JP5210693B2 - Enzyme cleansing powder - Google Patents
Enzyme cleansing powder Download PDFInfo
- Publication number
- JP5210693B2 JP5210693B2 JP2008103834A JP2008103834A JP5210693B2 JP 5210693 B2 JP5210693 B2 JP 5210693B2 JP 2008103834 A JP2008103834 A JP 2008103834A JP 2008103834 A JP2008103834 A JP 2008103834A JP 5210693 B2 JP5210693 B2 JP 5210693B2
- Authority
- JP
- Japan
- Prior art keywords
- powder
- washing powder
- face washing
- face
- olefin
- 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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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 23
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- ICUTUKXCWQYESQ-UHFFFAOYSA-N triclocarban Chemical compound C1=CC(Cl)=CC=C1NC(=O)NC1=CC=C(Cl)C(Cl)=C1 ICUTUKXCWQYESQ-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Cosmetics (AREA)
Description
本発明は、配合成分である酵素に対する優れた安定性、優れた起泡性、優れた使用感、および皮膚への低刺激性を具備する洗顔パウダーに関する。 The present invention relates to a facial cleansing powder having excellent stability with respect to an enzyme as a compounding component, excellent foaming property, excellent feeling of use, and low irritation to skin.
従来、洗顔パウダーに使用される酵素としては、パパインなど植物起源の蛋白分解酵素が用いられていたが、かかる酵素は蛋白分解作用が弱く、酵素の本来の目的としての毛穴につまった蛋白質の汚れ、および角質化した皮膚の洗浄を充分に行うことができなかった。また、微生物由来の酵素を配合する洗顔パウダーについても、従来のものは、酵素の安定化が充分に図られていない等の理由から、必ずしも満足する洗浄効果が得られていなかった。一方、毛穴の汚れや角質化した皮膚の清浄手段として美容皮膚科等で実施されるケミカルピーリングは、角質のみを選択的に除去することが難しく、ともすると皮膚の基底層や真皮にまで影響が及ぶことがあり、皮膚刺激性という点で必ずしも満足なものとは言えていない。 Conventionally, plant-derived proteolytic enzymes such as papain have been used as facial cleansing powders, but such enzymes are weak in proteolytic action, and the soil of proteins clogged in the pores as the original purpose of the enzyme. In addition, the keratinized skin could not be sufficiently washed. Further, as for the face washing powder containing the enzyme derived from the microorganism, the conventional face washing powder does not always have a satisfactory washing effect because the enzyme is not sufficiently stabilized. On the other hand, chemical peeling, which is carried out in cosmetic dermatology as a means of cleaning pore dirt and keratinized skin, is difficult to selectively remove only the keratin, possibly affecting the skin's basal layer and dermis. The skin irritation is not always satisfactory.
粉末状の洗顔パウダーは、液体の原料を配合することによるブロッキングやぼたつき感が起きやすく、また製品の吸湿性による流動性の変化を抑制するために加えられる界面活性剤や他の成分等の配合に制限があり、優れた起泡性および使用感を両立させることが困難であると言われている。粉末状洗浄剤において、優れた起泡性を得るためのアニオン界面活性剤としては、アルキル硫酸塩やアルキルリン酸塩等が知られている。しかし、これらは刺激性が誘発されるために使用感に劣る。一方、刺激が温和な界面活性剤としては、種々知られており、中でもＮ−アシルアミノ酸塩等が良く知られている。しかしながら、優れた起泡性および使用感を両立させ、刺激性が少なく、酵素を配合したときにその安定性が保たれる界面活性剤として、必ずしも満足するものは得られていない。 Powdered facial cleansing powder is prone to blocking and stickiness caused by mixing liquid ingredients, and surfactants and other ingredients added to suppress changes in fluidity due to moisture absorption of the product It is said that it is difficult to achieve both excellent foaming properties and feeling of use. Alkyl sulfates, alkyl phosphates, and the like are known as anionic surfactants for obtaining excellent foamability in powder detergents. However, these are inferior to the feeling of use because irritation is induced. On the other hand, various mild surfactants are known, and among them, N-acyl amino acid salts and the like are well known. However, a satisfactory surfactant is not necessarily obtained as a surfactant that has both excellent foaming properties and a feeling of use, is less irritating, and maintains its stability when an enzyme is added.
微生物起源の蛋白分解酵素を配合した洗顔パウダーについての開示がある（特許文献１）。当該洗顔パウダーはポリアクリル酸ナトリウムを配合することにより酵素の安定化が図られること、滑らかな泡立ちが実現することを効果とするものである。洗浄剤成分としてＮ−ラウリル−Ｌ−グルタミン酸モノナトリウムなどの界面活性剤が含まれることが開示されているが、Ｎ−アシルアミノ酸塩、アシルイセチオン酸塩、およびオレフィンスルホン酸塩の併用についての開示はない。また、該洗顔パウダーには、ソルビトールおよびグリシルグリシンに関する開示はない。 There is a disclosure of a facial cleansing powder containing a microbial proteolytic enzyme (Patent Document 1). The facial cleansing powder is effective in stabilizing the enzyme by blending sodium polyacrylate and realizing smooth foaming. Although it is disclosed that surfactants such as monosodium N-lauryl-L-glutamate are included as a detergent component, disclosure regarding the combined use of N-acyl amino acid salts, acyl isethionates, and olefin sulfonates is disclosed. Absent. Moreover, there is no disclosure regarding sorbitol and glycylglycine in the face washing powder.
アシルイセチオン酸塩とＮ−アシルアミノ酸塩とを一定の割合で配合することにより、優れた起泡性と皮膚への低刺激性等の使用感を両立させた粉末状洗浄剤組成物についての開示がある（特許文献２）。当該洗浄剤組成物には蛋白分解酵素は配合されていない。また、一般的な記載として、当該洗浄剤組成物に糖類を配合することが出来る旨の開示があるが、特定の糖類を配合した場合の効果等についての開示、示唆はない。ポリアクリル酸Ｎａおよびグリシルグリシンに関する開示はない。 Disclosure of a powdery detergent composition that combines excellent foaming properties and low skin irritation feeling by blending acyl isethionate and N-acyl amino acid salt at a certain ratio Yes (Patent Document 2). The detergent composition does not contain a proteolytic enzyme. Further, as a general description, there is a disclosure that a saccharide can be blended in the cleaning composition, but there is no disclosure or suggestion about an effect or the like when a specific saccharide is blended. There is no disclosure regarding poly (sodium acrylate) and glycylglycine.
