JP2002308962A - Emulsified composition - Google Patents
Emulsified compositionInfo
- Publication number
- JP2002308962A JP2002308962A JP2001112251A JP2001112251A JP2002308962A JP 2002308962 A JP2002308962 A JP 2002308962A JP 2001112251 A JP2001112251 A JP 2001112251A JP 2001112251 A JP2001112251 A JP 2001112251A JP 2002308962 A JP2002308962 A JP 2002308962A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- present
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 77
- -1 polyoxyethylene Polymers 0.000 claims abstract description 28
- 239000000839 emulsion Substances 0.000 claims abstract description 26
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 11
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 19
- 239000000194 fatty acid Substances 0.000 claims description 19
- 229930195729 fatty acid Natural products 0.000 claims description 19
- 239000002537 cosmetic Substances 0.000 claims description 10
- 229930006000 Sucrose Natural products 0.000 claims description 6
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000007762 w/o emulsion Substances 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 abstract description 11
- 239000008307 w/o/w-emulsion Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 16
- 239000012071 phase Substances 0.000 description 16
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 14
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 11
- 235000019198 oils Nutrition 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 235000021355 Stearic acid Nutrition 0.000 description 10
- 150000004665 fatty acids Chemical class 0.000 description 10
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 10
- 239000008117 stearic acid Substances 0.000 description 10
- 239000007764 o/w emulsion Substances 0.000 description 9
- 229920005862 polyol Polymers 0.000 description 9
- 150000003077 polyols Chemical class 0.000 description 9
- 235000011187 glycerol Nutrition 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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- 235000019437 butane-1,3-diol Nutrition 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 6
- QFOHBWFCKVYLES-UHFFFAOYSA-N Butylparaben Chemical compound CCCCOC(=O)C1=CC=C(O)C=C1 QFOHBWFCKVYLES-UHFFFAOYSA-N 0.000 description 6
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 6
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 6
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 6
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- GZIFEOYASATJEH-VHFRWLAGSA-N δ-tocopherol Chemical compound OC1=CC(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 GZIFEOYASATJEH-VHFRWLAGSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 4
- 239000004006 olive oil Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229940093430 polyethylene glycol 1500 Drugs 0.000 description 4
- 229940032094 squalane Drugs 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000003760 tallow Substances 0.000 description 4
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 3
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 3
- 235000021357 Behenic acid Nutrition 0.000 description 3
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 3
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 3
- GZIFEOYASATJEH-UHFFFAOYSA-N D-delta tocopherol Natural products OC1=CC(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 GZIFEOYASATJEH-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 241000208467 Macadamia Species 0.000 description 3
- 229940116226 behenic acid Drugs 0.000 description 3
- 229940067596 butylparaben Drugs 0.000 description 3
- 239000010495 camellia oil Substances 0.000 description 3
- 235000010389 delta-tocopherol Nutrition 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 125000005456 glyceride group Chemical group 0.000 description 3
- XJNUECKWDBNFJV-UHFFFAOYSA-N hexadecyl 2-ethylhexanoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C(CC)CCCC XJNUECKWDBNFJV-UHFFFAOYSA-N 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 description 3
- 239000004292 methyl p-hydroxybenzoate Substances 0.000 description 3
- 229960002216 methylparaben Drugs 0.000 description 3
- 229960002446 octanoic acid Drugs 0.000 description 3
- 235000008390 olive oil Nutrition 0.000 description 3
- 229960005323 phenoxyethanol Drugs 0.000 description 3
- 229950004354 phosphorylcholine Drugs 0.000 description 3
- PYJNAPOPMIJKJZ-UHFFFAOYSA-N phosphorylcholine chloride Chemical compound [Cl-].C[N+](C)(C)CCOP(O)(O)=O PYJNAPOPMIJKJZ-UHFFFAOYSA-N 0.000 description 3
- 108010021724 tonin Proteins 0.000 description 3
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 3
- 239000002446 δ-tocopherol Substances 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 2
- 229960000735 docosanol Drugs 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 235000020778 linoleic acid Nutrition 0.000 description 2
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000008385 outer phase Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 2
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical class CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 1
- AVBJHQDHVYGQLS-UHFFFAOYSA-N 2-(dodecanoylamino)pentanedioic acid Chemical compound CCCCCCCCCCCC(=O)NC(C(O)=O)CCC(O)=O AVBJHQDHVYGQLS-UHFFFAOYSA-N 0.000 description 1
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 1
- LEACJMVNYZDSKR-UHFFFAOYSA-N 2-octyldodecan-1-ol Chemical compound CCCCCCCCCCC(CO)CCCCCCCC LEACJMVNYZDSKR-UHFFFAOYSA-N 0.000 description 1
- GECRRQVLQHRVNH-MRCUWXFGSA-N 2-octyldodecyl (z)-octadec-9-enoate Chemical compound CCCCCCCCCCC(CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC GECRRQVLQHRVNH-MRCUWXFGSA-N 0.000 description 1
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical class CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound 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 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- 239000004264 Petrolatum Substances 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- BTFJIXJJCSYFAL-UHFFFAOYSA-N arachidyl alcohol Natural products CCCCCCCCCCCCCCCCCCCCO BTFJIXJJCSYFAL-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 229940116224 behenate Drugs 0.000 description 1
- UKMSUNONTOPOIO-UHFFFAOYSA-M behenate Chemical compound CCCCCCCCCCCCCCCCCCCCCC([O-])=O UKMSUNONTOPOIO-UHFFFAOYSA-M 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 229940082483 carnauba wax Drugs 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- LAGWVZPUXSKERV-UHFFFAOYSA-N cyclohexane;isocyanic acid Chemical compound N=C=O.C1CCCCC1 LAGWVZPUXSKERV-UHFFFAOYSA-N 0.000 description 1
- UREBDLICKHMUKA-CXSFZGCWSA-N dexamethasone Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@@H](C)[C@@](C(=O)CO)(O)[C@@]1(C)C[C@@H]2O UREBDLICKHMUKA-CXSFZGCWSA-N 0.000 description 1
- 229960003957 dexamethasone Drugs 0.000 description 1
- 125000005131 dialkylammonium group Chemical group 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 229940008099 dimethicone Drugs 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-M hexadecanoate Chemical compound CCCCCCCCCCCCCCCC([O-])=O IPCSVZSSVZVIGE-UHFFFAOYSA-M 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000008384 inner phase Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 229940119170 jojoba wax Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 229940114937 microcrystalline wax Drugs 0.000 description 1
- 229940105132 myristate Drugs 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 229940066842 petrolatum Drugs 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000010464 refined olive oil Substances 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 230000009291 secondary effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Medicinal Preparation (AREA)
- Cosmetics (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、化粧料などの皮膚
外用剤に有用な乳化組成物に関する。TECHNICAL FIELD The present invention relates to an emulsified composition useful for an external preparation for skin such as cosmetics.
