JP2005344061A - Polyamino acid derivative composition having thickening, foaming or foam increasing action - Google Patents
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Abstract
Description
本発明は、非イオン性のポリマーであって、その溶液が増粘および／または起泡もしくは増泡作用を有し、その泡はきめ細かく高い強度を持ち、かつ高い生体適合性と生分解性を併せ持つポリアミノ酸誘導体組成物に関する。 The present invention is a nonionic polymer whose solution has thickening and / or foaming or foaming action, the foam has fine and high strength, and high biocompatibility and biodegradability. The present invention also relates to a polyamino acid derivative composition that is also present.
従来、化粧品用等の増粘剤としては、カルボマーに代表されるポリアクリル酸やポリアクリル酸エステルなどのアクリル酸系ポリマー、またはメタクリル酸系ポリマー、ポリスチレンスルホン酸ナトリウム、カルボキシメチルセルロースやアルギン酸に代表される多糖類などが用いられてきた。しかしながら、これらは原料に刺激性の物質を含み、生体への適合性に問題がある。また、ポリアミノ酸系増粘剤としてはイオン性のアミノ酸樹脂が報告されている（特許文献１、特許文献２）。しかしながら、これらイオン性ポリマーの溶液はチャージを有する電解質、即ち塩などの存在下では顕著に粘度低下を招く欠点がある。 Conventionally, as a thickener for cosmetics and the like, it is represented by acrylic acid polymers such as polyacrylic acid and polyacrylic acid ester represented by carbomer, or methacrylic acid polymers, sodium polystyrene sulfonate, carboxymethylcellulose and alginic acid. Polysaccharides have been used. However, these contain irritating substances in the raw materials and have a problem in compatibility with living bodies. In addition, ionic amino acid resins have been reported as polyamino acid thickeners (Patent Documents 1 and 2). However, these ionic polymer solutions have a drawback that the viscosity is significantly reduced in the presence of a charged electrolyte, that is, a salt.
一方、起泡増泡剤としては脂肪酸、脂肪族アルコール、脂肪酸アルカノールアミド、脂肪酸アミドプロピルベタイン、サポニンに代表される配糖体などが用いられてきた。しかしながらこれらは泡立ち性、泡の持続性、水溶解性に問題があり、特に電解質の存在や弱酸性領域での使用では、剤に沈殿を生じたり、泡立ち性を顕著に悪化させることが分かっている。また、ポリアミノ酸系起泡増泡剤の原料としては、イオン性のアミノ酸樹脂が報告されている（特許文献３、特許文献４）。しかしながら、これらイオン性ポリマーの溶液は先に述べた増粘剤と同様、チャージを有する電解質存在下では顕著に起泡性低下を招く欠点がある。上記の通り、これらの諸問題を解決するポリアミノ酸系増粘剤や起泡増泡剤はこれまで存在しなかった。
近年、生活用品、衛生用品、医療用品等、人に身近な製品の材料は、生体に影響を与えない生体適合材料であり、且つ生分解性であることが必要とされて来ている。特に化粧品等、直接肌に触れる剤に配合されるものは肌に優しい生体適合性を有するものの要求がある。また、例えば化粧品、外用剤などにはミネラル成分をはじめとする塩類を配合する。これら塩類などの電解質の配合に対して増粘性または起泡増泡性を低下させないことは、化粧品分野に限らず重要な課題である。 In recent years, materials of products familiar to humans such as daily necessities, hygiene products, and medical products are required to be biocompatible materials that do not affect the living body and to be biodegradable. In particular, those that are blended in cosmetics and the like that directly touch the skin are required to have skin-friendly biocompatibility. In addition, for example, cosmetics, external preparations and the like are mixed with salts including mineral components. It is an important issue not only in the cosmetics field but not to lower the viscosity or foaming property with respect to the blending of electrolytes such as these salts.
すなわち本発明は、非イオン性のポリマーであって、その溶液が増粘作用または起泡増泡作用を有し、塩の存在下でも増粘作用や起泡増泡作用を低下させることなく、かつ高い生体適合性と生分解性を併せ持つポリアミノ酸誘導体組成物を提供することを目的とする。 That is, the present invention is a nonionic polymer, and the solution has a thickening action or a foaming foaming action, without reducing the thickening action or foaming foaming action even in the presence of a salt, Another object of the present invention is to provide a polyamino acid derivative composition having both high biocompatibility and biodegradability.
ポリアミノ酸は自然界に広く分布し、生物体内の蛋白質構成要素として存在し、生体適合性については非常に良好な性質を有している。また、生分解性も有するので、生体内で使用しても、また外部環境下に廃棄されても速やかに分解される。したがって、先に述べたような各種用途において、非常に有用なポリマーである。
本発明者らは上記の目的を達成するために鋭意検討した結果、生体適合性に優れたアミノ酸を原料とした特定の構造単位を有するポリアミノ酸誘導体で、特定の溶媒に溶解して増粘作用および／または起泡もしくは増泡作用を有し、その非イオン性によって、塩類など電解質の存在に対して増粘作用の低下を防止することができることを見出し、本発明を完成した。
本発明は非イオン性のポリマーであって、その溶液が増粘作用および／または起泡もしくは増泡作用を有し、塩の存在下でも増粘作用や起泡増泡作用を低下させることなく、かつ高い生体適合性と生分解性を併せ持つポリアミノ酸誘導体組成物である。
Polyamino acids are widely distributed in nature, exist as protein constituents in living organisms, and have very good properties for biocompatibility. Moreover, since it also has biodegradability, it is rapidly decomposed even if it is used in vivo or discarded in the external environment. Therefore, it is a very useful polymer in various applications as described above.
As a result of diligent investigations to achieve the above-mentioned object, the present inventors are polyamino acid derivatives having a specific structural unit made from an amino acid excellent in biocompatibility, and are dissolved in a specific solvent to increase the viscosity. It has been found that it has a foaming or foaming action, and its nonionicity can prevent a decrease in the thickening action with respect to the presence of an electrolyte such as a salt, thereby completing the present invention.
The present invention is a nonionic polymer whose solution has a thickening action and / or foaming or foaming action, and does not reduce the thickening action or foaming foaming action even in the presence of a salt. And a polyamino acid derivative composition having both high biocompatibility and biodegradability.
即ち、本発明は、
１．非イオン性ポリアミノ酸誘導体を含有する溶液が、増粘および／または起泡もしくは増泡することを特徴とするポリアミノ酸誘導体組成物、
２．前記溶液が水溶液である前記１記載のポリアミノ酸誘導体組成物、
３．前記溶液が、塩存在下で増粘および／または起泡もしくは増泡することを特徴とする前記１または２記載のポリアミノ酸誘導体組成物、
４．ポリアミノ酸誘導体が、ポリアスパラギン酸誘導体である前記１〜３の何れかに記載のポリアミノ酸誘導体組成物、
５．下記一般式（Ｉ）又は（II）
That is, the present invention
1. A polyamino acid derivative composition, wherein the solution containing the nonionic polyamino acid derivative is thickened and / or foamed or foamed,
2. 2. The polyamino acid derivative composition according to 1 above, wherein the solution is an aqueous solution.
