸、ブドウ糖、ホルムアルデヒドスルホキシラートなどの金属塩等の還元性有機化合物、チオ硫酸ナトリウム、亜硫酸ナトリウム、重亜硫酸ナトリウム、メタ重亜硫酸ナトリウム等の還元性無機化合物、塩化第一鉄、ロンガリット、二酸化チオ尿素などを例示できる。これら還元剤は、全ラジカル重合性不飽和単量体１００重量部に対して、０．０５〜５．０重量部程度の量を用いるのが好ましい。 Moreover, in order to obtain an acrylic resin (A) by emulsion polymerization, a reducing agent can be used together with the water-soluble polymerization initiator as desired. Thereby, it becomes easy to accelerate the emulsion polymerization rate or to carry out emulsion polymerization at a low temperature. Examples of such reducing agents include reducing organic compounds such as metal salts such as ascorbic acid, tartaric acid, citric acid, glucose, formaldehyde sulfoxylate, sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium metabisulfite. Examples thereof include reducing inorganic compounds such as ferrous chloride, Rongalite, and thiourea dioxide. These reducing agents are preferably used in an amount of about 0.05 to 5.0 parts by weight with respect to 100 parts by weight of the total radical polymerizable unsaturated monomer.
重合温度は、各重合開始剤の重合開始温度以上とする。例えば、アゾ系重合開始剤では、通常７０℃程度とすればよい。重合時間は特に制限されないが、通常２〜２４時間である。
なお、前記した重合開始剤によらずとも、光化学反応や、放射線照射等によっても重合を行うことができる。
The polymerization temperature is equal to or higher than the polymerization start temperature of each polymerization initiator. For example, in the case of an azo polymerization initiator, the temperature is usually about 70 ° C. The polymerization time is not particularly limited, but is usually 2 to 24 hours.
In addition, it can superpose | polymerize also by a photochemical reaction, radiation irradiation, etc. irrespective of an above described polymerization initiator.
＜炭素数４以下の低級アルコール（Ｂ）＞
本発明で使用する炭素数４以下の低級アルコールとしては、以下の例には限定されないが、メタノール、エタノール、ｎ-プロパノール、イソプロパノール、ｎ-ブタノール、イソブタノール、tert-ブタノールが挙げられ、人体や爪に対する影響を考慮するとエタノールがより好ましい。
炭素数４以下の低級アルコールのみだと、美爪料の乾燥が早く成膜性に影響する場合があるので、アクリル樹脂溶液に水を含めることが好ましい。これら低級アルコールと水とを併用する場合、両者の割合は美爪料としての乾燥性や成膜性を考慮し、任意に決めることができ、好ましくはアルコール／水＝２０〜８０／８０〜２０（重量比）である。
<Lower alcohol (B) having 4 or less carbon atoms>
Examples of the lower alcohol having 4 or less carbon atoms used in the present invention include, but are not limited to, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tert-butanol. Considering the influence on the nail, ethanol is more preferable.
If only a lower alcohol having 4 or less carbon atoms is used, drying of the nail polish may affect the film-forming property quickly, so it is preferable to include water in the acrylic resin solution. When these lower alcohols and water are used in combination, the ratio of the two can be arbitrarily determined in consideration of drying properties and film-forming properties as a nail material, preferably alcohol / water = 20-80 / 80-20. (Weight ratio).
＜アルカリ性化合物（Ｃ）＞
本発明に用いられるアルカリ性化合物（Ｃ）は、乾燥後の美爪料を爪から水で除去する際の水除去性を付与する機能を担う。即ち、乾燥後の皮膜中にある程度（Ｃ）成分が残存することによって、速やかな水除去性を確保することができる。
<Alkaline compound (C)>
The alkaline compound (C) used in the present invention bears the function of imparting water removability when the nail polish after drying is removed from the nail with water. In other words, when the component (C) remains to some extent in the dried film, quick water removability can be ensured.
アルカリ性化合物（Ｃ）としては、以下の例には限定されないが、各種アミン化合物、水酸化ナトリウムのような室温（２５℃）程度で固形の物、アンモニア等が挙げられる。乾燥後の皮膜中への残存を考慮すると、揮発し易すぎるアンモニアよりも、沸点（以下、ｂｐという。）０℃以上のアルカリ性化合物が好ましく、ｂｐが２０℃以上のアルカリ性化合物がより好ましい。また、爪や皮膚に対する影響を考慮すると、揮発性のない水酸化ナトリウム等よりも、揮発性のもの、例えば、各種アミン化合物の方が好ましい。より具体的にはｂｐが５０〜２５０℃の各種アミン化合物が特に好ましい。 Examples of the alkaline compound (C) include, but are not limited to, the following examples, various amine compounds, solid substances such as sodium hydroxide at about room temperature (25 ° C.), ammonia, and the like. Considering the remaining in the film after drying, an alkaline compound having a boiling point (hereinafter referred to as bp) of 0 ° C. or higher is preferable and an alkaline compound having a bp of 20 ° C. or higher is more preferable than ammonia that is easily volatilized. In consideration of the effect on nails and skin, volatile compounds such as various amine compounds are preferred over non-volatile sodium hydroxide. More specifically, various amine compounds having a bp of 50 to 250 ° C. are particularly preferable.
ｂｐが０℃以上の揮発性のアルカリ化合物としては、以下の例には限定されないが、エチルアミン（ｂｐ：３８．０℃、以下同様）ジエチルアミン（５５．５℃）、トリエチルアミン（８９．５℃）、２−エチルヘキシルアミン（１６９℃）、３−メトキシプロピルアミン（１１６℃）、３−エトシキプロピルアミン（１３５℃）、ジイソブチルアミン（１４０℃）、モノエタノールアミン（１７０．５℃）、ジエタノールアミン（２６８℃）、トリエタノールアミン（３６０℃）、イソプロピルアミン（３２．４℃）、ジイソプロピルアミン（８４．１℃）、イソプロパノールアミン（１６０℃）、Ｎ，Ｎ−ジイソプロパノールアミン（２４９℃）、２−アミノ−２−メチル−１−プロパノール（１６５℃）、２−（ジメチルアミノ）−２−メチルプロパノール（１６０℃）、Ｎ，Ｎ−ジメチルエタノールアミン（１３５℃）、Ｎ，Ｎ−ジエチルエタノールアミン（１６２℃）、Ｎ，Ｎ−ジブチルエタノールアミン（２２９℃）、Ｎ−（２−アミノエチル）エタノールアミン（２４４℃）、Ｎ−メチルジエタノールアミン（２４７℃）、Ｎ−メチルエタノールアミン（１５９℃）、３−アミノ−１−プロパノール（１８７℃）、モルホリン（１２８℃）、ｎ―メチルモルホリン（１１６℃）等が挙げられる。 The volatile alkali compound having a bp of 0 ° C. or higher is not limited to the following examples, but ethylamine (bp: 38.0 ° C., the same shall apply hereinafter) diethylamine (55.5 ° C.), triethylamine (89.5 ° C.) 2-ethylhexylamine (169 ° C.), 3-methoxypropylamine (116 ° C.), 3-ethoxypropylamine (135 ° C.), diisobutylamine (140 ° C.), monoethanolamine (170.5 ° C.), diethanolamine ( 268 ° C), triethanolamine (360 ° C), isopropylamine (32.4 ° C), diisopropylamine (84.1 ° C), isopropanolamine (160 ° C), N, N-diisopropanolamine (249 ° C), 2 -Amino-2-methyl-1-propanol (165 ° C.), 2- (dimethylamino) -2 Methylpropanol (160 ° C), N, N-dimethylethanolamine (135 ° C), N, N-diethylethanolamine (162 ° C), N, N-dibutylethanolamine (229 ° C), N- (2-aminoethyl) ) Ethanolamine (244 ° C), N-methyldiethanolamine (247 ° C), N-methylethanolamine (159 ° C), 3-amino-1-propanol (187 ° C), morpholine (128 ° C), n-methylmorpholine ( 116 ° C.).
アクリル樹脂溶液を得るには、第１の方法として、（Ｃ）成分を、（Ｂ）成分もしくは（Ｂ）成分と水との混合物に予め溶解しておいて、該アルカリ溶液中でアクリル系単量体を重合し、アクリル樹脂（Ａ）の均一溶液を得ることもできるし、あるいは、第２の方法として、（Ｂ）成分もしくは（Ｂ）成分と水との混合物中でアクリル単量体を重合後、アクリル樹脂（Ａ）の溶液ないし分散体に（Ｂ）成分もしくは（Ｂ）成分と水との混合物及び（Ｃ）成分を加えて、アクリル樹脂（Ａ）の均一溶液を得ることもできるが、後者（第２の方法）が好ましい。
後者（第２の方法）の場合、さらに、第（２−１）の方法として、アクリル樹脂（Ａ）の均一溶液に、後述する着色剤（Ｄ）等を加えて本発明の美爪料を得ることもできるし、あるいは、第（２−２）の方法として、アクリル樹脂（Ａ）の溶液ないし分散体に、アルカリ性化合物（Ｃ）及び後述する着色剤（Ｄ）等を加え、アクリル樹脂（Ａ）の均一溶液を含有する本発明の美爪料を得ることもでき、後者（２−２）がより好ましい。
In order to obtain an acrylic resin solution, as a first method, the component (C) is previously dissolved in the component (B) or a mixture of the component (B) and water, and the acrylic resin is dissolved in the alkaline solution. The monomer can be polymerized to obtain a uniform solution of the acrylic resin (A). Alternatively, as the second method, the acrylic monomer can be used in the component (B) or a mixture of the component (B) and water. After polymerization, a uniform solution of the acrylic resin (A) can be obtained by adding the component (B) or a mixture of the component (B) and water and the component (C) to the acrylic resin (A) solution or dispersion. However, the latter (second method) is preferable.
