JP2687141B2 - Novel chitosan compound, method for producing the compound, and moisturizing agent containing the compound - Google Patents
Novel chitosan compound, method for producing the compound, and moisturizing agent containing the compoundInfo
- Publication number
- JP2687141B2 JP2687141B2 JP18126388A JP18126388A JP2687141B2 JP 2687141 B2 JP2687141 B2 JP 2687141B2 JP 18126388 A JP18126388 A JP 18126388A JP 18126388 A JP18126388 A JP 18126388A JP 2687141 B2 JP2687141 B2 JP 2687141B2
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- compound
- general formula
- chitosan
- ethanediyl
- oxy
- Prior art date
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Description
【発明の詳細な説明】 産業上の利用分野 本発明は新規なキトサン化合物およびその製造方法に
関するものであり、本発明の新規なキトサン化合物は保
湿剤として有用なものである。TECHNICAL FIELD The present invention relates to a novel chitosan compound and a method for producing the same, and the novel chitosan compound of the present invention is useful as a moisturizing agent.
従来の技術 近年、化粧品用の保湿剤や医薬品原料としてヒアルロ
ン酸が注目されている。ヒアルロン酸は多量の水と結合
してゲルを形成し、皮膚の水分を保持し皮膚を柔軟にす
る作用を有し、さらに関節の湿潤作用と関連を持ち、化
粧品、眼科・外科用医薬品原料として広く用いられてい
る。2. Description of the Related Art In recent years, hyaluronic acid has attracted attention as a moisturizer for cosmetics and a raw material for pharmaceuticals. Hyaluronic acid binds to a large amount of water to form a gel, has the effect of retaining skin moisture and softening the skin, and is related to the moisturizing action of joints, and is used as a raw material for cosmetics and ophthalmic / surgical drugs. Widely used.
従来、ヒアルロン酸の製造方法としては、牛の眼のガ
ラス液、ニワトリのトサカなどの生体内の組織から単離
精製する方法と、ストレプトコッカス属の微生物を利用
した醗酵法（特開昭58−56692号）が知られている。前
者の方法ではコストが極めて高くなり、後者の方法は特
殊な設備を必要とする欠点がある。そこでヒアルロン酸
と同程度の性能を有する安価な代替物が求められてい
る。Conventionally, as a method for producing hyaluronic acid, a glass liquid of cattle, a method of isolating and purifying from tissues in vivo such as chicken mackerel, and a fermentation method using a microorganism of the genus Streptococcus (JP 58-56692A). No.) is known. The former method is extremely expensive, and the latter method has the drawback of requiring special equipment. Therefore, there is a need for an inexpensive alternative that has the same performance as hyaluronic acid.
発明が解決しようとする課題 本発明者等は、ムコ多糖類の一種であるキトサンをヒ
アルロン酸代替物の原料として鋭意研究を重ね、本発明
を完成するに至った。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The inventors of the present invention have conducted intensive studies using chitosan, which is one of the mucopolysaccharides, as a raw material for a hyaluronic acid substitute, and completed the present invention.
本発明の目的は、工業的に製造可能で安価な優れた保
湿力を有する新規な保湿剤を提供することにある。An object of the present invention is to provide a novel moisturizer having an excellent moisturizing power which can be industrially produced and is inexpensive.
課題を解決するための手段および作用 本発明の課題は、特定の新規なキトサン化合物を用い
ることにより解決される。Means and Actions for Solving the Problems The problems of the present invention are solved by using a specific novel chitosan compound.
すなわち本発明は、一般式（Ｉ） 〔式中、Ｒは炭素数１〜４のアルキル基を表し、ｍは10
〜1000、ｎは１〜200の整数を表す〕 で示される新規なキトサン化合物とその製造方法および
一般式（Ｉ）で示される新規なキトサン化合物を含む保
湿剤に関するものである。That is, the present invention provides a compound represented by the general formula (I): [In the formula, R represents an alkyl group having 1 to 4 carbon atoms, and m is 10
To 1000, n represents an integer of 1 to 200], a method for producing the same, and a humectant containing the novel chitosan compound represented by the general formula (I).
本発明のキトサン化合物は、前記一般式（Ｉ）で示し
たように新規化合物である。The chitosan compound of the present invention is a novel compound as shown in the above general formula (I).
一般式（Ｉ）で示されるキトサン化合物は、以下の方
法により製造される。The chitosan compound represented by the general formula (I) is produced by the following method.
すなわち、一般式（II） 〔式中、Ｒは炭素数１〜４のアルキル基を表し、ｎは１
〜200の整数を表す〕 で示されるα−（カルボキシメチル）−ω−アルコキシ
ポリ（オキシ−1,2−エタンジイル）を一般式（III） 〔式中、Ｘは塩酸または酢酸を表し、ｍは10〜1000の整
数を表す〕 で示されるキトサン塩にグラフト化することにより一般
式（Ｉ）の新規なキトサン化合物が得られる。That is, the general formula (II) [In the formula, R represents an alkyl group having 1 to 4 carbon atoms, and n is 1
Represents an integer of from 200] to α- (carboxymethyl) -ω-alkoxypoly (oxy-1,2-ethanediyl) represented by the general formula (III) [Wherein, X represents hydrochloric acid or acetic acid, and m represents an integer of 10 to 1000], and a novel chitosan compound of the general formula (I) can be obtained by grafting the chitosan salt.
本発明の新規なキトサン化合物の出発物質となる前記
一般式（III）のキトサン塩は、菌・藻類からエビやカ
ニなどの甲殻類等下等動物の組織中に広く分布するムコ
多糖類の１種であるキチンを脱アセチル化した後、塩酸
塩または酢酸塩とすることにより容易に得られる。The chitosan salt represented by the general formula (III), which is a starting material of the novel chitosan compound of the present invention, is a mucopolysaccharide widely distributed in tissues of lower animals such as crustaceans such as shrimp and crab from fungi / algae. It is easily obtained by deacetylating the seed chitin and then converting it into a hydrochloride or acetate.
本発明の新規なキトサン化合物の他の原料となる前記
一般式（II）のα−（カルボキシメチル）−ω−アルコ
キシポリ（オキシ−1,2−エタンジイル）は、ポリエチ
レングリコールモノアルキルエーテルの末端のヒドロキ
シ基を液相酸化によりカルボキシメチル化して得られ
る。The α- (carboxymethyl) -ω-alkoxypoly (oxy-1,2-ethanediyl) of the above-mentioned general formula (II), which is another raw material of the novel chitosan compound of the present invention, is a terminal of polyethylene glycol monoalkyl ether. It is obtained by carboxymethylating a hydroxy group by liquid phase oxidation.
一般式（II）のα−（カルボキシメチル）−ω−アル
コキシポリ（オキシ−1,2−エタンジイル）のＲとして
好ましいのは、メチル基またはエチル基である。Preferred as R of α- (carboxymethyl) -ω-alkoxypoly (oxy-1,2-ethanediyl) of the general formula (II) is methyl group or ethyl group.
一般式（III）のキトサン塩に一般式（II）のα−
（カルボキシメチル）−ω−アルコキシポリ（オキシ−
1,2−エタンジイル）をグラフト化するには以下の方法
が挙げられる。The chitosan salt of the general formula (III) is added to the α-of the general formula (II)
(Carboxymethyl) -ω-alkoxy poly (oxy-
The following method may be mentioned for grafting 1,2-ethanediyl).
例えばα−（カルボキシメチル）−ω−アルコキシポ
リ（オキシ−1,2−エタンジイル）にトリクロロ酢酸ペ
ンタクロロフェニル、カルボキシイミダゾール、Ｎ−ヒ
ドロキシスクシンイミド／ジシクロヘキシルカルボジイ
ミド等を反応させ、末端に活性基を導入し、キトサン塩
と反応させグラフト化する方法が好適である。For example, α- (carboxymethyl) -ω-alkoxypoly (oxy-1,2-ethanediyl) is reacted with pentachlorophenyl trichloroacetate, carboxyimidazole, N-hydroxysuccinimide / dicyclohexylcarbodiimide, etc. to introduce an active group at the terminal, A method of reacting with a chitosan salt and grafting is preferable.
本発明の新規なキトサン化合物の製造方法の一実施態
様を述べると以下のようになる。One embodiment of the method for producing the novel chitosan compound of the present invention will be described below.
一般式（II）のα−（カルボキシメチル）−ω−アル
コキシポリ（オキシ−1,2−エタンジイル）とトリクロ
ロ酢酸ペンタクロロフェニルを室温下でピリジン等の溶
媒中で反応させて、α−（カルボキシメチル）−ω−ア
ルコキシポリ（オキシ−1,2−エタンジイル）を得た
後、その生成物に一般式（III）のキトサン塩酸をアル
カリ触媒存在下にジメチルスルホキシド等の溶媒中で反
応させた後、精製、再結晶することにより一般式（Ｉ）
のキトサン化合物が得られる。Α- (carboxymethyl) -ω-alkoxypoly (oxy-1,2-ethanediyl) of the general formula (II) is reacted with pentachlorophenyl trichloroacetate at room temperature in a solvent such as pyridine to obtain α- (carboxymethyl). ) -Ω-Alkoxypoly (oxy-1,2-ethanediyl) is obtained, and then the product is reacted with chitosan hydrochloric acid of the general formula (III) in the presence of an alkali catalyst in a solvent such as dimethyl sulfoxide, The compound of general formula (I) can be obtained by purification and recrystallization.
A chitosan compound of is obtained.
本発明の新規なキトサン化合物の代表的なものとして
は、第１表に示す化合物が挙げられる。Representative examples of the novel chitosan compound of the present invention include the compounds shown in Table 1.
本発明の新規なキトサン化合物は、化粧品、医薬、農
薬等に配合される保湿剤として最適であり、その保湿力
はヒアルロン酸と同等かそれ以上の効力を有している。
そのため、化粧品等に保湿剤として単独で使用できるの
みならず、他の保湿剤と併用してもよい。 INDUSTRIAL APPLICABILITY The novel chitosan compound of the present invention is most suitable as a moisturizing agent to be blended in cosmetics, pharmaceuticals, agricultural chemicals, etc., and its moisturizing power is equal to or higher than that of hyaluronic acid.
Therefore, it can be used alone as a moisturizer in cosmetics and the like, and may be used in combination with other moisturizers.
実施例１（化合物１の製造） ｎ＝７のα−（カルボキシメチル）−ω−メトキシポ
リ（オキシ−1,2−エタンジイル）1.8gとトリクロロ酢
酸ペンタクロロフェニル2.2gをピリジン50ml中室温で６
時間反応後、減圧濃縮によりピリジンを除き、反応物を
得た。この反応物とキトサン塩酸塩（ｍ＝30）1gをトリ
エチルアミン0.71mlを加えたジメチルスルホキシド100m
l中で、室温下12時間撹拌し反応させた後、反応液をア
セトンに投入し、沈殿物を得た。得られた沈殿物をさら
に蒸留水に溶解し、水酸化ナトリウムでpHを7.5にした
後、再びアセトンへ投入し、沈殿物を得た。その沈殿物
を、アセトン、クロロホルム、メタノールで十分洗浄
し、第１表の化合物１を0.46g得た。Example 1 (Preparation of Compound 1) 1.8 g of α- (carboxymethyl) -ω-methoxypoly (oxy-1,2-ethanediyl) with n = 7 and 2.2 g of pentachlorophenyl trichloroacetate were added to 50 ml of pyridine at room temperature for 6 times.
After reacting for an hour, pyridine was removed by concentration under reduced pressure to obtain a reaction product. This reaction product and 1 g of chitosan hydrochloride (m = 30) were added with 0.71 ml of triethylamine and 100 m of dimethyl sulfoxide was added.
After stirring for 12 hours at room temperature in 1 l to react, the reaction solution was poured into acetone to obtain a precipitate. The obtained precipitate was further dissolved in distilled water, adjusted to pH 7.5 with sodium hydroxide, and then poured into acetone again to obtain a precipitate. The precipitate was thoroughly washed with acetone, chloroform and methanol to obtain 0.46 g of compound 1 in Table 1.
このものは水およびジメチルスホキシドに可溶であ
り、メタノール、エタノール、アセトン、クロロホルム
およびジメチルホルムアミドには不溶であった。It was soluble in water and dimethylsulfoxide and insoluble in methanol, ethanol, acetone, chloroform and dimethylformamide.
未反応アミノ基をコロイド滴定により定量し、得られ
た化合物１のグラフト化率を算出したところ、26％であ
った。The unreacted amino group was quantified by colloid titration, and the grafting ratio of the obtained compound 1 was calculated to be 26%.
なお、各種分析結果は以下の通りであった。 The results of various analyzes are as follows.
IR ν:1670〜1550cm-1（−NHCO−）、1150〜1030cm-1 （−COC−）1 H−NMR δ:3.6ppm（−CH2CH2O−） 実施例２（化合物２の製造） 実施例１の平均重合度30のキトサンを平均重合度100
のキトサンに代え、さらに平均重合度７のα−（ペンタ
クロロフェニルカルボキシメチル）−ω−メトキシポリ
（オキシ−1,2−エタンジイル）に代えて、平均重合度2
0のα−（カルボキシメチル）−ω−メトキシポリ（オ
キシ−1,2−エタンジイル）を3.3g用いた他は実施例１
に準じて反応を行い、化合物２を0.64g得た。IR ν: 1670 to 1550 cm -1 (-NHCO-), 1150 to 1030 cm -1 (-COC-) 1 H-NMR δ: 3.6 ppm (-CH 2 CH 2 O-) Example 2 (Production of compound 2) Chitosan having an average degree of polymerization of 30 in Example 1 was added with an average degree of polymerization of 100.
In place of α- (pentachlorophenylcarboxymethyl) -ω-methoxypoly (oxy-1,2-ethanediyl) having an average degree of polymerization of 7
Example 1 except 3.3 g of 0-α- (carboxymethyl) -ω-methoxypoly (oxy-1,2-ethanediyl) was used.
The reaction was performed according to the procedure described above to obtain 0.64 g of compound 2.
実施例３（化合物３の製造） 実施例１の平均重合度30のキトサンを平均重合度500
のキトサンに代え、さらに平均重合度７のα−（カルボ
キシメチル）−ω−メトキシポリ（オキシ−1,2−エタ
ンジイル）に代えて、平均重合度90のα−（カルボキシ
メチル）−ω−メトキシポリ（オキシ−1,2−エタンジ
イル）を7.5g用いた他は実施例１に準じて反応を行い、
化合物３を1.2g得た。Example 3 (Production of Compound 3) Chitosan having an average degree of polymerization of 30 in Example 1 was converted to an average degree of polymerization of 500.
In place of α- (carboxymethyl) -ω-methoxypoly (oxy-1,2-ethanediyl) having an average degree of polymerization of 7 in place of α- (carboxymethyl) -ω-methoxypoly ( (Oxy-1,2-ethanediyl) was used according to the same procedure as in Example 1 except that 7.5 g was used,
1.2 g of compound 3 was obtained.
実施例４（化合物４の製造） 実施例１の平均重合度７のα−（カルボキシメチル）
−ω−メトキシポリ（オキシ−1,2−エタンジイル）に
代えて、平均重合度７のα−（カルボキシメチル）−ω
−エトキシポリ（オキシ−1,2−エタンジイル）を1.8g
用いた他は実施例１に準じて反応を行い、化合物４を0.
51g得た。Example 4 (Production of Compound 4) α- (carboxymethyl) having an average degree of polymerization of 7 in Example 1
Α- (carboxymethyl) -ω having an average degree of polymerization of 7 in place of −ω-methoxypoly (oxy-1,2-ethanediyl)
1.8 g of -ethoxypoly (oxy-1,2-ethanediyl)
The reaction was carried out in the same manner as in Example 1 except that the compound 4 was added in an amount of 0.
51g was obtained.
実施例５（化合物５の製造） 実施例１の平均重合度30のキトサンを平均重合度100
のキトサンに代え、さらに平均重合度７のα−（カルボ
キシメチル）−ω−メトキシポリ（オキシ−1,2−エタ
ンジイル）に代えて、平均重合度20のα−（カルボキシ
メチル）−ω−エトキシポリ（オキシ−1,2−エタンジ
イル）を3.2g用いた他は実施例１に準じて反応を行い、
化合物５を0.71g得た。Example 5 (Production of Compound 5) Chitosan having an average degree of polymerization of 30 in Example 1 was treated with an average degree of polymerization of 100.
In place of α- (carboxymethyl) -ω-methoxypoly (oxy-1,2-ethanediyl) having an average degree of polymerization of 7 in place of α- (carboxymethyl) -ω-ethoxypoly ( (Oxy-1,2-ethanediyl) was used in the same manner as in Example 1 except that 3.2 g was used,
0.71 g of compound 5 was obtained.
実施例６（化合物６の製造） 実施例１の平均重合度30のキトサンを平均重合度500
のキトサンに代え、さらに平均重合度７のα−（カルボ
キシメチル）−ω−メトキシポリ（オキシ−1,2−エタ
ンジイル）に代えて、平均重合度20のα−（カルボキシ
メチル）−ω−エトキシポリ（オキシ−1,2−エタンジ
イル）を7.5g用いた他は実施例１に準じて反応を行い、
化合物６を1.3g得た。Example 6 (Production of Compound 6) Chitosan having an average degree of polymerization of 30 in Example 1 was treated with an average degree of polymerization of 500.
In place of α- (carboxymethyl) -ω-methoxypoly (oxy-1,2-ethanediyl) having an average degree of polymerization of 7 in place of α- (carboxymethyl) -ω-ethoxypoly ( (Oxy-1,2-ethanediyl) was used according to the same procedure as in Example 1 except that 7.5 g was used,
1.3 g of compound 6 was obtained.
実施例７、比較例１ 実施例１〜６で得た化合物１〜６の保水作用をヒアル
ロン酸、尿素と比較した。試験方法は次の通りである。
結果を第２表に示した。Example 7, Comparative Example 1 The water retention effect of the compounds 1 to 6 obtained in Examples 1 to 6 was compared with that of hyaluronic acid and urea. The test method is as follows.
The results are shown in Table 2.
［吸湿試験法］ 硫酸アンモニウム飽和水溶液により相対湿度81％とし
たデシケーターと炭酸カリウム飽和水溶液によって相対
湿度を43％としたデシケーターを20℃恒温室中に用意
し、乾燥した各試料を直径4.5cmの結晶皿に1gを精秤
し、デシケーターに放置した。放置40時間後に各試量の
重量を精秤した。放置測定重量から吸湿量を次式によっ
て増加率として求めた。[Moisture absorption test method] A desiccator having a relative humidity of 81% with a saturated aqueous solution of ammonium sulfate and a desiccator having a relative humidity of 43% with a saturated aqueous solution of potassium carbonate were prepared in a thermostatic chamber at 20 ° C, and each dried sample was crystallized to have a diameter of 4.5 cm. 1 g was precisely weighed on a plate and left in a desiccator. After leaving for 40 hours, the weight of each sample was precisely weighed. The moisture absorption amount was determined as the rate of increase by the following equation from the weight measured after standing.
吸湿増加率＝［（Wn−Wo）/Wo］×100 Wo:放置前の重量 Wn:放置後の重量 ［保湿試験法］ 各試料に約10％の水を加えた後、結晶皿中に精秤採取
し、炭酸カリウム飽和水溶液（相対湿度43％）を含むデ
シケータ中に放置し、20℃恒温室に放置した。放置40時
間後に各試料を精秤した。保湿性の指標として次式の水
分残存率を用いた。Moisture absorption increase rate = [(Wn-Wo) / Wo] x 100 Wo: Weight before standing Wn: Weight after standing [Moisture retention test method] After adding about 10% water to each sample, add it to the crystal dish. The sample was weighed, left in a desiccator containing a saturated aqueous solution of potassium carbonate (43% relative humidity), and left in a thermostatic chamber at 20 ° C. After 40 hours of standing, each sample was precisely weighed. The water retention rate of the following formula was used as an index of moisturizing property.
水分残存率＝（Hn/Ho）×100 ＝［（Wn−Ｓ）／（Wo−Ｓ）］×100 Ho:添加水分量 Hn:放置後の水分量 Wo:放置前の含水試料重量 Wn:放置後の試料重量 S:乾燥試料重量 第２表の結果から、本発明の新規なキトサン化合物は
ヒアルロン酸と同程度の保水性を有する化合物であり、
保湿剤として有用なことが分かる。Moisture remaining rate = (Hn / Ho) x 100 = [(Wn-S) / (Wo-S)] x 100 Ho: Moisture content added Hn: Moisture content after leaving Wo: Water-containing sample weight before leaving Wn: Leave Sample weight after S: Dry sample weight From the results in Table 2, the novel chitosan compound of the present invention is a compound having a water retention capacity comparable to that of hyaluronic acid,
It turns out that it is useful as a moisturizer.
発明の効果 本発明の新規なキトサン化合物は、ヒアルロン酸と同
程度の保水性を有し、化粧品および医薬品原料として最
適である。EFFECTS OF THE INVENTION The novel chitosan compound of the present invention has a water retention capacity comparable to that of hyaluronic acid, and is optimal as a raw material for cosmetics and pharmaceuticals.
Claims (3)
〜1000、ｎは１〜200の整数を表す〕 で示されるキトサン化合物。1. The compound of the general formula (I) [In the formula, R represents an alkyl group having 1 to 4 carbon atoms, and m is 10
To 1000, and n represents an integer of 1 to 200].
〜200の整数を表す〕 で示されるα−（カルボキシメチル）−ω−アルコキシ
ポリ（オキシ−1,2−エタンジイル）を一般式（III） 〔式中、Ｘは塩酸または酢酸を表し、ｍは10〜1000の整
数を表す〕 で示されるキトサン塩にグラフト化することを特徴とす
る一般式（Ｉ） 〔式中、Ｒ、ｍ、ｎは前記定義に同じ〕 で示されるキトサン化合物の製造方法。2. A compound of the general formula (II) [In the formula, R represents an alkyl group having 1 to 4 carbon atoms, and n is 1
Represents an integer of from 200] to α- (carboxymethyl) -ω-alkoxypoly (oxy-1,2-ethanediyl) represented by the general formula (III) [Wherein, X represents hydrochloric acid or acetic acid, and m represents an integer of 10 to 1000] and is grafted to a chitosan salt represented by the general formula (I). [Wherein R, m, and n are the same as defined above].
〜1000、ｎは１〜200の整数を表す〕 で示される少なくとも１種のキトサン化合物を含有する
ことを特徴とする保湿剤。3. A compound of the general formula (I) [In the formula, R represents an alkyl group having 1 to 4 carbon atoms, and m is 10
To 1000, n represents an integer of 1 to 200], and a moisturizing agent containing at least one chitosan compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18126388A JP2687141B2 (en) | 1988-07-20 | 1988-07-20 | Novel chitosan compound, method for producing the compound, and moisturizing agent containing the compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18126388A JP2687141B2 (en) | 1988-07-20 | 1988-07-20 | Novel chitosan compound, method for producing the compound, and moisturizing agent containing the compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0232101A JPH0232101A (en) | 1990-02-01 |
| JP2687141B2 true JP2687141B2 (en) | 1997-12-08 |
Family
ID=16097643
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18126388A Expired - Fee Related JP2687141B2 (en) | 1988-07-20 | 1988-07-20 | Novel chitosan compound, method for producing the compound, and moisturizing agent containing the compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2687141B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU8282298A (en) * | 1997-07-03 | 1999-01-25 | National Starch And Chemical Investment Holding Corporation | Chitosan derivatives and methods of manufacturing the same |
| GB9713980D0 (en) * | 1997-07-03 | 1997-09-10 | Danbiosyst Uk | New conjugates |
| ATE393171T1 (en) | 1998-11-10 | 2008-05-15 | Netech Inc | FUNCTIONAL CHITOSAND DERIVATIVES |
-
1988
- 1988-07-20 JP JP18126388A patent/JP2687141B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0232101A (en) | 1990-02-01 |
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