JP2004307414A - W/o/w emulsion skin care preparation for external use and method for producing the same - Google Patents

W/o/w emulsion skin care preparation for external use and method for producing the same Download PDF

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Publication number
JP2004307414A
JP2004307414A JP2003104350A JP2003104350A JP2004307414A JP 2004307414 A JP2004307414 A JP 2004307414A JP 2003104350 A JP2003104350 A JP 2003104350A JP 2003104350 A JP2003104350 A JP 2003104350A JP 2004307414 A JP2004307414 A JP 2004307414A
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Prior art keywords
emulsion
fatty acid
skin
acid ester
water
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JP2003104350A
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JP4282358B2 (en
Inventor
Takahisa Hirayama
高久 平山
Yoichi Yashiro
洋一 八代
Kunihiro Miyamoto
國寛 宮本
Michio Kitahara
路郎 北原
Satoru Nakada
悟 中田
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Nonogawa Shoji Ltd
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Nonogawa Shoji Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a W/O/W emulsion skin care preparation for external use, having preservation stability, skin safety and sense of use improved by formulating an alkyl acrylate copolymer, a fatty acid ester of dextrin and a water-soluble active ingredient such as an ascorbic acid derivative; and to provide a method for producing the skin care preparation. <P>SOLUTION: The W/O/W emulsion skin care preparation for external use is obtained by formulating the water-soluble active ingredient such as the ascorbic acid derivative in a W/O/W emulsion comprising an acrylic acid-alkyl methacrylate copolymer and the fatty acid ester of the dextrin. The W/O/W emulsion is obtained by dispersing and emulsifying inner water phase parts containing the water-soluble active ingredient in an oil phase part containing the fatty acid ester of the dextrin, and dispersing and emulsifying the resultant emulsion in an outer aqueous phase part containing the acrylic acid-alkyl methacrylate copolymer. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【0001】
【発明の属する技術分野】
本発明は、W/O/Wエマルション皮膚外用組成物およびその製造方法に関する。さらに詳しくは、保存安定性や皮膚安全性、使用感(延展性、粘稠性、保湿性)などに優れたW/O/Wエマルション皮膚外用組成物およびその製造方法に関する。
【0002】
【従来の技術】
アクリル酸メタクリル酸アルキル共重合体は主として水溶性増粘剤として利用されているが、親水性乳化剤としての機能も具備しているためにO/Wエマルションが調製可能である(特許文献1)。さらに、オイルゲル化剤として知られるデキストリン脂肪酸エステルは、親油性乳化剤としても働くためにW/Oエマルションが調製できる(特許文献2)。これら2種類の高分子を使用してエマルション調製を行うと、従来の各種低分子界面活性剤を用いた場合と比較したときに、皮膚安全性が高く、同等かそれ以上の乳化能を有し、使用感のよりよい皮膚外用組成物が得られる。
一方、現在汎用されているエマルション皮膚外用組成物にはO/WまたはW/Oエマルションがあるが、新たな使用感を付与するエマルション皮膚外用組成物としてW/O/Wエマルション皮膚外用組成物が注目されている。そして、アクリル酸メタクリル酸アルキル共重合体またはデキストリン脂肪酸エステルを利用して、W/O/Wエマルションを得る方法もいくつか示されている(特許文献3〜5)。
