JP3586682B2 - Cleansing cosmetics - Google Patents

Cleansing cosmetics Download PDF

Info

Publication number
JP3586682B2
JP3586682B2 JP2002366767A JP2002366767A JP3586682B2 JP 3586682 B2 JP3586682 B2 JP 3586682B2 JP 2002366767 A JP2002366767 A JP 2002366767A JP 2002366767 A JP2002366767 A JP 2002366767A JP 3586682 B2 JP3586682 B2 JP 3586682B2
Authority
JP
Japan
Prior art keywords
weight
less
iob
water
component
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.)
Expired - Fee Related
Application number
JP2002366767A
Other languages
Japanese (ja)
Other versions
JP2004026791A (en
Inventor
真規 清水
ひろ子 津田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kao Corp
Original Assignee
Kao Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to JP2002366767A priority Critical patent/JP3586682B2/en
Application filed by Kao Corp filed Critical Kao Corp
Priority to EP03715385A priority patent/EP1488775B1/en
Priority to US10/508,013 priority patent/US20050180942A1/en
Priority to CNB038069016A priority patent/CN100381112C/en
Priority to PCT/JP2003/003412 priority patent/WO2003080004A1/en
Priority to AU2003227189A priority patent/AU2003227189A1/en
Priority to KR1020047015137A priority patent/KR100978433B1/en
Priority to TW092106759A priority patent/TWI348380B/en
Publication of JP2004026791A publication Critical patent/JP2004026791A/en
Application granted granted Critical
Publication of JP3586682B2 publication Critical patent/JP3586682B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Description

【0001】
【発明の属する技術分野】
本発明は、クレンジング化粧料に関し、更に詳細には、透明で美麗な液状を呈し、優れたクレンジング力を有するとともに、水で濡れた皮膚に使用しても白濁を起こすことがないクレンジング化粧料に関する。
【0002】
【従来の技術】
従来、水で洗い流して使用するか又はふき取って使用する化粧落とし用のクレンジング化粧料としては、油成分を配合したクリーム状、乳液状、ゲル状、溶液状の形態のものがあり、これらは非イオン界面活性剤で油成分及び水を乳化又は可溶化して製造されている。例えば、特許文献1が挙げられる。
【0003】
しかしながら、従来の油性クレンジング化粧料は、水で濡れた皮膚に使用すると、水の介在により、乳化物や懸濁物となって白濁して外観が悪くなるとともに、油性汚れに対するクレンジング力が著しく低下し、さらには使用感が悪くなることがあるため、特に浴室での使用には不向きであった。
【0004】
これまでに、安定な可溶化状態を得るための多くの研究がなされ、10〜20%程度の多価アルコールを添加したり、特定の界面活性剤を使用する等の方法が提案されているが、濡れた皮膚に使用することを想定した、オイルを主成分としたクレンジング化粧料については、未だ十分に満足できるものは提供されていない。例えば、特許文献2、特許文献3には、特定の非イオン界面活性剤と水酸基を有する水溶性化合物、液状油及び水を含有するクレンジング用組成物が提案されているが、これらのものは粘度が300mPa・s以上の組成物が大部分であり、油性メイク(特に油性マスカラ)に対するなじみや浮きが悪いという問題があった。また、浴室等で、濡れた皮膚に使用する場合には、水分の混入によって、しっかりとした液晶構造をとってしまうなど、増粘してメイクに対する洗浄力が大きく低下したり、白く濁って油性メイクに対する洗浄力が大きく低下するなど、十分な耐水性を備えているとは言えず、十分満足できるものではなかった。
【0005】
【特許文献1】
特開平3−161428号公報
【特許文献2】
特開平4−5213号公報
【特許文献3】
特開平6−219923号公報
【0006】
【発明が解決しようとする課題】
本発明の目的は、透明な液状を呈し、多量の水が混入しても増粘や白濁を起こさず、クレンジング力の低下や外観及び使用感の悪さを生じない、耐水性のあるクレンジング化粧料を提供することにある。
【0007】
【課題を解決するための手段】
本発明者らは、有意な量の水が混入しても乳化や懸濁によって白濁したり、大きく増粘したりしない油性透明液状組成物が設計できれば、浴室や洗面台など手や顔が濡れた環境下で使用することができ、クレンジング力の低下及び外観や使用感の悪化が生じないクレンジング化粧料を提供することができること、そしてかかる組成物は特定の界面活性剤と油剤を組み合わせることにより達成できることを見出した。
【0008】
本発明は、次の成分(A)〜(E):
(A)IOBが0.75〜1.2で、かつHLB8.0未満のポリグリセリンモノ脂肪酸エステル 2〜7重量%、
(B)IOBが1.1以上であって、ポリグリセリン脂肪酸エステル以外の非イオン界面活性剤 5〜30重量%、
(C)液体油成分 50〜85重量%、
(D)12重量%以下の水、
(E)IOBが0.6以下で炭素数18以下の高級アルコール若しくは高級脂肪酸、又はIOBが0.8以下のポリオキシエチレンモノアルキルエーテル 0.5〜15重量%
を含有する組成物であって、該組成物100重量部に対して50重量部の水を加えたときに白濁しない透明な液状クレンジング化粧料を提供するものである。
【0009】
【発明の実施の形態】
本発明で用いる成分(A)は、IOBが0.75〜1.2のポリグリセリン脂肪酸エステルである。IOBがこの範囲外のものでは、十分な耐水性を得ることができなかったり、洗い流し時にぬるつき感が肌に残りやすくなり、好ましくない。
ここで、IOBとは、有機概念図(藤田穆、有機化合物の予測と有機概念図、化学の領域 Vol.11,No.10(1957)719−725)に基づき求められる無機性値及び有機性値の比(Inorganic Organic Balance)を表わすもので、次式により求められる。
【0010】
【数1】

