JPH0415762B2 - - Google Patents
Info
- Publication number
- JPH0415762B2 JPH0415762B2 JP60108004A JP10800485A JPH0415762B2 JP H0415762 B2 JPH0415762 B2 JP H0415762B2 JP 60108004 A JP60108004 A JP 60108004A JP 10800485 A JP10800485 A JP 10800485A JP H0415762 B2 JPH0415762 B2 JP H0415762B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- oil
- polyoxyalkylene
- weight
- oil emulsion
- 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.)
- Expired - Lifetime
Links
- 239000002537 cosmetic Substances 0.000 claims description 25
- 235000001014 amino acid Nutrition 0.000 claims description 22
- 229920002545 silicone oil Polymers 0.000 claims description 19
- 239000012071 phase Substances 0.000 claims description 17
- 239000007762 w/o emulsion Substances 0.000 claims description 17
- -1 amino acid salt Chemical class 0.000 claims description 15
- 150000001413 amino acids Chemical class 0.000 claims description 13
- 229920001296 polysiloxane Polymers 0.000 claims description 12
- 239000002736 nonionic surfactant Substances 0.000 claims description 9
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 8
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 8
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 8
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical group OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 claims description 7
- 239000008346 aqueous phase Substances 0.000 claims description 7
- ONJPCDHZCFGTSI-NJYHNNHUSA-N CC(C)CCCCCCCCCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCCCCCCCCCC(C)C)[C@H]1OC[C@H](O)[C@H]1O Chemical compound CC(C)CCCCCCCCCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCCCCCCCCCC(C)C)[C@H]1OC[C@H](O)[C@H]1O ONJPCDHZCFGTSI-NJYHNNHUSA-N 0.000 claims description 6
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 claims description 6
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 4
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 4
- 235000003704 aspartic acid Nutrition 0.000 claims description 4
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 4
- 235000013922 glutamic acid Nutrition 0.000 claims description 4
- 239000004220 glutamic acid Substances 0.000 claims description 4
- LPROEOFOFNXVBR-UHFFFAOYSA-N 2,4,6,8,10,12,14,16-octamethyl-1,3,5,7,9,11,13,15-octaoxa-2,4,6,8,10,12,14,16-octasilacyclohexadecane Chemical compound C[SiH]1O[SiH](C)O[SiH](C)O[SiH](C)O[SiH](C)O[SiH](C)O[SiH](C)O[SiH](C)O1 LPROEOFOFNXVBR-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 3
- CMPDPBDUZTUXAD-UHFFFAOYSA-N [3-hydroxy-2-(16-methylheptadecanoyloxy)propyl] 16-methylheptadecanoate Chemical compound CC(C)CCCCCCCCCCCCCCC(=O)OCC(CO)OC(=O)CCCCCCCCCCCCCCC(C)C CMPDPBDUZTUXAD-UHFFFAOYSA-N 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims 1
- 229950004959 sorbitan oleate Drugs 0.000 claims 1
- 239000003921 oil Substances 0.000 description 29
- 235000019198 oils Nutrition 0.000 description 23
- 229940024606 amino acid Drugs 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 239000003755 preservative agent Substances 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 229940057995 liquid paraffin Drugs 0.000 description 9
- 230000002335 preservative effect Effects 0.000 description 9
- 239000003205 fragrance Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N squalane Chemical compound CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 8
- 238000005342 ion exchange Methods 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 5
- 229940058015 1,3-butylene glycol Drugs 0.000 description 5
- 239000013543 active substance Substances 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 235000006708 antioxidants Nutrition 0.000 description 5
- 235000019437 butane-1,3-diol Nutrition 0.000 description 5
- 239000008269 hand cream Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- PXEDJBXQKAGXNJ-QTNFYWBSSA-L disodium L-glutamate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](N)CCC([O-])=O PXEDJBXQKAGXNJ-QTNFYWBSSA-L 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 4
- 229940032094 squalane Drugs 0.000 description 4
- ZAKOWWREFLAJOT-CEFNRUSXSA-N D-alpha-tocopherylacetate Chemical compound CC(=O)OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C ZAKOWWREFLAJOT-CEFNRUSXSA-N 0.000 description 3
- 239000004471 Glycine Substances 0.000 description 3
- 150000007513 acids Chemical class 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