だが、アクリル酸メタクリル酸アルキル共重合体とデキストリン脂肪酸エステルの併用に関しては未だ報告されていない。現在知られているこれらの事例はW/O/Wエマルションの安定性を高めることを目的として、多量の各種低分子界面活性剤と組み合わせているために皮膚安全性に注意しなければならなかったり、他の増粘剤と組み合わせているために使用感がよくなかったりというように何らかの問題を含んでいる。
また、アスコルビン酸誘導体にはシミやソバカスの原因となるメラニンの生成抑制や還元、排出促進などの効果があることが知られており、多くの美白化粧品の有効成分(美白剤)として利用されている(非特許文献1)。しかし、アスコルビン酸誘導体に限らず種々の水溶性活性成分の水溶液の中には非常に不安定で空気中の酸素によって酸化されて分解してしまうものがあるため、その分解を防御する手段の確立が求められている。
【0003】
【特許文献1】
特開平8−126831号公報
【特許文献2】
特許3236926号公報
【特許文献3】
特開2002−275029号公報
【特許文献4】
特開平11−33391号公報
【特許文献5】
特公平7−530号公報
【非特許文献1】
関根 茂、外5名、「化粧品ハンドブック」、日光ケミカルズ株式会社、外2社、平成8年11月、P.462−465
【0004】
【発明が解決しようとする課題】
つまり現存する問題点としては、第一に保存安定性や皮膚安全性、使用感などという面で必ずしもすべてを満足しているW/O/Wエマルション皮膚外用組成物のものがないことであり、第二にアスコルビン酸誘導体などの水溶性活性成分が水溶液中では非常に不安定で分解されやすいことである。
本発明は上記従来技術の課題であるアスコルビン酸誘導体などの水溶性活性成分の安定性が高められ、かつ保存安定性や皮膚安全性、使用感といった問題をすべて解決した、W/O/Wエマルション皮膚外用組成物およびその製造方法を提供することを目的とする。
【0005】
【課題を解決するための手段】
本発明者等は上記事項に鑑みて、よりよいW/O/Wエマルション皮膚外用組成物を得るべく鋭意検討した結果、まず、デキストリン脂肪酸エステルを用いて、アスコルビン酸誘導体などの水溶性活性成分を含む内水相部を分散させたW/Oエマルションを調製した後に、アクリル酸メタクリル酸アルキル共重合体を含む外水相中に分散乳化させることで、水溶性活性成分の安定性を高め、かつW/O/Wエマルション皮膚外用組成物の保存安定性や使用感といった点で従来よりも優れたものを得ることに成功し、本発明を完成させるに至った。
【0006】
すなわち、本発明はアスコルビン酸誘導体などの水溶性活性成分を安定な状態で含有した、アクリル酸メタクリル酸アルキル共重合体とデキストリン脂肪酸エステルから構成されるW/O/Wエマルション皮膚外用組成物およびその製造方法を提供する発明である。なお、本発明において「W/O/Wエマルション皮膚外用組成物」とは、広く外皮に適用可能な組成物のことを意味するものであり、具体的な製品の化粧剤、医薬品、医薬部外品等の薬事法上等の区別を問うものではない。
【0007】
以下、本発明の構成について詳述する。
【0008】
本発明で用いられるアクリル酸メタクリル酸アルキル共重合体は好ましくは分子量が50万〜300万、アルキル基の炭素数が10〜30であり、市販されているものの具体例としてはペミュレンTR−1やペミュレンTR−2(いずれもB.F.Goodrich製)が挙げられる。また、デキストリン脂肪酸エステルは好ましくは糖重合度が5〜50、糖単位当りのエステル置換度が1.0〜2.5、脂肪酸の炭素数が8〜24のものであり、市販されているものの具体例としてはレオパールTLやレオパールKL、レオパールTT(いずれも千葉製粉製)が挙げられる。この範囲外では乳化安定性や使用性などに何らかの問題点があるために好ましくない場合がある。アクリル酸メタクリル酸アルキル共重合体とデキストリン脂肪酸エステルは共に公知の方法で製造されたものを本発明の皮膚外用組成物に配合することができ、また例として挙げた以外の市販のものを用いることができる。
【0009】
アクリル酸メタクリル酸アルキル共重合体は水溶性増粘剤の役割だけでなく親水性乳化剤としても効果を発揮している。その配合量は特に限定されないが、好ましくは0.05〜5%、さらに好ましくは0.1〜2%とすると、十分な乳化能を示して保存安定性の顕著な向上が見られる。また、デキストリン脂肪酸エステルはオイルゲル化剤ならびに親油性乳化剤としての役割も持つ。この配合量も特に限定はされないが、好ましくは0.05〜10%、さらに好ましくは0.1〜5%とすると、十分な乳化能を示して保存安定性も顕著に向上する。これら2種類の乳化剤については、それぞれの濃度範囲未満では十分な乳化能を望みにくい場合があり、反対に濃度範囲を超えて配合した場合には乳化能の増強は認められにくく不経済であるうえに、よれやきしみといった使用感の問題が生じることがある。反対に濃度範囲内にあるときには、他の界面活性剤や増粘剤を配合していなくても満足できる乳化能が確保される。
【0010】
本発明で用いられる水溶性活性成分とは外皮に適用可能な成分であれば特に限定されない。具体例を挙げるならば、アミノ酸とそのペプチドやタンパク質、コラーゲン、ビタミン、多価アルコールや多糖類、その他の各種動植物抽出物や合成物などが考えられる。これらの水溶性活性成分は公知の方法で製造されたものを本発明皮膚外用組成物に配合することができ、市販のものを用いることができる。また、その配合量については特に限定されるものではない。
【0011】
