JP2014076977A - Skin washing agent composition - Google Patents
Skin washing agent composition Download PDFInfo
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- JP2014076977A JP2014076977A JP2012226661A JP2012226661A JP2014076977A JP 2014076977 A JP2014076977 A JP 2014076977A JP 2012226661 A JP2012226661 A JP 2012226661A JP 2012226661 A JP2012226661 A JP 2012226661A JP 2014076977 A JP2014076977 A JP 2014076977A
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- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 238000005406 washing Methods 0.000 title abstract description 8
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 36
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 35
- 229930195729 fatty acid Natural products 0.000 claims abstract description 35
- 239000000194 fatty acid Substances 0.000 claims abstract description 35
- -1 polyoxyethylene Polymers 0.000 claims abstract description 28
- 239000002280 amphoteric surfactant Substances 0.000 claims abstract description 23
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 8
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 7
- 229960003237 betaine Drugs 0.000 claims abstract description 6
- MQOCIYICOGDBSG-UHFFFAOYSA-M potassium;hexadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCC([O-])=O MQOCIYICOGDBSG-UHFFFAOYSA-M 0.000 claims abstract description 6
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 claims abstract description 5
- PYJBVGYZXWPIKK-UHFFFAOYSA-M potassium;tetradecanoate Chemical compound [K+].CCCCCCCCCCCCCC([O-])=O PYJBVGYZXWPIKK-UHFFFAOYSA-M 0.000 claims abstract description 4
- 239000011833 salt mixture Substances 0.000 claims abstract description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 11
- 125000002252 acyl group Chemical group 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 229960003080 taurine Drugs 0.000 claims description 3
- HIDKSOTTZRMUML-UHFFFAOYSA-M potassium;dodecanoate Chemical compound [K+].CCCCCCCCCCCC([O-])=O HIDKSOTTZRMUML-UHFFFAOYSA-M 0.000 claims description 2
- 239000006260 foam Substances 0.000 abstract description 35
- 238000005187 foaming Methods 0.000 abstract description 35
- 239000000516 sunscreening agent Substances 0.000 abstract description 29
- 239000002537 cosmetic Substances 0.000 abstract description 24
- 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 abstract description 9
- 229910052708 sodium Inorganic materials 0.000 abstract description 9
- 239000011734 sodium Substances 0.000 abstract description 9
- 239000003240 coconut oil Substances 0.000 abstract description 7
- 235000019864 coconut oil Nutrition 0.000 abstract description 7
- KAKVFSYQVNHFBS-UHFFFAOYSA-N (5-hydroxycyclopenten-1-yl)-phenylmethanone Chemical compound OC1CCC=C1C(=O)C1=CC=CC=C1 KAKVFSYQVNHFBS-UHFFFAOYSA-N 0.000 abstract description 4
- 229940096992 potassium oleate Drugs 0.000 abstract description 3
- FFDGPVCHZBVARC-UHFFFAOYSA-N N,N-dimethylglycine Chemical compound CN(C)CC(O)=O FFDGPVCHZBVARC-UHFFFAOYSA-N 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- WCENBULLAYPQBU-UHFFFAOYSA-N 2-[carboxymethyl(dodecyl)amino]acetic acid;sodium Chemical compound [Na].CCCCCCCCCCCCN(CC(O)=O)CC(O)=O WCENBULLAYPQBU-UHFFFAOYSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000003599 detergent Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000011538 cleaning material Substances 0.000 description 11
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 8
- 239000000344 soap Substances 0.000 description 8
- 210000000245 forearm Anatomy 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 4
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 4
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 239000012459 cleaning agent Substances 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- 229960002446 octanoic acid Drugs 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- 230000001815 facial effect Effects 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 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 2
- 239000005639 Lauric acid Substances 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- 206010040880 Skin irritation Diseases 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ZJDCURJWFBQZMS-UHFFFAOYSA-L disodium;2-[carboxylatomethyl(dodecyl)amino]acetate Chemical compound [Na+].[Na+].CCCCCCCCCCCCN(CC([O-])=O)CC([O-])=O ZJDCURJWFBQZMS-UHFFFAOYSA-L 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000002563 ionic surfactant Substances 0.000 description 2
- 229960004488 linolenic acid Drugs 0.000 description 2
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 235000021313 oleic acid Nutrition 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- POXKBECONNAUAP-UHFFFAOYSA-N potassium;tetradecanoic acid Chemical compound [K].CCCCCCCCCCCCCC(O)=O POXKBECONNAUAP-UHFFFAOYSA-N 0.000 description 2
- 239000002453 shampoo Substances 0.000 description 2
- 230000036556 skin irritation Effects 0.000 description 2
- 231100000475 skin irritation Toxicity 0.000 description 2
- 230000005808 skin problem Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 2
- 239000004475 Arginine Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920006197 POE laurate Polymers 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- COTJVGBAHUVVHH-UHFFFAOYSA-N [Na].C(CCCCC)(=O)N(CCS(=O)(=O)O)C Chemical compound [Na].C(CCCCC)(=O)N(CCS(=O)(=O)O)C COTJVGBAHUVVHH-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 210000002374 sebum Anatomy 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 229940104261 taurate Drugs 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Abstract
Description
本発明は、洗顔料、ボディシャンプー、ハンドソープ等の皮膚用洗浄剤組成物に関し、更に詳しくは、使用時の延びがよく、メイクアップ化粧料等の皮膚化粧料、特にサンスクリーン剤に対して、クレンジング力が高く、かつ泡立ちおよび泡質に優れるとともに、すすぎ後のさっぱり感に優れ、つっぱり感が生じ難い皮膚用洗浄剤組成物に関する。 The present invention relates to a skin cleanser composition such as a facial cleanser, body shampoo, hand soap and the like, and more particularly, it has a good elongation during use and is suitable for skin cosmetics such as makeup cosmetics, especially sunscreen agents. The present invention relates to a skin cleansing composition having high cleansing power, excellent foaming and foam quality, excellent refreshing feeling after rinsing, and hardly causing a refreshing feeling.
マスカラ、口紅、ファンデーション等のメイクアップ化粧料は、肌を美しく見せ、外界の刺激から肌を保護する効果を有し、女性の生活には欠かせないものとなっている。また、スキンケアの意識の高まりから、日焼け予防のサンスクリーン剤が男女問わず使用されるようになってきている。しかし、これらメイクアップ化粧料やサンスクリーン剤等の皮膚化粧料は、油性成分や無機顔料を多量に含んでいるため、皮膚の毛穴を塞ぎ、新陳代謝を妨げるとともに、皮膚化粧料自体が徐々に酸化されるため、長時間の使用は肌トラブルの原因となる場合がある。このため１日１回はクレンジング料を用いて皮膚化粧料を除去する必要がある。 Makeup cosmetics such as mascara, lipstick and foundation have the effect of making the skin beautiful and protecting the skin from external stimuli, and are indispensable for women's lives. In addition, sunscreening sunscreen agents are being used by both men and women due to increased awareness of skin care. However, skin cosmetics such as makeup cosmetics and sunscreen agents contain a large amount of oily components and inorganic pigments, so that they block the pores of the skin, prevent metabolism, and gradually oxidize the skin cosmetics themselves. Therefore, long-term use may cause skin problems. For this reason, it is necessary to remove skin cosmetics once a day using a cleansing material.