In the case of the latter (second method), as the method (2-1), the coloring agent (D) described later is added to the uniform solution of the acrylic resin (A) to add the beauty nail material of the present invention. Alternatively, as the method (2-2), an alkaline compound (C) and a colorant (D) described later are added to the solution or dispersion of the acrylic resin (A), and the acrylic resin ( A beautiful nail material of the present invention containing a uniform solution of A) can also be obtained, and the latter (2-2) is more preferred.
＜着色剤（Ｄ）＞
本発明に用いられる着色剤（Ｄ）としては、従来から化粧品に配合される顔料、染料が挙げられ、顔料を用いる場合には後述する顔料分散剤（Ｅ）を用いることが好ましい。
顔料としては、以下の例には限定されないが、チタンホワイト（酸化チタン）、チタンブラック、亜鉛華、べんがら、酸化クロム、鉄黒、コバルトブルー、アルミナホワイト、酸化鉄黄、ビリジアン、硫化亜鉛、リトポン、カドミウムエロー、朱、ガドミウムレッド、黄鉛、モリブデードオレンジ、ジンククロメート、ストロンチウムクロメート、ホワイトカーボン、群青、鉛白、紺青、マンガンバイオレット、アルミニウム粉、真鍮粉等の無機顔料、フタロシアニン系、アゾ系、アントラキノン系、キナクリドン系、ジオキサジン系、ジケトピロロピロール系、イソインドリノン系、イソインドリン系、キノフタロン系、アントラピリジン系、アンサンスロン系、インダンスロン系、フラバンスロン系、ペリノン系、ペリレン系顔料、カーボンブラック、黒鉛等の有機顔料及び酸性染料のレーキ顔料、魚鱗箔、各種雲母チタン、セリサイト、マスコバイト、アコヤ貝末、アワビ貝末、タカセ貝末等のパール顔料を用いることが出来る。
また、光沢を得るための無着色の美爪料の場合は、着色力が殆ど無い体質顔料を用いることができる。体質顔料としては、以下の例には限定されないが、バライト粉、沈降性硫酸バリウム、炭酸バリウム、炭酸石灰粉、沈降性炭酸カルシウム、石膏、アスベスト、クレー、シリカ粉、微粉ケイ酸、軽藻土、タルク、塩基性炭酸マグネシウム、アルミナホワイト、グロスホワイト、サチンホワイト、燐酸三カルシウム、ヒドロキシアパタイト等が挙げられる。
<Colorant (D)>
Examples of the colorant (D) used in the present invention include pigments and dyes that are conventionally blended in cosmetics. When a pigment is used, it is preferable to use a pigment dispersant (E) described later.
Examples of the pigment include, but are not limited to, titanium white (titanium oxide), titanium black, zinc white, red pepper, chromium oxide, iron black, cobalt blue, alumina white, iron oxide yellow, viridian, zinc sulfide, lithopone , Cadmium yellow, vermilion, cadmium red, yellow lead, molybdate orange, zinc chromate, strontium chromate, white carbon, ultramarine, lead white, bitumen, manganese violet, aluminum powder, brass powder and other inorganic pigments, phthalocyanine series, azo , Anthraquinone, quinacridone, dioxazine, diketopyrrolopyrrole, isoindolinone, isoindoline, quinophthalone, anthrapyridine, ansanthrone, indanthrone, flavanthrone, perinone, perylene Pigment, car Down black, organic pigments and lake pigments, fish scale foil of acid dyes such as graphite, various types of mica titanium, sericite, muscovite, pearl oyster end, abalone shellfish the end, it is possible to use a pearl pigment of Takase shell powder, and.
In the case of a non-colored beauty nail material for obtaining gloss, extender pigments having almost no coloring power can be used. The extender pigment is not limited to the following examples, but barite powder, precipitated barium sulfate, barium carbonate, lime carbonate powder, precipitated calcium carbonate, gypsum, asbestos, clay, silica powder, finely divided silicic acid, light algal soil , Talc, basic magnesium carbonate, alumina white, gloss white, satin white, tricalcium phosphate, hydroxyapatite and the like.
また、顔料表面に樹脂を修飾または被覆させて、顔料単体でも分散性を持たせた自己分散型顔料も使用する事ができる。
さらに本発明では、後述する顔料分散剤（Ｅ）を用いて、上記顔料を予め（Ｂ）成分中に分散させておいてから、上述のアクリル系樹脂（Ａ）の均一溶液と合わせて本発明の美爪料を得ることもできる。
In addition, a self-dispersing pigment in which the pigment surface is modified or coated so that the pigment itself is dispersible can also be used.
Furthermore, in the present invention, the pigment is dispersed in the component (B) in advance using the pigment dispersant (E) described later, and then combined with the above-mentioned homogeneous solution of the acrylic resin (A). You can also get a beautiful nail material.
本発明で用いられる染料としては、以下の例には限定されないが、ニトロ系の染料、酸性染料、塩基性染料、分散染料等が挙げられ、通常の化粧品等に使用し得る水溶性酸性染料であれば特に制限されず、例えば、赤色１２０号、黄色４号、黄色５号、赤色２０１号、赤色２２７号、橙色２０５号、かっ色２０１号、赤色５０２号、赤色５０３号、赤色５０４号、赤色５０６号、橙色４０２号、黄色４０２号、黄色４０６号、黄色４０７号、赤色２１３号、赤色２１４号、赤色３号、赤色１０４号、赤色１０５号の（１）、赤色１０６号、緑色２号、緑色３号、橙色２０７号、黄色２０２号の（１）、黄色２０２号の（２）、青色２０２号、青色２０３号、青色２０５号、青色２号、黄色２０３号、青色２０１号、緑色２０１号、青色１号、赤色２３０号の（１）、赤色２３１号、赤色２３２号、緑色２０４号、緑色２０５号、赤色４０１号、黄色４０３号の（１）、緑色４０１号、緑色４０２号、黒色４０１号、紫色４０１号、 等が挙げられる。求める美爪料の色調によって、染料及び顔料を選択して用いる。 The dyes used in the present invention are not limited to the following examples, but include nitro dyes, acid dyes, basic dyes, disperse dyes, and the like, which are water-soluble acid dyes that can be used for ordinary cosmetics and the like. If there is no particular limitation, for example, red 120, yellow 4, yellow 5, red 201, red 227, orange 205, brown 201, red 502, red 503, red 504, Red 506, Orange 402, Yellow 402, Yellow 406, Yellow 407, Red 213, Red 214, Red 3, Red 104, Red 105 (1), Red 106, Green 2 No. 3, Green No. 3, Orange No. 207, Yellow No. 202 (1), Yellow No. 202 (2), Blue No. 202, Blue No. 203, Blue No. 205, Blue No. 2, Yellow No. 203, Blue No. 201, Green 201, blue 1 Color 230 (1), Red 231, Red 232, Green 204, Green 205, Red 401, Yellow 403 (1), Green 401, Green 402, Black 401, Purple 401 No., etc. A dye and a pigment are selected and used according to the color tone of the desired nail material.
＜顔料分散剤（Ｅ）＞
着色剤（Ｄ）として、例えば酸化チタンやパール系顔料などの比重の高い顔料を用いると、美爪料を長期間静置した場合に高比重の顔料が沈降することがある。
このような場合、容器を振るなどの簡単な操作により再分散できる事が望ましい。沈降した顔料が固くなり再分散しにくいと、爪に塗った場合に、塗膜の色が薄く、隠ぺい力が弱く、塗膜に色斑ができる場合がある。そこで、本発明では、沈降しやすい顔料の沈降を抑制・防止したり、沈降した後の再分散性を向上したりするために、顔料分散剤（Ｅ）を使用することができる。顔料分散剤（Ｅ）を含有することによって、上記効果の他、塗膜の濃度（着色力）、光沢を向上したりすることができる。
<Pigment dispersant (E)>
When a pigment having a high specific gravity such as titanium oxide or a pearl pigment is used as the colorant (D), the pigment having a high specific gravity may precipitate when the nail polish is left standing for a long period of time.