Figure 0003586682
【0011】
IOBが0.75〜1.2のポリグリセリン脂肪酸エステルとしては、グリセリンの重合度が2〜6のポリグリセリンと脂肪酸とのエステルが好ましく、特に炭素数12〜18の脂肪酸と重合度2のポリグリセリンとのモノエステルが好ましい。
成分(A)のポリグリセリン脂肪酸エステルは、2種以上を用いることもでき、全組成中に1〜15重量%、特に2〜7重量%含有するのが、十分な耐水性が得られるとともに、使用感が良好であるので好ましい。
【0012】
成分(B)の非イオン界面活性剤は、IOBが1.1以上、好ましくは1.2〜2.0の水溶性のものである。IOBが1.1未満のものでは、十分な耐水性を得ることができないとともに、さっぱりとした洗い流し性も得られない。
【0013】
具体的には、ポリオキシエチレンモノ脂肪酸エステル、脂肪酸ポリオキシエチレングリセリル(ポリオキシエチレン鎖を付加したグリセリンと脂肪酸のエステル)、モノ脂肪酸ポリオキシエチレングリセリン(モノ脂肪酸グリセリンにポリオキシエチレン鎖を付加した構造)、アルキルグルコシド、ポリオキシエチレンソルビタン脂肪酸エステル等が挙げられる。特に、ポリオキシエチレンモノ脂肪酸エステル、脂肪酸ポリオキシエチレングリセリル、モノ脂肪酸ポリオキシエチレングリセリン、アルキルグルコシドが、低粘度かつ、耐水性に優れた組成物を作ることができ、好ましい。更に具体的には、ポリオキシエチレンモノラウレート(IOB=1.34)、モノヤシ油脂肪酸ポリオキシエチレングリセリン(IOB=1.22)、アルキル鎖C9〜11で糖縮合度1〜2のアルキルグルコシド(IOB=1.84)が、口紅などの色物に対し、水分存在下(濡れた皮膚上でマッサージする時や洗い流し時)で良好な洗浄力を発揮するので好ましい。これらの成分を配合することにより、幅広いメイク汚れに対して優れた洗浄力を有する耐水性の高い油性クレンジング化粧料を得ることができる。
【0014】
成分(B)の非イオン界面活性剤は、2種以上を用いることもでき、全組成中に5〜30重量%、特に7〜16重量%含有するのが、十分な耐水性が得られるとともに、洗い流し性が良好であり好ましい。
【0015】
成分(C)の液体油成分は、25℃において流動性を示し、透明なものである。
かかる液体油成分としては、通常化粧料に使用されるものであれば特に制限されず、例えば流動パラフィン、流動イソパラフィン、ポリイソブテン、スクワラン等の炭化水素油;アルキル−1,3−ジメチルブチルエーテル等のエーテル油;パルミチン酸イソプロピル、ミリスチン酸イソプロピル、2−エチルヘキサン酸セチル、イソノナン酸トリデシル等のモノエステル油;トリ(2−エチルヘキサン酸)グリセリン、トリ(カプリル酸・カプリン酸)グリセリン等のトリエステル油;オリーブ油、ホホバ油、マカダミアナッツ油等の植物性油;デカメチルシクロペンタシロキサン、メチルフェニルポリシロキサン等のシリコーン油などを用いることができる。
【0016】
これらのうち、デカメチルシクロペンタシロキサン;炭素数20〜30で、かつ無機性値が75以下の油が、水を可溶化するのに効果的であり好ましい。ここで、無機性値とは、前記のIOBを求める際に用いる有機概念図により決定される値である。
炭素数20〜30で、かつ無機性値が75以下の油としては、例えば平均炭素数20〜30の流動パラフィン(例えば、カネダ社製、ハイコールK230;無機性値0、平均炭素数24等)、流動イソパラフィン(例えば、日本油脂社製、パームリームEX;無機性値0、平均炭素数21等)、スクワラン(無機性値0、平均炭素数30)、パルミチン酸イソプロピル(無機性値60、炭素数19)、イソノナン酸イソトリデシル(無機性値60、炭素数22)、2−エチルヘキサン酸セチル(無機性値60、炭素数24)、ヘキサデシル−1,3−ジメチルブチルエーテル(無機性値20、炭素数22)等が挙げられる。
【0017】
成分(C)の液体油成分は、2種以上を用いることもでき、全組成中に50〜85重量%、特に70〜85重量%含有するのが、油性メイクの洗浄力に優れており好ましい。また、その中でも特にデカメチルシクロペンタシロキサン;炭素数20〜30で、かつ無機性値が75以下の油を全組成中に40〜85重量%含有するのが好ましい。
【0018】
成分(D)の水は、全組成中に0〜12重量%、好ましくは2〜7重量%含有される。12重量%を超えると、半透明になったり、経時で相分離を起こすため好ましくない。
【0019】
本発明のクレンジング化粧料には、更に、成分(E)として、IOBが0.6以下の高級アルコール若しくは高級脂肪酸、又はIOBが0.8以下のポリオキシエチレンモノアルキルエーテルを含有できる。成分(E)を含有させることにより、成分(A)の配合量を減らした場合でも高い耐水性を維持することが可能となり、また、成分(A)を多量に配合した場合に生じ易い、洗い流し時の肌のぬるつきを低減することができる。
【0020】
このような高級アルコールとしては、炭素数18以下のもので、例えばミリスチルアルコール(IOB=0.36)、イソステアリルアルコール(IOB=0.29)、オレイルアルコール(IOB=0.28)等が挙げられる。
高級脂肪酸としては、イソステアリン酸(IOB=0.56)等が挙げられる。
また、ポリオキシエチレンモノアルキルエーテルとしては、ポリオキシエチレン鎖(POE)の重合度が5以下のものが好ましく、例えばPOE(3.3)モノアルキルエーテル(C9〜11)(IOB=0.77)等が挙げられる。
【0021】
成分(E)は、2種以上を用いることもでき、高級アルコール、高級脂肪酸、ポリオキシエチレンモノアルキルエーテルから選ばれる2種以上を組合わせて用いることもできる。成分(E)は、全組成中に0.5〜15重量%、特に2.1〜8重量%含有するのが、すすぎ時の感触に優れるので好ましい。
【0022】
また、本発明のクレンジング化粧料は、前記成分以外に、例えば非イオン界面活性剤の溶解性の微調節や使用感の向上のため、1,3−ブチレングリコール、プロピレングリコール、グリセリン等の多価アルコール類、エチルカルビトール等のグリコールエーテル類、エタノール等のアルコール類を含有させることができる。これらのアルコール系成分の含有量は、経時で相分離したりしない安定な透明の組成物にするため、5重量%以下、特に2重量%以下であるのが好ましい。
【0023】
さらに、粘度を調節するための、超微粒子シリカ、パルミチン酸デキストリン、有機性ベントナイト等の増粘剤;クエン酸、リン酸などの有機酸、無機酸;無機塩類、アニオン界面活性剤、カチオン界面活性剤、両性界面活性剤、高分子ポリマー、殺菌剤、紫外線吸収剤、酸化防止剤、キレート剤、香料、色素、エキス類、薬効剤等も含有できる。
【0024】
本発明のクレンジング化粧料は、所定の成分を適宜混合することによって得られ、常温で固体の原料については一度溶解した後に、全成分を均一に混合することにより、容易に製造することができる。
【0025】
本発明のクレンジング化粧料は、該組成物100重量部に対して50重量部の水を加えたときに白濁しないものである。ここで、白濁とは、乳化や懸濁に起因するものであり、28〜30℃にて、濁度計(デジタル比色計 mini photo 5;10mmΦガラスセル;三紳工業社製)で波長530nmにおいて精製水をリファレンスにして測定した透過率を、酸化チタン(酸化チタンJA−C、粒径0.1〜0.5μm程度:テイカ社製)の0.02重量%懸濁水溶液の透過率と比較し、0.02重量%酸化チタン懸濁水溶液の透過率より低いものを白濁とする。
【0026】
また、本発明のクレンジング化粧料は、透明な液状のものである。透明とは、濁度計で波長530nmにおいて精製水をリファレンスにして測定した透過率が、0.001重量%酸化チタン懸濁水溶液の透過率より高い状態をいう(色素や粉体等の配合がある場合は、それらを含まない状態で測定して透明であれば、本発明の範囲に含まれるとする)。また、液状とは、25℃における粘度が1000mPa・s(B型粘度計、ローター2、30rpm)以下の状態をいう。25℃において該組成物の粘度は300mPa・s以下、特に100mPa・s以下であるのが好ましい。また、該組成物100重量部に対して50重量部の水を加えて混合していくとき、25℃における粘度が常に2000mPa・s以下であるのが好ましく、特に常に1000mPa・s以下であるのが好ましい。
【0027】
【実施例】
実施例1〜7、比較例1〜7
表1及び表2に示す組成のクレンジング化粧料を製造し、得られたクレンジング化粧料の外観、性状、メイク落ち、水を混合したときの透過率、メイク落ち、洗い流し性、及び総合評価について評価した。結果を表1及び表2に併せて示す。
【0028】
(製法)
<実施例1〜7>
成分(A)、(E)及びその他の成分を、成分(C)に加温して完全に溶解した後、成分(B)及び(D)を加えて均一に混合して、クレンジング化粧料を得た。
<比較例1〜7>
成分(A)、(E)及びその他の成分を、成分(C)に加温して完全に溶解した後、成分(B)及び(D)を加えて均一に混合して、クレンジング化粧料を得た。
【0029】
(評価方法)
(1)外観;
25℃において、濁度計(デジタル比色計 mini photo 5;10mmΦガラスセル;三紳工業社製)で波長530nmにおいて精製水をリファレンスにして透過率を測定し、0.001重量%酸化チタン懸濁水溶液の透過率より高いものを「透明」とし、0.001重量%酸化チタン懸濁水溶液の透過率より低く、0.02重量%酸化チタン懸濁水溶液の透過率より高いものを「半透明」とした。
【0030】
(2)性状;
25℃において、B型粘度計(ローター2、30rpm)で測定した粘度が、1000mPa・s以下のものを「液状」とした。
【0031】
(3)メイク落ち;
油性メイク落ち;マスカラ(メイベリン社製、ダイアルマスカラ)を前腕部に直径約1.5cmに薄く塗り、3時間放置して乾燥させた後、各クレンジング化粧料(又は水50重量部と混合したもの)約25mgをのせ、指で軽く30回マッサージした。その後、流水で洗い流し、マスカラの残り具合を目視で観察し、以下の基準で判定した。
口紅メイク落ち;口紅(花王社製、オーブ ルージュライブリッシュRS415)を前腕部に直径約1.5cmに薄く塗り、3時間放置して乾燥させた後、各クレンジング化粧料(又は水50重量部と混合したもの)約25mgをのせ、指で軽く30回マッサージした。その後、流水で洗い流し、口紅の残り具合を目視で観察し、以下の基準で判定した。
◎:メイクの落ちが良好かつ浮きが早い。
○:メイクの落ちが良好。
○△:メイクの落ちがやや良好。
△:メイクの落ちがやや不良。
×:メイクの落ちが不良。
【0032】
(4)水と混合したときの透過率;
各クレンジング化粧料と水10重量部又は50重量部を混合した試料について、濁度計(デジタル比色計 mini photo 5;10mmΦガラスセル;三紳工業社製)で波長530nmにおいて精製水をリファレンスにして透過率を測定し、酸化チタン(酸化チタンJA−C、粒径0.1〜0.5μm程度:テイカ社製)の懸濁水溶液の透過率と比較して、以下の基準で評価した。
A:0.001重量%酸化チタン懸濁水溶液の透過率より高い。
B:0.008重量%酸化チタン懸濁水溶液の透過率より高く、0.001重量%酸化チタン懸濁水溶液の透過率より低い。
C:0.02重量%酸化チタン懸濁水溶液の透過率より高く、0.008重量%酸化チタン懸濁水溶液の透過率より低い。
D:0.02重量%酸化チタン懸濁水溶液の透過率より低い。
なお、本発明においては、手の平や顔面上の環境に相当する25〜35℃の範囲内に水分が自重の50重量%混入しても白濁しない領域を持つことが好ましく、測定は各クレンジング化粧料100重量部に精製水を10重量部又は50重量部混合したものを、28〜30℃に温度を調節してから均一に混合した直後に行った。
【0033】
(5)洗い流し性;
各クレンジング化粧料を約2g前腕部に塗布し、ぬるま湯で洗い流したときの洗い流し易さを評価した。
◎:ぬめり感がなくなり、洗い流しやすい。
○:洗い流しやすい。
△:洗い流しにくい。
×:いつまでも肌に油が残り、洗い流すことができない。
