JP3760287B2 - Cosmetics - Google Patents

Description

【０００７】
［式中、ＲはＨ又はアセチル基（−ＣＯＣＨ₃）である。］
【０００８】
一方、上記グルコサミン及び／又はＮ−アセチルグルコサミンとエステル化する有機酸としては、安息香酸又はフタル酸を必須とし、用途に応じて選択又は組み合わせて用いることができる。
【０００９】
また、必須成分である上記安息香酸又はフタル酸に加えて、さらに炭素数１〜２２の脂肪酸を組み合わせた有機酸とのエステルとしても良い。炭素数１〜２２の脂肪酸はその目的や用途に応じて適宜選択することが出来、飽和、不飽和、直鎖状、側鎖状のいずれであっても良く、二種以上を組み合わせて使用することもできる。かかる脂肪酸としては、例えば、酢酸、２−エチルヘキサン酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、リノレン酸、リノール酸等が挙げられる。
【００１０】
これらのエステル化反応は、通常のエステル類の合成方法に従い実施することが出来、例えば、グルコサミン及び／又はＮ−アセチルグルコサミンを溶媒中で加熱溶解し、それに安息香酸及び／又はフタル酸並びに必要に応じて炭素数１〜２２の脂肪酸のハロゲン化物もしくは無水物及び適宜触媒を加えて反応を行うことにより実施される。
【００１１】
以上のようにして得られた反応生成物をさらに必要に応じて洗浄、抽出、再結晶などの手段で精製することにより、目的とするグルコサミン誘導体を得ることができる。
【００１２】
本発明のグルコサミン誘導体を化粧料に配合する場合、その配合量は特に限定されないが、全組成の０．０１〜８０重量％（以下、単に「％」で示す）、特に０．１〜５０％とすることが好ましく、また二種以上を組み合わせて配合することも可能である。
【００１３】
本発明のグルコサミン誘導体を配合する化粧料は皮膜を形成するタイプが好ましく、例えば美爪料、マスカラ、アイライナー等が挙げられる。剤型は特に限定されず、液状、乳液状、クリーム状、ゲル状等種々の形態に配合することが出来る。
【００１４】
また、本発明の化粧料には化粧料成分として一般に使用されている界面活性剤、油剤、粉体、樹脂、溶剤、可塑剤、アルコール類、高分子物質、増粘剤、防腐剤、保湿剤、殺菌剤、酸化防止剤、紫外線吸収剤、美容剤、染料、香料等の成分を本発明の効果を損なわない範囲で任意に配合することが出来る。
【００１５】
【実施例】
以下に実施例を挙げて本発明をさらに説明するが、本発明はこれら実施例に何等限定されるものではない。
【００１６】
製造例１
Ｎ−アセチルグルコサミン安息香酸エステルの合成Ｎ−アセチルグルコサミン５ｇ、無水安息香酸２１ｇ及び触媒として４−ジメチルアミノピリジン１ｇをＮ，Ｎ−ジメチルホルムアミド（以下、「ＤＭＦ」と示す）１００ｇに添加し、攪拌しながら８０℃に加熱して３時間反応させた。反応終了後、反応液を過剰量の水に注いで生成物を洗浄した後、これを酢酸エチルで抽出し、さらに希アルカリ水溶液及び水で洗浄した。酢酸エチル層を脱水後、酢酸エチルを留去して白色粉末状のＮ−アセチルグルコサミン安息香酸エステル８．７ｇを得た。なお、このものの置換度は３．２であった。製造例１のＩＲチャートを図１に示す。
【００１７】
製造例２
グルコサミンフタル酸・酢酸混合エステルの合成グルコサミン５ｇ、無水フタル酸９ｇ、無水酢酸６ｇ及び触媒として４−ジメチルアミノピリジン１ｇをＤＭＦ１００ｇに添加し、攪拌しながら８０℃に加熱して３時間反応させた。反応終了後、反応液を製造例１と同様に後処理して白色粉末状のグルコサミンフタル酸・酢酸混合エステル１３．８ｇを得た。なお、このものの置換度は２．９であった。
【００１８】
製造例３
Ｎ−アセチルグルコサミン安息香酸・パルミチン酸混合エステルＮ−アセチルグルコサミン５ｇ及び触媒としてピリジン１５ｇをＤＭＦ１００ｇに添加し、攪拌しながら８０℃に加熱し、ベンゾイルクロライド１０ｇ及びパルミチン酸クロライド６．５ｇを滴下して３時間反応させた。反応終了後、過剰量の水に反応液を注いで生成物を洗浄した後、温メタノールで洗浄した。次にこれを酢酸エチルで抽出後、希塩酸、希アルカリ水溶液及び水で洗浄し、脱水した後酢酸エチルを留去して白色粉末状のＮ−アセチルグルコサミン安息香酸・パルミチン酸混合エステル９．２ｇを得た。なお、このものの置換度は２．８であった。
【００１９】
製造例４
グルコサミン安息香酸・２−エチルヘキサン酸混合エステルグルコサミン５ｇ及び触媒としてピリジン１５ｇをＤＭＦに添加し、攪拌しながら８０℃に加熱し、ベンゾイルクロライド１４ｇ及び２−エチルヘキサン酸クロライド２ｇを滴下して３時間反応させた。反応終了後、反応液を製造例３と同様に後処理して白色粉末状のグルコサミン安息香酸・２−エチルヘキサン酸混合エステル１１．４ｇを得た。なお、このものの置換度は３．１であった。
【００２０】
（評価）
下記表に示す組成の実施例１〜５及び比較例１〜３の美爪料を製造し、官能評価及び皮膜特性評価を行った。
【００２１】
【表１】