In such a case, it is desirable to be able to redisperse by a simple operation such as shaking the container. If the settled pigment is hard and difficult to redisperse, when applied to the nail, the color of the coating film is thin, the hiding power is weak, and color spots may be formed on the coating film. Therefore, in the present invention, the pigment dispersant (E) can be used in order to suppress / prevent sedimentation of a pigment that easily settles, or to improve redispersibility after sedimentation. By containing the pigment dispersant (E), in addition to the above effects, the coating film concentration (coloring power) and gloss can be improved.
本発明における顔料分散剤（Ｅ）としては、例えば、界面活性剤、樹脂型分散剤、有機色素残基または複素環残基含有アミン誘導体の中から、単独もしくは組み合わせて用いることができる。 As the pigment dispersant (E) in the present invention, for example, a surfactant, a resin-type dispersant, an organic dye residue, or a heterocyclic residue-containing amine derivative can be used alone or in combination.
ところで、本発明の美爪料は、上記したように低級アルコール（Ｂ）もしくは低級アルコール（Ｂ）と水との混合物を液状媒体とする。従って、顔料分散剤（Ｅ）として樹脂型分散剤を用いる場合には、これら液体媒体との親和性に富むと共に、（Ｃ）成分によって収縮したり析出したりしないことが好ましい。
界面活性剤としては、以下の例には限定されないが、例えば、ノニオン系界面活性剤としては、ポリエチレンオキサイドアルキルエーテル、ポリエチレンオキサイドアルキルフェニルエーテル、ポリエチレンオキサイド−ポリプロピレンオキサイドブロックコポリマー等、アニオン系界面活性剤としては、例えばアルキルベンゼンスルホネート、アルキルナフタレン−スルホネート、ポリエチレンオキサイドアルキルエーテルサルフェート等、カチオン系界面活性剤としては、脂肪族炭化水素基を有する第１級、第２級、第３級アミン塩、第４級アンモニウム塩等が挙げられる。
樹脂型分散剤としては、以下の例には限定されないが、例えば、スチレン・アクリル酸共重合体、スチレン・マレイン酸共重合体、スチレン・アクリル酸アルキル共重合体及びスチレン・マレイン酸アルキル共重合体が挙げられ、これらの群より選ばれる樹脂型分散剤を用いると、顔料が沈降した場合も強固な塊とならず、再分散しやすいので好ましい。
By the way, as described above, the nail polish of the present invention uses the lower alcohol (B) or a mixture of the lower alcohol (B) and water as a liquid medium. Therefore, when a resin-type dispersant is used as the pigment dispersant (E), it is preferable that the pigment dispersant (E) has high affinity with the liquid medium and does not shrink or precipitate due to the component (C).
The surfactant is not limited to the following examples. For example, nonionic surfactants include anionic surfactants such as polyethylene oxide alkyl ether, polyethylene oxide alkylphenyl ether, polyethylene oxide-polypropylene oxide block copolymer, and the like. As the cationic surfactant, for example, alkylbenzene sulfonate, alkyl naphthalene-sulfonate, polyethylene oxide alkyl ether sulfate, etc., primary, secondary, tertiary amine salts having an aliphatic hydrocarbon group, fourth Class ammonium salt etc. are mentioned.
The resin-type dispersant is not limited to the following examples. For example, styrene / acrylic acid copolymer, styrene / maleic acid copolymer, styrene / alkyl acrylate copolymer, and styrene / alkyl maleic acid copolymer are used. It is preferable to use a resin-type dispersant selected from these groups, because even if the pigment settles, it does not form a strong lump and is easily redispersed.
上記の樹脂型分散剤の重量平均分子量は５,０００〜２０,０００であることが好ましく、５,０００〜１０,０００であることがより好ましい。重量平均分子量が５,０００未満だと分散樹脂その物の耐性が不足し易く、塗膜物性などが悪化することがある。重量平均分子量が２０,０００を越えると顔料分散能力が低下するのであまり好ましくない。
上記スチレン・アクリル酸共重合体等の群から選ばれる顔料分散剤（Ｅ）の酸価は１５０〜２５０であることが好ましく、１６０〜２３０であることがより好ましい。酸価が１５０未満だと顔料分散能力が低下し易く、２５０を越えると分散樹脂その物の耐性が不足し、塗膜物性などが悪化する傾向にあるので好ましくない。
The resin type dispersant preferably has a weight average molecular weight of 5,000 to 20,000, more preferably 5,000 to 10,000. If the weight average molecular weight is less than 5,000, the dispersion resin itself may be insufficiently resistant, and the physical properties of the coating film may be deteriorated. When the weight average molecular weight exceeds 20,000, the pigment dispersing ability is lowered, which is not preferable.
The acid value of the pigment dispersant (E) selected from the group such as the styrene / acrylic acid copolymer is preferably 150 to 250, and more preferably 160 to 230. If the acid value is less than 150, the pigment dispersing ability tends to be lowered, and if it exceeds 250, the dispersion resin itself is insufficient in resistance and the physical properties of the coating film tend to deteriorate.
＜増粘剤（Ｆ）＞
本発明では、顔料等の着色剤（Ｄ）の沈降速度を遅くして良好な経時安定性を確保し、適切な塗工性を得るために増粘剤（Ｆ）を使用することが出来る。
本発明で使用できる増粘剤（Ｆ）としては、以下の例には限定されないが、ヘクトライト、ベントナイト、モンモリロナイト、バイデライト等と称される天然スメクタイト系粘土及びそれらに類似もしくは近似の合成粘土等のいわゆる粘土増粘剤、鎖状の２次凝集に依って液体に擬塑性及び構造粘性を与える微粒子シリカ、超微粒子酸化アルミニウム、超微粒子酸化チタン等の一次粒径が５０ｎｍ以下の無機微粒子粉体、分子量の大きな（アクリル系樹脂、ポリビニルピロリドン、ポリエチレングリコール、カルボキシビニルポリマー等の）水溶性高分子、およびキサンタンガム、ウェランガム、グアーガム、タラカントガム、ローカストビーンガム、メチルセルロース、ヒドロキシエチルセルロース、カルボキシメチルセルロース、蛋白、酸化スターチ等の増粘多糖類さらにはポリウレタンなどの会合性増粘剤等が挙げられる。
<Thickener (F)>
In the present invention, the thickener (F) can be used to slow down the sedimentation rate of the colorant (D) such as a pigment to ensure good stability over time and to obtain appropriate coating properties.
The thickener (F) that can be used in the present invention is not limited to the following examples, but natural smectite clays such as hectorite, bentonite, montmorillonite, beidellite, and similar or similar synthetic clays. So-called clay thickeners, fine particle silica, ultrafine particle aluminum oxide, ultrafine particle titanium oxide, etc. that give liquid pseudoplasticity and structural viscosity by chain secondary aggregation , Water-soluble polymers having a large molecular weight (such as acrylic resin, polyvinyl pyrrolidone, polyethylene glycol, carboxyvinyl polymer) and xanthan gum, welan gum, guar gum, taracant gum, locust bean gum, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, protein, Further thickening polysaccharides such as starches may include associative thickeners such as such as polyurethane.
なかでも天然及び合成粘土増粘剤、分子量の大きな水溶性高分子、キサンタンガム、ウェランガム、及びキサンタンガムまたはウェランガムとグアーガム等のガラクトナンマンを併用した増粘多糖類は、水分により著しく膨潤するため、顔料が凝集するときの立体障害となり好ましい。 Among them, natural and synthetic clay thickeners, water-soluble polymers having a large molecular weight, xanthan gum, welan gum, and thickened polysaccharides using xanthan gum or galactanman such as welan gum and guar gum are swelled remarkably by moisture. This is preferable because it causes steric hindrance when agglomerates.
キサンタンガムとしては、以下の例には限定されないが、サンエース（商品名、三栄源エスエフアイ社製）、ケルトロール（商品名、大日本製薬社製）が挙げられる。アクリル系樹脂の増粘剤としては、以下の例には限定されないが、ストラクチャー（商品名、日本エヌエスシー社製）、アキュリン（商品名、ロームアンドハース社製）、アクペック（商品名、住友精化社製）が挙げられる。 Examples of xanthan gum include, but are not limited to, san ace (trade name, manufactured by Saneigen SFFI Co., Ltd.) and celtrol (trade name, manufactured by Dainippon Pharmaceutical Co., Ltd.). The thickening agent for acrylic resin is not limited to the following examples, but structure (trade name, manufactured by NSC Japan), aculine (trade name, manufactured by Rohm and Haas), Akpec (trade name, Sumitomo Seiki) For example).
