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JP2008150303A - Skin cleanser - Google Patents

Skin cleanser Download PDF

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Publication number
JP2008150303A
JP2008150303A JP2006338182A JP2006338182A JP2008150303A JP 2008150303 A JP2008150303 A JP 2008150303A JP 2006338182 A JP2006338182 A JP 2006338182A JP 2006338182 A JP2006338182 A JP 2006338182A JP 2008150303 A JP2008150303 A JP 2008150303A
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Prior art keywords
fatty acid
skin cleanser
skin
carbon atoms
foam
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JP2006338182A
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JP4963601B2 (en
Inventor
Natsuko Higashinishida
奈都子 東西田
Masanori Shimizu
真規 清水
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Kao Corp
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Kao Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To obtain a skin cleanser having an excellent foam quality from the initial stage of foaming. <P>SOLUTION: The skin cleanser comprises (A) an anionic surfactant, (B) a higher fatty acid and/or a higher alcohol and (C) (c1) a polyoxyethylene alkyl ether represented by general formula (1): R<SP>1</SP>-O-(CH<SB>2</SB>CH<SB>2</SB>O)<SB>m</SB>-H (wherein, R<SP>1</SP>is a 8-20C branched alkyl group; m is an average addition molar number of ethylene oxide of 10-20) and/or (c2) a polyoxyethylene sorbitan fatty acid ester containing a 8-20C fatty acid residue and having an average addition molar number of 1-30. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、泡質が良好な皮膚洗浄剤に関する。   The present invention relates to a skin cleanser with good foam quality.

洗顔料、全身洗浄料等の皮膚洗浄剤においては、洗浄力が高いことに加えて、使用感をより高めるために、起泡性や泡質等の泡性能に優れることが求められている。このため、種々の界面活性剤等を組合わせた皮膚洗浄剤が検討されている。例えば、特許文献1には、特定のリン酸エステル塩型界面活性剤と、ミリスチン酸又はミリスチルアルコールを組合わせた皮膚洗浄剤組成物が記載されている。この皮膚洗浄剤組成物は、泡立ちが良好であるものの、泡立て初期においては、泡のきめやクリーミィさの点で十分満足できるものではなかった。   In the case of skin cleansing agents such as facial cleansers and whole body cleansing agents, in addition to high detergency, in order to enhance the feeling of use, it is required to have excellent foam performance such as foaming properties and foam quality. For this reason, skin cleansing agents combining various surfactants and the like have been studied. For example, Patent Document 1 describes a skin cleansing composition in which a specific phosphate ester type surfactant is combined with myristic acid or myristyl alcohol. Although this skin cleansing composition had good foaming, it was not satisfactory in terms of foam texture and creaminess in the early stage of foaming.

一方、非石鹸系アニオン界面活性剤、両性界面活性剤、HLB6〜18のノニオン界面活性剤及びミセルの成長促進剤としての高級アルコールを組合わせた液体洗浄剤組成物が提案されている(特許文献2)。しかして、このような液体洗浄剤組成物は、洗浄力や低温安定性に優れることが示されているものの、泡質については記載されていない。
特開2006−206443号公報 特開2004−91522号公報
On the other hand, a liquid detergent composition comprising a combination of a non-soap anionic surfactant, an amphoteric surfactant, a nonionic surfactant having an HLB of 6 to 18 and a higher alcohol as a micelle growth promoter has been proposed (Patent Literature). 2). Thus, although such a liquid detergent composition has been shown to be excellent in detergency and low-temperature stability, no foam quality is described.
JP 2006-206443 A JP 2004-91522 A

本発明の目的は、泡立ての初期から泡質が良好な皮膚洗浄剤を提供することにある。   An object of the present invention is to provide a skin cleanser having good foam quality from the beginning of foaming.

本発明者らは、アニオン界面活性剤と、高級脂肪酸及び/又は高級アルコールに加え、特定の非イオン界面活性剤を組合わせて用いることにより、泡立ての初期から泡のきめが細かくクリーミィで、硬くて弾力のある泡を与える皮膚洗浄剤が得られることを見出した。   The present inventors use a combination of an anionic surfactant, a higher fatty acid and / or a higher alcohol, and a specific nonionic surfactant in combination so that the foam texture is fine, creamy and hard from the beginning of foaming. It has been found that a skin cleanser that gives elastic foam can be obtained.