メイクアップ化粧料やサンスクリーン剤等の皮膚化粧料の多くは、汗等で流れ落ちるのを防ぐため、皮膚に塗布した後も親油性を保つように工夫されていることから、通常の洗顔料に用いられている石けんなどのイオン性界面活性剤では充分に除去することが困難である。そのため、第一段階として、皮膚化粧料となじみやすい油性成分を多く含んだ洗浄料（メイク落とし）を用いて等の皮膚化粧料を除去し、第二段階として石けんなどのイオン性界面活性剤（洗顔フォーム）を主成分とした洗浄料を泡立たせて素肌洗いを行い、メイク落としの残存油分を皮膚上の皮脂、泥、チリ、汚れと共に洗い流すことで、すっきり感あるいはさっぱり感といった満足感を得ていた。 Many skin cosmetics such as makeup cosmetics and sunscreen agents are designed to maintain oleophilic properties even after being applied to the skin in order to prevent them from flowing off due to sweat, etc. It is difficult to remove sufficiently with an ionic surfactant such as soap used. Therefore, as a first step, the skin cosmetics such as soaps are removed using a cleansing agent (makeup remover) that contains a lot of oily components that are easily compatible with the skin cosmetics, and as a second step, ionic surfactants such as soap ( Cleans the skin by foaming a cleansing agent that is mainly made of face-washing foam, and the remaining oil from the makeup remover is washed away along with the sebum, mud, dust, and dirt on the skin. It was.
このような二段階の洗浄、いわゆるダブルクレンジングを必要とする理由は、油性成分を主成分とする洗浄料では、使用後に水ですすいでも、皮膚上に残った油性成分が十分除去できず、さっぱりした洗浄感が得られないためであり、また、石けんなどの泡立たせて使う素肌洗い用の洗浄料のみでは、皮膚化粧料の油性成分に覆われた顔料や色素などを肌上から十分に除去できないためである。しかし、化粧行為の迅速性や簡便性が求められつつある近年、ダブルクレンジングは手間がかかる行為であり、また、二度の洗浄により、肌への負担が大きいといった問題を生じることもあった。 The reason why such two-stage cleaning, so-called double cleansing, is necessary is that a cleaning agent mainly composed of an oil component cannot sufficiently remove the oil component remaining on the skin even if it is rinsed with water after use. In addition, it is possible to remove the pigments and pigments covered with the oily components of skin cosmetics from the skin with only cleansing detergents that are used by lathering with soap or the like. This is because it cannot be done. However, in recent years when quick and simple makeup is required, double cleansing is a time-consuming action, and there has been a problem that a large burden on the skin is caused by washing twice.
石けんなどの泡立たせて使う洗浄料には泡立ちおよび泡質の良さが求められている。これは豊富でクリーミーな泡による緩衝作用によって皮膚への刺激を低減する効果があるためである。更に、泡立ちが良いほど洗浄した際の満足感が得られる傾向にあり、また泡質がクリーミーで細かいほど皮膚の毛穴などの小さな部位にも入りこめることから汚れのかき出しに優れているといった利点がある。しかしながら、石けんを主成分とした洗浄料は、泡立ちおよび泡質は優れている一方で、すすぎ後につっぱり感を生じることがあった。 The detergent used for foaming soap and the like is required to have good foaming and foam quality. This is because there is an effect of reducing skin irritation by the buffering action by the rich and creamy foam. In addition, there is a tendency that the better the foaming, the better the satisfaction of washing, and the finer the foam quality, the better it can be applied to small areas such as skin pores, and the better it is to remove dirt. is there. However, the detergent mainly composed of soap is excellent in foaming and foam quality, but sometimes has a feeling of tension after rinsing.
また、スキンケア意識の高まりから、男女問わずサンスクリーン剤を使用することが多くなってきているが、男性はダブルクレンジングを行う習慣がほとんどないため、通常の洗顔では油性成分等の除去が不十分であり、さっぱりした洗浄感が得られず、更に肌トラブルの原因になりうることもあった。 In addition, sunscreen preparations are increasingly used by both men and women due to increased skin care awareness, but since men do not have the habit of double cleansing, removal of oily components and the like is insufficient with normal facial cleansing. In addition, a refreshing feeling of cleaning could not be obtained, which could cause skin problems.
したがって、一回の洗浄のみでメイクアップ化粧料やサンスクリーン剤等の皮膚化粧料を効果的に除去する作用と、泡立ちおよび泡質がよく洗浄後にさっぱり感を付与する作用を併せ持つダブルクレンジング不要の皮膚用洗浄料の開発が強く望まれていた。 Therefore, there is no need for double cleansing, which has the effect of effectively removing skin cosmetics such as makeup cosmetics and sunscreen agents with only one washing, and the effect that foaming and foam quality provide a refreshing feeling after washing. The development of a skin cleanser has been strongly desired.
このような洗浄料としては例えば、特許文献１において、非イオン性界面活性剤、水酸基を有する水溶性化合物および油性成分を含有する１相型クレンジング用組成物が提案されている。この洗浄料は使用時の伸び、クレンジング力は良いものの、油性成分を多量に配合しているため、すすぎ後にぬめり感が残るばかりか、泡立たせたせることが困難であり、さっぱり感は得られ難かった。 As such a detergent, for example, Patent Document 1 proposes a one-phase cleansing composition containing a nonionic surfactant, a water-soluble compound having a hydroxyl group, and an oil component. Although this cleaning agent has good elongation and cleansing power when used, it contains a large amount of oily ingredients, so it will not only feel slimy after rinsing, it will be difficult to make it foam, and a refreshing feeling will be difficult to obtain. It was.
特許文献２では、脂肪酸アルカノールアミドと、油性成分１０〜５０％と陰イオン性界面活性剤とを含有する、ダブルクレンジング不要の泡立つ洗浄剤組成物が提案されている。また特許文献３では、液状の油性成分５０〜９０質量％、陰イオン性界面活性剤及び非イオン性界面活性剤の組み合わせからなる、ダブルクレンジング不要の気泡性洗浄料が提案されている。
これら洗浄料は液状の油性成分を１０％以上含有するため、クレンジング力は良いものの、使用後のぬめり感が残りさっぱりと洗い上げることはできず、ダブルクレンジングが必要になるときもあった。
Patent Document 2 proposes a foaming detergent composition that does not require double cleansing and contains a fatty acid alkanolamide, an oily component of 10 to 50%, and an anionic surfactant. Patent Document 3 proposes a foaming cleansing agent that does not require double cleansing and is a combination of a liquid oily component of 50 to 90% by mass, an anionic surfactant, and a nonionic surfactant.
Since these cleansing agents contain 10% or more of a liquid oily component, the cleansing power is good, but the slimy feeling after use remains and cannot be washed cleanly, and double cleansing is sometimes required.
そこで、油性成分を含まなくてもクレンジング力があり、更に泡立たせることができる洗浄料が提案されている。
例えば特許文献４において、高級脂肪酸塩、タウレート型陰イオン性界面活性剤、両性界面活性剤又は半極性界面活性剤、およびポリオキシエチレン脂肪酸エステル型非イオン性界面活性剤を含有する洗浄剤組成物が提案されている。この洗浄料は、皮膚刺激性が低く、クリーミーな泡質でつっぱり感が少なくさっぱりと洗い上げることができるが、サンスクリーン剤に対するクレンジング力については、満足いくものではなかった。
Therefore, there has been proposed a cleaning material that has cleansing power and can be further foamed without containing an oily component.