3. 3. The polyamino acid derivative composition according to 1 or 2, wherein the solution is thickened and / or foamed or foamed in the presence of a salt,
4). The polyamino acid derivative composition according to any one of 1 to 3, wherein the polyamino acid derivative is a polyaspartic acid derivative,
5). The following general formula (I) or (II)
（式中、Ｒ１は炭素原子数３〜１８の炭化水素基を示し、Ｒ２はヘテロ原子を含んでも構わない炭素原子数１〜２０の炭化水素基を示す。）
で表されるα型又はβ型ポリアスパラギン酸単量体単位の少なくとも１種類の単量体単位を含む前記１〜４の何れかに記載のポリアミノ酸誘導体組成物、
６．前記一般式（Ｉ）におけるＲ１が、ヘキシル基、オクチル基、デシル基、ドデシル基、テトラデシル基、オクタデシル基およびイソプロピル基からなる群から選択され、一般式（II）におけるＲ2が、Ｎ，Ｎ−ジメチルアミノプロピル基、Ｎ，Ｎ−ジエチルアミノプロピル基、ヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシブチル基、ヒドロキシペンチル基、ヒドロキシエトキシエチル基、メトキシメチル基、メトキシエチル基、メトキシプロピル基、メトキシブチル基、メトキシペンチル基、エトキシメチル基、エトキシエチル基、エトキシプロピル基、エトキシブチル基およびエトキシペンチル基からなる群から選択される少なくとも1種類を含む前記５記載のポリアミノ酸誘導体組成物、
７．前記１〜６の何れかに記載のポリアミノ酸誘導体組成物を含有することを特徴とする増粘剤または起泡増泡剤、
８．前記７記載の増粘剤または起泡増泡剤を含有することを特徴とする化粧料または外用剤、
に関する。
(In the formula, R 1 represents a hydrocarbon group having 3 to 18 carbon atoms, and R 2 represents a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom.)
The polyamino acid derivative composition according to any one of 1 to 4 above, comprising at least one monomer unit of an α-type or β-type polyaspartic acid monomer unit represented by:
6). R 1 in the general formula (I) is selected from the group consisting of hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, octadecyl group and isopropyl group, and R 2 in the general formula (II) is N, N-dimethylaminopropyl group, N, N-diethylaminopropyl group, hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, hydroxypentyl group, hydroxyethoxyethyl group, methoxymethyl group, methoxyethyl group, methoxypropyl 6. The polyamino acid derivative composition according to 5 above, comprising at least one selected from the group consisting of a group, a methoxybutyl group, a methoxypentyl group, an ethoxymethyl group, an ethoxyethyl group, an ethoxypropyl group, an ethoxybutyl group, and an ethoxypentyl group ,
7). A thickener or a foaming foaming agent comprising the polyamino acid derivative composition according to any one of 1 to 6,
8). Cosmetic or external preparation characterized by containing the thickener or foaming foaming agent of said 7,
About.
本発明によれば、生体適合性に優れたアミノ酸を原料とした特定の構造単位を有するポリアミノ酸誘導体を含有する組成物が増粘作用および／または起泡もしくは増泡作用を有し、化粧品分野を初めとする生活用品、衛生用品、医療用品等、人に身近な製品の材料に配合する場合はもとより、当該材料中に塩類など電解質が存在する場合においても、その非イオン性によって、塩類など電解質の存在に対して増粘作用の低下を防止することができる。従って、本発明によれば、非イオン性のポリマーであって、その溶液が増粘作用および／または起泡もしくは増泡作用を有し、塩の存在下でも増粘作用や起泡増泡作用を低下させることなく、かつ高い生体適合性と生分解性を併せ持つポリアミノ酸誘導体組成物を提供することができる。 According to the present invention, a composition containing a polyamino acid derivative having a specific structural unit made from an amino acid excellent in biocompatibility has a thickening action and / or foaming or foaming action. Not only when blended into the materials of products that are familiar to humans, such as daily necessities, hygiene products, medical supplies, etc., but even when electrolytes such as salts are present in the materials, salts etc. It is possible to prevent a decrease in the thickening action with respect to the presence of the electrolyte. Therefore, according to the present invention, the nonionic polymer has a thickening action and / or foaming or foaming action, and the thickening action and foaming foaming action even in the presence of a salt. It is possible to provide a polyamino acid derivative composition having both high biocompatibility and biodegradability without lowering.
以下、本発明を詳細に説明する。
本発明は、非イオン性ポリアミノ酸誘導体を含有する溶液が、増粘および／または起泡もしくは増泡することを特徴とするポリアミノ酸誘導体組成物に関するものである。
Hereinafter, the present invention will be described in detail.
The present invention relates to a polyamino acid derivative composition characterized in that a solution containing a nonionic polyamino acid derivative is thickened and / or foamed or foamed.
本発明において、ポリアミノ酸とは、アミノ酸がペプチド縮重合した重合体をも包含する。また本発明において、重合体及びポリマーは相互に等価な意味である。重合体（ポリマー）を構成する単量体単位の配列の様式は、共重合体（コポリマー）である場合はランダム共重合体、ブロック共重合体、グラフト共重合体の何れでもよい。また、重合体（ポリマー）の分子鎖は、線状、大環状、分岐状、星状、三次元網目状のいずれでも良い。本発明において、炭化水素基は、直鎖状、分岐状、環状の何れでもよく、原子団の中に、Ｎ、Ｏ、Ｓ等のＣやＨ以外の原子が含まれていてもよい。 In the present invention, the polyamino acid also includes a polymer obtained by peptide condensation polymerization of amino acids. In the present invention, a polymer and a polymer are equivalent to each other. The arrangement of the monomer units constituting the polymer (polymer) may be any of a random copolymer, a block copolymer, and a graft copolymer in the case of a copolymer (copolymer). Further, the molecular chain of the polymer (polymer) may be any of linear, macrocyclic, branched, star, and three-dimensional network. In the present invention, the hydrocarbon group may be linear, branched or cyclic, and atoms other than C and H such as N, O and S may be contained in the atomic group.
本発明のポリアミノ酸誘導体は、その基本骨格がアミノ酸誘導体の単量体単位から成るものであればよく、特に制限はないが、特に、ポリアスパラギン酸誘導体であることが好ましい。具体的には、下記一般式（Ｉ）又は（II） The polyamino acid derivative of the present invention is not particularly limited as long as its basic skeleton is composed of a monomer unit of an amino acid derivative, and is particularly preferably a polyaspartic acid derivative. Specifically, the following general formula (I) or (II)
（式中、Ｒ１は炭素原子数３〜１８の炭化水素基を示し、Ｒ２はヘテロ原子を含んでも構わない炭素原子数１〜２０の炭化水素基を示す。）
で表されるα型又はβ型ポリアスパラギン酸単量体単位の少なくとも１種類を含むポリアスパラギン酸誘導体が好ましい。
(In the formula, R 1 represents a hydrocarbon group having 3 to 18 carbon atoms, and R 2 represents a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom.)
A polyaspartic acid derivative containing at least one type of α-type or β-type polyaspartic acid monomer unit represented by
一般式（II）の割合が多くなればＲ２で示される親水性基の影響が大きくなるため、ポリマーの水溶性が大きくなり、また一般式（I）の割合が多くなればＲ１で示される疎水性基の影響が大きくなるため、水には溶け難く脂溶性が大きくなる。 If the ratio of the general formula (II) increases, the influence of the hydrophilic group represented by R 2 increases, so that the water solubility of the polymer increases, and if the ratio of the general formula (I) increases, the ratio is represented by R 1 . Since the influence of the hydrophobic group to be increased becomes large, it is difficult to dissolve in water and the fat solubility is increased.