本発明は、次の成分(A)、(B)及び(C):
(A)アニオン界面活性剤、
(B)高級脂肪酸及び/又は高級アルコール、
(C)(c1)一般式(1)
1-O-(CH2CH2O)m-H (1)
(式中、R1は炭素数8〜20の分岐アルキル基を示し、mはエチレンオキシドの平均付加モル数を表す10〜20の数である)
で表わされるポリオキシエチレンアルキルエーテル、及び/又は
(c2)炭素数8〜20の脂肪酸残基を有し、エチレンオキシドの平均付加モル数が1〜30であるポリオキシエチレンソルビタン脂肪酸エステル
を含有する皮膚洗浄剤を提供するものである。
The present invention includes the following components (A), (B) and (C):
(A) an anionic surfactant,
(B) higher fatty acids and / or higher alcohols,
(C) (c1) General formula (1)
R 1 —O— (CH 2 CH 2 O) m —H (1)
(Wherein R 1 represents a branched alkyl group having 8 to 20 carbon atoms, and m is a number of 10 to 20 representing the average number of moles of ethylene oxide added)
And / or (c2) skin containing a polyoxyethylene sorbitan fatty acid ester having a fatty acid residue having 8 to 20 carbon atoms and an average added mole number of ethylene oxide of 1 to 30 A cleaning agent is provided.

本発明の洗浄剤組成物は泡質が良好であり、泡立ての初期から泡のきめが細かくクリーミィであり、硬くて弾力のある泡が得られるものである。   The detergent composition of the present invention has a good foam quality, has a fine and creamy foam from the beginning of frothing, and provides a hard and elastic foam.

本発明で用いる成分(A)のアニオン界面活性剤としては、例えば、アルキルリン酸エステル塩、アルカンスルホン酸塩、アルキル硫酸塩、アシル化アミノ酸塩、ポリオキシエチレンアルキルエーテル硫酸塩、アルキルベンゼンスルホン酸塩、N−アシル−N−メチルタウリン塩、アルファオレフィンスルホン酸塩、高級脂肪酸エステルスルホン酸塩、アルキルエーテル酢酸塩、ポリオキシエチレンアルキルエーテル酢酸塩等が挙げられる。これらのうち、ポリオキシエチレンアルキルエーテル硫酸塩、アルキルリン酸エステル塩、アシル化アミノ酸塩、ポリオキシエチレンアルキルエーテル酢酸塩が好ましく、特に、ポリオキシエチレンアルキルエーテル硫酸塩、モノアルキルリン酸エステル塩、アシル化アミノ酸塩が好ましい。
ここで用いられる塩としては、ナトリウム、カリウム、マグネシウム等の金属塩;アンモニウム塩;モノエタノールアンモニウム塩、ジエタノールアンモニウム塩、トリエタノールアンモニウム塩等の有機アンモニウム塩などが好ましい。
Examples of the anionic surfactant of component (A) used in the present invention include alkyl phosphate ester salts, alkane sulfonates, alkyl sulfates, acylated amino acid salts, polyoxyethylene alkyl ether sulfates, and alkyl benzene sulfonates. N-acyl-N-methyl taurate, alpha olefin sulfonate, higher fatty acid ester sulfonate, alkyl ether acetate, polyoxyethylene alkyl ether acetate, and the like. Of these, polyoxyethylene alkyl ether sulfate, alkyl phosphate ester salt, acylated amino acid salt, and polyoxyethylene alkyl ether acetate salt are preferred, and in particular, polyoxyethylene alkyl ether sulfate, monoalkyl phosphate ester salt, Acylated amino acid salts are preferred.
As the salt used here, metal salts such as sodium, potassium and magnesium; ammonium salts; organic ammonium salts such as monoethanolammonium salt, diethanolammonium salt and triethanolammonium salt are preferable.

成分(A)のアニオン界面活性剤は、1種以上を用いることができ、全組成中に10〜40質量%、特に10〜25質量%含有するのが、泡立ちと泡質をともに満足できる点で好ましい。   One or more anionic surfactants of component (A) can be used, and 10 to 40% by mass, especially 10 to 25% by mass in the total composition can satisfy both foaming and foam quality. Is preferable.

本発明で用いる成分(B)の高級脂肪酸及び高級アルコールとしては、平均炭素数11〜18のアシル基又はアルキル基を有するものが好ましく、直鎖タイプのものがより好ましい。具体的には、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ラウリルアルコール、ミリスチルアルコール、パルミチルアルコール、ステアリルアルコール等が挙げられる。   As the higher fatty acid and higher alcohol of the component (B) used in the present invention, those having an average carbon number of 11 to 18 acyl group or alkyl group are preferred, and those of a straight chain type are more preferred. Specific examples include lauric acid, myristic acid, palmitic acid, stearic acid, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol and the like.

