JP3649299B2 - Water-soluble thickener and cosmetics containing the same - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は（メタ）アクリル酸またはその塩、（メタ）アクリルアミドアルキルスルホン酸またはその塩、架橋性単量体を共重合して得られる、もしくは得られた共重合体を更にアルカリ剤で中和して得られる、酸性下あるいは塩水溶液中においても粘度を低下させることの少ない水溶性増粘剤に関するものであり、例えば医薬品や化粧品を含む広汎な分野に利用できる。
【０００２】
また、本発明は、上記水溶性増粘剤を配合した化粧料に関するものであり、例えば、皮膚や毛髪を含む広汎な化粧料に利用できる。
【０００３】
【従来の技術】
医薬品および化粧品を含む広汎な分野で使用できる水溶性増粘剤としては、種々の多糖類、ゼラチンなどの天然高分子、ポリオキシエチレン、架橋ポリ（メタ）アクリル酸などの合成高分子、モンモリロナイト、シリカなどの無機鉱物などが挙げられる。特に、これらの中でも架橋ポリ（メタ）アクリル酸は安価で増粘効果が高く、少量でゲル化するため、医薬品および化粧品業界で高頻度で用いられている。
【０００４】
また、特に化粧料においては、増粘剤あるいは安定化剤として上記の水溶性増粘剤を配合している。
【０００５】
【発明が解決しようとする課題】
しかしながら、架橋ポリ（メタ）アクリル酸はｐＨ５以下の酸性下や塩の存在する水溶液中では、カルボキシル基の解離が抑えられ、粘度が極端に低下しゲル化しなくなる。このため、酸性条件や塩共存系が要求される処方では使えない。特に、使用性が重要なポイントを占める化粧品のゲル化剤としては、この特徴が致命的な欠点となることもある。例えば、ｐＨ５以下の酸性条件下では、増粘剤として用いられる架橋ポリ（メタ）アクリル酸は急激に粘度低下を起こすため、十分な粘度を保持するためにはその配合量を大幅に増やさなければならず、その結果、使用性が悪くなる。また、架橋ポリ（メタ）アクリル酸で増粘ゲル化させた化粧料を肌に塗布しようとすると、肌表面に存在する塩で水分を離してしまい、上滑り感のある使用性となってしまう。発汗直後の使用に際しては、特にこの上滑り感が顕著に現われる。
【０００６】
本発明者らは、こうした事情にかんがみ、医薬品および化粧品を含めた広汎な分野で使用可能で、高い増粘効果やゲル化機能を有する物質を探すべく、鋭意研究を重ねた結果、（メタ）アクリル酸またはその塩、（メタ）アクリルアミドアルキルスルホン酸またはその塩、架橋性単量体を共重合して得られる、水溶性増粘剤及びこれを配合した化粧料が上記課題を解決することを見出し、本発明を完成するに至った。
【０００７】
【課題を解決するための手段】
すなわち、本発明は、（メタ）アクリル酸及びまたはその塩と、（メタ）アクリルアミドアルキルスルホン酸及びまたはその塩と、架橋性単量体とを、重合開始剤により、共重合して得られる、もしくは得られた共重合体を更にアルカリ剤で中和して得られる、酸性下あるいは塩水溶液中においても、粘度を低下させることの少ない水溶性増粘剤を提供するものである。
また、本発明は、（メタ）アクリル酸及びまたはその塩と、（メタ）アクリルアミドアルキルスルホン酸及びまたはその塩と、架橋性単量体とを、重合開始剤により、共重合して得られる、もしくは得られた共重合体を更にアルカリ剤で中和して得られる耐酸性、耐塩性を有する化粧品医薬品用水溶性増粘剤を提供するものである。
【０００８】
また、本発明は上記水溶性増粘剤の（メタ）アクリル酸単位が４５〜９０モル％、（メタ）アクリルアミドアルキルスルホン酸単位が１０〜５５モル％含有され、更に架橋性単量体が０.００１〜２.０モル％含有されることを特徴とする上記記載の耐酸性、耐塩性を有する化粧品医薬品用水溶性増粘剤を提供するものである。
【０００９】
さらに、本発明は、上記記載の水溶性増粘剤を配合した耐酸、耐塩性に優れ、しかも使用性の良好な化粧料を提供するものである。
【００１０】
以下、本発明の構成について詳述する。
本発明において水溶性増粘剤として用いられる共重合体は、（メタ）アクリル酸及びまたはその塩と、（メタ）アクリルアミドアルキルスルホン酸及びまたはその塩と、架橋性単量体から得られる。（メタ）アクリルアミドアルキルスルホン酸はその塩を使用しても良く、その塩を単独あるいは（メタ）アクリルアミドアルキルスルホン酸と併用して共重合しても良い。
【００１１】
（メタ）アクリルアミドアルキルスルホン酸の塩としては、例えば、アルカリ金属、アンモニア、トリエチルアミン、トリエタノールアミン等の有機アミン塩を用いることが出来る。
【００１２】