一般式（Ｉ）の単量体単位において、Ｒ１は炭素原子数３〜１８の炭化水素基を示す。
一般式（Ｉ）のＲ1の炭素原子数３〜１８の炭化水素基としては、疎水性で飽和又は不飽和の炭化水素基が挙げられる。Ｒ1の具体例としては、プロピル基、ブチル基、ペンチル基、ヘキシル基、オクチル基、ドデシル基、オクタデシル基等の直鎖状アルキル基；イソプロピル基、イソブチル基、イソペンチル基、イソヘキシル基等の分岐状アルキル基；シクロブチル基、シクロペンチル基、シクロヘキシル基等のシクロアルキル基；シクロブチルメチル基、シクロペンチルメチル基、シクロヘキシルメチル基、シクロブチルエチル基、シクロペンチルエチル基、シクロヘキシルエチル基、シクロブチルプロピル基、シクロペンチルプロピル基、シクロヘキシルプロピル基、シクロブチルブチル基、シクロペンチルブチル基、シクロヘキシルブチル基等のシクロアルキルアルキル基；プロペニル基、ブテニル基、ペンテニル基、ヘキセニル基等のアルケニル基が挙げられる。
In the monomer unit of the general formula (I), R 1 represents a hydrocarbon group having 3 to 18 carbon atoms.
Examples of the hydrocarbon group having 3 to 18 carbon atoms of R 1 in the general formula (I) include hydrophobic, saturated or unsaturated hydrocarbon groups. Specific examples of R 1 include linear alkyl groups such as propyl group, butyl group, pentyl group, hexyl group, octyl group, dodecyl group, octadecyl group; branched isopropyl group, isobutyl group, isopentyl group, isohexyl group, etc. Alkyl group; cycloalkyl group such as cyclobutyl group, cyclopentyl group, cyclohexyl group; cyclobutylmethyl group, cyclopentylmethyl group, cyclohexylmethyl group, cyclobutylethyl group, cyclopentylethyl group, cyclohexylethyl group, cyclobutylpropyl group, cyclopentyl Cycloalkylalkyl groups such as propyl group, cyclohexylpropyl group, cyclobutylbutyl group, cyclopentylbutyl group, cyclohexylbutyl group; alkenyl groups such as propenyl group, butenyl group, pentenyl group, hexenyl group It is below.
一般式（II）の単量体単位において、Ｒ２はヘテロ原子を含んでも構わない炭素原子数１〜２０の炭化水素基を示す。
一般式（II）のＲ2のヘテロ原子を含んでも構わない炭素原子数１〜２０の炭化水素基としては、親水性でＮ、Ｏ、Ｓ等を含んでいてもよい飽和又は不飽和の炭化水素基が挙げられる。Ｒ2の具体例としては、ヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシブチル基、ヒドロキシペンチル基、ヒドロキシヘキシル基、ヒドロキシヘプチル基、ヒドロキシオクチル基等のヒドロキシアルキル基；ジメチルアミノ基、ジエチルアミノ基、ジプロピルアミノ基、ジブチルアミノ基等のジアルキルアミノ基；アザプロピル基、アザブチル基、アザペンチル基、アザヘキシル基、Ｎ,Ｎ−ジメチルアミノブチル基、Ｎ,Ｎ−ジメチルアミノプロピル基、Ｎ,Ｎ−ジメチルアミノエチル基、Ｎ,Ｎ−ジメチルアミノメチル基、Ｎ,Ｎ−ジエチルアミノブチル基、Ｎ,Ｎ−ジエチルアミノプロピル基、Ｎ,Ｎ−ジエチルアミノエチル基、Ｎ,Ｎ−ジエチルアミノメチル基等のアザアルキル基；アザプロペニル基、アザブテニル基、アザペンテニル基、アザヘキセニル基、Ｎ,Ｎ−ジメチルアミノプロペニル基、Ｎ,Ｎ−ジメチルアミノブテニル基、Ｎ,Ｎ−ジメチルアミノヘキセニル基、Ｎ,Ｎ−ジエチルアミノプロペニル基等のアザアルケニル基；オキサエチル基、オキサプロピル基、オキサブチル基、オキサペンチル基、オキサヘキシル基、オキサヘプチル基、オキサオクチル基等のオキサアルキル基；オキサプロペニル基、オキサブテニル基、オキサペンテニル基、オキサヘキセニル基、オキサヘプテニル基、オキサオクテニル基等のオキサアルキケニル基；チオブチル基、チオペンチル基、チオヘキシル基、チオヘプチル基、チオオクチル基等のチオアルキル基；チオペンテニル基、チオヘキセニル基、チオヘプテニル基、チオオクテニル基等のチオアルケニル基；ヒドロキシエトキシエチル基、ヒドロキシエトキシプロピル基、ヒドロキシエトキシブチル基、ヒドロキシプロポキシエチル基、ヒドロキシプロポキシプロピル基、ヒドロキシプロポキシブチル基等のヒドロキシアルコキシアルキル基；メトキシエトキシエチル基、メトキシエトキシプロピル基、メトキシエトキシブチル基、メトキシプロポキシエチル基、メトキシプロポキシプロピル基、メトキシプロポキシブチル基等のアルコキシアルコキシアルキル基などが挙げられる。
In the monomer unit of the general formula (II), R 2 represents a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom.
The hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom of R 2 in the general formula (II) is a saturated or unsaturated carbon atom which is hydrophilic and may contain N, O, S or the like. A hydrogen group is mentioned. Specific examples of R 2 include hydroxyalkyl groups such as hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, hydroxypentyl group, hydroxyhexyl group, hydroxyheptyl group, hydroxyoctyl group; dimethylamino group, diethylamino group Group, dipropylamino group such as dipropylamino group, dibutylamino group; azapropyl group, azabutyl group, azapentyl group, azahexyl group, N, N-dimethylaminobutyl group, N, N-dimethylaminopropyl group, N, N- Azaalkyl groups such as dimethylaminoethyl group, N, N-dimethylaminomethyl group, N, N-diethylaminobutyl group, N, N-diethylaminopropyl group, N, N-diethylaminoethyl group, N, N-diethylaminomethyl group; Azapropenyl group, azabute Azaalkenyl such as nyl, azapentenyl, azahexenyl, N, N-dimethylaminopropenyl, N, N-dimethylaminobutenyl, N, N-dimethylaminohexenyl, N, N-diethylaminopropenyl Group: Oxaalkyl group such as oxaethyl group, oxapropyl group, oxabutyl group, oxapentyl group, oxahexyl group, oxaheptyl group, oxaoctyl group; oxapropenyl group, oxabutenyl group, oxapentenyl group, oxahexenyl group, oxaheptenyl group Oxaalkenyl group such as oxaoctenyl group; thioalkyl group such as thiobutyl group, thiopentyl group, thiohexyl group, thioheptyl group, thiooctyl group; thioalkenyl group such as thiopentenyl group, thiohexenyl group, thioheptenyl group, thiooctenyl group Hydroxyl group; hydroxyalkoxyalkyl group such as hydroxyethoxyethyl group, hydroxyethoxypropyl group, hydroxyethoxybutyl group, hydroxypropoxyethyl group, hydroxypropoxypropyl group, hydroxypropoxybutyl group; methoxyethoxyethyl group, methoxyethoxypropyl group, methoxy Examples thereof include alkoxyalkoxyalkyl groups such as ethoxybutyl group, methoxypropoxyethyl group, methoxypropoxypropyl group, and methoxypropoxybutyl group.
好ましくは一般式（I）において、Ｒ１がヘキシル基、オクチル基、デシル基、ドデシル基、テトラデシル基、オクタデシル基およびイソプロピル基からなる群から選択される基であり、一般式（II）において、Ｒ２がＮ，Ｎ−ジメチルアミノプロピル基、Ｎ，Ｎ−ジエチルアミノプロピル基、ヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシブチル基、ヒドロキシペンチル基、ヒドロキシエトキシエチル基、メトキシメチル基、メトキシエチル基、メトキシプロピル基、メトキシブチル基、メトキシペンチル基、エトキシメチル基、エトキシエチル基、エトキシプロピル基、エトキシブチル基およびエトキシペンチル基からなる群から選択される基である。 Preferably, in the general formula (I), R 1 is a group selected from the group consisting of a hexyl group, an octyl group, a decyl group, a dodecyl group, a tetradecyl group, an octadecyl group and an isopropyl group. In the general formula (II), R 2 is N, N-dimethylaminopropyl group, N, N-diethylaminopropyl group, hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, hydroxypentyl group, hydroxyethoxyethyl group, methoxymethyl group, methoxy It is a group selected from the group consisting of an ethyl group, a methoxypropyl group, a methoxybutyl group, a methoxypentyl group, an ethoxymethyl group, an ethoxyethyl group, an ethoxypropyl group, an ethoxybutyl group, and an ethoxypentyl group.