蛋白分解酵素の安定化剤および当該安定化剤を配合した洗浄剤が開示されており（特許文献３）、当該安定化剤の一例としてグリシルグリシンが開示されている。洗浄剤の例として蛋白分解酵素を配合した洗顔パウダーの実施例があり、界面活性剤として、Ｎ−ラウロイル−Ｌ−グルタミン酸Ｎａおよびヤシ油脂肪酸エチルエステルスルホン酸Ｎａが配合されている。ソルビトールの使用に関する記載はない。
本発明の目的は、配合成分である酵素に対する優れた安定性、優れた起泡性、優れた使用感、および皮膚への低刺激性を具備する洗顔パウダーを提供することにある。 An object of the present invention is to provide a facial cleansing powder having excellent stability with respect to the enzyme as a blending component, excellent foaming properties, excellent usability, and low skin irritation.
本発明者らは、配合成分である酵素に対する優れた安定性、優れた起泡性、優れた使用感、および皮膚への低刺激性を具備する洗顔パウダーの組成について鋭意検討を重ねた結果、微生物起源のタンパク分解酵素；Ｎ−アシルアミノ酸塩、アシルイセチオン酸塩、およびオレフィンスルホン酸塩からなる界面活性剤；ソルビトール；ポリアクリル酸Ｎａ；グリシルグリシンを配合した洗顔パウダーが、上記課題を解決することを確認し、本発明を完成させた。 As a result of earnestly examining the composition of the facial cleansing powder having excellent stability, excellent foaming property, excellent usability, and low irritation to the skin, the present inventors have obtained an excellent stability with respect to the enzyme as a blending component. Proteolytic enzyme of microbial origin; surfactant comprising N-acyl amino acid salt, acyl isethionate, and olefin sulfonate; sorbitol; polyacrylic acid Na; facial cleansing powder containing glycylglycine solves the above problems This was confirmed and the present invention was completed.
すなわち、本発明は、
（１）微生物起源のタンパク分解酵素；Ｎ−アシルアミノ酸塩、アシルイセチオン酸塩、およびオレフィンスルホン酸塩からなる界面活性剤；ソルビトール；ポリアクリル酸Ｎａ；グリシルグリシンを含有する洗顔パウダーである。
具体的には、
（２）Ｎ−アシルアミノ酸塩がラウロイルグルタミン酸Ｎａ、アシルイセチオン酸塩がココイルイセチオン酸Ｎａ、オレフィンスルホン酸塩がオレフィン（Ｃ１４−１６）スルホン酸Ｎａである上記（１）記載の洗顔パウダー、
（３）Ｎ−アシルアミノ酸塩、アシルイセチオン酸塩、オレフィンスルホン酸塩の配合比が２〜３：１〜２：１〜２であることを特徴とする上記（１）または（２）記載の洗顔パウダー、
（４）Ｎ−アシルアミノ酸塩、アシルイセチオン酸塩、およびオレフィンスルホン酸塩を洗顔パウダー全量に対して各１０〜２０％、３〜７％、３〜７％配合することを特徴とする上記（１）〜（３）のいずれかに記載の洗顔パウダー、
（５）ソルビトールの配合量が洗顔パウダー全量に対して５〜７％であることを特徴とする上記（１）〜（４）のいずれかに記載の洗顔パウダーである。
なお、洗顔パウダーの組成において「％」は特記しない限り「質量％」を示す。
また、本発明は、
（１）’微生物起源のタンパク分解酵素；ラウロイルグルタミン酸Ｎａ、ココイルイセチオン酸Ｎａ、およびオレフィン（Ｃ１４−１６）スルホン酸Ｎａからなる界面活性剤；ソルビトール；ポリアクリル酸Ｎａ；グリシルグリシンを含有する洗顔パウダーであって、該洗顔パウダー全量に対して、ソルビトールを５〜１０％配合することを特徴とする洗顔パウダーである。
より具体的には、
（２）’ラウロイルグルタミン酸Ｎａ、ココイルイセチオン酸Ｎａ、オレフィン（Ｃ１４−１６）スルホン酸Ｎａの配合比が２〜３：１〜２：１〜２であることを特徴とする上記（１）’記載の洗顔パウダー、
（３）’ラウロイルグルタミン酸Ｎａ、ココイルイセチオン酸Ｎａ、およびオレフィン（Ｃ１４−１６）スルホン酸Ｎａを洗顔パウダー全量に対して各１０〜２０％、３〜７％、３〜７％配合することを特徴とする上記（１）’または（２）’記載の洗顔パウダー、
（４）’微生物起源のタンパク分解酵素を洗顔パウダー全量に対して０．０１〜５％配合することを特徴とする上記（１）’〜 （３）’のいずれかに記載の洗顔パウダー、
（５）’洗顔パウダー全量に対して、微生物起源のタンパク分解酵素 ０．２％；ラウロイルグルタミン酸Ｎａ １５％、ココイルイセチオン酸Ｎａ ５％、およびオレフィン（Ｃ１４−１６）スルホン酸Ｎａ ５％；ソルビトール ７％；ポリアクリル酸Ｎａ １．２％；グリシルグリシン ０．０１％を含有する洗顔パウダーである。
なお、洗顔パウダーの組成において「％」は特記しない限り「質量％」を示す。
That is, the present invention
(1) Proteolytic enzyme of microbial origin; a surfactant comprising N-acyl amino acid salt, acyl isethionate, and olefin sulfonate; sorbitol; polyacrylic acid Na; glycylglycine.
In particular,
(2) The face washing powder according to the above (1), wherein the N-acyl amino acid salt is Nauroyl glutamate, the acyl isethionate is Na cocoyl isethionate, and the olefin sulfonate is Na olefin (C14-16) sulfonate,
(3) The face wash according to (1) or (2) above, wherein the compounding ratio of N-acyl amino acid salt, acyl isethionate, and olefin sulfonate is 2 to 3: 1 to 2: 1 to 2 powder,
(4) N-acyl amino acid salt, acyl isethionate, and olefin sulfonate are blended in an amount of 10 to 20%, 3 to 7%, and 3 to 7%, respectively, based on the total amount of the face washing powder (1) )-(3) facial cleansing powder,
(5) The face washing powder according to any one of (1) to (4) above, wherein the blending amount of sorbitol is 5 to 7% with respect to the total amount of the face washing powder.
