JP2002212020A - Scrub cosmetic - Google Patents
Scrub cosmeticInfo
- Publication number
- JP2002212020A JP2002212020A JP2001012140A JP2001012140A JP2002212020A JP 2002212020 A JP2002212020 A JP 2002212020A JP 2001012140 A JP2001012140 A JP 2001012140A JP 2001012140 A JP2001012140 A JP 2001012140A JP 2002212020 A JP2002212020 A JP 2002212020A
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- Prior art keywords
- spherical
- carbon particles
- effect
- particles
- cosmetic
- Prior art date
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- Cosmetics (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する利用分野】本発明は、角質除去、皮脂汚
れ除去および脱臭効果に優れ、皮膚に対する刺激が少な
く使用感に優れたスクラブ化粧料に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a scrub cosmetic which is excellent in removing keratin, removing sebum stains and deodorizing, has little irritation to the skin, and is excellent in use feeling.
【０００２】[0002]
【従来の技術】近年、老化した角質細胞などを除去し、
適度な刺激を皮膚に与えることによって新陳代謝を促進
する目的で、スクラブ剤を配合した化粧料が提供されて
きている。かかるスクラブ剤としては、植物の内果皮や
種子或いは種子核の粉砕物の天然系や、ナイロン粉末，
ポリエチレン粉末等合成樹脂系などが用いられている。
しかし、これらのスクラブ剤には吸着能力がないため、
毛穴に詰まった油汚れの洗浄力は弱く、脱臭能を備えて
いなかった。一方、木炭や活性炭などの多孔質カーボン
は、比表面積が大きく吸着性に富むことから、従来より
吸着剤や脱臭剤として広く使用されており、また、その
吸着力を利用したスクラブ化粧料も知られている（例え
ば、特開平１０−２５２２３号公報）。2. Description of the Related Art In recent years, aging keratinocytes and the like have been removed,
Cosmetics containing a scrub agent have been provided for the purpose of promoting metabolism by giving an appropriate stimulus to the skin. Examples of such a scrub agent include a natural type of a crushed plant endocarp and seeds or seed kernels, nylon powder,
Synthetic resin materials such as polyethylene powder are used.
However, since these scrubbing agents do not have adsorption capacity,
The oil dirt clogging the pores was weak in detergency and did not have deodorizing ability. On the other hand, porous carbon such as charcoal and activated carbon has been widely used as an adsorbent and a deodorant because it has a large specific surface area and is highly adsorbent. (For example, JP-A-10-25223).
【０００３】[0003]
【発明が解決しようとする課題】しかしながらこれらの
多孔質カーボンは、何れも粉砕物であり、不定形で角張
った形状をしている。このため、スクラブ剤として使用
した場合、汚れ除去効果および脱臭効果は高いものの皮
膚への刺激が強すぎて、痛みや不快感を生じることがあ
った。また、従来より粒径の小さなカーボン粒子（例え
ば５μｍ程度以下）が化粧料の配合剤として使用されて
いるが、顔料としての使用目的であり、スクラブ効果を
目的としたものとは異なっていた。However, each of these porous carbons is a crushed product and has an irregular and angular shape. For this reason, when used as a scrub agent, although the stain removing effect and the deodorizing effect are high, the irritation to the skin is too strong, which may cause pain and discomfort. Further, carbon particles having a smaller particle size (for example, about 5 μm or less) have been used as a compounding agent for cosmetics, but they are intended for use as pigments, and are different from those intended for scrubbing effect.