なお、一般式（Ｉ）及び（II）中のＲ１とＲ２は、それぞれ複数の異なる基から構成されていてもよい。 Note that R 1 and R 2 in the general formulas (I) and (II) may each be composed of a plurality of different groups.
本発明のポリアミノ酸誘導体において、α−アミド型単量体単位及びβ−アミド型単量体単位は、何れか一方のみが存在していてもよく、両者が併存していてもよい。併存している場合、α−アミド型単量体単位とβ−アミド型単量体単位の比率は特に限定されない。 In the polyamino acid derivative of the present invention, only one of the α-amide type monomer unit and the β-amide type monomer unit may exist, or both may coexist. When they coexist, the ratio of the α-amide type monomer unit to the β-amide type monomer unit is not particularly limited.
本発明で用いられるポリアミノ酸誘導体は、例えば、ポリこはく酸イミドを原料として製造できる。
ポリこはく酸イミドは、従来より知られる各種の方法で製造でき、例えば、J.Am.Chem.Soc.,80,3361(1985) には、アスパラギン酸を２００℃で２〜３時間加熱縮合させることにより、ポリこはく酸イミドを製造する方法が開示されている。特公昭４８−２０６３８号公報には、８５％のリン酸を触媒としてロータリーエバポレーターを使用して薄膜状でアスパラギン酸の反応を行うことにより、高分子量のポリこはく酸イミドを得る方法が開示されている。米国特許第５０５７５９７号には、工業的にポリこはく酸イミドを得る方法として、流動床によりポリアスパラギン酸を加熱縮合させる方法が開示されている。また。さらに高分子量のポリこはく酸イミドを必要とする場合には、上記の方法で得られたポリこはく酸イミドを、ジシクロヘキシルカルボジイミドなどの縮合剤で処理することにより連結することもできる。
The polyamino acid derivative used in the present invention can be produced using, for example, polysuccinimide as a raw material.
Polysuccinimide can be produced by various conventionally known methods. For example, in J. Am. Chem. Soc., 80, 3361 (1985), aspartic acid is heated and condensed at 200 ° C. for 2 to 3 hours. Thus, a method for producing polysuccinimide is disclosed. Japanese Patent Publication No. 48-20638 discloses a method of obtaining a high molecular weight polysuccinimide by reacting aspartic acid in a thin film using a rotary evaporator with 85% phosphoric acid as a catalyst. Yes. US Pat. No. 5,057,597 discloses a method for industrially obtaining polysuccinimide by heat condensation of polyaspartic acid in a fluidized bed. Also. Further, when a high molecular weight polysuccinimide is required, the polysuccinimide obtained by the above method can be linked by treating with a condensing agent such as dicyclohexylcarbodiimide.
本発明のポリアミノ酸誘導体を製造する為に使用するポリこはく酸イミドの分子量は、所望の特性を有する生成物が実質的に得られれば特に制限されない。一般的には、ポリこはく酸イミドの分子量は、２０００〜５０００００程度が好ましく、１００００〜４０００００程度がより好ましく、１５０００〜２０００００程度が特に好ましい。この分子量は、ゲル・パーミエーション・クロマトグラフィーで、Ｎ,Ｎ−ジメチルホルムアミド溶液中、４５℃で測定し、ポリスチレン標準で求めた値である。使用するポリこはく酸イミドの分子量が低ければ、得られるポリアミノ酸誘導体の分子量も低くなり、ポリこはく酸イミドの分子量が高ければ、得られるポリアミノ酸誘導体の分子量も高くなる。 The molecular weight of the polysuccinimide used for producing the polyamino acid derivative of the present invention is not particularly limited as long as a product having desired characteristics is substantially obtained. Generally, the molecular weight of polysuccinimide is preferably about 2000 to 500000, more preferably about 10000 to 400000, and particularly preferably about 15000 to 200000. This molecular weight is a value obtained by measuring with a gel permeation chromatography at 45 ° C. in an N, N-dimethylformamide solution and using a polystyrene standard. If the molecular weight of the polysuccinimide used is low, the molecular weight of the resulting polyamino acid derivative will be low, and if the molecular weight of the polysuccinimide is high, the molecular weight of the polyamino acid derivative obtained will also be high.
本発明のポリこはく酸イミドからポリアミノ酸誘導体を製造する際の方法は、特に制限されず、例えば、以下の製造方法が挙げられる。先ず、ポリこはく酸イミドを適当な溶媒に溶解する。この溶媒としては、ポリこはく酸イミドが溶解し、アミン類との反応で副反応を起こさなければ特に限定されない。例えば、Ｎ,Ｎ−ジメチルホルムアミド、ジメチルスルホキシド、スルホラン等が用いられる。 The method in particular when manufacturing a polyamino acid derivative from the polysuccinimide of this invention is not restrict | limited, For example, the following manufacturing methods are mentioned. First, polysuccinimide is dissolved in a suitable solvent. The solvent is not particularly limited as long as polysuccinimide is dissolved and no side reaction is caused by reaction with amines. For example, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane and the like are used.
この溶媒中で、ポリこはく酸イミドのイミド環に対して、ドデシルアミン、オクタデシルアミン、Ｎ,Ｎ−ジメチルアミノプロピルアミン、２−アミノエタノール、３−アミノプロパノール、４−アミノブタノール等のアミン類を反応させる。ポリこはく酸イミドのイミド環のモル数に対して、アミン類を１倍モル添加し反応を行うと、アミン類はイミド環を開環させて付加し、側鎖のグラフト構造を形成する。 In this solvent, amines such as dodecylamine, octadecylamine, N, N-dimethylaminopropylamine, 2-aminoethanol, 3-aminopropanol, 4-aminobutanol are added to the imide ring of polysuccinimide. React. When the reaction is performed by adding 1 mole of amine to the number of moles of the imide ring of polysuccinimide, the amine is added by opening the imide ring to form a side chain graft structure.
次いで、得られた反応混合物を、貧溶媒中に排出する。この貧溶媒としては、ポリアミノ酸誘導体が沈殿し、その後濾過乾燥した際に、ポリアミノ酸誘導体の結晶中に残存しないような溶媒であれば特に限定されない。例えば、アセトニトリル、アセトン、メタノール、エタノール等が用いられる。上述のようにして得た沈殿を濾取し、貧溶媒で洗浄し、乾燥することにより、目的のポリアミノ酸誘導体が得られる。 The resulting reaction mixture is then discharged into a poor solvent. The poor solvent is not particularly limited as long as the polyamino acid derivative is precipitated and then filtered and dried so that it does not remain in the crystal of the polyamino acid derivative. For example, acetonitrile, acetone, methanol, ethanol or the like is used. The target polyamino acid derivative is obtained by filtering the precipitate obtained as described above, washing with a poor solvent, and drying.
