WO2017081897A1 - ポンプフォーマー用洗浄剤組成物 - Google Patents
ポンプフォーマー用洗浄剤組成物 Download PDFInfo
- Publication number
- WO2017081897A1 WO2017081897A1 PCT/JP2016/073444 JP2016073444W WO2017081897A1 WO 2017081897 A1 WO2017081897 A1 WO 2017081897A1 JP 2016073444 W JP2016073444 W JP 2016073444W WO 2017081897 A1 WO2017081897 A1 WO 2017081897A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- fatty acid
- higher fatty
- mass
- soap
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 50
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 86
- 229930195729 fatty acid Natural products 0.000 claims abstract description 86
- 239000000194 fatty acid Substances 0.000 claims abstract description 86
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 82
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000344 soap Substances 0.000 claims abstract description 47
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims abstract description 25
- 235000021314 Palmitic acid Nutrition 0.000 claims abstract description 24
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 24
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 24
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000008117 stearic acid Substances 0.000 claims abstract description 24
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims abstract description 22
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229960003237 betaine Drugs 0.000 claims abstract description 16
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims abstract description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 14
- XPALGXXLALUMLE-UHFFFAOYSA-N 2-(dimethylamino)tetradecanoic acid Chemical compound CCCCCCCCCCCCC(N(C)C)C(O)=O XPALGXXLALUMLE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005639 Lauric acid Substances 0.000 claims abstract description 11
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000021360 Myristic acid Nutrition 0.000 claims abstract description 6
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 25
- 239000003599 detergent Substances 0.000 claims description 15
- 150000005846 sugar alcohols Polymers 0.000 claims description 14
- 229940105990 diglycerin Drugs 0.000 claims description 3
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 claims description 3
- 239000006260 foam Substances 0.000 abstract description 33
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- -1 fatty acid salts Chemical class 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 230000002688 persistence Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000012459 cleaning agent Substances 0.000 description 3
- 239000003240 coconut oil Substances 0.000 description 3
- 235000019864 coconut oil Nutrition 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- KHAVLLBUVKBTBG-UHFFFAOYSA-N dec-9-enoic acid Chemical compound OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- BITHHVVYSMSWAG-KTKRTIGZSA-N (11Z)-icos-11-enoic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCC(O)=O BITHHVVYSMSWAG-KTKRTIGZSA-N 0.000 description 2
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- OXQGTIUCKGYOAA-UHFFFAOYSA-N 2-Ethylbutanoic acid Chemical compound CCC(CC)C(O)=O OXQGTIUCKGYOAA-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
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- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
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- 238000005259 measurement Methods 0.000 description 2
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- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 235000019865 palm kernel oil Nutrition 0.000 description 2
- 239000003346 palm kernel oil Substances 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 1
- HRLPTSDRCFNHPE-UHFFFAOYSA-N 2,2,3,3-tetramethylnonanoic acid Chemical compound CCCCCCC(C)(C)C(C)(C)C(O)=O HRLPTSDRCFNHPE-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- OILUAKBAMVLXGF-UHFFFAOYSA-N 3,5,5-trimethyl-hexanoic acid Chemical compound OC(=O)CC(C)CC(C)(C)C OILUAKBAMVLXGF-UHFFFAOYSA-N 0.000 description 1
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 description 1
- XZOYHFBNQHPJRQ-UHFFFAOYSA-N 7-methyloctanoic acid Chemical compound CC(C)CCCCCC(O)=O XZOYHFBNQHPJRQ-UHFFFAOYSA-N 0.000 description 1
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- FKLSONDBCYHMOQ-UHFFFAOYSA-N 9E-dodecenoic acid Natural products CCC=CCCCCCCCC(O)=O FKLSONDBCYHMOQ-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) 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
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004166 Lanolin Chemical class 0.000 description 1
- 235000021353 Lignoceric acid Nutrition 0.000 description 1
- CQXMAMUUWHYSIY-UHFFFAOYSA-N Lignoceric acid Natural products CCCCCCCCCCCCCCCCCCCCCCCC(=O)OCCC1=CC=C(O)C=C1 CQXMAMUUWHYSIY-UHFFFAOYSA-N 0.000 description 1