In the composition of the face washing powder, “%” means “% by mass” unless otherwise specified.
The present invention also provides:
(1) 'Proteolytic enzyme of microbial origin; surfactant composed of sodium lauroyl glutamate, sodium cocoyl isethionate, and olefin (C14-16) sulfonate; sorbitol; sodium polyacrylate; glycylglycine A face washing powder comprising 5 to 10% sorbitol based on the total amount of the face washing powder.
More specifically,
(2) The above-mentioned (1) ', wherein the blending ratio of' Nauroyl glutamate Na, cocoyl isethionate Na, olefin (C14-16) sulfonate Na is 2 to 3: 1 to 2: 1 to 2 '. Facial cleansing powder,
(3) 'Nauroyl glutamate Na, cocoyl isethionate Na, and olefin (C14-16) sulfonate Na are blended in amounts of 10 to 20%, 3 to 7%, and 3 to 7%, respectively, based on the total amount of the face washing powder. The facial cleansing powder according to (1) ′ or (2) ′ described above,
(4) The facial cleansing powder according to any one of (1) to (3) above, wherein 0.01 to 5% of a proteolytic enzyme of microbial origin is added to the total amount of the facial cleansing powder,
(5) 'Proteolytic enzyme of microbial origin 0.2%; Lauroyl glutamate Na 15%, cocoyl isethionate Na 5%, and olefin (C14-16) sulfonate Na 5%; sorbitol 7%; a facial cleansing powder containing 1.2% Na polyacrylate; 0.01% glycylglycine.
In the composition of the face washing powder, “%” means “% by mass” unless otherwise specified.
本発明の洗顔パウダーは、微生物起源のタンパク分解酵素にＮ−アシルアミノ酸塩、アシルイセチオン酸塩およびオレフィンスルホン酸塩からなる界面活性剤、ソルビトール、ポリアクリル酸Ｎａおよびグリシルグリシンを組み合わせることにより、配合成分である酵素に対する優れた安定性、製品としての優れた起泡性、優れた使用感、および皮膚への低刺激性が達成された。 The face-washing powder of the present invention is formulated by combining a microbial-origin proteolytic enzyme with a surfactant comprising N-acylamino acid salt, acyl isethionate and olefin sulfonate, sorbitol, polyacrylic acid Na and glycylglycine. Excellent stability to the component enzyme, excellent foamability as a product, excellent usability, and low irritation to the skin were achieved.
本発明に用いる微生物起源のタンパク分解酵素としては、ＡＳＰプロテアーゼ、放線菌プロテアーゼ、黒麹菌プロテアーゼ等の微生物起源の酵素を用いることができるが、これらに限定されるものでなく、枯草菌プロテアーゼ等のＡＳＰ、放線菌、黒麹菌以外の微生物により産生される酵素も用いることができる。また、医薬部外品原料規格に記載されているプロテアーゼ（１）（枯草菌由来）またはプロテアーゼ（２）（放線菌由来）を用いることもできる。洗顔パウダー全量に占めるタンパク分解酵素の配合量は０．０１〜５％が好ましく、０．１〜１％がより好ましい。 As the proteolytic enzyme derived from microorganisms used in the present invention, enzymes derived from microorganisms such as ASP protease, actinomycete protease, and black koji mold protease can be used. However, the present invention is not limited to these. Enzymes produced by microorganisms other than ASP, actinomycetes, and black koji molds can also be used. Moreover, protease (1) (derived from Bacillus subtilis) or protease (2) (derived from actinomycetes) described in the quasi-drug raw material standard can also be used. The blending amount of the proteolytic enzyme in the total amount of the face washing powder is preferably 0.01 to 5%, more preferably 0.1 to 1%.
本発明に用いる界面活性剤のうち、Ｎ−アシルアミノ酸塩としては、例えば、ラウロイ
ルグルタミン酸Ｎａ、ヤシ油脂肪酸アシルグルタミン酸トリエタノールアミン、ミリスチルグルタミン酸Ｋ、オレイルグルタミン酸Ｎａ等が挙げられ、ラウロイルグルタミン酸Ｎａが好ましい。洗顔パウダー全量に占めるＮ−アシルアミノ酸塩の配合量は例えば５〜３０％が挙げられ、好ましくは１０〜２０％が挙げられ、１５％が最も好ましい。アシルイセチオン酸塩としては、例えば、ココイルイセチオン酸Ｎａ（ヤシ油脂肪酸エチルエステルスルホン酸Ｎａ）、ラウリン酸エチルエステルスルホン酸Ｎａ、ヤシ油脂肪酸エチルエステルスルホン酸トリエタノールアミン等が挙げられ、ココイルイセチオン酸Ｎａが好ましい。洗顔パウダー全量に占めるアシルイセチオン酸塩の配合量は例えば２〜１５％が挙げられ、好ましくは３〜７％が挙げられ、５％が最も好ましい。オレフィンスルホン酸塩としては、例えば、炭素原子数１４〜１６のオレフィンからなるオレフィン（Ｃ１４−１６）スルホン酸Ｎａ（テトラデセンスルホン酸Ｎａ、等）が好適な例として挙げられる。洗顔パウダー全量に占めるオレフィンスルホン酸塩の配合量は例えば２〜１５％が挙げられ、好ましくは３〜７％が挙げられ、５％が最も好ましい。界面活性剤の組合せは、ラウロイルグルタミン酸Ｎａとココイルイセチオン酸Ｎａとオレフィン（Ｃ１４−１６）スルホン酸Ｎａとの組合せが好ましく、これらの配合比は、２〜３：１〜２：１〜２であることが好ましく、３：１：１であることがより好ましい。洗顔パウダー全量に占める界面活性剤の配合量としては、例えば、１５〜５０％が挙げられ、好ましくは２０〜３０％が挙げられ、２５％配合することがさらに好ましく、より具体的には、ラウロイルグルタミン酸Ｎａとココイルイセチオン酸Ｎａとオレフィン（Ｃ１４−１６）スルホン酸Ｎａとをそれぞれ、１０〜２０％、３〜７％、３〜７％配合することが好ましく、上記３成分をそれぞれ、１５％、５％、５％配合することが最も好ましい。なお、本発明の洗顔パウダーは、本発明の目的が損なわれない範囲において、上記必須の界面活性剤の他に、他の界面活性剤を配合することができる。
