JP5917204B2 - Skin cleanser composition - Google Patents
Skin cleanser composition Download PDFInfo
- Publication number
- JP5917204B2 JP5917204B2 JP2012049098A JP2012049098A JP5917204B2 JP 5917204 B2 JP5917204 B2 JP 5917204B2 JP 2012049098 A JP2012049098 A JP 2012049098A JP 2012049098 A JP2012049098 A JP 2012049098A JP 5917204 B2 JP5917204 B2 JP 5917204B2
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- JP
- Japan
- Prior art keywords
- component
- mass
- skin
- alkyl
- components
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims description 95
- 125000000217 alkyl group Chemical group 0.000 claims description 74
- -1 alkyl ether carboxylic acid Chemical class 0.000 claims description 62
- 239000002245 particle Substances 0.000 claims description 58
- 238000004140 cleaning Methods 0.000 claims description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- 239000003945 anionic surfactant Substances 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 210000003491 skin Anatomy 0.000 description 76
- 238000004519 manufacturing process Methods 0.000 description 29
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- 238000005187 foaming Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- 238000004817 gas chromatography Methods 0.000 description 18
- 239000006260 foam Substances 0.000 description 17
- 238000005406 washing Methods 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 235000014113 dietary fatty acids Nutrition 0.000 description 15
- 239000000194 fatty acid Substances 0.000 description 15
- 229930195729 fatty acid Natural products 0.000 description 15
- 239000000843 powder Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 13
- 238000009826 distribution Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- 229910052700 potassium Inorganic materials 0.000 description 9
- 239000011591 potassium Substances 0.000 description 9
- 239000008213 purified water Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 8
- 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 8
- 239000011734 sodium Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 235000013339 cereals Nutrition 0.000 description 7
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 210000002374 sebum Anatomy 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 125000003342 alkenyl group Chemical group 0.000 description 6
- 239000008399 tap water Substances 0.000 description 6
- 235000020679 tap water Nutrition 0.000 description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 5
- 229940024606 amino acid Drugs 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 5
- 239000003599 detergent Substances 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229960003237 betaine Drugs 0.000 description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 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
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 239000011148 porous material Substances 0.000 description 4
- 230000001953 sensory effect Effects 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- 241000282994 Cervidae Species 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 206010000496 acne Diseases 0.000 description 3
- 150000001447 alkali salts Chemical class 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- KPUNOVLMCQQCSK-UHFFFAOYSA-N diazomethane;ethoxyethane Chemical compound C=[N+]=[N-].CCOCC KPUNOVLMCQQCSK-UHFFFAOYSA-N 0.000 description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 2
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- VZUNGTLZRAYYDE-UHFFFAOYSA-N N-methyl-N'-nitro-N-nitrosoguanidine Chemical compound O=NN(C)C(=N)N[N+]([O-])=O VZUNGTLZRAYYDE-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229960000541 cetyl alcohol Drugs 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 239000011538 cleaning material Substances 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000002704 decyl 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])* 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
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- 206010016256 fatigue Diseases 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
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- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 238000011086 high cleaning Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
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- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 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 2
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- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 2
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- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
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Landscapes
- Cosmetics (AREA)
- Detergent Compositions (AREA)
Description
本発明は、皮膚洗浄剤組成物に関する。 The present invention relates to a skin cleansing composition.
皮膚洗浄剤においては、その洗浄効果や洗浄時の洗浄実感を高めるため、洗浄剤に粒子を配合したスクラブ洗浄剤が知られている。スクラブ洗浄剤を使用した場合、粒子が毛穴や皮溝などの皮膚の細かい凹凸の中に入り込み、毛穴や皮溝にある皮脂や汚れを除去すると同時に、使用者にその粒子の粒の感触を感じさせる。従って、洗浄剤の粒子は汚れが落ちたという満足感を使用者に与えることができる。 In the case of a skin cleanser, a scrub cleanser in which particles are mixed with the cleanser is known in order to enhance its cleansing effect and clean feeling during cleaning. When scrub cleaner is used, the particles get into the fine irregularities of the skin, such as pores and skin grooves, removing the sebum and dirt in the pores and skin grooves, and at the same time, the user feels the grain of the particles. Let Therefore, the user can be satisfied that the detergent particles have been cleaned.
例えば、特許文献１には、特定の組成の脂肪酸及びその塩と水不溶性粒子を組み合わせることにより、泡立ちとすすぎ性に優れた洗浄組成物が得られることが記載されている。
特許文献２には、脂肪酸塩と特定の非イオン界面活性剤にメントールを配合することによって洗浄後の爽快感を付与し、洗浄実感を高める技術について記載されている。
For example, Patent Document 1 describes that a cleaning composition having excellent foaming and rinsing properties can be obtained by combining a fatty acid having a specific composition and a salt thereof with water-insoluble particles.
Patent Document 2 describes a technique for enhancing refreshing feeling by adding refreshment after washing by blending menthol with a fatty acid salt and a specific nonionic surfactant.
また、特許文献３には、高級脂肪酸塩と特定のアミノ酸系界面活性剤、及び水不溶性固体粉体を組み合わせることにより、高級脂肪酸塩によるすすぎ中のきしみ感の低減や、使用後のつっぱり感や乾燥感を抑えることのできる洗浄剤組成物が記載されている。 In Patent Document 3, a combination of a higher fatty acid salt, a specific amino acid surfactant, and a water-insoluble solid powder reduces the squeaking feeling during rinsing with the higher fatty acid salt, Detergent compositions that can reduce dryness are described.
特許文献４には、特定の粒度分布を有する炭酸水素ナトリウム粒子と、脂肪酸塩を含有することで、また、特許文献５には、高級脂肪酸又はその塩とポリオキシエーテルカルボン酸又はその塩、そして、特定のＩＯＢ値である両親媒性物質と水不溶性粒子を組み合わせることにより、泡質をコントロールし、洗浄時の粒子の適度な粒感を持続的に感じさせることとで、スクラブによる洗浄効果を高め、洗浄実感も高めることができる皮膚洗浄剤が記載されている。 Patent Document 4 contains sodium hydrogen carbonate particles having a specific particle size distribution and a fatty acid salt. Patent Document 5 discloses a higher fatty acid or a salt thereof and a polyoxyether carboxylic acid or a salt thereof, and By combining an amphiphilic substance with a specific IOB value and water-insoluble particles, the foam quality is controlled, and a moderate grain feel of the particles at the time of washing is continuously felt, so that the scrubbing effect by scrubbing can be achieved. A skin cleanser that can enhance and enhance the cleansing experience is described.
しかし、特許文献１では、すすぎ時に特有のきしみ感が強く、『肌の脂を取りきってしまった感じ』、『何かが残っている感じ』など、肌への悪影響を連想させ、洗浄後は、肌が乾燥しザラザラする、皮脂が過剰に出てすぐにベタついてしまう感じがするなど、洗浄後少時間経過後の洗浄実感に課題があった。
特許文献２では、冷感剤による洗浄実感を高めることができるが、使用者によっては冷涼感を好まない場合もあり、技術の応用範囲が限定されることや、洗浄後少時間経過後においては、冷涼感は失われているため、経時での洗浄実感の持続についての課題は解決されない。
特許文献３、４及び５では、若干の改善は見られるものの、洗浄後少時間経過後における洗浄実感の持続性についての課題は解決されていない。
However, in Patent Document 1, there is a strong squeaky feeling at the time of rinsing, which is associated with adverse effects on the skin such as “feeling that you have completely removed the oil” and “feeling that something remains”, after washing However, there was a problem with the feeling of washing after a short time after washing, such as the skin becoming dry and gritty, or feeling that the sebum was excessive and immediately sticky.
In patent document 2, although the washing | cleaning actual feeling by a cooling agent can be improved, depending on a user, a cooling feeling may be unfavorable, and the application range of a technique is limited, and after a short time passes after washing | cleaning. However, since the cool feeling is lost, the problem about the persistence of the cleaning feeling over time cannot be solved.
In Patent Documents 3, 4 and 5, although some improvement is seen, the problem about the persistence of the cleaning feeling after a lapse of a short time after cleaning is not solved.
本発明は、泡立ちとすすぎ性に優れるとともに、洗浄後少時間経過後においてもなめらかな肌感触が持続し、高い洗浄実感が得られる皮膚洗浄剤組成物に関する。 The present invention relates to a skin cleanser composition that is excellent in foaming and rinsing properties, maintains a smooth skin feel even after a lapse of a short time after cleaning, and provides a high cleaning feeling.
本発明者らは、特定の分布を有するアルキルエーテルカルボン酸又はその塩と、水不溶性粒子を組み合わせて用いれば、上記課題を解決した皮膚洗浄剤組成物が得られることを見出した。 The present inventors have found that a skin cleansing composition that solves the above problems can be obtained by using a combination of an alkyl ether carboxylic acid having a specific distribution or a salt thereof and water-insoluble particles.
本発明は、次の成分（Ａ）及び（Ｂ）：
（Ａ）一般式（１）
The present invention includes the following components (A) and (B):
(A) General formula (1)
（式中、Ｒ1は炭素数４〜２２のアルキル基を示し、ｎは０〜２０の数を示し、Ｍは水素原子、アルカリ金属、アルカリ土類金属、アンモニウム又は有機アンモニウムを示す）
で表されるアルキルエーテルカルボン酸又はその塩であって、Ｒ1の平均炭素数が１０．８〜１２．８であり、ｎ＝０の成分を９．６質量％を超え２７質量％以下、ｎ＝１の成分とｎ＝２の成分を合計で２１質量％以上４０質量％未満含むアルキルエーテルカルボン酸又はその塩、
（Ｂ）平均粒径５０〜５００μｍの水不溶性粒子
を含有する皮膚洗浄剤組成物を提供するものである。
(In the formula, R 1 represents an alkyl group having 4 to 22 carbon atoms, n represents a number of 0 to 20, and M represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, or organic ammonium).
In which the average carbon number of R 1 is 10.8 to 12.8, and the component of n = 0 exceeds 9.6% by mass and is 27% by mass or less, an alkyl ether carboxylic acid or a salt thereof containing a component of n = 1 and a component of n = 2 in total of 21% by mass or more and less than 40% by mass,
(B) A skin cleansing composition containing water-insoluble particles having an average particle size of 50 to 500 μm is provided.
本発明の皮膚洗浄剤組成物は、洗浄剤としての基本性能である泡立ちと肌への優しさを有し、すすぎ性に優れるとともに、毛穴周辺および皮溝等の肌の凸凹部分の汚れをしっかりと落とすことができる。また、洗浄後少時間経過後においても、洗浄直後に感じるなめらかな肌感触が続き、高い洗浄実感を付与することができる。 The skin cleanser composition of the present invention has foaming, which is a basic performance as a cleanser, and gentleness to the skin, is excellent in rinsing properties, and firmly removes dirt on convex skin concave portions such as pores and skin grooves. Can be dropped. In addition, even after a short time has passed since washing, the smooth skin feel immediately after washing continues, and a high washing feeling can be imparted.
本発明で用いる成分（Ａ）のアルキルエーテルカルボン酸又はその塩は、一般式（１）で表されるものである。
式中、Ｒ1は炭素数４〜２２のアルキル基であり、炭素数６〜２０のアルキル基、更に炭素数８〜１８のアルキル基が好ましく、炭素数８〜１６、更には炭素数１０〜１６のアルキル基がより好ましい。また、Ｒ1のアルキル鎖は、直鎖又は分岐鎖のいずれでも良いが、起泡性の点から、直鎖アルキル基が好ましい。また、Ｒ1の平均炭素数は１０．８〜１２．８であり、好ましくは１０．８〜１２．５であり、より好ましくは１２．１〜１２．４である。この範囲内であれば、起泡性及び泡質、さらに低温安定性の点で優れるので好ましい。
また、Ｒ1は２種以上のアルキル基を含むことが好ましく、一番含有量の多いアルキル鎖長を有する成分が５５質量％以上９７質量％未満であるのが好ましく、６０〜９５質量％がより好ましく、さらに７０〜９５質量％であるのが、泡量及び泡質に優れるので好ましい。
The alkyl ether carboxylic acid of component (A) or a salt thereof used in the present invention is represented by the general formula (1).
In the formula, R 1 is an alkyl group having 4 to 22 carbon atoms, preferably an alkyl group having 6 to 20 carbon atoms, more preferably an alkyl group having 8 to 18 carbon atoms, 8 to 16 carbon atoms, and further 10 to 10 carbon atoms. 16 alkyl groups are more preferred. The alkyl chain of R 1 may be either a straight chain or a branched chain, but a straight chain alkyl group is preferred from the viewpoint of foamability. The average carbon number of R 1 is 10.8 to 12.8, preferably 10.8 to 12.5, and more preferably 12.1 to 12.4. If it is in this range, it is excellent in terms of foamability and foam quality, and stability at low temperature, which is preferable.
R 1 preferably contains two or more alkyl groups, and the component having the largest alkyl chain length is preferably 55% by mass or more and less than 97% by mass, and 60 to 95% by mass. More preferably, it is preferably 70 to 95% by mass because the foam amount and foam quality are excellent.