- SUZRRICLUFMAQD-UHFFFAOYSA-N N-Methyltaurine Chemical class CNCCS(O)(=O)=O SUZRRICLUFMAQD-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000021319 Palmitoleic acid Nutrition 0.000 description 1
- 239000005643 Pelargonic acid Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- BAZMYXGARXYAEQ-UHFFFAOYSA-N alpha-ethyl valeric acid Chemical compound CCCC(CC)C(O)=O BAZMYXGARXYAEQ-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
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- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229940114079 arachidonic acid Drugs 0.000 description 1
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- 239000003899 bactericide agent Substances 0.000 description 1
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- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229920006319 cationized starch Polymers 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XZJZNZATFHOMSJ-KTKRTIGZSA-N cis-3-dodecenoic acid Chemical compound CCCCCCCC\C=C/CC(O)=O XZJZNZATFHOMSJ-KTKRTIGZSA-N 0.000 description 1
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- MRUAUOIMASANKQ-UHFFFAOYSA-N cocamidopropyl betaine Chemical group CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O MRUAUOIMASANKQ-UHFFFAOYSA-N 0.000 description 1
- 229940073507 cocamidopropyl betaine Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
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- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940108623 eicosenoic acid Drugs 0.000 description 1
- BITHHVVYSMSWAG-UHFFFAOYSA-N eicosenoic acid Natural products CCCCCCCCC=CCCCCCCCCCC(O)=O BITHHVVYSMSWAG-UHFFFAOYSA-N 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- FARYTWBWLZAXNK-WAYWQWQTSA-N ethyl (z)-3-(methylamino)but-2-enoate Chemical compound CCOC(=O)\C=C(\C)NC FARYTWBWLZAXNK-WAYWQWQTSA-N 0.000 description 1
- 230000001815 facial effect Effects 0.000 description 1
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- 235000011187 glycerol Nutrition 0.000 description 1
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- JMOLZNNXZPAGBH-UHFFFAOYSA-N hexyldecanoic acid Chemical compound CCCCCCCCC(C(O)=O)CCCCCC JMOLZNNXZPAGBH-UHFFFAOYSA-N 0.000 description 1
- 229950004531 hexyldecanoic acid Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- YAQXGBBDJYBXKL-UHFFFAOYSA-N iron(2+);1,10-phenanthroline;dicyanide Chemical compound [Fe+2].N#[C-].N#[C-].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 YAQXGBBDJYBXKL-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
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- OYHQOLUKZRVURQ-AVQMFFATSA-N linoelaidic acid Chemical compound CCCCC\C=C\C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-AVQMFFATSA-N 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
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- 235000019198 oils Nutrition 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
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- 239000002453 shampoo Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts 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
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
-
- 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
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/34—Alcohols
-
- 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
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/36—Carboxylic acids; Salts or anhydrides 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
- A61K8/40—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
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/90—Betaines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2065—Polyhydric alcohols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/40—Specific cleaning or washing processes
- C11D2111/42—Application of foam or a temporary coating on the surface to be cleaned
Definitions
- the present invention relates to a cleaning composition that is housed in a non-gas type foam discharge container having a porous film such as a pump former, and is discharged in the form of foam through the porous film at the time of use. More specifically, the present invention relates to a cleaning composition for a pump former that is excellent in foam persistence and foam elasticity, has good low-temperature stability, and does not cause clogging.
- a liquid detergent composition that is contained in a non-gas type foam discharge container such as a pump former and discharged from the container in a foam state when used is known.
- This type of cleaning composition is mixed with air and discharged in the form of foam when passing through the porous membrane provided in the container.