また、得られる共重合体の（メタ）アクリルアミドアルキルスルホン酸単位をアルカリ剤で中和して本発明の水溶性増粘剤としても良い。
【００１３】
共重合の重合方法としては、溶液重合法、乳化重合法、塊状重合法等の公知の重合法で重合すれば良い。
【００１４】
重合開始剤としては、ラジカル重合を開始する能力を有するものであれば特に制限はないが、例えば、過酸化ベンゾイル、アゾビスイソブチロニトリル、過硫酸カリウム、過硫酸アンモニウム等が挙げられる。
【００１５】
なお、上記の方法で得られる共重合体は、酸性下、あるいは塩水溶液中においても粘度を低下させることの少ない水溶性増粘剤という本発明の効果を損なわない範囲で、（メタ）アクリル酸単位及び（メタ）アクリルアミドアルキルスルホン酸単位以外に、他のビニルモノマーからなる単位を含んでも良い。
【００１６】
本発明に使用する架橋性単量体は、一分子中に少なくとも２個の重合性二重結合を有し、（メタ）アクリル酸またはその塩、および（メタ）アクリルアミドアルキルスルホン酸またはその塩またはその塩を溶かす反応溶媒に溶解し、しかも共重合性が良くて効率よく架橋構造を取り得ることが必須である。
【００１７】
そのような架橋性単量体としては、エチレングリコールジアクリレート、エチレングリコールメタクリレート、ジエチレングリコールアクリレート、ジエチレングリコールジメタクリレート、トリメチロールプロパントリアクリレート、N,N'ーメチレンビスアクリルアミド、N,N'ーエチレンビスアクリルアミド、イソシアヌル酸トリアリル、ペンタエリスリトールジメタクリレートなどの中から選ばれた１種または２種以上を用いることができる。
【００１８】
また、本発明の共重合体である水溶性増粘剤の（メタ）アクリル酸またはその塩の含有量は４５〜９０モル％、（メタ）アクリルアミドアルキルスルホン酸またはその塩の含有量は１０〜５５モル％が好ましい。本発明の水溶性増粘剤の粘性は強解離基であるスルホニル基に基づく静電的反発による分子鎖の延び、スルホニル基とカルボキシル基間あるいはカルボキシル基同士の水素結合による高分子網目構造の発達に起因しているが、（メタ）アクリル酸またはその塩の含有量が４５モル％以下では上記の水素結合の形成が減少するため十分な粘度が得られない場合がある。また、（メタ）アクリル酸またはその塩の含有量が９０モル％以上すなわち（メタ）アクリルアミドアルキルスルホン酸またはその塩の含有量が１０モル％以下ではスルホニル基に基づく静電的反発、スルホニル基とカルボキシル基間の水素結合が共に減少するため同じく粘度は減少する場合がある。
【００１９】
本発明に用いられる架橋性単量体の使用量は、（メタ）アクリル酸またはその塩、および（メタ）アクリルアミドアルキルスルホン酸またはその塩またはその塩の全モル数に対し、０．００１〜２．０モル％が好ましい。０．００１ モル％以下で調製された水溶性増粘剤はそのゲル化能力が低い場合がる。また、２．０モル％以上で調製された水溶性増粘剤は水中に分散した場合、弾性ゲル化するため、好ましい使用性が得られない場合がある。
【００２０】
得られる水溶性増粘剤の分子量は１０万〜５００万で、加える架橋剤及び求められる粘度により調節する。
【００２１】
次に、本発明で得られる化粧料は、上記水溶性増粘剤の１種または２種以上を配合して製造されるが、好ましい配合量は、０．０１〜１０重量％、さらに好ましくは、０．１〜５重量％である。
【００２２】
なお、上記水溶性増粘剤を化粧料に配合する場合、酸性下、あるいは塩水溶液中においても粘度を低下させることの少ない化粧料を得るという本発明の効果を損なわない範囲で、水溶性増粘剤の（メタ）アクリル酸単位及び（メタ）アクリルアミドアルキルスルホン酸単位以外に、他のビニルモノマーからなる単位を含んでも良い。
【００２３】
本発明で得られる化粧料はその目的に応じて油性基材、界面活性剤、粉体、保湿剤、紫外線吸収剤、アルコール類、キレート剤、pH調製剤、防腐剤、酸化防止剤、増粘剤、薬剤、色素、香料、水等を発明の効果を損なわない範囲で適宜配合することができる。
【００２４】
本発明の化粧料の調製法は特に制限されないが、前記水溶性増粘剤を水に溶解したものを、水性基材として用いることにより、化粧水、美容液、染毛料などを調製出来る。また、油性基材と混合攪拌することにより、乳化化粧料を調製可能である。
【００２５】
【実施例】
以下、実施例によって本発明をさらに具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
【００２６】
「実施例１：水溶性増粘剤の製造」