【００２２】
（製造方法）
成分１〜１５を混合溶解し、成分１６を添加して均一に混合して美爪料を得る。
【００２３】
（評価方法）
１．官能評価
専門評価パネル１５名により、「塗布のしやすさ」、「乾きの速さ」、「光沢」、「もちの良さ」について５段階評価し、更にその平均点により判定した。
（評価） （内容）
５点 ： 非常に良好
４点 ： 良好
３点 ： 普通
２点 ： やや不良
１点 ： 不良
（判定）
◎：平均点４．５点以上
○：平均点４．０点以上４．５点未満
△：平均点３．０点以上４．０点未満
×：平均点３．０点未満
【００２４】
２．耐水性・耐油性試験
ナイロン板上に６ミルのドクターブレードを用いて上記美爪料の薄膜を形成した。これを自然乾燥させたナイロン板を試験サンプルとして、耐水性は水に、耐油性は人工皮脂に各々１０分間浸してその膜状態を観察した。評価基準は以下に示す。
（評価） （内容）
◎ ： 強い耐性を示し、非常に良好である。
○ ： 耐性を示し、良好である。
△ ： やや剥離の傾向がみられる。
× ： 明らかに剥離、膨潤等の膜状態の変化がみられる。
【００２５】
３．クロスカット試験
上記２の試験と同様に調製した試験サンプルを用いて、一般の塗料の付着性評価で用いられているクロスカット試験（１ｍｍ×１ｍｍで１００個の碁盤目を作成）を実施した。評価基準は以下に示す。
（評価） （内容）
◎ ： 薄膜が正方形できれいに残る。
○ ： 薄膜がほとんど正方形で残る。
△ ： 薄膜が不定形となる。
× ： 薄膜のめくれ、損傷が著しい。
上記各試験方法によって得られた結果を表２に示す。
【００２６】
【表２】