- ZAKOWWREFLAJOT-UHFFFAOYSA-N d-alpha-Tocopheryl acetate Natural products CC(=O)OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C ZAKOWWREFLAJOT-UHFFFAOYSA-N 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 3
- 229960001153 serine Drugs 0.000 description 3
- 229940042585 tocopherol acetate Drugs 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 description 2
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920002385 Sodium hyaluronate Polymers 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- XMXOIHIZTOVVFB-JIZZDEOASA-L disodium;(2s)-2-aminobutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](N)CC([O-])=O XMXOIHIZTOVVFB-JIZZDEOASA-L 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229940010747 sodium hyaluronate Drugs 0.000 description 2
- YWIVKILSMZOHHF-QJZPQSOGSA-N sodium;(2s,3s,4s,5r,6r)-6-[(2s,3r,4r,5s,6r)-3-acetamido-2-[(2s,3s,4r,5r,6r)-6-[(2r,3r,4r,5s,6r)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2- Chemical compound [Na+].CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 YWIVKILSMZOHHF-QJZPQSOGSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- DRAWQKGUORNASA-UHFFFAOYSA-N (2-hydroxy-3-octadec-9-enoyloxypropyl) octadec-9-enoate Chemical compound CCCCCCCCC=CCCCCCCCC(=O)OCC(O)COC(=O)CCCCCCCC=CCCCCCCCC DRAWQKGUORNASA-UHFFFAOYSA-N 0.000 description 1
- DSEKYWAQQVUQTP-XEWMWGOFSA-N (2r,4r,4as,6as,6as,6br,8ar,12ar,14as,14bs)-2-hydroxy-4,4a,6a,6b,8a,11,11,14a-octamethyl-2,4,5,6,6a,7,8,9,10,12,12a,13,14,14b-tetradecahydro-1h-picen-3-one Chemical compound C([C@H]1[C@]2(C)CC[C@@]34C)C(C)(C)CC[C@]1(C)CC[C@]2(C)[C@H]4CC[C@@]1(C)[C@H]3C[C@@H](O)C(=O)[C@@H]1C DSEKYWAQQVUQTP-XEWMWGOFSA-N 0.000 description 1
- HEGROCUPGYNROZ-DKWTVANSSA-N (2s)-2,4-diamino-4-oxobutanoic acid;sodium Chemical compound [Na].OC(=O)[C@@H](N)CC(N)=O HEGROCUPGYNROZ-DKWTVANSSA-N 0.000 description 1
- 239000000263 2,3-dihydroxypropyl (Z)-octadec-9-enoate Substances 0.000 description 1
- BKMUDUXPSVRLFZ-UHFFFAOYSA-N 2-methyl-1,3,5,7,9,2,4,6,8,10-pentaoxapentasilecane Chemical compound C[SiH]1O[SiH2]O[SiH2]O[SiH2]O[SiH2]O1 BKMUDUXPSVRLFZ-UHFFFAOYSA-N 0.000 description 1
- RZRNAYUHWVFMIP-GDCKJWNLSA-N 3-oleoyl-sn-glycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-GDCKJWNLSA-N 0.000 description 1
- CYDQOEWLBCCFJZ-UHFFFAOYSA-N 4-(4-fluorophenyl)oxane-4-carboxylic acid Chemical compound C=1C=C(F)C=CC=1C1(C(=O)O)CCOCC1 CYDQOEWLBCCFJZ-UHFFFAOYSA-N 0.000 description 1
- 239000004475 Arginine Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- AGPKZVBTJJNPAG-WHFBIAKZSA-N L-isoleucine Chemical compound CC[C@H](C)[C@H](N)C(O)=O AGPKZVBTJJNPAG-WHFBIAKZSA-N 0.000 description 1
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 1
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 description 1
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 1
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 description 1
- 239000004166 Lanolin Substances 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- 241001442654 Percnon planissimum Species 0.000 description 1
- 239000004264 Petrolatum Substances 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 description 1
- 239000004473 Threonine Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- LDDUCKDUDZVHLN-UHFFFAOYSA-N [2-hydroxy-3-[2-hydroxy-3-(16-methylheptadecanoyloxy)propoxy]propyl] 16-methylheptadecanoate Chemical compound CC(C)CCCCCCCCCCCCCCC(=O)OCC(O)COCC(O)COC(=O)CCCCCCCCCCCCCCC(C)C LDDUCKDUDZVHLN-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 1
- 239000003212 astringent agent Substances 0.000 description 1
- XNEFYCZVKIDDMS-UHFFFAOYSA-N avobenzone Chemical compound C1=CC(OC)=CC=C1C(=O)CC(=O)C1=CC=C(C(C)(C)C)C=C1 XNEFYCZVKIDDMS-UHFFFAOYSA-N 0.000 description 1
- 239000004204 candelilla wax Substances 0.000 description 1
- 235000013868 candelilla wax Nutrition 0.000 description 1
- 229940073532 candelilla wax Drugs 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 229940061607 dibasic sodium phosphate Drugs 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001815 facial effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- IUJAMGNYPWYUPM-UHFFFAOYSA-N hentriacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC IUJAMGNYPWYUPM-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229960000310 isoleucine Drugs 0.000 description 1
- AGPKZVBTJJNPAG-UHFFFAOYSA-N isoleucine Natural products CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229960000448 lactic acid Drugs 0.000 description 1
- 235000019388 lanolin Nutrition 0.000 description 1