また、式中、ｎは０〜２０の数を示し、０〜１２がより好ましい。なお、ｎは、エチレンオシキシドの付加モル数を示すが、成分（Ａ）の組成中の平均付加モル数（ｎの平均値）は、泡立ちが良好である点から、１．５〜１０が好ましく、２．５〜６．４がより好ましく、２．５〜３．７がさらに好ましく、２．５〜３．４がさらに好ましく、２．８〜３．４がさらに好ましく、２．８〜３．１がさらに好ましい。
成分（Ａ）のアルキルエーテルカルボン酸又はその塩は、一般式（１）において、ｎ＝０の成分を９．６質量％を超え２７質量％以下、好ましくは９．８〜２７質量％、より好ましくは９．９〜２７質量％、更に好ましくは９．９〜１６質量％、より好ましくは９．９〜１５質量％含むものである。この範囲内とすることにより、泡量、泡質に優れる。
さらに、ｎ＝１の成分とｎ＝２の成分を合計で２１〜４０質量％未満、好ましくは２７〜３７質量％、より好ましくは２７〜３６．５質量％、さらに好ましくは３５〜３６．１質量％含むのが、泡質、泡量の観点から好ましい。
Moreover, in formula, n shows the number of 0-20, and 0-12 are more preferable. In addition, although n shows the addition mole number of ethylene oxyoxide, the average addition mole number (average value of n) in a composition of a component (A) is 1.5-10 from the point that foaming is favorable. Preferably, 2.5 to 6.4 is more preferable, 2.5 to 3.7 is more preferable, 2.5 to 3.4 is more preferable, 2.8 to 3.4 is more preferable, and 2.8 to 3.1 is more preferable.
In the general formula (1), the alkyl ether carboxylic acid of the component (A) or a salt thereof is more than 9.6% by mass and less than 27% by mass, preferably 9.8 to 27% by mass, compared with the component of n = 0. Preferably it contains 9.9-27 mass%, More preferably, it is 9.9-16 mass%, More preferably, it contains 9.9-15 mass%. By setting it within this range, the foam amount and foam quality are excellent.
Furthermore, the total of n = 1 component and n = 2 component is less than 21 to 40% by mass, preferably 27 to 37% by mass, more preferably 27 to 36.5% by mass, and further preferably 35 to 36.1. It is preferable from the viewpoint of the foam quality and the amount of foam to contain mass%.
また、式中、Ｍとしては、水素原子；ナトリウム、カリウム等のアルカリ金属；カルシウム、マグネシウム等のアルカリ土類金属；アンモニウム；モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等のアルカノールアミン由来のアンモニウムなどが挙げられる。これらの中で、起泡性、低温安定性、経時での着色のなさの点から、アルカリ金属が好ましい。 In the formula, M represents a hydrogen atom; an alkali metal such as sodium or potassium; an alkaline earth metal such as calcium or magnesium; an ammonium; an ammonium derived from an alkanolamine such as monoethanolamine, diethanolamine or triethanolamine; Can be mentioned. Among these, alkali metals are preferable from the viewpoints of foamability, low-temperature stability, and lack of coloration over time.
成分（Ａ）のアルキルエーテルカルボン酸又はその塩は、一般式（１）中、ｎ＝０、１、２、３、４の成分の質量割合が、Ｒ1の組成のうち最大含有量のアルキル鎖長成分において、（ｎ＝０成分の質量）：（ｎ＝１成分の質量）：（ｎ＝２成分の質量）：（ｎ＝３成分の質量）：（ｎ＝４成分の質量）＝１：０．９９〜３．５０：０．８９〜３．００：０．７６〜３．００：０．６３〜１．５２であることが、起泡性、洗浄性、すすぎ時のきしみ感の両立性の点から、好ましい。 In the general formula (1), the alkyl ether carboxylic acid of the component (A) or a salt thereof is an alkyl having the maximum content in the composition of R 1 in which the mass ratio of the components of n = 0, 1, 2, 3, 4 In the chain length component, (n = 0 component mass): (n = 1 component mass): (n = 2 component mass): (n = 3 component mass): (n = 4 component mass) = 1: 0.99 to 3.50: 0.89 to 3.00: 0.76 to 3.00: 0.63 to 1.52 is foaming property, detergency, and squeaky feeling during rinsing From the viewpoint of compatibility, it is preferable.
また、一般式（１）中、ｎ＝０の成分を９．９質量％以上１２質量％未満含み、Ｒ1の組成のうち最大含有量のアルキル鎖長成分において、（ｎ＝０成分の質量）：（ｎ＝１成分の質量）：（ｎ＝２成分の質量）：（ｎ＝３成分の質量）：（ｎ＝４成分の質量）＝１：１．５３〜１．８７：１．５９〜２．２５：１．３３〜２．１６：１．１４〜１．５２となるか、又は、ｎ＝０の成分を１２質量％以上１７質量％以下含み、Ｒ1の組成のうち最大含有量のアルキル鎖長成分において、（ｎ＝０成分の質量）：（ｎ＝１成分の質量）：（ｎ＝２成分の質量）：（ｎ＝３成分の質量）：（ｎ＝４成分の質量）＝１：０．９９〜１．３４：０．８９〜１．４０：０．７６〜１．２３：０．６３〜０．９９となるのが、泡質、泡量の観点から好ましい。 Further, in the general formula (1), the component of n = 0 include less than 9.9 wt% 12 wt%, in the alkyl chain length components of the maximum content of the composition of R 1, the (n = 0 component mass ): (Mass of n = 1 component): (mass of n = 2 component): (mass of n = 3 component): (mass of n = 4 component) = 1: 1.53-1.87: 1. 59 to 2.25: 1.33 to 2.16: 1.14 to 1.52, or 12 to 17% by mass of the n = 0 component, and the maximum among the compositions of R 1 In the alkyl chain length component of content, (mass of n = 0 component): (mass of n = 1 component): (mass of n = 2 component): (mass of n = 3 component): (n = 4 component) Mass) = 1: 0.99 to 1.34: 0.89 to 1.40: 0.76 to 1.23: 0.63 to 0.99 from the viewpoint of foam quality and foam amount. preferable .
さらに、一般式（１）中、ｎ＝０の成分を９．９〜１１．５質量％含み、Ｒ1の組成のうち最大含有量のアルキル鎖長成分において、（ｎ＝０成分の質量）：（ｎ＝１成分の質量）：（ｎ＝２成分の質量）：（ｎ＝３成分の質量）：（ｎ＝４成分の質量）＝１：１．５８〜１．８４：１．７２〜２．１７：１．４９〜２．００：１．１４〜１．５２となるか、又は、一般式（１）中、ｎ＝０の成分を１３〜１５質量％含み、Ｒ1の組成のうち最大含有量のアルキル鎖長成分において、（ｎ＝０成分の質量）：（ｎ＝１成分の質量）：（ｎ＝２成分の質量）：（ｎ＝３成分の質量）：（ｎ＝４成分の質量）＝１：１．００〜１．３１：０．９３〜１．３４：０．７９〜１．１８：０．６３〜０．９９となるのが、泡質、泡量の点から好ましい。 Further, in the general formula (1), the component of n = 0 contains 9.9 to 11.5% by mass, and in the alkyl chain length component of the maximum content in the composition of R 1 , (mass of n = 0 component) : (N = 1 component mass): (n = 2 component mass): (n = 3 component mass): (n = 4 component mass) = 1: 1.58-1.84: 1.72 To 2.17: 1.49 to 2.00: 1.14 to 1.52, or, in the general formula (1), the component of n = 0 is contained in an amount of 13 to 15% by mass, and the composition of R 1 In the maximum alkyl chain length component, (n = 0 component mass): (n = 1 component mass): (n = 2 component mass): (n = 3 component mass): (n = Mass of 4 components) = 1: 1.00 to 1.31: 0.93 to 1.34: 0.79 to 1.18: 0.63 to 0.99 From the point of view, it is preferable.
成分（Ａ）において、一般式（１）中、Ｒ1は炭素数４〜２２のアルキル基であり、Ｒ1の平均炭素数は１０．８〜１２．８であり、また、一番含有量の多いアルキル鎖長を有する成分が５５質量％以上９７質量％未満であり、更に、ｎは０〜２０の数を示し、ｎの付加モル数の平均値は、１．５〜１０、さらには２．５〜６．４であり、ｎ＝０の成分を９．８〜２７質量％、ｎ＝１の成分とｎ＝２の成分を合計で２７〜３７質量％含有することが好ましい。また、式中、Ｍとしては、水素原子、ナトリウム、カリウム、アンモニウムが好ましい。このようにすることで、起泡を早めることができる。 In the component (A), in the general formula (1), R 1 is an alkyl group having 4 to 22 carbon atoms, the average carbon number of R 1 is 10.8 to 12.8, and the most content The component having a large alkyl chain length is 55% by mass or more and less than 97% by mass, n represents a number of 0 to 20, and the average value of the number of added moles of n is 1.5 to 10, It is 2.5-6.4, It is preferable to contain 9.8-27 mass% of the component of n = 0, and 27-37 mass% of the component of n = 1 and the component of n = 2 in total. In the formula, M is preferably a hydrogen atom, sodium, potassium, or ammonium. In this way, foaming can be accelerated.
成分（Ａ）において、一般式（１）中、Ｒ1は炭素数６〜２０のアルキル基が好ましく、Ｒ1の平均炭素数は１０．８〜１２．８であり、また、一番含有量の多いアルキル鎖長を有する成分が５５質量％以上９７質量％未満であり、更に、ｎは０〜２０の数を示し、ｎの平均値は、２．５〜３．７であり、ｎ＝０の成分を９．８〜２７質量％、ｎ＝１の成分とｎ＝２の成分を合計で２７〜３７質量％含有することが好ましい。また、式中、Ｍとしては、水素原子、ナトリウム、カリウム、アンモニウムが好ましい。このようにすることで、起泡性を早めることができる。 In the component (A), in the general formula (1), R 1 is preferably an alkyl group having 6 to 20 carbon atoms, and the average carbon number of R 1 is 10.8 to 12.8. The component having a large alkyl chain length is 55% by mass or more and less than 97% by mass, n represents a number from 0 to 20, the average value of n is 2.5 to 3.7, and n = It is preferable to contain 9.8 to 27% by mass of 0 component and 27 to 37% by mass in total of n = 1 component and n = 2 component. In the formula, M is preferably a hydrogen atom, sodium, potassium, or ammonium. By doing in this way, foamability can be accelerated.
成分（Ａ）において、一般式（１）中、Ｒ1は炭素数８〜１８のアルキル基であり、Ｒ1の平均炭素数は１０．８〜１２．８であり、また、一番含有量の多いアルキル鎖長を有する成分が５５質量％以上９７質量％未満であり、更に、ｎは０〜２０の数を示し、ｎの平均値は、２．５〜３．４であり、ｎ＝０の成分を９．９〜２７質量％、ｎ＝１の成分とｎ＝２の成分を合計で２７〜３６．５質量％含有することが好ましい。また、式中、Ｍとしては、水素原子、ナトリウム、カリウム、アンモニウムが好ましい。このようにすることで、すすぎ時のストップフィーリング性を強めることができる。 In the component (A), in the general formula (1), R 1 is an alkyl group having 8 to 18 carbon atoms, the average carbon number of R 1 is 10.8 to 12.8, and the most content The component having a large alkyl chain length is 55% by mass or more and less than 97% by mass, n represents a number of 0 to 20, and the average value of n is 2.5 to 3.4. It is preferable to contain 9.9 to 27% by mass of 0 component and 27 to 36.5% by mass in total of n = 1 component and n = 2 component. In the formula, M is preferably a hydrogen atom, sodium, potassium, or ammonium. By doing in this way, the stop feeling property at the time of a rinse can be strengthened.
成分（Ａ）において、一般式（１）中、Ｒ1は炭素数８〜１６のアルキル基であり、Ｒ1の平均炭素数は１０．８〜１２．５であり、また、一番含有量の多いアルキル鎖長を有する成分が６０〜９５質量％であり、更に、ｎは０〜２０の数を示し、ｎの平均値は、２．８〜３．４であり、ｎ＝０の成分を９．９〜１６質量％、ｎ＝１の成分とｎ＝２の成分を合計で２７〜３６．５質量％含むものが好ましい。また、式中、Ｍとしては、水素原子、ナトリウム、カリウム、アンモニウムが好ましい。このようにすることで、泡量、泡質を向上させることができる。 In the component (A), in the general formula (1), R 1 is an alkyl group having 8 to 16 carbon atoms, the average carbon number of R 1 is 10.8 to 12.5, and the most content The component having a large alkyl chain length is 60 to 95% by mass, n represents a number of 0 to 20, the average value of n is 2.8 to 3.4, and n = 0 Is preferably 9.9 to 16% by mass and contains 27 to 36.5% by mass in total of n = 1 and n = 2. In the formula, M is preferably a hydrogen atom, sodium, potassium, or ammonium. By doing in this way, foam amount and foam quality can be improved.
成分（Ａ）において、一般式（１）中、Ｒ1は炭素数１０〜１６のアルキル基であり、Ｒ1の平均炭素数は１２．１〜１２．４であり、また、一番含有量の多いアルキル鎖長を有する成分が７０〜９５質量％であり、更に、ｎは０〜２０の数を示し、ｎの平均値は、２．８〜３．１であり、ｎ＝０の成分を９．９〜１５質量％、ｎ＝１の成分とｎ＝２の成分を合計で３５〜３６．１質量％含むものが好ましい。また、式中、Ｍとしては、水素原子、ナトリウム、カリウム、アンモニウムが好ましい。このようにすることで、泡量、泡質、を向上させることができる。 In the component (A), in the general formula (1), R 1 is an alkyl group having 10 to 16 carbon atoms, the average carbon number of R 1 is 12.1 to 12.4, and the most content The component having a large alkyl chain length is 70 to 95% by mass, n represents a number of 0 to 20, the average value of n is 2.8 to 3.1, and n = 0 Is preferably 9.9 to 15% by mass and contains 35 to 36.1% by mass in total of n = 1 and n = 2. In the formula, M is preferably a hydrogen atom, sodium, potassium, or ammonium. By doing in this way, the amount of foams and foam quality can be improved.