２−アクリルアミド−２−メチルプロパンスルホン酸 ７ｇ（２５．７モル％相当）を純水 ７ｍｌに溶解し、それにアクリル酸７ｇ（７３．８モル％相当）を加え、冷却後、N,N'ーメチレンビスアクリルアミド ０．１ｇ（０．５モル％相当）を溶解させた。これに水酸化ナトリウム４．５ｇを純水１３ｍｌに溶解した溶液を冷却下で添加した後、更に過硫酸カリウム０．０５ｇを加え溶解させた。一方、ｎ−ヘキサン４００ｍｌにソルビタンモノステアレート２ｇを添加し、窒素気流下にて３５℃まで昇温して溶解させた後、攪拌下、上記の水溶液を徐添し乳化させた。６０℃まで昇温し、６時間反応させた後、室温まで冷却し、デカンテーションにより油層を除去した。水層をｎ−ヘキサン２００ｍｌにより数回洗浄し、沈殿物を分取後、真空乾燥して目的とする水溶性増粘剤である共重合体を得た。
【００２７】
「実施例２：水溶性増粘剤の製造」
２−アクリルアミド−２−メチルプロパンスルホン酸１４．５ｇ（５０．２モル％相当）、アクリル酸 ５ｇ（ ４９．８モル％相当）及びN,N'ーメチレンビスアクリルアミド ４．３×１０-3ｇを純水２０ｍｌに添加し、更に過硫酸カリウム０．０５ｇを加え溶解させた。この溶液をn-ヘキサン２００ｍｌ中に窒素気流下にて滴下し、６０℃で一晩反応させた。デカンテーションによりｎーヘキサンを除去した後、残った沈殿をメタノールに膨潤させて分取し、真空乾燥して目的とする水溶性増粘剤である共重合体を得た。
【００２８】
「実施例３：水溶性増粘剤の製造」
２−アクリルアミド−２−メチルプロパンスルホン酸２．２ｇ（１０．３モル％相当）、アクリル酸６．５ｇ（８７．８モル％相当）及びN,N'ーメチレンビスアクリルアミド０．３ｇ（１．９モル％相当）を純水２０ｍｌに添加した後、更に過硫酸カリウム０．０５ｇを溶解させた。一方、ｎ−ヘキサン４００ｍｌにソルビタンモノステアレート２ｇを添加し、窒素気流下にて３５℃まで昇温して溶解させた後、攪拌下、上記の水溶液を徐添し、６０℃まで昇温して６時間反応させた。反応液を室温まで冷却し、デカンテーションによって油層を除去した。水層をｎーヘキサン２００ｍｌにより数回洗浄し、沈殿物を分取後、真空乾燥して目的とする水溶性増粘剤である共重合体を得た。
【００２９】
上記実施例１により得られた水溶性増粘剤の４００ＭＨｚ−ＮＭＲ及びＦＴ−ＩＲチャートをそれぞれ図１及び図２に示す。４００ＭＨｚ−ＮＭＲは重水を溶媒として測定し、検出されたピークの化学シフトからアクリル酸単位のメチレン及びメチンプロトン、２−アクリルアミド−２−メチルプロパンスルホン酸単位のメチル、メチレン及びメチンプロトンを確認した。
【００３０】
ＦＴ−ＩＲはＫＢｒ法にて測定し、３４００ｃｍ-1付近及び１７００ｃｍ-1、１４１２ｃｍ-1、１２２４ｃｍ-1にカルボン酸由来の吸収を、１１９２ｃｍ-1、１０４８ｃｍ-1、６２７ｃｍ-1にスルホン酸由来の吸収を確認した。
【００３１】
次ぎに、実施例２で製造した水溶性増粘剤１％水溶液（実施例）及びハイビスワコー１０５（和光純薬社製）の１％水溶液（比較例）のｐＨを１０Ｎ水酸化ナトリウム水溶液にて調節し、各ｐＨにおける粘度をＢ型粘度計を用いて６ｒｐｍ、２５℃の条件で測定した。図３に粘度測定結果を示した。図３の結果より、実施例２で製造した水溶性増粘剤はどのｐＨ領域においても安定に粘度を保持することがわかった。
【００３２】
実施例２で製造した水溶性増粘剤１％水溶液（実施例）及びハイビスワコー１０５（和光純薬社製）の１％水溶液（比較例）を１Ｎ水酸化ナトリウム水溶液にてｐＨ３に調節し、イオン強度０.０１及び０.１における粘度をＥ型粘度計を用いて２０ｒｐｍ、２５℃の条件で測定した。イオン強度は塩化ナトリウムを用いて調節した。「表１」に粘度測定結果を示した。実施例２で製造した水溶性増粘剤は比較例と比べて耐塩性に優れていることがわかった。
【００３３】
【表１】
「化粧料の実施例及び比較例」
［実施例４、５、比較例１、２］
「表２」に、Ｏ／Ｗ型クリームである実施例４、５及び比較例１、２の処方とその評価結果を示す。水溶性増粘剤は実施例１で製造したものを配合した。「表２」から本発明の化粧料が、安定性及び使用性に優れていることがわかる。
【００３５】
【表２】
○：全く分離がみられない。
△：ごくわずかに油分が分離する。
×：著しい油分の分離が認められる。
安定性（０℃１カ月）評価法
○：変化なし。
△：ごくわずかにゲル化が見られる。
×：著しいゲル化が見られる。
使用性（とれ、べたつきのなさ）評価法
○：専門パネル10名中6名以上が良好と回答した。
△：専門パネル10名中4名以上が良好と回答した。
×：専門パネル10名中4名未満が良好と回答した。
【００３６】
「実施例６、比較例３、４」