本発明で用いられる水溶性活性成分の一種であるアスコルビン酸誘導体にはアスコルビン酸リン酸エステル、アスコルビン酸アルキルエステル、アスコルビン酸硫酸エステル等が挙げられる。具体的には、L−アスコルビン酸−2−リン酸エステル、L−アスコルビン酸−3−リン酸エステル、DL−α−トコフェロール−2−L−アスコルビン酸リン酸ジエステル等のアスコルビン酸リン酸エステル、パルミチン酸L−アスコルビル、イソステアリン酸L−アスコルビル、ジオレイン酸L−アスコルビル等のアスコルビン酸アルキルエステル、L−アスコルビン酸−2−硫酸エステル、L−アスコルビン酸−3−硫酸エステル等のアスコルビン酸硫酸エステル等が挙げられ、これらの塩に関しても使用可能である。例えばナトリウム塩やカリウム塩等のアルカリ金属塩、カルシウム塩やマグネシウム塩等のアルカリ土類金属塩を用いることができる。
【0012】
また、アスコルビン酸配糖体に関しても用いることができる。具体的にはマンノース、フルクトース、ガラクトース、キシロース、アラビノース等の配糖体がある。
【0013】
アスコルビン酸誘導体は公知の方法で製造されたものを本発明皮膚外用組成物に配合することができ、市販のものを用いることができる。
【0014】
アスコルビン酸誘導体の配合量については特に限定されないが、0.01〜20%とすることが好ましい。0.01%未満では相乗的な美白効果が望めない場合があり、20%を超えて含有することは可能であるが、美白効果の顕著な増加は認められず経済的ではない。また、トコフェロール誘導体を添加することでより一層の美白効果を望むことができる。
【0015】
本発明におけるW/O/Wエマルション皮膚外用組成物の製造方法については特に限定されず、常法によって製造できるが、好ましくは次述のような製造方法で調製すると保存安定性に優れたW/O/Wエマルション皮膚外用組成物が得られる。まず、デキストリン脂肪酸エステルを含有する油相部に水溶性活性成分を含む内水相部を分散乳化してW/Oエマルションを得る。この時の乳化温度は好ましくは60〜90℃、さらに好ましくは70〜85℃とすることで、より微細な粒子を持つ安定なW/Oエマルションを調製できる。その後、好ましくは70℃以下の温度条件で、このW/Oエマルション部をアクリル酸メタクリル酸アルキル共重合体が含有された外水相部に分散乳化させることによって、W/O/Wエマルション皮膚外用組成物が調製できる。
【0016】
本発明の皮膚外用組成物は上記必須成分の他に、通常の化粧料、医薬部外品、医薬品等に用いられる各種成分、例えば油性成分、乳化剤、保湿剤、増粘剤、薬効成分、防腐剤、顔料、粉体、pH調整剤、紫外線吸収剤、抗酸化剤、香料等を適宜配合することができる。
【0017】
【発明の効果】
本発明では、アクリル酸メタクリル酸アルキル共重合体とデキストリン脂肪酸エステルによって構成されるW/O/Wエマルションの内水相部にアスコルビン酸誘導体などの水溶性活性成分を配合することにより、水溶性活性成分の分解を防ぎ、かつ保存安定性や皮膚安全性、使用感が改善されたW/O/Wエマルション皮膚外用組成物およびその製造方法が提供される。
【0018】
【実施例】
表1にはアクリル酸メタクリル酸アルキル共重合体に替えて、種々の親水性界面活性剤や水溶性増粘剤を使用したときのアスコルビン酸誘導体や製剤自体の経時的安定性および使用感について検討した結果を示す。また、表2にはデキストリン脂肪酸エステルを他の親油性界面活性剤や油溶性増粘剤に替えたときの製剤の経時的安定性や使用感について検討した結果を示す。
なお、製剤の製造方法についてはすべて同様の手順で行った。まず、80℃の温度下で油相部と内水相部を分散乳化してW/Oエマルションを調製した後に、このW/Oエマルションと外水相部を分散乳化させて30℃まで冷却し、目的とするW/O/Wエマルション製剤を得た。
それぞれの製剤におけるアスコルビン酸誘導体の安定性確認には液体クロマトグラフ法で定量して判断した。測定は室温と40℃で6ヶ月間経過後に行い、判定基準は下記の4段階で評価した。
アスコルビン酸誘導体安定性評価項目
◎:調製直後の定量測定値と比較して6ヵ月後の測定値が範囲±3%以内に入っている。
○:6ヵ月後の測定値が範囲±5%以内に入っている。
△:6ヵ月後の測定値が範囲±10%以内に入っている。
×:6ヵ月後の測定値が範囲±10%以上に外れている。
製剤の経時観察について室温は1年経過後、50℃は2ヵ月経過後に評価を行い、指標には下記の4段階の保存安定性評価項目を用いた。
保存安定性評価項目
◎:相状態の変化がほとんど認められない。
○:顕微鏡で観察すると若干の乳化粒子径の増大が確認できる。
△:相分離は確認できないが、顕微鏡で観察すると顕著な乳化粒子径の増大が確認できる。
×:二相に分離していることが目視でも確認できる。
また、使用感評価については20人のパネラーに本発明皮膚外用組成物を実際に使用してもらい評価した。塗布時の延展性、粘稠性、塗布後の保湿性について下記の5段階の使用感評価項目で評点付けをしてもらった。
使用感評価項目
5点:非常に良好
4点:良好
3点:普通
2点:悪い
1点:非常に悪い
得られた合計点を下記に示す4段階の使用感点数評価に従って最終的な判断をした。
使用感点数評価
◎:合計点数80点以上、使用感は非常に良い。
○:合計点数70点以上、使用感は良い。
△:合計点数50点以上、使用感は悪い。
×:合計点数50点以下、使用感は非常に悪い。
なお、各試料については通常使用されており、実際に市販されている原料を採用した。
【0019】
【表1】種々の親水性界面活性剤や水溶性増粘剤を使用したW/O/Wエマルションとの比較

Figure 2004307414
【0020】
【表2】種々の親油性界面活性剤や油溶性増粘剤を使用したW/O/Wエマルションとの比較
Figure 2004307414
【0021】
表1および表2の結果より、アクリル酸メタクリル酸アルキル共重合体とデキストリン脂肪酸エステルを配合することにより、安定性や使用感に優れたW/O/Wエマルション皮膚外用組成物が得られることがわかった。また、内水相部のアスコルビン酸誘導体の安定性が高いことも実証された。
【0022】
表3にアクリル酸メタクリル酸アルキル共重合体を様々な割合で配合した製剤を調製し、製剤自体の経時的変化および使用感について検討した結果を示す。また、表4にはデキストリン脂肪酸エステルを様々な割合で配合した製剤の経時的変化および使用感を検討した結果を示す。なお、それぞれの製造方法に関しては前述の表1、表2と同様に行い、アスコルビン酸誘導体や製剤の保存安定性および使用感評価も同じ指標で行った。