【0034】
(6)総合評価;
10人の専門評価パネラーが、各クレンジング化粧料を使用して評価した。まず、顔に口紅及び油性マスカラを塗布し、約3時間おいて乾燥させた。次に、一度よく濡らしてから軽く水をきった状態の手に、各クレンジング化粧料を約2gとり、鏡を見ながら顔全体に伸ばして、メイクとなじませた後、ぬるま湯で洗い流した。この時の外観、メイク落ち、洗い流し性の総合的な評価を以下の基準で行った。
◎:10人中8人以上が良いと答えた。
○:10人中6〜7人が良いと答えた。
△:10人中4〜5人が良いと答えた。
×:10人中3人以下が良いと答えた。
【0035】
【表1】
Figure 0003586682
【0036】
【表2】
Figure 0003586682
【0037】
実施例8〜9、比較例8〜12
表3に示す組成のクレンジング化粧料を実施例1〜7及び比較例1〜7と同様に製造し、同様に、得られたクレンジング化粧料の外観、性状、メイク落ち、水を混合したときの透過率、メイク落ち、洗い流し性、及び総合評価について評価した。また、クレンジング化粧料の粘度を、以下の方法により測定した。結果を表4に示す。
【0038】
粘度の測定;
25℃において、B型粘度計(ローター2、30rpm)で測定した。粘度計の針が振り切れる場合は、必要に応じてローター3、4を用いた。
【0039】
【表3】
Figure 0003586682
【0040】
【表4】
Figure 0003586682
【0041】
【発明の効果】
本発明のクレンジング化粧料は、透明で美麗な液状を呈し、水が混入されても使用中は可溶化状態を維持して白濁することがなく、クレンジング力が低下せず、使用感も良好である。水で濡れた皮膚にも使用することができ、特に浴室での使用に好適である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a cleansing cosmetic, and more particularly, to a cleansing cosmetic that presents a clear and beautiful liquid, has excellent cleansing power, and does not cause cloudiness even when used on skin wet with water. .
[0002]
[Prior art]
Conventionally, as a cleansing cosmetic for makeup removal which is used after washing or wiping off with water, there are cream, emulsion, gel, and solution forms containing an oil component. It is manufactured by emulsifying or solubilizing an oil component and water with an ionic surfactant. For example, Patent Document 1 is cited.
[0003]
However, conventional oil-based cleansing cosmetics, when used on water-wetted skin, become emulsified or suspended due to the presence of water and become cloudy, resulting in a poor appearance and markedly reduced cleansing power against oily stains. In addition, since the feeling of use may be worsened, it is not particularly suitable for use in a bathroom.
[0004]
Many studies have been made to obtain a stable solubilized state, and methods such as adding about 10 to 20% of a polyhydric alcohol and using a specific surfactant have been proposed. As for cleansing cosmetics containing oil as a main component, which are supposed to be used on wet skin, there have not yet been provided satisfactory cleansing cosmetics. For example, Patent Document 2 and Patent Document 3 propose a cleansing composition containing a specific nonionic surfactant, a water-soluble compound having a hydroxyl group, a liquid oil and water. Most of the compositions had a viscosity of 300 mPa · s or more, and there was a problem of poor adaptation or floating to oily makeup (particularly oily mascara). In addition, when used on wet skin in bathrooms, etc., the inclusion of moisture causes a firm liquid crystal structure to be taken. It could not be said that it had sufficient water resistance, such as a large decrease in the detergency of makeup, and was not sufficiently satisfactory.
[0005]
[Patent Document 1]
Japanese Patent Application Laid-Open No. 3-161428 [Patent Document 2]
JP-A-4-5213 [Patent Document 3]
JP-A-6-219923
[Problems to be solved by the invention]
An object of the present invention is a water-resistant cleansing cosmetic that exhibits a transparent liquid state, does not cause thickening or cloudiness even when a large amount of water is mixed therein, does not cause a decrease in cleansing power, and does not deteriorate the appearance and feeling of use. Is to provide.
[0007]
[Means for Solving the Problems]
The present inventors have designed an oil-based transparent liquid composition that does not become cloudy due to emulsification or suspension even if a significant amount of water is mixed, and does not greatly increase the viscosity, so that hands and faces such as bathrooms and washbasins can get wet. Can be used in a cold environment, can provide a cleansing cosmetic that does not cause a decrease in cleansing power and a deterioration in appearance and feeling of use, and such a composition is obtained by combining a specific surfactant and an oil agent. I found what I could achieve.
[0008]
The present invention comprises the following components (A) to (E):
(A) 2 to 7 % by weight of a polyglycerol monofatty acid ester having an IOB of 0.75 to 1.2 and an HLB of less than 8.0,
(B) 5 to 30% by weight of a nonionic surfactant other than polyglycerin fatty acid ester having IOB of 1.1 or more,
(C) a liquid oil component of 50 to 85% by weight,
(D) 12% by weight or less of water,
(E) a higher alcohol or fatty acid having an IOB of 0.6 or less and a carbon number of 18 or less, or a polyoxyethylene monoalkyl ether having an IOB of 0.8 or less 0.5 to 15% by weight
A transparent liquid cleansing cosmetic which does not become cloudy when 50 parts by weight of water is added to 100 parts by weight of the composition.
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
The component (A) used in the present invention is a polyglycerin fatty acid ester having an IOB of 0.75 to 1.2. If the IOB is out of this range, sufficient water resistance cannot be obtained, or a slimy feeling tends to remain on the skin during washing, which is not preferable.
Here, the IOB is an organic conceptual diagram (Atsushi Fujita, Prediction of Organic Compounds and Organic Conceptual Diagram, Chemistry, Vol. 11, No. 10 (1957) 719-725). It represents a ratio of values (Inorganic Organic Balance) and is obtained by the following equation.
[0010]