- 229940039717 lanolin Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000000845 maltitol Substances 0.000 description 1
- VQHSOMBJVWLPSR-WUJBLJFYSA-N maltitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O VQHSOMBJVWLPSR-WUJBLJFYSA-N 0.000 description 1
- 235000010449 maltitol Nutrition 0.000 description 1
- 229940035436 maltitol Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 229940066842 petrolatum Drugs 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- DQAKJEWZWDQURW-UHFFFAOYSA-N pyrrolidonecarboxylic acid Chemical class OC(=O)N1CCCC1=O DQAKJEWZWDQURW-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229960001790 sodium citrate Drugs 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- 239000001540 sodium lactate Substances 0.000 description 1
- 229940005581 sodium lactate Drugs 0.000 description 1
- 235000011088 sodium lactate Nutrition 0.000 description 1
- 229940045920 sodium pyrrolidone carboxylate Drugs 0.000 description 1
- HYRLWUFWDYFEES-UHFFFAOYSA-M sodium;2-oxopyrrolidine-1-carboxylate Chemical compound [Na+].[O-]C(=O)N1CCCC1=O HYRLWUFWDYFEES-UHFFFAOYSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 235000010356 sorbitol Nutrition 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
- A61K8/064—Water-in-oil emulsions, e.g. Water-in-silicone emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
- A61K8/585—Organosilicon compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Dermatology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Cosmetics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
[産業上の利用分野]
本発明は安定で使用感の優れた油中水型乳化化
粧料に関する。さらに詳しくは、シリコン油を多
量に配合していながらも安定で、使用感の優れた
油中水型乳化化粧料に関する。
[従来の技術]
従来、油中水型乳化化粧料に使用される油分と
して流動パラフインやスクワランなどの炭化水素
系のものが多く知られ、これらは肌表面をオイル
膜でカバーし水分蒸発を防ぐことから肌荒れなど
に効果があると考えられている。
これらの油分を使用したフエーシヤル化粧料は
トリートメント効果の高い製品として発売され、
また、メーキヤツプ化粧料では、撥水性に優れ、
化粧くずれが少ない製品として市場で発売されて
いる。
一方、油分としてシリコン油を配合した油中水
型乳化化粧料はなめらかな使用性を持ち撥水性に
優れている。とりわけ、揮発性シリコンを配合し
た化粧料は塗布時ののびが良く、のばすにつれて
揮発性シリコン油が揮発して、肌表面上に残存す
るオイル分をすくなくする為、密着性がよく、ま
た皮脂や汗に強く、化粧くずれしにくい製品がで
きるという特徴がある。
[発明が解決しようとする問題点]
しかしながら、シリコン油は安定な油中水型乳
化系を得るのが非常に難しいという欠点を有して
おり、これを多量に配合しかつ市販に耐えうる安
定性を有する油中水型乳化化粧料は、強く要望さ
れているのにもかかわらず得られていない。これ
まで安定性の良好なシリコン油の油中水型乳化化
粧料を得るための方法として、ワツクス類を増加
し固化させる方法またはシリカを用いる方法など
が知られているが、いずれの方法ものびが重くな
りべたつくなどの欠点があつた。
本発明者らは、こうした事情にかんがみ鋭意検
討した結果、シリコン油を30%以上配合した油相
において、アミノ酸および/またはアミノ酸塩を
含有した水相と特定の界面活性剤を用いることに
より安定で使用感触の優れた油中水型乳化化粧料
が得られることを見出し、本発明を完成するに至
つた。
[問題点を解決するための手段]
すなわち本発明は(A)シリコン油が油相成分中の
30%以上である油相と(B)アミノ酸および/または
アミノ酸塩が水相成分中の0.1%以上である水相
と(C)親油性非イオン界面活性剤とからなり、(A):
(B)が重量比で1:1〜1:5であり(C)が全成分中
の2重量%以上である油中水型乳化化粧料であ
る。以下に、本発明の構成について詳述する。
本発明でもちいられるシリコン油は従来用いら
れるもので良いが、具体的にはジメチルポリシロ
キサン、メチルフエニルポリシロキサン、デカメ
チルシクロペンタシロキサン、オクタメチルシク
ロオクタシロキサンが挙げられ、これらの中でも
特にデカメチルシクロペンタシロキサン、オクタ
メチルシクロオクタシロキサンなどの揮発性シリ
コン油が好ましい。
また、シリコン油の配合量は、他の油相成分の
量と関係するが、油相成分中の30%以上であるこ
とが好ましい。すなわち、シリコン油の配合量が
油相成分の30%以下の場合は、油相の性質が他の
配合油分の性質に近くなるので、他の配合油分に
適した親油性非イオン界面活性剤を使用すること
ができる。しかし、シリコン油の配合量が他の油
相成分の30%以上になると、従来の親油性非イオ
ン界面活性剤では、安定な乳化状態を作れず、分
離してしまうため、本発明の親油性非イオン界面
活性剤が安定した乳化状態を保持するために必要
となる。次いで、本発明で用いられる親油性非イ
オン界面活性剤は、ソルビタンセスキイソステア
レート、ソルビタンジイソステアレート、ソルビ
タンセスキオレート、ソルビタンジオレート、グ
リセリルジオレート、グリセリルジイソステアレ
ートおよび下記[1]、[2]、[3]の構造式をも
つ界面活性剤。
{一般式[1]、[2]、[3]中、Rはメチル基
または一部がフエニル基、R′は水素または炭素
数1〜12のアルキル基、pは1〜5の数、qは2
〜3の数、x、m、nは平均数でポリオキシアル
キレン変性ホルガノポリシロキサンが分子中にポ
リオキシアルキレン基を5〜40重量%含有し且つ
該ポリオキシアルキレン変性オルガノポリシロキ
サンの分子量が1000以上になるような数値を表
す。}であり、これらの界面活性剤は、シリコン
油を30%以上含有する油相成分を乳化し、安定な
油中水型乳化系をつくる。
さらに、ソルビタンセスキイソステアレート、
ソルビタンジイソステアレート、ソルビタンセス
キオレート、ソルビタンジオレート、グリセリル
ジオレート、グリセリルジイソステアレートおよ
び[1][2][3]の一般式をもつ活性剤のうち
ポリオキシアルキレン基の重量%が5〜40重量%
で分子量が1000以上のものと、アミノ酸および/
またはアミノ酸塩類を組合せることにより飛躍的
に安定性が向上する。
さらに、本発明で用いられるアミノ酸は通常知
られるアミノ酸でよく、例えばグリシン、アラニ
ン、バリン、ロイシン、イソロイシン、セリン、
トレオニン、フエニルアラニン等のモノアミノモ
ノカルボン酸、アスパラギン酸、グルタミン酸等
のモノアミノジカルボン酸、アルギニン、リジン
等のジアミノモノカルボン酸および/またはその
塩類が挙げられる。これらのアミノ酸および/ま
たはアミノ酸塩類が使用されるが、とりわけ、ア
スパラギン酸、グルタミン酸などの酸性アミノ酸
のナトリウム塩またはカリウム塩は本発明の親油
性非イオン界面活性剤と乳化して安定な油中水型
乳化化粧料をつくる。
本発明で用いられるアミノ酸および/またはア
ミノ酸塩類の濃度は水相成分中の0.1%以上であ
るが、0.1%以下の場合ではその効果が現れず多
量に配合した場合は析出が生じ好ましくない。こ
のため、本発明に用いるアミノ酸および/または
アミノ酸塩類の濃度は好ましくは0.1%〜20%で
ある。
また、本発明は(A)シリコン油が油相成分中の30
%以上である油相と(B)アミノ酸および/またはア
ミノ酸塩類が水相成分中の0.1%以上である水相
と(C)親油性非イオン界面活性剤の配合料は、(A)中
のシリコン油の量および(B)中のアミノ酸の量と(C)
中の親油性活性剤の量を調整することにより、安
定性や使用感を調整できるのであるが、安定性が
よくかつ使用感触がべたつかず、さつぱりし、の
びをよくするには水相成分を多く配合することが
必要となり、好ましくは(A):(B)が重量比で1:1
〜1:5で(C)が全成分中の2%以上がよく、特に
好ましは(A):(B)が重量比で1:2〜1:4であ
る。
このように、本発明の油中水型乳化化粧料は水
相成分を多量に配合できることも特徴のひとつで
あり、このためさつぱりとした使用感触を出しや
すく、従来の油中水型乳化化粧料に比べその使用
感触は画期的である。
本発明の乳化化粧料には上記の必須成分に加え