- higher fatty acid soaps that are widely used as cleaning components are excellent in foaming properties and detergency
- long chain higher fatty acid salts having more than 12 carbon atoms cause crystal precipitation at a low temperature, and the porous film of the pump former There was a problem of causing clogging.
- Patent Document 1 does not contain a higher fatty acid soap as a cleaning component, and contains (a) a short chain length acyltaurine salt, (b) an amphoteric surfactant, and (c) a cationized starch.
- a liquid detergent composition for a pump former that is free from clogging, stably obtains a creamy foam quality even at a low temperature, and has a conditioning effect.
- Patent Document 2 There is a cleaning composition for pump formers containing alcohol (including propylene glycol of less than 20% by mass) (Patent Document 2).
- the cleaning composition of Patent Document 2 is characterized by not only excellent foam quality and low-temperature stability, but also can be easily washed away with a small amount of water.
- the present invention further improves the above-described conventional technology, exhibits a sufficient cleaning effect without suppressing the blending amount of the higher fatty acid soap, and has stability that does not cause clogging due to crystal precipitation even when stored at a low temperature. It is an object of the present invention to provide a cleaning composition for a pump former that can obtain a foam having excellent durability and elasticity.
- the present inventors have conducted intensive research, and as a result, blended high-grade fatty acid soaps having different chain lengths in a predetermined ratio so as to have a foam quality excellent in sustainability and elasticity.
- the inventors have found that it is possible to obtain a cleaning composition that does not clog even at low temperatures, and have completed the present invention.
- the present invention (A) lauryldimethylaminoacetic acid betaine; (B) 4 to 15% by mass of a higher fatty acid soap formed from fatty acids having 5 to 25 carbon atoms; A cleaning composition discharged in a former container containing The fatty acid having 5 to 25 carbon atoms is (B-1) 30-80% by mass of lauric acid, based on the total weight of fatty acids forming the higher fatty acid soap, (B-2) 5-30 mass% of myristic acid based on the total weight of fatty acids forming the higher fatty acid soap, and (b-3) 5-35 mass% of the total weight of fatty acids forming the higher fatty acid soap.
- the ratio [(a) / (b)] of the blending amount of (a) lauryldimethylaminoacetic acid betaine and (b) the blending amount of higher fatty acid soap is in the range of 0.4 to 1.5.
- a cleaning composition is provided.
- the cleaning composition of the present invention has good foam quality with excellent foam persistence, high foam elasticity, excellent low-temperature stability, and causes clogging of the pump former even when stored at low temperatures. Absent.
- foam persistence means the property that the foam of the detergent discharged from the former container maintains the foam shape without being immediately crushed when applied to the skin and acclimatized.
- foam elasticity means that the foam of the cleaning agent discharged from the former container has a moist feeling with an appropriate elasticity.
- the lauryldimethylaminoacetic acid betaine (also referred to as N-lauryldimethylaminoacetic acid betaine) used in the present invention is a compound having a structure represented by the following formula (1).
- the blending amount of lauryldimethylaminoacetic acid betaine in the cleaning composition of the present invention is determined based on the blending amount of the higher fatty acid soap described later, but is usually 2 to 20% by mass, preferably 2.5 to 18% by mass. %, More preferably 3 to 15% by mass, but not limited thereto, a range included in the above range, for example, a range such as 2 to 9% by mass, 3 to 8% by mass, or 4 to 7% by mass It can also be.
- the cleaning composition of the present invention contains a higher fatty acid soap as a cleaning component.
- the higher fatty acid soap in the present invention is formed from a salt of a fatty acid anion having 5 to 25 carbon atoms and a counter cation.
- the fatty acid having 5 to 25 carbon atoms is a carboxylic acid having a structure in which a carboxyl group is bonded to a linear or branched saturated or unsaturated monovalent hydrocarbon group such as an alkyl group or an alkylene group, The hydrocarbon group may be optionally substituted with a hydroxyl group or the like.