(Equation 1)
Figure 0003586682
[0011]
As the polyglycerol fatty acid ester having an IOB of 0.75 to 1.2, an ester of a polyglycerin having a polymerization degree of glycerin of 2 to 6 and a fatty acid is preferable. Monoesters with glycerin are preferred.
As the polyglycerin fatty acid ester of the component (A), two or more kinds can be used, and the content of 1 to 15% by weight, particularly 2 to 7% by weight in the whole composition, provides sufficient water resistance, It is preferable because the usability is good.
[0012]
The nonionic surfactant of the component (B) is a water-soluble surfactant having an IOB of 1.1 or more, preferably 1.2 to 2.0. If the IOB is less than 1.1, sufficient water resistance cannot be obtained, and refreshing washability cannot be obtained.
[0013]
Specifically, polyoxyethylene monofatty acid ester, fatty acid polyoxyethylene glyceryl (ester of glycerin and fatty acid with polyoxyethylene chain added), monofatty acid polyoxyethylene glycerin (polyoxyethylene chain added to monofatty acid glycerin Structures), alkyl glucosides, polyoxyethylene sorbitan fatty acid esters, and the like. In particular, polyoxyethylene monofatty acid ester, fatty acid polyoxyethylene glyceryl, monofatty acid polyoxyethylene glycerin, and alkyl glucoside are preferable because they can form a composition having low viscosity and excellent water resistance. More specifically, polyoxyethylene monolaurate (IOB = 1.34), monococonut oil fatty acid polyoxyethylene glycerin (IOB = 1.22), alkyl glucoside having alkyl chain C9-11 and sugar condensation degree 1-2. (IOB = 1.84) is preferable because it exerts a good detergency on a colored substance such as lipstick in the presence of moisture (when massaged or washed off on wet skin). By blending these components, a highly water-resistant oil-based cleansing cosmetic having excellent detergency against a wide range of makeup stains can be obtained.
[0014]
Two or more nonionic surfactants of the component (B) can be used, and if they are contained in the entire composition in an amount of 5 to 30% by weight, particularly 7 to 16% by weight, sufficient water resistance can be obtained and , Good washability is preferable.
[0015]
The liquid oil component of component (C) exhibits fluidity at 25 ° C. and is transparent.
The liquid oil component is not particularly limited as long as it is usually used in cosmetics, and examples thereof include hydrocarbon oils such as liquid paraffin, liquid isoparaffin, polyisobutene, and squalane; ethers such as alkyl-1,3-dimethylbutyl ether Oil; monoester oils such as isopropyl palmitate, isopropyl myristate, cetyl 2-ethylhexanoate, and tridecyl isononanoate; triester oils such as glycerin tri (2-ethylhexanoate) and tri (caprylic acid / capric acid) glycerin Vegetable oils such as olive oil, jojoba oil and macadamia nut oil; and silicone oils such as decamethylcyclopentasiloxane and methylphenylpolysiloxane.
[0016]
Among them, decamethylcyclopentasiloxane; an oil having 20 to 30 carbon atoms and an inorganic value of 75 or less is preferable because it is effective for solubilizing water. Here, the inorganic value is a value determined by an organic conceptual diagram used when obtaining the IOB.
As an oil having 20 to 30 carbon atoms and an inorganic value of 75 or less, for example, liquid paraffin having an average carbon number of 20 to 30 (for example, Hi-Kol K230 manufactured by Kaneda; inorganic value 0, average carbon number 24, etc.) Liquid isoparaffin (for example, manufactured by NOF CORPORATION, Palm Ream EX; inorganic value 0, average carbon number 21), squalane (inorganic value 0, average carbon number 30), isopropyl palmitate (inorganic value 60, carbon number 19), isotridecyl isononanoate (inorganic value 60, carbon number 22), cetyl 2-ethylhexanoate (inorganic value 60, carbon number 24), hexadecyl-1,3-dimethylbutyl ether (inorganic value 20, carbon number 22).
[0017]
As the liquid oil component (C), two or more liquid oil components can be used, and the content of the liquid oil component is preferably from 50 to 85% by weight, particularly preferably from 70 to 85% by weight in the whole composition, because the detergency of the oily makeup is excellent. . Further, among them, it is particularly preferable to contain decamethylcyclopentasiloxane; an oil having 20 to 30 carbon atoms and an inorganic value of 75 or less, in an amount of 40 to 85% by weight in the whole composition.
[0018]
The water of component (D) is contained in the total composition in an amount of 0 to 12% by weight, preferably 2 to 7% by weight. If it exceeds 12% by weight, it is not preferable because it becomes translucent or causes phase separation over time.
[0019]
The cleansing cosmetic of the present invention may further contain, as component (E), a higher alcohol or fatty acid having an IOB of 0.6 or less, or a polyoxyethylene monoalkyl ether having an IOB of 0.8 or less. By containing the component (E), it is possible to maintain high water resistance even when the amount of the component (A) is reduced, and it is easy to wash out when a large amount of the component (A) is mixed. It is possible to reduce the slimy skin at the time.
[0020]