なお、本発明の成分（Ａ）において、Ｒ1のアルキル鎖長の分布、Ｒ1の平均アルキル鎖長、ｎ＝０の成分量、ｎの平均付加モル数、ｎ＝０、１、２、３、４の成分の質量割合は、一般式（１）で表されるアルキルエーテルカルボン酸をガスクロマトグラフィーによる分析を行い、以下のようにして求める。 Incidentally, in the components of the present invention (A), the distribution of alkyl chain length of R 1, the average alkyl chain length of R 1, components of n = 0, average addition mole number of n, n = 0, 1, 2, The mass ratio of the components 3 and 4 is determined as follows by analyzing the alkyl ether carboxylic acid represented by the general formula (1) by gas chromatography.
〔Ｒ1のアルキル鎖長の分布〕
ガスクロマトグラフィーより得られるピーク面積のうち、ｎ＝０モルに相当する各アルキル鎖長のピーク面積を求め、それらの総和を１００とし、各アルキル鎖長分布の百分率を求めた。ｎ＝１〜３モルにおいても同様に計算し、ｎ＝０〜３モルの各アルキル鎖長分布の百分率の値を平均し、Ｒ1のアルキル鎖長の分布を求めた（これより、Ｒ1の組成のうち最も多く含有するアルキル基成分を特定できる）。
[Distribution of alkyl chain length of R 1 ]
Of the peak areas obtained by gas chromatography, the peak area of each alkyl chain length corresponding to n = 0 mol was determined, and the sum of these was determined as 100, and the percentage of each alkyl chain length distribution was determined. also calculated similarly in n = 1 to 3 mol, and the average value of the percentage of each alkyl chain length distribution of n = 0 to 3 mol, determined the distribution of alkyl chain length of R 1 (from which, R 1 The alkyl group component containing the largest amount of the composition can be specified).
〔Ｒ1の平均アルキル鎖長〕
上記のようにして求めたＲ1のアルキル鎖長の分布より、各成分の割合を求め、得られた割合に対応するアルキル鎖長分の炭素数を各々掛け、これらの総和を得た。これを平均アルキル鎖長とした。
[Average alkyl chain length of R 1 ]
From the distribution of the alkyl chain length of R 1 determined as described above, the ratio of each component was determined, and the carbon number corresponding to the alkyl chain length corresponding to the ratio thus obtained was multiplied to obtain the sum of these. This was defined as the average alkyl chain length.
〔ｎ＝０の成分量、ｎ＝１の成分とｎ＝２の成分の合計量〕
Ｒ1の組成のうち、最も多く含有するアルキル鎖長を特定し、その成分のｎ＝０〜１０に相当するガスクロマトグラフィーの面積を合計した。その合計量を１００％として、ｎ＝０の成分量、ｎ＝１の成分とｎ＝２の成分の合計量を算出した。
[Component amount of n = 0, total amount of component of n = 1 and component of n = 2]
Among the compositions of R 1 , the most abundant alkyl chain length was specified, and the areas of gas chromatography corresponding to n = 0 to 10 of the components were totaled. The total amount was set to 100%, and the total amount of n = 0, n = 1 and n = 2 was calculated.
〔ｎの平均付加モル数〕
Ｒ1の組成のうち最も多く含有するアルキル鎖長を特定し、その成分のｎ＝０〜１０に相当するガスクロマトグラフィーの面積を合計した（ｎが１１以上のものは微量であり、計算から除いた）。その合計量を１として、ｎ＝０〜１０の各々の割合を求めた。この割合に、各々の付加モル数を掛け、これらの合計をｎの平均付加モル数とした。
[Average number of moles of n added]
The most alkyl chain length contained in the composition of R 1 was specified, and the areas of the gas chromatography corresponding to n = 0 to 10 of the components were totaled (the ones with n of 11 or more are trace amounts. Excluded). The total amount was set to 1, and the ratio of each of n = 0 to 10 was obtained. This ratio was multiplied by the number of moles added, and the sum of these was taken as the average number of moles added.
〔ｎ＝０、ｎ＝１、ｎ＝２、ｎ＝３、ｎ＝４の成分の質量割合〕
ＥＯ付加モル数の異なる各成分の質量割合に関しては、ガスクロマトグラフィーにより得られるピーク面積から、上記に示した方法でＲ1のアルキル鎖長の分布を求め、Ｒ1の組成のうち最大含有量のアルキル鎖長成分を特定し、その最大成分のｎ＝０、ｎ＝１、ｎ＝２、ｎ＝３、ｎ＝４の面積比から特定した。
[Mass ratio of components of n = 0, n = 1, n = 2, n = 3, n = 4]
Regarding the mass ratio of each component having a different number of EO addition moles, the distribution of the alkyl chain length of R 1 is obtained from the peak area obtained by gas chromatography by the method described above, and the maximum content of the composition of R 1 The alkyl chain length component was identified from the area ratio of n = 0, n = 1, n = 2, n = 3, and n = 4 of the maximum component.
成分（Ａ）のアルキルエーテルカルボン酸又はその塩は、前記のような組成を有するもので、すすぎの点から、全組成中に０．５〜３０質量％含有するのが好ましく、１〜２５質量％がより好ましく、更に、２〜２０質量％含有されるのが好ましい。 The component (A) alkyl ether carboxylic acid or salt thereof has the composition as described above. From the viewpoint of rinsing, the total composition preferably contains 0.5 to 30% by mass, and 1 to 25% by mass % Is more preferable, and 2 to 20% by mass is further preferable.
本発明で用いる成分（Ｂ）の水不溶性粒子は、平均粒径が５０〜５００μｍのものである。
具合的には、酸化チタン、タルク、カオリン、ベントナイト、塩化ナトリウム、シリカ、雲母チタン等の無機粉体や、シリコーンパウダー、シルクパウダー、麻繊維パウダー、セルロース又はその誘導体等の糖類や、ポリエチレン、ポリプロピレン、酸化ポリエチレン、エチレンアクリル酸コポリマー、ポリスチレン、ナイロン、アクリル樹脂等の合成高分子である有機粉体が挙げられる。
The water-insoluble particles of the component (B) used in the present invention have an average particle size of 50 to 500 μm.
Specifically, inorganic powders such as titanium oxide, talc, kaolin, bentonite, sodium chloride, silica, and mica titanium, sugars such as silicone powder, silk powder, hemp fiber powder, cellulose or derivatives thereof, polyethylene, polypropylene And organic powders that are synthetic polymers such as polyethylene oxide, ethylene acrylic acid copolymer, polystyrene, nylon, and acrylic resin.
また、上記の水不溶性粒子を一次粒子とし、結合剤（バインダー）を用いて複数の粉体を結合させた造粒粉体を用いることもできる。結合剤としては、例えばポリビニルアルコール及び／又はその誘導体、ポリ（メタ）アクリル酸アルカリ塩、（メタ）アクリル酸エステル共重合物のアルカリ塩、アクリル酸／マレイン酸共重合物のアルカリ塩、ポリビニルピロリドン等の合成品；メチルセルロース、エチルセルロース、カルボキシメチルセルロース、ヒドロキシアルキルセルロース、澱粉誘導体等の半合成品；澱粉、海草類、植物粘質物、タンパク質などの天然高分子が用いられる。 Further, a granulated powder in which the above water-insoluble particles are used as primary particles and a plurality of powders are bonded using a binder (binder) can also be used. Examples of the binder include polyvinyl alcohol and / or derivatives thereof, poly (meth) acrylic acid alkali salt, alkali salt of (meth) acrylic acid ester copolymer, alkali salt of acrylic acid / maleic acid copolymer, polyvinylpyrrolidone, and the like. Synthetic products such as; semi-synthetic products such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyalkyl cellulose, starch derivatives; and natural polymers such as starch, seaweeds, plant mucilage, and proteins.
これら水不溶性粒子の中で、水不溶性の造粒粉体が好ましい。
その中でも、ポリビニルアルコール及び／又はその誘導体を結合剤として用いると、すすぎ時にすすぎ水によって造粒粉体が容易に崩壊し、すすぎ性が高くなるため、より好ましいと考えられる。更に好ましい造粒粉体としては、平均粒径１〜７０μｍであるセルロースの一次粒子を、マレイン酸変性ポリビニルアルコールを結合剤として造粒し、平均粒径５０〜５００μｍとした造粒粉体が挙げられる。この粒子は、洗浄過程及びすすぎ過程において、すすぎ水や涙によって容易に粒子が崩壊するため、皮膚の損傷やかゆみの発生が少なく、また、洗い流し性が極めて良好であり、より好ましい。
Among these water-insoluble particles, water-insoluble granulated powder is preferable.
Among these, when polyvinyl alcohol and / or a derivative thereof is used as a binder, it is considered more preferable because the granulated powder easily disintegrates by rinsing water at the time of rinsing and the rinsing property becomes high. A more preferable granulated powder is a granulated powder having an average particle diameter of 1 to 70 μm, granulated with maleic acid-modified polyvinyl alcohol as a binder, and having an average particle diameter of 50 to 500 μm. It is done. These particles are more preferable because the particles are easily disintegrated by rinsing water and tears in the washing process and the rinsing process, so that the skin is less damaged and itchy, and the washability is very good.
成分（Ｂ）の水不溶粒子は、平均粒径（レーザ回析／散乱式粒度分布測定装置ＬＡ−９１０（堀場製）にて測定、平均粒径はメジアン径を用いた）が５０〜５００μｍのものである。このようにすることで、泡立てて使用したときに粒子を感じやすくでき、毛穴や皮溝に対する洗浄力を向上させることができる。適度な粒感と洗浄効果、洗浄実感との両立のためには、平均粒径が６０〜４００μｍであるのが好ましい。
また、大きな粒子（平均粒径２４０〜５００μｍ、好ましくは平均粒径２５０〜３５０μｍ）と小さな粒子（平均粒径５０〜１３０μｍ、好ましくは平均粒径８０〜１２０μｍ）を組み合わせて使用するのが好ましい。なお、この場合は、粒子径２００μｍ未満の粒子の平均径と、粒子径２００μｍ以上の粒子の平均径と分けて考える。更に、大きな粒子と小さな粒子の質量割合が、（平均粒径２４０〜５００μｍ、好ましくは平均粒径２５０〜３５０μｍ）／（平均粒径５０〜１３０μｍ、好ましくは平均粒径８０〜１２０μｍ）＝１／２〜１／１２、更には、１／３〜１／１０であるのが、より洗浄効果が高くなるので好ましい。
The water-insoluble particles of the component (B) have an average particle size (measured with a laser diffraction / scattering type particle size distribution analyzer LA-910 (manufactured by Horiba), and the average particle size uses a median diameter) of 50 to 500 μm. Is. By doing in this way, it can make it easy to feel particle | grains when used by foaming, and can improve the cleaning power with respect to a pore or a skin groove. In order to achieve both an appropriate grain feeling, a cleaning effect and a cleaning feeling, the average particle diameter is preferably 60 to 400 μm.
Further, it is preferable to use a combination of large particles (average particle size of 240 to 500 μm, preferably average particle size of 250 to 350 μm) and small particles (average particle size of 50 to 130 μm, preferably average particle size of 80 to 120 μm). In this case, the average diameter of particles having a particle diameter of less than 200 μm and the average diameter of particles having a particle diameter of 200 μm or more are considered separately. Furthermore, the mass ratio of the large particles to the small particles is (average particle size of 240 to 500 μm, preferably average particle size of 250 to 350 μm) / (average particle size of 50 to 130 μm, preferably average particle size of 80 to 120 μm) = 1 / It is preferable that the ratio is from 2 to 1/12, and further from 1 to 3 to 1/10 because the cleaning effect becomes higher.
成分（Ｂ）は、１種又は２種以上を用いることができ、使用者に皮膚洗浄剤として提供する際に、剤を手に取ったときに適度な粒感が得られる、という点から、全組成中に１〜２５質量％含有するのが好ましく、更に、２〜１５質量％含有されるのが好ましい。 Ingredient (B) can be used singly or in combination of two or more, and when provided to the user as a skin cleanser, when the agent is picked up, an appropriate grain feel can be obtained. The total composition preferably contains 1 to 25% by mass, and more preferably 2 to 15% by mass.
石鹸のみを洗浄基剤とした洗浄剤は、高アルカリ性で、肌に対し高浸透性であり、皮膚を膨潤させやすい。このため、粒子を含む洗浄剤は、洗浄効果は高いが、場合によっては必要以上に古くなった角層を取り除くことになる。この結果、洗浄後は、なめらかな肌感触を得ることができるが、小時間（洗浄後、２時間くらい）経過後、肌がかさついたり、多量の皮脂の分泌を促すことになり、洗浄直後に得られるなめらかな肌感触が持続しない。これに対し、本発明の構成では、適度な泡立ち性と泡質から、粒子の肌の当たりがやさしくなることを見出した。この結果、適度な角層除去となり、必要以上に肌の脱脂を起こさず、皮脂の分泌が抑制され、なめらかな肌感触が持続すると考えられる。
本発明の皮膚洗浄剤組成物において、使用時における泡立ちと適度な粒感、洗浄効果、洗浄実感の両立の点から、成分（Ａ）及び（Ｂ）の質量割合は、（Ａ）：（Ｂ）＝１：１０〜１０：１が好ましく、１：５〜５：１が好ましい。
A cleaning agent using only soap as a cleaning base is highly alkaline, highly permeable to the skin, and easily swells the skin. For this reason, although the cleaning agent containing particles has a high cleaning effect, in some cases, the stratum corneum that is older than necessary is removed. As a result, a smooth skin feel can be obtained after washing, but after a short period of time (about 2 hours after washing), the skin becomes thick and prompts the secretion of a large amount of sebum. The smooth skin feel that can be obtained is not sustained. On the other hand, in the structure of this invention, it discovered that the contact | win of the skin of particle | grains became easy from moderate foaming property and foam quality. As a result, it is considered that the stratum corneum is removed appropriately, the skin is not degreased more than necessary, the sebum secretion is suppressed, and the smooth skin feel is maintained.