【0023】
【表3】アクリル酸メタクリル酸アルキル共重合体の様々な濃度における試験結果
Figure 2004307414
【0024】
【表4】デキストリン脂肪酸エステルの様々な濃度における試験結果
Figure 2004307414
【0025】
表3および表4の結果より、アクリル酸メタクリル酸アルキル共重合体の配合量については、好ましくは0.05〜5%、さらに好ましくは0.1〜2%とすると、十分な乳化能を示して保存安定性の顕著な向上が見られる。また、デキストリン脂肪酸エステルの配合量については、好ましくは0.05〜10%、さらに好ましくは0.1〜5%とすると、十分な乳化能を示して保存安定性も顕著に向上する。
【0026】
表1から表4の結果より、アクリル酸メタクリル酸アルキル共重合体とデキストリン脂肪酸エステルからW/O/Wエマルションを生成し、その内水相部に水溶性活性成分であるアスコルビン酸誘導体を含有させることにより、保存安定性や使用感などに優れた有用なW/O/Wエマルション皮膚外用組成物が提供できることが明らかとなった。
【0027】
【発明の実施の形態】
以下に本発明を詳細に説明するための実施例を挙げるが、本発明はこれらに限定されるものではない。
【0028】
実施例1 高機能クリーム
配合成分 配合量(重量%)
(1) デキストリン脂肪酸エステル
(レオパールTL) 0.4
(2) 酢酸トコフェロール 0.3
(3) スクワラン 11.3
(4) ミリスチン酸オクチルドデシル 8.0
(5) メチルフェニルポリシロキサン 4.0
(6) 香料 0.2
(7) アスコルビン酸リン酸ナトリウム 8.0
(8) クエン酸ナトリウム 8.0
(9) 硫酸アルミニウムカリウム 0.1
(10)グリチルリチン酸ジカリウム 0.1
(11)アクリル酸メタクリル酸アルキル共重合体
(ペミュレンTR−1) 0.6
(12)1,3−ブチレングリコール 8.0
(13)パラベン 適 量
(14)グリセリン 8.0
(15)水酸化カリウム 適 量
(16)精製水 残 余
【0029】
〔製法〕(16)の一部に(7)、(8)を溶解し、(1)〜(6)の油相部に75℃の温度下で添加し乳化、W/Oエマルションを得た。これを一部の(16)に(9)〜(14)を分散溶解させた外水相部と混合し、残りの(16)で溶解させた(15)で中和し、均一分散させる。
【0030】
実施例2 乳液
配合成分 配合量(重量%)
(1) デキストリン脂肪酸エステル
(レオパールTT) 0.2
(2) POE(4)グリセリルモノステアレート 0.1
(3) シクロメチコン 5.0
(4) ジカプリン酸ネオペンチルグリコール 5.0
(5) 香料 0.1
(6) クエン酸カリウム 2.0
(7) アスコルビン酸リン酸マグネシウム 3.0
(8) アクリル酸メタクリル酸アルキル共重合体
(ペミュレンTR−2) 0.2
(9) モノステアリン酸デカグリセリル 0.5
(10)コハク酸トコフェロールカルシウム 8.0
(11)1,3−ブチレングリコール 5.0
(12)パラベン 適 量
(13)グリセリン 10.0
(14)エデト酸塩 0.1
(15)アミノメチルプロパンジオール 適 量
(16)精製水 残 余
【0031】
〔製法〕(16)の一部に(6)、(7)を溶解し、(1)〜(5)の油相部に80℃の温度下で添加し乳化、W/Oエマルションを得た。これを一部の(16)に(8)〜(14)を分散溶解させた外水相部と混合し、残りの(16)で溶解させた(15)で中和し、均一分散させる。
【0032】
実施例3 美白クリーム
配合成分 配合量(重量%)
(1) デキストリン脂肪酸エステル
(レオパールKL) 2.0
(2) 流動パラフィン 10.0
(3) ジメチコン 5.0
(4) ニコチン酸トコフェロール 2.0
(5) 香料 0.2
(6) クエン酸ナトリウム 2.0
(7) アスコルビン酸硫酸カリウム 10.0
(8) ポリリン酸ナトリウム 0.1
(9) アクリル酸メタクリル酸アルキル共重合体
(ペミュレンTR−1) 1.0
(10)モノオレイン酸デカグリセリル 0.5
(11)1,3−ブチレングリコール 5.0
(12)パラベン 適 量
(13)グリセリン 11.0
(14)水酸化カリウム 適 量
(15)精製水 残 余
【0033】
〔製法〕(15)の一部に(6)〜(8)を溶解し、(1)〜(5)の油相部に70℃の温度下で添加し乳化、W/Oエマルションを得た。これを一部の(15)に(9)〜(13)を分散溶解させた外水相部と混合し、残りの(15)で溶解させた(14)で中和し、均一分散させる。
【0034】
実施例1〜3で示した本発明品は、アクリル酸メタクリル酸アルキル共重合体とデキストリン脂肪酸エステルからW/O/Wエマルションを生成し、その内水相部には水溶性活性成分であるアスコルビン酸誘導体が含有されたW/O/Wエマルション皮膚外用組成物であり、保存安定性や皮膚安全性、使用感といった面で満足のできるものであった。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a W / O / W emulsion skin external composition and a method for producing the same. More specifically, the present invention relates to a W / O / W emulsion skin external composition excellent in storage stability, skin safety, feeling of use (spreadability, stickiness, moisturizing properties) and the like, and a method for producing the same.