- fatty acids having 5 to 25 carbon atoms include caproic acid, heptanoic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, caproleic acid, undecylenic acid, lauroleic acid, 2-ethylbutanoic acid, isopentanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, isononanoic acid, 3,5,5-trimethylhexanoic acid, tridecanoic acid, tetramethylnonanoic acid, myristic acid, pentadecanoic acid, palmitic acid, stearic acid, arachidic acid, behenic acid , Lignoceric acid, serotic acid, myristic acid, palmitoleic acid, oleic acid, elaidic acid, gondoic acid, erucic acid, cerakoleic acid, linoleic acid, l
- the fatty acid soap used in the present invention includes an embodiment that does not include a fatty acid soap formed from a branched chain fatty acid or an unsaturated fatty acid.
- the detergent composition of the present invention comprises (b-1) lauric acid and (b-2) myristic acid and (b-3) a linear saturated fatty acid containing at least one selected from palmitic acid and stearic acid. Contains higher fatty acid soaps that are formed.
- (B-1) Lauric acid
- the higher fatty acid soap in the present invention contains 30 to 80% by mass of the fatty acid soap formed from lauric acid, based on the total weight of fatty acids forming the higher fatty acid soap.
- (B-2) Myristic acid
- the higher fatty acid soap in the present invention contains 5 to 30% by mass of the fatty acid soap formed from lauric acid, based on the total weight of fatty acids forming the higher fatty acid soap.
- the higher fatty acid soap in the present invention is a fatty acid soap formed of at least one selected from palmitic acid and stearic acid, and is 5% of the total weight of fatty acids forming the higher fatty acid soap. Contains ⁇ 35% by mass. If the total amount of palmitic acid and stearic acid exceeds 35% by mass, sufficient low temperature stability may not be obtained.
- the blending amount of palmitic acid and / or stearic acid is preferably 5 to 30% by mass, more preferably 5 to 25% by mass. %, And more preferably 5 to 20% by mass.
- the at least one selected from palmitic acid and stearic acid includes an embodiment containing only one of palmitic acid or stearic acid and an embodiment containing both palmitic acid and stearic acid.
- the blending ratio of palmitic acid and stearic acid [palmitic acid / stearic acid] is preferably in the range of 0.4 to 2.5. This numerical range includes an arbitrary range included in 0.4 to 2.5 (for example, 0.4 to 2.0 or 1.0 to 2.0) and all numerical values included in the range.
- the detergent composition of the present invention contains palmitic acid (carbon number 16) and / or stearic acid (carbon number 18).
- a foam having good sustainability can be obtained and the low temperature stability is also excellent.
- palmitic acid having a large number of carbon atoms in addition to lauric acid and myristic acid, which have been conventionally used and The improvement in low-temperature stability by adding stearic acid is an effect that cannot be predicted by those skilled in the art.
- the counter cation for neutralizing the higher fatty acid anion is preferably an alkali metal cation, particularly a potassium cation.
- the (a) higher fatty acid soap in the present invention does not contain fatty acid arginine salts and methyl taurine salts.
- the blending amount of the (b) higher fatty acid soap in the cleaning composition of the present invention is 4 to 15% by mass, preferably 5 to 12% by mass, more preferably 5 to 10% by mass, and further preferably 6 to 8% by mass. %.
- the compounding quantity of a higher fatty acid soap means the total compounding quantity of a higher fatty acid and a neutralizing agent (for example, potassium hydroxide).
- the ratio [(a) / (b)] of (a) the blending amount of lauryldimethylaminoacetic acid betaine and (b) the blending amount of higher fatty acid soap is 0.4 to 1.
- the blending ratio is more preferably in the range of 0.5 to 1.2. When the blending ratio is less than 0.4, sufficient low temperature stability cannot be obtained.
- the detergent composition of the present invention preferably contains a polyhydric alcohol in addition to the essential components (a) lauryldimethylaminoacetic acid betaine and (b) higher fatty acid soap.