「表３」に酸性染毛料の処方を示す。水溶性増粘剤は実施例２で製造したものを使用した。調製法は常法に従った。得られた各試料の粘度及びｐＨは「表３」のとおりであり、ほぼ同程度であった。次にこれら各試料の安定性及び使用性を評価した結果、実施例６は良好であった。これに対し、比較例３は経時でゲル化し使用性に劣るものであった。また、比較例４は経時で粘度が低下し使用性に劣るものであった。
【００３７】
【表３】
「実施例７」
「表４」にヘアジェルの処方を示す。水溶性増粘剤は実施例３で製造したものを使用した。常法により調製された実施例７はたれ落ちがない良好な使用性を示すヘアジェルであった。
【００３９】
【表４】
【発明の効果】
本発明の水溶性増粘剤によれば、酸性下あるいは塩水溶液中においても粘度を低下させることの少ない耐酸性と耐塩性を有する水性の増粘ゲル化剤を提供できる。例えば、医薬品や化粧品を含む広汎な分野に利用できる。このような耐塩耐酸性のある合成高分子からなる水溶性増粘剤は、これまで、化粧品、医薬品を含む広汎な分野において存在しない。
【００４１】
本発明の化粧料は、優れた耐酸性と耐塩性を有しており、体表面の塩によって引き起される粘度低下や離水現象が防げるため、上滑り感のない化粧料を提供できる。また、同時配合する薬物の安定ｐＨ領域が弱酸性であるため、通常では処方上ｐＨの制限がある場合でも本化粧料は全く問題なく、優れた安定性と使用性を示すものである。
【図面の簡単な説明】
【図１】実施例１で得られた水溶性増粘剤の４００ＭＨｚ−ＮＭＲスペクトルである。
【図２】実施例１で得られた水溶性増粘剤のＦＴ−ＩＲスペクトルである。
【図３】実施例２で製造した水溶性増粘剤の各ｐＨにおける粘度をＢ型粘度計を用いて６ｒｐｍ、２５℃の条件で測定した粘度測定結果である。[0001]
BACKGROUND OF THE INVENTION
The present invention is obtained by copolymerizing (meth) acrylic acid or a salt thereof, (meth) acrylamide alkyl sulfonic acid or a salt thereof, and a crosslinkable monomer, or neutralizing the obtained copolymer with an alkali agent. Thus obtained water-soluble thickeners that are less likely to reduce the viscosity even in an acidic or aqueous salt solution, can be used in a wide range of fields including pharmaceuticals and cosmetics.
[0002]
Moreover, this invention relates to the cosmetics which mix | blended the said water-soluble thickener, For example, it can utilize for the extensive cosmetics containing skin and hair.
[0003]
[Prior art]
Water-soluble thickeners that can be used in a wide range of fields including pharmaceuticals and cosmetics include various polysaccharides, natural polymers such as gelatin, synthetic polymers such as polyoxyethylene and cross-linked poly (meth) acrylic acid, montmorillonite, Examples thereof include inorganic minerals such as silica. Among these, in particular, crosslinked poly (meth) acrylic acid is inexpensive, has a high thickening effect, and gels in a small amount, so that it is frequently used in the pharmaceutical and cosmetic industries.
[0004]
Particularly in cosmetics, the above-mentioned water-soluble thickener is blended as a thickener or stabilizer.