Such higher alcohols have 18 or less carbon atoms and include, for example, myristyl alcohol (IOB = 0.36), isostearyl alcohol (IOB = 0.29), oleyl alcohol (IOB = 0.28) and the like. Can be
Examples of higher fatty acids include isostearic acid (IOB = 0.56).
The polyoxyethylene monoalkyl ether preferably has a degree of polymerization of a polyoxyethylene chain (POE) of 5 or less. For example, POE (3.3) monoalkyl ether (C9-11) (IOB = 0.77) ) And the like.
[0021]
As the component (E), two or more types can be used, and two or more types selected from higher alcohols, higher fatty acids, and polyoxyethylene monoalkyl ethers can be used in combination. Component (E) is preferably contained in the entire composition in an amount of 0.5 to 15% by weight, particularly 2.1 to 8% by weight, because the feel during rinsing is excellent.
[0022]
In addition, the cleansing cosmetic of the present invention may contain, in addition to the above-mentioned components, polyvalent resins such as 1,3-butylene glycol, propylene glycol, and glycerin in order to finely adjust the solubility of the nonionic surfactant and improve the feeling of use. Alcohols, glycol ethers such as ethyl carbitol, and alcohols such as ethanol can be contained. The content of these alcohol components is preferably 5% by weight or less, particularly preferably 2% by weight or less in order to obtain a stable and transparent composition which does not undergo phase separation with time.
[0023]
Furthermore, thickeners such as ultrafine silica, dextrin palmitate, and organic bentonite for adjusting viscosity; organic acids such as citric acid and phosphoric acid; inorganic acids; inorganic salts, anionic surfactants and cationic surfactants Agents, amphoteric surfactants, high molecular polymers, bactericides, ultraviolet absorbers, antioxidants, chelating agents, fragrances, pigments, extracts, medicinal agents and the like.
[0024]
The cleansing cosmetic of the present invention can be obtained by appropriately mixing predetermined components, and can be easily produced by dissolving once a raw material which is solid at room temperature and then uniformly mixing all components.
[0025]
The cleansing cosmetic of the present invention does not become cloudy when 50 parts by weight of water is added to 100 parts by weight of the composition. Here, the cloudiness is caused by emulsification or suspension, and a wavelength of 530 nm is measured at 28 to 30 ° C. using a turbidimeter (digital colorimeter mini photo5; 10 mmφ glass cell; manufactured by Sanshin Kogyo KK). The transmittance measured with reference to purified water in Example 1 was the transmittance of a 0.02% by weight aqueous suspension of titanium oxide (titanium oxide JA-C, particle size: about 0.1 to 0.5 μm: manufactured by Teica). By comparison, those having a transmittance lower than that of the 0.02% by weight aqueous titanium oxide suspension are regarded as cloudy.
[0026]
The cleansing cosmetic of the present invention is a transparent liquid. Transparent refers to a state in which the transmittance measured with a turbidimeter at a wavelength of 530 nm using purified water as a reference is higher than the transmittance of a 0.001% by weight aqueous solution of titanium oxide suspension. In some cases, if they are measured without containing them and they are transparent, they are included in the scope of the present invention). The term “liquid” refers to a state in which the viscosity at 25 ° C. is 1000 mPa · s (B-type viscometer, rotor 2, 30 rpm) or less. At 25 ° C., the viscosity of the composition is preferably 300 mPa · s or less, particularly preferably 100 mPa · s or less. When 50 parts by weight of water is added to and mixed with 100 parts by weight of the composition, the viscosity at 25 ° C. is preferably always 2000 mPa · s or less, and particularly preferably 1000 mPa · s or less. Is preferred.
[0027]
【Example】
Examples 1 to 7, Comparative Examples 1 to 7
The cleansing cosmetics having the compositions shown in Tables 1 and 2 were produced, and the obtained cleansing cosmetics were evaluated for appearance, properties, makeup removal, transmittance when mixed with water, makeup removal, washability, and overall evaluation. did. The results are shown in Tables 1 and 2.
[0028]
(Production method)
<Examples 1 to 7>
After the components (A), (E) and other components are completely dissolved by heating the component (C), the components (B) and (D) are added and uniformly mixed to prepare a cleansing cosmetic. Obtained.
<Comparative Examples 1 to 7>
After the components (A), (E) and other components are completely dissolved by heating the component (C), the components (B) and (D) are added and uniformly mixed to prepare a cleansing cosmetic. Obtained.
[0029]
(Evaluation method)
(1) Appearance;
At 25 ° C., the transmittance was measured with a turbidimeter (digital colorimeter mini photo 5; 10 mmφ glass cell; manufactured by Sanshin Kogyo) at a wavelength of 530 nm with reference to purified water, and 0.001% by weight titanium oxide suspension was measured. Those having a transmittance higher than that of the turbid aqueous solution are regarded as “transparent”, and those having a transmittance lower than the transmittance of the 0.001% by weight aqueous solution of titanium oxide and higher than the transmittance of the aqueous solution of 0.02% by weight titanium oxide are referred to as “translucent”. "