- the polyhydric alcohol that can be blended can be selected from those usually blended in cosmetics and the like, such as glycerin, propylene glycol, dipropylene glycol, 1,3-butylene glycol, ethylene glycol, polyethylene glycol, sorbitol, etc. Is mentioned.
- the blending amount of the polyhydric alcohol is not particularly limited, but is usually 10 to 50% by mass, preferably 20 to 50% by mass, more preferably 25 to 40% by mass.
- the cleaning composition of the present invention may contain other optional components usually used in the liquid cleaning composition within a range that does not impair the effects of the present invention.
- These 1 type (s) or 2 or more types can be selected arbitrarily and can be mix
- the cleaning composition of the present invention is not limited.
- the viscosity measured at a temperature of 30 ° C. using a B-type rotational viscometer is 40 mPa ⁇ s or less, preferably 30 mPa ⁇ s or less, more preferably 20 mPa ⁇ s.
- the cleaning composition of the present invention can be produced according to a conventional method using the above-described essential components and optional components.
- the prepared cleaning composition of the present invention is accommodated in a non-gas type foam discharge container having a porous film.
- the non-gas type foam discharge container used in the present invention is of any known type as long as a certain amount of liquid detergent composition is mixed with a certain amount of air and discharged from the container at the time of use as a foam state. But you can. Specifically, for example, a squeeze foamer that is used by pressing the torso of a soft container with fingers, a pump former that is used by pressing the head of a cap equipped with a pump mechanism with fingers, and the like. .
- the liquid detergent composition in the container is discharged from the container discharge port as a foam by passing a mixture obtained by mixing the liquid detergent composition with air through the porous membrane (one to a plurality of sheets). It is like that.
- porous film of the pump former container examples include a sponge, a sintered body, and a net, but a thin net is preferable from the viewpoint of usability.
- a coarseness of about 30 to 400 mesh is preferably used.
- the cleaning composition of the present invention is suitably provided in the form of a facial cleanser, body soap, hand soap, shampoo, etc. as a cleaning agent for hair or skin contained in a pump former container.
- a detergent was prepared according to a conventional method with the composition described in each example of the following table. About the cleaning agent obtained in each case, the following items were evaluated according to the following criteria.
- (1) Stability at low temperature After the prepared detergent composition is filled in a vial of hard glass and stored in an evaluation room maintained at each temperature ( ⁇ 10 to 5 ° C.) for 24 hours and one week, the detergent The low temperature stability of the composition was visually observed and evaluated according to the following evaluation criteria.
- Foam quality (foam durability, foam elasticity, when the detergent composition of each example contained in a pump former container (mesh 200 ⁇ 305) is discharged in the form of foam and actually used. ) was evaluated by the expert panel. Evaluation was performed according to the following criteria. [Evaluation criteria] A: Very good B: Excellent C: Inferior In addition, the thing whose evaluation result is A or B is equipped with the characteristic sufficient to provide as goods.
- Comparative Example 5 in which the amount ratio is out of the range of the present invention (0.4 to 1.5) sufficient low temperature stability was not obtained.
- Comparative Example 6 Comparative Example 6 in which the blending amount of the higher fatty acid soap is less than 4% by mass is inferior in the persistence of the foam as in Comparative Example 1, and Comparative Example 7 in which the viscosity of the composition exceeds 30 mPa ⁇ s is It was difficult to discharge with a mer. Further, Comparative Example 8 in which N-lauryldimethylaminoacetic acid betaine was replaced with cocamidopropyl betaine (coconut oil fatty acid amidopropyl betaine) was inferior in low-temperature stability.
- Example 4 and 6-8 when compared with Example 9 containing palmitic acid and stearic acid in total of 30% by mass or more as the fatty acids forming the higher fatty acid soap, Examples 4 and 6-8 having a blending amount of 20-30% by mass, In Examples 2, 3 and 5 which are 20% by mass or less, it was confirmed that precipitation or the like did not occur even under severer low temperature conditions, and that it was particularly suitable for use in cold regions in winter.