【００２７】
上記結果からも明らかなように、本発明品のグルコサミン誘導体を配合した美爪料は優れた官能特性を有し、皮膜の耐水、耐油性及び付着性も良好であった。
【００２８】
実施例６ 美爪料
（成分） （％）
１．ニトロセルロース １５．０
２．アルキッド樹脂 ４．０
３．シュークロースベンゾエート ２．０
４．グルコサミン誘導体（製造例２） ４．０
５．グルコサミン誘導体（製造例３） ３．０
６．クエン酸アセチルトリエチル ５．０
７．ｄｌ−カンフル ０．５
８．有機性ベントナイト １．５
９．イソプロパノール ５．０
１０．酢酸ブチル ２７．０
１１．酢酸エチル ９．０
１２．ブタノール ３．０
１３．トルエン 残量
１４．色材 適量
【００２９】
（製造方法）成分１〜１３を混合溶解し、成分１４を添加して均一に混合して美爪料を得る。実施例６は、塗布し易く、さらにもちが良好で、耐水・耐油性にも優れた美爪料であった。
【００３０】
実施例７ アイライナー
（成分） （％）
１．アクリル酸エチル・メタクリル酸メチル ２５．０
共重合体エマルション
２．ステアリン酸 ５．０
３．セタノール ０．５
４．ミツロウ ０．５
５．グルコサミン誘導体（製造例４） ２．０
６．セスキオレイン酸ソルビタン ０．５
７．モノオレイン酸ポリオキシエチレン ０．５
ソルビタン（２０Ｅ．Ｏ．）
８．色材 適量
９．トリエタノールアミン ０．５
１０．防腐剤 適量
１１．精製水 残量
【００３１】
（製造方法）
Ａ：成分２〜７を加熱溶解する。
Ｂ：成分８〜１１を加熱溶解する。
Ｃ：ＡにＢを添加して乳化混合し、成分１を添加して混合した後冷却してアイライナーを得る。
実施例７は、皮膜形成性に優れ、伸びが良く、耐水性及び耐油性に優れたものであった。
【００３２】
【発明の効果】
本発明で用いるグルコサミン誘導体は優れた皮膜特性を有し、このグルコサミン誘導体を含有する化粧料は、皮膜形成性に優れ、皮膜の耐水性、耐油性及び付着性が良好で、使用感に優れるものである。
【図面の簡単な説明】
【図１】製造例１のＩＲチャートである。 [0001]
[Industrial application fields]
The present invention relates to cosmetics containing a glucosamine derivative, more particularly, film strength, excellent drying property, and a cosmetic containing the glucosamine-induced body having good adhesion and durability.
[0002]
[Prior art]
Conventionally, beauty nails, mascara, eyeliner and the like are known as cosmetics having film-forming ability. These form a film on the nails and skin and produce a cosmetic effect. For example, film-forming agents, solvents, plasticizers, resins, pigments, etc. are used for beauty nails, and synthetic emulsions, oils, pigments, surfactants, etc., are used for mascara and eyeliner in consideration of usability and functionality. Various blends.
[0003]
[Problems to be solved by the invention]
However, the nitrocellulose used as the main film forming agent of the nail polish is inferior in adhesion and durability although it is excellent in the hardness and drying property of the film. In order to improve these drawbacks, various plasticizers and resins are combined and blended. However, a satisfactory one has not yet been obtained. In addition, when synthetic emulsions are used for mascara, eyeliner, etc., it is difficult to balance drying speed, water resistance, coating strength, adhesion, etc., and it should be satisfactory in terms of usability and functionality. It was rare.
[0004]
[Means for Solving the Problems]
In view of the above situation, as a result of intensive studies, the present inventors have found that a glucosamine derivative useful as a cosmetic raw material can be obtained by esterifying glucosamine and / or N-acetylglucosamine with a specific compound. It came to be completed. That is, the present invention is a cosmetic, wherein the glucosamine and / or N- acetylglucosamine, in that it contains glucosamine induce body made of an ester of an organic acid to benzoic acid and / or phthalic acid as an essential component. This will be described in detail below.
[0005]
Glucosamine and N-acetylglucosamine used in the present invention are a kind of amino sugar represented by the following chemical formula.
[0006]
[Chemical 1]