For example, in Patent Document 4, a detergent composition containing a higher fatty acid salt, a taurate type anionic surfactant, an amphoteric surfactant or a semipolar surfactant, and a polyoxyethylene fatty acid ester type nonionic surfactant Has been proposed. This cleansing agent has a low skin irritation, a creamy foam quality, and it can be washed cleanly, but the cleansing power to the sunscreen agent was not satisfactory.
特許文献５では、ポリグリセリンとアルキルグルコシド型非イオン性界面活性剤を組み合わせたクレンジング組成物が提案されている。この洗浄料は、メイクアップ化粧料を落とし、その後、水を加えることで、泡立たせてからすすぐことができるものだが、クレンジング力、泡立ち、泡質およびすすぎ後のさっぱり感は十分ではなかった。 In patent document 5, the cleansing composition which combined the polyglycerin and the alkyl glucoside type nonionic surfactant is proposed. This cleansing agent can be rinsed by removing make-up cosmetics and then adding water to make it foam, but cleansing power, foaming, foam quality and refreshing feeling after rinsing are not sufficient.
このように特許文献１〜３の洗浄料は、クレンジング力は高いものの、ぬめり感が残りやすく、更に泡立てて洗うことはできないため、洗浄後にさっぱり感が得られ難かった。また、特許文献４および５の洗浄料はいずれもメイクアップ化粧料に対してはある程度の効果があるものの、酸化チタン、酸化亜鉛などの無機物や紫外線吸収剤を大量に含み、かつ肌との密着性を上げたサンスクリーン剤に対しては十分な効果が得られていないのが実状である。また、メイクアップ化粧料やサンスクリーン剤等の皮膚化粧料に対して泡立ちや泡質も満足のできるものではなかった。 As described above, although the cleaning materials of Patent Documents 1 to 3 have high cleansing power, they tend to remain slimy and cannot be washed by foaming, so that it is difficult to obtain a refreshing feeling after cleaning. Moreover, although the cleaning materials of Patent Documents 4 and 5 have some effects on makeup cosmetics, they contain a large amount of inorganic substances such as titanium oxide and zinc oxide and ultraviolet absorbers, and are in close contact with the skin. The actual condition is that a sufficient effect is not obtained for the sunscreen agent having improved properties. Moreover, foaming and foam quality were not satisfactory for skin cosmetics such as makeup cosmetics and sunscreen agents.
本発明は、上記課題を解決するものであり、その目的は、使用時の延びがよく、メイクアップ化粧料等の皮膚化粧料、特にサンスクリーン剤に対して、クレンジング力が高く、かつ泡立ちおよび泡質に優れるとともに、すすぎ後のさっぱり感に優れ、つっぱり感が生じ難い皮膚用洗浄剤組成物を提供することである。 The present invention solves the above-mentioned problems, and its purpose is that it has a good elongation during use, has a high cleansing power, and has a high foaming power for skin cosmetics such as makeup cosmetics, particularly sunscreen agents. It is an object of the present invention to provide a skin cleansing composition that has excellent foam quality, excellent refreshing feeling after rinsing, and does not easily cause a feeling of refreshing.
本発明者らは、上記課題を解決するために鋭意検討を行った結果、下記に示すａ、ｂ、ｃ、およびｄの特定の界面活性剤を所定量組み合わせることにより、上記課題を解決できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by combining predetermined amounts of specific surfactants a, b, c, and d shown below. The headline and the present invention were completed.
すなわち本発明は、下記のａ、ｂ、ｃ、およびｄの各成分を含有し、ａ成分が８〜３０質量％、ｂ成分が２〜１５質量％、ｃ成分が０．５〜１０質量％、ｄ成分が２〜２０質量％、ａ成分とｄ成分の質量比ａ／ｄが０．７〜４であることを特徴とする皮膚用洗浄剤組成物である。
ａ．ラウリン酸カリウム塩２０〜６０質量％、ミリスチン酸カリウム塩５〜４０質量％、パルミチン酸カリウム塩０〜５質量％、およびオレイン酸カリウム塩２０〜６０質量％である脂肪酸カリウム塩混合物
ｂ．式（１）で示されるアミドアミノ酸型両性界面活性剤、式（２）で示されるアミドベタイン型両性界面活性剤、および式（３）で示されるアルキルイミノジカルボン酸型両性界面活性剤から選ばれる１種または２種以上の両性界面活性剤
ｃ．式（４）で示されるアシルメチルタウリン型陰イオン性界面活性剤
ｄ．ポリオキシエチレン脂肪酸グリセリル型非イオン性界面活性剤
That is, the present invention contains the following components a, b, c, and d, the component a is 8 to 30% by mass, the component b is 2 to 15% by mass, and the component c is 0.5 to 10% by mass. , D component is 2-20 mass%, and mass ratio a / d of a component and d component is 0.7-4, It is a cleaning composition for skin characterized by the above-mentioned.
a. Fatty acid potassium salt mixture which is 20-60% by weight lauric acid potassium salt, 5-40% by weight myristic acid potassium salt, 0-5% by weight palmitic acid potassium salt, and 20-60% by weight oleic acid potassium salt b. It is selected from the amide amino acid type amphoteric surfactant represented by the formula (1), the amide betaine type amphoteric surfactant represented by the formula (2), and the alkyliminodicarboxylic acid type amphoteric surfactant represented by the formula (3). One or more amphoteric surfactants
c. Acylmethyl taurine type anionic surfactant represented by the formula (4)
d. Polyoxyethylene fatty acid glyceryl type nonionic surfactant
本発明の皮膚用洗浄剤組成物は、使用時の延びがよく、メイクアップ化粧料やサンスクリーン剤に対して、クレンジング力が高く、かつ泡立ちおよび泡質に優れるとともに、すすぎ後のさっぱり感に優れ、つっぱり感が生じ難いという特長を有する。 The skin cleanser composition of the present invention has a good elongation during use, has a high cleansing power and excellent foaming and foam quality compared to makeup cosmetics and sunscreen agents, and a refreshing feeling after rinsing. It has the feature that it is excellent and does not easily cause a sense of tension.
以下、本発明の実施形態を説明する。本発明の皮膚用洗浄剤組成物は、上記のａ、ｂ、ｃ、およびｄの各成分を含有する。ａ成分から順次説明する。 Embodiments of the present invention will be described below. The skin cleansing composition of the present invention contains the components a, b, c, and d described above. The a component will be described in order.
〔ａ成分〕
本発明に用いられるａ成分は、その組成がラウリン酸カリウム塩２０〜６０質量％、ミリスチン酸カリウム塩５〜４０質量％、パルミチン酸カリウム塩０〜５質量％、およびオレイン酸カリウム塩２０〜６０質量％の混合物であり、好ましくはラウリン酸カリウム塩２５〜５５質量％、ミリスチン酸カリウム塩７〜３５質量％、パルミチン酸カリウム塩１〜４質量％、およびオレイン酸カリウム塩２５〜５０質量％の脂肪酸カリウム塩の混合物、より好ましくはラウリン酸カリウム塩３５〜５５質量％、ミリスチン酸カリウム塩１０〜３０質量％、パルミチン酸カリウム塩２〜４質量％、およびオレイン酸カリウム塩３０〜４０質量％の脂肪酸カリウム塩の混合物である。
[Component a]
The component a used in the present invention has a composition of 20 to 60% by mass of potassium laurate, 5 to 40% by mass of potassium myristic acid, 0 to 5% by mass of potassium palmitate, and 20 to 60% of oleic acid. A mixture of 25% to 55% by weight of potassium laurate, 7 to 35% by weight of potassium myristate, 1 to 4% by weight of potassium palmitate, and 25 to 50% by weight of potassium oleate. A mixture of fatty acid potassium salts, more preferably 35 to 55% by weight of potassium laurate, 10 to 30% by weight of potassium myristic acid, 2 to 4% by weight of potassium palmitate, and 30 to 40% by weight of potassium oleate It is a mixture of fatty acid potassium salts.