[0005]
[Problems to be solved by the invention]
However, cross-linked poly (meth) acrylic acid has an acidic pH of 5 or lower or in an aqueous solution containing a salt, dissociation of carboxyl groups is suppressed, the viscosity is extremely lowered, and gelation does not occur. For this reason, it cannot be used in a formulation that requires acidic conditions or a salt coexistence system. In particular, as a gelling agent for cosmetics, where usability occupies an important point, this feature may be a fatal defect. For example, under acidic conditions of
[0006]
In view of these circumstances, the present inventors have conducted extensive research to find a substance that can be used in a wide range of fields including pharmaceuticals and cosmetics and has a high thickening effect and a gelling function. A water-soluble thickener obtained by copolymerizing acrylic acid or a salt thereof, (meth) acrylamide alkyl sulfonic acid or a salt thereof, and a crosslinkable monomer, and a cosmetic containing the same solve the above problems. The headline and the present invention were completed.
[0007]
[Means for Solving the Problems]
That is, the present invention is obtained by copolymerizing (meth) acrylic acid and / or a salt thereof, (meth) acrylamide alkylsulfonic acid and / or a salt thereof, and a crosslinkable monomer with a polymerization initiator. Alternatively, the present invention provides a water-soluble thickener which is obtained by further neutralizing the obtained copolymer with an alkali agent and hardly reduces the viscosity even in an acidic or salt solution.
Further, the present invention is obtained by copolymerizing (meth) acrylic acid and / or a salt thereof, (meth) acrylamide alkylsulfonic acid and / or a salt thereof, and a crosslinkable monomer with a polymerization initiator, Alternatively, the present invention provides a water-soluble thickener for cosmetics and drugs having acid resistance and salt resistance obtained by further neutralizing the obtained copolymer with an alkali agent .
[0008]
In the present invention, the water-soluble thickener contains 45 to 90 mol% of (meth) acrylic acid units, 10 to 55 mol% of (meth) acrylamidoalkylsulfonic acid units, and further contains 0 crosslinkable monomer. The present invention provides a water-soluble thickener for cosmetics and medicines having the acid resistance and salt resistance described above, characterized by containing 0.001 to 2.0 mol%.
[0009]
Furthermore, this invention provides the cosmetics which were excellent in the acid resistance and salt resistance which mix | blended the above-mentioned water-soluble thickener, and were also excellent in usability.
[0010]
Hereinafter, the configuration of the present invention will be described in detail.
The copolymer used as a water-soluble thickener in the present invention is obtained from (meth) acrylic acid and / or a salt thereof, (meth) acrylamide alkylsulfonic acid and / or a salt thereof, and a crosslinkable monomer. (Meth) acrylamide alkyl sulfonic acid may be used as a salt thereof, or the salt may be used alone or in combination with (meth) acrylamide alkyl sulfonic acid.
[0011]
As the salt of (meth) acrylamide alkyl sulfonic acid, for example, an organic amine salt such as alkali metal, ammonia, triethylamine, triethanolamine or the like can be used.
[0012]
Moreover, the (meth) acrylamide alkylsulfonic acid unit of the copolymer obtained may be neutralized with an alkali agent to form the water-soluble thickener of the present invention.
[0013]
As a polymerization method for copolymerization, polymerization may be performed by a known polymerization method such as a solution polymerization method, an emulsion polymerization method, or a bulk polymerization method.
[0014]
The polymerization initiator is not particularly limited as long as it has the ability to initiate radical polymerization, and examples thereof include benzoyl peroxide, azobisisobutyronitrile, potassium persulfate, and ammonium persulfate.
[0015]
The copolymer obtained by the above method is (meth) acrylic acid within a range that does not impair the effect of the present invention, which is a water-soluble thickener that hardly reduces the viscosity even under acidic conditions or in an aqueous salt solution. In addition to the unit and the (meth) acrylamide alkyl sulfonic acid unit, a unit composed of another vinyl monomer may be included.
[0016]
The crosslinkable monomer used in the present invention has at least two polymerizable double bonds in one molecule, (meth) acrylic acid or a salt thereof, and (meth) acrylamidoalkylsulfonic acid or a salt thereof or It is essential that the salt be dissolved in a reaction solvent that dissolves the salt, has good copolymerizability, and can take a crosslinked structure efficiently.
[0017]
Such crosslinkable monomers include ethylene glycol diacrylate, ethylene glycol methacrylate, diethylene glycol acrylate, diethylene glycol dimethacrylate, trimethylolpropane triacrylate, N, N'-methylenebisacrylamide, N, N'-ethylenebisacrylamide. One or two or more selected from triallyl isocyanurate, pentaerythritol dimethacrylate, and the like can be used.