【０００４】[0004]
【発明が解決しようとする課題】本発明者らは、かかる
課題を解決すべく鋭意検討した結果、球状の多孔質カー
ボン粒子をスクラブ剤として用いることにより、適度な
角質除去効果やマッサージ効果を有しながら、皮脂汚れ
除去効果が高く、脱臭効果に優れ、皮膚に対する刺激が
少なく使用感に優れること、特に毛穴につまったような
汚れを効果的に除去できること、を見出し本発明に至っ
た。すなわち、本発明は、（１）粒子直径が１５〜５０
０μｍの球状の多孔質カーボン粒子を配合したことを特
徴とするスクラブ化粧料を提供するもので、より具体的
には（２）球状の多孔質カーボン粒子がセルロース球状
粒子を炭素化したものであることを特徴とする上記
（１）記載のスクラブ化粧料、を提供するものである。The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, by using spherical porous carbon particles as a scrubbing agent, they have an appropriate exfoliating effect and a massage effect. However, they have found that they have a high sebum dirt removing effect, are excellent in deodorizing effect, are less irritating to the skin, and are excellent in usability, and in particular can effectively remove dirt clogged in pores, and have reached the present invention. That is, according to the present invention, (1) the particle diameter is 15 to 50;
The present invention provides a scrub cosmetic comprising 0 μm spherical porous carbon particles, and more specifically (2) spherical porous carbon particles obtained by carbonizing cellulose spherical particles. A scrub cosmetic according to the above (1), which is characterized in that:
【０００５】本発明で用いられる球状の多孔質カーボン
粒子は、微細な細孔を有するものでＢＥＴ比表面積が好
ましくは、１０ｍ2 ／ｇ以上、より好ましくは１００ｍ
2 ／ｇ、さらに好ましくは５００ｍ2 ／ｇ以上である。
比表面積が１０ｍ2 ／ｇよりも小さいものは、吸着能力
が低く、特に皮脂汚れの除去効果が小さいばかりでな
く、脱臭効果もほとんど無いことから、１０ｍ2 ／ｇ以
上のものが望ましい。また球状のカーボン粒子の直径
は、１５〜５００μｍ、好ましくは、２０〜１００μｍ
の範囲のものが適当である。粒径によって脱臭効果は変
わらないものの、直径が１５μｍより小さいカーボン粒
子は、スクラブ効果が小さく、角質除去効果が小さい。
また、粒子直径５００μｍより大きい球状カーボン粒子
は、使用感が悪くなることから上記の範囲の粒径のもの
が望ましい。また、カーボン粒子は球状のため、ローリ
ング効果によって、従来の粉砕型のカーボン粒子にはな
い優れた使用感を有する。それ故、本発明の化粧料は、
皮膚上の老廃物や毛穴に詰まった皮脂汚れを良好に吸着
除去し得ることができ、かつ、皮膚に違和感や刺激性を
与えることなく滑らかな使用感を呈する。[0005] The spherical porous carbon particles used in the present invention have fine pores and a BET specific surface area of preferably 10 m 2 / g or more, more preferably 100 m 2 / g or more.
2 / g, more preferably 500 m 2 / g or more.
Specific surface area is less than 10 m 2 / g, the adsorption capacity is low, in particular not only a small effect of removing sebum, deodorizing effect since little, 10 m 2 / g or more it is desirable. The diameter of the spherical carbon particles is 15 to 500 μm, preferably 20 to 100 μm.
Those in the range are suitable. Although the deodorizing effect does not change depending on the particle size, carbon particles having a diameter smaller than 15 μm have a small scrub effect and a small exfoliating effect.
In addition, spherical carbon particles having a particle diameter larger than 500 μm have a particle diameter in the above-mentioned range because the feeling of use is deteriorated. In addition, since the carbon particles are spherical, they have an excellent feeling of use that is not found in conventional pulverized carbon particles due to the rolling effect. Therefore, the cosmetic of the present invention
Waste products and sebum dirt clogged in pores on the skin can be satisfactorily adsorbed and removed, and a smooth feeling of use can be obtained without giving the skin uncomfortable feeling and irritation.