本発明のポリアミノ酸誘導体組成物は、非イオン性ポリアミノ酸誘導体を少なくとも１種以上含有するものであり、通常は、これらを適当な溶媒に溶解した溶液の形態が好ましい。本発明の組成物としては、他のポリアミノ酸誘導体を含んでいても構わない。さらに、上記の他、必要に応じて、香料、防腐剤、安定剤、ミネラル成分、着色料、洗浄剤等の補助成分（添加剤）を含んでいても良い。 The polyamino acid derivative composition of the present invention contains at least one nonionic polyamino acid derivative, and usually a solution in which these are dissolved in an appropriate solvent is preferable. The composition of the present invention may contain other polyamino acid derivatives. In addition to the above, auxiliary components (additives) such as fragrances, preservatives, stabilizers, mineral components, colorants, and cleaning agents may be included as necessary.
本発明の組成物において、非イオン性ポリアミノ酸誘導体と溶媒の混合比に特に制限はなく、どのような混合割合であっても構わない。通常、非イオン性ポリアミノ酸誘導体濃度で０．１〜６０重量％、好ましくは、１〜３０重量％である。また場合によっては、非イオン性ポリアミノ酸誘導体のみであっても構わない。また、他のポリアミノ酸誘導体配合する場合は実質的に増粘性や増泡性を損なわない範囲で配合できる。通常、ポリアミノ酸誘導体濃度で１０重量％以下、好ましくは５重量％以下である。同様に補助成分も実質的に増粘性や増泡性を損なわない範囲で配合できる。通常、配合濃度で２０重量％以下、好ましくは１０重量％以下である。 In the composition of the present invention, the mixing ratio of the nonionic polyamino acid derivative and the solvent is not particularly limited, and any mixing ratio may be used. Usually, the nonionic polyamino acid derivative concentration is 0.1 to 60% by weight, preferably 1 to 30% by weight. In some cases, only nonionic polyamino acid derivatives may be used. Moreover, when mix | blending another polyamino acid derivative, it can mix | blend in the range which does not impair a viscosity increase or foam increase property substantially. Usually, the polyamino acid derivative concentration is 10% by weight or less, preferably 5% by weight or less. Similarly, auxiliary components can be blended within a range that does not substantially impair the thickening and foaming properties. Usually, the blending concentration is 20% by weight or less, preferably 10% by weight or less.
本発明の非イオン性ポリアミノ酸誘導体としては、非イオン性のポリアミノ酸誘導体であれば良く、特に制限はないが、本発明においては、上記に説明したポリアミノ酸誘導体が好適に用いられる。より具体的には、アスパラギン酸ラウリルアミド−ヒドロキシエチルアミド共重合体、アスパラギン酸ラウリルアミド−ヒドロキシプロピルアミド共重合体、アスパラギン酸ラウリルアミド−ヒドロキシブチルアミド共重合体、アスパラギン酸ラウリルアミド−メトキシエチルアミド共重合体、アスパラギン酸ラウリルアミド−メトキシプロピルアミド共重合体、アスパラギン酸ラウリルアミド−ヒドロキシエトキシエチルアミド共重合体、アスパラギン酸ラウリルアミド−ジメチルアミノエチルアミド共重合体、アスパラギン酸ラウリルアミド−ジメチルアミノプロピルアミド共重合体、アスパラギン酸デシルアミド−ヒドロキシエチルアミド共重合体、アスパラギン酸デシルアミド−ヒドロキシプロピルアミド共重合体、アスパラギン酸デシルアミド−メトキシエチルアミド共重合体、アスパラギン酸デシルアミド−ヒドロキシエトキシエチルアミド共重合体、アスパラギン酸デシルアミド−ジメチルアミノプロピルアミド共重合体、アスパラギン酸オクチルアミド−ヒドロキシエチルアミド共重合体、アスパラギン酸オクチルアミド−ヒドロキシプロピルアミド共重合体、アスパラギン酸オクチルアミド−メトキシエチルアミド共重合体、アスパラギン酸オクチルアミド−ヒドロキシエトキシエチルアミド共重合体、アスパラギン酸オクチルアミド−ジメチルアミノプロピルアミド共重合体等が挙げられる。 The nonionic polyamino acid derivative of the present invention is not particularly limited as long as it is a nonionic polyamino acid derivative. In the present invention, the polyamino acid derivative described above is preferably used. More specifically, aspartic acid laurylamide-hydroxyethylamide copolymer, aspartic acid laurylamide-hydroxypropylamide copolymer, aspartic acid laurylamide-hydroxybutyramide copolymer, aspartic acid laurylamide-methoxyethylamide Copolymer, Aspartic acid laurylamide-methoxypropylamide copolymer, Aspartic acid laurylamide-hydroxyethoxyethylamide copolymer, Aspartic acid laurylamide-dimethylaminoethylamide copolymer, Aspartic acid laurylamide-dimethylaminopropyl Amide copolymer, Aspartic acid decylamide-hydroxyethylamide copolymer, Aspartic acid decylamide-hydroxypropylamide copolymer, Aspartic acid Silamide-methoxyethylamide copolymer, aspartic acid decylamide-hydroxyethoxyethylamide copolymer, aspartic acid decylamide-dimethylaminopropylamide copolymer, aspartic acid octylamide-hydroxyethylamide copolymer, aspartic acid octylamide- Examples thereof include a hydroxypropylamide copolymer, an aspartic acid octylamide-methoxyethylamide copolymer, an aspartic acid octylamide-hydroxyethoxyethylamide copolymer, an aspartic acid octylamide-dimethylaminopropylamide copolymer, and the like.
本発明のポリアミノ酸誘導体は、その溶液が増粘性を有するか、または起泡増泡性を有するか、その両方の機能を有することを特徴とする。粘度測定の具体的な方法は次の通りである。まず、ポリアミノ酸誘導体を水又はその他の溶媒を使用して溶解し任意の濃度の溶液を調製する。この溶液をレオメーターにて一定温度で粘度測定を行う。特に、塩存在下での粘度挙動を測定する場合は予め一定濃度の塩を溶解した溶液を調製し、これに任意の濃度のポリアミノ酸誘導体を溶解することによって溶液を調製して測定する。起泡増泡性測定の具体的な方法は次の通りである。まず、ポリアミノ酸誘導体を水又はその他の溶媒を使用して溶解し任意の濃度の溶液を調製する。この溶液をメスシリンダー中に一定量入れ、任意の振幅一定数振とうする。泡量の体積を測定し経時変化を記録する。ポリアミノ酸誘導体の溶液が増粘性や起泡増泡性を有するという特性を付与する為には、例えば、水溶液中でそれらの機能を有する場合、ポリアミノ酸誘導体の側鎖基の種類と含有比率、ポリアミノ酸誘導体の分子量（例えば、原料ポリこはく酸イミドの分子量により調整可能）、その他、水に溶解するポリアミノ酸の濃度、溶媒の種類など、諸条件を所望に応じて設定すればよい。 The polyamino acid derivative of the present invention is characterized in that the solution has a thickening property or a foaming property, or has both functions. A specific method for measuring the viscosity is as follows. First, a polyamino acid derivative is dissolved using water or another solvent to prepare a solution having an arbitrary concentration. The viscosity of this solution is measured with a rheometer at a constant temperature. In particular, when measuring the viscosity behavior in the presence of a salt, a solution in which a salt at a certain concentration is dissolved is prepared in advance, and a solution is prepared by dissolving a polyamino acid derivative at an arbitrary concentration in the solution. A specific method for measuring the foaming property is as follows. First, a polyamino acid derivative is dissolved using water or another solvent to prepare a solution having an arbitrary concentration. A fixed amount of this solution is placed in a graduated cylinder and shaken at a fixed number of arbitrary amplitudes. Measure the volume of foam and record the change over time. In order to give the property that the polyamino acid derivative solution has thickening and foaming foaming properties, for example, when it has these functions in an aqueous solution, the type and content ratio of the side chain group of the polyamino acid derivative, Various conditions such as the molecular weight of the polyamino acid derivative (for example, adjustable by the molecular weight of the raw material polysuccinimide), the concentration of the polyamino acid dissolved in water, the type of solvent, and the like may be set as desired.