In the skin cleanser composition of the present invention, the mass ratio of the components (A) and (B) is (A) :( B from the viewpoint of coexistence of foaming at the time of use and appropriate grain feeling, cleaning effect, and cleaning feeling. ) = 1: 10 to 10: 1 is preferable, and 1: 5 to 5: 1 is preferable.
本発明の皮膚洗浄剤組成物は、さらに、（Ｃ）成分（Ａ）以外のアニオン界面活性剤を含有することができ、泡立ち性を早め、且つ洗浄効果を高め、すすぎ中の肌感触をコントロールすることができる。 The skin cleanser composition of the present invention can further contain an anionic surfactant other than the component (A) (C), speeds up foaming, enhances the cleaning effect, and controls the skin feel during rinsing. can do.
成分（Ｃ）のアニオン界面活性剤としては、通常の皮膚洗浄剤に用いられるものであれば良く、例えば、脂肪酸塩、アルキル（エーテル）硫酸塩、アリル（エーテル）硫酸塩、アルキルベンゼンスルホン酸塩、アルカンスルホン酸塩、オレフィンスルホン酸塩、アルキルエーテルスルホン酸塩、グリセリンエーテルスルホン酸塩、αメチルエステルスルホン酸塩、スルホ脂肪酸塩、アルキル硫酸塩、脂肪アルコールエーテル硫酸塩、グリセリンエーテル硫酸塩、ヒドロキシ混合エーテル硫酸塩、モノグリセリド（エーテル）硫酸塩、脂肪酸アミド（エーテル）硫酸塩、モノアルキルスルホコハク酸塩、ジアルキルスルホコハク酸塩、モノアルキルスルホスクシンアミド酸塩、ジアルキルスルホスクシンアミド酸塩、スルホトリグリセライド、アミドエーテルカルボン酸塩及びその塩、脂肪酸イセチオネート、脂肪酸サルコシネート、脂肪酸タウライド；アシルラクチレート、アシル酒石酸塩、アシルグルタミン酸塩、アシルアスパラギン酸塩等のＮ−アシルアミノ酸塩；アルキルオリゴグルコシド硫酸塩、プロテイン脂肪酸縮合物（小麦ベースの植物産物）、アルキ The anionic surfactant of component (C) may be any anionic surfactant that can be used in ordinary skin cleansing agents, such as fatty acid salts, alkyl (ether) sulfates, allyl (ether) sulfates, alkylbenzene sulfonates, Alkane sulfonate, olefin sulfonate, alkyl ether sulfonate, glycerin ether sulfonate, α methyl ester sulfonate, sulfo fatty acid salt, alkyl sulfate, fatty alcohol ether sulfate, glycerine ether sulfate, hydroxy mixed Ether sulfate, monoglyceride (ether) sulfate, fatty acid amide (ether) sulfate, monoalkylsulfosuccinate, dialkylsulfosuccinate, monoalkylsulfosuccinamide, dialkylsulfosuccinate, sulfotriglyceride, Mido ether carboxylates and salts thereof, fatty acid isethionate, fatty acid sarcosinate, fatty acid tauride; N-acyl amino acid salts such as acyl lactylate, acyl tartrate, acyl glutamate, acyl aspartate; alkyl oligoglucoside sulfate, protein fatty acid Condensate (wheat-based plant product), Archi
これらのうち、脂肪酸塩、アルキル（エーテル）硫酸塩、Ｎ−アシルアミノ酸塩が好ましい。
脂肪酸塩としては、一般式（２）
Of these, fatty acid salts, alkyl (ether) sulfates, and N-acyl amino acid salts are preferred.
As the fatty acid salt, the general formula (2)
（式中、Ｒ2は炭素数９〜２１の直鎖又は分岐鎖のアルキル基又はアルケニル基を示し、Ｙはアルカリ金属、アンモニウム、アルカノールアミン由来のアンモニウム又は塩基性アミノ酸を示す）
で表されるものが好ましい。
より具体的には、例えば、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、アラキン酸、ベヘニン酸等の塩が挙げられる。これらの塩としては、ナトリウム、カリウム等のアルカリ金属；アンモニウム；モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等のアルカノールアミン由来のアンモニウム；アルギニン、リジン等の塩基性アミノ酸などが挙げられる。
(Wherein R 2 represents a linear or branched alkyl or alkenyl group having 9 to 21 carbon atoms, and Y represents an alkali metal, ammonium, alkanolamine-derived ammonium or basic amino acid)
The thing represented by these is preferable.
More specifically, for example, salts such as lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, arachidic acid, behenic acid and the like can be mentioned. Examples of these salts include alkali metals such as sodium and potassium; ammonium; ammonium derived from alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine; and basic amino acids such as arginine and lysine.
また、アルキル（エーテル）硫酸塩としては、一般式（３） Moreover, as alkyl (ether) sulfate, general formula (3)
（式中、Ｒ3は炭素数８〜２２の直鎖又は分岐鎖のアルキル基又はアルケニル基を示し、ｐは０〜２０の数を示し、Ｚは水素原子、又は、アルカリ金属、アルカリ土類金属、アンモニウム、アルキルアンモニウム、アルカノールアンモニウム及びグルクアンモニウムから選ばれるカチオンを示す）
で表されるものが好ましい。
(In the formula, R 3 represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms, p represents a number of 0 to 20, Z represents a hydrogen atom, an alkali metal, an alkaline earth, or the like. A cation selected from metal, ammonium, alkylammonium, alkanolammonium and glucammonium)
The thing represented by these is preferable.
アルキル（エーテル）硫酸塩は、（アルコキシル）アルコールの硫酸モノエステル塩であり、アルコールを硫酸化した後、水酸化ナトリウム、トリエタノールアミン等の塩基で中和することにより得られる。
本発明において、一般式（３）中、Ｒ3は炭素数１２〜１８の直鎖又は分岐鎖のアルキル基又はアルケニル基が好ましく、更に、炭素数１２〜１４の直鎖又は分岐鎖のアルキル基又はアルケニル基が好ましい。
一般式（３）中、ｐは０．５〜１２が好ましく、０．５〜５、更に０．５〜３がより好ましい。
Alkyl (ether) sulfate is a monoester salt of (alkoxyl) alcohol, and is obtained by sulfating alcohol and then neutralizing with a base such as sodium hydroxide or triethanolamine.
In the present invention, in general formula (3), R 3 is preferably a linear or branched alkyl group or alkenyl group having 12 to 18 carbon atoms, and further a linear or branched alkyl group having 12 to 14 carbon atoms. Or an alkenyl group is preferable.
In general formula (3), p is preferably 0.5 to 12, more preferably 0.5 to 5, and even more preferably 0.5 to 3.
Ｎ−アシルアミノ酸塩としては、一般式（４） As N-acylamino acid salt, general formula (4)
（式中、Ｒ4は直鎖又は分岐鎖の炭素数７〜２１のアルキル基又はアルケニル基を示し、Ｒ5は水素原子又は炭素数１〜４のアルキル基若しくはアルケニル基を示し、Ｒ6は水素原子又は-(ＣＨ2)qＲ7（Ｒ7は水素原子、ヒドロキシル基又は−ＣＯＯＭを示し、ｑは０〜
３を示す）を示し、Ｍは水素原子、アルカリ金属又はアルカノールアミンを示す）
で表されるものが好ましい。
(Wherein R 4 represents a linear or branched alkyl group or alkenyl group having 7 to 21 carbon atoms, R 5 represents a hydrogen atom or an alkyl group or alkenyl group having 1 to 4 carbon atoms, and R 6 represents A hydrogen atom or — (CH 2 ) q R 7 (R 7 represents a hydrogen atom, a hydroxyl group or —COOM, and q represents 0 to 0
3 represents), and M represents a hydrogen atom, an alkali metal or an alkanolamine)
The thing represented by these is preferable.
式（４）中、Ｒ4としては、炭素数６〜１８のアルキル基が好ましく、更に炭素数１０〜１４のアルキル基が好ましい。Ｒ5としては、水素原子、炭素数１〜４のアルキル基が好ましく、更に水素原子、メチル基が好ましい。Ｒ6としては、水素原子、-(ＣＨ2)qＲ6が好ましい。Ｍとしては、カリウム、トリエタノールアミンが好ましい。 In formula (4), R 4 is preferably an alkyl group having 6 to 18 carbon atoms, and more preferably an alkyl group having 10 to 14 carbon atoms. R 5 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group. R 6 is preferably a hydrogen atom, — (CH 2 ) q R 6 . M is preferably potassium or triethanolamine.
式（４）で表されるＮ−アシルアミノ酸塩のうち、好ましいものとしては、Ｎ−ココイルグリシン、Ｎ−ラウロイルグルタミン酸、Ｎ−ミリストイルグルタミン酸、Ｎ−ラウロイル−Ｎ−メチルグリシン、Ｎ−ラウロイル−β−アラニン、Ｎ−ミリストイル−β−アラニン、Ｎ−ラウロイルアスパラギン酸、Ｎ−ラウロイルセリン等；またこれらのナトリウム、カリウム等のアルカリ金属塩；モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等のアルカノールアミン塩などが挙げられる。なお、一般式（４）で表わされる化合物には、Ｌ体、Ｄ体、ラセミ体があるが、本発明においては、これらのいずれをも使用することができる。 Of the N-acylamino acid salts represented by the formula (4), N-cocoylglycine, N-lauroylglutamic acid, N-myristoylglutamic acid, N-lauroyl-N-methylglycine, N-lauroyl-β are preferable. -Alanine, N-myristoyl-β-alanine, N-lauroylaspartic acid, N-lauroylserine, etc .; and alkali metal salts such as sodium and potassium; Alkanolamine salts such as monoethanolamine, diethanolamine, triethanolamine, etc. Is mentioned. The compound represented by the general formula (4) includes L-form, D-form, and racemate, and any of these can be used in the present invention.
成分（Ｃ）は、１種以上を用いることができ、泡性能及び洗浄効果を高め、すすぎ中の肌感触をコントロールする点から、全組成中に０．５〜３０質量％含有するのが好ましく、１〜２５質量％がより好ましく、更に、２〜２０質量％がより好ましい。 One or more components (C) can be used, and it is preferable to contain 0.5 to 30% by mass in the total composition from the viewpoint of improving foam performance and cleaning effect and controlling the skin feel during rinsing. 1 to 25% by mass is more preferable, and 2 to 20% by mass is more preferable.
また、本発明において、成分（Ａ）及び（Ｃ）の質量割合は、すすぎ中における肌感触がなめらかで、すすぎ中において、汚れが落ちたという洗浄実感を高める点から、（Ａ）：（Ｃ）＝５：１〜１：７が好ましく、３：１〜１：５がより好ましく、更に２：１〜１：４がより好ましい。 Further, in the present invention, the mass ratio of the components (A) and (C) is such that the skin feel during rinsing is smooth, and the cleaning feeling that dirt has been removed during rinsing increases (A) :( C ) = 5: 1 to 1: 7 is preferable, 3: 1 to 1: 5 is more preferable, and 2: 1 to 1: 4 is more preferable.
本発明の皮膚洗浄剤組成物は、更に、（Ｄ）ポリオールを含有することができ、洗い上がりの肌にしっとり感を付与し、肌のなめらかさを向上させることができる。 The skin cleansing composition of the present invention can further contain (D) a polyol, can give a moist feeling to the washed-out skin, and can improve the smoothness of the skin.
成分（Ｄ）のポリオールとしては、例えば、ソルビトール、グリセリン、ブチレングリコール、プロピレングリコール、ジプロピレングリコール、エリスリトール、マンニトール、キシリトール等が挙げられる。
これらのうち、ソルビトール、グリセリン、キシリトールが好ましい。
Examples of the component (D) polyol include sorbitol, glycerin, butylene glycol, propylene glycol, dipropylene glycol, erythritol, mannitol, xylitol and the like.
Of these, sorbitol, glycerin, and xylitol are preferable.
成分（Ｄ）のポリオールは、１種以上を用いることができ、洗浄直後の肌のつっぱりを抑え、洗い上がりの肌表面に適度なしっとり感を与え、肌のなめらかさを向上させる点から、全組成中に、３〜７０質量％含有するのが好ましく、５〜６０質量％がより好ましく、更に１０〜５０質量％が好ましい。 One or more types of the component (D) polyol can be used, from the point of suppressing the firmness of the skin immediately after washing, giving a moderate moist feeling to the washed-out skin surface, and improving the smoothness of the skin. It is preferable to contain 3-70 mass% in a composition, 5-60 mass% is more preferable, Furthermore, 10-50 mass% is preferable.