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Abstract
Description
(a)ラウリルジメチルアミノ酢酸ベタインと、
(b)炭素数5~25の脂肪酸から形成される高級脂肪酸石鹸4~15質量%と、
を含有するフォーマー容器で吐出される洗浄料組成物であって、
前記炭素数5~25の脂肪酸が、
(b-1)高級脂肪酸石鹸を形成する脂肪酸全重量に対して30~80質量%のラウリン酸、
(b-2)高級脂肪酸石鹸を形成する脂肪酸全重量に対して5~30質量%のミリスチン酸、及び
(b-3)高級脂肪酸石鹸を形成する脂肪酸全重量に対して5~35質量%の、パルミチン酸及びステアリン酸から選択される少なくとも一種を含み、
前記(a)ラウリルジメチルアミノ酢酸ベタインの配合量と(b)高級脂肪酸石鹸の配合量との比率[(a)/(b)]が0.4~1.5の範囲内であることを特徴とする洗浄剤組成物を提供する。
本明細書における「泡の持続性」とは、フォーマー容器から吐出された洗浄剤の泡が、肌に塗布して馴染ませる際に、直ぐにつぶれずに泡形状を持続する性質を意味し、「泡の弾力性」とはフォーマー容器から吐出された洗浄剤の泡が適度な弾力を有するもちもちした感触を呈することを意味する。
(a)ラウリルジメチルアミノ酢酸ベタイン
本発明で用いられるラウリルジメチルアミノ酢酸ベタイン(N-ラウリルジメチルアミノ酢酸ベタインとも表記する)は、下記式(1)で表される構造を有する化合物である。
C12H25-N+(CH3)2-CH2COO- …(1)
本発明の洗浄剤組成物は、洗浄成分として高級脂肪酸石鹸を含有する。本発明における高級脂肪酸石鹸は、炭素数5~25の脂肪酸アニオンと対カチオンとの塩から形成される。炭素数5~25の脂肪酸は、直鎖状又は分岐鎖状の飽和又は不飽和の一価炭化水素基、例えばアルキル基、アルキレン基等にカルボキシル基が結合した構造を有するカルボン酸であり、前記炭化水素基は任意に水酸基等で置換されていてもよい。
本発明における高級脂肪酸石鹸は、ラウリン酸から形成される脂肪酸石鹸を、高級脂肪酸石鹸を形成する脂肪酸全重量に対して30~80質量%含有する。
(b-2)ミリスチン酸
本発明における高級脂肪酸石鹸は、ラウリン酸から形成される脂肪酸石鹸を、高級脂肪酸石鹸を形成する脂肪酸全重量に対して5~30質量%含有する。
本発明における高級脂肪酸石鹸は、パルミチン酸及びステアリン酸から選択される少なくとも一種から形成される脂肪酸石鹸を、高級脂肪酸石鹸を形成する脂肪酸全重量に対して5~35質量%含有する。パルミチン酸及びステアリン酸の合計配合量が35質量%を超えると十分な低温安定性が得られない場合がある。冬季の寒冷地等の低温安定性が特に求められる環境で使用する場合には、パルミチン酸及び/又はステアリン酸の配合量を5~30質量%とするのが好ましく、より好ましくは5~25質量%、さらに好ましくは5~20質量%である。
一般に、高級脂肪酸の鎖長(炭素数)が増加すると結晶析出が起こりやすいと考えられていることに鑑みれば、従来から汎用されていたラウリン酸及びミリスチン酸に加えて炭素数の多いパルミチン酸及び/又はステアリン酸を配合することにより低温安定性が向上したことは当業者が予測できない効果である。
本発明の洗浄剤組成物は、(a)ラウリルジメチルアミノ酢酸ベタイン、及び(b)高級脂肪酸石鹸という必須成分に加えて、多価アルコールを配合するのが好ましい。
配合され得る多価アルコールは、化粧料等に通常配合されるものから選択することができ、例えば、グリセリン、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、エチレングリコール、ポリエチレングリコール、ソルビトール等が挙げられる。
なお、以下の実施例等における配合量は特記しない限り質量%である。
各例で得られた洗浄剤について、以下の項目について下記の基準に従って評価した。
(1)低温安定性
調製した洗浄剤組成物を硬質ガラスのバイアルビンに充填し、各温度(-10~5℃)に保持された評価室において24時間及び1週間保存させた後、洗浄剤組成物の低温安定性を目視で観察し、下記評価基準で評価した。