本発明の美爪料は、アクリル樹脂（Ａ）、低級アルコール（Ｂ）もしくは低級アルコール（Ｂ）と水との混合物、アルカリ性化合物（Ｃ）、着色剤（Ｄ）、顔料分散剤（Ｅ）、増粘剤（Ｆ）の合計１００重量％中に、各成分を（Ａ）／（Ｂ）もしくは（Ｂ）と水との混合物／（Ｃ）／（Ｄ）／（Ｅ）／（Ｆ）＝３〜５０／４０〜９０／０．１〜２０／０．０１〜２０／０．０００１〜２０／０．０１〜１０（重量％）の割合で含むことが好ましく、５〜２０／４５〜８５／１〜１０／０．１〜１０／０．００１〜１０／０．１〜５（重量％）の割合で含むことがより好ましい。 The nail polish of the present invention comprises an acrylic resin (A), a lower alcohol (B) or a mixture of a lower alcohol (B) and water, an alkaline compound (C), a colorant (D), a pigment dispersant (E), In a total of 100% by weight of the thickener (F), each component is mixed with (A) / (B) or (B) and water / (C) / (D) / (E) / (F) = It is preferable to contain in the ratio of 3-50 / 40-90 / 0.1-20 / 0.01-20 / 0.0001-20 / 0.01-10 (weight%), 5-20 / 45-85 More preferably, it is contained at a ratio of / 1 to 10 / 0.1 to 10 / 0.001 to 10 / 0.1 to 5 (% by weight).
アクリル樹脂（Ａ）の美爪料中の量が、３重量％未満だと皮膜形成機能をほとんど発揮出来なくなり、他方５０重量％を越えると美爪料の粘度が高くなりすぎて爪に塗りにくくなる。
低級アルコール（Ｂ）もしくは低級アルコール（Ｂ）と水との混合物の美爪料中の量が、４０重量％未満になると美爪料の粘度が高くなりすぎて爪に塗りにくくなる。他方、９０重量％を超えると美爪料の造膜性成分が相対的に少なくなり、隠蔽力、着色力等が低下する傾向にある。また、低級アルコール（Ｂ）と水とを併用する場合、両者の割合は乾燥性や成膜性を考慮し、任意に決めることができ、好ましくはアルコール／水＝２０〜８０／８０〜２０（重量比）である。
アルカリ性化合物（Ｃ）の美爪料中の量が、０．１重量％未満だと中和不足のために水除去性が著しく低下し、他方２０重量％を越えると美爪料のｐＨが高くなりすぎて爪や肌に対して刺激が強くなる。
着色剤（Ｄ）の美爪料中の量が、０．０１重量％未満だとほとんど着色しない状態であるし、他方２０重量％を越えると保存安定性が悪化する傾向にある。
顔料分散剤（Ｅ）の美爪量料の量が、２０重量％を超えると皮膜強度を低下させてしまう場合がある。
増粘剤（Ｆ）の美爪料中の量が、１０重量％を超えると塗布性や塗布後の固着性が悪くなる傾向にある。
本発明の美爪料は水により除去し得るものである。水には、冷水、温水及び熱湯を含み、特に温度を限定しない。但し、美爪料の塗膜が爪に形成されていることを考慮すると、５〜４５℃の水により除去するのが好ましい。この範囲だと、人間が不快に感じず、火傷の心配もない。
If the amount of the acrylic resin (A) in the nail polish is less than 3% by weight, the film forming function can hardly be exhibited. On the other hand, if it exceeds 50% by weight, the viscosity of the nail polish becomes too high and it is difficult to apply to the nail. Become.
When the amount of the lower alcohol (B) or a mixture of the lower alcohol (B) and water in the nail polish is less than 40% by weight, the viscosity of the nail polish becomes too high and it becomes difficult to apply to the nail. On the other hand, if it exceeds 90% by weight, the film-forming components of the nail polish are relatively reduced, and the hiding power, coloring power and the like tend to be reduced. Moreover, when using together lower alcohol (B) and water, the ratio of both can be determined arbitrarily in consideration of drying property and film formability, Preferably alcohol / water = 20-80 / 80-20 ( Weight ratio).
If the amount of the alkaline compound (C) in the nail polish is less than 0.1% by weight, the water removability is remarkably lowered due to insufficient neutralization, and if it exceeds 20% by weight, the pH of the nail polish is high. Too much irritation to nails and skin.
When the amount of the colorant (D) in the nail polish is less than 0.01% by weight, the colorant is hardly colored, and when it exceeds 20% by weight, the storage stability tends to deteriorate.
If the amount of the nail amount of the pigment dispersant (E) exceeds 20% by weight, the film strength may be lowered.
When the amount of the thickener (F) in the nail polish exceeds 10% by weight, the coating property and the fixing property after coating tend to deteriorate.
The nail polish of the present invention can be removed with water. Water includes cold water, hot water, and hot water, and the temperature is not particularly limited. However, considering that the coating film of the beauty nail material is formed on the nail, it is preferably removed with water at 5 to 45 ° C. In this range, humans do not feel uncomfortable and there is no fear of burns.
以下、実施例によって本願発明の効果をさらに詳細に説明するが、本願発明はこれらに限定されるものではない。 Hereinafter, the effects of the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.
［実施例１］
＜共重合体溶液の合成＞
攪拌器、温度計、滴下ロート及び還流器を備えた反応容器に、イオン交換水２２．５重量部、エタノール１２７．７重量部、アクリル酸ブチル３８．８重量部、メタクリル酸メチル８８．１重量部、アクリル酸３３．８重量部、及び２，２’−アゾビスイソブチロニトリル（重合開始剤）１．８重量部とを仕込んだ。
[Example 1]
<Synthesis of copolymer solution>
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 22.5 parts by weight of ion-exchanged water, 127.7 parts by weight of ethanol, 38.8 parts by weight of butyl acrylate, 88.1 parts by weight of methyl methacrylate. Part, 33.8 parts by weight of acrylic acid, and 1.8 parts by weight of 2,2′-azobisisobutyronitrile (polymerization initiator).
次に、滴下槽に、イオン交換水２２．５重量部、エタノール１２７．７重量部、アクリル酸ブチル３８．８重量部、メタクリル酸メチル８８．１重量部、アクリル酸１１．３重量部、及び２，２’−アゾビスイソブチロニトリル（重合開始剤）１．２重量部を仕込み、撹拌した。 Next, 22.5 parts by weight of ion exchange water, 127.7 parts by weight of ethanol, 38.8 parts by weight of butyl acrylate, 88.1 parts by weight of methyl methacrylate, 11.3 parts by weight of acrylic acid, and 1.2 parts by weight of 2,2′-azobisisobutyronitrile (polymerization initiator) was charged and stirred.
反応容器の液温を７０℃に昇温し、十分に窒素置換した後、液温を７０℃に保ちながら滴下槽内のモノマー溶液を３時間かけて滴下し、更に同温度で３時間攪拌を継続し、重合した。
反応終了後、温度を３０℃まで冷却し、イオン交換水５９．２重量部とエタノール２８２．８重量部と２−アミノ−２−メチル・プロパノール５５．７重量部を添加してｐＨを８．５とし、不揮発分濃度３０．０％の共重合体溶液を得た。
得られた溶液の共重合体のゲルパーミエーションクロマトグラフィによるポリスチレン換算の重量平均分子量は１００，０００、酸価は（１１７mgＫＯＨ／g）、ガラス転移温度（計算値）は５０℃であった。
After the temperature of the reaction vessel was raised to 70 ° C. and sufficiently purged with nitrogen, the monomer solution in the dropping tank was dropped over 3 hours while maintaining the temperature of the solution at 70 ° C., and further stirred at the same temperature for 3 hours. Continued and polymerized.
After completion of the reaction, the temperature was cooled to 30 ° C., 59.2 parts by weight of ion exchange water, 282.8 parts by weight of ethanol and 55.7 parts by weight of 2-amino-2-methylpropanol were added to adjust the pH to 8. And a copolymer solution having a nonvolatile content concentration of 30.0% was obtained.
The copolymer of the obtained solution had a polystyrene-reduced weight average molecular weight of 100,000 by gel permeation chromatography, an acid value of (117 mgKOH / g), and a glass transition temperature (calculated value) of 50 ° C.
＜顔料分散ペーストの調整＞
顔料分散ペーストを調整した。具体的には、アクリル系高分子共重合体（高分子分散体、商品名“ジョンクリルJ67”（ジョンソンポリマー（株）社製、重量平均分子量１２,５００、酸価２１３、不揮発分９８%以上、スチレン−アクリル酸系）２．０重量部、イオン交換水７７．５重量部、及び２−アミノ−２−メチルプロパノール（中和剤）０．５重量％を混合攪拌し、水溶液を得た。次に、得られた水溶液に、酸化チタン（顔料）２０．０重量部を加え、粗分散を行った後、ガラスビーズ（直径０．５mm）を１００部添加し、ビーズミル分散器を用いて１時間湿式粉砕処理及び分散処理を行った。この分散液を５μｍのメンブレンフィルタで粗大粒子及び塵を除去して顔料ペーストを得た。
<Adjustment of pigment dispersion paste>
A pigment dispersion paste was prepared. Specifically, acrylic polymer copolymer (polymer dispersion, trade name “John Krill J67” (manufactured by Johnson Polymer Co., Ltd., weight average molecular weight 12,500, acid value 213, nonvolatile content 98% or more) Styrene-acrylic acid system) 2.0 parts by weight, ion-exchanged water 77.5 parts by weight, and 2-amino-2-methylpropanol (neutralizing agent) 0.5% by weight were mixed and stirred to obtain an aqueous solution. Next, 20.0 parts by weight of titanium oxide (pigment) is added to the obtained aqueous solution, and after coarse dispersion, 100 parts of glass beads (diameter 0.5 mm) are added, and a bead mill disperser is used. A wet pulverization treatment and a dispersion treatment were carried out for 1 hour, and coarse particles and dust were removed from the dispersion with a 5 μm membrane filter to obtain a pigment paste.