本発明の皮膚洗浄剤組成物は、更に、（Ｅ）高分子増粘剤を含有することができ、粒子の分散安定性や使用時の使い勝手を向上させることができる。
具体的には、アクリル酸・メタクリル酸アルキル共重合体が好ましく、例えば、カーボポールＥＴＤ２０２０、カーボポール１３４２、カーボポール１３８２、ペムレンＴＲ−１、ペムレンＴＲ−２（以上、Lubrizol社製）等の市販品を用いることができる。
The skin cleanser composition of the present invention can further contain (E) a polymer thickener, and can improve the dispersion stability of the particles and usability during use.
Specifically, an acrylic acid / alkyl methacrylate copolymer is preferable, and for example, commercially available products such as Carbopol ETD2020, Carbopol 1342, Carbopol 1382, Pemlen TR-1, and Pemlen TR-2 (above, Lubrizol). Product can be used.
成分（Ｅ）の高分子増粘剤は、１種以上を用いることができ、容器から手に取り易く、使用時に水と混合した際に非常に溶けやすくて伸ばしやすくなる点から、全組成中に０．０５〜３質量％含有するのが好ましく、０．１〜２質量％、更に０．２〜１質量％含有するのがより好ましい。 One or more polymer thickeners of component (E) can be used, and are easy to take out from the container, and are very easy to dissolve and extend when mixed with water during use. It is preferable to contain 0.05-3 mass%, 0.1-2 mass%, and also 0.2-1 mass% is more preferable.
さらに、本発明の皮膚洗浄剤組成物は、ラウリルジメチルアミノ酢酸ベタイン、ラウリルジメチルアミンオキサイド、２−アルキル−Ｎ−カルボキシメチル−Ｎ−ヒドロキシエチルイミダゾリニウムベタイン、ラウリン酸アミドプロピルベタイン、ラウリルヒドロキシスルホベタインなどの両性界面活性剤（Ｆ）や、（ジ）グリセリンモノ脂肪酸エステルや（ジ）グリセリンモノアルキルエーテル、ポリオキシエチレンアルキルエーテルなどのノニオン界面活性剤（Ｇ）を組み合わせて用いることにより、さらに低温保存後の成分（Ｂ）の安定性（浮遊や沈降を防ぐ）を確保することができる。 Further, the skin cleansing composition of the present invention comprises lauryldimethylaminoacetic acid betaine, lauryldimethylamine oxide, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauric acid amidopropyl betaine, lauryl hydroxysulfo. By using a combination of an amphoteric surfactant (F) such as betaine, and a nonionic surfactant (G) such as (di) glycerin monofatty acid ester, (di) glycerin monoalkyl ether, or polyoxyethylene alkyl ether, It is possible to ensure the stability of the component (B) after storage at low temperature (prevent floating and settling).
本発明の皮膚洗浄剤組成物は、更に溶媒として水を含有することができる。水は、全組成中に、好ましくは３０〜９０質量％、より好ましくは４０〜８０質量％含有することができ、洗浄剤組成物を構成する前記成分及びその他成分の残部となる。 The skin cleansing composition of the present invention can further contain water as a solvent. Water can be contained in the total composition, preferably 30 to 90% by mass, more preferably 40 to 80% by mass, and becomes the balance of the above-mentioned components and other components constituting the cleaning composition.
本発明の皮膚洗浄剤組成物は、更に、通常の洗浄剤に用いられる成分、例えば、成分（Ａ）、（Ｃ）、（Ｆ）及び（Ｇ）以外の界面活性剤、成分（Ｄ）以外の保湿剤、油性成分、殺菌剤、抗炎症剤、防腐剤、キレート剤、無機塩類、パール化剤、香料、冷感剤、色素、紫外線吸収剤、酸化防止剤、植物エキス等を含有することができる。 The skin cleanser composition of the present invention further includes components used in ordinary cleansing agents, for example, surfactants other than components (A), (C), (F) and (G), other than component (D). Contains moisturizers, oil components, bactericides, anti-inflammatory agents, antiseptics, chelating agents, inorganic salts, pearlizing agents, perfumes, cooling agents, dyes, UV absorbers, antioxidants, plant extracts, etc. Can do.
本発明の皮膚洗浄剤組成物は、例えば、以下の方法により製造することができる。すなわち、７０℃以上に加熱した精製水に、成分（Ａ）を添加して溶解する。必要に応じて成分（Ｃ）、（Ｆ）を加え、溶解し均一にする。また、必要に応じて、一部の精製水に成分（Ｅ）を分散させ、上記の溶液に添加する。その後、塩基（例えば水酸化カリウムなど）によってこの溶液を中和する。次に、室温まで冷却して成分（Ｂ）、必要に応じて更に成分（Ｄ）、（Ｇ）を添加し、均一（成分（Ｂ）に関しては均一分散）になるまで攪拌し、皮膚洗浄剤組成物を得ることができる。 The skin cleansing composition of the present invention can be produced, for example, by the following method. That is, the component (A) is added and dissolved in purified water heated to 70 ° C. or higher. Add components (C) and (F) as necessary to dissolve and homogenize. Moreover, a component (E) is disperse | distributed to some purified water as needed, and it adds to said solution. The solution is then neutralized with a base (such as potassium hydroxide). Next, cool to room temperature, add component (B), and if necessary, add components (D) and (G), and stir until uniform (uniform dispersion with respect to component (B)). A composition can be obtained.
本発明の皮膚洗浄剤組成物は、例えば、洗顔料、ボディーソープ、ハンドソープ等として好適であり、特にボディーソープが好ましい。
本発明の皮膚洗浄剤組成物を用いて皮膚を洗浄する方法は、例えば、以下のとおりである。すなわち、本発明の皮膚洗浄剤組成物を身体、つまり顔、手足、胴体などの身体皮膚部に適量を適用し、泡立てて洗浄した後、シャワー等の温水を利用してすすぐ方法である。また、タオル、スポンジ、ブラシ等の洗浄補助具に適量を適用し、泡立てて洗浄することもできる。
The skin cleansing composition of the present invention is suitable as, for example, a face wash, body soap, hand soap, etc., and body soap is particularly preferred.
The method for washing the skin using the skin cleansing composition of the present invention is, for example, as follows. That is, the skin cleansing composition of the present invention is a method of applying an appropriate amount to the body, that is, the body skin such as the face, limbs, and torso, washing with foaming, and then rinsing using warm water such as a shower. In addition, an appropriate amount can be applied to cleaning aids such as towels, sponges, brushes, etc., and foamed for cleaning.
〈測定方法〉
本発明において、アルキルエーテルカルボン酸のアルキル組成、ＥＯ付加モル分布及び各成分の比率は、ガスクロマトグラフィー（ＧＣ）により、以下の分析方法で測定した。
なお、断りのない限り「％」は質量％を示す。
<Measuring method>
In the present invention, the alkyl composition, EO addition molar distribution, and ratio of each component of the alkyl ether carboxylic acid were measured by gas chromatography (GC) by the following analytical method.
Unless otherwise indicated, “%” indicates mass%.
（ＧＣ分析条件）
ＧＣ機器；アジレントテクノロジー社製、７８９０Ａ
カラム；アジレントテクノロジー社製、ＤＢ−５
（３０ｍ、内径０．２５mm、膜厚０．２５μｍ）
検出器；ＦＩＤ
キャリア；ヘリウムガス、１mL／min
昇温条件；１００℃から３２５℃まで５℃／minで昇温。その後、３５分間３２５℃を保持。
(GC analysis conditions)
GC equipment; Agilent Technologies, 7890A
Column; manufactured by Agilent Technologies, DB-5
(30m, inner diameter 0.25mm, film thickness 0.25μm)
Detector; FID
Carrier; helium gas, 1mL / min
Temperature rising condition: Temperature raised from 100 ° C. to 325 ° C. at 5 ° C./min. Then, hold 325 ° C. for 35 minutes.
（サンプルの前処理方法）
アルキルエーテルカルボン酸１５０mgをメタノール５０mLで溶解した。また、洗浄剤組成物については、アルキルエーテルカルボン酸として１５０mgとなるよう採取し、メタノール５０mLで溶解した。なお、洗浄剤組成物がポリオキシエチレンアルキルエーテル硫酸塩などの強アニオン性の界面活性剤を含む場合、それらが２５０mg以下となるように採取した。この溶液１mLを採取して、あらかじめメタノール４mLでコンディショニングを行った固相カートリッジ（Biotage製、Isolute SAX、１g、３mL、500-0100-B）に適用し、１０mL丸底試験管に通過液を捕集した。その後、ギ酸４．６ｇに１００mLのメタノールを加えた溶液６mLで溶出し、溶出液についても同じ試験管に捕集した。捕集した溶液は、５０℃に加温したブロックヒーターに設置し、窒素ガスを吹き込み、１mL程度まで濃縮した後、さらに室温下で窒素ガスを吹き込み乾燥させた。そこに、ジアゾメタン−エーテル溶液２mLを加え、攪拌しながら室温下で１０分間放置し誘導体化を行った。その後、室温下で窒素ガスを吹き込み、５００μＬ以下になるまで濃縮した後、クロロホルムを加えて５００μＬとし、ＧＣ分析に供した。
なお、ジアゾメタン−エーテル溶液は、ジアゾメタン生成装置（宮本理研工業製、ＧＭ−５０）を用い、以下の手順で調製した。第１と第２の受け器、第２と第３の受け器をシリコンゴム栓およびテフロン（登録商標）製チューブで連結する。第２の受け器に、Ｎ−メチル−Ｎ'−ニトロ−Ｎ−ニトロソグアニジン０．８ｇを採取し、２．５mLのイオン交換水を加えた。第３の受け器に、ｔ−ブチルメチルエーテル１０mLを採取した。第１、第２、第３の受け器を氷冷した。続いて第２の受け器に、プラスチックシリンジを備え付け、このシリンジ中に水酸化ナトリウム２０ｇをイオン交換水１００mLに溶解させた溶液３mLを入れた。この水酸化ナトリウム水溶液をゆっくりと滴下してジアゾメタンガスを生成させ、第１の受け器側から静かに窒素ガスを吹き込み、第３の受け器のｔ−ブチルメチルエーテルに溶解させて、ジアゾメタン−エーテル溶液を得た。
上記サンプルの前処理における試薬は、以下のものを使用した。
メタノール（関東化学製、高速液体クロマトグラフィー用、25183-1B）
ギ酸（和光純薬工業製、試薬特級、066-00461）
クロロホルム（関東化学製、鹿１級、07278-01）
Ｎ−メチル−Ｎ’−ニトロ−Ｎ−ニトロソグアニジン（関東化学製、鹿１級、25596-51）
ｔ−ブチルメチルエーテル（関東化学製、鹿特級、04418-00）
水酸化ナトリウム（和光純薬工業製、特級、196-13761）
(Sample pretreatment method)
150 mg of alkyl ether carboxylic acid was dissolved in 50 mL of methanol. Moreover, about the cleaning composition, it extract | collected so that it might become 150 mg as alkyl ether carboxylic acid, and melt | dissolved in 50 mL of methanol. In addition, when the detergent composition contained a strong anionic surfactant such as polyoxyethylene alkyl ether sulfate, it was collected so as to be 250 mg or less. Take 1 mL of this solution and apply it to a solid-phase cartridge (Biotage, Isolute SAX, 1 g, 3 mL, 500-0100-B) that has been conditioned in advance with 4 mL of methanol, and collect the passing solution in a 10 mL round bottom test tube. Gathered. Thereafter, elution was performed with 6 mL of a solution obtained by adding 100 mL of methanol to 4.6 g of formic acid, and the eluate was also collected in the same test tube. The collected solution was placed in a block heater heated to 50 ° C., blown with nitrogen gas, concentrated to about 1 mL, and further blown with nitrogen gas at room temperature to dry. Thereto, 2 mL of a diazomethane-ether solution was added, and the mixture was allowed to stand at room temperature for 10 minutes with stirring for derivatization. Thereafter, nitrogen gas was blown at room temperature, and the mixture was concentrated to 500 μL or less, and then chloroform was added to make 500 μL, which was subjected to GC analysis.
In addition, the diazomethane-ether solution was prepared in the following procedures using the diazomethane production | generation apparatus (Miyamoto Riken Kogyo make, GM-50). The first and second receivers and the second and third receivers are connected with a silicone rubber stopper and a Teflon (registered trademark) tube. In a second receiver, 0.8 g of N-methyl-N′-nitro-N-nitrosoguanidine was collected and 2.5 mL of ion exchange water was added. In a third receiver, 10 mL of t-butyl methyl ether was collected. The first, second and third receivers were ice-cooled. Subsequently, a plastic syringe was attached to the second receiver, and 3 mL of a solution in which 20 g of sodium hydroxide was dissolved in 100 mL of ion-exchanged water was placed in this syringe. This sodium hydroxide aqueous solution is slowly added dropwise to produce diazomethane gas, and nitrogen gas is gently blown from the first receiver side, dissolved in t-butyl methyl ether of the third receiver, and diazomethane-ether A solution was obtained.
The following reagents were used in the sample pretreatment.