脂肪酸カリウム塩の混合物は、予め脂肪酸カリウム塩としたものを混合したものでもよく、また、それぞれの脂肪酸を含有する脂肪酸の混合物をまとめてカリウム塩としたものでもよい。
本発明の皮膚用洗浄剤組成物は、ａ成分を構成する脂肪酸カリウム塩以外の脂肪酸カリウム塩を、本発明の効果を損なわない範囲で、含有していてもよく、上記ａ成分を１００質量％としたとき、ａ成分以外の脂肪酸カリウム塩を５質量％程度まで含有させることができる。
The mixture of the fatty acid potassium salt may be a mixture of the fatty acid potassium salt in advance, or a mixture of fatty acids containing the respective fatty acids may be combined into a potassium salt.
The skin cleanser composition of the present invention may contain a fatty acid potassium salt other than the fatty acid potassium salt constituting the component a within a range not impairing the effects of the present invention, and the component a is 100% by mass. , Fatty acid potassium salts other than the component a can be contained up to about 5% by mass.
〔ｂ成分〕
本発明に用いられるｂ成分は、式（１）で示されるアミドアミノ酸型両性界面活性剤、式（２）で示されるアミドベタイン型両性界面活性剤、および式（３）で示されるアルキルイミノジカルボン酸型両性界面活性剤から選ばれる１種または２種以上の両性界面活性剤である。
[Component b]
The component b used in the present invention includes an amide amino acid type amphoteric surfactant represented by the formula (1), an amide betaine type amphoteric surfactant represented by the formula (2), and an alkyliminodicarboxylic compound represented by the formula (3). One or more amphoteric surfactants selected from acid-type amphoteric surfactants.
式（１）中のＲ１ＣＯおよび式（２）中のＲ２ＣＯはアシル基であり、炭素数８〜２０の脂肪酸残基である。かかる脂肪酸残基としては、具体的に脂肪酸名で表記すると、例えばカプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、イソステアリン酸、オレイン酸、リノール酸、リノレン酸等の脂肪酸が挙げられる。また、混合脂肪酸由来のアシル基を用いることができ、かかる混合脂肪酸としては、ヤシ油脂肪酸、パーム油脂肪酸等が挙げられる。好ましいアシル基は、炭素数８〜１８の範囲のものであり、より好ましくは炭素数８〜１６の範囲のものである。炭素数が８未満の場合は泡立ちおよび泡質が低下することがあり、２０を超える場合は安定性に問題を生じることがある。 R 1 CO in the formula (1) and R 2 CO in the formula (2) are acyl groups and are fatty acid residues having 8 to 20 carbon atoms. Examples of such fatty acid residues include specific fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, and linolenic acid. Can be mentioned. Moreover, the acyl group derived from a mixed fatty acid can be used, and examples of the mixed fatty acid include coconut oil fatty acid and palm oil fatty acid. Preferred acyl groups are those having 8 to 18 carbon atoms, more preferably those having 8 to 16 carbon atoms. When the number of carbon atoms is less than 8, foaming and foam quality may be deteriorated. When the number of carbon atoms exceeds 20, the stability may be deteriorated.
式（２）中のｌは２〜４の整数であり、好ましくは３である。 L in Formula (2) is an integer of 2-4, Preferably it is 3.
また、式（１）中のＭ１は、アルカリ金属、１／２アルカリ土類金属、アンモニウム、有機アンモニウムまたは塩基性アミノ酸陽イオンを示し、例えば、カリウム、ナトリウム、１／２マグネシウム、１／２カルシウム、アンモニウム、トリエタノールアンモニウム、リジンの陽イオン性残基、アルギニンの陽イオン性残基等が挙げられ、好ましくはカリウム、ナトリウムである。 M 1 in the formula (1) represents an alkali metal, ½ alkaline earth metal, ammonium, organic ammonium or a basic amino acid cation, for example, potassium, sodium, ½ magnesium, ½ Examples include calcium, ammonium, triethanolammonium, a lysine cationic residue, an arginine cationic residue, and the like, preferably potassium and sodium.
式（３）中のＲ３は炭素数８〜２０のアルキル基またはアルケニル基であり、具体的には、ラウリル基、ミリスチル基、パルミチル基、ステアリル基、イソステアリル基等のアルキル基、オレイル基等のアルケニル基が挙げられ、アルキル基はヤシ油アルキル基等の混合脂肪酸由来のアルキル基であってもよい。好ましいアルキル基またはアルケニル基は炭素数８〜１８、より好ましくは１０〜１４の範囲のものである。炭素数が８未満の場合は泡立ちおよび泡質が低下することがあり、２０を超える場合は安定性に問題を生じることがある。 R 3 in the formula (3) is an alkyl group or alkenyl group having 8 to 20 carbon atoms, specifically, an alkyl group such as a lauryl group, a myristyl group, a palmityl group, a stearyl group, an isostearyl group, or an oleyl group. And the alkyl group may be an alkyl group derived from a mixed fatty acid such as a coconut oil alkyl group. Preferred alkyl or alkenyl groups are those having 8 to 18 carbon atoms, more preferably 10 to 14 carbon atoms. When the number of carbon atoms is less than 8, foaming and foam quality may be deteriorated. When the number of carbon atoms exceeds 20, the stability may be deteriorated.
式（３）中のＭ２およびＭ３はそれぞれ水素原子またはアルカリ金属を示し、Ｍ２とＭ３は同一でも、異なっていても良く、例えば水素原子、カリウム、ナトリウムが挙げられ、好ましくは水素原子またはナトリウムである。また、式（３）中のｍおよびｎはそれぞれ独立して１〜３の整数であり、好ましくは１または２の整数であり、より好ましくはｍおよびｎがともに１である。ｍまたはｎが０の場合は安定性が低下することがあり、３を超える場合は泡質が低下することがある。 M 2 and M 3 in the formula (3) each represent a hydrogen atom or an alkali metal, and M 2 and M 3 may be the same or different, and examples thereof include a hydrogen atom, potassium and sodium, preferably hydrogen. Atom or sodium. Further, m and n in the formula (3) are each independently an integer of 1 to 3, preferably an integer of 1 or 2, and more preferably m and n are both 1. When m or n is 0, the stability may decrease, and when it exceeds 3, the foam quality may decrease.