て、必要に応じて通常の化粧料に配合される成分
を配合しうる。たとえば、水相成分としてプロピ
レングリコール、ジプロピレングリコール、1−
3ブチレングリコール、グリセリン、マルチトー
ル、ソルビトール、ポリエチレングリコール、ヒ
アルロン酸ナトリウム、ピロリドンカルボン酸塩
類等の保湿剤や、油相成分としてワセリン、ラノ
リン、セレシン、マイクロクリスタリンワツク
ス、カルナバロウ、キヤンデリラロウ、高級脂肪
酸、高級アルコール等の固型または半固型油分、
スクワラン、流動パラフイン、エステル油、トリ
グリセライド等の流動油分、その他、所望に応じ
て無機顔料や有機顔料等の色材、カチオン性活性
剤、アニオン性活性剤、非イオン性活性剤等の界
面活性剤、ビタミンE、ビタンEアセテート等の
薬剤、収れん剤、酸化防止剤、防腐剤、香料およ
びクエン酸、クエン酸ナトリウム、乳酸、乳酸ナ
トリウム、第2リン酸ナトリウム等のPH調整剤ま
たは有機変性モンモリロナイト等の増粘剤、紫外
線吸収剤等を本発明の油中水型乳化化粧料に適宜
配合することができる。
〔実施例〕
次に本発明を実施例をもつて詳細に説明する。
本発明はこれにより限定されるものではない。
実施例中の配合量は重量%である。実施例に先立
ち各実施例で採用した評価方法を説明する。
(安定性)
所定の方法で作成した油中水型乳化化粧料を0
℃、室温、37℃の恒温槽内に放置して、一定期間
後の安定性を下記の評価基準に従つて評価した。
分離 凝集なし 〇
〃 僅かにあり △
〃 あり ×
(使用性)
女性パネル20名を用いて、のび、さつぱり、も
ち、フイツト感などの使用性を下記の評価基準に
従つて評価した。
良いと答えた人数が15名以上 〇
〃 7名〜14名 △
〃 6名以下 ×
実施例1 ハンドクリーム
デカメチルシクロペンタシロキサン 10.0
ジメチルポリシロキサン(6cs) 5.0
流動パラフイン(120cs) 5.0
ポリオキシアルキレン変性
オルガノポリシロキサン[一般式1]
(ポリオキシアルキレン重量20%
平均分子量6200) 5.0
香 料 0.2
イオン交換水 65.6
L−グルタミン酸ナトリウム 4.0
1,3ブチレングリコール 5.0
防腐剤 0.2
(製法)
の油相を70℃に加熱しておく。これにあらか
じめ70℃に加熱したを添加し、乳化分散後室温
まで撹拌冷却して目的のハンドクリームを得る。
以下実施例及び比較例の製造方法は実施例1の
方法に準ずる。
(結果)
表1に示したごとく、本実施例のハンドクリー
ムは安定性、使用性ともに良好な成績を示した。
実施例2 ハンドクリーム
オクタメチルシクロテトラシロキサン 5.0
デカメチルシクロペンタシロキサン 5.0
ジメチルポリシロキサン(6cs) 5.0
流動パラフイン(70cs) 5.0
ソルビタンジイソステアレート 8.0
香 料 0.2
イオン交換水 62.5
L−セリン 1.0
L−アスパラギン酸ナトリウム 3.0
プロピレングリコール 5.0
防腐剤 0.3
(結果)
表1に示した如く、本実施例のハンドクリーム
は安定性、使用性ともに良好な成績を示した。
比較例 1
デカメチルシクロペンタシロキサン 10.0
ジメチルポリシロキサン(6cs) 5.0
流動パラフイン(70cs) 5.0
ポリオキシアルキレン変性
オルガノポリシロキサン[一般式1]
ポリオキシアルキレン重量20%平均分子量
6200) 5.0
香 料 0.2
イオン交換水 65.6
1,3ブチレングリコール 5.0
防腐剤 0.2
(結果)
安定性、使用性の評価結果を表1に示した。
比較例 2
デカメチルシクロペンタシロキサン 10.0
ジメチルポリシロキサン(6cs) 5.0
流動パラフイン(70cs) 5.0
グリセリルモノオレート 5.0
香 料 0.2
イオン交換水 65.6
L−グルタミン酸ナトリウム 4.0
1,3ブチレングリコール 5.0
防腐剤 0.2
(結果)
安定性、使用性の評価結果を表1に示した。
比較例 3
流動パラフイン(70cs) 25.0
ジグリセリンジイソステアレート 6.0
香 料 0.2
イオン交換水 59.6
L−グルタミン酸ナトリウム 4.0
1,3ブチレングリコール 5.0
防腐剤 0.2
(結果)
安定性、使用性の評価結果を表1に示した。
[Industrial Application Field] The present invention relates to a water-in-oil emulsion cosmetic that is stable and has an excellent feeling of use. More specifically, the present invention relates to a water-in-oil emulsion cosmetic that is stable and has an excellent feel when used, even though it contains a large amount of silicone oil. [Conventional technology] Hydrocarbon-based oils such as liquid paraffin and squalane are conventionally known as oils used in water-in-oil emulsified cosmetics, and these oils cover the skin surface with an oil film to prevent water evaporation. Therefore, it is thought to be effective for treating rough skin. Facial cosmetics using these oils are released as products with high treatment effects,
In addition, makeup cosmetics have excellent water repellency,
It is sold on the market as a product that does not leave makeup smudged. On the other hand, water-in-oil emulsion cosmetics containing silicone oil as the oil component are smooth to use and have excellent water repellency. In particular, cosmetics containing volatile silicone spread easily when applied, and as they spread, the volatile silicone oil evaporates, reducing the amount of oil remaining on the skin surface, resulting in good adhesion. It is characterized by being able to produce products that are sweat resistant and do not easily remove makeup. [Problems to be solved by the invention] However, silicone oil has the disadvantage that it is very difficult to obtain a stable water-in-oil emulsion system, and it is difficult to obtain a stable water-in-oil emulsion system by blending a large amount of silicone oil and creating a stable water-in-oil emulsion system. Although water-in-oil type emulsified cosmetics having the same properties are strongly desired, they have not yet been obtained. Until now, methods for obtaining highly stable water-in-oil emulsified cosmetics made from silicone oil have been known, such as increasing and solidifying waxes or using silica. It had drawbacks such as being heavy and sticky. In view of these circumstances, the inventors of the present invention have made extensive studies and found that an oil phase containing 30% or more silicone oil can be stabilized by using an aqueous phase containing amino acids and/or amino acid salts and a specific surfactant. The present inventors have discovered that a water-in-oil emulsion cosmetic with an excellent feel during use can be obtained, and have completed the present invention. [Means for solving the problems] That is, the present invention provides (A) silicone oil in the oil phase component.