＜美爪料＞
得られた顔料分散ペースト３重量部、得られた共重合体溶液５０重量部、ベントナイト（増粘剤）５％水分散液２０重量部、イオン交換水１２重量部、及びエタノール１５重量部を混合して、美爪料を調製し、後述する方法及び基準に従って基本物性及び実用物性を評価した。
<Beautiful nails>
3 parts by weight of the obtained pigment dispersion paste, 50 parts by weight of the obtained copolymer solution, 20 parts by weight of 5% bentonite (thickener) aqueous dispersion, 12 parts by weight of ion-exchanged water, and 15 parts by weight of ethanol are mixed. Then, nail preparations were prepared, and the basic physical properties and practical physical properties were evaluated according to the methods and standards described later.
［実施例２］
攪拌器、温度計、滴下ロート及び還流器を備えた反応容器に、イオン交換水２２．５重量部、エタノール１２７．７重量部、アクリル酸ブチル３８．８重量部、メタクリル酸メチル７６．２重量部、アクリル酸３４．４重量部、及び２，２’−アゾビスイソブチロニトリル（重合開始剤）０．９重量部を仕込んだ。
[Example 2]
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 22.5 parts by weight of ion exchange water, 127.7 parts by weight of ethanol, 38.8 parts by weight of butyl acrylate, 76.2 parts by weight of methyl methacrylate. Part, 34.4 parts by weight of acrylic acid, and 0.9 part by weight of 2,2′-azobisisobutyronitrile (polymerization initiator) were charged.
次に、滴下槽に、イオン交換水２２．５重量部、エタノール１２７．７重量部、アクリル酸ブチル３８．８重量部、メタクリル酸メチル７６．２重量部、アクリル酸３４．３重量部、及び２，２’−アゾビスイソブチロニトリル（重合開始剤）０．６重量部を仕込み、撹拌した。 Next, 22.5 parts by weight of ion exchange water, 127.7 parts by weight of ethanol, 38.8 parts by weight of butyl acrylate, 76.2 parts by weight of methyl methacrylate, 34.3 parts by weight of acrylic acid, and 0.6 part by weight of 2,2′-azobisisobutyronitrile (polymerization initiator) was charged and stirred.
反応容器の液温を７０℃に昇温し、十分に窒素置換した後、実施例１と同様に重合し、反応終了後、温度を３０℃まで冷却し、イオン交換水３１．７重量部とエタノール２８２．８重量部と２−アミノ−２−メチル・プロパノール８４．９重量部を添加してｐＨを８．４とし、不揮発分濃度３０．０％の共重合体溶液を得た。
得られた溶液の共重合体のゲルパーミエーションクロマトグラフィによるポリスチレン換算の重量平均分子量は１８０，０００、酸価は１７９(mgＫＯＨ／g)、ガラス転移温度（計算値）は５０℃であった。
以下、実施例１と同様にして美爪料を調製し、評価した。
The temperature of the reaction vessel was raised to 70 ° C. and sufficiently purged with nitrogen, and then polymerized in the same manner as in Example 1. After the reaction was completed, the temperature was cooled to 30 ° C., and 31.7 parts by weight of ion-exchanged water was added. 282.8 parts by weight of ethanol and 84.9 parts by weight of 2-amino-2-methyl-propanol were added to adjust the pH to 8.4 to obtain a copolymer solution having a nonvolatile content concentration of 30.0%.
The copolymer of the obtained solution had a polystyrene-reduced weight average molecular weight of 180,000, an acid value of 179 (mgKOH / g), and a glass transition temperature (calculated value) of 50 ° C. by gel permeation chromatography.
Hereinafter, nail preparations were prepared and evaluated in the same manner as in Example 1.
［実施例３］
攪拌器、温度計、滴下ロート及び還流器を備えた反応容器に、イオン交換水２２．５重量部、エタノール１２７．７重量部、アクリル酸ブチル３８．８重量部、メタクリル酸メチル９５．１重量部、アクリル酸１５．４重量部、及び２，２’−アゾビスイソブチロニトリル（重合開始剤）３．６重量部を仕込んだ。
[Example 3]
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 22.5 parts by weight of ion exchange water, 127.7 parts by weight of ethanol, 38.8 parts by weight of butyl acrylate, 95.1 parts by weight of methyl methacrylate. Part, 15.4 parts by weight of acrylic acid, and 3.6 parts by weight of 2,2′-azobisisobutyronitrile (polymerization initiator).
次に、滴下槽に、イオン交換水２２．５重量部、エタノール１２７．７重量部、アクリル酸ブチル３８．８重量部、メタクリル酸メチル９５．１重量部、アクリル酸１５．４重量部、２，２’−アゾビスイソブチロニトリル（重合開始剤）２．４重量部を仕込み、撹拌した。 Next, 22.5 parts by weight of ion exchange water, 127.7 parts by weight of ethanol, 38.8 parts by weight of butyl acrylate, 95.1 parts by weight of methyl methacrylate, 15.4 parts by weight of acrylic acid, , 2'-azobisisobutyronitrile (polymerization initiator) 2.4 parts by weight was charged and stirred.
反応容器の液温を７０℃に昇温し、十分に窒素置換した後、実施例１と同様に重合し、反応終了後、温度を３０℃まで冷却し、イオン交換水７４．１重量部とエタノール２８２．８重量部と２−アミノ−２−メチル・プロパノール３８．１重量部を添加してｐＨを８．７とし、不揮発分濃度３０．０％の共重合体溶液を得た。
得られた溶液の共重合体のゲルパーミエーションクロマトグラフィによるポリスチレン換算の重量平均分子量は８０，０００、酸価は８０(mgＫＯＨ／g)、ガラス転移温度（計算値）は５０℃であった。
以下、実施例１と同様にして美爪料を調製し、評価した。
The temperature of the reaction vessel was raised to 70 ° C. and sufficiently purged with nitrogen, and then polymerized in the same manner as in Example 1. After completion of the reaction, the temperature was cooled to 30 ° C., and 74.1 parts by weight of ion-exchanged water was added. 282.8 parts by weight of ethanol and 38.1 parts by weight of 2-amino-2-methyl-propanol were added to adjust the pH to 8.7, and a copolymer solution having a nonvolatile content concentration of 30.0% was obtained.
The copolymer of the obtained solution had a polystyrene equivalent weight average molecular weight of 80,000, an acid value of 80 (mg KOH / g), and a glass transition temperature (calculated value) of 50 ° C. as determined by gel permeation chromatography.
Hereinafter, nail preparations were prepared and evaluated in the same manner as in Example 1.
［比較例４’］
アクリル樹脂の中和に用いた「２−アミノ−２−メチル・プロパノール５５．７部」の代わりに「２５％アンモニア水」を４２．３重量部用いた以外は実施例１と同様にして、ｐＨを８．８、不揮発分濃度３０．０％の共重合体溶液を得、以下同様にして美爪料を得た。
[ Comparative Example 4 ′ ]
Except for using 42.3 parts by weight of “25% aqueous ammonia” instead of “55.7 parts of 2-amino-2-methylpropanol” used for neutralization of the acrylic resin, the same as in Example 1, A copolymer solution having a pH of 8.8 and a non-volatile content of 30.0% was obtained.
［比較例１］
攪拌器、温度計、滴下ロート及び還流器を備えた反応容器に、イオン交換水２２．５重量部、エタノール１２７．７重量部、アクリル酸ブチル３８．８重量部、メタクリル酸メチル９５．１重量部、アクリル酸１５．４重量部、及び２，２’−アゾビスイソブチロニトリル（重合開始剤）０．４重量部とを仕込んだ。
[Comparative Example 1]
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 22.5 parts by weight of ion exchange water, 127.7 parts by weight of ethanol, 38.8 parts by weight of butyl acrylate, 95.1 parts by weight of methyl methacrylate. Parts, 15.4 parts by weight of acrylic acid, and 0.4 parts by weight of 2,2′-azobisisobutyronitrile (polymerization initiator).
次に、滴下槽に、イオン交換水２２．５重量部、エタノール１２７．７重量部、アクリル酸ブチル３８．８重量部、メタクリル酸メチル９５．１重量部、アクリル酸１５．４重量部、及び２，２’−アゾビスイソブチロニトリル（重合開始剤）０．３重量部を仕込み、撹拌した。 Next, in the dropping tank, 22.5 parts by weight of ion exchange water, 127.7 parts by weight of ethanol, 38.8 parts by weight of butyl acrylate, 95.1 parts by weight of methyl methacrylate, 15.4 parts by weight of acrylic acid, and 0.3 part by weight of 2,2′-azobisisobutyronitrile (polymerization initiator) was charged and stirred.