【0002】[0002]
【従来の技術】乳化組成物は化粧料、トイレタリー、食
品或いは医薬品の分野に於いて、有用な製剤として広く
使用されている。これは、乳化剤系に於いては、そのま
までは均一に分散して存在しにくい、油性成分と水性成
分とが均一な状態で存在しており、これら2成分の作用
を併せ持つことが出来るためである。この様な乳化組成
物において最も問題となることは安定性である。これ
は、元々乳化系が準安定系であり、些少な系の変化が直
ちに安定性に影響を及ぼすためである。この様な傾向
は、数ある乳化形態の中でも外相に油相が存在するよう
な系、取り分け、内相に水中油乳化物が存在し、外相が
油相であるような油中水中油乳化剤形では著しく、取り
分け油相の粘度が下がる40℃(高温)での保存安定性
は重要である。言い換えれば、外相に油相が存在する乳
化形態では、高温安定性の確保が重要な課題となってい
る。この様な課題解決には未だ統一的な基準が存在せ
ず、剤形化研究の試行錯誤の積み重ねにより、製剤化せ
ざるを得ないのが現状であった。2. Description of the Related Art Emulsion compositions are widely used as useful preparations in the fields of cosmetics, toiletries, foods and pharmaceuticals. This is because, in the emulsifier system, the oily component and the aqueous component are present in a uniform state, and are difficult to exist as they are, and the two components can be combined. . The most important issue in such an emulsified composition is stability. This is because the emulsifying system is originally a metastable system, and a slight change in the system immediately affects the stability. Such a tendency is considered to be an oil-in-water-in-oil emulsified dosage form in which an oil phase is present in the outer phase among the various emulsified forms, in particular, an oil-in-water emulsion is present in the inner phase and the outer phase is the oil phase. In particular, storage stability at 40 ° C. (high temperature) at which the viscosity of the oil phase lowers is important. In other words, in the emulsified form in which the oil phase is present in the external phase, securing high-temperature stability is an important issue. There has not yet been a unified standard for solving such problems, and at present, it has been necessary to formulate a formulation through repeated trial and error of formulation research.
【0003】一方、ジポリヒドロキシステアリン酸ポリ
オキシエチレンと1,1−メチレン−ビス(4−イソシ
アネートシクロヘキサン)ポリプロピレングリコール共
重合体とを含有することを特徴とする、乳化組成物、取
り分け、油中水中油乳化物のような外相に油相が存在す
る乳化組成物は全く知られていない。従って、この様な
構成の乳化組成物が高温域で安定性に優れることも全く
知られていない。On the other hand, emulsified compositions containing polyoxyethylene dipolyhydroxystearate and 1,1-methylene-bis (4-isocyanatocyclohexane) polypropylene glycol copolymer are characterized in that There is no known emulsion composition in which an oil phase exists in an external phase such as an oil-in-water emulsion. Therefore, it is not known at all that the emulsified composition having such a constitution has excellent stability in a high temperature range.
【0004】[0004]
【発明が解決しようとする課題】本発明は、この様な状
況下なされたものであり、高温安定性に優れる新規乳化
組成物を提供することを課題とする。The present invention has been made under such circumstances, and an object of the present invention is to provide a novel emulsified composition having excellent high-temperature stability.
【0005】[0005]
【課題の解決手段】この様な状況に鑑みて、本発明者ら
は、高温安定性に優れる新規乳化組成物を求めて鋭意研
究努力を重ねた結果、ジポリヒドロキシステアリン酸ポ
リオキシエチレンと1,1−メチレン−ビス(4−イソ
シアネートシクロヘキサン)ポリプロピレングリコール
共重合体とを含有することを特徴とする、乳化組成物に
その様な特性を見出し発明を完成させるに至った。即
ち、本発明は、以下に示す技術に関するものである。 (1)ジポリヒドロキシステアリン酸ポリオキシエチレ
ンと1,1−メチレン−ビス(4−イソシアネートシク
ロヘキサン)ポリプロピレングリコール共重合体とを含
有することを特徴とする、乳化組成物。 (2)外相に油相が存在することを特徴とする、(1)
に記載の乳化組成物。 (3)油中水中油乳化剤形であることを特徴とする、
(1)又は(2)に記載の乳化組成物。 (4)高温安定性に優れることを特徴とする、(1)〜
(3)何れか1項に記載の乳化組成物。 (5)皮膚外用剤であることを特徴とする、(1)〜
(4)何れか1項に記載の乳化組成物。 (6)化粧料であることを特徴とする、(1)〜(5)
何れか1項に記載の乳化組成物。 (7)更にショ糖脂肪酸エステルを含有することを特徴
とする、(1)〜(6)何れか1項に記載の乳化組成
物。 以下、本発明について、実施の形態を中心に更に詳細に
説明を加える。In view of such circumstances, the present inventors have made intensive research efforts for a novel emulsion composition having excellent high-temperature stability. , 1-methylene-bis (4-isocyanatocyclohexane) polypropylene glycol copolymer, and found such characteristics in an emulsified composition, thereby completing the invention. That is, the present invention relates to the following technology. (1) An emulsified composition containing polyoxyethylene dipolyhydroxystearate and 1,1-methylene-bis (4-isocyanatocyclohexane) polypropylene glycol copolymer. (2) The oil phase is present in the external phase, (1)
3. The emulsified composition according to item 1. (3) an oil-in-water-in-oil emulsifying agent form,
The emulsion composition according to (1) or (2). (4) excellent in high-temperature stability, (1) to
(3) The emulsified composition according to any one of the above items. (5) It is a skin external preparation, (1) to
(4) The emulsion composition according to any one of (1) to (4). (6) (1) to (5) characterized in that it is a cosmetic.
An emulsified composition according to any one of the preceding claims. (7) The emulsified composition according to any one of (1) to (6), further comprising a sucrose fatty acid ester. Hereinafter, the present invention will be described in more detail focusing on embodiments.