(B) an aqueous phase in which amino acids and/or amino acid salts are 0.1% or more of the water phase components; and (C) a lipophilic nonionic surfactant; (A):
This is a water-in-oil emulsion cosmetic in which (B) is present in a weight ratio of 1:1 to 1:5 and (C) is present in an amount of 2% by weight or more based on the total components. The configuration of the present invention will be explained in detail below. The silicone oil used in the present invention may be any conventionally used silicone oil, but specific examples include dimethylpolysiloxane, methylphenylpolysiloxane, decamethylcyclopentasiloxane, and octamethylcyclooctasiloxane. Volatile silicone oils such as methylcyclopentasiloxane and octamethylcyclooctasiloxane are preferred. The amount of silicone oil to be blended is related to the amount of other oil phase components, but it is preferably 30% or more of the oil phase components. In other words, if the blended amount of silicone oil is 30% or less of the oil phase components, the properties of the oil phase will be close to those of other blended oils, so a lipophilic nonionic surfactant suitable for the other blended oils should be used. can be used. However, when the amount of silicone oil blended exceeds 30% of other oil phase components, conventional lipophilic nonionic surfactants cannot create a stable emulsified state and separate, so the lipophilic surfactant of the present invention A nonionic surfactant is required to maintain a stable emulsified state. Next, the lipophilic nonionic surfactants used in the present invention include sorbitan sesquiisostearate, sorbitan diisostearate, sorbitan sesquiolate, sorbitandiolate, glyceryldiolate, glyceryl diisostearate and the following [1] , [2], a surfactant having the structural formula of [3]. {In the general formulas [1], [2], [3], R is a methyl group or a partially phenyl group, R' is hydrogen or an alkyl group having 1 to 12 carbon atoms, p is a number of 1 to 5, q is 2
The numbers x, m, and n are average numbers, and the polyoxyalkylene-modified organopolysiloxane contains 5 to 40% by weight of polyoxyalkylene groups in the molecule, and the molecular weight of the polyoxyalkylene-modified organopolysiloxane is Represents a numerical value greater than or equal to 1000. }, and these surfactants emulsify the oil phase component containing 30% or more silicone oil to create a stable water-in-oil emulsion system. In addition, sorbitan sesquiisostearate,
Sorbitan diisostearate, sorbitan sesquiolate, sorbitan diolate, glyceryl dioleate, glyceryl diisostearate and the active agents having the general formulas [1][2][3] have a weight percent of polyoxyalkylene groups. 5-40% by weight
and those with a molecular weight of 1000 or more, amino acids and/or
Alternatively, the stability can be dramatically improved by combining amino acid salts. Furthermore, the amino acids used in the present invention may be commonly known amino acids, such as glycine, alanine, valine, leucine, isoleucine, serine,
Examples include monoaminomonocarboxylic acids such as threonine and phenylalanine, monoaminodicarboxylic acids such as aspartic acid and glutamic acid, diaminomonocarboxylic acids such as arginine and lysine, and/or salts thereof. These amino acids and/or amino acid salts may be used, especially sodium or potassium salts of acidic amino acids such as aspartic acid, glutamic acid, etc., which can be emulsified with the lipophilic nonionic surfactants of the present invention to form stable water-in-oil surfactants. Create emulsified cosmetics. The concentration of the amino acid and/or amino acid salt used in the present invention is 0.1% or more in the aqueous phase component, but if the concentration is 0.1% or less, the effect will not be apparent, and if a large amount is added, precipitation will occur, which is not preferable. Therefore, the concentration of the amino acid and/or amino acid salt used in the present invention is preferably 0.1% to 20%. In addition, the present invention provides that (A) silicone oil is 30% of the oil phase component.
% or more of the oil phase, (B) the aqueous phase where the amino acids and/or amino acid salts are 0.1% or more of the water phase components, and (C) the lipophilic nonionic surfactant in (A). Amount of silicone oil and amount of amino acids in (B) and (C)
Stability and feel can be adjusted by adjusting the amount of lipophilic active agent in the mixture, but in order to achieve good stability, a non-sticky feel, a crisp feel, and good spreadability, it is necessary to use an aqueous phase. It is necessary to mix a large amount of ingredients, preferably (A):(B) in a weight ratio of 1:1.
The weight ratio of (A) to (B) is preferably 1:2 to 1:4. As described above, one of the characteristics of the water-in-oil emulsified cosmetic of the present invention is that it can contain a large amount of water phase components, which makes it easier to produce a refreshing feel when using it, compared to conventional water-in-oil emulsified cosmetics. Its feel is revolutionary compared to cosmetics. In addition to the above-mentioned essential ingredients, the emulsified cosmetic composition of the present invention may contain, if necessary, components that are included in ordinary cosmetic compositions. For example, propylene glycol, dipropylene glycol, 1-
Moisturizing agents such as 3-butylene glycol, glycerin, maltitol, sorbitol, polyethylene glycol, sodium hyaluronate, pyrrolidone carboxylates, and oil phase components such as petrolatum, lanolin, ceresin, microcrystalline wax, carnauba wax, candelilla wax, higher fatty acids, Solid or semi-solid oils such as higher alcohols,
Liquid oils such as squalane, liquid paraffin, ester oils, triglycerides, etc., coloring materials such as inorganic pigments and organic pigments, and surfactants such as cationic active agents, anionic active agents, and nonionic active agents as required. , vitamin E, vitamin E acetate, etc., astringents, antioxidants, preservatives, fragrances, and PH regulators such as citric acid, sodium citrate, lactic acid, sodium lactate, dibasic sodium phosphate, or organically modified montmorillonite, etc. Thickeners, ultraviolet absorbers, and the like can be appropriately blended into the water-in-oil emulsion cosmetic of the present invention. [Example] Next, the present invention will be explained in detail with reference to an example. The present invention is not limited thereby.