成分(B)としては、高級脂肪酸及び高級アルコールを組合わせて用いることもできる。成分(B)は、高級脂肪酸と高級アルコールの合計量で、全組成中に0.5〜5質量%、特に1〜3質量%含有するのが、クリーミィな泡を与え、洗浄剤組成物の保存安定性を向上させるので好ましい。   As the component (B), a higher fatty acid and a higher alcohol can be used in combination. Component (B) is a total amount of higher fatty acid and higher alcohol, and 0.5 to 5% by mass, particularly 1 to 3% by mass in the total composition gives creamy foam, This is preferable because storage stability is improved.

次に、成分(C)は、泡立ての初期から泡質を良くし、クリーミィで硬い泡を得ることを意図して用いられる成分であり、そのうち、(c1)のポリオキシエチレンアルキルエーテルは、前記一般式(1)で表わされるもので、R1が炭素数8〜20の分岐アルキル基であり、特に、炭素数12〜14の分岐アルキル基であるのが好ましい。R1が直鎖アルキル基のものでは、泡立ての初期から良好な泡質を得ることはできない。また、mはエチレンオキシドの平均付加モル数を表す10〜20の数であり、特に、12〜20であるのが好ましい。 Next, the component (C) is a component that is used to improve the foam quality from the initial stage of foaming and to obtain a creamy and hard foam. Among them, the polyoxyethylene alkyl ether of (c1) It is represented by the general formula (1), and R 1 is a branched alkyl group having 8 to 20 carbon atoms, and particularly preferably a branched alkyl group having 12 to 14 carbon atoms. If R 1 is a linear alkyl group, good foam quality cannot be obtained from the beginning of foaming. Moreover, m is a number of 10 to 20 representing the average added mole number of ethylene oxide, and is particularly preferably 12 to 20.

一方、(c2)のポリオキシエチレンソルビタン脂肪酸エステルは、炭素数8〜20の脂肪酸残基を有し、特に、炭素数14〜18の脂肪酸残基を有するのが好ましい。また、一分子あたりのエチレンオキシドの平均付加モル数は、合計で1〜30、特に15〜25であるのが好ましい。   On the other hand, the polyoxyethylene sorbitan fatty acid ester (c2) has a fatty acid residue having 8 to 20 carbon atoms, and particularly preferably has a fatty acid residue having 14 to 18 carbon atoms. The average number of moles of ethylene oxide added per molecule is preferably 1 to 30, particularly 15 to 25 in total.

成分(C)としては、特に(c1)のポリオキシエチレン分岐アルキルエーテル(1)が、泡立て初期からの泡質、泡の硬さの点でより好ましい。また、(c1)と(c2)を組合わせて用いることもできる。
成分(C)は、全組成中に1〜5質量%、特に1.5〜3質量%含有するのが、泡立て初期の泡質及び泡の硬さの点で好ましい。
Especially as a component (C), the polyoxyethylene branched alkyl ether (1) of (c1) is more preferable at the point of the foam quality from the initial stage of foaming, and the hardness of foam. Also, (c1) and (c2) can be used in combination.
The component (C) is preferably contained in the total composition in an amount of 1 to 5% by mass, particularly 1.5 to 3% by mass, from the viewpoint of foam quality at the initial stage of foaming and foam hardness.

本発明の皮膚洗浄剤は、更に、(D)一般式(2)   The skin cleanser of the present invention further comprises (D) the general formula (2)

Figure 2008150303
Figure 2008150303

(式中、R2は炭素数4〜10の炭化水素基を示す)
で表わされるグリセリルエーテルを含有することができ、泡立ち、泡量の増強により、泡のボリュームが増し、よりクリーミィな感触を得ることができる。
(Wherein R 2 represents a hydrocarbon group having 4 to 10 carbon atoms)
The glyceryl ether represented by the formula (1) can be contained, and the foam volume is increased by enhancing foaming and foam quantity, and a creamier feel can be obtained.

3としては、炭素数4〜10のアルキル基又はアルケニル基が好ましく、例えば、n−ブチル基、イソブチル基、tert−ブチル基、n−ペンチル基、イソペンチル基、n−ヘキシル基、イソヘキシル基、n−ヘプチル基、n−オクチル基、2−エチルヘキシル基、n−ノニル基、n−デシル基等のアルキル基が好ましい。 R 3 is preferably an alkyl group or alkenyl group having 4 to 10 carbon atoms, such as an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, an n-hexyl group, an isohexyl group, Alkyl groups such as n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group and n-decyl group are preferred.