【0006】[0006]
【発明の実施の形態】(1)本発明の乳化組成物に含ま
れるジポリヒドロキシステアリン酸ポリオキシエチレン 本発明の乳化組成物が含有する、ポリヒドロキシステア
リン酸ポリオキシエチレンは、ポリエチレングリコール
をアルカリ存在下、ポリ(12−ヒドロキシステアリン
酸)に塩化チオニル等のハロゲン化剤を反応させて調製
した、酸クロライドを反応させることにより得ることが
できる。この時、酸クロライドの量を多めにするとジ以
上のポリエステルが得られるし、この量が少なければモ
ノエステル等のアシル化率の低いものが得られる。この
場合、ポリエチレングリコールのサイズとしては、平均
分子量で400〜6000が好ましい。一方、他方の構
成要素である、ポリ(12−ヒドロキシステアリン酸)
は、この必須成分中で疎水基となる部分で、そのサイズ
としては平均分子量1000〜3000であることが好
ましい。この様なジポリヒドロキシステアリン酸ポリオ
キシエチレンの中には既に市販されているものがあり、
本発明ではその様な市販品を利用することもできる。こ
の様な市販品の内、特に好ましいものは、ウニケマ社よ
り市販されている、「アラセルP−135」である。こ
のものは、ポリエチレングリコール(平均分子量150
0)のポリ(12−ヒドロキシステアリン酸)のジエス
テルであり、その平均分子量は約5000である。本発
明の乳化組成物に於いては、ジポリヒドロキシステアリ
ン酸ポリオキシエチレンは唯一種を含有することもでき
るし、二種以上を組み合わせて含有することもできる。
これらは、本発明の乳化系に於いて連続相を安定に存在
させる作用を有する。これらの好ましい含有量は、乳化
組成物全量に対する、これらの総量で0.1〜10重量
%が好ましく、1〜5重量%が更に好ましい。これは、
この量範囲において、安定な乳化組成物が得られるから
である。BEST MODE FOR CARRYING OUT THE INVENTION (1) Polyoxyethylene dipolyhydroxystearate contained in the emulsified composition of the present invention The polyoxyethylene polyhydroxystearate contained in the emulsified composition of the present invention is obtained by mixing polyethylene glycol with an alkali. It can be obtained by reacting acid chloride prepared by reacting poly (12-hydroxystearic acid) with a halogenating agent such as thionyl chloride in the presence. At this time, if the amount of the acid chloride is increased, a polyester having two or more diacids can be obtained. If the amount is small, a low acylation rate such as a monoester can be obtained. In this case, the polyethylene glycol preferably has an average molecular weight of 400 to 6000. On the other hand, the other component, poly (12-hydroxystearic acid)
Is a portion which becomes a hydrophobic group in this essential component, and preferably has an average molecular weight of 1,000 to 3,000 in size. Some of these polyoxyethylene dipolyhydroxystearates are already commercially available,
In the present invention, such commercially available products can also be used. Among such commercially available products, particularly preferred is "Aracel P-135", which is commercially available from Unichema. This is polyethylene glycol (average molecular weight 150
0) is a diester of poly (12-hydroxystearic acid) having an average molecular weight of about 5000. In the emulsified composition of the present invention, polyoxyethylene dipolyhydroxystearate may contain only one kind, or may contain two or more kinds in combination.
These have the effect of allowing the continuous phase to stably exist in the emulsification system of the present invention. The preferable content thereof is preferably 0.1 to 10% by weight, more preferably 1 to 5% by weight, based on the total amount of the emulsified composition. this is,
This is because a stable emulsion composition can be obtained in this amount range.
【0007】(2)本発明の乳化組成物に含まれる1,
1−メチレン−ビス(4−イソシアネートシクロヘキサ
ン)ポリプロピレングリコール共重合体 本発明の乳化組成物は、1,1−メチレン−ビス(4−
イソシアネートシクロヘキサン)ポリプロピレングリコ
ール共重合体を含有することを特徴とする。このもの
は、皮膚上にバリア機能を有する被膜を形成することが
知られており、この目的で化粧料などの皮膚外用剤に含
有されている。このものは既に市販されているものもあ
り、本発明の乳化組成物においてはこの様な市販品を使
用することができる。好ましい市販品としては、例え
ば、日本サーファクタント株式会社より販売されている
ポリオールプレポリマー2が好ましく例示できる。かか
る1,1−メチレン−ビス(4−イソシアネートシクロ
ヘキサン)ポリプロピレングリコール共重合体は唯一種
を含有させることもできるし、二種以上を組み合わせて
含有させることもできる。1,1−メチレン−ビス(4
−イソシアネートシクロヘキサン)ポリプロピレングリ
コール共重合体の好ましい含有量は、乳化組成物全量に
対して、総量で、0.1〜10重量%であり、更に好ま
しくは、0.5〜5重量%である。これは、多すぎると
乳化性を阻害する場合があり、少なすぎると、高温域で
安定化作用が得られない場合があるからである。(2) 1,1 contained in the emulsified composition of the present invention
1-methylene-bis (4-isocyanatocyclohexane) polypropylene glycol copolymer The emulsion composition of the present invention comprises 1,1-methylene-bis (4-
(Isocyanate cyclohexane) polypropylene glycol copolymer. This is known to form a film having a barrier function on the skin, and is contained in a skin external preparation such as a cosmetic for this purpose. Some of these are already commercially available, and such commercially available products can be used in the emulsion composition of the present invention. As a preferable commercial product, for example, polyol prepolymer 2 sold by Nippon Surfactant Co., Ltd. can be preferably exemplified. Such 1,1-methylene-bis (4-isocyanatocyclohexane) polypropylene glycol copolymer may contain only one kind or two or more kinds in combination. 1,1-methylene-bis (4
-Isocyanate cyclohexane) The preferable content of the polypropylene glycol copolymer is 0.1 to 10% by weight, more preferably 0.5 to 5% by weight, based on the total amount of the emulsion composition. If the amount is too large, the emulsifiability may be impaired. If the amount is too small, a stabilizing effect may not be obtained in a high temperature range.
【0008】(3)本発明の乳化組成物の形態 本発明の乳化組成物の形態として好ましいものは、油相
が外相に存在する形態であり、この様な形態としては、
例えば、油の連続相の中に水滴が存在する油中水乳化形
態、油の連続相中に水中油乳化物が存在する油中水中油
乳化形態などが例示でき、これらの中では油中水中油乳
化形態が特に好ましく挙げられる。これは、本発明の蔗
糖脂肪酸エステルの添加による、低温安定性の向上効果
がこの乳化形態で特に著しいからである。この様な形態
においては、塗布時において心地よい使用感を有すると
いう副次的効果も発現する。好ましい態様として、この
様な乳化形態をとる、本発明の乳化組成物の適用分野と
しては、乳化物が適用される分野であれば特段の限定は
されず、例えば、食品、化粧料、医薬品などが好ましく
例示できる。これらの内、特に好ましいものは、本発明
の乳化組成物の使用感の良い利点を最大限生かせるから
である。(3) Form of the emulsified composition of the present invention A preferable form of the emulsified composition of the present invention is a form in which an oil phase is present in an external phase.
For example, a water-in-oil emulsified form in which water droplets are present in a continuous phase of oil, an oil-in-water-in-oil emulsified form in which an oil-in-water emulsion is present in a continuous phase of oil, etc. An oil emulsified form is particularly preferred. This is because the addition of the sucrose fatty acid ester of the present invention significantly improves the low-temperature stability in this emulsified form. In such a form, a secondary effect of having a comfortable use feeling at the time of application is also exhibited. As a preferred embodiment, the field of application of the emulsified composition of the present invention, which takes such an emulsified form, is not particularly limited as long as it is a field to which the emulsion is applied. For example, foods, cosmetics, pharmaceuticals and the like Can be preferably exemplified. Among them, particularly preferable ones are those which can make the best use of the good use feeling of the emulsified composition of the present invention.