Among the surfactants used in the present invention, N-acyl amino acid salts include, for example, lauroyl glutamic acid Na, coconut oil fatty acid acyl glutamic acid triethanolamine, myristyl glutamic acid K, oleyl glutamic acid Na and the like, and lauroyl glutamic acid Na is preferable. . The blending amount of the N-acyl amino acid salt in the total amount of the face washing powder is, for example, 5 to 30%, preferably 10 to 20%, and most preferably 15%. Examples of acyl isethionate include cocoyl isethionate Na (coconut oil fatty acid ethyl ester sulfonate Na), lauric acid ethyl ester sulfonate Na, coconut oil fatty acid ethyl ester sulfonate triethanolamine, and the like. Acid Na is preferred. The amount of acyl isethionate in the total amount of the face washing powder is, for example, 2 to 15%, preferably 3 to 7%, and most preferably 5%. Preferred examples of the olefin sulfonate include olefin (C14-16) sulfonate Na (tetradecene sulfonate Na, etc.) composed of olefins having 14 to 16 carbon atoms. The blending amount of the olefin sulfonate in the total amount of the face washing powder is, for example, 2 to 15%, preferably 3 to 7%, and most preferably 5%. The combination of the surfactant is preferably a combination of Nauroyl glutamate, Na cocoyl isethionate and Na olefin (C14-16) sulfonate, and the blending ratio of these is 2-3: 1 to 2: 1-2. Preferably, it is preferably 3: 1: 1. The amount of the surfactant occupying in the Cleansing Powder entire amount, for example, include 15 to 50%, preferably include 20-30%, more preferably be formulated 25%, more specifically, Preferably, lauroyl glutamate Na, cocoyl isethionate Na and olefin (C14-16) sulfonate Na are blended in an amount of 10 to 20%, 3 to 7% and 3 to 7%, respectively. %, 5%, and 5% are most preferable. In addition, the face-washing powder of this invention can mix | blend other surfactant other than the said essential surfactant in the range which does not impair the objective of this invention.
本発明に用いるソルビトールは、市販のものを用いることができる。白色の粉末または結晶性粉末で、例えば日本薬局方または医薬部外品原料規格のものが使用できる。洗顔パウダー全量に占めるソルビトールの配合量は５〜１０％が好ましく、５〜７％がより好ましく、７％が最も好ましい。ソルビトールを配合することにより、ソルビトールを含まない場合、あるいは、他の糖（例えば、マルトース、グルコース、等）を配合した場合に比し、優れた酵素安定化効果と使用感が達成される。
本発明に用いるポリアクリル酸Ｎａは市販のものを用いることができる。白色粉末で、例えば食品添加物使用基準または医薬部外品原料規格のものが使用できる。洗顔パウダー全量に占めるポリアクリル酸Ｎａの配合量は例えば０．５〜５％が挙げられ、１〜２％が好ましい。
本発明に用いるグリシルグリシンは市販のものを用いることができる。白色の結晶性の粉末で、例えば医薬部外品原料規格のものが使用できる。洗顔パウダー全量に占めるグリシルグリシンの配合量は例えば０．００１〜０．１％が挙げられ、０．０１％が好ましい。
A commercially available product can be used as the sorbitol used in the present invention. A white powder or a crystalline powder, for example, a Japanese pharmacopoeia or quasi-drug material standard can be used. The blending amount of sorbitol in the total amount of the face washing powder is preferably 5 to 10%, more preferably 5 to 7%, and most preferably 7%. By blending sorbitol, an excellent enzyme stabilizing effect and usability can be achieved as compared with the case where sorbitol is not contained or when other saccharides (for example, maltose, glucose, etc.) are blended.
As the polyacrylic acid Na used in the present invention, a commercially available product can be used. For example, a white powder having a food additive usage standard or a quasi-drug material standard can be used. As for the compounding quantity of polyacrylic acid Na which occupies for face washing powder whole quantity, 0.5-5% is mentioned, for example, 1-2% is preferable.
A commercially available glycylglycine used in the present invention can be used. A white crystalline powder, for example, a quasi-drug material standard can be used. The blending amount of glycylglycine in the total amount of the face washing powder is, for example, 0.001 to 0.1%, preferably 0.01%.
本発明の洗顔パウダーには、本発明の目的が損なわれない範囲内で、若しくは更に本発明の効果を向上させたり、他の目的のために、通常、洗顔パウダーに配合し得る各種成分を配合することができる。このような他の成分としては、例えば、無機顔料、天然色素、保湿剤、抗炎症剤、殺菌剤、酸化防止剤、香料およびこれらの混合物等が挙げられ、これらは１種または２種以上組合せて使用することができる。 The facial cleansing powder of the present invention is blended with various components that can be usually blended into the facial cleansing powder within the range where the object of the present invention is not impaired, or for further improving the effects of the present invention or for other purposes. can do. Examples of such other components include inorganic pigments, natural dyes, humectants, anti-inflammatory agents, bactericides, antioxidants, perfumes, and mixtures thereof, and these are used alone or in combination of two or more. Can be used.