本発明のポリアミノ酸誘導体組成物を含有することによって得られる増粘剤や起泡増泡剤は、必要に応じて、色素、香料、アルコール、防腐剤、顔料、抗酸化剤、流動パラフィン、界面活性剤、水溶性高分子、塩類、ミネラル成分、ｐＨ調節剤などを本発明のポリアミノ酸誘導体の機能を損なわない範囲内で添加してもよく、これらが添加された増粘剤、或いは起泡増泡剤も本発明に含まれる。増粘剤や起泡増泡剤の形態は、特に限定されるものではなく、また製造については従来知られている方法を採用することができる。本発明の増粘剤や起泡増泡剤は、化粧料や外用剤に配合したり、増粘性、起泡増泡性を必要とする剤等に添加して用いられるものである．
本発明の増粘性を有するポリアミノ酸誘導体組成物の配合先は、化粧料一般、具体的には化粧水、保湿液、洗顔オイル、クレンジングオイル、クレンジングミルク、クレンジングローション、マッサージオイル、モイスチャータリーム、シェービングオイル、シェービングローション、シェームース、日焼け止めローション、日焼け用オイル、ボディーローション、ボディーシャンプー、ヘアシャンプー、ヘアリンス、ヘアートリートメント、養毛オイル、ヘアオイル、ヘアムース、香油、ヘアリキッド、セットローション、ヘアスプレー、ヘアブリーチ、カラーリンス、カラースプレー、パーマネントウェーブ液、ハンドローションが挙げられる。
Thickeners and foaming foaming agents obtained by containing the polyamino acid derivative composition of the present invention are dyes, fragrances, alcohols, preservatives, pigments, antioxidants, liquid paraffin, interfaces as necessary. An active agent, a water-soluble polymer, a salt, a mineral component, a pH adjuster, and the like may be added within a range that does not impair the function of the polyamino acid derivative of the present invention. A foam booster is also included in the present invention. The form of the thickener or the foaming foaming agent is not particularly limited, and a conventionally known method can be adopted for production. The thickener and foaming foaming agent of the present invention are used in cosmetics and external preparations or added to agents that require thickening and foaming foaming properties.
The blending destination of the polyamino acid derivative composition with thickening according to the present invention is generally used in cosmetics, specifically, lotion, moisturizing liquid, facial cleansing oil, cleansing oil, cleansing milk, cleansing lotion, massage oil, moisture cream, Shaving oil, shaving lotion, shaving mousse, sunscreen lotion, tanning oil, body lotion, body shampoo, hair shampoo, hair rinse, hair treatment, hair nourishing oil, hair oil, hair mousse, perfume oil, hair liquid, set lotion, hair spray, hair Examples include bleach, color rinse, color spray, permanent wave liquid, and hand lotion.
本発明の外用剤は外用医薬品に配合するもの全般が挙げられ、湿布剤、鎮痛剤、冷却剤、除熱剤、保温剤、消毒殺菌剤、角質軟化剤、抗真菌剤、日焼防止剤、皮膚漂白剤、皮膚着色剤、肉芽発生剤、表皮形成剤、養毛発毛剤、防臭剤、発汗抑制剤、ビタミン剤などが挙げられる。 Examples of the external preparation of the present invention include all of those blended in external medicines, such as poultices, analgesics, cooling agents, heat removal agents, heat retention agents, disinfecting disinfectants, keratin softeners, antifungal agents, sunscreen agents, Examples include skin bleaching agents, skin coloring agents, granulation agents, epidermis forming agents, hair nourishing agents, deodorants, antiperspirants, vitamins and the like.
本発明の化粧料または外用剤における上記増粘剤や起泡増泡剤の配合量としては、ポリアミノ酸誘導体の含有量０．０１質量％以上が好ましく、更に好ましくは０．１質量％以上である。これよりも少ない含有量であれば充分な増粘性や起泡増泡性が得られない可能性がある。 The blending amount of the thickener and the foaming foaming agent in the cosmetic or external preparation of the present invention is preferably 0.01% by mass or more, more preferably 0.1% by mass or more of the polyamino acid derivative. is there. If the content is less than this, there is a possibility that sufficient thickening or foaming property cannot be obtained.
以下、実施例により本発明を具体的に説明するが、本発明はこれらの実施例によって何等限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by these Examples.
本実施例において、原料のポリこはく酸イミド（以下ＰＳＩと略記する）としては、重量平均分子量（以下Ｍｗと略記する）が９７０００のものを用いた。このＭｗは、ゲル・パーミエーション・クロマトグラフィーで、Ｎ,Ｎ−ジメチルホルムアミド（以下ＤＭＦと略記する）溶液中、４５℃で測定し、ポリスチレン標準で求めた値である。また、反応容器としては、攪拌機、ヒーター、温度計及び窒素ラインを備えたセパラブル・フラスコを使用し、反応中は反応系を充分に攪拌しながら実施した。 In this example, a raw material polysuccinimide (hereinafter abbreviated as PSI) having a weight average molecular weight (hereinafter abbreviated as Mw) of 97000 was used. This Mw is a value determined by gel permeation chromatography, measured at 45 ° C. in an N, N-dimethylformamide (hereinafter abbreviated as DMF) solution, and obtained with a polystyrene standard. In addition, a separable flask equipped with a stirrer, a heater, a thermometer, and a nitrogen line was used as the reaction vessel, and the reaction system was sufficiently stirred during the reaction.
本実施例において、原料のポリこはく酸イミド（以下ＰＳＩと略記する）としては、重量平均分子量（以下Ｍｗと略記する）が９５０００のものを用いた。このＭｗは、ゲル・パーミエーション・クロマトグラフィーで、Ｎ,Ｎ−ジメチルホルムアミド（以下ＤＭＦと略記する）溶液中、４５℃で測定し、ポリスチレン標準で求めた値である。また、反応容器としては、攪拌機、ヒーター、温度計及び窒素ラインを備えたセパラブル・フラスコを使用し、反応中は反応系を充分に攪拌しながら実施した。 In this example, a raw material polysuccinimide (hereinafter abbreviated as PSI) having a weight average molecular weight (hereinafter abbreviated as Mw) of 95,000 was used. This Mw is a value determined by gel permeation chromatography, measured at 45 ° C. in an N, N-dimethylformamide (hereinafter abbreviated as DMF) solution, and obtained with a polystyrene standard. In addition, a separable flask equipped with a stirrer, a heater, a thermometer, and a nitrogen line was used as the reaction vessel, and the reaction system was sufficiently stirred during the reaction.
まず反応容器内にＰＳＩ９．４０ｇとＤＭＦ３４.００ｇを入れ、７０℃加熱下で完全に溶解させた。次いで、ｎ−ドデシルアミン（以下ＬＡと略記する）８．６５ｇ（こはく酸イミド単位に対して５５モル％）と、ヒドロキシプロピルアミン（以下ＡＰと略記する）３．３８ｇ（こはく酸イミド単位に対して４５モル％）を添加し、反応容器内の温度を７０℃に保ちながら６時間反応させ、次いで反応容器を冷却し、室温になったところで一晩静置させた。その後、反応液をアセトニトリル３００ｍＬ中に攪拌しながら排出することにより反応物を沈澱させ、濾過により回収し、ポリアスパラギン酸誘導体を得た。 First, 9.40 g of PSI and 34.00 g of DMF were put in a reaction vessel and completely dissolved under heating at 70 ° C. Then, n-dodecylamine (hereinafter abbreviated as LA) 8.65 g (55 mol% based on succinimide unit) and hydroxypropylamine (hereinafter abbreviated as AP) 3.38 g (based on succinimide unit) 45 mol%) was added, and the reaction was continued for 6 hours while maintaining the temperature in the reaction vessel at 70 ° C., then the reaction vessel was cooled and allowed to stand overnight when it reached room temperature. Thereafter, the reaction solution was discharged into 300 mL of acetonitrile while stirring to precipitate the reaction product, which was recovered by filtration to obtain a polyaspartic acid derivative.