【0009】(4)本発明の乳化組成物 本発明の乳化組成物は、上記の必須成分を含み、好まし
い形態として上記に示した油相を外相として有する乳化
形態をとることを特徴とする。本発明の乳化組成物で
は、上記必須の成分以外に、通常乳化組成物で使用され
る任意の成分を、本発明の効果を損なわない範囲に於い
て含有することが出来る。この様な任意の成分として
は、例えば、スクワラン、ワセリン、マイクロクリスタ
リンワックス等の炭化水素類、ホホバ油、カルナウバワ
ックス,オレイン酸オクチルドデシル等のエステル類、
オリーブ油、牛脂、椰子油等のトリグリセライド類、ス
テアリン酸、オレイン酸、リチノレイン酸等の脂肪酸、
オレイルアルコール、ステアリルアルコール、オクチル
ドデカノール等の高級アルコール、スルホコハク酸エス
テルやポリオキシエチレンアルキル硫酸ナトリウム等の
アニオン界面活性剤類、アルキルベタイン塩等の両性界
面活性剤類、ジアルキルアンモニウム塩等のカチオン界
面活性剤類、ソルビタン脂肪酸エステル、脂肪酸モノグ
リセライド、これらのポリオキシエチレン付加物、ポリ
オキシエチレンアルキルエーテル、ポリオキシエチレン
脂肪酸エステル等の非イオン界面活性剤類、ポリエチレ
ングリコール、グリセリン、1,3−ブタンジオール等
の多価アルコール類、増粘・ゲル化剤、酸化防止剤、紫
外線吸収剤、色剤、防腐剤、粉体等を好ましく例示でき
る。これらの内、特に好ましいものは、低温安定性に好
ましい寄与をするオリーブ油であり、中でも不純物をカ
ラムクロマトグラフィーなどで取り除いたオリーブ油
は、低温安定性向上作用が著しいので特に好ましい。こ
の様な精製オリーブ油としては、クロダ社より市販され
ている「クロピュアOL」が好ましく例示できる。この
様なオリーブ油の好ましい含有量は、0.1〜10重量
%であり、更に好ましくは、0.5〜5重量%である。
これらの必須の成分と任意の成分とを常法に従って処理
することにより、本発明の乳化組成物は製造することが
出来る。(4) Emulsified Composition of the Present Invention The emulsified composition of the present invention is characterized in that it contains the above essential components and has a preferred form of an emulsified form having the above-described oil phase as an external phase. The emulsified composition of the present invention may contain, in addition to the essential components described above, optional components usually used in the emulsified composition as long as the effects of the present invention are not impaired. Such optional components include, for example, hydrocarbons such as squalane, petrolatum, and microcrystalline wax, jojoba oil, carnauba wax, esters such as octyldodecyl oleate,
Triglycerides such as olive oil, beef tallow, and coconut oil; fatty acids such as stearic acid, oleic acid, and ritinoleic acid;
Higher alcohols such as oleyl alcohol, stearyl alcohol and octyl dodecanol; anionic surfactants such as sulfosuccinates and sodium polyoxyethylene alkyl sulfate; amphoteric surfactants such as alkyl betaine salts; cationic interfaces such as dialkyl ammonium salts. Activators, nonionic surfactants such as sorbitan fatty acid esters, fatty acid monoglycerides, their polyoxyethylene adducts, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, polyethylene glycol, glycerin, 1,3-butanediol And the like, polyhydric alcohols such as, for example, thickening / gelling agents, antioxidants, ultraviolet absorbers, coloring agents, preservatives, and powders. Of these, particularly preferred are olive oils that make a favorable contribution to low-temperature stability, and among them, olive oil from which impurities have been removed by column chromatography or the like is particularly preferred because of its remarkable effect of improving low-temperature stability. As such a refined olive oil, "Cropure OL" commercially available from Kuroda can be preferably exemplified. The preferred content of such olive oil is 0.1 to 10% by weight, more preferably 0.5 to 5% by weight.
The emulsion composition of the present invention can be produced by treating these essential components and optional components according to a conventional method.
【0010】又、本発明の乳化組成物は任意成分とし
て、ショ糖脂肪酸エステルを含有することが好ましい。
本発明の乳化組成物が好ましく含有する蔗糖脂肪酸エス
テルは、本発明の乳化組成物の乳化系に於いて、低温域
の安定性をも向上させる作用を有する。本発明の乳化組
成物で使用することの出来る蔗糖脂肪酸エステルとして
は、通常この様な乳化組成物で使用されているものであ
れば特段の限定無く使用することが出来、例えば、ラウ
リン酸エステル、ミリスチン酸エステル、パルミチン酸
エステル、ステアリン酸エステル、ベヘン酸エステル、
オレイン酸エステル、リノール酸エステル、リノレイン
酸エステル、リチノレイン酸エステル、酢酸エステル、
イソステアリン酸エステル、イソオクタン酸エステル及
びこれらの混合エステル等が例示でき、好ましいものと
しては飽和脂肪酸で炭素数が12以上の脂肪酸のエステ
ルが例示できるが、特に好ましいものは、エステルを構
成する脂肪酸組成がステアリン酸を中心とするものであ
って、かかる脂肪酸組成が大凡ステアリン酸:パルミチ
ン酸=7:3のステアリン酸・パルミチン酸混合脂肪酸
のものが特に好ましい。この様なものとしては第一工業
製薬株式会社より市販されている「シュガーワックスS
E−10」が特に好ましく例示できる。本発明の乳化組
成物に於けるこの様なシュガーワックスの好ましい含有
量は、乳化組成物全量に対して、0.1〜10重量%で
あり、更に好ましくは、0.5〜5重量%である。これ
は少なすぎると安定化効果が得られない場合があり、多
すぎると処方の自由度を阻害したりする場合があるから
である。The emulsion composition of the present invention preferably contains a sucrose fatty acid ester as an optional component.
The sucrose fatty acid ester preferably contained in the emulsified composition of the present invention has an effect of also improving the stability in a low-temperature region in the emulsified system of the emulsified composition of the present invention. The sucrose fatty acid ester that can be used in the emulsion composition of the present invention can be used without any particular limitation as long as it is usually used in such an emulsion composition. For example, lauric ester, Myristate, palmitate, stearate, behenate,
Oleic acid ester, linoleic acid ester, linoleic acid ester, ritinoleic acid ester, acetate ester,
Examples thereof include isostearic acid esters, isooctanoic acid esters, and mixed esters thereof. Preferred examples include esters of fatty acids having 12 or more carbon atoms with saturated fatty acids. Particularly preferred are those having a fatty acid composition constituting an ester. Particularly preferred is a stearic acid-based palmitic acid mixed fatty acid having a stearic acid: palmitic acid ratio of about 7: 3, which is mainly composed of stearic acid. Such a product is commercially available from Daiichi Kogyo Seiyaku Co., Ltd. “Sugar wax S”
E-10 "can be particularly preferably exemplified. The preferred content of such sugar wax in the emulsion composition of the present invention is 0.1 to 10% by weight, more preferably 0.5 to 5% by weight, based on the total weight of the emulsion composition. is there. This is because if the amount is too small, the stabilizing effect may not be obtained, and if the amount is too large, the freedom of formulation may be impaired.