Methanol (manufactured by Kanto Chemical, for high performance liquid chromatography, 25183-1B)
Formic acid (manufactured by Wako Pure Chemical Industries, reagent special grade, 066-00461)
Chloroform (manufactured by Kanto Chemical, deer grade 1, 07278-01)
N-methyl-N'-nitro-N-nitrosoguanidine (manufactured by Kanto Chemical, deer grade 1, 25596-51)
t-Butyl methyl ether (manufactured by Kanto Chemical, deer special grade, 04418-00)
Sodium hydroxide (Wako Pure Chemical Industries, special grade, 196-13761)
〈製造例〉
本発明の皮膚洗浄剤組成物に用いる成分（Ａ）のアルキルエーテルカルボン酸塩は、例えば、以下のようにして製造することができる。なお、断りのない限り「％」は質量％を示す。
製造例１
攪拌および温度調節機能を備えたステンレス製オートクレーブに、ラウリルアルコール［商品名：カルコール２０９８、花王製］１１４４ｇ（６．１４モル）、ミリスチルアルコール［商品名：カルコール４０９８、花王製］６０．２ｇ（０．２８１モル）、水酸化カリウム２．６８ｇ（０．０４７８モル）を仕込み、減圧脱水を行った。次いで、エチレンオキサイド（ＥＯ）９９６ｇ（２２.６モル）を１５５℃にて導入し、反応温度１５５℃、反応圧力０.４ＭＰａで２時間反応を行った。反応終了後、８０℃、６kPaの減圧条件で３０分間攪拌し、未反応のエチレンオキサイドを除去した後、窒素を導入し常圧にし、４.８２ｇ（０.０４８２モル）の９０％乳酸をオートクレーブ内に加え、８０℃で３０分間攪拌し、ＥＯ付加モル数３.５５モルのアルキルエトキシレート（以下、「生成ＡＥ」ともいう）を得た。
攪拌機能、温度調節機能及び酸素ガス導入管を取り付けたガラス製反応容器に、上記生成物９０ｇ（０．２モル）と、４８％水酸化ナトリウム水溶液１６．７ｇ（水酸化ナトリウムとして０．２モル）、パラジウム−白金−ビスマス系触媒（活性炭にパラジウム４％、白金１％及びビスマス５％を担持、含水率５０％）０．９ｇ、水４９４．４ｇをそれぞれ仕込んだ。攪拌条件下、液温を７０℃まで昇温し、酸素を２７モル％（対生成ＡＥ／時間）の割合で吹き込みながら、反応温度７０℃で３．５時間接触酸化反応をさせた。反応率は８９％であった。
反応終了後、反応液から触媒を濾別し、アルキルエーテルカルボン酸Ｎａ塩の水溶液を得た。続いて、３５％塩酸を加え、分液操作を実施し、アルキルエーテルカルボン酸を得た。これをＥＣ１とする。
<Production example>
The alkyl ether carboxylate of component (A) used for the skin cleansing composition of the present invention can be produced, for example, as follows. Unless otherwise indicated, “%” indicates mass%.
Production Example 1
In a stainless steel autoclave equipped with stirring and temperature control functions, 1144 g (6.14 mol) of lauryl alcohol [trade name: Calcoal 2098, manufactured by Kao], 60.2 g (0 trade name: Calcoal 4098, manufactured by Kao) .281 mol) and 2.68 g (0.0478 mol) of potassium hydroxide were added and dehydration under reduced pressure was performed. Next, 996 g (22.6 mol) of ethylene oxide (EO) was introduced at 155 ° C., and the reaction was carried out at a reaction temperature of 155 ° C. and a reaction pressure of 0.4 MPa for 2 hours. After completion of the reaction, the mixture was stirred for 30 minutes at 80 ° C. under reduced pressure of 6 kPa to remove unreacted ethylene oxide, and then nitrogen was introduced to normal pressure, and 4.82 g (0.0482 mol) of 90% lactic acid was autoclaved. In addition, the mixture was stirred at 80 ° C. for 30 minutes to obtain an alkyl ethoxylate (hereinafter also referred to as “produced AE”) having an EO addition mole number of 3.55 mol.
In a glass reaction vessel equipped with a stirring function, temperature control function and oxygen gas introduction tube, 90 g (0.2 mol) of the above product and 16.7 g of 48% aqueous sodium hydroxide solution (0.2 mol as sodium hydroxide) ), Palladium-platinum-bismuth catalyst (supporting 4% palladium, 1% platinum and 5% bismuth on activated carbon, water content 50%) 0.9 g and 494.4 g water, respectively. Under stirring conditions, the liquid temperature was raised to 70 ° C., and a catalytic oxidation reaction was carried out at a reaction temperature of 70 ° C. for 3.5 hours while blowing oxygen at a rate of 27 mol% (vs. production AE / hour). The reaction rate was 89%.
After completion of the reaction, the catalyst was filtered off from the reaction solution to obtain an aqueous solution of alkyl ether carboxylic acid Na salt. Subsequently, 35% hydrochloric acid was added, and a liquid separation operation was performed to obtain an alkyl ether carboxylic acid. This is EC1.
ガスクロマトグラフィーの分析の結果、ＥＣ１は、一般式（１）において、Ｍ＝Ｈ、Ｒ1はラウリル基／ミリスチル基＝９５／５、平均炭素数は１２．１、ｎの平均値は２．８、ｎ＝０の成分を１４．７質量％含み、ｎ＝１の成分とｎ＝２の成分の合計量は３６．１質量％であった。
また、ＥＯ付加モル数の異なる各成分の比率に関しても、Ｒ1の組成のうち最大成分の測定値から算出した結果、（ｎ＝０成分の質量）：（ｎ＝１成分の質量）：（ｎ＝２成分の質量）：（ｎ＝３成分の質量）：（ｎ＝４成分の質量）＝１：１．２２：１．２３：１．０６：０．８３であった。
As a result of analysis by gas chromatography, EC1 is M = H in the general formula (1), R 1 is lauryl group / myristyl group = 95/5, the average carbon number is 12.1, and the average value of n is 2. 8, The component of n = 0 was contained 14.7 mass%, and the total amount of the component of n = 1 and the component of n = 2 was 36.1 mass%.
In addition, regarding the ratio of each component having a different number of EO addition moles, as a result of calculation from the measured value of the maximum component of the R 1 composition, (n = 0 component mass): (n = 1 component mass): ( n = 2 mass of component): (mass of n = 3 component): (mass of n = 4 component) = 1: 1.22: 1.23: 1.06: 0.83.
製造例２
製造例１に倣い、デシルアルコール［商品名：カルコール１０９８、花王製］、ラウリルアルコール［商品名：カルコール２０９８、花王製］、ミリスチルアルコール［商品名：カルコール４０９８、花王製］、セチルアルコール［商品名：カルコール６０９８、花王製］を質量比１０／７０／１５／５に混合した原料にＥＯを反応させ、ＥＯ付加モル数３．５５モルのアルキルエトキシレートを得た。これを実施例１同様、酸化反応を行い、得られたアルキルエーテルカルボン酸塩を塩酸処理することにより、アルキルエーテルカルボン酸を得た。
Production Example 2
Following production example 1, decyl alcohol [trade name: Calcoal 1098, manufactured by Kao], lauryl alcohol [trade name: Calcoal 2098, manufactured by Kao], myristyl alcohol [trade name: Calcoal 4098, manufactured by Kao], cetyl alcohol [trade name] : Calcoal 6098, manufactured by Kao] at a mass ratio of 10/70/15/5 was reacted with EO to obtain an alkyl ethoxylate having 3.55 mol of EO added. This was subjected to an oxidation reaction as in Example 1, and the resulting alkyl ether carboxylate was treated with hydrochloric acid to obtain an alkyl ether carboxylic acid.
ガスクロマトグラフィーの分析の結果、一般式（１）において、Ｍ＝Ｈ、Ｒ1はデシル基／ラウリル基／ミリスチル基／パルミチル基=１０／７０／１５／５、平均炭素数は１２．３、ｎの平均値は３．３、ｎ＝０の成分を１５．２質量％含み、ｎ＝１の成分とｎ＝２の成分の合計量は３１．４質量％であった。
また、ＥＯ付加モル数の異なる各成分の比率に関しても、Ｒ1の組成のうち最大成分の測定値から算出した結果、（ｎ＝０成分の質量）：（ｎ＝１成分の質量）：（ｎ＝２成分の質量）：（ｎ＝３成分の質量）：（ｎ＝４成分の質量）＝１：１．０７：１．００：０．８５：０．６７であった。
As a result of analysis by gas chromatography, in general formula (1), M = H, R 1 is decyl group / lauryl group / myristyl group / palmityl group = 10/70/15/5, average carbon number is 12.3, The average value of n was 3.3 and 15.2% by mass of n = 0 components, and the total amount of n = 1 and n = 2 components was 31.4% by mass.
In addition, regarding the ratio of each component having a different number of EO addition moles, as a result of calculation from the measured value of the maximum component of the R 1 composition, (n = 0 component mass): (n = 1 component mass): ( n = 2 mass of component): (n = mass of 3 component): (mass of n = 4 component) = 1: 1.07: 1.00: 0.85: 0.67.
製造例３
攪拌、温度調節機能を取り付けたガラス製反応容器に、ラウリルアルコール３７２ｇ（２．００モル）を仕込み、攪拌条件下、液温を７０℃まで昇温させ、モノクロロ酢酸ナトリウム２５６ｇ（２．２０モル）及び水酸化ナトリウム８８ｇ（２．２０モル）を分割して加えながら、５時間反応を行った。反応終了後、析出物を濾別し、続いて３５％塩酸を加え、酸型化し、アルキルエーテルカルボン酸を得た（一般式（１）において、Ｍ＝Ｈ、Ｒ１はラウリル基、ｎ＝０）。
Production Example 3
372 g (2.00 mol) of lauryl alcohol was charged into a glass reaction vessel equipped with stirring and temperature control functions, the liquid temperature was raised to 70 ° C. under stirring conditions, and 256 g (2.20 mol) of sodium monochloroacetate. The reaction was carried out for 5 hours while adding 88 g (2.20 mol) of sodium hydroxide in portions. After completion of the reaction, the precipitate was separated by filtration and subsequently acidified by adding 35% hydrochloric acid to obtain an alkyl ether carboxylic acid (in the general formula (1), M = H, R1 is a lauryl group, n = 0 ).
製造例４
製造例１に倣い、デシルアルコールを原料にＥＯを反応させ、ＥＯ付加モル数３.５５モルのアルキルエトキシレートを得た。これを実施例１同様、酸化反応を行い、得られたアルキルエーテルカルボン酸塩を塩酸処理することにより、アルキルエーテルカルボン酸を得た。
ガスクロマトグラフィーの分析の結果、一般式（１）において、Ｍ＝Ｈ、Ｒ1はデシル基、ｎの平均値は３．１、ｎ＝０の成分を１６質量％含み、ｎ＝１の成分とｎ＝２の成分の合計量は３７質量％であった。
Production Example 4
Following Production Example 1, EO was reacted with decyl alcohol as a raw material to obtain an alkyl ethoxylate having 3.55 moles of EO added. This was subjected to an oxidation reaction as in Example 1, and the resulting alkyl ether carboxylate was treated with hydrochloric acid to obtain an alkyl ether carboxylic acid.
As a result of gas chromatography analysis, in general formula (1), M = H, R 1 is a decyl group, n has an average value of 3.1, n = 0 contains 16% by mass, and n = 1 The total amount of n = 2 components was 37% by mass.
製造例５
製造例１に倣い、ラウリルアルコールを原料にＥＯを反応させ、ＥＯ付加モル数３.５５モルのアルキルエトキシレートを得た。これを実施例１同様、酸化反応を行い、得られたアルキルエーテルカルボン酸塩を塩酸処理することにより、アルキルエーテルカルボン酸を得た。
ガスクロマトグラフィーの分析の結果、一般式（１）において、Ｍ＝Ｈ、Ｒ1はラウリル基、ｎの平均値は３．１、ｎ＝０の成分を１６質量％含み、ｎ＝１の成分とｎ＝２の成分の合計量は３７質量％であった。
また、ＥＯ付加モル数の異なる各成分の比率に関しても、Ｒ1の組成のうち最大成分の測定値から算出した結果、（ｎ＝０成分の質量）：（ｎ＝１成分の質量）：（ｎ＝２成分の質量）：（ｎ＝３成分の質量）：（ｎ＝４成分の質量）＝１：１．１９：１．１３：０．９４：１であった。
Production Example 5
Following Production Example 1, EO was reacted with lauryl alcohol as a raw material to obtain an alkyl ethoxylate having 3.55 moles of EO added. This was subjected to an oxidation reaction as in Example 1, and the resulting alkyl ether carboxylate was treated with hydrochloric acid to obtain an alkyl ether carboxylic acid.
As a result of analysis by gas chromatography, in general formula (1), M = H, R 1 is a lauryl group, n has an average value of 3.1, n = 0 contains 16% by mass, and n = 1 The total amount of n = 2 components was 37% by mass.
In addition, regarding the ratio of each component having a different number of EO addition moles, as a result of calculation from the measured value of the maximum component of the R 1 composition, (n = 0 component mass): (n = 1 component mass): ( n = 2 mass of component): (mass of n = 3 component): (mass of n = 4 component) = 1: 1.19: 1.13: 0.94: 1.
製造例６
製造例１に倣い、ミリスチルアルコールを原料にＥＯを反応させ、ＥＯ付加モル数３.５５モルのアルキルエトキシレートを得た。これを実施例１同様、酸化反応を行い、得られたアルキルエーテルカルボン酸塩を塩酸処理することにより、アルキルエーテルカルボン酸を得た。
ガスクロマトグラフィーの分析の結果、一般式（１）において、Ｍ＝Ｈ、Ｒ1はミリスチル基、ｎの平均値は３．１、ｎ＝０の成分を１６質量％含み、ｎ＝１の成分とｎ＝２の成分の合計量は３７質量％であった。
Production Example 6
According to Production Example 1, EO was reacted with myristyl alcohol as a raw material to obtain an alkyl ethoxylate having 3.55 moles of EO added. This was subjected to an oxidation reaction as in Example 1, and the resulting alkyl ether carboxylate was treated with hydrochloric acid to obtain an alkyl ether carboxylic acid.