【０００６】本発明で用いる球状の多孔質カーボン粒子
は、通常、プラスチック、セルロース等の高分子物質の
球状粒子を不活性ガス雰囲気下で炭化処理するか、ター
ル、ピッチなどの有機物を造粒後不活性ガス雰囲気下で
炭化処理することにより製造される。高分子物質の球状
粒子の作成は、プラスチックの分野で通常行われてい
る、懸濁重合、粒状重合等の重合方法によるほか、分散
液を凝固剤と混合して球状に凝固させるセルロース粒子
の製法などが利用できる。前者の方法には、炭化処理の
点で架橋重合するプラスチック等が好ましい。The spherical porous carbon particles used in the present invention are usually prepared by carbonizing spherical particles of a high molecular substance such as plastic or cellulose in an inert gas atmosphere or granulating organic substances such as tar and pitch. It is manufactured by carbonizing under an inert gas atmosphere. The production of spherical particles of a polymer substance is carried out by a polymerization method such as suspension polymerization or granular polymerization, which is usually performed in the field of plastics, and a method of producing cellulose particles by mixing a dispersion with a coagulant to coagulate spherically. Etc. are available. In the former method, a plastic or the like that undergoes cross-linking polymerization in terms of carbonization is preferable.
【０００７】球状のカーボン粒子の比表面積は、主に炭
化処理条件によって制御できる。使用できる高分子物質
の球状粒子としては、比較的安価であること、炭化処理
時に発生する副生物が有害でないこと、細孔をコントロ
ールし易いことから、球状のセルロース粒子を用いるこ
とが好ましい。かかる球状のセルロース粒子を得る方法
は任意であるが、例えば、特開昭６２−２４６９３５号
公報に記載されているもの等を例示することができる。
セルロースとしては、該公報に記載されるように天然セ
ルロース、再生セルロース等のほか、これらと水溶性の
高分子化合物を合わせて用いることができる。これらは
目的とする球状粒子の大きさや炭化処理条件に応じて任
意に選択することができる。[0007] The specific surface area of the spherical carbon particles can be controlled mainly by carbonization conditions. As the spherical particles of the polymer substance that can be used, spherical cellulose particles are preferably used because they are relatively inexpensive, have no harmful by-products generated during the carbonization treatment, and are easy to control the pores. The method for obtaining such spherical cellulose particles is arbitrary, and examples thereof include those described in JP-A-62-246935.
As the cellulose, natural cellulose, regenerated cellulose and the like, as described in the publication, and water-soluble polymer compounds can be used in combination. These can be arbitrarily selected according to the desired size of the spherical particles and carbonization conditions.
【０００８】セルロース球状粒子から多孔質カーボン粒
子を調製する方法の一例を以下に示す。 （０）吸着水除去プロセス 球状セルロース粒子に吸着する吸着水を除去するため、
真空下で１００〜２５０℃で加熱する。 （１）脱水縮合プロセス その後、乾燥空気もしくは酸素通気下２５０℃〜３５０
℃、好ましくは、２７０℃〜３３０℃で、脱水縮合す
る。 （２）炭化処理プロセス 炭化処理は、３５０℃〜１５００℃、好ましくは５００
℃〜９００℃で、窒素等の不活性ガス雰囲気下で所定時
間、加熱する。 （３）賦活処理プロセス さらに必要に応じて比表面積を上げるために賦活処理を
行うことができる。賦活処理は、炭化処理後、炭酸ガ
ス、水蒸気やその他の酸化ガス雰囲気下で、３５０℃〜
１５００℃、好ましくは５００℃〜１０００℃で行う。An example of a method for preparing porous carbon particles from cellulose spherical particles is described below. (0) Adsorbed water removal process In order to remove the adsorbed water adsorbed on the spherical cellulose particles,
Heat at 100-250 ° C under vacuum. (1) Dehydration / condensation process Thereafter, under dry air or oxygen aeration at 250 ° C to 350 ° C.
C., preferably at 270.degree. (2) Carbonization process Carbonization is performed at 350 ° C to 1500 ° C, preferably 500 ° C.
C. to 900.degree. C. for a predetermined time in an atmosphere of an inert gas such as nitrogen. (3) Activation treatment process An activation treatment can be further performed, if necessary, to increase the specific surface area. After the carbonization treatment, the activation treatment is performed at 350 ° C. or below in an atmosphere of carbon dioxide gas, water vapor or other oxidizing gas.
It is carried out at 1500 ° C, preferably at 500 ° C to 1000 ° C.