反応容器の液温を７０℃に昇温し、十分に窒素置換した後、実施例１と同様に重合し、反応終了後、温度を３０℃まで冷却し、イオン交換水７９．４重量部とエタノール２８２．８重量部と２−アミノ−２−メチル・プロパノール３８．１重量部を添加してｐＨを８．２とし、不揮発分濃度３０．０％の共重合体溶液を得た。
得られた溶液の共重合体のゲルパーミエーションクロマトグラフィによるポリスチレン換算の重量平均分子量は２５０，０００、酸価は８０(mgＫＯＨ／g)、ガラス転移温度（計算値）は５０℃であった。
以下、実施例１と同様にして美爪料を調製し、評価した。
The temperature of the reaction vessel was raised to 70 ° C. and sufficiently purged with nitrogen, and then polymerized in the same manner as in Example 1. After completion of the reaction, the temperature was cooled to 30 ° C., and 79.4 parts by weight of ion-exchanged water was added. 282.8 parts by weight of ethanol and 38.1 parts by weight of 2-amino-2-methyl-propanol were added to adjust the pH to 8.2 to obtain a copolymer solution having a nonvolatile content concentration of 30.0%.
The copolymer of the obtained solution had a polystyrene-reduced weight average molecular weight of 250,000, an acid value of 80 (mg KOH / g), and a glass transition temperature (calculated value) of 50 ° C. by gel permeation chromatography.
Hereinafter, nail preparations were prepared and evaluated in the same manner as in Example 1.
［比較例２］
攪拌器、温度計、滴下ロート及び還流器を備えた反応容器に、イオン交換水２２．５重量部、エタノール１２７．７重量部、アクリル酸ブチル３８．８重量部、メタクリル酸メチル６２．７重量部、アクリル酸４７．８重量部、及び２，２’−アゾビスイソブチロニトリル（重合開始剤）１．８重量部を仕込んだ。
[Comparative Example 2]
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 22.5 parts by weight of ion exchange water, 127.7 parts by weight of ethanol, 38.8 parts by weight of butyl acrylate, 62.7 parts by weight of methyl methacrylate. Part, 47.8 parts by weight of acrylic acid, and 1.8 parts by weight of 2,2′-azobisisobutyronitrile (polymerization initiator).
次に、滴下槽に、イオン交換水２２．５重量部、エタノール１２７．７重量部、アクリル酸ブチル３８．８重量部、メタクリル酸メチル６２．７重量部、アクリル酸４７．８重量部、及び２，２’−アゾビスイソブチロニトリル（重合開始剤）１．２重量部を仕込み、撹拌した。 Next, in the dropping tank, 22.5 parts by weight of ion exchange water, 127.7 parts by weight of ethanol, 38.8 parts by weight of butyl acrylate, 62.7 parts by weight of methyl methacrylate, 47.8 parts by weight of acrylic acid, and 1.2 parts by weight of 2,2′-azobisisobutyronitrile (polymerization initiator) was charged and stirred.
反応容器の液温を７０℃に昇温し、十分に窒素置換した後、実施例１と同様に重合し、反応終了後、温度を３０℃まで冷却し、イオン交換水３２．２重量部とエタノール２４７．８重量部と２−アミノ−２−メチル・プロパノール１１８重量部を添加してｐＨを８．４とし、不揮発分濃度３０．０％の共重合体溶液を得た。
得られた溶液の共重合体のゲルパーミエーションクロマトグラフィによるポリスチレン換算の重量平均分子量は１００，０００、酸価は２４９(mgＫＯＨ／g)、ガラス転移温度（計算値）は５０℃であった。
以下、実施例１と同様にして美爪料を調製し、評価した。
［比較例３］
The temperature of the reaction vessel was raised to 70 ° C. and sufficiently purged with nitrogen, and then polymerized in the same manner as in Example 1. After completion of the reaction, the temperature was cooled to 30 ° C., and 32.2 parts by weight of ion-exchanged water was added. Ethanol (247.8 parts by weight) and 2-amino-2-methyl-propanol (118 parts by weight) were added to adjust the pH to 8.4 to obtain a copolymer solution having a nonvolatile content concentration of 30.0%.
The copolymer of the obtained solution had a polystyrene-reduced weight average molecular weight of 100,000 by gel permeation chromatography, an acid value of 249 (mgKOH / g), and a glass transition temperature (calculated value) of 50 ° C.
Hereinafter, nail preparations were prepared and evaluated in the same manner as in Example 1.
[Comparative Example 3]
攪拌器、温度計、滴下ロート及び還流器を備えた反応容器に、イオン交換水２２．５重量部、エタノール１２７．７重量部、アクリル酸ブチル３８．８重量部、メタクリル酸メチル８８．１重量部、アクリル酸３３．８重量部、及び２，２’−アゾビスイソブチロニトリル（重合開始剤）９．０重量部を仕込んだ。 In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 22.5 parts by weight of ion-exchanged water, 127.7 parts by weight of ethanol, 38.8 parts by weight of butyl acrylate, 88.1 parts by weight of methyl methacrylate. Part, 33.8 parts by weight of acrylic acid, and 9.0 parts by weight of 2,2′-azobisisobutyronitrile (polymerization initiator).
次に、滴下槽に、イオン交換水２２．５重量部、エタノール１２７．７重量部、アクリル酸ブチル３８．８重量部、メタクリル酸メチル８８．１重量部、アクリル酸１１．３重量部、及び２，２’−アゾビスイソブチロニトリル（重合開始剤）６．０重量部を仕込み、撹拌した。 Next, 22.5 parts by weight of ion exchange water, 127.7 parts by weight of ethanol, 38.8 parts by weight of butyl acrylate, 88.1 parts by weight of methyl methacrylate, 11.3 parts by weight of acrylic acid, and 6.0 parts by weight of 2,2′-azobisisobutyronitrile (polymerization initiator) was charged and stirred.
反応容器の液温を７０℃に昇温し、十分に窒素置換した後、実施例１と同様に重合し、反応終了後、温度を３０℃まで冷却し、イオン交換水４７．２重量部とエタノール２８２．８重量部と２−アミノ−２−メチル・プロパノール５５．７重量部を添加してｐＨを８．５とし、不揮発分濃度３０．２％の共重合体溶液を得た。
得られた溶液の共重合体のゲルパーミエーションクロマトグラフィによるポリスチレン換算の重量平均分子量は２０，０００、酸価は１１７(mgＫＯＨ／g)、ガラス転移温度（計算値）は５０℃であった。
以下、実施例１と同様にして美爪料を調製し、評価した。
After the temperature of the reaction vessel was raised to 70 ° C. and sufficiently purged with nitrogen, polymerization was conducted in the same manner as in Example 1. After completion of the reaction, the temperature was cooled to 30 ° C., and 47.2 parts by weight of ion-exchanged water was added. 282.8 parts by weight of ethanol and 55.7 parts by weight of 2-amino-2-methyl propanol were added to adjust the pH to 8.5, thereby obtaining a copolymer solution having a nonvolatile content concentration of 30.2%.
The copolymer of the obtained solution had a weight average molecular weight in terms of polystyrene by gel permeation chromatography of 20,000, an acid value of 117 (mgKOH / g), and a glass transition temperature (calculated value) of 50 ° C.
Hereinafter, nail preparations were prepared and evaluated in the same manner as in Example 1.
［比較例４］
攪拌器、温度計、滴下ロート及び還流器を備えた反応容器に、イオン交換水２２．５重量部、エタノール１２７．７重量部、アクリル酸ブチル３８．８重量部、メタクリル酸メチル１００．８重量部、アクリル酸９．７重量部、及び２，２’−アゾビスイソブチロニトリル（重合開始剤）９．０重量部を仕込んだ。
[Comparative Example 4]
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux vessel, 22.5 parts by weight of ion-exchanged water, 127.7 parts by weight of ethanol, 38.8 parts by weight of butyl acrylate, 100.8 parts by weight of methyl methacrylate Part, 9.7 parts by weight of acrylic acid, and 9.0 parts by weight of 2,2′-azobisisobutyronitrile (polymerization initiator).
次に、滴下槽に、イオン交換水２２．５重量部、エタノール１２７．７重量部、アクリル酸ブチル３８．８重量部、メタクリル酸メチル１００．８重量部、アクリル酸９．７重量部、及びお２，２’−アゾビスイソブチロニトリル（重合開始剤）６．０重量部を仕込み、撹拌した。 Next, 22.5 parts by weight of ion exchange water, 127.7 parts by weight of ethanol, 38.8 parts by weight of butyl acrylate, 100.8 parts by weight of methyl methacrylate, 9.7 parts by weight of acrylic acid, and 6.0 parts by weight of 2,2′-azobisisobutyronitrile (polymerization initiator) was charged and stirred.