ｂ成分としては、式（１）で示されるアミドアミノ酸型両性界面活性剤では、例えば、Ｎ−ココイル−Ｎ’−ヒドロキシエチル−Ｎ’−カルボキシメチルエチレンジアミンナトリウム〔日油（株）製「ニッサンアノンＧＬＭ−Ｒ−ＬＶ」）、式（２）で示されるアミドベタイン型両性界面活性剤では、例えば、ヤシ油脂肪酸アミドプロピルジメチルアミノ酢酸ベタイン〔日油（株）製「ニッサンアノンＢＤＦ−Ｒ」）、式（３）で示されるアルキルイミノジカルボン酸型両性界面活性剤では、例えば、ラウリルイミノジ酢酸ナトリウム〔日油（株）製「ニッサンアノンＬＡ」〕等が挙げられる。ｂ成分として、式（１）〜式（３）の各両性界面活性剤から選ばれる１種または２種以上を用いることができるし、同じ式で表わされる２種以上の両性界面活性剤を用いることもできる。 As the component b, in the amide amino acid type amphoteric surfactant represented by the formula (1), for example, N-cocoyl-N′-hydroxyethyl-N′-carboxymethylethylenediamine sodium [manufactured by NOF Corporation “Nissan Anon” GLM-R-LV "), an amide betaine amphoteric surfactant represented by the formula (2), for example, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine [manufactured by NOF Corporation" Nissan Anon BDF-R "] Examples of the alkyliminodicarboxylic acid type amphoteric surfactant represented by the formula (3) include sodium lauryliminodiacetate [“Nissan Anon LA” manufactured by NOF Corporation] and the like. As the component b, one or more amphoteric surfactants selected from the amphoteric surfactants of the formulas (1) to (3) can be used, or two or more amphoteric surfactants represented by the same formula can be used. You can also.
〔ｃ成分〕
本発明に用いられるｃ成分は、式（４）で示されるアシルメチルタウリン型陰イオン性界面活性剤である。式中のＲ４ＣＯはアシル基であり、炭素数８〜２０の脂肪酸残基である。かかる脂肪酸残基としては、ｂ成分の説明において挙げられた脂肪酸残基と同一のものが挙げられ、好ましくは炭素数８〜１８、より好ましくは８〜１６の範囲のものである。炭素数が８未満の場合は泡立ちおよび泡質が低下することがあり、２０を超える場合は安定性に問題を生じることがある。
また、式中のＭ４は、ｂ成分中のＭ１と同一のものが挙げられ、好ましくはカリウム、ナトリウムである。
[Component c]
The component c used in the present invention is an acylmethyl taurine type anionic surfactant represented by the formula (4). R 4 CO in the formula is an acyl group and is a fatty acid residue having 8 to 20 carbon atoms. Examples of the fatty acid residue include the same fatty acid residues as those described in the description of the component b, and preferably those having 8 to 18 carbon atoms, more preferably 8 to 16 carbon atoms. When the number of carbon atoms is less than 8, foaming and foam quality may be deteriorated. When the number of carbon atoms exceeds 20, the stability may be deteriorated.
In the formula, M 4 may be the same as M 1 in the component b, and is preferably potassium or sodium.
ｃ成分として具体的には、Ｎ−ココイル−Ｎ−メチルタウリンナトリウム〔日油（株）製「ダイヤポンＫ−ＳＦ」〕、Ｎ−カプロイル−Ｎ−メチルタウリンナトリウム〔日油（株）製「ダイヤポンＨＦ−ＳＦ」〕等が挙げられる。ｃ成分として１種又は２種以上を用いることができる。 Specific examples of the c component include N-cocoyl-N-methyltaurine sodium (“Diapon K-SF” manufactured by NOF Corporation), N-caproyl-N-methyltaurine sodium [manufactured by NOF Corporation “Diapon”. HF-SF "] and the like. 1 type (s) or 2 or more types can be used as c component.
〔ｄ成分〕
本発明に用いられるｄ成分は、ポリオキシエチレン脂肪酸グリセリル型非イオン性界面活性剤であり、グリセリンの水酸基が脂肪酸によりエステル化され、更にポリオキシエチレン基が付加している非イオン性界面活性剤である。
構成する脂肪酸残基としては、例えば、炭素数６〜１８の脂肪酸残基である。かかる脂肪酸残基としては、具体的に脂肪酸名で表記すると、例えば、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、イソステアリン酸等の飽和脂肪酸、オレイン酸、リノール酸、リノレン酸等の不飽和脂肪酸が挙げられる。また、混合脂肪酸由来の脂肪酸残基を用いることができ、具体的に混合脂肪酸名として表記すると、例えば、カプリル酸／カプリン酸、ヤシ油脂肪酸、パーム油脂肪酸等が挙げられる。脂肪酸残基の炭素数が６未満の場合は、クレンジング力が低下することがあり、炭素数が１８を超える場合は、泡立ちや泡質が低下することがある。
[D component]
The d component used in the present invention is a polyoxyethylene fatty acid glyceryl-type nonionic surfactant, a nonionic surfactant in which the hydroxyl group of glycerin is esterified with a fatty acid and a polyoxyethylene group is further added. It is.
Examples of the fatty acid residue to be configured are fatty acid residues having 6 to 18 carbon atoms. Such fatty acid residues are specifically expressed by fatty acid names. For example, saturated fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and isostearic acid, oleic acid, linoleic acid, and linolenic acid. Examples include unsaturated fatty acids such as acids. Moreover, the fatty acid residue derived from a mixed fatty acid can be used. When specifically described as a mixed fatty acid name, for example, caprylic acid / capric acid, coconut oil fatty acid, palm oil fatty acid and the like can be mentioned. When the number of carbon atoms of the fatty acid residue is less than 6, cleansing power may be reduced, and when the number of carbon atoms exceeds 18, foaming and foam quality may be reduced.
グリセリン１分子に対するオキシエチレン基の平均付加モル数は、好ましくは３〜５０であり、より好ましくは６〜３０である。平均付加モル数が３未満では、泡立ちが低下するうえに配合が困難になることがあり、５０を超えると、クレンジング力が低下することがある。
グリセリン１分子に対するエステルの数は、好ましくは１〜２である。
ｄ成分として具体的には、ポリオキシエチレン（カプリル酸／カプリン酸）グリセリル（８Ｅ．Ｏ．）〔日油（株）製「ユニグリＭＣ−２０８」〕、ポリオキシエチレンヤシ油脂肪酸グリセリル（７Ｅ．Ｏ．）〔日油（株）製「ユニグリＭＫ−２０７Ｇ」〕、ポリオキシエチレンヤシ油脂肪酸グリセリル（３０Ｅ．Ｏ．）〔日油（株）製「ユニグリＭＫ−２３０」〕等が挙げられる。ｄ成分として１種又は２種以上を用いることができる。
The average number of moles of oxyethylene group added to one molecule of glycerin is preferably 3 to 50, more preferably 6 to 30. If the average number of added moles is less than 3, foaming may be reduced and blending may be difficult, and if it exceeds 50, cleansing power may be reduced.
The number of esters per molecule of glycerin is preferably 1-2.
Specific examples of the d component include polyoxyethylene (caprylic acid / capric acid) glyceryl (8E.O.) ["UNIGURI MC-208" manufactured by NOF Corporation], polyoxyethylene coconut oil fatty acid glyceryl (7E.O.). O.) ["UNIGURI MK-207G" manufactured by NOF Corporation], polyoxyethylene coconut oil fatty acid glyceryl (30E.O.) ["UNIGURI MK-230" manufactured by NOF Corporation], and the like. 1 type (s) or 2 or more types can be used as d component.