A:良好(析出物・沈殿物がなく外観の変化がない。目詰まりを起こす可能性が無い)
B:不良(析出物・沈殿物があり品質上問題がある。目詰まりを起こす可能性がある)
通常の使用環境であれば、少なくとも-5℃~+5℃で24時間及び+5℃で1週間の保存を終えた時点での評価が「A」であれば商品として提供できる十分な特性を備えている。
ポンプフォーマー容器(メッシュ200×305)に収容した各例の洗浄剤組成物を泡状に吐出させて実使用した際の泡質(泡の持続性、泡の弾力性)について専門パネルが評価した。評価は以下の基準に従って実施した。
[評価基準]
A:非常に優れている
B:優れている
C:劣っている
なお、評価結果がA又はBであるものは、商品として提供するのに十分な特性を備えている。
各例で調製した洗浄剤組成物について、B型粘度計(ローターNo.1、60rpm)を用い、30℃の粘度を測定した。測定結果を各表に示す。
Claims (6)
- (a)ラウリルジメチルアミノ酢酸ベタインと、
(b)炭素数5~25の脂肪酸から形成される高級脂肪酸石鹸4~15質量%と、
を含有するフォーマー容器で吐出される洗浄料組成物であって、
前記炭素数5~25の脂肪酸が、
(b-1)高級脂肪酸石鹸を形成する脂肪酸全重量に対して30~80質量%のラウリン酸、
(b-2)高級脂肪酸石鹸を形成する脂肪酸全重量に対して5~30質量%のミリスチン酸、及び
(b-3)高級脂肪酸石鹸を形成する脂肪酸全重量に対して5~35質量%の、パルミチン酸及びステアリン酸から選択される少なくとも一種を含み、
前記(a)ラウリルジメチルアミノ酢酸ベタインの配合量と(b)高級脂肪酸石鹸の配合量との比率[(a)/(b)]が0.4~1.5の範囲内であることを特徴とする洗浄剤組成物。 - 前記(b-3)が、パルミチン酸及びステアリン酸の両方を含む、請求項1に記載の洗浄剤組成物。
- パルミチン酸とステアリン酸との配合量比率[パルミチン酸/ステアリン酸]が0.4~2.5の範囲内である、請求項2に記載の洗浄剤組成物。
- (c)多価アルコールをさらに含む、請求項1から3のいずれか一項に記載の洗浄剤組成物。
- 前記(c)多価アルコールが、IOB=3~4の多価アルコールを含む、請求項4に記載の洗浄剤組成物。
- 前記IOB=3~4の多価アルコールがジグリセリンである、請求項5に記載の洗浄剤組成物。
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SG11201803734XA SG11201803734XA (en) | 2015-11-12 | 2016-08-09 | Cleanser composition for a pump-foamer |
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Also Published As
Publication number | Publication date |
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JP6178382B2 (ja) | 2017-08-09 |
SG11201803734XA (en) | 2018-06-28 |
KR20180068998A (ko) | 2018-06-22 |
TWI675912B (zh) | 2019-11-01 |
TW201716564A (zh) | 2017-05-16 |
JP2017088555A (ja) | 2017-05-25 |
HK1251452A1 (zh) | 2019-02-01 |
KR102004746B1 (ko) | 2019-07-29 |
CN108348430B (zh) | 2022-02-15 |
CN108348430A (zh) | 2018-07-31 |
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