反応容器内の液温を７０℃に昇温し、十分に窒素置換した後、実施例１と同様に重合し、反応終了後、温度を３０℃まで冷却し、イオン交換水４７．２重量部とエタノール２８２．８重量部と２−アミノ−２−メチル・プロパノール５５．７重量部添加してｐＨを８．５とし、不揮発分濃度３０．２％の共重合体溶液を得た。
得られた溶液の共重合体のゲルパーミエーションクロマトグラフィによるポリスチレン換算の重量平均分子量は２０，０００、酸価は５０(mgＫＯＨ／g)、ガラス転移温度（計算値）は５０℃であった。
以下、実施例１と同様にして美爪料を調製し、評価した。
The liquid temperature in the reaction vessel was raised to 70 ° C. and sufficiently purged with nitrogen, and then polymerized in the same manner as in Example 1. After completion of the reaction, the temperature was cooled to 30 ° C. and 47.2 parts by weight of ion-exchanged water. And 282.8 parts by weight of ethanol and 55.7 parts by weight of 2-amino-2-methyl-propanol were added to adjust the pH to 8.5, thereby obtaining a copolymer solution having a nonvolatile content concentration of 30.2%.
The resulting solution copolymer had a polystyrene-reduced weight average molecular weight of 20,000, an acid value of 50 (mg KOH / g), and a glass transition temperature (calculated value) of 50 ° C. as determined by gel permeation chromatography.
Hereinafter, nail preparations were prepared and evaluated in the same manner as in Example 1.
［比較例５］
攪拌器、温度計、滴下ロート及び還流器を備えた反応容器に、イオン交換水２２．５重量部、エタノール１２７．７重量部、アクリル酸ブチル３８．８重量部、メタクリル酸メチル９５．１重量部、アクリル酸１５．４重量部、及び２，２’−アゾビスイソブチロニトリル（重合開始剤）３６重量部を仕込んだ。
[Comparative Example 5]
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 22.5 parts by weight of ion exchange water, 127.7 parts by weight of ethanol, 38.8 parts by weight of butyl acrylate, 95.1 parts by weight of methyl methacrylate. Part, 15.4 parts by weight of acrylic acid, and 36 parts by weight of 2,2′-azobisisobutyronitrile (polymerization initiator).
次に、滴下槽に、イオン交換水２２．５重量部、エタノール１２７．７重量部、アクリル酸ブチル３８．８重量部、メタクリル酸メチル９５．１重量部、アクリル酸１５．４重量部、及び２，２’−アゾビスイソブチロニトリル（重合開始剤）２４重量部を仕込み、撹拌した。 Next, in the dropping tank, 22.5 parts by weight of ion exchange water, 127.7 parts by weight of ethanol, 38.8 parts by weight of butyl acrylate, 95.1 parts by weight of methyl methacrylate, 15.4 parts by weight of acrylic acid, and 24 parts by weight of 2,2′-azobisisobutyronitrile (polymerization initiator) was charged and stirred.
反応容器内の液温を７０℃に昇温し、十分に窒素置換した後、実施例１と同様に重合し、反応終了後、温度を３０℃まで冷却し、イオン交換水２０．１重量部とエタノール２８２．８重量部と２−アミノ−２−メチル・プロパノール３８．１重量部を添加してｐＨを８．７とし、不揮発分濃度３０．０％の共重合体溶液を得た。
得られた溶液の共重合体のゲルパーミエーションクロマトグラフィによるポリスチレン換算の重量平均分子量は５，０００、酸価は８０(mgＫＯＨ／g)、ガラス転移温度（計算値）は５０℃であった。
以下、実施例１と同様にして美爪料を調製し、評価した。
The liquid temperature in the reaction vessel was raised to 70 ° C. and sufficiently purged with nitrogen, and then polymerized in the same manner as in Example 1. After the reaction was completed, the temperature was cooled to 30 ° C., and 20.1 parts by weight of ion-exchanged water. And 282.8 parts by weight of ethanol and 38.1 parts by weight of 2-amino-2-methyl-propanol were added to adjust the pH to 8.7, and a copolymer solution having a nonvolatile content concentration of 30.0% was obtained.
The copolymer of the obtained solution had a polystyrene-reduced weight average molecular weight of 5,000, an acid value of 80 (mg KOH / g), and a glass transition temperature (calculated value) of 50 ° C. as determined by gel permeation chromatography.
Hereinafter, nail preparations were prepared and evaluated in the same manner as in Example 1.
［比較例６］
攪拌器、温度計、滴下ロート及び還流器を備えた反応容器に、イオン交換水３００．８部及びアクアロンＫＨ−１０（反応性乳化剤、第一工業製薬社製）５．９重量部を仕込んだ。
[Comparative Example 6]
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux vessel, 300.8 parts of ion-exchanged water and 5.9 parts by weight of Aqualon KH-10 (reactive emulsifier, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) were charged. .
次に、滴下槽に、アクリル酸２−エチルヘキシル６８．１重量部、スチレン６１．５重量部、メタクリル酸メチル１３８．３重量部、アクリル酸３０．８重量部、ラウリルメルカプタン（連鎖移動剤）１．５重量部、イオン交換水２９４．１重量部、及びアクアロンＫＨ−１０（反応性乳化剤、第一工業製薬社製）５．９重量部をあらかじめ混合してプレエマルジョンを作成し、その得られたプレエマルジョンうちの５％を反応容器にさらに加えた。 Next, in the dropping tank, 68.1 parts by weight of 2-ethylhexyl acrylate, 61.5 parts by weight of styrene, 138.3 parts by weight of methyl methacrylate, 30.8 parts by weight of acrylic acid, lauryl mercaptan (chain transfer agent) 1 5 parts by weight, ion-exchanged water 294.1 parts by weight, and Aqualon KH-10 (reactive emulsifier, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 5.9 parts by weight are mixed in advance to obtain a pre-emulsion. An additional 5% of the pre-emulsion was added to the reaction vessel.
反応容器内の液温を６０℃に昇温し、十分に窒素置換した後、過硫酸カリウム（重合開始剤）の５％水溶液６．０部とメタ重亜硫酸ナトリウム（還元剤）の１％水溶液１４．７重量部を添加し重合を開始した。
反応系内を７０℃で５分間保持した後、内温を７０℃に保ちながらプレエマルジョンの残りと過硫酸カリウムの５％水溶液９．８部とメタ重亜硫酸ナトリウムの１％水溶液２４．６重量部を３時間かけて滴下し、更に３時間攪拌を継続した。なお乳化重合中、重合反応液のｐＨは３．０に保った。反応終了後、温度を３０℃まで冷却し、２−アミノ−２−メチル・プロパノールを３８．１重量部添加して、ｐＨを８．５とし、不揮発分濃度３０．５％の水性分散体を得た。水性分散体中の分散粒子の平均粒子径は７０ｎｍであった。
得られた水性分散体を室温で乾燥して樹脂粉末を作成し、これをテトラヒドロフラン（ＴＨＦ）に溶解した。この溶液の共重合体のゲルパーミエーションクロマトグラフィによるポリスチレン換算の重量平均分子量は８０，０００、酸価は８０(mgＫＯＨ／g)、ガラス転移温度（計算値）は５０℃であった。
以下、実施例１と同様にして、顔料分散ペースト３重量部、上記共重合体の水性分散体５０重量部、ベントナイト（増粘剤）５％水分散液２０重量部、イオン交換水１２重量部、及びエタノール１５部を混合して、美爪料を調製し、評価した。
尚、上記の美爪料とは別途に、上記共重合体の水性分散体５０重量部、イオン交換水１２重量部、エタノール１５部を混合したが（増粘剤なし）、上記共重合体は溶解しなかった。
After the temperature in the reaction vessel was raised to 60 ° C. and sufficiently substituted with nitrogen, 6.0 parts of 5% aqueous solution of potassium persulfate (polymerization initiator) and 1% aqueous solution of sodium metabisulfite (reducing agent) 14.7 parts by weight were added to initiate polymerization.
After maintaining the reaction system at 70 ° C. for 5 minutes, while maintaining the internal temperature at 70 ° C., the rest of the pre-emulsion, 9.8 parts of a 5% aqueous solution of potassium persulfate, and 24.6 wt. Of a 1% aqueous solution of sodium metabisulfite The portion was added dropwise over 3 hours, and stirring was further continued for 3 hours. During the emulsion polymerization, the pH of the polymerization reaction solution was kept at 3.0. After completion of the reaction, the temperature was cooled to 30 ° C., 38.1 parts by weight of 2-amino-2-methyl propanol was added to adjust the pH to 8.5, and an aqueous dispersion having a nonvolatile content concentration of 30.5% was obtained. Obtained. The average particle diameter of the dispersed particles in the aqueous dispersion was 70 nm.
The obtained aqueous dispersion was dried at room temperature to prepare a resin powder, which was dissolved in tetrahydrofuran (THF). The copolymer of this solution had a polystyrene equivalent weight average molecular weight of 80,000, an acid value of 80 (mg KOH / g), and a glass transition temperature (calculated value) of 50 ° C. as determined by gel permeation chromatography.