ａ成分の含有量は、組成物全量中に８〜３０質量％であり、好ましくは１０〜２５質量％、より好ましくは１２〜２０質量％である。８質量％未満では泡立ち、泡質およびさっぱり感が低下することがあり、３０質量％を超えると、使用時の延び、すすぎ後のつっぱり感が生じることがあるほか、クレンジング力が低下することもあり、経時安定性に問題が生じることもある。 Content of a component is 8-30 mass% in a composition whole quantity, Preferably it is 10-25 mass%, More preferably, it is 12-20 mass%. If it is less than 8% by mass, foaming, foam quality and refreshing feeling may be reduced, and if it exceeds 30% by mass, a feeling of stretching after use and a feeling of refreshing after rinsing may occur, and cleansing power may also be reduced. In addition, there may be a problem with stability over time.
ｂ成分の含有量は、組成物全量中に２〜１５質量％であり、好ましくは３〜１２質量％、より好ましくは５〜１０質量％である。２質量％未満では、泡立ち、クレンジング力が低下し、つっぱり感が生じることがあるほか、経時安定性に問題が生じることがある。１５質量％を超えると、すすぎ時やすすぎ後の不快なぬめり感が増加し、さっぱり感が低下することがある。 Content of b component is 2-15 mass% in the composition whole quantity, Preferably it is 3-12 mass%, More preferably, it is 5-10 mass%. If it is less than 2% by mass, foaming and cleansing force may be reduced, and a feeling of tension may be generated, and a problem may occur in stability over time. If it exceeds 15% by mass, unpleasant slimy feeling after rinsing or after rinsing may increase, and the refreshing feeling may decrease.
ｃ成分の含有量は、組成物全量中に０．５〜１０質量％であり、好ましくは１〜７質量％、より好ましくは１．５〜５質量％である。０．５質量％未満では、泡質、クレンジング力が低下し、つっぱり感が生じることがある。１０質量％を超えると、すすぎ後に不快なぬめり感が生じ、さっぱり感が低下することがある。 Content of c component is 0.5-10 mass% in the composition whole quantity, Preferably it is 1-7 mass%, More preferably, it is 1.5-5 mass%. If it is less than 0.5% by mass, the foam quality and cleansing power may be reduced, and a feeling of tension may occur. If it exceeds 10% by mass, an unpleasant slimy feeling may occur after rinsing and the refreshing feeling may be lowered.
ｄ成分の含有量は、組成物全量中に２〜２０質量％であり、好ましくは５〜１８質量％、より好ましくは７〜１６質量％である。２質量％未満では、使用時の延び、クレンジング力が低下し、つっぱり感が生じることがある。２０質量％を超えると、泡立ち、泡質およびつっぱり感が生じることがある。 Content of d component is 2-20 mass% in the composition whole quantity, Preferably it is 5-18 mass%, More preferably, it is 7-16 mass%. If it is less than 2% by mass, the elongation during use, the cleansing force may be reduced, and a feeling of tension may occur. When it exceeds 20 mass%, foaming, foam quality and a feeling of tension may occur.
また、ａ成分とｄ成分の質量比ａ／ｄは０．７〜４であり、好ましくは１〜３．５、より好ましくは１〜３である。質量比ａ／ｄが０．７未満では、泡立ち、泡質およびさっぱり感が低下し、つっぱり感を生じることがある。質量比ａ／ｄが４を超えると、使用時の延び、泡立ちが低下し、つっぱり感を生じることがある。 Moreover, mass ratio a / d of a component and d component is 0.7-4, Preferably it is 1-3.5, More preferably, it is 1-3. When the mass ratio a / d is less than 0.7, foaming, foam quality, and a refreshing feeling are lowered, and a feeling of tension may be generated. When the mass ratio a / d exceeds 4, elongation during use and foaming may decrease, and a feeling of tension may be generated.
本発明の皮膚用洗浄剤組成物は、通常の方法に従って製造することができる。本発明の皮膚用洗浄剤組成物の形態は液状であり、溶剤として水又は低級アルコール、特に水を用いたものが好ましい。本発明の皮膚用洗浄剤組成物において、通常、溶剤として３５〜８５質量％を含有させることができる。
また、本発明の皮膚用洗浄剤組成物は、肌（皮膚）の洗浄を目的とした様々な使用形態に適用することができ、例えば洗顔料、ボディシャンプー、ハンドソープ等として用いることができる。特に、メイクアップ化粧料やサンスクリーン剤のクレンジング料として好適に用いることができる。
The skin cleansing composition of the present invention can be produced according to a usual method. The form of the skin cleanser composition of the present invention is liquid, and a solvent using water or a lower alcohol, particularly water, is preferred. In the skin cleansing composition of the present invention, usually 35 to 85% by mass can be contained as a solvent.
The skin cleansing composition of the present invention can be applied to various usage forms for the purpose of cleaning the skin (skin), and can be used, for example, as a facial cleanser, body shampoo, hand soap and the like. In particular, it can be suitably used as a cleansing material for makeup cosmetics and sunscreen agents.
本発明の皮膚用洗浄剤組成物においては、本発明の効果を阻害しない範囲で、皮膚用洗浄剤に常用されている添加剤を含有させることも可能である。 The skin cleansing composition of the present invention can contain additives commonly used in skin cleansing agents as long as the effects of the present invention are not impaired.
以下、実施例および比較例を挙げて本発明をさらに具体的に説明する。
表１（実施例１〜７）および表２（比較例１〜８）に示す皮膚用洗浄剤組成物（以下、洗浄料とも言う。）を調製し、下記の方法により評価した。
なお、表１および表２において、各成分の数値は組成物全量中の含有量（質量％）を示す。また、ａ／ｄはａ成分とｄ成分の質量比を示す。ただし、比較例７および８においては、ａ成分とｄ’成分の質量比（ａ／ｄ’）を示す。
Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples.
Skin cleansing compositions (hereinafter also referred to as cleaning agents) shown in Table 1 (Examples 1 to 7) and Table 2 (Comparative Examples 1 to 8) were prepared and evaluated by the following methods.
In Tables 1 and 2, the numerical value of each component indicates the content (% by mass) in the total amount of the composition. Moreover, a / d shows mass ratio of a component and d component. However, in Comparative Examples 7 and 8, the mass ratio (a / d ′) between the a component and the d ′ component is shown.
（１）使用時の延び
２０名の女性（２１才〜３５才）をパネラーとし、左手前腕内側に洗浄料０．１ｇをとり、右手人差し指で円を描くように擦った。
２点：使用時に延びが良いと感じた場合。
１点：使用時に延びがやや良い感じた場合。
０点：使用時に延びが悪いと感じた場合。
(1) Elongation during use Twenty women (21 to 35 years old) were panelists, and 0.1 g of cleaning material was taken inside the left forearm and rubbed in a circle with the right index finger.
2 points: When the extension feels good during use.
1 point: When the extension feels somewhat good during use.
0 points: When it is felt that the elongation is bad during use.
（２）Ｏ／Ｗ型サンスクリーン剤に対するクレンジング力
２０名の女性（２１才〜３５才）をパネラーとし、市販のＯ／Ｗ型サンスクリーン剤（ＳＰＦ；５０、ＰＡ＋＋＋）を左手前腕部に直径２センチ程塗布し、乾燥させたのち、洗浄料０．１ｇを用いてサンスクリーン剤となじませるように３０秒間擦ったのち、水ですすいだ。
２点：水ですすいだ後、充分汚れが落ちたと感じた場合。
１点：水ですすいだ後、ほとんど汚れが落ちたと感じた場合。
０点：明らかに汚れ落ちが悪いと感じた場合。
(2) Cleansing power for O / W sunscreen agent 20 females (21 to 35 years old) as panelists and commercially available O / W type sunscreen agent (SPF; 50, PA ++) on the left forearm After about 2 centimeters of application and drying, it was rubbed with 0.1 g of cleaning material for 30 seconds so as to blend in with the sunscreen agent, and then rinsed with water.