無機顔料としては、例えば、無水ケイ酸、ケイ酸マグネシウム、タルク、カオリン、ベントナイト、マイカ、雲母チタン、オキシ塩化ビスマス、酸化ジルコニウム、酸化マグネシウム、酸化亜鉛、炭酸カルシウム、炭酸マグネシウム、黄酸化鉄、ベンガラ、黒酸化鉄、グンジョウ、酸化クロム、水酸化クロム、カーボンブラック、カラミンまたはこれらの混合物等が挙げられる。天然色素としては、β−カロチン、ハイビスカス色素、サーフル
イエロー、カカオ色素、リボフラビン、クロロフィル、カラメルまたはこれらの混合物等が挙げられる。保湿剤としては、例えば、ヒアルロン酸、コンドロイチン硫酸、デルマタン硫酸、ヘパラン硫酸、ヘパリンおよびケランタン硫酸等のムコ多糖類およびこれらの塩；スフィンゴ脂質、コレステロール、リン脂質等の生体脂質；パントテン酸誘導体；コラーゲン、エラスチン、ケラチン等のタンパク質、これらの誘導体およびこれらの塩；アミノ酸、乳酸ナトリウム、ピロリドンカルボン酸ナトリウム等のＮＭＦ成分；アボガド油、ヒマシ油、オリーブ油、カカオ油、椿油、ヤシ油、木ロウ、ホホバ油、グレープシード油等の植物性油脂類；スクワラン、流動パラフィン、マイクロクリスタリンワックス、セレシンワックス、パラフィンワックス、ワセリン等の炭化水素類；セタノール、ステアリルアルコール、ヘキシルデカノール、オクチルドデカノール等の高級アルコール類；メチルポリシロキサン、デカメチルシクロペンタシロキサン等のシリコーン類；カミツレ抽出物、ダイズ抽出物、イチョウ抽出物、ローズマリー抽出物、オウバク抽出物、コンフリー抽出物、レイシ抽出物等の植物由来の抽出物またはこれらの混合物等が挙げられる。抗炎症剤としては、例えば、グリチルリチン酸、グリチルレチン酸、サリチル酸、メフェナム酸、フェニルブタゾン、インドメタシン、イブプロフェン、ケトプロフェン、アラントイン、グアイアズレン、これらの誘導体およびその塩またはこれらの混合物等が挙げられる。殺菌剤としては、例えば、塩化リゾチウム、安息香酸塩、ソルビン酸塩、デヒドロ酢酸塩、パラオキシ安息香酸エステル、塩化ベンゼトニウム、フェノキシエタノール、グルコン酸クロルヘキシジン、イソプロピルメチルフェノール、塩化セチルピリジニウム、ピロクトンオラミン、ジンクピリチオン、２，２，４'−トリクロロ−２'−ヒドロキシフェニルエーテル、トリクロカルバン、トリクロサン、塩化ベンザルコニウムまたはこれらの混合物等が挙げられる。酸化防止剤としては、例えば、ジブチルヒドロキシトルエン、ブチルヒドロキシアニソール、没食子酸プロピル、アスコルビン酸、ビタミンＥ類またはこれらの混合物等が挙げられる。
上記のほかに、粉末洗浄剤に基剤として使用されるデンプン（コーンスターチ等）、タルクなどがある。
本発明の洗顔パウダーを調製するには、上記各種原料成分を、公知の粉末化方法により粉末状とすることにより得ることができる。本発明により得られる洗顔パウダーは、水やお湯等に溶解して使用することができる。
本発明の洗顔パウダーは、美白化粧水と組み合わせて使用することができる。本発明の洗顔パウダーと美白化粧水とを組み合わせて使用することにより、美白有効成分の皮膚内への浸透性が高まる。
Examples of the inorganic pigment include silicic anhydride, magnesium silicate, talc, kaolin, bentonite, mica, mica titanium, bismuth oxychloride, zirconium oxide, magnesium oxide, zinc oxide, calcium carbonate, magnesium carbonate, yellow iron oxide, bengara , Black iron oxide, gunjo, chromium oxide, chromium hydroxide, carbon black, calamine or a mixture thereof. Examples of natural pigments include β-carotene, hibiscus pigment, surf yellow, cacao pigment, riboflavin, chlorophyll, caramel, and mixtures thereof. Examples of the humectant include mucopolysaccharides and salts thereof such as hyaluronic acid, chondroitin sulfate, dermatan sulfate, heparan sulfate, heparin and kelantan sulfate; biological lipids such as sphingolipid, cholesterol and phospholipid; pantothenic acid derivatives; collagen Proteins such as elastin and keratin, derivatives thereof and salts thereof; NMF components such as amino acids, sodium lactate and sodium pyrrolidone carboxylate; avocado oil, castor oil, olive oil, cacao oil, coconut oil, coconut oil, tree wax, jojoba Vegetable oils such as oil, grape seed oil; hydrocarbons such as squalane, liquid paraffin, microcrystalline wax, ceresin wax, paraffin wax, petrolatum; cetanol, stearyl alcohol, hexyldecanol, octyl Higher alcohols such as decanol; silicones such as methylpolysiloxane and decamethylcyclopentasiloxane; chamomile extract, soybean extract, ginkgo extract, rosemary extract, buckwheat extract, comfrey extract, litchi extract And plant-derived extracts or mixtures thereof. Examples of the anti-inflammatory agent include glycyrrhizic acid, glycyrrhetinic acid, salicylic acid, mefenamic acid, phenylbutazone, indomethacin, ibuprofen, ketoprofen, allantoin, guaiazulene, derivatives thereof and salts thereof or a mixture thereof. Examples of the disinfectant include lysotium chloride, benzoate, sorbate, dehydroacetate, p-hydroxybenzoate, benzethonium chloride, phenoxyethanol, chlorhexidine gluconate, isopropylmethylphenol, cetylpyridinium chloride, piroctone olamine, zinc pyrithione. 2,2,4′-trichloro-2′-hydroxyphenyl ether, triclocarban, triclosan, benzalkonium chloride or a mixture thereof. Examples of the antioxidant include dibutylhydroxytoluene, butylhydroxyanisole, propyl gallate, ascorbic acid, vitamins E, or a mixture thereof.
In addition to the above, there are starch (such as corn starch), talc and the like used as a base for powder detergents.
In order to prepare the face-washing powder of the present invention, the above-mentioned various raw material components can be obtained by making them into powder by a known pulverization method. The face washing powder obtained by the present invention can be used by dissolving in water, hot water or the like.
The face washing powder of the present invention can be used in combination with a whitening lotion. By using the facial cleansing powder and whitening lotion of the present invention in combination, the permeability of the whitening active ingredient into the skin is enhanced.
以下実施例、比較例および試験例により、本発明を更に詳細に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although an Example, a comparative example, and a test example demonstrate this invention further in detail, this invention is not limited to these.
実施例１、比較例１および試験例１〜３
表１に示す実施例１、比較例１の各成分を常法により混合、篩過して、洗顔パウダーを製造し、容器に充填した。容器は蓋付きプラスチック製容器で、蓋を閉じた状態で保存試験を行った。実施例１、比較例１の洗顔パウダーの４０℃、１２０日保存後の酵素力価を測定した結果を試験例１として表１中に記載した。
また、実施例１の洗顔パウダーについては、モニター３３名に対して実施した使用感の評価結果を、比較例１の洗顔パウダーについては、モニター２９名に対して実施した使用感の評価結果を、それぞれ試験例２および試験例３として表２および表３に示した。
モニターは、年齢２０〜５０才の女性から選択した。
Example 1, Comparative Example 1 and Test Examples 1-3
Each component of Example 1 and Comparative Example 1 shown in Table 1 was mixed and sieved by a conventional method to produce a face washing powder, which was filled in a container. The container was a plastic container with a lid, and a storage test was conducted with the lid closed. The results of measuring the enzyme titer of the face washing powder of Example 1 and Comparative Example 1 after storage at 40 ° C. for 120 days are shown in Table 1 as Test Example 1.