【0011】[0011]
【実施例】以下に、本発明について、実施例を挙げて更
に詳細に説明を加えるが、本発明がこれら実施例にの
み、限定されないことは言うまでもない。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but it goes without saying that the present invention is not limited to these examples.
【0012】<実施例1>次に示す処方に従って本発明
の乳化組成物1を作成した。即ち、イ、ロの成分を70
℃に加熱し、イにロを攪拌しながら徐々に加え、乳化
し、攪拌冷却して油中水乳化組成物1を得た。このもの
は化粧料として好適であった。別途、この乳化組成物の
ポリオールプレポリマー2(1,1−メチレン−ビス
(4−イソシアネートシクロヘキサン)ポリプロピレン
グリコール共重合体)を水に置換した比較例1も作成し
た。更に、乳化組成物1と比較例1とを40℃での保存
試験を行った。この結果を硬度の変化として表1に示
す。硬度はカードメーターを用い、100gの荷重で1
6φのアタッチメントを付けて測定した。これより、本
発明の乳化組成物が高温安定性に優れることが判る。
又、このものは滑らかなのび特性を有しており、化粧料
として好適であった。 イ 「アラセルP−135」 2 重量部 フェメチコン 10 重量部 ジメチコン 5 重量部 「クロピュアOL」 3 重量部 クリル6 1 重量部 シュガーエステルSE−10 1 重量部 ロ グリセリン 5.4重量部 ポリエチレングリコール1500 3 重量部 「ポリオールプレポリマー2」 2 重量部 水 69.6重量部Example 1 An emulsified composition 1 of the present invention was prepared according to the following formulation. That is, the components a and b are 70
The mixture was heated to 0 ° C., and the mixture was gradually added to the mixture while stirring, emulsified, and stirred and cooled to obtain a water-in-oil emulsion composition 1. This was suitable as a cosmetic. Separately, Comparative Example 1 was also prepared in which the polyol prepolymer 2 (1,1-methylene-bis (4-isocyanatocyclohexane) polypropylene glycol copolymer) of this emulsion composition was replaced with water. Further, the emulsified composition 1 and the comparative example 1 were subjected to a storage test at 40 ° C. The results are shown in Table 1 as changes in hardness. Hardness was measured using a card meter and the hardness was 1
The measurement was performed with a 6φ attachment. This indicates that the emulsified composition of the present invention has excellent high-temperature stability.
In addition, it had a smooth growth property and was suitable as a cosmetic. A “Aracel P-135” 2 parts by weight Femethicone 10 parts by weight Dimethicone 5 parts by weight “Cropure OL” 3 parts by weight Crill 61 1 part by weight Sugar ester SE-10 1 part by weight glycerin 5.4 parts by weight Polyethylene glycol 1500 3 parts by weight Part "Polyol prepolymer 2" 2 parts by weight Water 69.6 parts by weight
【0013】[0013]
【表1】 [Table 1]
【0014】<実施例2>下記に示す処方に従って、本
発明の乳化組成物を作成した。即ち、イ、ロをそれぞれ
70℃に加熱し、イにロを徐々に加えて中間水中油乳化
物1を得た。これを用いて、更にハ、ニ、ホをそれぞれ
80℃に加熱し、ハにニを徐々に加え、最後にホを加え
攪拌冷却して本発明の乳化組成物である、油中水中油乳
化組成物2(実施例2)を得た。このものは、更に滑ら
かなのび特性を有しており、化粧料として好適であっ
た。ポリオールプレポリマーを水に置換して比較例2も
作製した。これらの安定性を40℃保存での硬度変化と
して、表2に示す。硬度は実施例1と同様に求めた。こ
れより、多重エマルジョンとすることにより本発明のポ
リオールプレポリマーの添加効果がより如実に現れてい
ることがわかる。 イ 10%水酸化カリウム水溶液 0.1重量部 1,3−ブタンジオール 3 重量部 水 15.5重量部 ロ ベヘニルアルコール 0.4重量部 水添牛脂 0.1重量部 スクワラン 5 重量部 シュガーワックスSE−10 2 重量部 フェノキシエタノール 0.2重量部 混合脂肪酸トリグリセライド* 0.1重量部 ベヘン酸 0.1重量部 ステアリン酸 0.5重量部 グリセリン 3 重量部 ハ メチルパラベン 0.1重量部 1,3−ブタンジオール 5 重量部 グリセリン 5 重量部 ポリエチレングリコール1500 1 重量部 ポリMPC*** 0.1 重量部 「ポリオールプレポリマー2」 2 重量部 水 24.88重量部 ニ 「アラセルP−135」 1 重量部 「エルデュウPS−304」** 0.1 重量部 マカデミア脂肪酸フィトステリル 0.5重量部 椿油 0.5重量部 デカメチルシクロペンタシロキサン 4 重量部 2−エチルヘキサン酸セチル 19 重量部 「クロピュアOL」 1 重量部 クリル6 1 重量部 ブチルパラベン 0.1重量部 δトコフェロール 0.02重量部 ホ 中間水中油乳化物1 30 重量部 トウキエキス 1 重量部 チョレイエキス 0.7重量部 トウニンエキス 0.8重量部 チンピエキス 0.5重量部 *N−ラウロイル−L−グルタミン酸ジ(フィトステリ
ル・−2−オクチルドデシル) **トリ(カプリン酸・カプリル酸・ミリスチン酸・ス
テアリン酸)グリセライド ***ポリメタクリロイルオキシエチルホスホリルコリ
ンExample 2 An emulsified composition of the present invention was prepared according to the following formulation. That is, (a) and (b) were each heated to 70 ° C., and (b) was gradually added to (a) to obtain an intermediate oil-in-water emulsion 1. Using this, C, D and E are each heated to 80 ° C., D is gradually added to C, and finally E is added and stirred and cooled to obtain an oil-in-water-in-oil emulsified composition of the present invention. Composition 2 (Example 2) was obtained. This product had a smoother spreading property and was suitable as a cosmetic. Comparative Example 2 was also made by replacing the polyol prepolymer with water. The stability is shown in Table 2 as a change in hardness after storage at 40 ° C. The hardness was determined in the same manner as in Example 1. From this, it can be seen that the effect of adding the polyol prepolymer of the present invention is more clearly exhibited by forming a multiple emulsion. A 10% aqueous solution of potassium hydroxide 0.1 part by weight 1,3-butanediol 3 parts by weight Water 15.5 parts by weight Lo behenyl alcohol 0.4 parts by weight Hydrogenated tallow 0.1 part by weight Squalane 5 parts by weight Sugar wax SE- 10 2 parts by weight Phenoxyethanol 0.2 parts by weight Mixed fatty acid triglyceride * 0.1 parts by weight Behenic acid 0.1 parts by weight Stearic acid 0.5 parts by weight Glycerin 3 parts by weight C methyl paraben 0.1 parts by weight 1,3-butanediol 5 parts by weight Glycerin 5 parts by weight Polyethylene glycol 1500 1 part by weight Poly MPC *** 0.1 part by weight "Polyol prepolymer 2" 2 parts by weight Water 24.88 parts by weight D "Arcel P-135" 1 part by weight "Eldew" PS-304 "** 0.1 part by weight Macadamia fatty acid phytosteryl 5 parts by weight Camellia oil 0.5 parts by weight Decamethylcyclopentasiloxane 4 parts by weight Cetyl 2-ethylhexanoate 19 parts by weight "Cropure OL" 1 part by weight Crill 6 1 part by weight Butyl paraben 0.1 part by weight δ Tocopherol 0.02 Parts by weight E Intermediate oil-in-water emulsion 1 30 parts by weight Touki extract 1 part by weight Chorei extract 0.7 part by weight Tonin extract 0.8 part by weight Chimpi extract 0.5 part by weight * N-lauroyl-L-glutamate di (phytosteryl- 2-octyldodecyl) ** tri (capric acid, caprylic acid, myristic acid, stearic acid) glyceride *** polymethacryloyloxyethyl phosphorylcholine
【0015】[0015]
【表2】 [Table 2]
【0016】<実施例3>下記に示す処方に従って、本
発明の乳化組成物を作成した。即ち、イ、ロをそれぞれ
70℃に加熱し、イにロを徐々に加えて中間水中油乳化
物1を得た。これを用いて、更にハ、ニ、ホをそれぞれ
80℃に加熱し、ハにニを徐々に加え、最後にホを加え
攪拌冷却して本発明の乳化組成物である、油中水中油乳
化組成物3(実施例3)を得た。このものは、更に滑ら
かなのび特性を有しており、化粧料として好適であっ
た。ポリオールプレポリマーを水に置換して比較例2も
作製した。これらの安定性を40℃保存での硬度変化と
して、表3に示す。硬度は実施例1と同様に求めた。こ
れより、本発明の乳化組成物においては、1,1−メチ
レン−ビス(4−イソシアネートシクロヘキサン)ポリ
プロピレングリコール共重合体の好ましい含有量は0.