2 points: When it is felt that the dirt has been sufficiently removed after rinsing with water.
1 point: When it feels that dirt has almost disappeared after rinsing with water.
0 points: When it is clearly felt that dirt is not removed.
（３）Ｗ／Ｏ型サンスクリーン剤に対するクレンジング力
２０名の女性（２１才〜３５才）をパネラーとし、市販のＷ／Ｏ型サンスクリーン剤（ＳＰＦ；５０＋、ＰＡ＋＋＋）を左手前腕部に直径２センチ程塗布し、乾燥させたのち、洗浄料０．１ｇを用いてサンスクリーン剤となじませるように３０秒間擦ったのち、水ですすいだ。
２点：水ですすいだ後、充分汚れが落ちたと感じた場合。
１点：水ですすいだ後、ほとんど汚れが落ちたと感じた場合。
０点：明らかに汚れ落ちが悪いと感じた場合。
(3) Cleansing power for W / O type sunscreen agent 20 females (21 to 35 years old) as panelists and commercially available W / O type sunscreen agent (SPF; 50+, PA ++++) on the left forearm After about 2 centimeters of application and drying, it was rubbed with 0.1 g of cleaning material for 30 seconds so as to blend in with the sunscreen agent, and then rinsed with water.
2 points: When it is felt that the dirt has been sufficiently removed after rinsing with water.
1 point: When it feels that dirt has almost disappeared after rinsing with water.
0 points: When it is clearly felt that dirt is not removed.
（４）泡立ち
２０名の女性（２１才〜３５才）をパネラーとし、市販のＯ／Ｗ型サンスクリーン剤（ＳＰＦ；５０、ＰＡ＋＋＋）を左手前腕部に直径２センチ程塗布し、乾燥させたのち、洗浄料０．５ｇを用いてサンスクリーン剤となじませるように３０秒間マッサージした。その後、水でぬらした右手で、マッサージした部分を５０往復擦って泡立てた。
２点：泡立ちがとても良いと感じた場合。
１点：泡立ちがやや良いと感じた場合。
０点：泡立たないと感じた場合。
(4) Foaming 20 women (21 to 35 years old) were panelists, and a commercially available O / W type sunscreen agent (SPF; 50, PA ++) was applied to the left forearm about 2 cm in diameter and dried. After that, massage was performed for 30 seconds using 0.5 g of the cleaning material so as to blend in with the sunscreen agent. Then, with the right hand wet with water, the massaged part was rubbed 50 times and bubbled.
2 points: When foaming feels very good.
1 point: When foaming feels slightly good.
0 point: When it felt that it was not foamed.
（５）泡質
２０名の女性（２１才〜３５才）をパネラーとし、市販のＯ／Ｗ型サンスクリーン剤（ＳＰＦ；５０、ＰＡ＋＋＋）を左手前腕部に直径２センチ程塗布し、乾燥させたのち、洗浄料０．５ｇを用いてサンスクリーン剤となじませるように３０秒間マッサージした。その後、水でぬらした右手で、マッサージした部分を５０往復擦って泡立てた。
２点：泡質がとてもきめ細かいと感じた場合。
１点：泡質がきめ細かいと感じた場合。
０点：泡質が粗いと感じた場合。
(5) Foam quality 20 women (21 to 35 years old) are panelists, and a commercially available O / W type sunscreen agent (SPF; 50, PA ++) is applied to the left forearm about 2 cm in diameter and dried. After that, massage was performed for 30 seconds using 0.5 g of the cleaning material so as to blend in with the sunscreen agent. Then, with the right hand wet with water, the massaged part was rubbed 50 times and bubbled.
2 points: When the foam feels very fine.
1 point: When the foam feels fine.
0 point: When the foam feels rough.
（６）すすぎ後のさっぱり感
２０名の女性（２１才〜３５才）をパネラーとし、市販のＯ／Ｗ型サンスクリーン剤（ＳＰＦ；５０、ＰＡ＋＋＋）を左手前腕部に直径２センチ程塗布し、乾燥させたのち、洗浄料０．５ｇを用いてＯ／Ｗ型サンスクリーン剤となじませるように３０秒間マッサージした。その後、水でぬらした右手で、マッサージした部分を５０往復擦って泡立てた。最後に水で５秒間すすいだ。
２点：さっぱり感があると感じた場合。
１点：ややさっぱり感があると感じた場合。
０点：さっぱり感がないと感じた場合。
(6) Refreshing feeling after rinsing 20 women (21 to 35 years old) are panelists, and a commercially available O / W type sunscreen agent (SPF; 50, PA ++) is applied to the left forearm about 2 cm in diameter. After drying, massage was performed for 30 seconds using 0.5 g of cleaning material so as to blend in with the O / W type sunscreen agent. Then, with the right hand wet with water, the massaged part was rubbed 50 times and bubbled. Finally, rinse with water for 5 seconds.
2 points: When you feel refreshed.
1 point: When you feel a little refreshed.
0 points: When it is felt that there is no refreshing feeling.
（７）すすぎ後のつっぱり感
２０名の女性（２１才〜３５才）をパネラーとし、市販のＯ／Ｗ型サンスクリーン剤（ＳＰＦ；５０、ＰＡ＋＋＋）を左手前腕部に直径２センチ程塗布し、乾燥させたのち、洗浄料０．５ｇを用いてＯ／Ｗ型サンスクリーン剤となじませるように３０秒間マッサージした。その後、水でぬらした右手で、マッサージした部分を５０往復擦って泡立てた。最後に水で５秒間すすいだ。
２点：つっぱり感が全くないと感じた場合。
１点：つっぱり感がほとんどないと感じた場合。
０点：つっぱり感があると感じた場合。
(7) Tightness feeling after rinsing 20 women (21 to 35 years old) are panelists, and a commercially available O / W type sunscreen agent (SPF; 50, PA ++) is applied to the left forearm about 2 cm in diameter. After drying, massage was performed for 30 seconds using 0.5 g of cleaning material so as to blend in with the O / W type sunscreen agent. Then, with the right hand wet with water, the massaged part was rubbed 50 times and bubbled. Finally, rinse with water for 5 seconds.
2 points: When you feel that there is no sense of tension.
1 point: When it feels that there is almost no sense of squeezing.
0 points: When you feel a sense of tension.
上記（１）〜（７）について下記の基準で評価して、表１および表２にそれぞれ示した。なお、「◎」および「○」を合格と評価した。
◎：合計点が３５点以上
○：合計点が３０点以上３５点未満
△：合計点が２０点以上３０点未満
×：合計点が２０点未満
The above (1) to (7) were evaluated according to the following criteria and shown in Table 1 and Table 2, respectively. “◎” and “◯” were evaluated as acceptable.
◎: Total score is 35 or more ○: Total score is 30 or more and less than 35 △: Total score is 20 or more and less than 30 ×: Total score is less than 20
（８）経時安定性
各洗浄料を０℃、室温、４５℃の各温度条件下でそれぞれ１カ月間保存し、その外観を観察し下記のように評価し、表１および表２にそれぞれ示した。なお、「○」を合格とした。
○：いずれの温度でも外観の変化がない。
×：いずれかの温度において白濁や分離が認められる。
(8) Stability over time Each cleaning material was stored for 1 month at each temperature of 0 ° C., room temperature, and 45 ° C., its appearance was observed and evaluated as follows, and shown in Table 1 and Table 2, respectively. It was. In addition, "(circle)" was set as the pass.