成分(D)は、1種以上を用いることができ、全組成中に0.5〜5質量%、特に0.5〜3質量%含有するのが、泡立ちと泡質をともに満足できる点で好ましい。   One or more types of component (D) can be used, and 0.5 to 5% by mass, particularly 0.5 to 3% by mass of the total composition can satisfy both foaming and foam quality. preferable.

本発明の皮膚洗浄剤は、前記成分以外に通常の洗浄剤組成物に用いられる成分、例えば、前記以外の界面活性剤、香料、保湿剤、抗ニキビ剤、酸化防止剤、抗フリーラジカル剤、乳白剤、安定剤、エモリエント剤、ヒドロキシ酸、ビタミン類、セラミド類、防腐剤、金属イオン封鎖剤、増粘剤、紫外線吸収剤、紫外線防御剤、無機塩、顔料、その他化粧料に一般的に用いられる薬剤、あるいはエタノール等の有機溶媒物質や揮発性成分などを含有することができる。   The skin cleanser of the present invention is a component used in a normal cleanser composition in addition to the above components, for example, surfactants other than those described above, perfumes, moisturizers, anti-acne agents, antioxidants, anti-free radical agents, Generally used in opacifiers, stabilizers, emollients, hydroxy acids, vitamins, ceramides, preservatives, sequestering agents, thickeners, UV absorbers, UV protection agents, inorganic salts, pigments, and other cosmetics It can contain chemicals used, organic solvent substances such as ethanol, volatile components, and the like.

本発明の皮膚洗浄剤は、水で20倍に希釈した水溶液のpHが5〜7、特にpH5.5〜6.5であるのが、皮膚への刺激が少なく、優れた洗浄力が損なわれることなく洗浄時の泡立ちが良好となるので好ましい。
かかる弱酸性〜中性領域のpHの洗浄剤組成物中において、成分(B)の高級脂肪酸は、脂肪酸と脂肪酸塩の混合した状態として存在していると考えられる。
In the skin cleanser of the present invention, the pH of an aqueous solution diluted 20-fold with water is 5 to 7, particularly pH 5.5 to 6.5, and there is little irritation to the skin and the excellent cleaning power is impaired. This is preferable because the foaming during washing is improved.
In such a weakly acidic to neutral pH detergent composition, the higher fatty acid of component (B) is considered to exist as a mixture of fatty acid and fatty acid salt.

皮膚洗浄剤のpHは、必要に応じて、塩酸、硫酸、リン酸等の無機酸;クエン酸、コハク酸、乳酸、リンゴ酸、ピロリドンカルボン酸、酒石酸、グリコール酸、アスコルビン酸等の有機酸;グルタミン酸、アスパラギン酸等の酸性アミノ酸;水酸化ナトリウム、水酸化カリウム等の水酸化物;アンモニア又はアンモニア水;アルギニン、リジン等の塩基性アミノ酸などのpH調整剤を用いて調整することができる。
なお、pHは、皮膚洗浄剤を精製水にて20倍に希釈し、撹拌して5質量%水溶液を得た後、pHメーター(例えば、堀場製作所製、型番F−22)を用い、20℃で測定した値である。
If necessary, the pH of the skin cleanser is an inorganic acid such as hydrochloric acid, sulfuric acid or phosphoric acid; an organic acid such as citric acid, succinic acid, lactic acid, malic acid, pyrrolidone carboxylic acid, tartaric acid, glycolic acid or ascorbic acid; It can be adjusted using a pH adjuster such as acidic amino acids such as glutamic acid and aspartic acid; hydroxides such as sodium hydroxide and potassium hydroxide; ammonia or aqueous ammonia; basic amino acids such as arginine and lysine.
In addition, after diluting the skin cleaning agent 20 times with purified water and stirring to obtain a 5% by mass aqueous solution, the pH was adjusted to 20 ° C. using a pH meter (for example, model number F-22, manufactured by Horiba, Ltd.) It is the value measured by.

本発明の皮膚洗浄剤は、含有成分を秤量し、水又は水を主体としアルコール等の他の水溶性溶剤を含む水性媒体に、任意の順序で混合及び攪拌することにより製造することができる。混合、溶解の順序は、特に制限されない。   The skin cleansing agent of the present invention can be produced by weighing the components contained therein and mixing and stirring in an arbitrary order in water or an aqueous medium mainly containing water and containing other water-soluble solvents such as alcohol. The order of mixing and dissolution is not particularly limited.