The blending amounts in the examples are weight %. Prior to the examples, evaluation methods adopted in each example will be explained. (Stability) A water-in-oil emulsion cosmetic prepared by a specified method is
℃, room temperature, and in a constant temperature bath at 37℃, and the stability after a certain period of time was evaluated according to the following evaluation criteria. Separation No aggregation 〇 〃 Slightly △ 〃 Yes × (Usability) Using 20 female panels, usability such as spreadability, crispness, stickiness, and firmness was evaluated according to the following evaluation criteria. 15 or more people answered that it was good 〇 〃 7 to 14 people △ 〃 6 or less people × Example 1 Hand cream Decamethylcyclopentasiloxane 10.0 Dimethylpolysiloxane (6cs) 5.0 Liquid paraffin (120cs) 5.0 Modified with polyoxyalkylene Organopolysiloxane [General formula 1] (Polyoxyalkylene weight 20% Average molecular weight 6200) 5.0 Fragrance 0.2 Ion-exchanged water 65.6 Sodium L-glutamate 4.0 1,3-butylene glycol 5.0 Preservative 0.2 (Production method) The oil phase of Heat it to. To this is added preheated to 70°C, and after emulsification and dispersion, the mixture is stirred and cooled to room temperature to obtain the desired hand cream. The manufacturing methods of Examples and Comparative Examples below are based on the method of Example 1. (Results) As shown in Table 1, the hand cream of this example showed good results in both stability and usability. Example 2 Hand cream Octamethylcyclotetrasiloxane 5.0 Decamethylcyclopentasiloxane 5.0 Dimethylpolysiloxane (6cs) 5.0 Liquid paraffin (70cs) 5.0 Sorbitan diisostearate 8.0 Fragrance 0.2 Ion exchange water 62.5 L-serine 1.0 L-asparagine Sodium acid 3.0 Propylene glycol 5.0 Preservative 0.3 (Results) As shown in Table 1, the hand cream of this example showed good results in both stability and usability. Comparative example 1 Decamethylcyclopentasiloxane 10.0 Dimethylpolysiloxane (6cs) 5.0 Liquid paraffin (70cs) 5.0 Polyoxyalkylene modified organopolysiloxane [General formula 1] Polyoxyalkylene weight 20% average molecular weight
6200) 5.0 Fragrance 0.2 Ion-exchanged water 65.6 1,3-butylene glycol 5.0 Preservative 0.2 (Results) Table 1 shows the evaluation results of stability and usability. Comparative example 2 Decamethylcyclopentasiloxane 10.0 Dimethylpolysiloxane (6cs) 5.0 Liquid paraffin (70cs) 5.0 Glyceryl monooleate 5.0 Fragrance 0.2 Ion exchange water 65.6 Sodium L-glutamate 4.0 1,3-butylene glycol 5.0 Preservative 0.2 (Results) Table 1 shows the evaluation results of stability and usability. Comparative example 3 Liquid paraffin (70cs) 25.0 Diglycerin diisostearate 6.0 Fragrance 0.2 Ion exchange water 59.6 Sodium L-glutamate 4.0 1,3-butylene glycol 5.0 Preservative 0.2 (Results) The evaluation results of stability and usability are shown. Shown in 1.
【表】
実施例 3〜6
表2に示す配合品を調整し、安定性、使用性を
評価した。評価結果を表2中に示した。
比較例 4、5
表2に示す配合品を調整し、安定性、使用性を
評価した。評価結果を表2中に示した。
実施例 7〜10
表3に示す配合品を調整し、安定性、使用性を
評価した。評価結果を表3中に示した。
比較例 6
表3に示す配合品を調整し、安定性、使用性を
評価した。評価結果を表3中に示した。[Table] Examples 3 to 6 The formulations shown in Table 2 were prepared and evaluated for stability and usability. The evaluation results are shown in Table 2. Comparative Examples 4 and 5 The formulations shown in Table 2 were prepared and evaluated for stability and usability. The evaluation results are shown in Table 2. Examples 7 to 10 The formulations shown in Table 3 were prepared and evaluated for stability and usability. The evaluation results are shown in Table 3. Comparative Example 6 The formulations shown in Table 3 were prepared and evaluated for stability and usability. The evaluation results are shown in Table 3.
【表】【table】
【表】【table】
【表】
実施例11 乳液
オクタメチルシクロテトラシロキサン 10.0
ジメチルボリシロキサン(6cs) 10.0
セチルイソオクタネート 2.0
流動パラフイン(120cs) 2.0
ソルビタンジイソステアレート 3.0
ポリオキシアルキレン変性
オルガノポリシロキサン[一般式3]
(ポリオキシアルキレン基17重量%平均分子量
6000) 3.0
酸化防止剤 適 量
香 料 〃
イオン交換水 63.7
L−セリン 1.0
L−アスパラギン酸ナトリウム 2.0
グリセリン 3.0
ヒアルロン酸ナトリウム 0.1
防腐剤 0.2
実施例12 ヘアクリーム
オクタメチルシクロテトラシロキサン 10.0
フエニルポリシロキサン 5.0
スクワラン 4.0
シリコンワツクス 1.0
グリセリルジオレート 2.0
ポリオキシアルキレン変性
オルガノポリシロキサン[一般式2]
(ポリオキシアルキレン基15重量%平均分子量
9000) 4.0
酸化防止剤 0.05
ビタミンEアセテート 0.1
イオン交換水 67.05
グリシン 2.0
ロイシン 1.0
チロシン 0.5
プロピレングリコール 3.0
防腐剤 0.3
実施例13 サンタンローシヨン
ジメチルポリシロキサン(6cs) 5.0
デカメチルシクロペナタシロキサン 3.0
オリーブ油 5.0
流動パラフイン(70cs) 5.0
4−tert−ブチル−4′−メトキシ−ジベンゾイ
ルメタン 0.3
ジメチルオクチルPAPA 1.0
ポリオキシアルキレン変性
オルガノポリシロキサン[一般式1]
(ポリオキシアルキレン基20重量%平均分子量
2000) 6.0
微粒子酸化チタン 1.0
酸化防止剤 0.05
香 料 0.3
イオン交換水 61.05
ジプロピレングリコール 5.0
L−グルタミン酸ナトリウム 5.0
ピロリドンカルボン酸ナトリウム 2.0
防腐剤 0.3
実施例14 マツサージクリーム
デカメチルシクロペナタシロキサン 5.0
ジメチルポリシロキサン(6cs) 5.0
流動パラフイン(70cs) 10.0
スクワラン 5.0
ソルビタンジイソステアレート 4.0
ポリオキシアルキレン変性
オルガノポリシロキサン[一般式1]
(ポリオキシアルキレン基15重量%平均分子量
3000) 3.0
ビタミンEアセテート 0.1
酸化防止剤 0.05
香 料 0.3
イオン交換水 58.35
L−アスパラギン酸ナトリウム 2.0
グリシン 2.0
グリセリン 2.0
1,3−ブチレングリコール 3.0
防腐剤 0.2
[発明の効果]
本発明は、上述してきた通りの構成であるから
安定性に優れ、使用感がさつぱりした油中水型乳
化化粧料を得ることができる。[Table] Example 11 Emulsion octamethylcyclotetrasiloxane 10.0 Dimethylborisiloxane (6cs) 10.0 Cetyl isooctanate 2.0 Liquid paraffin (120cs) 2.0 Sorbitan diisostearate 3.0 Polyoxyalkylene modified organopolysiloxane [General formula 3] Polyoxyalkylene group 17% by weight average molecular weight