このポリアスパラギン酸誘導体の１０％水溶液を調製しレオメーターによる粘度測定を温度３０℃、応力１Ｐａで行った結果、６．８ｋＰａ・ｓの粘度を得た。 As a result of preparing a 10% aqueous solution of this polyaspartic acid derivative and measuring the viscosity with a rheometer at a temperature of 30 ° C. and a stress of 1 Pa, a viscosity of 6.8 kPa · s was obtained.
実施例１で合成したポリマーの１％水溶液を調製し粘度測定を行った結果、１．９ｋＰａ・ｓの粘度を得た。 As a result of preparing a 1% aqueous solution of the polymer synthesized in Example 1 and measuring the viscosity, a viscosity of 1.9 kPa · s was obtained.
ＬＡの使用量を７．８７ｇ（こはく酸イミド単位に対して５０モル％）、イソプロパノールアミン（以下ｉＡＰと略記する）の使用量を３．７６ｇ（こはく酸イミド単位に対して５０モル％）に変更したこと以外は、実施例１と同様にしてポリアスパラギン酸誘導体を合成した。このポリアスパラギン酸誘導体の１％水溶液を調製し、レオメーターによる粘度測定を温度５℃、応力１Ｐａで行った結果、２８０Ｐａ・ｓの粘度を得た。 The amount of LA used is 7.87 g (50 mol% with respect to the succinimide unit), and the amount of isopropanolamine (hereinafter abbreviated as iAP) is 3.76 g (50 mol% with respect to the succinimide unit). A polyaspartic acid derivative was synthesized in the same manner as in Example 1 except for the change. A 1% aqueous solution of this polyaspartic acid derivative was prepared, and the viscosity was measured with a rheometer at a temperature of 5 ° C. and a stress of 1 Pa. As a result, a viscosity of 280 Pa · s was obtained.
［実施例４〜８］
疎水性アミンをＸとし親水性アミンをＹとして、ＸとＹの比、測定温度、ポリマー濃度を変える以外は実施例１と同様に合成し、粘度測定を行った。実施例をまとめて表１に示した。
[Examples 4 to 8]
Viscosity was measured by synthesizing in the same manner as in Example 1 except that the hydrophobic amine was X and the hydrophilic amine was Y, and the ratio of X and Y, measurement temperature, and polymer concentration were changed. Examples are summarized in Table 1.
［実施例９］
実施例６で合成したポリマーを０．１％ＮａＣｌ水溶液で溶解し、１０％濃度溶液を調製した。粘度測定を温度３０℃、応力１Ｐａで行った結果、１１０Ｐａ・ｓの粘度を得た。
[Example 9]
The polymer synthesized in Example 6 was dissolved in a 0.1% NaCl aqueous solution to prepare a 10% concentration solution. As a result of measuring the viscosity at a temperature of 30 ° C. and a stress of 1 Pa, a viscosity of 110 Pa · s was obtained.
［実施例１０］
実施例６で合成したポリマーを０．５％ＮａＣｌ水溶液で溶解し、１０％濃度溶液を調製した。粘度測定を温度３０℃、応力１Ｐａで行った結果、１３１Ｐａ・ｓの粘度を得た。
[Example 10]
The polymer synthesized in Example 6 was dissolved in a 0.5% NaCl aqueous solution to prepare a 10% concentration solution. As a result of measuring the viscosity at a temperature of 30 ° C. and a stress of 1 Pa, a viscosity of 131 Pa · s was obtained.
［実施例１１］
実施例６で合成したポリマーを１．０％ＮａＣｌ水溶液で溶解し、１０％濃度溶液を調製した。粘度測定を温度３０℃、応力１Ｐａで行った結果、１８９Ｐａ・ｓの粘度を得た。
[Example 11]
The polymer synthesized in Example 6 was dissolved in 1.0% NaCl aqueous solution to prepare a 10% concentration solution. As a result of measuring the viscosity at a temperature of 30 ° C. and a stress of 1 Pa, a viscosity of 189 Pa · s was obtained.
［比較例１］
カルボキシメチルセルロースナトリウム（以下ＣＭＣと略記する）の１％水溶液を調製し、粘度測定を温度５℃、応力１Ｐａで行った結果、１３２Ｐａ・ｓの粘度を得た。
[Comparative Example 1]
A 1% aqueous solution of sodium carboxymethylcellulose (hereinafter abbreviated as CMC) was prepared, and the viscosity was measured at a temperature of 5 ° C. and a stress of 1 Pa. As a result, a viscosity of 132 Pa · s was obtained.
［比較例２］
ＣＭＣの１％水溶液を調製し、粘度測定を温度３０℃、応力１Ｐａで行った結果、５６Ｐａ・ｓの粘度を得た。
[Comparative Example 2]
As a result of preparing a 1% aqueous solution of CMC and measuring the viscosity at a temperature of 30 ° C. and a stress of 1 Pa, a viscosity of 56 Pa · s was obtained.
［比較例３］
アルギン酸ナトリウムの１％水溶液を調製し、粘度測定を温度３０℃、応力１Ｐａで行った結果、０．００９Ｐａ・ｓの粘度を得た。
[Comparative Example 3]
As a result of preparing a 1% aqueous solution of sodium alginate and measuring the viscosity at a temperature of 30 ° C. and a stress of 1 Pa, a viscosity of 0.009 Pa · s was obtained.
［比較例４］
カルボマーの１％水溶液を調製し、粘度測定を温度３０℃、応力１Ｐａで行った結果、２１７００Ｐａ・ｓの粘度を得た。
[Comparative Example 4]
As a result of preparing a 1% aqueous solution of carbomer and measuring the viscosity at a temperature of 30 ° C. and a stress of 1 Pa, a viscosity of 21700 Pa · s was obtained.
［比較例５］
カルボマーを０．１％ＮａＣｌ水溶液で溶解し、１％濃度溶液を調製した。粘度測定を温度３０℃、応力１Ｐａで行った結果、０．０２Ｐａ・ｓの粘度を得た。
[Comparative Example 5]
The carbomer was dissolved in 0.1% NaCl aqueous solution to prepare a 1% concentration solution. As a result of measuring the viscosity at a temperature of 30 ° C. and a stress of 1 Pa, a viscosity of 0.02 Pa · s was obtained.
［比較例６］
架橋ポリアスパラギン酸ナトリウム塩（ＳＡＰと略する）の１％水溶液を調製し、粘度測定を温度３０℃、応力１Ｐａで行った結果、０．８Ｐａ・ｓの粘度を得た。
[Comparative Example 6]
As a result of preparing a 1% aqueous solution of crosslinked polyaspartic acid sodium salt (abbreviated as SAP) and measuring the viscosity at a temperature of 30 ° C. and a stress of 1 Pa, a viscosity of 0.8 Pa · s was obtained.
［比較例７］
ＳＡＰを０．１％ＮａＣｌ水溶液で溶解し、１％濃度溶液を調製した。粘度測定を温度３０℃、応力１Ｐａで行った結果、０．１Ｐａ・ｓの粘度を得た。
[Comparative Example 7]
SAP was dissolved in 0.1% NaCl aqueous solution to prepare a 1% concentration solution. As a result of measuring the viscosity at a temperature of 30 ° C. and a stress of 1 Pa, a viscosity of 0.1 Pa · s was obtained.