本発明の皮膚洗浄剤は、液状又はペースト状の組成物として得られ、30℃における粘度は500〜3000mPa・s、特に1000〜2500mPa・sの範囲であることが、ポンプ等の容器から排出し易く、泡立てが容易である点で好ましい。
粘度は、皮膚洗浄剤を100mL瓶(アズワン 規格瓶PS−No.11)に入れ、30℃の恒温槽で3時間静置したのち、B型粘度計(TOKIMEC INC.製、ローターNo.3、30rpm)で測定する。
The skin cleanser of the present invention is obtained as a liquid or paste-like composition, and the viscosity at 30 ° C. is from 500 to 3000 mPa · s, particularly from 1000 to 2500 mPa · s. It is preferable in that it is easy and foaming is easy.
Viscosity was obtained by placing the skin cleanser in a 100 mL bottle (As One Standard Bottle PS-No. 11) and allowing it to stand for 3 hours in a thermostatic bath at 30 ° C., and then using a B-type viscometer (TOKIMEC INC., Rotor No. 3, 30 rpm).

本発明の皮膚洗浄剤は、洗顔料、全身洗浄料、ハンドソープ、クレンジング剤等とすることができる。   The skin cleanser of the present invention can be a facial cleanser, whole body cleanser, hand soap, cleansing agent and the like.

実施例1〜7及び比較例1〜4
表1に表す成分を秤量して水中に添加し、50℃で充分攪拌して、皮膚洗浄剤組成物(ボディーシャンプー)を得た。水で20倍に希釈した水溶液のpHを、pHメーター(堀場製作所製、型番F−22)により測定した。また、泡立て初期の泡質、十分泡立てたときの泡質及び泡の硬さを評価した。泡立ては、両手をお湯(約40℃)であらかじめ適度に濡らし、各皮膚洗浄剤約1gを手に取って行い、評価した。結果を表1に併せて示す。
Examples 1-7 and Comparative Examples 1-4
The components shown in Table 1 were weighed and added to water, and stirred well at 50 ° C. to obtain a skin cleanser composition (body shampoo). The pH of the aqueous solution diluted 20 times with water was measured with a pH meter (manufactured by Horiba, model number F-22). Moreover, the foam quality at the initial stage of foaming, the foam quality when sufficiently foamed, and the hardness of the foam were evaluated. For foaming, both hands were appropriately wetted with hot water (about 40 ° C.) in advance, and about 1 g of each skin cleansing agent was taken and evaluated. The results are also shown in Table 1.

(評価方法)
(1)泡立て初期の泡質:
専門評価者10名が、各皮膚洗浄剤について、泡を立て始めたときの泡質(泡のきめ細かさ、クリーミィさ)を官能評価した。「泡質がよい」と評価した評価者の人数を示した。
(Evaluation methods)
(1) Initial foam quality:
Ten professional evaluators performed sensory evaluation of the foam quality (fineness of foam, creaminess) when foaming was started for each skin cleansing agent. The number of evaluators who evaluated “good foam quality” was shown.

(2)十分泡立てたときの泡質:
専門評価者10名が、各皮膚洗浄剤について、約20秒泡を立てた後の泡質(泡のきめ細かさ、クリーミィさ)を官能評価した。「泡質がよい」と評価した評価者の人数を示した。
(2) Foam quality when fully foamed:
Ten professional evaluators performed sensory evaluation of the foam quality (fineness of foam, creaminess) after foaming for about 20 seconds for each skin cleansing agent. The number of evaluators who evaluated “good foam quality” was shown.

(3)泡の硬さ:
専門評価者10名が、各皮膚洗浄剤について、約20秒泡を立てた後の泡の弾力を官能評価した。「泡に弾力がある」と評価した評価者の人数を示した。
(3) Hardness of foam:
Ten professional evaluators performed sensory evaluation on the elasticity of the foam after foaming for about 20 seconds for each skin cleanser. The number of evaluators who evaluated that “the foam is elastic” was shown.