5〜5重量%が特に好ましいことがわかる。 イ 10%水酸化カリウム水溶液 0.1重量部 1,3−ブタンジオール 3 重量部 水 15.5重量部 ロ ベヘニルアルコール 0.4重量部 水添牛脂 0.1重量部 スクワラン 5 重量部 シュガーワックスSE−10 2 重量部 フェノキシエタノール 0.2重量部 混合脂肪酸トリグリセライド* 0.1重量部 ベヘン酸 0.1重量部 ステアリン酸 0.5重量部 グリセリン 3 重量部 ハ メチルパラベン 0.1重量部 1,3−ブタンジオール 5 重量部 グリセリン 5 重量部 ポリエチレングリコール1500 1 重量部 ポリMPC*** 0.1 重量部 「ポリオールプレポリマー2」 1 重量部 水 25.88重量部 ニ 「アラセルP−135」 1 重量部 「エルデュウPS−304」** 0.1 重量部 マカデミア脂肪酸フィトステリル 0.5重量部 椿油 0.5重量部 デカメチルシクロペンタシロキサン 4 重量部 2−エチルヘキサン酸セチル 19 重量部 「クロピュアOL」 1 重量部 クリル6 1 重量部 ブチルパラベン 0.1重量部 δトコフェロール 0.02重量部 ホ 中間水中油乳化物1 30 重量部 トウキエキス 1 重量部 チョレイエキス 0.7重量部 トウニンエキス 0.8重量部 チンピエキス 0.5重量部 *N−ラウロイル−L−グルタミン酸ジ(フィトステリ
ル・−2−オクチルドデシル) **トリ(カプリン酸・カプリル酸・ミリスチン酸・ス
テアリン酸)グリセライド ***ポリメタクリロイルオキシエチルホスホリルコリ
ンExample 3 An emulsified composition of the present invention was prepared according to the following formulation. That is, (a) and (b) were each heated to 70 ° C., and (b) was gradually added to (a) to obtain an intermediate oil-in-water emulsion 1. Using this, C, D and E are each heated to 80 ° C., D is gradually added to C, and finally E is added and stirred and cooled to obtain oil-in-water-in-oil emulsified composition of the present invention. Composition 3 (Example 3) was obtained. This product had a smoother spreading property and was suitable as a cosmetic. Comparative Example 2 was also made by replacing the polyol prepolymer with water. The stability is shown in Table 3 as a change in hardness after storage at 40 ° C. The hardness was determined in the same manner as in Example 1. Thus, in the emulsified composition of the present invention, the preferable content of 1,1-methylene-bis (4-isocyanatocyclohexane) polypropylene glycol copolymer is 0.1.
It turns out that 5-5 weight% is especially preferable. A 10% aqueous potassium hydroxide solution 0.1 part by weight 1,3-butanediol 3 parts by weight Water 15.5 parts by weight Lo behenyl alcohol 0.4 parts by weight Hydrogenated tallow 0.1 part by weight Squalane 5 parts by weight Sugar wax SE- 10 2 parts by weight Phenoxyethanol 0.2 parts by weight Mixed fatty acid triglyceride * 0.1 parts by weight Behenic acid 0.1 parts by weight Stearic acid 0.5 parts by weight Glycerin 3 parts by weight C methyl paraben 0.1 parts by weight 1,3-butanediol 5 parts by weight Glycerin 5 parts by weight Polyethylene glycol 1500 1 part by weight Poly MPC *** 0.1 part by weight "Polyol prepolymer 2" 1 part by weight Water 25.88 parts by weight d "Arcel P-135" 1 part by weight "Eldew" PS-304 "** 0.1 part by weight Macadamia fatty acid phytosteryl 5 parts by weight Camellia oil 0.5 parts by weight Decamethylcyclopentasiloxane 4 parts by weight Cetyl 2-ethylhexanoate 19 parts by weight "Cropure OL" 1 part by weight Crill 6 1 part by weight Butyl paraben 0.1 part by weight δ Tocopherol 0.02 Parts by weight E Intermediate oil-in-water emulsion 1 30 parts by weight Touki extract 1 part by weight Chorei extract 0.7 part by weight Tonin extract 0.8 part by weight Chimpi extract 0.5 part by weight * N-lauroyl-L-glutamate di (phytosteryl- 2-octyldodecyl) ** tri (capric acid, caprylic acid, myristic acid, stearic acid) glyceride *** polymethacryloyloxyethyl phosphorylcholine
【0017】[0017]
【表3】 [Table 3]
【0018】<実施例4>下記に示す処方に従って、本
発明の乳化組成物を作成した。即ち、イ、ロをそれぞれ
70℃に加熱し、イにロを徐々に加えて中間水中油乳化
物1を得た。これを用いて、更にハ、ニ、ホをそれぞれ
80℃に加熱し、ハにニを徐々に加え、最後にホを加え
攪拌冷却して本発明の乳化組成物である、油中水中油乳
化組成物4(実施例4);皮膚外用医薬を得た。 イ 10%水酸化カリウム水溶液 0.1重量部 1,3−ブタンジオール 3 重量部 水 15.5重量部 ロ ベヘニルアルコール 0.4重量部 水添牛脂 0.1重量部 デキサメタゾン 1 重量部 スクワラン 5 重量部 シュガーワックスSE−10 2 重量部 フェノキシエタノール 0.2重量部 混合脂肪酸トリグリセライド* 0.1重量部 ベヘン酸 0.1重量部 ステアリン酸 0.5重量部 グリセリン 3 重量部 ハ メチルパラベン 0.1重量部 1,3−ブタンジオール 5 重量部 グリセリン 5 重量部 ポリエチレングリコール1500 1 重量部 ポリMPC*** 0.1 重量部 「ポリオールプレポリマー2」 2 重量部 水 21.88重量部 ニ 「アラセルP−135」 1 重量部 「エルデュウPS−304」** 0.1 重量部 マカデミア脂肪酸フィトステリル 0.5重量部 椿油 0.5重量部 デカメチルシクロペンタシロキサン 4 重量部 2−エチルヘキサン酸セチル 19 重量部 「クロピュアOL」 1 重量部 クリル6 1 重量部 ブチルパラベン 0.1重量部 δトコフェロール 0.02重量部 ホ 中間水中油乳化物1 30 重量部 トウキエキス 1 重量部 チョレイエキス 0.7重量部 トウニンエキス 0.8重量部 チンピエキス 0.5重量部 *N−ラウロイル−L−グルタミン酸ジ(フィトステリ
ル・−2−オクチルドデシル) **トリ(カプリン酸・カプリル酸・ミリスチン酸・ス
テアリン酸)グリセライド ***ポリメタクリロイルオキシエチルホスホリルコリ