Moreover, about the face-washing powder of Example 1, the evaluation result of the feeling of use implemented with respect to 33 monitors was used, and about the face-washing powder of Comparative Example 1, the evaluation result of the feeling of use carried out with respect to 29 monitors was obtained. The results are shown in Table 2 and Table 3 as Test Example 2 and Test Example 3, respectively.
The monitor was selected from women aged 20-50.
表１の結果から明らかなように、４０℃、１２０日という過酷な条件下において、本発明の実施例１の洗顔パウダーは、比較例１の洗顔パウダーに比し、高い酵素力価が維持された。
また、表２および表３から明らかなように、総合的な使用感の観点で、比較例１の洗顔パウダーがどちらかというと不満である人の数が多かったのに対し、本発明の実施例１の洗顔パウダーは、８０％以上の人が好き、またはやや好きと回答しており、優れた使用感が確認された。
As is clear from the results in Table 1, under the severe conditions of 40 ° C. and 120 days, the face washing powder of Example 1 of the present invention maintains a higher enzyme titer than the face washing powder of Comparative Example 1. It was.
In addition, as apparent from Tables 2 and 3, from the viewpoint of overall usability, the number of people who were dissatisfied with the face-washing powder of Comparative Example 1 was rather high. 80% or more of the face washing powders of Example 1 answered that they liked or slightly liked it, and an excellent usability was confirmed.
試験例４
界面活性剤の配合比、配合量を決定するに際し、洗顔パウダー全量に対するラウロイルグルタミン酸Ｎａの配合量を９〜３０％の範囲で、ココイルイセチオン酸Ｎａの配合量を３〜１０％の範囲で、オレフィン（Ｃ１４−１６）スルホン酸Ｎａの配合量を３〜１０％の範囲で適宜変更し、残部をコーンスターチとして各成分を常法により混合、篩過して、複数の洗顔パウダーを製造した。また、上記の３種の界面活性剤のうちの２成分をそれぞれ７〜１８％の範囲で適宜配合し、残部をコーンスターチとする洗顔パウダーを同様に複数製造し、対照とした。得られた洗顔パウダーを、それぞれ１０人のパネルに使用してもらい、起泡性、低ぬめり性および低刺激性の観点から評価した。
上記３種の界面活性剤を配合した洗顔パウダーにおいて、対照洗顔パウダーに比し、より好ましい結果が得られた。とりわけ、ラウロイルグルタミン酸Ｎａを洗顔パウダー全量に対して１５％、ココイルイセチオン酸Ｎａを５％、オレフィン（Ｃ１４−１６）スルホン酸Ｎａを５％配合した洗顔パウダーにおいて最も優れた評価が得られた。
Test example 4
In determining the blending ratio and blending amount of the surfactant, the blending amount of sodium lauroyl glutamate relative to the total amount of the face washing powder is in the range of 9 to 30%, and the blending amount of Na cocoyl isethionate is in the range of 3 to 10%. The blending amount of the olefin (C14-16) sulfonic acid Na was appropriately changed within a range of 3 to 10%, and the remainder was mixed with corn starch and sieved by a conventional method to produce a plurality of face washing powders. Further, two components of the above-mentioned three kinds of surfactants were appropriately blended within a range of 7 to 18%, respectively, and a plurality of face washing powders having the remainder as corn starch were similarly produced and used as controls. The obtained facial cleansing powder was used for 10 panels each and evaluated from the viewpoints of foaming properties, low sliminess and low irritation.
In the face washing powder containing the above three surfactants, more preferable results were obtained as compared with the control face washing powder. In particular, the most excellent evaluation was obtained in the face washing powder containing 15% of lauroyl glutamate Na based on the total amount of the face washing powder, 5% Na of cocoyl isethionate and 5% of olefin (C14-16) sulfonate Na.
試験例５
実施例１および比較例１の洗顔パウダーならびに市販の酵素配合洗顔パウダー（プロテアーゼ（１）を配合する市販洗顔パウダーＡ、およびパパインを配合する市販洗顔パウダーＢ〜Ｄ）について、その酵素活性を、医薬部外品原料規格２００６中に記載の「プロテアーゼ力価試験法」に準じて実施した。
実施例１の洗顔パウダーの酵素活性を１００とした場合の相対酵素活性（％）を表４に示した。
Test Example 5
For the face washing powder of Example 1 and Comparative Example 1 and a commercially available enzyme-containing face-washing powder (a commercially available face-washing powder A containing Protease (1) and a commercially available face-washing powder B to D containing papain), the enzyme activity was determined as a pharmaceutical product. This was carried out in accordance with the “Protease titer test method” described in the quasi-material standard 2006.
Table 4 shows the relative enzyme activity (%) when the facial cleansing powder of Example 1 is defined as 100.
試験例６
実施例１の洗顔パウダー、プロテアーゼ（１）を配合する市販の酵素配合洗顔パウダー（市販洗顔パウダーＡ）および対照洗顔パウダー（実施例１の組成からプロテアーゼ（１）を除いた組成物）について、角質層除去効果を比較した。すなわち、ヒト皮膚に各洗顔パウダーの２５％水溶液を２分間処置した後、常法により表層をテープストリップし、タンパクをBrilliant Blue, Gentian Violet Bにて染色後、２００倍の光学顕微鏡にて検鏡、評価した。
実施例１の洗顔パウダーでは、タンパクの染色像がほとんど認められず、確実な角質層除去効果が確認されたのに対し、市販洗顔パウダーＡおよび対照洗顔パウダーの検鏡像は、試験開始前に採取したサンプルの検鏡像との差異が認められず、角質除去効果は確認できなかった。
Test Example 6
About the facial cleansing powder of Example 1, a commercially available enzyme-containing facial cleansing powder (commercial facial cleansing powder A) containing protease (1) and a control facial cleansing powder (a composition obtained by removing protease (1) from the composition of Example 1) The layer removal effect was compared. Specifically, human skin was treated with a 25% aqueous solution of each face-washing powder for 2 minutes, then the surface layer was tape stripped by a conventional method, the protein was stained with Brilliant Blue, Gentian Violet B, and examined with a 200 × optical microscope. ,evaluated.