[0018]
Further, the content of (meth) acrylic acid or a salt thereof of the water-soluble thickener which is a copolymer of the present invention is 45 to 90 mol%, and the content of (meth) acrylamide alkylsulfonic acid or a salt thereof is 10 to 10. 55 mol% is preferred. The viscosity of the water-soluble thickener of the present invention is that the molecular chain is extended by electrostatic repulsion based on the sulfonyl group that is a strong dissociation group, and the development of a polymer network structure by hydrogen bonding between the sulfonyl group and the carboxyl group or between the carboxyl groups. However, when the content of (meth) acrylic acid or a salt thereof is 45 mol% or less, the formation of the hydrogen bond is reduced, so that a sufficient viscosity may not be obtained. In addition, when the content of (meth) acrylic acid or a salt thereof is 90 mol% or more, that is, the content of (meth) acrylamide alkylsulfonic acid or a salt thereof is 10 mol% or less, electrostatic repulsion based on a sulfonyl group, Viscosity may also decrease because both hydrogen bonds between carboxyl groups decrease.
[0019]
The amount of the crosslinkable monomer used in the present invention is 0.001 to 2 with respect to the total number of moles of (meth) acrylic acid or a salt thereof and (meth) acrylamidoalkylsulfonic acid or a salt thereof or a salt thereof. 0.0 mol% is preferred. A water-soluble thickener prepared at 0.001 mol% or less may have a low gelling ability. Moreover, since the water-soluble thickener prepared by 2.0 mol% or more will be elastic-gelled when disperse | distributing in water, preferable usability may not be acquired.
[0020]
The obtained water-soluble thickener has a molecular weight of 100,000 to 5,000,000, and is adjusted according to the crosslinking agent to be added and the required viscosity.
[0021]
Next, the cosmetic obtained in the present invention is produced by blending one or more of the above-mentioned water-soluble thickeners, but the preferred blending amount is 0.01 to 10% by weight, more preferably 0.1 to 5% by weight.
[0022]
When the above-mentioned water-soluble thickener is blended in cosmetics, the solubility in water is increased within a range that does not impair the effect of the present invention to obtain cosmetics that are less likely to reduce viscosity even under acidic conditions or in an aqueous salt solution. In addition to the (meth) acrylic acid unit and the (meth) acrylamide alkyl sulfonic acid unit of the sticking agent, a unit composed of another vinyl monomer may be included.
[0023]
The cosmetics obtained in the present invention are oily base materials, surfactants, powders, moisturizers, ultraviolet absorbers, alcohols, chelating agents, pH adjusters, preservatives, antioxidants, thickeners depending on the purpose. Agents, drugs, pigments, fragrances, water, and the like can be appropriately blended within a range that does not impair the effects of the invention.
[0024]
The method for preparing the cosmetic composition of the present invention is not particularly limited, but a cosmetic solution, cosmetic liquid, hair dye, etc. can be prepared by using the water-soluble thickener dissolved in water as an aqueous base material. Moreover, emulsified cosmetics can be prepared by mixing and stirring with an oily base material.
[0025]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples.
[0026]
"Example 1: Production of water-soluble thickener"
7 g (corresponding to 25.7 mol%) of 2-acrylamido-2-methylpropanesulfonic acid was dissolved in 7 ml of pure water, 7 g of acrylic acid (corresponding to 73.8 mol%) was added thereto, and after cooling, N, N′- 0.1 g (equivalent to 0.5 mol%) of methylene bisacrylamide was dissolved. To this was added a solution prepared by dissolving 4.5 g of sodium hydroxide in 13 ml of pure water under cooling, and 0.05 g of potassium persulfate was further added and dissolved. On the other hand, 2 g of sorbitan monostearate was added to 400 ml of n-hexane, and the mixture was heated to 35 ° C. and dissolved in a nitrogen stream, and then the above aqueous solution was gradually added and emulsified with stirring. After heating up to 60 degreeC and making it react for 6 hours, it cooled to room temperature and removed the oil layer by decantation. The aqueous layer was washed several times with 200 ml of n-hexane, and the precipitate was collected and dried under vacuum to obtain a copolymer which was the target water-soluble thickener.
[0027]
"Example 2: Production of water-soluble thickener"
14.5 g (corresponding to 50.2 mol%) of 2-acrylamido-2-methylpropanesulfonic acid, 5 g of acrylic acid (corresponding to 49.8 mol%) and 4.3 × 10 −3 g of N, N′-methylenebisacrylamide It was added to 20 ml of pure water, and 0.05 g of potassium persulfate was further added and dissolved. This solution was dropped into 200 ml of n-hexane under a nitrogen stream and reacted at 60 ° C. overnight. After removing n-hexane by decantation, the remaining precipitate was swelled in methanol, collected, and dried in vacuo to obtain a desired water-soluble thickener copolymer.