[0002]
[Prior art]
Alkyl acrylate alkyl methacrylate copolymers are mainly used as water-soluble thickeners, but they also have a function as a hydrophilic emulsifier, so that an O / W emulsion can be prepared (Patent Document 1). Furthermore, a dextrin fatty acid ester known as an oil gelling agent also works as a lipophilic emulsifier, so that a W / O emulsion can be prepared (Patent Document 2). When an emulsion is prepared using these two types of polymers, the skin safety is high and the emulsifying ability is equal to or higher than that of the case using conventional various low molecular surfactants. Thus, a composition for external use on the skin with a better feeling of use can be obtained.
On the other hand, there are O / W and W / O emulsions as currently used emulsion skin external compositions, and W / O / W emulsion skin external compositions as emulsion skin external compositions that impart a new feeling of use. Attention has been paid. Some methods of obtaining a W / O / W emulsion using an alkyl acrylate alkyl methacrylate copolymer or a dextrin fatty acid ester are also disclosed (Patent Documents 3 to 5).
However, no report has been made yet on the combined use of an alkyl acrylate methacrylate copolymer and a dextrin fatty acid ester. In these known cases, the safety of W / O / W emulsions must be considered in order to enhance the stability of the emulsions in combination with a large amount of various low molecular surfactants. However, there are some problems such as the feeling of use being poor due to the combination with other thickeners.
In addition, ascorbic acid derivatives are known to have the effect of suppressing, reducing, and promoting the production of melanin, which causes spots and freckles, and are used as an active ingredient (whitening agent) of many whitening cosmetics. (Non-Patent Document 1). However, not only ascorbic acid derivatives but also various aqueous solutions of water-soluble active ingredients are extremely unstable and may be oxidized and decomposed by oxygen in the air. Is required.
[0003]
[Patent Document 1]
JP-A-8-126831 [Patent Document 2]
Japanese Patent No. 3236926 [Patent Document 3]
JP 2002-275029 A [Patent Document 4]
JP-A-11-33391 [Patent Document 5]
Japanese Patent Publication No. 7-530 [Non-Patent Document 1]
Shigeru Sekine, 5 others, "Cosmetics Handbook", Nikko Chemicals Co., Ltd., 2 other companies, November 1996, p. 462-465
[0004]
[Problems to be solved by the invention]
That is, the existing problems are, first of all, that there is no W / O / W emulsion skin external composition which satisfies all requirements in terms of storage stability, skin safety, feeling of use, and the like. Second, water-soluble active ingredients such as ascorbic acid derivatives are very unstable and easily decomposed in an aqueous solution.
The present invention provides a W / O / W emulsion in which the stability of a water-soluble active ingredient such as an ascorbic acid derivative, which is a problem of the prior art, is improved, and all problems such as storage stability, skin safety, and feeling of use are solved. An object of the present invention is to provide a composition for external use on the skin and a method for producing the same.
[0005]
[Means for Solving the Problems]
In view of the above, the present inventors have conducted intensive studies to obtain a better W / O / W emulsion skin external composition. As a result, first, a dextrin fatty acid ester was used to prepare a water-soluble active ingredient such as an ascorbic acid derivative. After preparing a W / O emulsion in which the internal aqueous phase portion is dispersed, the emulsion is dispersed and emulsified in an external aqueous phase containing an alkyl methacrylate copolymer to enhance the stability of the water-soluble active ingredient, and The present inventors succeeded in obtaining a W / O / W emulsion composition for external use on the skin which was superior to the conventional composition in terms of storage stability and feeling of use, and completed the present invention.
[0006]
That is, the present invention provides a W / O / W emulsion external skin composition comprising an alkyl methacrylate copolymer and a dextrin fatty acid ester, which contains a water-soluble active ingredient such as an ascorbic acid derivative in a stable state, and its composition. It is an invention that provides a manufacturing method. In the present invention, the “w / o / w emulsion skin external composition” means a composition that can be widely applied to the outer skin, and includes cosmetics, pharmaceuticals, and quasi-drugs of specific products. It does not question the distinction of pharmaceutical products under the Pharmaceutical Affairs Law.
[0007]
Hereinafter, the configuration of the present invention will be described in detail.
[0008]
The alkyl acrylate alkyl methacrylate copolymer used in the present invention preferably has a molecular weight of 500,000 to 3,000,000, and an alkyl group having 10 to 30 carbon atoms. Specific examples of commercially available products include Pemulen TR-1 and And Pemulen TR-2 (both manufactured by BF Goodrich). The dextrin fatty acid ester preferably has a degree of sugar polymerization of 5 to 50, a degree of ester substitution per saccharide unit of 1.0 to 2.5, and a fatty acid having 8 to 24 carbon atoms. Specific examples include Leopearl TL, Leopearl KL, and Leopearl TT (all manufactured by Chiba Flour Milling). Outside this range, there are some problems in emulsion stability, usability, and the like, which may not be preferable. Alkyl acrylate alkyl methacrylate copolymer and dextrin fatty acid ester can both be produced by a known method and blended in the composition for external use on skin of the present invention. Can be.
[0009]
The alkyl acrylate alkyl methacrylate copolymer is effective not only as a water-soluble thickener but also as a hydrophilic emulsifier. The blending amount is not particularly limited, but is preferably 0.05 to 5%, more preferably 0.1 to 2%, so that sufficient emulsifying ability is exhibited and storage stability is remarkably improved. The dextrin fatty acid ester also has a role as an oil gelling agent and a lipophilic emulsifier. Although the amount is not particularly limited, it is preferably 0.05 to 10%, more preferably 0.1 to 5%, so that sufficient emulsifying ability is exhibited and storage stability is remarkably improved. When these two types of emulsifiers are less than the respective concentration ranges, it may be difficult to obtain a sufficient emulsifying ability. On the other hand, when the emulsifying agents are blended beyond the concentration range, enhancement of the emulsifying ability is hardly recognized and is uneconomical. In some cases, problems such as twisting and squeaking may occur. On the other hand, when the concentration is within the range, a satisfactory emulsifying ability can be ensured even when no other surfactant or thickener is added.