[0007]
[Wherein, R is H or an acetyl group (—COCH ₃ ). ]
[0008]
On the other hand, as the organic acid to be esterified with the glucosamine and / or N-acetylglucosamine, benzoic acid or phthalic acid is essential, and can be selected or combined according to use.
[0009]
Moreover, in addition to the said essential benzoic acid or phthalic acid, it is good also as an ester with the organic acid which combined the C1-C22 fatty acid. The fatty acid having 1 to 22 carbon atoms can be appropriately selected according to its purpose and use, and may be saturated, unsaturated, linear or side chain, and used in combination of two or more. You can also. Examples of such fatty acids include acetic acid, 2-ethylhexanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linolenic acid, linoleic acid, and the like.
[0010]
These esterification reactions can be carried out according to a general method for synthesizing esters, for example, glucosamine and / or N-acetylglucosamine is dissolved in a solvent by heating, and then benzoic acid and / or phthalic acid and if necessary Accordingly, the reaction is carried out by adding a halide or anhydride of a fatty acid having 1 to 22 carbon atoms and an appropriate catalyst.
[0011]
The desired glucosamine derivative can be obtained by further purifying the reaction product obtained as described above by means such as washing, extraction, and recrystallization as necessary.
[0012]
When the glucosamine derivative of the present invention is blended in a cosmetic, the blending amount is not particularly limited, but is 0.01 to 80% by weight (hereinafter simply indicated as “%”), particularly 0.1 to 50% of the total composition. It is also preferable that two or more types can be combined.
[0013]
The cosmetic material containing the glucosamine derivative of the present invention is preferably of a type that forms a film, and examples thereof include beauty nail materials, mascara, and eyeliner. A dosage form is not specifically limited, It can mix | blend with various forms, such as liquid form, emulsion, cream form, and gel form.
[0014]
Further, surfactants, oils, powders, resins, solvents, plasticizers, alcohols, polymer substances, thickeners, preservatives, moisturizers generally used as cosmetic ingredients in the cosmetics of the present invention are used. Ingredients such as bactericides, antioxidants, ultraviolet absorbers, beauty agents, dyes, fragrances and the like can be optionally blended within a range that does not impair the effects of the present invention.
[0015]
【Example】
EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples.
[0016]
Production Example 1
Synthesis of N-acetylglucosamine benzoate ester 5 g of N-acetylglucosamine, 21 g of benzoic anhydride and 1 g of 4-dimethylaminopyridine as a catalyst are added to 100 g of N, N-dimethylformamide (hereinafter referred to as “DMF”) and stirred. Then, the mixture was heated to 80 ° C. and reacted for 3 hours. After completion of the reaction, the reaction solution was poured into an excess amount of water to wash the product, then extracted with ethyl acetate, and further washed with a dilute alkaline aqueous solution and water. After the ethyl acetate layer was dehydrated, the ethyl acetate was distilled off to obtain 8.7 g of white powdered N-acetylglucosamine benzoate. The degree of substitution of this product was 3.2. An IR chart of Production Example 1 is shown in FIG.
[0017]
Production Example 2
Synthesis of Glucosamine Phthalic Acid / Acetic Acid Mixed Ester 5 g of glucosamine, 9 g of phthalic anhydride, 6 g of acetic anhydride and 1 g of 4-dimethylaminopyridine as a catalyst were added to 100 g of DMF, heated to 80 ° C. with stirring and reacted for 3 hours. After completion of the reaction, the reaction solution was post-treated in the same manner as in Production Example 1 to obtain 13.8 g of a white powdery glucosamine phthalic acid / acetic acid mixed ester. In addition, the substitution degree of this thing was 2.9.
[0018]
Production Example 3
N-acetylglucosamine benzoic acid / palmitic acid mixed ester 5 g of N-acetylglucosamine and 15 g of pyridine as a catalyst are added to 100 g of DMF, heated to 80 ° C. with stirring, and 10 g of benzoyl chloride and 6.5 g of palmitic acid chloride are added dropwise. The reaction was performed for 3 hours. After completion of the reaction, the reaction solution was poured into an excess amount of water to wash the product, and then washed with warm methanol. Next, this was extracted with ethyl acetate, washed with dilute hydrochloric acid, dilute alkaline aqueous solution and water, dehydrated, and then ethyl acetate was distilled off to obtain 9.2 g of N-acetylglucosamine benzoic acid / palmitic acid mixed ester in the form of white powder. Obtained. The degree of substitution of this product was 2.8.
[0019]
Production Example 4
Glucosamine benzoic acid and 2-ethylhexanoic acid mixed ester 5 g of glucosamine and 15 g of pyridine as a catalyst are added to DMF, heated to 80 ° C. with stirring, 14 g of benzoyl chloride and 2 g of 2-ethylhexanoic acid chloride are added dropwise for 3 hours. Reacted. After completion of the reaction, the reaction solution was post-treated in the same manner as in Production Example 3 to obtain 11.4 g of a white powdery mixed ester of glucosamine benzoic acid and 2-ethylhexanoic acid. The degree of substitution of this product was 3.1.
[0020]
(Evaluation)
The nail polish of Examples 1-5 of the composition shown to the following table | surface and Comparative Examples 1-3 was manufactured, and sensory evaluation and film | membrane characteristic evaluation were performed.
[0021]
[Table 1]