[0028]
"Example 3: Production of water-soluble thickener"
2.2 g of 2-acrylamido-2-methylpropanesulfonic acid (corresponding to 10.3 mol%), 6.5 g of acrylic acid (corresponding to 87.8 mol%) and 0.3 g of N, N′-methylenebisacrylamide (1. 9 mol%) was added to 20 ml of pure water, and 0.05 g of potassium persulfate was further dissolved. On the other hand, 2 g of sorbitan monostearate was added to 400 ml of n-hexane, and the solution was heated to 35 ° C. and dissolved in a nitrogen stream, then the above aqueous solution was gradually added with stirring, and the temperature was raised to 60 ° C. For 6 hours. The reaction solution was cooled to room temperature, and the oil layer was removed by decantation. The aqueous layer was washed several times with 200 ml of n-hexane, and the precipitate was collected and dried under vacuum to obtain a copolymer which was the target water-soluble thickener.
[0029]
400 MHz-NMR and FT-IR charts of the water-soluble thickener obtained in Example 1 are shown in FIGS. 1 and 2, respectively. 400 MHz-NMR was measured using heavy water as a solvent, and methylene and methine protons of acrylic acid units and methyl, methylene and methine protons of 2-acrylamido-2-methylpropanesulfonic acid units were confirmed from the chemical shift of the detected peak.
[0030]
FT-IR was measured by KBr method, 3400 cm -1 and around 1700cm -1, 1412cm -1, the absorption derived from a carboxylic acid 1224cm -1, 1192cm -1, 1048cm -1 , derived from sulfonic acid 627cm -1 Absorption was confirmed.
[0031]
Next, the pH of the 1% aqueous solution (Example) of the water-soluble thickener prepared in Example 2 and the 1% aqueous solution (Comparative Example) of Hibiswaco 105 (manufactured by Wako Pure Chemical Industries, Ltd.) was adjusted with a 10N aqueous sodium hydroxide solution. The viscosity at each pH was measured using a B-type viscometer under the conditions of 6 rpm and 25 ° C. FIG. 3 shows the viscosity measurement results. From the results of FIG. 3, it was found that the water-soluble thickener produced in Example 2 stably maintained the viscosity in any pH range.
[0032]
A 1% aqueous solution (Example) of a water-soluble thickener prepared in Example 2 and a 1% aqueous solution (Comparative Example) of Hibiswako 105 (manufactured by Wako Pure Chemical Industries, Ltd.) were adjusted to pH 3 with a 1N sodium hydroxide aqueous solution, Viscosities at ionic strengths of 0.01 and 0.1 were measured using an E-type viscometer at 20 rpm and 25 ° C. The ionic strength was adjusted using sodium chloride. Table 1 shows the viscosity measurement results. It turned out that the water-soluble thickener manufactured in Example 2 is excellent in salt tolerance compared with the comparative example.
[0033]
[Table 1]
"Examples of cosmetics and comparative examples"
[Examples 4 and 5, Comparative Examples 1 and 2]
In “Table 2”, formulations of Examples 4 and 5 and Comparative Examples 1 and 2 which are O / W type creams and evaluation results thereof are shown. As the water-soluble thickener, the one produced in Example 1 was blended. From “Table 2”, it can be seen that the cosmetic of the present invention is excellent in stability and usability.
[0035]
[Table 2]
(Triangle | delta): Oil component isolate | separates very slightly.
X: Significant separation of oil is observed.
Stability (0 ° C, 1 month) evaluation method ○: No change.
(Triangle | delta): Gelation is seen very slightly.
X: Significant gelation is observed.
Usability (treasure, non-stickiness) evaluation method ○: More than 6 out of 10 professional panelists answered that it was good.
△: More than 4 out of 10 specialized panels answered that it was good.
×: Less than 4 out of 10 specialized panels responded good.
[0036]
"Example 6, comparative examples 3 and 4"
“Table 3” shows the formulation of acidic hair dye. The water-soluble thickener used in Example 2 was used. The preparation method followed a conventional method. The viscosity and pH of the obtained samples were as shown in “Table 3” and were substantially the same. Next, as a result of evaluating the stability and usability of each sample, Example 6 was good. In contrast, Comparative Example 3 gelled with time and was inferior in usability. In Comparative Example 4, the viscosity decreased with time and the usability was poor.
[0037]
[Table 3]
"Example 7"
Table 4 shows the hair gel formulation. The water-soluble thickener used was that prepared in Example 3. Example 7 prepared by a conventional method was a hair gel showing good usability without sagging.
[0039]
[Table 4]
【The invention's effect】
According to the water-soluble thickener of the present invention, it is possible to provide an aqueous thickening gelling agent having acid resistance and salt resistance that hardly reduces the viscosity even under acidic conditions or in an aqueous salt solution. For example, it can be used in a wide range of fields including pharmaceuticals and cosmetics. Such a water-soluble thickener comprising a synthetic polymer having salt and acid resistance has not existed in a wide range of fields including cosmetics and pharmaceuticals.