［実施例１２］
実施例１で合成したポリマーの５％水溶液を調製し、２００ｍｌメスシリンダー中に２０ｍｌ装入し、振とう幅１５ｃｍで３０回振とうした。１分後泡の体積を測定した結果、９０ｍｌだった。その後経時変化を見た結果、５分後に９０ｍｌ（増泡率４．５倍）、３０分後に９０ｍｌ（増泡率４．５倍）、１０時間後に７５ｍｌ（増泡率４．０倍）だった。
[Example 12]
A 5% aqueous solution of the polymer synthesized in Example 1 was prepared, 20 ml was placed in a 200 ml graduated cylinder, and shaken 30 times with a shaking width of 15 cm. As a result of measuring the volume of the foam after 1 minute, it was 90 ml. As a result of looking at the change over time, 90 ml after 5 minutes (bubble increase rate 4.5 times), 90 ml after 30 minutes (bubble increase rate 4.5 times), and 75 ml after 10 hours (bubble increase rate 4.0 times). It was.
［実施例１３］
実施例１で合成したポリマーを０．１％ＮａＣｌ水溶液で溶解し、５％濃度溶液を調製した。２００ｍｌメスシリンダー中に２０ｍｌ装入し、振とう幅１５ｃｍで３０回振とうした。１分後泡の体積を測定した結果、９０ｍｌだった。その後経時変化を見た結果、５分後に９０ｍｌ（増泡率４．５倍）、３０分後に９０ｍｌ（増泡率４．５倍）、１０時間後に７５ｍｌ（増泡率４．０倍）だった。
[Example 13]
The polymer synthesized in Example 1 was dissolved in a 0.1% NaCl aqueous solution to prepare a 5% concentration solution. 20 ml was placed in a 200 ml graduated cylinder and shaken 30 times with a shaking width of 15 cm. As a result of measuring the volume of the foam after 1 minute, it was 90 ml. As a result of looking at the change over time, 90 ml after 5 minutes (bubble increase rate 4.5 times), 90 ml after 30 minutes (bubble increase rate 4.5 times), and 75 ml after 10 hours (bubble increase rate 4.0 times). It was.
［実施例１４〜１５］
希釈したＮａＣｌ水溶液の濃度を変えた以外は実施例１３と同様に操作した。結果は表２にまとめて示した。
[Examples 14 to 15]
The same operation as in Example 13 was performed except that the concentration of the diluted NaCl aqueous solution was changed. The results are summarized in Table 2.
［実施例１６〜２４］
ＸとＹの種類と比、測定温度、ポリマー濃度を変える以外は実施例１２と同様に操作した。実施例をまとめて表２に示した。
[Examples 16 to 24]
The same operation as in Example 12 was performed except that the types and ratios of X and Y, the measurement temperature, and the polymer concentration were changed. Examples are summarized in Table 2.
［比較例８〜９］
サポニンの濃度を変える以外は実施例１２と同様に操作した。比較例をまとめて表２に示した。
下記表１及び表２に、以上の各実施例及び比較例の結果をまとめて示す。
表１［実施例１〜１１、比較例１〜７］
[Comparative Examples 8-9]
The same operation as in Example 12 was performed except that the concentration of saponin was changed. The comparative examples are summarized in Table 2.
Tables 1 and 2 below collectively show the results of the above examples and comparative examples.
Table 1 [Examples 1-11, Comparative Examples 1-7]
表２［実施例１２〜２４、比較例８〜９］
Table 2 [Examples 12 to 24, Comparative Examples 8 to 9]
本発明のポリアミノ酸誘導体組成物は、化粧品分野を初めとして生活用品、衛生用品、医療用品等、人に身近な製品の材料において、生体に影響を与えない生体適合材料や、生分解性であることが必要とされ、塩類などの混合の影響を受けて欲しくない材料分野においても好適に配合、適用することが可能である。 The polyamino acid derivative composition of the present invention is a biocompatible material that does not affect the living body, and is biodegradable in materials of products familiar to humans such as daily life products, hygiene products, and medical products in the cosmetics field. Therefore, it can be suitably formulated and applied even in the field of materials that are not desired to be affected by mixing of salts and the like.
即ち、化粧品分野を初めとする生活用品、衛生用品、医療用品等、人に身近な製品の材料においては、ミネラル成分をはじめとする塩類や、補助成分が配合されているが、本発明のポリアミノ酸誘導体組成物を配合することにより、これら塩類などの電解質の配合に対して増粘性または起泡増泡性を低下させることがない。 That is, in the materials of daily life products such as cosmetics, hygiene products, medical products, etc., products familiar to human beings are blended with salts including mineral components and auxiliary components. By blending the amino acid derivative composition, the thickening or foaming property is not lowered with respect to blending of electrolytes such as these salts.
従って、本発明の組成物の配合例としては、例えば、化粧料としては、化粧水、保湿液、洗顔オイル、クレンジングオイル、クレンジングミルク、クレンジングローション、マッサージオイル、モイスチャータリーム、シェービングオイル、シェービングローション、シェームース、日焼け止めローション、日焼け用オイル、ボディーローション、ボディーシャンプー、ヘアシャンプー、ヘアリンス、ヘアートリートメント、養毛オイル、ヘアオイル、ヘアムース、香油、ヘアリキッド、セットローション、ヘアスプレー、ヘアブリーチ、カラーリンス、カラースプレー、パーマネントウェーブ液、ハンドローション等が挙げられ、、外用剤としては、湿布剤、鎮痛剤、冷却剤、除熱剤、保温剤、消毒殺菌剤、角質軟化剤、抗真菌剤、日焼防止剤、皮膚漂白剤、皮膚着色剤、肉芽発生剤、表皮形成剤、養毛発毛剤、防臭剤、発汗抑制剤、ビタミン剤等の外用医薬品に配合するもの全般が挙げられる。 Therefore, examples of the composition of the composition of the present invention include, for example, cosmetics such as lotion, moisturizing liquid, facial cleansing oil, cleansing oil, cleansing milk, cleansing lotion, massage oil, moisture cream, shaving oil, shaving lotion. , Shampoo, sunscreen lotion, tanning oil, body lotion, body shampoo, hair shampoo, hair rinse, hair treatment, hair nourishing oil, hair oil, hair mousse, perfume oil, hair liquid, set lotion, hair spray, hair bleach, color rinse, Color sprays, permanent wave liquids, hand lotions, etc., and external preparations include poultices, analgesics, cooling agents, heat removal agents, heat retention agents, disinfecting disinfectants, keratin softeners, antifungal agents, sunburn Prevention Agents, skin bleaching agents, skin coloring agents, granulation generator, skin forming agents, hair tonic hair growth agents, deodorants, antiperspirants, include general those formulated for external use medicines such as vitamins.
Claims (9)
で表されるα型又はβ型ポリアスパラギン酸単量体単位の少なくとも１種類の単量体単位を含む請求項１〜４の何れかに記載のポリアミノ酸誘導体組成物。 The following general formula (I) or (II)
The polyamino acid derivative composition according to any one of claims 1 to 4, comprising at least one monomer unit of an α-type or β-type polyaspartic acid monomer unit represented by:
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| US10259989B2 (en) | 2017-06-07 | 2019-04-16 | Kureha Corporation | Well-treatment fluid, method for forming fracture, and method for isolating wellbore |
| CN115449074A (en) * | 2022-09-02 | 2022-12-09 | 广州科罗德新材料科技有限公司 | Polyasparagine derivative thickener with side chain containing linear alkyl chain and lysine |
| JP7384325B1 (en) * | 2022-03-18 | 2023-11-21 | Dic株式会社 | Crosslinked product of modified polyaspartic acid or its salt, and thickening composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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