[0030]
(2) Properties;
At 25 ° C., those having a viscosity of 1000 mPa · s or less measured with a B-type viscometer (rotor 2, 30 rpm) were regarded as “liquid”.
[0031]
(3) makeup fall;
Oily makeup remover: Mascara (Dial Mascara, Maybelline Co., Ltd.) is applied thinly to the forearm to a diameter of about 1.5 cm, left to dry for 3 hours, and then mixed with each cleansing cosmetic (or 50 parts by weight of water) ) Put about 25mg and massaged lightly 30 times with fingers. Thereafter, the mascara was washed away with running water, and the remaining condition of the mascara was visually observed, and judged based on the following criteria.
Lipstick make-up; Apply lipstick (Kabu Corporation, Aube Rouge Liverish RS415) thinly on the forearm to a diameter of about 1.5 cm, let it dry for 3 hours, and then use each cleansing cosmetic (or 50 parts by weight of water). About 25 mg was placed on the mixture and massaged lightly 30 times with a finger. Thereafter, the lipstick was washed away with running water, and the remaining condition of the lipstick was visually observed, and judged according to the following criteria.
◎: The make-up is good and the floating is fast.
:: Good makeup removal.
○ △: Makeup is slightly good.
Δ: Makeup is slightly poor.
×: Poor makeup removal.
[0032]
(4) transmittance when mixed with water;
For a sample obtained by mixing 10 parts by weight or 50 parts by weight of water with each cleansing cosmetic, purified water was used as a reference at a wavelength of 530 nm using a turbidimeter (digital colorimeter mini photo 5; 10 mmΦ glass cell; manufactured by Sanshin Kogyo KK). The transmittance was measured by using the following criteria, and compared with the transmittance of an aqueous suspension of titanium oxide (titanium oxide JA-C, particle size: about 0.1 to 0.5 μm: manufactured by Teica).
A: Higher than the transmittance of a 0.001% by weight aqueous solution of titanium oxide suspension.
B: Higher than the transmittance of a 0.008% by weight aqueous solution of titanium oxide suspension, and lower than the transmittance of a 0.001% by weight aqueous solution of titanium oxide suspension.
C: Higher than the transmittance of a 0.02% by weight aqueous solution of titanium oxide suspension, and lower than the transmittance of a 0.008% by weight aqueous solution of titanium oxide suspension.
D: lower than the transmittance of a 0.02% by weight aqueous solution of titanium oxide suspension.
In the present invention, it is preferable to have a region that does not become clouded even if water is mixed at 50% by weight of its own weight within a range of 25 to 35 ° C. corresponding to the environment on the palm or the face. Immediately after mixing 100 parts by weight of purified water with 10 parts by weight or 50 parts by weight, the temperature was adjusted to 28 to 30 ° C., and then uniformly mixed.
[0033]
(5) washability;
About 2 g of each cleansing cosmetic was applied to the forearm, and the ease of rinsing when rinsing with lukewarm water was evaluated.
:: No slimy feeling, easy to wash off.
:: easy to wash off.
Δ: It is difficult to wash away.
×: Oil remains on the skin forever and cannot be washed away.
[0034]
(6) Comprehensive evaluation;
Ten expert evaluation panelists evaluated using each cleansing cosmetic. First, lipstick and oil-based mascara were applied to the face, and dried for about 3 hours. Next, about 2 g of each cleansing cosmetic was put on a hand that had been well wetted once and then lightly drained, spread over the entire face while looking in a mirror, and allowed to blend with the makeup, and then rinsed with lukewarm water. At this time, a comprehensive evaluation of the appearance, makeup removal, and washability was performed according to the following criteria.
A: Eight or more out of ten answered that they were good.
:: 6 to 7 out of 10 answered that they were good.
Δ: 4 to 5 out of 10 answered that they were good.
X: Three or less out of ten answered that they were good.
[0035]
[Table 1]
Figure 0003586682
[0036]
[Table 2]
Figure 0003586682
[0037]
Examples 8 to 9, Comparative Examples 8 to 12
Cleansing cosmetics having the compositions shown in Table 3 were produced in the same manner as in Examples 1 to 7 and Comparative Examples 1 to 7, and the appearance, properties, makeup removal, and water of the obtained cleansing cosmetics were similarly mixed. The transmittance, make-off, washability, and overall evaluation were evaluated. In addition, the viscosity of the cleansing cosmetic was measured by the following method. Table 4 shows the results.
[0038]
Measurement of viscosity;
At 25 ° C., the viscosity was measured with a B-type viscometer (rotor 2, 30 rpm). When the needle of the viscometer was shaken off, the rotors 3 and 4 were used as necessary.
[0039]
[Table 3]
Figure 0003586682
[0040]
[Table 4]
Figure 0003586682
[0041]
【The invention's effect】
The cleansing cosmetic composition of the present invention exhibits a clear and beautiful liquid state, maintains a solubilized state during use even when water is mixed, does not become cloudy, does not reduce cleansing power, and has a good usability. is there. It can be used on skin wet with water, and is particularly suitable for use in bathrooms.