[0022]
(Production method)
Components 1 to 15 are mixed and dissolved, and component 16 is added and mixed uniformly to obtain a nail polish.
[0023]
(Evaluation methods)
1. Sensory evaluation 15 expert evaluation panels evaluated five levels of “easy to apply”, “speed of drying”, “gloss” and “goodness of stickiness”, and further judged by the average score.
(Evaluation) (Content)
5 points: Very good 4 points: Good 3 points: Normal 2 points: Somewhat bad 1 point: Bad (judgment)
◎: Average point 4.5 points or more ○: Average point 4.0 points or more and less than 4.5 points Δ: Average point 3.0 points or more and less than 4.0 points ×: Average point less than 3.0 points
2. Water Resistance / Oil Resistance Test Using a 6 mil doctor blade on a nylon plate, the beautiful nail material thin film was formed. A nylon plate which was naturally dried was used as a test sample, and the film state was observed by immersing the water resistance in water and the oil resistance in artificial sebum for 10 minutes. Evaluation criteria are shown below.
(Evaluation) (Content)
(Double-circle): It shows the strong tolerance and is very favorable.
○: Shows resistance and is good.
Δ: Slight peeling tendency is observed.
X: Changes in the film state such as peeling and swelling are clearly observed.
[0025]
3. Cross-cut test Using the test sample prepared in the same manner as in the above-mentioned test 2, a cross-cut test (preparing 100 grids of 1 mm x 1 mm) used in general paint adhesion evaluation was performed. Evaluation criteria are shown below.
(Evaluation) (Content)
A: The thin film remains square and clean.
○: The thin film remains almost square.
Δ: The thin film is indefinite.
×: The thin film is turned over and damaged significantly.
Table 2 shows the results obtained by the above test methods.
[0026]
[Table 2]

[0027]
As is clear from the above results, the nail polish formulated with the glucosamine derivative of the present invention had excellent sensory characteristics, and the film had good water resistance, oil resistance and adhesion.
[0028]
Example 6 Beauty nail preparation (ingredient) (%)
1. Nitrocellulose 15.0
2. Alkyd resin 4.0
3. Sucrose benzoate 2.0
4). Glucosamine derivative (Production Example 2) 4.0
5. Glucosamine derivative (Production Example 3) 3.0
6). Acetyltriethyl citrate 5.0
7). dl-Camphor 0.5
8). Organic bentonite 1.5
9. Isopropanol 5.0
10. Butyl acetate 27.0
11. Ethyl acetate 9.0
12 Butanol 3.0
13. Toluene remaining amount 14. Appropriate amount of color material 【0029】
(Manufacturing method) Components 1 to 13 are mixed and dissolved, and component 14 is added and mixed uniformly to obtain a beauty nail material. Example 6 was a nail polish that was easy to apply, had a good texture, and was excellent in water resistance and oil resistance.
[0030]
Example 7 Eyeliner (component) (%)
1. Ethyl acrylate / methyl methacrylate 25.0
1. Copolymer emulsion Stearic acid 5.0
3. Cetanol 0.5
4). Beeslow 0.5
5. Glucosamine derivative (Production Example 4) 2.0
6). Sorbitan sesquioleate 0.5
7). Polyoxyethylene monooleate 0.5
Sorbitan (20E.O.)
8). Appropriate amount of coloring material 9. Triethanolamine 0.5
10. Preservative appropriate amount11. Purified water remaining amount [0031]
(Production method)
A: Components 2 to 7 are dissolved by heating.
B: Components 8 to 11 are dissolved by heating.
C: B is added to A and emulsified and mixed. Component 1 is added and mixed, and then cooled to obtain an eyeliner.
Example 7 was excellent in film-forming properties, good in elongation, and excellent in water resistance and oil resistance.
[0032]
【The invention's effect】
Glucosamine derivative used in the present invention have a superior film properties, cosmetics containing the glucosamine derivative is superior in film-forming, water resistance of the coating, has good oil resistance and adhesion, which is excellent in feeling of use It is.
[Brief description of the drawings]
1 is an IR chart of Production Example 1. FIG.

Claims (2)

A cosmetic comprising a glucosamine derivative comprising an ester of glucosamine and / or N-acetylglucosamine and an organic acid containing benzoic acid and / or phthalic acid as essential components. Organic acid, and benzoic acid and / or phthalic acid as an essential component, further cosmetic of claim 1, wherein you containing fatty acid having 1 to 22 carbon atoms.

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