As a result of analysis by gas chromatography, in general formula (1), M = H, R 1 is a myristyl group, n has an average value of 3.1, n = 0 contains 16% by mass, and n = 1 The total amount of n = 2 components was 37% by mass.
製造例７
製造例１に倣い、ラウリルアルコール、セチルアルコールを質量比２０／８０に混合した原料にＥＯ付加し、ＥＯ付加モル数３.５５モルのアルキルエトキシレートを得た。これを実施例１同様、酸化反応を行い、得られたアルキルエーテルカルボン酸塩を塩酸処理することにより、アルキルエーテルカルボン酸を得た。
ガスクロマトグラフィーの分析の結果、一般式（１）において、Ｍ＝Ｈ、Ｒ1はラウリル基／パルミチル基＝２０／８０、ｎの平均値は３．１、ｎ＝０の成分を１６質量％含み、ｎ＝１の成分とｎ＝２の成分の合計量は３７質量％であった。
Production Example 7
Following Production Example 1, EO was added to a raw material in which lauryl alcohol and cetyl alcohol were mixed at a mass ratio of 20/80 to obtain an alkyl ethoxylate having 3.55 moles of EO added. This was subjected to an oxidation reaction as in Example 1, and the resulting alkyl ether carboxylate was treated with hydrochloric acid to obtain an alkyl ether carboxylic acid.
As a result of analysis by gas chromatography, in general formula (1), M = H, R 1 is lauryl group / palmityl group = 20/80, n average value is 3.1, and n = 0 is 16% by mass. In addition, the total amount of the n = 1 component and the n = 2 component was 37% by mass.
製造例８
製造例１に倣い、ラウリルアルコールを原料にＥＯ反応させ、ＥＯ付加モル数４．０５モルのアルキルエトキシレートを得た。これを製造例１同様、酸化反応を行い、得られたアルキルエーテルカルボン酸塩を塩酸処理することにより、アルキルエーテルカルボン酸を得た。
Production Example 8
Following Production Example 1, lauryl alcohol was subjected to EO reaction as a raw material to obtain an alkyl ethoxylate having 4.05 moles of EO added. This was subjected to an oxidation reaction as in Production Example 1, and the resulting alkyl ether carboxylate was treated with hydrochloric acid to obtain an alkyl ether carboxylic acid.
ガスクロマトグラフィーの分析の結果、一般式（１）において、Ｍ＝Ｈ、Ｒ1はラウリル基、ｎの平均値は３．５、ｎ＝０の成分を１１．４質量％含み、ｎ＝１の成分とｎ＝２の成分の合計量は３０．６質量％であった。
また、ＥＯ付加モル数の異なる各成分の比率に関しても、Ｒ1の組成のうち最大成分の測定値から算出した結果、（ｎ＝０成分の質量）：（ｎ＝１成分の質量）：（ｎ＝２成分の質量）：（ｎ＝３成分の質量）：（ｎ＝４成分の質量）＝１：１．３１：１．３８：１．２５：１．０６であった。
As a result of analysis by gas chromatography, in general formula (1), M = H, R 1 is a lauryl group, n has an average value of 3.5, and n = 0 contains 11.4% by mass, n = 1 The total amount of the components and n = 2 was 30.6% by mass.
In addition, regarding the ratio of each component having a different number of EO addition moles, as a result of calculation from the measured value of the maximum component of the R 1 composition, (n = 0 component mass): (n = 1 component mass): ( n = 2 mass of component): (mass of n = 3 component): (mass of n = 4 component) = 1.1.31: 1.38: 1.25: 1.06.
製造例９
攪拌および温度調節機能を備えたステンレス製オートクレーブに、ラウリルアルコール［商品名：カルコール２０９８、花王製］１１４４ｇ（６．１４モル）、ミリスチルアルコール［商品名：カルコール４０９８、花王製］６０．２ｇ（０．２８１モル）、水酸化カリウム２．６ｇ（０．０４７８モル）を仕込み、減圧脱水を行った。次いで、エチレンオキサイド（ＥＯ）７１８ｇ（１６．３モル）を１５５℃にて導入し、反応温度１５５℃、反応圧力０.４ＭＰａで２時間反応を行った。反応終了後、冷却し、８０℃、６kPaの減圧条件で３０分間攪拌し、未反応のエチレンオキサイドを除去した後、窒素を導入し常圧にし、４.８２ｇ（０.０４８２モル）の９０％乳酸をオートクレーブ内に加え、８０℃で３０分間攪拌し、ＥＯ付加モル数２.５５モルのアルキルエトキシレートを得た。
攪拌、温度調節機能を取り付けたガラス製反応容器に、上記生成物６００ｇ（２．００モル）を仕込み、攪拌条件下、液温を７０℃まで昇温し、モノクロロ酢酸ナトリウム２５６ｇ（２．２０モル）及び水酸化ナトリウム８８ｇ（２．２０モル）を分割して加えながら、５時間反応を行った。反応終了後、３５％塩酸をｐＨが２．８になるまで加え、酸型化し油層を分取し、アルキルエーテルカルボン酸を得た。これをＥＣ６とする。
Production Example 9
In a stainless steel autoclave equipped with stirring and temperature control functions, 1144 g (6.14 mol) of lauryl alcohol [trade name: Calcoal 2098, manufactured by Kao], 60.2 g (0 trade name: Calcoal 4098, manufactured by Kao) .281 mol) and 2.6 g (0.0478 mol) of potassium hydroxide were added and dehydration under reduced pressure was performed. Subsequently, 718 g (16.3 mol) of ethylene oxide (EO) was introduced at 155 ° C., and the reaction was carried out at a reaction temperature of 155 ° C. and a reaction pressure of 0.4 MPa for 2 hours. After completion of the reaction, the mixture was cooled and stirred at 80 ° C. under a reduced pressure of 6 kPa for 30 minutes to remove unreacted ethylene oxide, then nitrogen was introduced to normal pressure, and 4.82 g (0.0482 mol) of 90% Lactic acid was added to the autoclave and stirred at 80 ° C. for 30 minutes to obtain an alkyl ethoxylate having 2.55 mol of EO added.
A glass reaction vessel equipped with stirring and temperature control functions was charged with 600 g (2.00 mol) of the above product, the temperature of the solution was raised to 70 ° C. under stirring conditions, and 256 g (2.20 mol) of sodium monochloroacetate was added. ) And 88 g (2.20 mol) of sodium hydroxide were added in portions, and the reaction was carried out for 5 hours. After completion of the reaction, 35% hydrochloric acid was added until the pH reached 2.8 to convert it into an acid form, and the oil layer was separated to obtain an alkyl ether carboxylic acid. This is EC6.
ガスクロマトグラフィーの分析の結果、一般式（１）において、Ｍ＝Ｈ、Ｒ1はラウリル基／ミリスチル基＝９４／６、平均炭素数は１２．１、ｎの平均値は３．１、ｎ＝０の成分を９．９質量％含み、ｎ＝１の成分とｎ＝２の成分の合計量は３５．４質量％であった。
また、ＥＯ付加モル数の異なる各成分の比率に関しても、Ｒ１の組成のうち最大成分の測定値から算出した結果、（ｎ＝０成分の質量）：（ｎ＝１成分の質量）：（ｎ＝２成分の質量）：（ｎ＝３成分の質量）：（ｎ＝４成分の質量）＝１：１．６５：１．９２：１．７４：１.３２であった。
As a result of analysis by gas chromatography, in general formula (1), M = H, R 1 is lauryl group / myristyl group = 94/6, average carbon number is 12.1, average value of n is 3.1, n = 0% component was included, and the total amount of the n = 1 component and the n = 2 component was 35.4% by mass.
In addition, regarding the ratio of each component having a different number of EO addition moles, as a result of calculation from the measured value of the maximum component of the composition of R1, (n = 0 component mass): (n = 1 component mass): (n = Mass of 2 components) :( mass of n = 3 components) :( mass of n = 4 components) = 1: 1.65: 1.92: 1.74: 1.32.
実施例中、ＥＣ２に関しては、製造例５、製造例６、製造例７で得られたアルキルエーテルカルボン酸を、各々質量割合で７８．７５／１５／６．２５の比で混合し、ＥＣ２とした。 In the examples, regarding EC2, the alkyl ether carboxylic acids obtained in Production Example 5, Production Example 6 and Production Example 7 were mixed at a mass ratio of 78.75 / 15 / 6.25, respectively. did.
実施例中、ＥＣ３に関しては、製造例２、製造例３で得られたアルキルエーテルカルボン酸を、各々質量割合で９０／１０の比で混合し、ＥＣ３とした。 In the examples, regarding EC3, the alkyl ether carboxylic acids obtained in Production Example 2 and Production Example 3 were mixed at a mass ratio of 90/10 to obtain EC3.
実施例中、ＥＣ４に関しては、製造例１で得られたＥＣ１と製造例４で得られたアルキルエーテルカルボン酸を、各々質量割合で４０／６０の比で混合し、Ｅ４とした。 In the examples, regarding EC4, EC1 obtained in Production Example 1 and the alkyl ether carboxylic acid obtained in Production Example 4 were mixed at a mass ratio of 40/60 to obtain E4.
実施例中、ＥＣ５に関しては、製造例２、製造例８で得られたアルキルエーテルカルボン酸を、各々質量割合で４０／６０の比で混合し、ＥＣ５とした。 In the examples, regarding EC5, the alkyl ether carboxylic acids obtained in Production Example 2 and Production Example 8 were mixed at a mass ratio of 40/60 to obtain EC5.
実施例１〜２７、比較例１〜６
表３〜９に示す組成の皮膚洗浄剤組成物を製造し、泡立ち、すすぎ性、洗浄効果、肌のなめらかさ（タオルドライ直後、２時間後）、すすぎ時の肌感触、しっとり感、室温安定性、低温保存後の室温安定性を評価した。結果を表３〜９に併せて示す。
なお、実施例で使用した成分（Ａ）の構成は、表１及び表２に示すとおりである。
また、実施例及び比較例で使用した市販のアルキルエーテルカルボン酸（ＡＫＹＰＯ ＲＬＭ２５（花王社製）、ＡＫＹＰＯ ＲＬＭ４５（花王社製）、ＡＫＹＰＯ ＲＬＭ１００ＮＶ（花王社製））の平均ＥＯ付加モル数は、販売元のカタログ値、ホームページで公開されている値を参考にした。不明なアルキル組成、ｎ＝０の成分量、ｎ＝１の成分とｎ＝２の成分の合計量に関しては上記方法で分析した。
Examples 1-27, Comparative Examples 1-6
Manufactures a skin cleanser composition having the composition shown in Tables 3 to 9, foaming, rinsing properties, cleaning effect, smooth skin (immediately after towel drying, 2 hours later), skin feel during rinsing, moist feeling, room temperature stability And room temperature stability after low temperature storage. A result is combined with Tables 3-9 and shown.
In addition, the structure of the component (A) used in the Example is as showing in Table 1 and Table 2.
Moreover, the average EO addition mole number of the commercially available alkyl ether carboxylic acid (AKYPO RLM25 (made by Kao company), AKYPO RLM45 (made by Kao company), AKYPO RLM100NV (made by Kao company)) used by the Example and the comparative example is sales. The original catalog value and the value published on the homepage were used as a reference. The unknown alkyl composition, the component amount of n = 0, and the total amount of the component of n = 1 and the component of n = 2 were analyzed by the above method.
（製造方法）
（１）実施例１〜２１、比較例１〜６については、７０℃以上に加熱した精製水約６０質量％に、成分（Ａ）、成分（Ｃ）を添加して完全に溶解させた。次に成分（Ａ）及び（Ｃ）を中和する量の水酸化カリウムを添加し、均一になるまで攪拌した。この後、これを室温まで冷却した。この溶液に、残部の水に成分（Ｂ）を分散させた液を添加し、成分（Ｂ）が均一に分散するまで攪拌し、目的とする皮膚洗浄剤組成物を得た。
(Production method)
(1) About Examples 1-21 and Comparative Examples 1-6, component (A) and component (C) were added and dissolved completely in about 60% by mass of purified water heated to 70 ° C. or higher. Next, an amount of potassium hydroxide that neutralizes components (A) and (C) was added and stirred until uniform. After this, it was cooled to room temperature. To this solution, a liquid in which the component (B) was dispersed in the remaining water was added and stirred until the component (B) was uniformly dispersed to obtain the intended skin cleansing composition.
（２）実施例２２〜２４については、７０℃以上に加熱した精製水約３０〜６０質量％に、成分（Ａ）、成分（Ｃ）を添加して完全に溶解させた。次に成分（Ａ）及び（Ｃ）を中和する量の水酸化カリウムを添加し、均一になるまで攪拌した。この後、これを室温まで冷却した。この溶液に、残部の水と成分（Ｄ）の混合液に成分（Ｂ）を分散させた液を添加し、成分（Ｂ）が均一に分散するまで攪拌し、目的とする皮膚洗浄剤組成物を得た。 (2) About Examples 22-24, the component (A) and the component (C) were added and completely dissolved in about 30-60 mass% of purified water heated to 70 ° C. or higher. Next, an amount of potassium hydroxide that neutralizes components (A) and (C) was added and stirred until uniform. After this, it was cooled to room temperature. To this solution, a liquid in which component (B) is dispersed in the remaining mixture of water and component (D) is added and stirred until component (B) is uniformly dispersed, and the intended skin cleansing composition Got.