In the face washing powder of Example 1, almost no protein staining image was observed, and a certain stratum corneum removal effect was confirmed. On the other hand, microscopic images of commercially available face washing powder A and control face washing powder were collected before the start of the test. No difference from the microscopic image of the sample was observed, and the keratin removal effect could not be confirmed.
試験例７
実施例１の洗顔パウダーについて、角質上層のみの除去効果を確認するために以下の試験を実施した。すなわち、３名の被験者を用いて、ヒト皮膚に実施例１の洗顔パウダーの２５％水溶液を２分間処置した後、常法により４回のテープストリップを実施し、得られたそれぞれのサンプル（各被験者について１層〜４層）についてタンパクをBrilliant Blue, Gentian Violet Bにて染色後、２００倍の光学顕微鏡にて検鏡、評価した。
１層目のサンプルについてはタンパクの染色像がほとんど認められず、確実な角質層除去効果が確認された。２層目のサンプルについては１層目に比べると弱いものの角質層除去効果が確認された。３層目および４層目のサンプルのタンパク染色像は、試験開始前に採取したサンプルの検鏡像との差異が認められず、実施例１の洗顔パウダーが角質上層のみの除去効果を有することが確認された。
Test Example 7
The following test was carried out on the face washing powder of Example 1 in order to confirm the effect of removing only the upper stratum corneum. That is, using 3 subjects, human skin was treated with a 25% aqueous solution of the face-washing powder of Example 1 for 2 minutes, and then tape stripping was carried out four times by a conventional method. The subject was stained with Brilliant Blue and Gentian Violet B for 1 layer to 4 layers), and then examined and evaluated with a 200 × optical microscope.
In the first layer sample, almost no protein staining image was observed, and a certain stratum corneum removal effect was confirmed. The second layer sample was weaker than the first layer, but the stratum corneum removal effect was confirmed. The protein-stained images of the third and fourth layer samples are not different from the microscopic images of the samples collected before the start of the test, and the face-washing powder of Example 1 has the effect of removing only the upper stratum corneum. confirmed.
試験例８
ヒトの皮膚に性状が近いとされるブタの皮膚を用いて、実施例１の洗顔パウダーの安全性を評価した。すなわち、ユカタンミニブタの皮膚に実施例１の洗顔パウダーの２５％水溶液、ならびに精製水を５分間処置した後、常法により皮膚組織断面の観察を実施し、無処置のものと比較した。
実施例１の洗顔パウダー処置群のサンプルは、角質層内部、表皮内部および真皮において、精製水処置群または無処置群と比較して組織学的な差異は認められず、実施例１の洗顔パウダーが角質層上層のみに作用し、安全であることが確認された。
Test Example 8
The safety of the face-washing powder of Example 1 was evaluated using porcine skin that is considered to be close to human skin. That is, the skin of Yucatan minipig was treated with a 25% aqueous solution of the face-washing powder of Example 1 and purified water for 5 minutes, and then the skin tissue cross-section was observed by a conventional method and compared with an untreated skin.
The sample of the face washing powder treatment group of Example 1 showed no histological differences in the stratum corneum, inside the epidermis and dermis compared to the purified water treatment group or the non-treatment group, and the face washing powder of Example 1 Has been confirmed to be safe only on the upper stratum corneum.
試験例９
実施例１の洗顔パウダーについて、パッチテストにより刺激性の有無を確認した。すなわち、健常人６０例に対し、実施例１の洗顔パウダーの０．２％水溶液（３０例）または１％水溶液（３０例）を用いて、常法による４８時間のクローズド・パッチテストを実施し、テープかぶれによる判定不能例１例を除く５９例について評価した。０．２％水溶液については４８時間後に（±）２例、７２時間後に（±）２例および貼付７日後に（±）１例が認められ、１％水溶液については４８時間後に（＋）１例、７２時間後に（±）１例、（＋）１例および貼付７日後に（±）１例が認められた。この結果から算出された皮膚刺激指数は、０．２％水溶液、１％水溶液でそれぞれ３．４および５．０となり、実施例１の洗顔パウダーが、きわめて低刺激性であることが確認された。
Test Example 9
About the face-washing powder of Example 1, the presence or absence of irritation was confirmed by the patch test. That is, a normal 48-hour closed patch test was conducted on 60 healthy subjects using the 0.2% aqueous solution (30 cases) or 1% aqueous solution (30 cases) of the facial cleansing powder of Example 1. In addition, 59 cases were evaluated except for one case that could not be determined due to tape rash. For 0.2% aqueous solution, (±) 2 cases were observed after 48 hours, (±) 2 cases after 72 hours and (±) 1 case after 7 days of application, and (+) 1 after 48 hours for 1% aqueous solution. Examples: (±) 1 case 72 hours later, (+) 1 case and (±) 1 case 7 days after application. The skin irritation index calculated from this result was 3.4 and 5.0 for the 0.2% aqueous solution and 1% aqueous solution, respectively, confirming that the face washing powder of Example 1 was extremely hypoallergenic. .
試験例１０
実施例１の洗顔パウダーについて、自分が敏感肌であると感じているモニター３２例を対象に、使用感に関する試験を実施した。すなわち、自身の肌を敏感肌（とても敏感肌、どちらかというと敏感肌）と認識している３０〜４５才の女性３２人を対象として、実施例１の洗顔パウダーを２日間で２回使用した後に、肌の変化の有無に関するアンケート調査を実施した。結果は、（良い意味での）肌の変化ありが７人（２２％）、（良い意味での）肌の変化ややありが１６人（５０％）、変化なしが８人（２５％）、（悪い意味での）肌の変化（つっぱり感）あり１人（３％）であった。試験を実施したモニターの７０％以上の人が、（良い意味での）肌の変化があった、あるいは、ややあったと回答しており、優れた使用感が確認された。なお、本試験においても副作用は認められず、実施例１の洗顔パウダーが敏感肌の人に対しても使用可能な低刺激性の組成物であることが確認された。
Test Example 10
About the face-washing powder of Example 1, the test regarding a usability | use_condition was implemented for 32 monitors who feel that they are sensitive skin. That is, the face washing powder of Example 1 is used twice in two days for 32 women aged 30 to 45 who recognize their skin as sensitive skin (very sensitive skin, rather sensitive skin). After that, we conducted a questionnaire survey on the presence or absence of skin changes. The results are 7 (22%) with skin changes (in a good sense), 16 (50%) with some skin changes (in a good sense), 8 (25%) without changes, One person (3%) had skin changes (in a bad sense). More than 70% of the monitors that conducted the test replied that they had changed or had a slight change in the skin (in a good sense), and an excellent usability was confirmed. In this test, no side effects were observed, and it was confirmed that the face washing powder of Example 1 was a hypoallergenic composition that could be used for people with sensitive skin.