[0010]
The water-soluble active ingredient used in the present invention is not particularly limited as long as it is an ingredient applicable to the outer skin. Specific examples include amino acids and their peptides, proteins, collagen, vitamins, polyhydric alcohols and polysaccharides, and various other plant and animal extracts and synthetics. Those water-soluble active ingredients which are produced by a known method can be blended in the composition for external use on the skin of the present invention, and commercially available ones can be used. Further, the amount is not particularly limited.
[0011]
Ascorbic acid derivatives, which are a kind of water-soluble active ingredient used in the present invention, include ascorbic acid phosphoric acid ester, ascorbic acid alkyl ester, ascorbic acid sulfate and the like. Specifically, ascorbic acid phosphates such as L-ascorbic acid-2-phosphate, L-ascorbic acid-3-phosphate, DL-α-tocopherol-2-L-ascorbic acid phosphate diester, Ascorbic acid alkyl esters such as L-ascorbyl palmitate, L-ascorbyl isostearate, L-ascorbyl dioleate, ascorbic acid sulfates such as L-ascorbic acid-2-sulfate, L-ascorbic acid-3-sulfate, etc. And these salts can also be used. For example, alkali metal salts such as sodium salt and potassium salt, and alkaline earth metal salts such as calcium salt and magnesium salt can be used.
[0012]
Further, it can be used for ascorbic acid glycoside. Specific examples include glycosides such as mannose, fructose, galactose, xylose, and arabinose.
[0013]
Ascorbic acid derivatives produced by a known method can be added to the skin external composition of the present invention, and commercially available products can be used.
[0014]
The amount of the ascorbic acid derivative is not particularly limited, but is preferably 0.01 to 20%. If it is less than 0.01%, a synergistic whitening effect may not be expected in some cases. It is possible to contain more than 20%, but no remarkable increase in whitening effect is observed and it is not economical. Further, by adding a tocopherol derivative, a further whitening effect can be expected.
[0015]
The method for producing the W / O / W emulsion skin external composition in the present invention is not particularly limited, and it can be produced by a conventional method. Preferably, W / O / W emulsion having excellent storage stability is prepared by the following production method. An O / W emulsion skin external composition is obtained. First, a W / O emulsion is obtained by dispersing and emulsifying an inner aqueous phase portion containing a water-soluble active ingredient in an oil phase portion containing a dextrin fatty acid ester. By setting the emulsification temperature at this time to preferably 60 to 90C, more preferably 70 to 85C, a stable W / O emulsion having finer particles can be prepared. Thereafter, this W / O emulsion part is preferably dispersed and emulsified in an external aqueous phase part containing an alkyl methacrylate acrylate copolymer under a temperature condition of preferably 70 ° C. or lower, so that a W / O / W emulsion for external use on the skin is obtained. A composition can be prepared.
[0016]
The composition for external use on the skin of the present invention, in addition to the above essential components, includes various components used in ordinary cosmetics, quasi-drugs, pharmaceuticals, and the like, such as oily components, emulsifiers, humectants, thickeners, medicinal components, and preservatives. Agents, pigments, powders, pH adjusters, ultraviolet absorbers, antioxidants, fragrances and the like can be appropriately compounded.
[0017]
【The invention's effect】
In the present invention, a water-soluble active ingredient such as an ascorbic acid derivative is blended in the inner aqueous phase of a W / O / W emulsion composed of an alkyl methacrylate copolymer and a dextrin fatty acid ester. Provided is a W / O / W emulsion skin external composition in which components are prevented from being decomposed and storage stability, skin safety and feeling of use are improved, and a method for producing the same.
[0018]
【Example】
Table 1 shows the temporal stability and usability of the ascorbic acid derivative and the preparation itself when various hydrophilic surfactants and water-soluble thickeners were used in place of the alkyl methacrylate copolymer. The results obtained are shown. In addition, Table 2 shows the results of examining the stability over time and the feeling of use of the preparation when the dextrin fatty acid ester was replaced with another lipophilic surfactant or an oil-soluble thickener.
In addition, about the manufacturing method of the preparation, all performed the same procedure. First, at a temperature of 80 ° C., an oil phase portion and an inner aqueous phase portion are dispersed and emulsified to prepare a W / O emulsion, and then the W / O emulsion and an outer aqueous phase portion are dispersed and emulsified and cooled to 30 ° C. The desired W / O / W emulsion formulation was obtained.
The stability of the ascorbic acid derivative in each preparation was determined by quantification by liquid chromatography. The measurement was performed at room temperature and 40 ° C. after a lapse of 6 months, and the evaluation criteria were evaluated according to the following four steps.
Ascorbic acid derivative stability evaluation item :: The measured value after 6 months is within ± 3% of the quantitative measured value immediately after preparation.
:: The measured value after 6 months is within the range ± 5%.
Δ: The measured value after 6 months falls within the range of ± 10%.
×: The measured value after 6 months is out of the range ± 10% or more.