Thereafter, in the same manner as in Example 1, 3 parts by weight of pigment dispersion paste, 50 parts by weight of the aqueous dispersion of the above copolymer, 20 parts by weight of a 5% bentonite (thickener) aqueous dispersion, and 12 parts by weight of ion-exchanged water. , And 15 parts of ethanol were mixed to prepare a nail polish and evaluated.
Separately from the above-mentioned nail polish, 50 parts by weight of the aqueous dispersion of the above copolymer, 12 parts by weight of ion-exchanged water, and 15 parts of ethanol were mixed (without thickener). It did not dissolve.
〔基本物性評価〕
成膜方法：各実施例及び比較例で調製した美爪料を乾燥膜厚で１２０μmになるようにガラス板に塗布し、２５℃にて１日間乾燥して皮膜を形成した。評価は以下の方法によって行った。
[Basic physical property evaluation]
Film forming method: The nail material prepared in each of the examples and comparative examples was applied to a glass plate so as to have a dry film thickness of 120 μm, and dried at 25 ° C. for 1 day to form a film. Evaluation was performed by the following method.
水除去性：ガラス板上に塗布・乾燥させた各美爪料皮膜を約２５℃のイオン交換水中に１時間浸漬した後の被膜の残存程度で評価を行った。
○：残膜なし
△：一部残膜あり
×：１００％残膜
Water-removability: Evaluation was made based on the degree of remaining film after each beauty nail coating applied and dried on a glass plate was immersed in ion-exchanged water at about 25 ° C. for 1 hour.
○: No residual film △: Partial residual film ×: 100% residual film
光沢：ガラス板上に塗布・乾燥させた各美爪料皮膜の光沢を日本電色（株）製変角光沢度計にて、照射角度６０゜，受光角度６０゜で測定した。 Gloss: The gloss of each nail coating applied and dried on a glass plate was measured with a variable angle gloss meter manufactured by Nippon Denshoku Co., Ltd. at an irradiation angle of 60 ° and a light receiving angle of 60 °.
乾燥性：ガラス板上に美爪料を塗工してから、塗工した各美爪料皮膜に指を押しつけた時に指紋跡がつかなくなる時間で判断した。 Dryability: Judged by the time when fingerprints were not applied when a finger was pressed against each coated beauty nail coating after applying a nail polish on a glass plate.
保存安定性：各実施例及び比較例で調製した美爪料を密閉容器に入れ、５０℃の恒温槽で１カ月静置した時に、美爪料に顔料の沈降や溶液の分離の有無で判断した。
○：沈降・分離全くなし
△：わずかに分離、またはわずかに沈降
×：沈降・分離発生
Storage stability: When the nail material prepared in each example and comparative example is placed in a sealed container and left to stand for 1 month in a thermostatic bath at 50 ° C., the presence or absence of pigment settling or separation of the solution is determined. did.
○: No sedimentation / separation △: Slight separation or slight sedimentation ×: Sedimentation / separation occurred
刷毛塗り性：各実施例及び比較例で調製した美爪料を刷毛で爪に塗工する際に塗工筋と、刷毛から糸引きの有無で判断した。
○：塗工筋・糸引き全くなし
△：わずかに塗工筋、またはわずかに糸引き
×：塗工筋が残り、糸引き発生
Brush coatability: When applying the nail material prepared in each Example and Comparative Example to the nail with a brush, it was judged by the presence of stringing from the coating streaks and the brush.
○: No coating streaks / threading at all △: Slightly coating streaks or slight threading ×: Coating streaks remain and stringing occurs
鉛筆硬度：試料の被塗布面にガラス板を用いた他はＪＩＳ Ｋ５４００の８．４．２に準じて行った。 Pencil hardness: The test was performed according to JIS K5400 8.4.2 except that a glass plate was used for the coated surface of the sample.
密着性（碁盤目試験）：試料の被塗布面にガラス板を用いた他はＪＩＳ Ｋ５４００の８．５．２の碁盤目テープ法に準じて行った。
具体的には試料の被塗布面にます目の数２５間隔２ｍｍの切り傷を作成し、そこにセロハン粘着テープを圧着させた後塗布面に対して９０゜方向に瞬間的に引き剥がした時の膜の残存状態で判断した。評価基準は記載にある通り１０段階評価で行った。数値が大きいほど密着していることを示す。
Adhesiveness (cross cut test): It was carried out according to the cross cut tape method of 8.5.2 of JIS K5400, except that a glass plate was used for the coated surface of the sample.
Specifically, when a cut with a spacing of several 25 mm is made on the surface to be coated of the sample, and a cellophane adhesive tape is pressure-bonded thereto, it is instantaneously peeled off in the 90 ° direction with respect to the coated surface. Judgment was made on the remaining state of the membrane. The evaluation criteria were 10-level evaluation as described. The larger the value, the closer it is.
耐屈曲性試験：屈曲性：厚さ５００ミクロンのナイロン板に各美爪料を成膜させた後、ナイロン板を屈曲し、塗膜が割れるまでの時間を評価した。なお、実用上４以上は必要である。
５：２日以上皮膜割れなし
４：１日で皮膜割れる
３：１２時間で皮膜割れる
２：６時間で皮膜割れる
１：１時間で皮膜割れる
Flex resistance test: Flexibility: Each nail material was formed on a nylon plate having a thickness of 500 microns, the nylon plate was bent, and the time until the coating film was cracked was evaluated. In practice, four or more are necessary.
5: No film cracking for 2 days or more 4: Film crack in 1 day 3: Film crack in 12 hours 2: Film crack in 6 hours 1: 1 Film crack in 1 hour
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| JP5456388B2 (en) * | 2009-07-03 | 2014-03-26 | 株式会社日本触媒 | UV-cutting agent for cosmetics and cosmetics using the same |
| JP6053288B2 (en) * | 2012-01-18 | 2016-12-27 | 三菱鉛筆株式会社 | Beauty nail composition |
| JP6393463B2 (en) * | 2012-09-14 | 2018-09-19 | 三菱鉛筆株式会社 | Aqueous beauty nail composition |
| WO2014152964A1 (en) * | 2013-03-14 | 2014-09-25 | Mycone Dental Supply Company, Inc. | Method of removing polymerized coatings for human nails, polymerized coating for human nails having improved removability, and two package system |
| JP6827234B2 (en) * | 2016-08-02 | 2021-02-10 | 東洋紡株式会社 | Nail coating |
| JP6777901B2 (en) * | 2016-08-02 | 2020-10-28 | 東洋紡株式会社 | Nail care agent |
| KR101775090B1 (en) * | 2017-07-20 | 2017-09-05 | 주식회사 케미팜스 | Aqueous dispersed color solution and aqueous nail polish composition using the same |
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| JPS6033362B2 (en) * | 1978-03-28 | 1985-08-02 | カネボウ株式会社 | new nail enamel |
| JPH04297408A (en) * | 1991-03-27 | 1992-10-21 | Kao Corp | Water-based manicure |
| JP3149287B2 (en) * | 1993-02-05 | 2001-03-26 | ユーホーケミカル株式会社 | Aqueous nail composition |
| JP2534194B2 (en) * | 1993-09-02 | 1996-09-11 | 花王株式会社 | Water-based nail polish |
| JP3513864B2 (en) * | 1995-06-30 | 2004-03-31 | 株式会社コーセー | Aqueous nail polish |
| JPH09202715A (en) * | 1996-01-24 | 1997-08-05 | Mitsubishi Pencil Co Ltd | Manicure |
| JPH1017813A (en) * | 1996-07-05 | 1998-01-20 | Toray Ind Inc | Ink for production of color filter, production of color filter, and color filter produced thereby |
| BR9915869A (en) * | 1998-12-01 | 2001-08-21 | Procter & Gamble | Detergent composition, comprising dirt suspending agent, for use with a disposable absorbent pad |
| JP2000327989A (en) * | 1999-05-18 | 2000-11-28 | Kawasaki Steel Corp | Coating composition and lubrication-treated metallic plate |
| DE19939326A1 (en) * | 1999-08-19 | 2001-02-22 | Basf Ag | Aqueous cosmetic composition, e.g. nail varnish or hair setting lotion, contains an emulsion polymer with a glass transition point above room temperature and a minimum film-forming temperature below this |
| EP1083184A3 (en) * | 1999-09-07 | 2002-07-17 | Basf Aktiengesellschaft | Silicon-containing polymers, their preparation and their use |
| JP4164209B2 (en) * | 1999-10-28 | 2008-10-15 | 信越化学工業株式会社 | Cosmetics |
| JP4461308B2 (en) * | 1999-11-25 | 2010-05-12 | 麻沼総業株式会社 | Beauty nail |
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| JP2004203917A (en) * | 2002-12-24 | 2004-07-22 | Mitsubishi Chemicals Corp | Block polymer forming microphase separation structure and cosmetic using the same |
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |