JPS601110A - Moisturizing agent - Google Patents

Abstract

PURPOSE:To provide a moisturizing agent having high safety and excellent moisture-absorbing and moisture-retaining properties, and containing an amorphous water-soluble partially deacetylated chitin containing specific amounts of N-acetyl-D-glucosamine and D-glucosamine as constituent components. CONSTITUTION:The objective moisturizing agent contains an amorphous water- soluble partially deacetylated chitin containing (A) N-acetyl-D-glucosamine and (B) D-glucosamine as constituent units, wherein the contents of (A) and (B) are 40-60% and 60-40%, respectively. The moisturizing agent exhibits excellent moisture-absorbing and retaining effects, and imparts the applied material with tackfree moist feeling because of its film-forming property originated from the polymeric structure. It has high safety and can be used as an additive to foods, cosmetics, etc. as well as to shoe polish, paint, paper products, etc. The chitin can be produced from crustaceans such as crab, shrimp, krill, etc. which is abundant in natural resources and has not hitherto been utilized effectively.

Description

【発明の詳細な説明】 本発明は水溶比部分脱アセチル化キチンを含有してなる
湿潤剤に関し、その目的とするところは安全比力稍ｉ石
＜、シかも吸湿性および保湿性にすぐれた湿潤剤を提供
することにある〇一般に化粧品、軟膏、菓子類の如く製
品中より水分が失われると品質を損なう製品、あるいは
皮膚用ローシ目ン、クリーム、化クリームなどの如く湿
潤性を賦与することを目的として用いる製品には吸湿性
の高い物質が湿潤剤として用いられて−る。吸湿能力の
高い物質には有機物、無機物を合わせるとかなりの種類
があるが、安全性あるいは製品の形態安定性への影響が
低いものであること等の必要性から実際に用いられる湿
潤剤の種類は限られている。さらに湿潤剤の備えるべき
性質として紘吸湿比すなわち水分を吸収する能力と同時
に、保湿比すなわち水分の蒸発を防ぐ能力がめられる。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a wetting agent containing water-soluble partially deacetylated chitin, and the object thereof is to have a safe specific strength, excellent hygroscopicity and moisturizing properties. The purpose of this product is to provide a moisturizing agent.Generally, products such as cosmetics, ointments, and confectionery that lose their quality when moisture is lost, or products that provide moisturizing properties such as skin lotions, creams, and creams. In products used for this purpose, highly hygroscopic substances are used as wetting agents. There are many types of substances with high moisture absorption capacity, including organic and inorganic substances, but the types of wetting agents that are actually used are limited due to the need to have a low impact on safety or product form stability. is limited. Furthermore, properties that a humectant should have include a high hygroscopic ratio, that is, the ability to absorb moisture, and a moisturizing ratio, that is, the ability to prevent moisture evaporation.

一般に用いられる湿潤剤はこれらの緒特性を所要のもの
とするために多くの場合複合して用いられる。しかしな
がら通常用−られる湿潤剤のうち、乳酸ナトリウム、ピ
ロリドンカルボン酸ナトリウム等の吸湿性の大きな物質
は鑞解賀であるために乳化阻害作用等の製品配合上好ま
しくない性質があり、使用量、用途が制限される。Commonly used wetting agents are often used in combination to achieve the desired properties. However, among the commonly used humectants, highly hygroscopic substances such as sodium lactate and sodium pyrrolidonecarboxylate have undesirable properties in product formulation, such as inhibiting emulsification, because they are hygroscopic substances, and their usage amounts and applications are limited. is limited.

一方、グリセリン、ソルビトール、プロピレングリコー
ル等のポリオール系湿潤剤は保湿性が比較的良好である
が、製品にべたつきが生じやすく、化粧品等に用−た場
合使用感に難点がある。また、最近適夏な吸保湿性を持
ち、使用感の良好な湿潤剤としてヒアルロン酸が注目さ
れているが、原料が鶏冠、ヒトの屓帯等の縮少天然物で
あり極めて列側であるため、その用途は自ら限定される
。On the other hand, polyol-based humectants such as glycerin, sorbitol, and propylene glycol have relatively good moisturizing properties, but tend to cause stickiness in products and have a disadvantage in feeling when used in cosmetics and the like. In addition, recently, hyaluronic acid has been attracting attention as a humectant that has moisture absorption properties suitable for summer and has a good feeling of use, but the raw materials are reduced natural products such as cockscomb and human ligament, so it is extremely difficult to use. Therefore, its use is self-limited.

そこで本発明者は吸保湿性に富み、しかも使゛　用感の
良好な湿潤剤を開発すべく、廉価な天然系品分子に着目
して鋭意検討を行った結果、資源として豊パで、しかも
現在のところ有効に活用されていない、かに、えび、お
きあみなどの甲殻類の主成分であるキチンを部分脱ア七
チル化して得られる７ＪＣ溶匪キチンが、湿潤剤として
曖れた特［生を有することを見い出し本発明を完成した
。Therefore, in order to develop a wetting agent that has high moisture absorption properties and is comfortable to use, the present inventors focused on inexpensive natural molecules and as a result, they discovered that they are abundant as a resource, and also have a good usability. 7JC-soluble chitin, which is obtained by partially deacylating chitin, which is the main component of crustaceans such as crabs, shrimps, and oysters, and which has not been effectively utilized at present, has ambiguous properties as a wetting agent. [The present invention was completed by discovering that the present invention has the following properties.

本発明に於ける水ｒｇ　ｒｈ部分脱アセチル化キチンは
、例えば、特開昭５５−４７４７９号公報記載の方法に
よりて天然産キチン粉末をアルカリを用いテ脱アセチル
化して得られ、Ｎ−アセチル−Ｄ−グルコサミンとＤ−
グルコサミンを構成単位とし、ｒり一アセチルーＤ−グ
ルコサミン学位の含量４０〜６０％、Ｄ−グルコサミン
単位の含量６０〜４０％であるところの非晶質の水溶性
脱アセチル化キチンが単独又は混合物として用いられる
。The water rg rh partially deacetylated chitin in the present invention is obtained by deacetylating naturally produced chitin powder using an alkali, for example, by the method described in JP-A-55-47479, and N-acetyl- D-glucosamine and D-
Amorphous water-soluble deacetylated chitin containing glucosamine as a constituent unit, containing 40 to 60% of acetyl-D-glucosamine units and 60 to 40% of D-glucosamine units, either alone or as a mixture. used.

さらに水溶性脱アセチル化キチンはＤ−グルコサミン単
位中のアミノ基を一部又は全部中和して用いてもよい。Furthermore, the water-soluble deacetylated chitin may be used after partially or completely neutralizing the amino groups in the D-glucosamine units.

中和に用いる酸としては塩酸、硫酸、リン酸等の無機酸
、酢酸、クエン酸、酪酸、乳酸、リンゴ酸、コハク酸、
グルコン酸、ピロリドンカルボン酸等の有機酸およびア
スパラギン酸、グルタミン酸、システィン酸、ホモシス
ティン酸等の酸性アミノ酸のいずれでもよい。Acids used for neutralization include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, citric acid, butyric acid, lactic acid, malic acid, succinic acid,
Any of organic acids such as gluconic acid and pyrrolidone carboxylic acid and acidic amino acids such as aspartic acid, glutamic acid, cystic acid, and homocystic acid may be used.

本発明の湿潤剤は後記実施例に示すごとく優れた吸保湿
性を示すとともに、高分子構造に由来する皮膜形成力に
よシ、被塗布物にべとつかずしつと９と、した感じを賦
与する。従って本発明の湿潤剤を大気中にさらして水分
を失なう傾向のある製品、例えば、靴クリーム、塗料、
紙製品等に添加することによって品質の維持向上に役立
つばかシでなく、繊維製品、複写紙、レコードなど帯電
性を嫌う製品に添加ないしは本発明の湿潤剤溶液に浸漬
するなどの処理を施すことによって製品に適度の吸湿性
を賦与し、さらにこのような処理を施した繊維製品はし
っとり感が増し風合も改良される。As shown in the Examples below, the wetting agent of the present invention not only exhibits excellent moisture absorption properties, but also imparts a non-sticky, moist feel to the coated object due to its film-forming ability derived from its polymer structure. . Therefore, products that tend to lose moisture by exposing the humectants of the invention to the atmosphere, such as shoe creams, paints, etc.
It is not just an additive that helps maintain and improve quality by adding it to paper products, etc., but it can also be added to textile products, copying paper, records, and other products that dislike static electricity, or can be treated by immersing them in the wetting agent solution of the present invention. This imparts appropriate hygroscopicity to the product, and textile products subjected to such treatment have an increased moist feel and improved hand.

このように本発明の湿潤剤は安全性の高い物質であるこ
とから、食品・化粧品等に添加することができ、特に化
粧品用湿潤剤として用いることにより製品形態の維持の
みならず、使用後の皮膚に適度な潤い滑らかさを賦与し
、皮膚あれを防ぐ効果を奏する。このような化粧品とし
てはヘアスプレー、ｕｄｈｌＪ、クレンジングクリーム
、化粧水、シャンプー、リンス、ヘアートリートメント
、乳液、ローシ胃ン、ひけそり用クリーム、コールドク
リーム、ハンドクリーム、パーマ液、　固型洗剤、液状
洗剤、汗とり剤などがあげられ、製品の形態によらず適
用することができる。Since the wetting agent of the present invention is a highly safe substance, it can be added to foods, cosmetics, etc. In particular, when used as a wetting agent for cosmetics, it not only maintains the product form but also improves the appearance of the product after use. It imparts appropriate moisture and smoothness to the skin and has the effect of preventing skin roughness. Such cosmetics include hair spray, udhlj, cleansing cream, lotion, shampoo, conditioner, hair treatment, emulsion, lotion, shaving cream, cold cream, hand cream, perm solution, solid detergent, and liquid detergent. , sweat removers, etc., and can be applied regardless of the form of the product.

本発明の湿潤ハ１ｊを各揮製品に添加した場合、その添
加量に応じた１１延潤比を賦与することができるが、通
−５１客０．０１〜１０ａ【晴％好ましくはα０５〜５
　ｍ　ｆｉｔ％ハｊいれば所１す１の目的を達成するこ
とができる。When the moistening ratio of the present invention is added to each volatile product, a spreading ratio of 11 can be given depending on the amount added, but the wetness ratio is preferably α05 to 5.
If m fit% is satisfied, the purpose of point 1 and 1 can be achieved.

さらに本発明の湿潤剤は他の湿潤剤例えばグリセリン、
プロピレグリコール、ソルビトール、ピロリドンカルボ
ン酸ナトリウム、乳酸ナトリウム、アミノ酸等と併用し
ても効果を損なわれることはない。さらに必要に応じ各
種界面活性剤、可溶化剤、油剤等と併用することもでき
る。Additionally, the humectants of the present invention may be combined with other humectants such as glycerin,
Even if it is used in combination with propyreglycol, sorbitol, sodium pyrrolidone carboxylate, sodium lactate, amino acids, etc., the effect will not be impaired. Furthermore, various surfactants, solubilizers, oil agents, etc. can be used in combination as necessary.

以下、実施例により具体的に説明する。Hereinafter, this will be explained in detail using examples.

実施例１ 本発明の湿潤剤である水溶注説アセチル化キチンの塩酸
部分中和物（脱アセチル化度５０％）および対照とした
湿潤剤の１％水溶液５ｇを湿度２５％の空気をＩ　Ｄ　
ｊ　／ｍの流ｕＬで尋人した２５℃の恒温恒湿槽中にお
ける水の乾燥による重ｖｉｔ減少から保湿性を調べた。Example 1 A partially neutralized hydrochloric acid solution of acetylated chitin (degree of deacetylation: 50%), which is a wetting agent of the present invention, and 5 g of a 1% aqueous solution of a control wetting agent were mixed with air at a humidity of 25%.
The moisture retention property was examined from the decrease in vitreous content due to drying of water in a constant temperature and humidity chamber at 25° C. at a flow rate of uL of 25°C.

その結果を図１に示す如く、本発明品祉対照に比べ良好
な保湿性を示した０さらに本発明の湿潤剤は中性で透明
に溶解したが、対照の鋭アセチル化度９ｏ％及び１００
％のキトサンは保湿性が低−ばかシでなく、水に下拵で
あり湿潤剤として社使いに＜＜、本発明の優位比が確認
された。また、本発明の湿潤剤の吸湿比を広【１１パル
スＮＭＲ法（７レグランスジヤーナル　硯（５）　、　
５９　（１９８２））にて調べたところ、表１に示すご
とく対照のヒアルロン酸と同等の吸湿性が認められた。As shown in FIG. 1, the wetting agent of the present invention exhibited better moisturizing properties than the control of the present invention.Furthermore, the wetting agent of the present invention was neutral and transparently dissolved;
% of chitosan has a low moisture retention property, is not resistant to water, and is used as a moisturizing agent for company use, confirming the superiority of the present invention. In addition, the moisture absorption ratio of the wetting agent of the present invention was widened [11 pulse NMR method (7 regrance journal inkstone (5),
59 (1982)), and as shown in Table 1, it was found to have the same hygroscopicity as the control hyaluronic acid.

の 表１　湿潤剤１％７Ｊ（耐液−−２０℃における不凍４
く喰（広ｒｌＪパルスＮＭＲ法）＊ （解凍過程における 一り１℃〜−１９Ｃの平均値） 実施例２ 次の処方のミルクローシ箇ンを調装した。Table 1 Wetting agent 1% 7J (Liquid resistance - Antifreeze at 20℃ 4
(Wide RLJ pulse NMR method) * (Average value of 1°C to -19°C during thawing process) Example 2 A milk roasted cup having the following formulation was prepared.

油相　流動パラフィン　１０，５　直ｈ【％ミツロウ　
１．０ ステアリルアルコール　１．５ イソパルミチルアルコール　１．２ ポリオキシエチレン（１０）グリセリル　２．４トリ　
イソステアレート 水相ｙＪ＜溶性脱アセチル化キチン　１．５（脱アセチ
ル化度５０％） 水　６２．０ ６０人の成人女子を２組に分けて、上記配合品および対
照として上記処方から湿潤剤を除−た配合品を使用した
ところ、本発明の配合品を用いた組からは使用感ならび
に使用後の感じがしっとりとして良いとの評価を得たの
に対し、湿　。Oil phase Liquid paraffin 10.5 Direct h [% Beeswax
1.0 Stearyl alcohol 1.5 Isopalmityl alcohol 1.2 Polyoxyethylene (10) glyceryl 2.4 Tri
Isostearate aqueous phase yJ<Soluble deacetylated chitin 1.5 (degree of deacetylation 50%) Water 62.0 Sixty adult women were divided into two groups and treated with the above formulation and a humectant from the above formulation as a control. When we used a blended product in which the blended product of the present invention was used, the group that used the blended product of the present invention evaluated that the feeling of use and after use was moist and good.

潤剤無添加品を用いた組は肌がややかさかさする傾向が
認められた。It was observed that the skin of the group using the product without any lubricant added tended to become slightly dry.

実施例６　ヘアシャンプー 次の処方のヘアシャンプーを調製した０ヤシ油Ｊ抗肪酸
アシルグルタミン酸 ジエタノールアミン埴　（３０％）　５０．ＯＪｌｉｌ
１％ヤシ油脂肪酸ジェタノールアミド　ムロクエン酸２
ナトリウム１．５７１（塩　２．０ポリオキシエチレン
グリコールモノステアレート１．０プロピレングリコー
ル　１．０ ポリオキシエチレンラノリンアルコール　２．０水ｍ曲
脱アセチル化キチン ピロリドンカルボン酸ｔＪ　分ｌ１５ （脱アセチル化ＩＪｊ’４０％） 水？ｄ比脱アセチル化キチン　［Ｌ５ （脱アセチル化度５５％） 水　４０．０ 本シャンプーは洗？４）　ａ　ｉ！ｊＩ髪にしっとり感
が付与され、本発明の湿潤剤未添加のものに比べて風合
がすぐれていた。Example 6 Hair Shampoo A hair shampoo with the following formulation was prepared: 0 coconut oil J anti-fatty acid acyl glutamate diethanolamine (30%) 50. OJlil
1% coconut oil fatty acid jetanolamide murocitric acid 2
Sodium 1.571 (Salt 2.0 Polyoxyethylene glycol monostearate 1.0 Propylene glycol 1.0 Polyoxyethylene lanolin alcohol 2.0 Water m Deacetylated chitin pyrrolidone carboxylic acid tJ Minutes 15 (Deacetylated IJj '40%) Water?d ratio deacetylated chitin [L5 (Degree of deacetylation 55%) Water 40.0 Does this shampoo wash?4) a i! jI hair was given a moist feel, and the texture was superior to that of the hair without the humectant of the present invention.

実施例４　饅頭の皮 次の処方に従りて組成物をａΔｌした。Example 4 Manju skin The composition was aΔl according to the following formulation.

小麦粉　１００ｇ ベーキングパウダー　５ｇ 白　砂　Ｉ＃６０ｇ 水　大さじ　５杯 水と白砂糖を合わせて熱し、ｍ解したところで放冷し、
小麦粉とベーキングパウダーヲ入してよく混合した。こ
の組成物を２分し、一方には水溶性部分説ア七チル化キ
チンの塩酸部分中和物（脱アセチル化度４８％）１％お
よび乳ｒＩｂナトリウム１％を添加した。Flour 100g Baking powder 5g White sand I#60g Water 5 tablespoons Heat the water and white sugar together, let it cool once it has dissolved.
Add the flour and baking powder and mix well. This composition was divided into two parts, and to one part were added 1% of a water-soluble partially neutralized hydrochloric acid partially a7tylated chitin (degree of deacetylation 48%) and 1% of sodium milk rIb.

両者の組成物を１ｎ分間蒸して饅頭の皮を製造した＠こ
の両者を１０日間室温にて窄気中にさらしたところ、本
発明の湿潤剤を添加したものには殆んど変化が認められ
なかったが、無添加のものは水分が損失してかさかさに
なった。Both compositions were steamed for 1 nm to produce manju wrappers. When both were exposed to narrow air at room temperature for 10 days, almost no changes were observed in those to which the wetting agent of the present invention was added. However, the one without additives lost moisture and became bulky.

【図面の簡単な説明】[Brief explanation of drawings]

図１は各洩湿晶ノ「りのＩ　Ｘ　７Ｊ（浴液（３ｇ）を
２５℃で２５％゛慴λ（を尋人した恒温恒湿槽中に放置
した際のｙＪ（分蒸発による経時的重油減少を示した図
面である。図中（イ）は本発明の水潰性説アセチル化キ
チン、（ロ）はヒアルロン酸、（ハ）はキトサン（脱ア
セチル化度９０％）、（判はキトサン（脱アセチル化度
１００％）、（旬は水のみを用いた場合の測定結果であ
る。 特許出願人　味の素株式会社 手続補正ｍ １．事ｆ４の表示 昭和５８年特ｉｉ’ｆ願第７５５６１　号２、発明の名
称 湿潤剤 ３、補ｉＬをする省 小作との関係　特許出願人 住所　東京都中火］ｇ京橋−丁目５番８月６、補正の対
象　明刺古の発明の詳細な説明の欄７、補正の内容 明細書箱９頁１１行目に記載の「ピロリドンカルボン酸
部分」を［ピロリドンカルボン酸部分中和物Ｊと訂正り
る。Figure 1 shows the yJ (time-lapse due to evaporation of each leaking crystal) when the bath liquid (3 g) was left in a constant temperature and humidity chamber containing 25% Fig. 2 is a drawing showing the reduction of heavy oil in the water. is the measurement result when using only chitosan (deacetylation degree 100%) and water. Patent applicant: Ajinomoto Co., Ltd. Procedural amendment m 1. Indication of matter f4 1982 Special application ii'f 75561 No. 2, Name of the invention Wetting agent 3, Relationship with provincial tenant farming that does supplementary l "Pyrrolidone carboxylic acid moiety" described in Explanation Column 7, Amendment Box 9, Line 11 is corrected as [Pyrrolidone Carboxylic Acid Partially Neutralized Product J].

Claims (1)

【特許請求の範囲】[Claims] Ｎ−ア七チルー１〕−グルコサミンとＤ−グルコサミン
を、構成単位とし、Ｎ−アセチル−Ｄ−グルコサミン単
位の合議４０〜６０％、Ｄ−グルコサミン単位の含！ｇ
５６０〜４０％であるところの非晶質の水溶性部分脱ア
セチル化キチンを含有することを特徴とする湿潤剤。N-acetyl-1]-glucosamine and D-glucosamine are used as constituent units, and the proportion of N-acetyl-D-glucosamine units is 40 to 60%, and the content of D-glucosamine units is 40 to 60%. g
A wetting agent characterized in that it contains 560-40% amorphous water-soluble partially deacetylated chitin.