【０００９】本発明のスクラブ化粧料において、球状の
多孔質カーボン粒子以外の成分は、通常スクラブ化粧料
に使用される油剤、脂肪酸類、界面活性剤、アルカリ物
質、アルコール類、エステル類、保湿剤、増粘剤、精製
水等の１種あるいは２種以上が用いられる。また、化粧
料は、クリーム状、ジェル状、ペースト状、液状、固形
状等の形態で提供される。球状の多孔質カーボン粒子の
化粧料への配合量は、特に限定されないが、化粧料全組
成の０．１〜５０重量％、好ましくは０．５〜１５重量
％配合するのが良い。配合量が０．１重量％より少ない
と皮脂汚れ除去効果や脱臭効果が弱く、また５０重量％
より多くなると使用感が悪くなり好ましくない。In the scrub cosmetic of the present invention, components other than the spherical porous carbon particles are oils, fatty acids, surfactants, alkali substances, alcohols, esters, humectants usually used in scrub cosmetics. , A thickener, purified water or the like. The cosmetic is provided in the form of a cream, a gel, a paste, a liquid, a solid, or the like. The amount of the spherical porous carbon particles to be added to the cosmetic is not particularly limited, but is preferably 0.1 to 50% by weight, preferably 0.5 to 15% by weight of the total composition of the cosmetic. If the amount is less than 0.1% by weight, the sebum dirt removing effect and the deodorizing effect are weak, and 50% by weight.
If the amount is more, the feeling of use becomes worse, which is not preferable.
【００１０】[0010]
【実施例】以下、本発明を実施例により更に詳細に説明
するが、本発明は、下記実施例により限定されるもので
はない。 製造例 特開昭６２−２４６９３５号公報記載の方法にて真球状
のセルロース粒子を調製し、乾燥後、篩い分けした（平
均粒径１００μｍ（７０〜１２５μｍ））。この球状の
セルロース粒子１００g を、真空下２００℃で５時間保
持し吸着水を除去した後、引き続き２８５℃で３時間処
理し、脱水縮合処理を行った。次に窒素ガス雰囲気下で
１０００℃で４時間処理後、自然冷却し、炭化処理を行
った。さらに炭酸ガス雰囲気下で９００℃まで１５時間
で昇温し、３時間２０分で５００℃まで降温後、自然冷
却し球状のカーボン粒子を得た。得られたカーボン粒子
の電子顕微鏡写真を図１に示す。カーボン粒子の平均粒
径は５０μｍでＢＥＴ比表面積は、６６３ｍ2 ／ｇであ
った。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. Production Example True spherical cellulose particles were prepared by the method described in JP-A-62-246935, dried, and sieved (average particle diameter 100 μm (70 to 125 μm)). 100 g of the spherical cellulose particles were held at 200 ° C. for 5 hours under vacuum to remove adsorbed water, and subsequently treated at 285 ° C. for 3 hours to carry out a dehydration condensation treatment. Next, after treatment at 1000 ° C. for 4 hours in a nitrogen gas atmosphere, the mixture was naturally cooled and carbonized. Further, the temperature was raised to 900 ° C. in a carbon dioxide gas atmosphere for 15 hours, lowered to 500 ° C. in 3 hours and 20 minutes, and then naturally cooled to obtain spherical carbon particles. FIG. 1 shows an electron micrograph of the obtained carbon particles. The average particle size of the carbon particles was 50 μm, and the BET specific surface area was 663 m 2 / g.
【００１１】実施例 表１中の成分１〜４を加熱溶解し７５℃に保ちながら、
製造例で得た球状の多孔質カーボン粒子（成分５）を加
え均一に分散した（Ａ液）。その他の成分６〜８を加熱
混合し７５℃に保った（Ｂ液）。Ａ液にＢ液を少しずつ
添加後、３０℃に冷却し、本発明のスクラブ化粧料（洗
顔化粧料）を得た。Example 1 Components 1 to 4 in Table 1 were dissolved by heating and maintained at 75 ° C.
The spherical porous carbon particles (component 5) obtained in Production Example were added and uniformly dispersed (Solution A). The other components 6 to 8 were mixed by heating and kept at 75 ° C (Solution B). After the solution B was added to the solution A little by little, the mixture was cooled to 30 ° C. to obtain a scrub cosmetic (facial cleansing cosmetic) of the present invention.