○: No change in appearance at any temperature.
X: Cloudiness or separation is observed at any temperature.
本発明の皮膚用洗浄剤組成物に係る実施例１〜７の洗浄料は、いずれも、使用時の延びがよく、サンスクリーン剤に対するクレンジング力が高く、泡立ちおよび泡質に優れ、つっぱり感がなくさっぱりと洗い上げることができ、経時安定性に優れていた。 The cleaning agents of Examples 1 to 7 according to the skin cleansing composition of the present invention all have good elongation during use, high cleansing power for sunscreen agents, excellent foaming and foam quality, and a feeling of tension. It was able to be washed cleanly and was excellent in stability over time.
これに対して比較例１〜８では十分な性能が得られていない。
比較例１はａ成分が少ないため、泡立ち、泡質、すすぎ後のさっぱり感が悪かった。また、Ｗ／Ｏサンスクリーン剤に対するクレンジング力も低下し、つっぱり感が生じた。
比較例２はｂ成分を含有していないため、クレンジング力、泡立ち、泡質、および経時安定性が悪く、さらにすすぎ後のつっぱり感が生じた。
比較例３はｃ成分を含有していないため、クレンジング力、泡質が低下し、すすぎ後のつっぱり感が生じた。
比較例４はｄ成分を含有していないため、使用時の延びが悪く、クレンジング力が低下し、さらにすすぎ後のつっぱり感を生じた。
On the other hand, in Comparative Examples 1-8, sufficient performance is not obtained.
Since the comparative example 1 had few a components, foaming, foam quality, and the refreshing feeling after a rinse were bad. Moreover, the cleansing power with respect to the W / O sunscreen agent also decreased, and a feeling of tension was generated.
Since Comparative Example 2 did not contain the component b, cleansing power, foaming, foam quality, and stability over time were poor, and a feeling of squeezing after rinsing occurred.
Since Comparative Example 3 did not contain the c component, cleansing power and foam quality were lowered, and a feeling of tension after rinsing occurred.
Since Comparative Example 4 did not contain the d component, the elongation at the time of use was poor, the cleansing force was lowered, and a feeling of tension after rinsing was generated.
比較例５はａ／ｄが小さいため、泡立ち、泡質、さっぱり感が低下し、さらにつっぱり感も生じた。
比較例６はａ／ｄが大きいため、使用時の延び、泡立ちが低下し、さらにすすぎ後のつっぱり感が生じた。
比較７はｄ成分に代えてモノラウリン酸ポリオキシエチレンソルビタン（１０Ｅ．Ｏ）を含有させたものであるので、使用時の延び、クレンジング力、泡立ち、泡質、およびすすぎ後のさっぱり感が悪かった。
比較例８はｄ成分に代えてポリオキシエチレンラウレート（９Ｅ．Ｏ）を含有させたものであるので、使用時の延び、クレンジング力、泡立ち、泡質、およびすすぎ後のさっぱり感が悪かった。
In Comparative Example 5, since a / d was small, foaming, foam quality, and a refreshing feeling were lowered, and further a feeling of refreshing was generated.
In Comparative Example 6, since a / d was large, elongation at the time of use and foaming were reduced, and a feeling of tension after rinsing occurred.
In Comparative Example 7, polyoxyethylene sorbitan monolaurate (10E.O) was used instead of the d component, so that the elongation during use, cleansing force, foaming, foam quality, and refreshing feeling after rinsing were poor. .
Since Comparative Example 8 contained polyoxyethylene laurate (9E.O) instead of d component, the elongation during use, cleansing force, foaming, foam quality, and refreshing feeling after rinsing were bad. .
Claims (1)
ａ．ラウリン酸カリウム塩２０〜６０質量％、ミリスチン酸カリウム塩５〜４０質量％、パルミチン酸カリウム塩０〜５質量％、およびオレイン酸カリウム塩２０〜６０質量％である脂肪酸カリウム塩混合物
ｂ．式（１）で示されるアミドアミノ酸型両性界面活性剤、式（２）で示されるアミドベタイン型両性界面活性剤、および式（３）で示されるアルキルイミノジカルボン酸型両性界面活性剤から選ばれる１種または２種以上の両性界面活性剤
ｃ．式（４）で示されるアシルメチルタウリン型陰イオン性界面活性剤
ｄ．ポリオキシエチレン脂肪酸グリセリル型非イオン性界面活性剤 Each of the following components a, b, c, and d is contained, the a component is 8 to 30% by mass, the b component is 2 to 15% by mass, the c component is 0.5 to 10% by mass, and the d component is 2%. A skin cleansing composition, characterized in that the mass ratio a / d of the a component and the d component is 0.7 to 4% by mass.
a. Fatty acid potassium salt mixture which is 20-60% by weight lauric acid potassium salt, 5-40% by weight myristic acid potassium salt, 0-5% by weight palmitic acid potassium salt, and 20-60% by weight oleic acid potassium salt b. It is selected from the amide amino acid type amphoteric surfactant represented by the formula (1), the amide betaine type amphoteric surfactant represented by the formula (2), and the alkyliminodicarboxylic acid type amphoteric surfactant represented by the formula (3). One or more amphoteric surfactants
c. Acylmethyl taurine type anionic surfactant represented by the formula (4)
d. Polyoxyethylene fatty acid glyceryl type nonionic surfactant
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| JP2016008206A (en) * | 2014-06-26 | 2016-01-18 | ロート製薬株式会社 | Detergent composition |
| JP2017197450A (en) * | 2016-04-25 | 2017-11-02 | 日油株式会社 | Hair shampoo composition |
| JP2019514891A (en) * | 2016-04-25 | 2019-06-06 | ロレアル | Hypoallergenic cleaning composition with makeup removal properties |
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| JPH11189788A (en) * | 1997-12-26 | 1999-07-13 | Nof Corp | Transparent gel-like detergent composition |
| JP2005239588A (en) * | 2004-02-25 | 2005-09-08 | Pola Chem Ind Inc | Face washing agent having excellent foam retention time |
| JP2007119394A (en) * | 2005-10-28 | 2007-05-17 | Pola Chem Ind Inc | Cosmetic having horny plug removal effect |
| JP2011126805A (en) * | 2009-12-16 | 2011-06-30 | Mandom Corp | Aqueous cleansing cosmetic |
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| JPH11189788A (en) * | 1997-12-26 | 1999-07-13 | Nof Corp | Transparent gel-like detergent composition |
| JP2005239588A (en) * | 2004-02-25 | 2005-09-08 | Pola Chem Ind Inc | Face washing agent having excellent foam retention time |
| JP2007119394A (en) * | 2005-10-28 | 2007-05-17 | Pola Chem Ind Inc | Cosmetic having horny plug removal effect |
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| JP2016008206A (en) * | 2014-06-26 | 2016-01-18 | ロート製薬株式会社 | Detergent composition |
| JP2017197450A (en) * | 2016-04-25 | 2017-11-02 | 日油株式会社 | Hair shampoo composition |
| JP2019514891A (en) * | 2016-04-25 | 2019-06-06 | ロレアル | Hypoallergenic cleaning composition with makeup removal properties |
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