Figure 2008150303
Figure 2008150303

Figure 2008150303
Figure 2008150303

Claims (4)

次の成分(A)、(B)及び(C):
(A)アニオン界面活性剤、
(B)高級脂肪酸及び/又は高級アルコール、
(C)(c1)一般式(1)
1-O-(CH2CH2O)m-H (1)
(式中、R1は炭素数8〜20の分岐アルキル基を示し、mはエチレンオキシドの平均付加モル数を表す10〜20の数である)
で表わされるポリオキシエチレンアルキルエーテル、及び/又は
(c2)炭素数8〜20の脂肪酸残基を有し、エチレンオキシドの平均付加モル数が1〜30であるポリオキシエチレンソルビタン脂肪酸エステル
を含有する皮膚洗浄剤。
The following components (A), (B) and (C):
(A) an anionic surfactant,
(B) higher fatty acids and / or higher alcohols,
(C) (c1) General formula (1)
R 1 —O— (CH 2 CH 2 O) m —H (1)
(Wherein R 1 represents a branched alkyl group having 8 to 20 carbon atoms, and m is a number of 10 to 20 representing the average number of moles of ethylene oxide added)
And / or (c2) skin containing a polyoxyethylene sorbitan fatty acid ester having a fatty acid residue having 8 to 20 carbon atoms and an average added mole number of ethylene oxide of 1 to 30 Washing soap.
水で20倍に希釈した水溶液のpHが5〜7である請求項1記載の皮膚洗浄剤。   The skin cleanser according to claim 1, wherein the pH of the aqueous solution diluted 20 times with water is 5-7. 更に、(D)一般式(2)
Figure 2008150303
(式中、R2は炭素数4〜10の炭化水素基を示す)
で表わされるグリセリルエーテルを含有する請求項1又は2記載の皮膚洗浄剤。
Furthermore, (D) General formula (2)
Figure 2008150303
(Wherein R 2 represents a hydrocarbon group having 4 to 10 carbon atoms)
The skin cleanser of Claim 1 or 2 containing the glyceryl ether represented by these.
成分(A)のアニオン界面活性剤が、モノアルキルリン酸エステル塩、アシル化アミノ酸塩及びポリオキシエチレンアルキルエーテル硫酸塩から選ばれるものである請求項1〜3のいずれか1項記載の皮膚洗浄剤。   The skin cleanser according to any one of claims 1 to 3, wherein the anionic surfactant of component (A) is selected from monoalkyl phosphate esters, acylated amino acid salts and polyoxyethylene alkyl ether sulfates. Agent.
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Cited By (3)

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JP2014231481A (en) * 2013-05-28 2014-12-11 ライオン株式会社 Skin detergent composition
JP2019014691A (en) * 2017-07-10 2019-01-31 クラシエホームプロダクツ株式会社 Detergent composition
JP7216444B1 (en) 2021-12-01 2023-02-01 アピ株式会社 external composition

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JPH0543428A (en) * 1991-08-13 1993-02-23 Lion Corp Cosmetic
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JPH10183177A (en) * 1996-10-21 1998-07-14 Kao Corp Cleaning agent composition
JP2001107097A (en) * 1999-10-12 2001-04-17 Kao Corp Cleaning agent composition
JP2001278742A (en) * 2000-03-27 2001-10-10 Kao Corp Skin cleansing agent
JP2004155716A (en) * 2002-11-07 2004-06-03 Kanebo Ltd Creamy skin cleanser
JP2005325187A (en) * 2004-05-13 2005-11-24 Asahi Kasei Chemicals Corp Cleanser composition
JP2006182907A (en) * 2004-12-27 2006-07-13 Kao Corp Detergent composition
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JPH0543428A (en) * 1991-08-13 1993-02-23 Lion Corp Cosmetic
JPH0920618A (en) * 1995-07-07 1997-01-21 Kao Corp Skin cleansing article
JPH10183177A (en) * 1996-10-21 1998-07-14 Kao Corp Cleaning agent composition
JP2001107097A (en) * 1999-10-12 2001-04-17 Kao Corp Cleaning agent composition
JP2001278742A (en) * 2000-03-27 2001-10-10 Kao Corp Skin cleansing agent
JP2004155716A (en) * 2002-11-07 2004-06-03 Kanebo Ltd Creamy skin cleanser
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Publication number Priority date Publication date Assignee Title
JP2014231481A (en) * 2013-05-28 2014-12-11 ライオン株式会社 Skin detergent composition
JP2019014691A (en) * 2017-07-10 2019-01-31 クラシエホームプロダクツ株式会社 Detergent composition
JP7204162B2 (en) 2017-07-10 2023-01-16 クラシエホームプロダクツ株式会社 detergent composition
JP7216444B1 (en) 2021-12-01 2023-02-01 アピ株式会社 external composition
JP2023081565A (en) * 2021-12-01 2023-06-13 アピ株式会社 external composition

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