試験例１１
実施例１の洗顔パウダーおよび対照洗顔パウダー（実施例１の組成からプロテアーゼ（１）を除いた組成物）に関し、薬用美白化粧水と併用した際の効果について評価した。すなわち、ヒト前腕外側を実施例１の洗顔パウダーまたは対照洗顔パウダーで５分間洗浄した後、アスコルビン酸２グルコシド（ＡＡ２Ｇ）を含有する薬用美白化粧水を同量塗布し、１時間後に、２０回のテープストリップを実施した。テープに付着した角質層からＡＡ２Ｇを抽出し、定量した。ＡＡ２Ｇ抽出量および全抽出量に占める割合を、１〜６層の合計、７〜１２層の合計および１３〜２０層の合計として表５にまとめた。
Test Example 11
Regarding the face washing powder of Example 1 and the control face washing powder (a composition obtained by removing protease (1) from the composition of Example 1), the effect when used in combination with a medicated whitening lotion was evaluated. That is, after the human forearm outer side was washed with the face washing powder or the control face washing powder of Example 1 for 5 minutes, the same amount of medicated whitening lotion containing ascorbic acid 2-glucoside (AA2G) was applied, and after 1 hour, 20 times A tape strip was performed. AA2G was extracted from the stratum corneum attached to the tape and quantified. The ratio of the AA2G extraction amount and the total extraction amount is summarized in Table 5 as the sum of 1 to 6 layers, the sum of 7 to 12 layers, and the sum of 13 to 20 layers.
効成分であるＡＡ２Ｇの中層および下層への浸透性が高まったことによるものと推定された。従って、実施例１の洗顔パウダーは、薬用美白化粧水と併用すると、より高い美白効果が期待される。
Claims (5)
（２）ラウロイルグルタミン酸Ｎａ、ココイルイセチオン酸Ｎａ、およびオレフィン（Ｃ１４−１６）スルホン酸Ｎａからなる界面活性剤
（３）ソルビトール
（４）ポリアクリル酸Ｎａ
（５）グリシルグリシン
を含有する洗顔パウダーであって、該洗顔パウダー全量に対して、ソルビトールを５〜１０％配合することを特徴とする洗顔パウダー。 (1) Proteolytic enzyme of microbial origin (2) Surfactant comprising Nauroyl glutamate, Na cocoyl isethionate , and olefin (C14-16) Na sulfonate (3) Sorbitol (4) Na polyacrylate
(5) Glycylglycine
A facial cleansing powder containing 5 to 10% of sorbitol based on the total amount of the facial cleansing powder.
（１）微生物起源のタンパク分解酵素 ０．２％(1) Proteolytic enzyme of microbial origin 0.2%
（２）ラウロイルグルタミン酸Ｎａ １５％、ココイルイセチオン酸Ｎａ ５％、およびオレフィン（Ｃ１４−１６）スルホン酸Ｎａ ５％(2) Lauroyl glutamate Na 15%, cocoyl isethionate Na 5%, and olefin (C14-16) sulfonate Na 5%
（３）ソルビトール ７％(3) Sorbitol 7%
（４）ポリアクリル酸Ｎａ １．２％(4) Polyacrylic acid Na 1.2%
（５）グリシルグリシン ０．０１％(5) Glycylglycine 0.01%
を含有する洗顔パウダー。Containing facial cleansing powder.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP6243672B2 (en) | 2012-09-20 | 2017-12-06 | 花王株式会社 | Cleaning composition for skin or hair |
| JP6235844B2 (en) | 2012-09-20 | 2017-11-22 | 花王株式会社 | Cleaning composition for skin or hair |
| JP6224390B2 (en) | 2012-09-20 | 2017-11-01 | 花王株式会社 | Internal olefin sulfonate composition and detergent composition containing the same |
| JP6300477B2 (en) | 2012-09-20 | 2018-03-28 | 花王株式会社 | Cleaning composition for skin or hair |
| JP6235843B2 (en) * | 2012-09-20 | 2017-11-22 | 花王株式会社 | Cleaning composition for skin or hair |
| JP6093740B2 (en) * | 2014-10-20 | 2017-03-08 | 株式会社ファンケル | Powder skin cleanser |
| JP5952932B1 (en) * | 2015-03-30 | 2016-07-13 | 株式会社ファンケル | Powder or granular skin cleansing composition |
| JP5952933B1 (en) * | 2015-03-30 | 2016-07-13 | 株式会社ファンケル | Skin cleansing composition |
| CN111956517B (en) * | 2020-09-20 | 2022-11-25 | 苏州蜜思肤化妆品股份有限公司 | Facial cleanser and preparation method thereof |
| WO2023017790A1 (en) | 2021-08-10 | 2023-02-16 | ロート製薬株式会社 | Cleaning composition and production method for same |
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| JPS60120810A (en) * | 1983-12-01 | 1985-06-28 | Tadao Shiraishi | Production of face washing powder containing enzyme |
| US5358656A (en) * | 1991-12-31 | 1994-10-25 | Lever Brothers Company, Division Of Conopco, Inc. | Compositions comprising glyceroglycolipids having an amine linkage as a surfactant or cosurfactant |
| JP2001026524A (en) * | 1999-07-13 | 2001-01-30 | Kansai Koso Kk | Powdery detergent composition |
| JP2001114624A (en) * | 1999-10-19 | 2001-04-24 | Mikimoto Pharmaceut Co Ltd | Composition for cosmetic and cleaning and storing solution |
| JP4886105B2 (en) * | 2000-07-25 | 2012-02-29 | 株式会社コーセー | Cleaning composition |
| JP2002322491A (en) * | 2001-04-23 | 2002-11-08 | Fancl Corp | Cleansing composition |
| JP4397269B2 (en) * | 2004-04-26 | 2010-01-13 | 関西酵素株式会社 | Proteolytic enzyme stabilizers, cosmetics and detergents |
| JP4834456B2 (en) * | 2006-05-12 | 2011-12-14 | 花王株式会社 | Powdered body wash composition |
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