[0041]
The cosmetic of the present invention has excellent acid resistance and salt resistance, and can prevent a decrease in viscosity and a water separation phenomenon caused by salt on the body surface. In addition, since the stable pH range of the drugs to be blended is weakly acidic, even if there is usually a restriction of pH in the formulation, the present cosmetic has no problem at all and exhibits excellent stability and usability.
[Brief description of the drawings]
1 is a 400 MHz-NMR spectrum of the water-soluble thickener obtained in Example 1. FIG.
2 is an FT-IR spectrum of the water-soluble thickener obtained in Example 1. FIG.
3 is a viscosity measurement result obtained by measuring the viscosity at each pH of the water-soluble thickener produced in Example 2 using a B-type viscometer under the conditions of 6 rpm and 25 ° C. FIG.
Claims (4)
水溶性増粘剤。The water-soluble thickener contains 45 to 90 mol% of (meth) acrylic acid units, 10 to 55 mol% of (meth) acrylamidoalkylsulfonic acid units, and further has a crosslinkable monomer of 0.001 to 2. The water-soluble thickener for cosmetics and medicines having acid resistance and salt resistance according to claim 1 or 2, characterized by containing 0 mol% .
Water-soluble thickener.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34559695A JP3649299B2 (en) | 1995-12-08 | 1995-12-08 | Water-soluble thickener and cosmetics containing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34559695A JP3649299B2 (en) | 1995-12-08 | 1995-12-08 | Water-soluble thickener and cosmetics containing the same |
Publications (2)
| Publication Number | Publication Date |
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| JPH09157130A JPH09157130A (en) | 1997-06-17 |
| JP3649299B2 true JP3649299B2 (en) | 2005-05-18 |
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| JP34559695A Expired - Fee Related JP3649299B2 (en) | 1995-12-08 | 1995-12-08 | Water-soluble thickener and cosmetics containing the same |
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Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1047716B1 (en) * | 1998-01-16 | 2006-12-06 | Societe D'exploitation De Produits Pour Les Industries Chimiques-Seppic | Thickening latex, method of production and cosmetic applications |
| JP2000355614A (en) | 1999-06-15 | 2000-12-26 | Sumitomo Seika Chem Co Ltd | Carboxylated polymer composition |
| DE50015912D1 (en) * | 1999-07-15 | 2010-06-10 | Clariant Produkte Deutschland | Water-soluble polymers and their use in cosmetic and pharmaceutical compositions |
| EP1233750B1 (en) | 1999-11-19 | 2004-08-11 | Societe D'exploitation De Produits Pour Les Industries Chimiques, S.E.P.P.I.C. | Novel positive latex and use in cosmetics |
| KR100690469B1 (en) * | 2000-02-22 | 2007-03-09 | 칼라 액세스, 인크. | Gelled Aqueous Cosmetic Compositions |
| JP4883844B2 (en) | 2001-04-05 | 2012-02-22 | 住友精化株式会社 | Carboxyl group-containing polymer particles |
| EP1550706A4 (en) * | 2002-10-04 | 2006-02-01 | Toagosei Co Ltd | Water-soluble thickener and liquid acidic detergent |
| CN1330731C (en) * | 2002-10-04 | 2007-08-08 | 东亚合成株式会社 | Water-soluble thickener and liquid acidic detergent |
| US7455848B2 (en) * | 2002-12-18 | 2008-11-25 | Nalco Company | Skin care composition containing an anionic polymer |
| JP2007146064A (en) * | 2005-11-30 | 2007-06-14 | Shiseido Co Ltd | Gel composition |
| JP4782025B2 (en) | 2007-01-19 | 2011-09-28 | 信越化学工業株式会社 | Silicone copolymer and cosmetic containing the same |
| KR100844181B1 (en) * | 2007-02-15 | 2008-07-04 | 애경정밀화학 주식회사 | Composition for manufacturing a carboxylic group containing polymer and a polymer prepared thereof |
| EP1961450A1 (en) * | 2007-02-20 | 2008-08-27 | Wella Aktiengesellschaft | Dyes for keratinic fibers comprising a special anionic thickener |
| JP5669399B2 (en) * | 2010-01-07 | 2015-02-12 | 三菱鉛筆株式会社 | Aqueous cosmetics |
| JP6548866B2 (en) * | 2014-02-10 | 2019-07-24 | 住友精化株式会社 | Thickener for weakly acidic cosmetic, and weakly acidic cosmetic containing the thickener |
| FR3113907B1 (en) | 2020-09-07 | 2023-05-05 | Snf Sa | USE IN HYDROALCOHOLIC COMPOSITIONS OF A COPOLYMER OBTAINED BY PRECIPITATION POLYMERIZATION |
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1995
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