With respect to the time-lapse observation of the preparation, evaluation was performed after one year at room temperature and two months at 50 ° C., and the following four-stage storage stability evaluation items were used as indices.
Storage stability evaluation item A: Almost no change in phase state was observed.
:: A slight increase in the emulsified particle diameter can be confirmed by observation with a microscope.
Δ: No phase separation was observed, but a remarkable increase in the emulsified particle diameter was observed when observed with a microscope.
X: It can be visually confirmed that the two phases are separated.
In addition, the evaluation of feeling of use was evaluated by having 20 panelists actually use the skin external composition of the present invention. The spreadability at the time of application, the viscosity, and the moisturizing property after the application were evaluated by the following five grades of usability evaluation items.
Usability evaluation item 5 points: Very good 4 points: Good 3 points: Normal 2 points: Bad 1 point: Very poor The final judgment is made according to the following four grades of usability score evaluation of the obtained total points. did.
Evaluation score of usability ◎: The total score is 80 points or more, and the usability is very good.
:: The total score is 70 points or more, and the usability is good.
Δ: The total score is 50 points or more, and the usability is poor.
X: The total score is 50 points or less, and the usability is very poor.
In addition, each sample was usually used, and the raw material actually marketed was used.
[0019]
Table 1 Comparison with W / O / W emulsions using various hydrophilic surfactants and water-soluble thickeners
Figure 2004307414
[0020]
Table 2 Comparison with W / O / W emulsions using various lipophilic surfactants and oil-soluble thickeners
Figure 2004307414
[0021]
From the results in Tables 1 and 2, it can be seen that a W / O / W emulsion skin external composition excellent in stability and usability can be obtained by blending the alkyl methacrylate copolymer and the dextrin fatty acid ester. all right. It was also demonstrated that the stability of the ascorbic acid derivative in the inner aqueous phase was high.
[0022]
Table 3 shows the results obtained by preparing formulations in which alkyl acrylate alkyl methacrylate copolymers were blended in various ratios and examining the changes over time and the feeling of use of the formulations themselves. In addition, Table 4 shows the results of examining the changes over time and the feeling of use of the preparations containing dextrin fatty acid esters in various ratios. In addition, about each manufacturing method, it carried out similarly to Table 1 and Table 2 mentioned above, and evaluated the storage stability and usability | use_condition of an ascorbic acid derivative and a formulation with the same parameter | index.
[0023]
Table 3 Test results at various concentrations of alkyl acrylate alkyl methacrylate copolymer
Figure 2004307414
[0024]
Table 4 Test results at various concentrations of dextrin fatty acid esters
Figure 2004307414
[0025]
From the results of Tables 3 and 4, the compounding amount of the alkyl acrylate alkyl methacrylate copolymer is preferably 0.05 to 5%, more preferably 0.1 to 2%, and shows a sufficient emulsifying ability. Remarkably improved storage stability. When the amount of the dextrin fatty acid ester is preferably 0.05 to 10%, more preferably 0.1 to 5%, sufficient emulsifying ability is exhibited and storage stability is remarkably improved.
[0026]
From the results in Tables 1 to 4, a W / O / W emulsion was formed from the alkyl methacrylate copolymer and the dextrin fatty acid ester, and the aqueous phase contained an ascorbic acid derivative as a water-soluble active ingredient. As a result, it has been clarified that a useful W / O / W emulsion external composition for skin having excellent storage stability and usability can be provided.
[0027]
BEST MODE FOR CARRYING OUT THE INVENTION
EXAMPLES Examples for describing the present invention in detail will be described below, but the present invention is not limited thereto.
[0028]
Example 1 Highly functional cream compounding ingredients Compounding amount (% by weight)
(1) Dextrin fatty acid ester (Leopearl TL) 0.4
(2) Tocopherol acetate 0.3
(3) Squalane 11.3
(4) Octyldodecyl myristate 8.0
(5) Methylphenyl polysiloxane 4.0
(6) Fragrance 0.2
(7) Sodium phosphate ascorbate 8.0
(8) Sodium citrate 8.0
(9) Potassium aluminum sulfate 0.1
(10) dipotassium glycyrrhizinate 0.1
(11) Acrylic acid alkyl methacrylate copolymer (Pemulen TR-1) 0.6
(12) 1,3-butylene glycol 8.0
(13) Paraben appropriate amount (14) Glycerin 8.0
(15) Appropriate amount of potassium hydroxide (16) Residue of purified water [0029]
[Production method] (7) and (8) were dissolved in a part of (16) and added to the oil phase of (1) to (6) at a temperature of 75 ° C to emulsify to obtain a W / O emulsion. . This is mixed with an external aqueous phase in which (9) to (14) are dispersed and dissolved in a part of (16), and neutralized with (15) dissolved in the remaining (16), and uniformly dispersed.
[0030]
Example 2 Emulsion compounding ingredients Compounding amount (% by weight)
(1) Dextrin fatty acid ester (Leopearl TT) 0.2
(2) POE (4) glyceryl monostearate 0.1
(3) Cyclomethicone 5.0
(4) Neopentyl glycol dicaprate 5.0
(5) Fragrance 0.1
(6) Potassium citrate 2.0
(7) Magnesium phosphate ascorbate 3.0
(8) Alkyl acrylate alkyl methacrylate copolymer (Pemulen TR-2) 0.2
(9) Decaglyceryl monostearate 0.5
(10) Tocopherol calcium succinate 8.0
(11) 1,3-butylene glycol 5.0
(12) Paraben dosage (13) Glycerin 10.0
(14) edetate 0.1
(15) Aminomethylpropanediol appropriate amount (16) Purified water residue
[Production method] (6) and (7) were dissolved in a part of (16), and added to the oil phase of (1) to (5) at a temperature of 80 ° C to emulsify to obtain a W / O emulsion. . This is mixed with an external aqueous phase in which (8) to (14) are dispersed and dissolved in a part of (16), neutralized with (15) dissolved in the remaining (16), and uniformly dispersed.