【００１２】 [0012]
【００１３】比較例１ 実施例において、球状の多孔質カーボン粒子を平均粒径
０．５μｍのカーボンブラックに代えた以外は、実施例
と同様に処理し、洗顔化粧料を得た。Comparative Example 1 A face-wash cosmetic was obtained in the same manner as in the example, except that the spherical porous carbon particles were replaced with carbon black having an average particle size of 0.5 μm.
【００１４】比較例２ 実施例において、球状の多孔質カーボンを含まない以外
は、実施例と同様に処理し、洗顔化粧料を得た。Comparative Example 2 A facial cleanser was obtained in the same manner as in the example except that spherical porous carbon was not used.
【００１５】評価例 上記実施例および比較例１および２で調製した洗顔化粧
料について、女性７名をパネルとする使用テストを行っ
た。評価は、各パネラーの使用中および使用後の評価を
下記の基準により評点し、評点の平均点を下記の４段階
評価基準を用いて判定した。結果を表２に示す。 （評点） ２ ： 良好、１ ： やや良好、０ ： 効果不明、
−１ ： 悪い （判定：評点の平均点、４段階評価基準） １．５以上 ： ◎ （非常に良好） １．０以上、１．５未満 ： ○ （良好） ０．５以上、１．０未満 ： △ （やや効果有り） ０．５未満 ： × （不良）Evaluation Example The facial cleansing cosmetics prepared in the above Examples and Comparative Examples 1 and 2 were subjected to a use test using seven women as panels. In the evaluation, the evaluation during and after use of each panel was evaluated according to the following criteria, and the average of the evaluations was determined using the following four-level evaluation criteria. Table 2 shows the results. (Score) 2: good, 1: fairly good, 0: effect unknown,
-1: bad (judgment: average score, four-level evaluation criteria) 1.5 or more: （(very good) 1.0 or more, less than 1.5: （(good) 0.5 or more, 1.0 Less than: △ (somewhat effective) Less than 0.5: × (poor)
【００１６】 [0016]
【００１７】上記の結果より、本発明のスクラブ化粧料
は、スクラブ効果が高いものの痛感などの不快感はな
く、使用感に優れるものであった。また、さっぱり感が
持続し、角質や毛穴に詰まった皮脂汚れ除去効果が高
く、使用中の消臭効果が高いものであった。From the above results, the scrub cosmetic of the present invention had a high scrub effect, but did not have any discomfort such as pain and was excellent in usability. In addition, the refreshing feeling was maintained, the effect of removing sebum stains clogged in keratin and pores was high, and the deodorizing effect during use was high.
【００１８】[0018]
【発明の効果】以上説明してきたように、本発明による
と、適度な角質除去効果やマッサージ効果を有しなが
ら、皮脂汚れ除去効果が高く、脱臭効果に優れ、皮膚に
対する刺激が少なく使用感に優れた、特に毛穴につまっ
たような汚れを効果的に除去できる、スクラブ化粧料が
提供される。As described above, according to the present invention, while having an appropriate exfoliating effect and a massage effect, the sebum dirt removing effect is high, the deodorizing effect is excellent, the skin is less irritating, and the feeling of use is improved. An excellent scrub cosmetic which can effectively remove dirt such as clogged pores is provided.
【図１】製造例で得られたカーボン粒子の電子顕微鏡写
真である。FIG. 1 is an electron micrograph of carbon particles obtained in a production example.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 向山 秀明 熊本県八代市植柳元町5595 (72)発明者 永岡 昭二 熊本県熊本市東町３−11−38 熊本県工業 技術センター内 (72)発明者 永田 正典 熊本県熊本市東町３−11−38 熊本県工業 技術センター内 Ｆターム(参考） 4C083 AB032 AB131 AB132 AC122 AC242 CC01 CC23 DD23 EE06 EE07 EE18 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hideaki Mukaiyama 5595 Ueyanagimotomachi, Yatsushiro-shi, Kumamoto (72) Inventor Shoji Nagaoka 3-11-38 Higashicho, Kumamoto-shi, Kumamoto Pref. Kumamoto Industrial Technology Center (72) Inventor Masanori Nagata 3-11-38 Higashicho, Kumamoto City, Kumamoto Prefecture F-term in Kumamoto Industrial Technology Center 4C083 AB032 AB131 AB132 AC122 AC242 CC01 CC23 DD23 EE06 EE07 EE18
Claims (3)
孔質カーボン粒子を配合することを特徴とするスクラブ
化粧料。1. A scrub cosmetic comprising spherical porous carbon particles having a particle diameter of 15 to 500 μm.