ンExample 4 An emulsion composition of the present invention was prepared according to the following formulation. That is, (a) and (b) were each heated to 70 ° C., and (b) was gradually added to (a) to obtain an intermediate oil-in-water emulsion 1. Using this, C, D and E are each heated to 80 ° C., D is gradually added to C, and finally E is added and stirred and cooled to obtain an oil-in-water-in-oil emulsified composition of the present invention. Composition 4 (Example 4); a skin external medicine was obtained. A 10% aqueous solution of potassium hydroxide 0.1 part by weight 1,3-butanediol 3 parts by weight Water 15.5 parts by weight Lobehenyl alcohol 0.4 parts by weight Hydrogenated tallow 0.1 part by weight Dexamethasone 1 part by weight Squalane 5 parts by weight Sugar wax SE-10 2 parts by weight Phenoxyethanol 0.2 parts by weight Mixed fatty acid triglyceride * 0.1 parts by weight Behenic acid 0.1 parts by weight Stearic acid 0.5 parts by weight Glycerin 3 parts by weight C methyl paraben 0.1 parts by weight 1, 3-butanediol 5 parts by weight Glycerin 5 parts by weight Polyethylene glycol 1500 1 part by weight Poly MPC *** 0.1 part by weight "Polyol prepolymer 2" 2 parts by weight Water 21.88 parts by weight D "Aracel P-135" 1 Parts by weight "Eldew PS-304" ** 0.1 parts by weight Macadamia Phytosteryl fatty acid 0.5 parts by weight Camellia oil 0.5 parts by weight Decamethylcyclopentasiloxane 4 parts by weight Cetyl 2-ethylhexanoate 19 parts by weight "Cropure OL" 1 part by weight Kuril 6 1 part by weight Butyl paraben 0.1 part by weight δ tocopherol 0.02 parts by weight E Intermediate oil-in-water emulsion 1 30 parts by weight Touki extract 1 part by weight Chorei extract 0.7 part by weight Tonin extract 0.8 part by weight Chimney extract 0.5 part by weight * N-lauroyl-L-glutamic acid Di (phytosteryl-2-octyldodecyl) ** tri (capric acid / caprylic acid / myristic acid / stearic acid) glyceride *** polymethacryloyloxyethyl phosphorylcholine
【0019】[0019]
【発明の効果】本発明によれば、高温安定性に優れる新
規乳化組成物を提供することができる。According to the present invention, a novel emulsified composition having excellent high-temperature stability can be provided.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 FI テーマコート゛(参考) A61K 9/113 A61K 9/113 B01F 17/34 B01F 17/34 17/42 17/42 C08L 5/00 C08L 5/00 75/08 75/08 Fターム(参考) 4C076 AA18 BB31 CC30 DD30 DD37 DD38 DD39 DD41 DD46 DD63 EE23 EE27 EE51 EE54 EE58 FF43 4C083 AA082 AA112 AA122 AB032 AC022 AC072 AC122 AC172 AC242 AC352 AC401 AC422 AC482 AD071 AD112 AD152 AD172 AD221 AD222 AD572 AD662 CC01 CC02 DD34 EE01 EE03 4D077 AA02 AA04 AA09 AB11 AB12 AC03 AC04 DC02Y DC02Z DC12Y DC12Z DC19Y DC19Z DC23Y DC33Y DD32Z 4J002 AB052 CK041 GB00 4J034 BA03 DA01 DH02 DH07 HA02 HA07 HC17 HC22 HC64 HC71 MA26 RA02 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) A61K 9/113 A61K 9/113 B01F 17/34 B01F 17/34 17/42 17/42 C08L 5/00 C08L 5/00 75/08 75/08 F term (reference) 4C076 AA18 BB31 CC30 DD30 DD37 DD38 DD39 DD41 DD46 DD63 EE23 EE27 EE51 EE54 EE58 FF43 4C083 AA082 AA112 AA122 AB032 AC022 AC072 AC122 AC172 AC242 AC352 AC401 AC422 AD07AD1121 AD222 AD572 AD662 CC01 CC02 DD34 EE01 EE03 4D077 AA02 AA04 AA09 AB11 AB12 AC03 AC04 DC02Y DC02Z DC12Y DC12Z DC19Y DC19Z DC23Y DC33Y DD32Z 4J002 AB052 CK041 GB00 4J034 BA03 DA01 DH02 DH07 HA02 HC07 HC07 HC02 HC07
Claims (7)
シエチレンと1,1−メチレン−ビス(4−イソシアネ
ートシクロヘキサン)ポリプロピレングリコール共重合
体とを含有することを特徴とする、乳化組成物。1. An emulsion composition comprising polyoxyethylene dihydroxystearate and 1,1-methylene-bis (4-isocyanatocyclohexane) polypropylene glycol copolymer.
る、請求項1に記載の乳化組成物。2. The emulsion composition according to claim 1, wherein an oil phase is present in the external phase.
する、請求項1又は2に記載の乳化組成物。3. The emulsified composition according to claim 1, which is in the form of an oil-in-water-in-oil emulsion.
請求項1〜3何れか1項に記載の乳化組成物。4. An excellent high-temperature stability.
The emulsion composition according to claim 1.
求項1〜4何れか1項に記載の乳化組成物。5. The emulsion composition according to claim 1, which is an external preparation for skin.
1〜5何れか1項に記載の乳化組成物。6. The emulsion composition according to claim 1, which is a cosmetic.