[0032]
Example 3 Whitening cream compounding ingredients Compounding amount (% by weight)
(1) Dextrin fatty acid ester (Leopearl KL) 2.0
(2) Liquid paraffin 10.0
(3) Dimethicone 5.0
(4) Tocopherol nicotinate 2.0
(5) Fragrance 0.2
(6) Sodium citrate 2.0
(7) Potassium ascorbate sulfate 10.0
(8) Sodium polyphosphate 0.1
(9) Alkyl acrylate alkyl methacrylate copolymer (Pemulen TR-1) 1.0
(10) Decaglyceryl monooleate 0.5
(11) 1,3-butylene glycol 5.0
(12) Paraben dosage (13) Glycerin 11.0
(14) Appropriate amount of potassium hydroxide (15) Residual purified water [0033]
[Production method] (6) to (8) were dissolved in a part of (15), and added to the oil phase of (1) to (5) at a temperature of 70 ° C. to obtain an emulsion to obtain a W / O emulsion. . This is mixed with an external aqueous phase in which (9) to (13) are dispersed and dissolved in a part of (15), neutralized with (14) dissolved in the remaining (15), and uniformly dispersed.
[0034]
The product of the present invention shown in Examples 1 to 3 produces a W / O / W emulsion from an alkyl methacrylate copolymer and a dextrin fatty acid ester. A W / O / W emulsion external composition containing an acid derivative, which was satisfactory in terms of storage stability, skin safety, and feeling of use.

Claims (7)

アクリル酸メタクリル酸アルキル共重合体およびデキストリン脂肪酸エステルを含有することを特徴とするW/O/Wエマルション皮膚外用組成物。A W / O / W emulsion skin external composition comprising an alkyl acrylate alkyl methacrylate copolymer and a dextrin fatty acid ester. 内水相部に水溶性活性成分を含有することを特徴とする請求項1に記載のW/O/Wエマルション皮膚外用組成物。The W / O / W emulsion external composition for skin according to claim 1, wherein the inner aqueous phase contains a water-soluble active ingredient. 内水相部にアスコルビン酸誘導体を含有することを特徴とする請求項1乃至2に記載のW/O/Wエマルション皮膚外用組成物。3. The W / O / W emulsion skin external composition according to claim 1, wherein the inner aqueous phase contains an ascorbic acid derivative. アクリル酸メタクリル酸アルキル共重合体が0.1〜2%配合されることを特徴とする請求項1乃至3に記載のW/O/Wエマルション皮膚外用組成物。The W / O / W emulsion skin external composition according to any one of claims 1 to 3, wherein 0.1 to 2% of an alkyl acrylate methacrylate copolymer is blended. デキストリン脂肪酸エステルが0.1〜5%配合されることを特徴とする請求項1乃至4に記載のW/O/Wエマルション皮膚外用組成物。The dermatological composition according to any one of claims 1 to 4, wherein the dextrin fatty acid ester is incorporated in an amount of 0.1 to 5%. アスコルビン酸誘導体が0.01〜20%配合されることを特徴とする請求項1乃至5に記載のW/O/Wエマルション皮膚外用組成物。The W / O / W emulsion skin external composition according to any one of claims 1 to 5, wherein the ascorbic acid derivative is incorporated in an amount of 0.01 to 20%. デキストリン脂肪酸エステルを含む油相部に水溶性活性成分を含む内水相部を分散乳化してW/Oエマルションを得て、さらに、既W/Oエマルションをアクリル酸メタクリル酸アルキル共重合体を含む外水相部に分散乳化することを特徴とするW/O/Wエマルション皮膚外用組成物の製造方法。A W / O emulsion is obtained by dispersing and emulsifying an inner aqueous phase portion containing a water-soluble active ingredient in an oil phase portion containing a dextrin fatty acid ester, and further, the W / O emulsion contains an alkyl acrylate alkyl methacrylate copolymer. A method for producing a W / O / W emulsion external composition for skin, comprising dispersing and emulsifying in an external aqueous phase.
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US9642792B2 (en) 2012-02-28 2017-05-09 Suntory Holdings Limited W/O/W emulsion having temporal stability and method for producing the same
US9655821B2 (en) 2013-04-05 2017-05-23 The Procter & Gamble Company Personal care composition comprising a pre-emulsified formulation
US10806688B2 (en) 2014-10-03 2020-10-20 The Procter And Gamble Company Method of achieving improved volume and combability using an anti-dandruff personal care composition comprising a pre-emulsified formulation
US9993404B2 (en) 2015-01-15 2018-06-12 The Procter & Gamble Company Translucent hair conditioning composition
US10912723B2 (en) 2016-01-20 2021-02-09 The Procter And Gamble Company Hair conditioning composition comprising monoalkyl glyceryl ether
KR20190091107A (en) 2018-01-26 2019-08-05 한국과학기술원 Double Emulsion From Phase Inversion and the Preparation Method Thereof

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