球状粒子を炭素化したものである、請求項１記載のスク
ラブ化粧料。2. The scrub cosmetic according to claim 1, wherein the spherical porous carbon particles are obtained by carbonizing cellulose spherical particles.
成の０．１〜５０重量％配合してなる、請求項１記載の
スクラブ化粧料。3. The scrub cosmetic according to claim 1, wherein spherical porous carbon particles are blended in an amount of 0.1 to 50% by weight based on the total composition of the cosmetic.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001012140A JP4565299B2 (en) | 2001-01-19 | 2001-01-19 | Scrub cosmetics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001012140A JP4565299B2 (en) | 2001-01-19 | 2001-01-19 | Scrub cosmetics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002212020A true JP2002212020A (en) | 2002-07-31 |
| JP4565299B2 JP4565299B2 (en) | 2010-10-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001012140A Expired - Fee Related JP4565299B2 (en) | 2001-01-19 | 2001-01-19 | Scrub cosmetics |
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| JP (1) | JP4565299B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005047908A (en) * | 2003-07-16 | 2005-02-24 | Taisho Pharmaceut Co Ltd | Antiinflammatory/analgesic composition for external use |
| KR101225958B1 (en) * | 2010-10-28 | 2013-01-29 | 하병조 | Foot cleansing Composition containing immobilized protease |
| WO2016117153A1 (en) * | 2015-01-22 | 2016-07-28 | 株式会社エム・イー・ティー | Scrub and method for using same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63238008A (en) * | 1987-03-25 | 1988-10-04 | Daicel Chem Ind Ltd | Cosmetic |
| JP2000159628A (en) * | 1998-11-27 | 2000-06-13 | Ichimaru Pharcos Co Ltd | Granule-formulated cosmetic composition |
| JP2000282093A (en) * | 1999-03-29 | 2000-10-10 | Masudaya:Kk | Cleaning material |
-
2001
- 2001-01-19 JP JP2001012140A patent/JP4565299B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63238008A (en) * | 1987-03-25 | 1988-10-04 | Daicel Chem Ind Ltd | Cosmetic |
| JP2000159628A (en) * | 1998-11-27 | 2000-06-13 | Ichimaru Pharcos Co Ltd | Granule-formulated cosmetic composition |
| JP2000282093A (en) * | 1999-03-29 | 2000-10-10 | Masudaya:Kk | Cleaning material |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005047908A (en) * | 2003-07-16 | 2005-02-24 | Taisho Pharmaceut Co Ltd | Antiinflammatory/analgesic composition for external use |
| JP4626202B2 (en) * | 2003-07-16 | 2011-02-02 | 大正製薬株式会社 | Piroxicam-containing external anti-inflammatory analgesic composition |
| KR101225958B1 (en) * | 2010-10-28 | 2013-01-29 | 하병조 | Foot cleansing Composition containing immobilized protease |
| WO2016117153A1 (en) * | 2015-01-22 | 2016-07-28 | 株式会社エム・イー・ティー | Scrub and method for using same |
| CN106456460A (en) * | 2015-01-22 | 2017-02-22 | 株式会社Met | Scrub and method for using same |
| KR101858461B1 (en) * | 2015-01-22 | 2018-05-16 | 가부시키가이샤 엠이티 | Scrub and method for using same |
| CN106456460B (en) * | 2015-01-22 | 2019-05-28 | 株式会社Met | Frosting agent and its application method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4565299B2 (en) | 2010-10-20 |
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