Claims (4)

次の成分(A)〜(E):
(A)IOBが0.75〜1.2で、かつHLB8.0未満のポリグリセリンモノ脂肪酸エステル 2〜7重量%、
(B)IOBが1.1以上であって、ポリグリセリン脂肪酸エステル以外の非イオン界面活性剤 5〜30重量%、
(C)液体油成分 50〜85重量%、
(D)12重量%以下の水、
(E)IOBが0.6以下で炭素数18以下の高級アルコール若しくは高級脂肪酸、又はIOBが0.8以下のポリオキシエチレンモノアルキルエーテル 0.5〜15重量%
を含有する組成物であって、該組成物100重量部に対して50重量部の水を加えたときに白濁しない透明な液状クレンジング化粧料。
The following components (A) to (E):
(A) 2-7 % by weight of a polyglycerol monofatty acid ester having an IOB of 0.75 to 1.2 and an HLB of less than 8.0,
(B) 5 to 30% by weight of a nonionic surfactant other than polyglycerin fatty acid ester having IOB of 1.1 or more,
(C) 50-85% by weight of a liquid oil component,
(D) 12% by weight or less of water,
(E) a higher alcohol or fatty acid having an IOB of 0.6 or less and a carbon number of 18 or less, or a polyoxyethylene monoalkyl ether having an IOB of 0.8 or less 0.5 to 15% by weight
A transparent liquid cleansing cosmetic that does not become cloudy when 50 parts by weight of water is added to 100 parts by weight of the composition.
成分(A)のポリグリセリンモノ脂肪酸エステルが、グリセリンの重合度が2〜6のポリグリセリンと脂肪酸とのエステルである請求項1記載のクレンジング化粧料。The cleansing cosmetic according to claim 1, wherein the polyglycerin monofatty acid ester of the component (A) is an ester of polyglycerin having a degree of polymerization of glycerin of 2 to 6 and a fatty acid. 成分(A)のポリグリセリンモノ脂肪酸エステルが、炭素数12〜18の脂肪酸と重合度2のポリグリセリンとのエステルである請求項1記載のクレンジング化粧料。The cleansing cosmetic according to claim 1, wherein the polyglycerin monofatty acid ester of the component (A) is an ester of a fatty acid having 12 to 18 carbon atoms and a polyglycerin having a polymerization degree of 2. 成分(B)の非イオン界面活性剤が、ポリオキシエチレンモノ脂肪酸エステル、脂肪酸ポリオキシエチレングリセリル、モノ脂肪酸ポリオキシエチレングリセリン及びアルキルグルコシドから選ばれる1種以上である請求項1〜3のいずれか1項記載のクレンジング化粧料。The nonionic surfactant of the component (B) is at least one selected from polyoxyethylene monofatty acid esters, fatty acid polyoxyethylene glyceryl, monofatty acid polyoxyethylene glycerin, and alkyl glucosides. The cleansing cosmetic according to claim 1.
JP2002366767A 2002-03-26 2002-12-18 Cleansing cosmetics Expired - Fee Related JP3586682B2 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
JP2002366767A JP3586682B2 (en) 2002-04-30 2002-12-18 Cleansing cosmetics
US10/508,013 US20050180942A1 (en) 2002-03-26 2003-03-20 Cleansing preparation
CNB038069016A CN100381112C (en) 2002-03-26 2003-03-20 Cleansing cosmetic
PCT/JP2003/003412 WO2003080004A1 (en) 2002-03-26 2003-03-20 Cleansing preparation
EP03715385A EP1488775B1 (en) 2002-03-26 2003-03-20 Cleansing preparation
AU2003227189A AU2003227189A1 (en) 2002-03-26 2003-03-20 Cleansing preparation
KR1020047015137A KR100978433B1 (en) 2002-03-26 2003-03-20 Cleansing preparation
TW092106759A TWI348380B (en) 2002-03-26 2003-03-26 Cleansing cosmetic