とを特徴とする、請求項1〜6何れか1項に記載の乳化
組成物。7. The emulsion composition according to claim 1, further comprising a sucrose fatty acid ester.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001112251A JP2002308962A (en) | 2001-04-11 | 2001-04-11 | Emulsified composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001112251A JP2002308962A (en) | 2001-04-11 | 2001-04-11 | Emulsified composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2002308962A true JP2002308962A (en) | 2002-10-23 |
JP2002308962A5 JP2002308962A5 (en) | 2008-05-01 |
Family
ID=18963703
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2001112251A Pending JP2002308962A (en) | 2001-04-11 | 2001-04-11 | Emulsified composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2002308962A (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008013515A (en) * | 2006-07-07 | 2008-01-24 | Pola Chem Ind Inc | Cosmetic having characteristic in feeling of use |
JP2012072064A (en) * | 2010-09-27 | 2012-04-12 | Fancl Corp | Water-in-oil type emulsion composition |
JP2012131733A (en) * | 2010-12-21 | 2012-07-12 | Fancl Corp | Water in oil type emulsified composition |
JP2012144444A (en) * | 2011-01-07 | 2012-08-02 | Mikimoto Pharmaceut Co Ltd | Water-in-oil type emulsified composition or o/w/o type emulsified composition |
WO2012165134A1 (en) * | 2011-05-27 | 2012-12-06 | ライオン株式会社 | Oral composition |
JP2014503545A (en) * | 2010-12-22 | 2014-02-13 | エイボン プロダクツ インコーポレーテッド | Cosmetic powder composition with good durability |
JP2019108286A (en) * | 2017-12-18 | 2019-07-04 | 日本メナード化粧品株式会社 | Water-in-oil type emulsified composition |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5610014B2 (en) * | 1972-07-21 | 1981-03-05 | ||
JPH0530904A (en) * | 1991-08-01 | 1993-02-09 | Otsuka Shokuhin Kk | W/o-type emulsified food composition having high water-content |
JPH07255377A (en) * | 1994-03-23 | 1995-10-09 | Fuji Oil Co Ltd | O/w-type emulsion composition having milky taste and stable taste and flavor |
JPH11246354A (en) * | 1997-12-29 | 1999-09-14 | Kose Corp | Water-in-oil type cosmetic |
JPH11315015A (en) * | 1998-05-01 | 1999-11-16 | Pixy:Kk | Cosmetic and its production |
JP2000204276A (en) * | 1999-01-11 | 2000-07-25 | Shiseido Co Ltd | Water-in-oil emulsion composition |
JP2001019609A (en) * | 1999-07-08 | 2001-01-23 | Pola Chem Ind Inc | Multiphase emulsion-form skin preparation for external use |
-
2001
- 2001-04-11 JP JP2001112251A patent/JP2002308962A/en active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5610014B2 (en) * | 1972-07-21 | 1981-03-05 | ||
JPH0530904A (en) * | 1991-08-01 | 1993-02-09 | Otsuka Shokuhin Kk | W/o-type emulsified food composition having high water-content |
JPH07255377A (en) * | 1994-03-23 | 1995-10-09 | Fuji Oil Co Ltd | O/w-type emulsion composition having milky taste and stable taste and flavor |
JPH11246354A (en) * | 1997-12-29 | 1999-09-14 | Kose Corp | Water-in-oil type cosmetic |
JPH11315015A (en) * | 1998-05-01 | 1999-11-16 | Pixy:Kk | Cosmetic and its production |
JP2000204276A (en) * | 1999-01-11 | 2000-07-25 | Shiseido Co Ltd | Water-in-oil emulsion composition |
JP2001019609A (en) * | 1999-07-08 | 2001-01-23 | Pola Chem Ind Inc | Multiphase emulsion-form skin preparation for external use |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008013515A (en) * | 2006-07-07 | 2008-01-24 | Pola Chem Ind Inc | Cosmetic having characteristic in feeling of use |
JP2012072064A (en) * | 2010-09-27 | 2012-04-12 | Fancl Corp | Water-in-oil type emulsion composition |
JP2012131733A (en) * | 2010-12-21 | 2012-07-12 | Fancl Corp | Water in oil type emulsified composition |
JP2014503545A (en) * | 2010-12-22 | 2014-02-13 | エイボン プロダクツ インコーポレーテッド | Cosmetic powder composition with good durability |
JP2012144444A (en) * | 2011-01-07 | 2012-08-02 | Mikimoto Pharmaceut Co Ltd | Water-in-oil type emulsified composition or o/w/o type emulsified composition |
WO2012165134A1 (en) * | 2011-05-27 | 2012-12-06 | ライオン株式会社 | Oral composition |
CN103582475A (en) * | 2011-05-27 | 2014-02-12 | 狮王株式会社 | Oral composition |
JPWO2012165134A1 (en) * | 2011-05-27 | 2015-02-23 | ライオン株式会社 | Oral composition |
JP2019108286A (en) * | 2017-12-18 | 2019-07-04 | 日本メナード化粧品株式会社 | Water-in-oil type emulsified composition |
JP7022422B2 (en) | 2017-12-18 | 2022-02-18 | 日本メナード化粧品株式会社 | Water-in-oil emulsification composition |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR101337811B1 (en) | Process for producing o/w microemulsion preparation for external application | |
KR20150116655A (en) | Cosmetic composition stabilizing insoluble functional ingredient | |
JP2002193740A (en) | O/w-type emulsified composition | |
WO1999025310A1 (en) | Water-in-oil emulsifier composition | |
JP6118546B2 (en) | Oil-in-water emulsion composition | |
KR101422276B1 (en) | Oil-in-water emulsified composition | |
EP1755545B1 (en) | Surfactant composition | |
JP2002308962A (en) | Emulsified composition | |
JPS63126542A (en) | Microemulsion | |
JP3902174B2 (en) | Method for producing oil-in-water emulsion composition | |
JP2010222317A (en) | Oil-in-water type emulsified cosmetic | |
JP2002308962A5 (en) | ||
JP6817001B2 (en) | Oil-in-water liquid bath salt | |
KR100985368B1 (en) | Liquid cosmetics | |
JP2009155225A (en) | Oil-containing cosmetic composition | |
JP2002029919A (en) | Low-temperature stable emulsion composition | |
JP4808445B2 (en) | W / O type emulsion composition | |
US8173112B2 (en) | Emulsified composition for hair | |
JP2004059526A (en) | Water-in-oil type emulsifying cosmetic | |
JP3978611B2 (en) | Cosmetic composition | |
JP2004189693A (en) | O/w-type emulsion cosmetic | |
JP6640556B2 (en) | Oil-in-water liquid bath agent and method for producing the same | |
JP2003095845A (en) | Translucent liquid cosmetic | |
JP5632129B2 (en) | Emulsion composition for hairdressing | |
JPH02215708A (en) | Water-in-oil type emulsion cosmetic |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080225 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080225 |
|
RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20080225 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20100202 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100209 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100412 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100511 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100712 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100817 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20101014 |
|
A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20110308 |