6000) 3.0 Antioxidant Appropriate amount Fragrance 〃 Ion exchange water 63.7 L-serine 1.0 Sodium L-aspartate 2.0 Glycerin 3.0 Sodium hyaluronate 0.1 Preservative 0.2 Example 12 Hair cream octamethylcyclotetrasiloxane 10.0 Phenylpolysiloxane 5.0 Squalane 4.0 Silicon wax 1.0 Glyceryldiolate 2.0 Polyoxyalkylene-modified organopolysiloxane [General formula 2] (Polyoxyalkylene group 15% by weight average molecular weight
9000) 4.0 Antioxidant 0.05 Vitamin E acetate 0.1 Ion exchange water 67.05 Glycine 2.0 Leucine 1.0 Tyrosine 0.5 Propylene glycol 3.0 Preservative 0.3 Example 13 Suntan lotion dimethylpolysiloxane (6cs) 5.0 Decamethylcyclopenatasiloxane 3.0 Olive oil 5. 0 flow Paraffin (70cs) 5.0 4-tert-butyl-4'-methoxy-dibenzoylmethane 0.3 Dimethyloctyl PAPA 1.0 Polyoxyalkylene-modified organopolysiloxane [General formula 1] (Polyoxyalkylene group 20% by weight average molecular weight
2000) 6.0 Particulate titanium oxide 1.0 Antioxidant 0.05 Fragrance 0.3 Ion exchange water 61.05 Dipropylene glycol 5.0 Sodium L-glutamate 5.0 Sodium pyrrolidone carboxylate 2.0 Preservative 0.3 Example 14 Pine surge cream decamethylcyclopenatasiloxane 5.0 Dimethylpolysiloxane (6cs) 5.0 Liquid paraffin (70cs) 10.0 Squalane 5.0 Sorbitan diisostearate 4.0 Polyoxyalkylene-modified organopolysiloxane [General formula 1] (Polyoxyalkylene group 15% by weight average molecular weight
3000) 3.0 Vitamin E acetate 0.1 Antioxidant 0.05 Flavor 0.3 Ion exchange water 58.35 Sodium L-aspartate 2.0 Glycine 2.0 Glycerin 2.0 1,3-butylene glycol 3.0 Preservative 0.2 [Effects of the invention] The present invention has the above-mentioned effects. With the same structure, a water-in-oil emulsion cosmetic with excellent stability and a refreshing feel can be obtained.
Claims (1)
下、単に%という)以上である油相と(B)アミノ酸
および/またはアミノ酸塩が水相成分中の0.1%
以上である水相と(C)親油型非イオン界面活性剤と
からなり、(A):(B)が重量比で1:1〜1:5であ
り(C)が全成分中の2%以上である油中水型乳化化
粧料。 2 シリコン油がジメチルポリシロキサン、メチ
ルフエニルポリシロキサン、デカメチルシクロペ
ンタシロキサン、またはオクタメチルシクロオク
タシロキサンである特許請求の範囲第1項記載の
油中水型乳化化粧料。 3 親油性非イオン界面活性剤がソルビタンセス
キイソステアレート、ソルビタンジイソステアレ
ート、ソルビタンセスキオレート、ソルビタンオ
レート、グリセリルジオレート、グリセリルジイ
ソステアレート、または下記一般式[1]、[2]、
[3]で示されるポリオキシアルキレン変性オル
ガノポリシロキサンである特許請求の範囲第1項
記載の油中水型乳化化粧料。 {一般式[1]、[2]、[3]中、Rはメチル基
または一部がフエニル基、R′は水素または炭素
数1〜12のアルキル基、pは1〜5の数、qは2
〜3の数、x、m、nは平均数でポリオキシアル
キレン変性ホルガノポリシロキサンが分子中にポ
リオキシアルキレン基を5〜40重量%含有し且つ
該ポリオキシアルキレン変性オルガノポリシロキ
サンの分子量が1000以上になるような数値を表
す。} 4 アミノ酸がアスパラギン酸、グルタミン酸で
ある特許請求の範囲第1項記載の油中水型乳化化
粧料。 5 アミノ酸塩がアスパラギン酸のナトリウム塩
またはカリウム塩あるいはグルタミン酸のナトリ
ウム塩またはカリウム塩である特許請求の範囲第
1項記載の油中水型乳化化粧料。[Scope of Claims] 1. (A) an oil phase in which silicone oil accounts for 30% by weight or more (hereinafter simply referred to as %) of the oil phase component, and (B) an amino acid and/or an amino acid salt of 0.1% by weight in the aqueous phase component. %
It consists of the above aqueous phase and (C) a lipophilic nonionic surfactant, in which the weight ratio of (A):(B) is 1:1 to 1:5, and (C) is 2 of the total components. % or more of water-in-oil emulsion cosmetics. 2. The water-in-oil emulsion cosmetic according to claim 1, wherein the silicone oil is dimethylpolysiloxane, methylphenylpolysiloxane, decamethylcyclopentasiloxane, or octamethylcyclooctasiloxane. 3 The lipophilic nonionic surfactant is sorbitan sesquiisostearate, sorbitan diisostearate, sorbitan sesquiolate, sorbitan oleate, glyceryldiolate, glyceryl diisostearate, or the following general formula [1], [2],
The water-in-oil emulsion cosmetic according to claim 1, which is a polyoxyalkylene-modified organopolysiloxane represented by [3]. {In the general formulas [1], [2], [3], R is a methyl group or a partially phenyl group, R' is hydrogen or an alkyl group having 1 to 12 carbon atoms, p is a number of 1 to 5, q is 2
The numbers x, m, and n are average numbers, and the polyoxyalkylene-modified organopolysiloxane contains 5 to 40% by weight of polyoxyalkylene groups in the molecule, and the molecular weight of the polyoxyalkylene-modified organopolysiloxane is Represents a numerical value greater than or equal to 1000. } 4. The water-in-oil emulsion cosmetic according to claim 1, wherein the amino acid is aspartic acid or glutamic acid. 5. The water-in-oil emulsion cosmetic according to claim 1, wherein the amino acid salt is a sodium or potassium salt of aspartic acid or a sodium or potassium salt of glutamic acid.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10800485A JPS61293903A (en) | 1985-05-20 | 1985-05-20 | Water-in-oil type emulsion cosmetic |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10800485A JPS61293903A (en) | 1985-05-20 | 1985-05-20 | Water-in-oil type emulsion cosmetic |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS61293903A JPS61293903A (en) | 1986-12-24 |
JPH0415762B2 true JPH0415762B2 (en) | 1992-03-19 |
Family
ID=14473541
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP10800485A Granted JPS61293903A (en) | 1985-05-20 | 1985-05-20 | Water-in-oil type emulsion cosmetic |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS61293903A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2505602A1 (en) | 2011-03-29 | 2012-10-03 | Shin-Etsu Chemical Co., Ltd. | Organopolysiloxane and cosmetic containing it |