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002128364 2002-04-30
JP2002366767A JP3586682B2 (en) 2002-04-30 2002-12-18 Cleansing cosmetics

Publications (2)

Publication Number Publication Date
JP2004026791A JP2004026791A (en) 2004-01-29
JP3586682B2 true JP3586682B2 (en) 2004-11-10

Family

ID=31189982

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2002366767A Expired - Fee Related JP3586682B2 (en) 2002-03-26 2002-12-18 Cleansing cosmetics

Country Status (1)

Country Link
JP (1) JP3586682B2 (en)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004083438A (en) * 2002-08-23 2004-03-18 Pola Chem Ind Inc Cosmetic for cleansing
JP4757446B2 (en) * 2004-01-09 2011-08-24 株式会社 資生堂 Oily cleansing composition
JP2005306823A (en) * 2004-04-26 2005-11-04 Kansai Koso Kk Oily cleansing cosmetic in which enzyme is formulated
JP4554404B2 (en) * 2005-03-11 2010-09-29 株式会社コーセー Liquid oily cosmetics
JP2006306780A (en) * 2005-04-28 2006-11-09 Kao Corp Liquid cleansing agent composition
JP5010290B2 (en) * 2007-01-15 2012-08-29 株式会社 資生堂 Hairdressing detergent and method for using the same
JP5013943B2 (en) * 2007-04-23 2012-08-29 株式会社 資生堂 Cosmetics
JP4274491B1 (en) * 2008-06-19 2009-06-10 株式会社資生堂 Cleansing cosmetics
JP2010248131A (en) * 2009-04-16 2010-11-04 Shiseido Co Ltd Skin cleansing agent
EP2730275B1 (en) 2011-07-04 2019-02-13 Kao Corporation Skin cleansing agent composition

Also Published As

Publication number Publication date
JP2004026791A (en) 2004-01-29

Similar Documents

Publication Publication Date Title
KR100978433B1 (en) Cleansing preparation
JP4602999B2 (en) Cleansing composition
JP2008184413A (en) Cleansing composition
KR20090086393A (en) Make-up remover cosmetic compositions
JP3586682B2 (en) Cleansing cosmetics
EP1952794B1 (en) Cleansing composition
JP6456612B2 (en) Skin cleanser composition
JP2009249324A (en) Oily cleansing cream
JP3964760B2 (en) Cleansing cosmetics
JP4373103B2 (en) Transparent liquid oily composition
JP6456613B2 (en) Skin cleanser composition
JP3532910B2 (en) Cleansing cosmetics
JP2003055128A (en) Transparent cosmetic composition
JP4763474B2 (en) Oily skin cleansing material
JP4746889B2 (en) Oily cleaning composition
JP2006176469A (en) Oily cleanser
JPH11246348A (en) Facial cleansing agent composition
JP2001288036A (en) Transparent cleansing cosmetic
JP3881953B2 (en) Liquid oily skin cleanser
JP2004115467A (en) Cleansing method
JP2003012456A (en) Cleansing preparation
JP4638018B2 (en) Oily cleaning agent
JP2006176470A (en) Oily cleanser
JP2004161631A (en) Composition for cleaning pore of skin
JP2005239616A (en) Oily skin cleanser

Legal Events

Date Code Title Description
A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20031203

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20040202

A02 Decision of refusal

Free format text: JAPANESE INTERMEDIATE CODE: A02

Effective date: 20040302

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20040506

A911 Transfer to examiner for re-examination before appeal (zenchi)

Free format text: JAPANESE INTERMEDIATE CODE: A911

Effective date: 20040630

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20040803

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20040809

R151 Written notification of patent or utility model registration

Ref document number: 3586682

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R151

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20080813

Year of fee payment: 4

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20080813

Year of fee payment: 4

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20090813

Year of fee payment: 5

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20090813

Year of fee payment: 5

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20100813

Year of fee payment: 6

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20110813

Year of fee payment: 7

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20110813

Year of fee payment: 7

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20120813

Year of fee payment: 8

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20120813

Year of fee payment: 8

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20130813

Year of fee payment: 9

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

LAPS Cancellation because of no payment of annual fees