（３）実施例２５〜２６については、７０℃以上に加熱した精製水約２０質量％に、成分（Ａ）、成分（Ｃ）を添加して完全に溶解させた。次に、成分（Ｅ）を約２５質量％の精製水に分散させ、上記の溶液に添加した。成分（Ａ）、（Ｃ）及び（Ｅ）を中和する量の水酸化カリウムを添加し、均一になるまで攪拌した。この後、これを室温まで冷却した。この溶液に、残部の水と成分（Ｄ）の混合液に成分（Ｂ）を分散させた液を添加し、成分（Ｂ）が均一に分散するまで攪拌し、目的とする皮膚洗浄剤組成物を得た。 (3) About Examples 25-26, component (A) and component (C) were added to about 20% by mass of purified water heated to 70 ° C. or higher and completely dissolved. Next, component (E) was dispersed in about 25% by mass of purified water and added to the above solution. An amount of potassium hydroxide that neutralizes components (A), (C), and (E) was added and stirred until uniform. After this, it was cooled to room temperature. To this solution, a liquid in which component (B) is dispersed in the remaining mixture of water and component (D) is added and stirred until component (B) is uniformly dispersed, and the intended skin cleansing composition Got.
（４）実施例２７については、７０℃以上に加熱した精製水約２０質量％に、成分（Ａ）、成分（Ｃ）を添加して完全に溶解させた。次に、成分（Ｅ）を約２５質量％の精製水に分散させ、上記の溶液に添加した。更に、成分（Ｆ）であるラウリルヒドロキシスルタインを添加した後、成分（Ａ）、（Ｃ）及び（Ｅ）を中和する量の水酸化カリウムを添加し、均一になるまで攪拌した。この後、これを室温まで冷却した。この溶液に、残部の精製水と成分（Ｄ）の混合液に成分（Ｂ）を分散させた液を添加し、成分（Ｂ）が均一に分散するまで攪拌させた後、成分（Ｇ）であるグリセリンモノ２−エチルヘキシルエーテルを添加、均一に分散するまで攪拌させ、目的とする皮膚洗浄剤組成物を得た。 (4) About Example 27, the component (A) and the component (C) were added and completely dissolved in about 20% by mass of purified water heated to 70 ° C. or higher. Next, component (E) was dispersed in about 25% by mass of purified water and added to the above solution. Furthermore, after adding component (F), lauryl hydroxysultain, an amount of potassium hydroxide that neutralizes components (A), (C), and (E) was added and stirred until uniform. After this, it was cooled to room temperature. To this solution, a liquid in which component (B) is dispersed in the remaining mixture of purified water and component (D) is added and stirred until component (B) is uniformly dispersed. A certain glycerin mono 2-ethylhexyl ether was added and stirred until evenly dispersed to obtain the intended skin cleansing composition.
（評価方法）
（１）泡立ち：
専門パネリスト５名により、各皮膚洗浄剤組成物１ｇを手に取り、少量の水を加え手で泡立てたときの泡立ちを、以下に示す５段階評価基準で官能評価し、それぞれの評点の平均値を求めた。
５；泡立ちが非常に良い。
４；泡立ちが良い。
３；泡立ちがやや良い。
２；どちらともいえない。
１；泡立ちが悪い。
(Evaluation method)
(1) Foaming:
Five expert panelists took 1 g of each skin cleanser composition, sensoryly evaluated the foaming when a small amount of water was added and foamed by hand according to the five-level evaluation criteria shown below, and the average value of each score Asked.
5; Foaming is very good.
4; Good foaming.
3; Foaming is slightly good.
2; Neither can be said.
1; Foaming is bad.
（２）すすぎ性：
専門パネリスト５名により、各皮膚洗浄剤組成物１ｇを手に取り、少量の水を加えて泡立てて洗顔した後に水道水ですすいだ。そのときのすすぎ性について、以下に示す５段階評価基準で官能評価し、それぞれの評点の平均値を求めた。
５；非常にすすぎやすい。
４；すすぎやすい。
３；ややすすぎやすい。
２；どちらともいえない。
１；すすぎにくい。
(2) Rinsability:
Five specialist panelists took 1 g of each skin cleanser composition, added a small amount of water, foamed and washed their face, then rinsed with tap water. The rinsing property at that time was subjected to sensory evaluation according to the following five-step evaluation criteria, and the average value of each score was obtained.
5; Very easy to rinse.
4; Easy to rinse.
3;
2; Neither can be said.
1; Hard to rinse.
（３）洗浄効果：
人前腕内側部７cm2の円を描き、色彩色差計（ミノルタ社製、ＣＲ−２００）を用いて測色する（基準色）。２０μＬのカーボンブラックで黒色に着色したモデルコメド皮脂（表１０）を上記円内に塗布し、３０分間放置した後、ステンレス製スパーテルを用いて、表面の余分なモデルコメド皮脂を取り除く。このとき、色差（ΔＥ１）を測定し、その値が２０〜２５の範囲であることを確認する。（この範囲を超えていた場合は、再びスパーテルを用い、ΔＥ１値が２０〜２５となるまで余分なモデルコメド皮脂を取り除く。）各皮膚洗浄剤組成物１ｇを少量（約２ｇ）の水道水を加えて手のひらで３０往復させて泡立てた泡を０．５ｇ用い、２０回マッサージして洗浄した後、水道水で洗い流した。洗浄後に再び基準色との色差を測色し（ΔＥ２）、下記式により、洗浄効果を求める。各皮膚洗浄剤組成物について５回繰り返し、その平均値を求めた。
(3) Cleaning effect:
Draw a circle of 7 cm 2 on the inner side of the human forearm and measure the color using a color difference meter (CR-200, manufactured by Minolta) (reference color). The model comedo sebum (Table 10) colored in black with 20 μL of carbon black is applied in the circle and allowed to stand for 30 minutes, and then the excess model comedo sebum on the surface is removed using a stainless steel spatula. At this time, the color difference (ΔE1) is measured and it is confirmed that the value is in the range of 20-25. (If this range is exceeded, use a spatula again to remove excess model comedo sebum until the ΔE1 value reaches 20 to 25.) 1 g of each skin cleanser composition with a small amount (about 2 g) of tap water. In addition, 0.5 g of foam which was made to reciprocate 30 times with a palm was used, massaged 20 times, washed, and then washed away with tap water. After the cleaning, the color difference from the reference color is measured again (ΔE2), and the cleaning effect is obtained by the following equation. Each skin cleansing composition was repeated 5 times, and the average value was determined.
（４）肌のなめらかさ：
専門パネリスト５名により、各皮膚洗浄剤組成物１ｇを手に取り、少量の水を加えて泡立てて洗顔した後に水道水ですすいだ。タオルドライした直後及び２時間後の肌のなめらかさについて、以下に示す５段階評価基準で官能評価し、それぞれの評点の平均値を求めた。
５；非常になめらかな感じがする。
４；なめらかな感じがする。
３；少しなめらかな感じがする。
２；どちらともいえない。
１；なめらかな感じがしない。
(4) Skin smoothness:
Five specialist panelists took 1 g of each skin cleanser composition, added a small amount of water, foamed and washed their face, then rinsed with tap water. The smoothness of the skin immediately after towel drying and after 2 hours was subjected to sensory evaluation according to the following five-level evaluation criteria, and the average value of each score was obtained.
5; It feels very smooth.
4; It feels smooth.
3; I feel a little smooth.
2; Neither can be said.
1; Does not feel smooth.
（５）すすぎ時の肌感触：
専門パネリスト５名により、各皮膚洗浄剤組成物１ｇを手に取り、少量の水を加えて泡立てて洗顔した後に水道水ですすいだ。そのときの肌感触について、以下に示す５段階評価基準で官能評価し、それぞれの評点の平均値を求めた。
５；非常に良い。
４；良い。
３；やや良い。
２；あまり良くない。
１；良くない。
(5) Skin feel when rinsing:
Five specialist panelists took 1 g of each skin cleanser composition, added a small amount of water, foamed and washed their face, then rinsed with tap water. The skin feel at that time was subjected to sensory evaluation according to the following five-level evaluation criteria, and the average value of each score was obtained.
5; Very good.
4; Good.
3; Somewhat good.
2; Not very good.
1; not good.
（６）しっとり感：
専門パネリスト５名により、各皮膚洗浄剤組成物１ｇを手に取り、少量の水を加えて泡立てて洗顔した後に水道水ですすいだ。タオルドライ後、肌のしっとりする感じについて、以下に示す５段階評価基準で官能評価し、それぞれの評点の平均値を求めた。
５；非常にしっとりする。
４；しっとりする。
３；ややしっとりする。
２；どちらともいえない。
１；しっとりしない。
(6) Moist feeling:
Five specialist panelists took 1 g of each skin cleanser composition, added a small amount of water, foamed and washed their face, then rinsed with tap water. After towel drying, the moist feeling of the skin was subjected to sensory evaluation according to the following five-level evaluation criteria, and the average value of each score was obtained.
5; very moist.
4; Moist.
3; Slightly moist.
2; Neither can be said.
1; not moist.
（７）室温安定性：
各皮膚洗浄剤組成物を容量１３０mLのガラス瓶に１００ｇ入れ、室温で１日間放置した後、皮膚洗浄剤組成物中の水不溶性粒子の浮遊（もしくは沈降）状態について目視観察し、以下に示す３段階評価基準で評価した。
○；水不溶性粒子が均一に分散している。
△；水不溶性粒子が不均一であるが、容易に均一に再分散することができる。
×；水不溶性粒子が不均一であり、再分散することができない。
(7) Room temperature stability:
100 g of each skin cleansing composition is put in a glass bottle with a capacity of 130 mL and left at room temperature for 1 day, and then the floating (or sedimentation) state of water-insoluble particles in the skin cleansing composition is visually observed, and the following three steps are shown. Evaluation was based on the evaluation criteria.
○: Water-insoluble particles are uniformly dispersed.
Δ: Water-insoluble particles are non-uniform, but can be easily re-dispersed uniformly.
X: Water-insoluble particles are non-uniform and cannot be redispersed.
（８）低温保存後の室温安定性：
各皮膚洗浄剤組成物を容量１３０mLのガラス瓶に１００ｇ入れ、−５℃の恒温保存庫で１週間放置した後、取り出し、室温に戻した後、皮膚洗浄剤組成物中の水不溶性粒子の浮遊（もしくは沈降）状態について目視観察し、以下に示す３段階評価基準で評価した。
○；水不溶性粒子が均一に分散している。
△；水不溶性粒子が不均一であるが、容易に均一に再分散することができる。
×；水不溶性粒子が不均一であり、再分散することができない。
(8) Room temperature stability after low temperature storage:
100 g of each skin cleansing composition was put in a glass bottle having a capacity of 130 mL, left in a constant temperature storage at −5 ° C. for 1 week, taken out, returned to room temperature, and then water-insoluble particles in the skin cleansing composition were floated ( (Or sedimentation) state was visually observed and evaluated according to the following three-stage evaluation criteria.
○: Water-insoluble particles are uniformly dispersed.
Δ: Water-insoluble particles are non-uniform, but can be easily re-dispersed uniformly.
X: Water-insoluble particles are non-uniform and cannot be redispersed.
実施例において用いた粉体の平均粒径の測定方法には、レーザ回析／散乱式粒度分布測定装置ＬＡ−９１０（堀場社製）を用い、粉体を水、又は、食塩水に適度に分散させた後、測定した。平均粒径はメジアン径を用いた。 As a method for measuring the average particle size of the powder used in the examples, a laser diffraction / scattering type particle size distribution measuring apparatus LA-910 (manufactured by Horiba) was used, and the powder was appropriately added to water or saline. Measurement was performed after dispersion. The median diameter was used as the average particle diameter.
実施例２８
以下に示す組成の洗顔料を、実施例２７と同様にして製造した。
Example 28
A face wash having the composition shown below was produced in the same manner as in Example 27.
実施例２９
以下に示す組成の洗顔料を、実施例２７と同様にして製造した。
Example 29
A face wash having the composition shown below was produced in the same manner as in Example 27.
実施例３０
以下に示す組成の全身洗浄料を、実施例２７と同様にして製造した。
Example 30
A whole body cleaning material having the following composition was produced in the same manner as in Example 27.
実施例３１
以下に示す組成の全身洗浄料を、実施例２７と同様にして製造した。
Example 31
A whole body cleaning material having the following composition was produced in the same manner as in Example 27.
実施例２８〜３１で得られた皮膚洗浄剤組成物はいずれも、泡立ち、すすぎ性及び洗浄効果に優れ、しっとり感が得られ、タオルドライ直後及び２時間後においても肌がなめらかで、安定性も良好であった。 All of the skin cleanser compositions obtained in Examples 28 to 31 were excellent in foaming, rinsing properties and cleansing effect, moist feeling was obtained, and the skin was smooth and stable immediately after towel drying and after 2 hours. Was also good.
Claims (13)
（Ａ）一般式（１）
（Ｂ）平均粒径５０〜５００μｍの水不溶性粒子
を含有し、成分（Ａ）及び（Ｂ）の質量割合が、（Ａ）：（Ｂ）＝１：１０〜１０：１である皮膚洗浄剤組成物。 The following components (A) and (B):
(A) General formula (1)
(B) A skin cleanser containing water-insoluble particles having an average particle size of 50 to 500 μm, and the mass ratio of components (A) and (B) being (A) :( B) = 1: 10 to 10: 1 Composition.
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