US10662294B2 (en) | 2016-03-28 | 2020-05-26 | Shin-Etsu Chemical Co., Ltd. | Organopolysiloxane, cosmetics, and method for manufacturing organopolysiloxane |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0720856B2 (en) * | 1988-12-01 | 1995-03-08 | 株式会社大塚製薬工場 | Composition for sterilizing and cleaning skin |
TWI255191B (en) * | 1999-04-16 | 2006-05-21 | Shiseido Co Ltd | High water content water-in-oil emulsified cosmetic composition |
KR100913689B1 (en) * | 2009-02-20 | 2009-08-24 | 화일약품주식회사 | Aqueous nanoemulsion composition containing conjugated linoleic acid |
CN102666663A (en) | 2009-10-23 | 2012-09-12 | 道康宁东丽株式会社 | Novel organopolysiloxane copolymer |
KR101925354B1 (en) | 2009-10-23 | 2018-12-05 | 다우 코닝 도레이 캄파니 리미티드 | Novel co-modified organopolysiloxane |
CN102648264B (en) | 2009-10-23 | 2015-08-19 | 道康宁东丽株式会社 | For thickening material or the jelling agent of the raw material based on oil |
CN102869728B (en) | 2010-04-29 | 2015-01-28 | 道康宁公司 | Cosmetic raw material |
JP5841348B2 (en) | 2010-04-30 | 2016-01-13 | 東レ・ダウコーニング株式会社 | Novel organopolysiloxane, surfactant containing the same, emulsion composition, powder treatment agent, thickener for oily raw material, gelling agent, gel composition, raw material for cosmetics, and external preparation containing these Cosmetics |
CN102906161B (en) | 2010-04-30 | 2014-10-22 | 道康宁东丽株式会社 | Novel organopolysiloxane, surfactant, emulsion composition, powder treatment agent, thickening agent of oil-based raw material, gelling agent, gel composition, and cosmetic raw material comprising novel organopolysiloxane, as well as, preparation for external use and cosmetic comprising the same |
WO2014104258A1 (en) | 2012-12-28 | 2014-07-03 | 東レ・ダウコーニング株式会社 | Method for producing transparent or semi-transparent liquid glycerin-derivative-modified silicone composition |
JP6480309B2 (en) | 2015-11-16 | 2019-03-06 | 信越化学工業株式会社 | Novel silicone compound and cosmetic containing the same |
JP6546127B2 (en) | 2016-07-14 | 2019-07-17 | 信越化学工業株式会社 | Novel silicone compound and cosmetic containing the same |
JP6881353B2 (en) | 2017-03-17 | 2021-06-02 | 信越化学工業株式会社 | Organic group-modified organosilicon resin, its manufacturing method, and cosmetics |
JP7358020B2 (en) | 2020-05-22 | 2023-10-10 | 信越化学工業株式会社 | Emulsifier and emulsifying composition containing the emulsifier |
JP7503028B2 (en) | 2021-07-09 | 2024-06-19 | 信越化学工業株式会社 | Crosslinked organosilicon resin, its manufacturing method, and cosmetic |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5146588A (en) * | 1974-10-19 | 1976-04-21 | Shiseido Co Ltd | |
JPS5539576A (en) * | 1978-09-14 | 1980-03-19 | Atsushi Yokomizo | Faucet |
JPS5679614A (en) * | 1979-12-03 | 1981-06-30 | Dow Corning | Personal care emulsion composition |
-
1985
- 1985-05-20 JP JP10800485A patent/JPS61293903A/en active Granted
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5146588A (en) * | 1974-10-19 | 1976-04-21 | Shiseido Co Ltd | |
JPS5539576A (en) * | 1978-09-14 | 1980-03-19 | Atsushi Yokomizo | Faucet |
JPS5679614A (en) * | 1979-12-03 | 1981-06-30 | Dow Corning | Personal care emulsion composition |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2505602A1 (en) | 2011-03-29 | 2012-10-03 | Shin-Etsu Chemical Co., Ltd. | Organopolysiloxane and cosmetic containing it |
US8697042B2 (en) | 2011-03-29 | 2014-04-15 | Shin-Etsu Chemical Co., Ltd. | Organopolysiloxane and cosmetic containing it |
US10662294B2 (en) | 2016-03-28 | 2020-05-26 | Shin-Etsu Chemical Co., Ltd. | Organopolysiloxane, cosmetics, and method for manufacturing organopolysiloxane |
Also Published As
Publication number | Publication date |
---|---|
JPS61293903A (en) | 1986-12-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JPH0415762B2 (en) | ||
EP0330369A1 (en) | Skin conditioning composition | |
JPH0420407B2 (en) | ||
JPH0513126B2 (en) | ||
JPH0662385B2 (en) | Emulsified composition | |
JP3667046B2 (en) | Fine emulsion composition | |
JP3829048B2 (en) | Oil-in-water emulsion composition | |
JP2000063234A (en) | Oil-in-water type cosmetic | |
JP2002068934A (en) | Water-in-oil type emulsion composition | |
JP2000351712A (en) | Solid water-in-oil type emulsified cosmetic | |
JP2006241038A (en) | Emulsion cosmetic | |
JP3313043B2 (en) | Water-in-oil emulsion composition | |
JPH11263721A (en) | Oil-in-water type gommage (peeling) cosmetic | |
JPH08245363A (en) | Solid o/w-type emulsion cosmetic | |
JPH0552807B2 (en) | ||
JP2001294512A (en) | Water-in-oil type emulsion cosmetic | |
JP3504038B2 (en) | Skin emulsified cosmetic | |
JPH04312512A (en) | Water-in-oil type emulsion cosmetic | |
JP3573337B2 (en) | Emulsion cosmetic for hair | |
JPH0513924B2 (en) | ||
JP3565332B2 (en) | Emulsion type solid cosmetic | |
JPH10167948A (en) | Cosmetic | |
JP3499979B2 (en) | Water-in-oil emulsion cosmetics | |
JP2003055141A (en) | W/o-type emulsion cosmetic | |
JP2000007547A (en) | Cosmetic |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
LAPS | Cancellation because of no payment of annual fees |