JP4089841B2 - Detergent containing a surfactant comprising a readily soluble acylated polylysine - Google Patents

Detergent containing a surfactant comprising a readily soluble acylated polylysine Download PDF

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JP4089841B2
JP4089841B2 JP06121298A JP6121298A JP4089841B2 JP 4089841 B2 JP4089841 B2 JP 4089841B2 JP 06121298 A JP06121298 A JP 06121298A JP 6121298 A JP6121298 A JP 6121298A JP 4089841 B2 JP4089841 B2 JP 4089841B2
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Prior art keywords
polylysine
acylated
acid
surfactant
readily soluble
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JPH11255892A (en
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秀一 松村
耕次 別府
昌平 梅澤
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Adeka Corp
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Adeka Corp
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Description

【0001】
【発明の属する技術分野】
本発明は界面活性剤として有用な、易溶性アシル化ポリリジンからなる界面活性剤を含む洗浄剤に関する。
【0002】
【従来の技術】
近年、地球規模の環境保全や人体に対する安全性への関心が高まり、「人や地球に優しい」製品は注目されている。界面活性剤としても、人体に対する刺激が少なく、安全性の高い製品や、環境に対する負荷の少ない生分解性の高い製品が望まれており、トイレタリー製品を中心に安全性や生分解性の高い界面活性剤の開発が進められている。
安全性が高い界面活性剤の原料として、アミノ酸がある。アミノ酸は蛋白質の構造単位であり、生体組織を構成するための重要な物質である。このようなアミノ酸を原料とするアミノ酸誘導体型界面活性剤は、安全で高い機能を有することが期待されている。従来知られているアミノ酸誘導体型界面活性剤としては、アシル化ペプチド、アシル化グルタミン酸等が挙げられる。アシル化ペプチドは、動植物の蛋白質を加水分解したポリペプチドをアシル化したもので、シャンプー等のトイレタリー製品に配合されている。
また、単一アミノ酸の縮合物であるポリグルタミン酸、ポリアスパラギン酸等は、合成皮革、表面処理剤、繊維原料、繊維加工、紙加工、フィルム、塗料、電気部品等に利用されていることが知られている。又、同様のポリリジンは食品保存剤、頭髪用化粧料、吸水ポリマー等として利用されている。
【0003】
【発明が解決しようとする課題】
ところで、このようなポリリジン縮合物をアシル化したアシル化ポリリジンが知られている。例えば、特開平5−246963号公報には、アシル化ポリリジンを利用した乳化剤、抗菌剤、食品添加剤等が開示されている。しかし、特開平5−246963号公報記載のアシル化ポリリジンは水や有機溶媒に溶解しないため、界面活性剤としての利用が制限されていた。これはアシル化剤として酸クロライドを使用していることが原因であると考えられる。
このような現状に鑑み、安全性や生物分解性の高い界面活性剤として、アシル化ポリリジンの水や各種の有機溶媒への溶解性の向上が求められていた。そこで本発明者らは、アシル化ポリリジンを製造する場合において、アシル化剤として脂肪酸無水物を使用した場合、酸クロライドを使用した場合とは明らかに物性が異なる化合物が得られることを発見した。
従って本発明の目的は、アシル化剤として脂肪酸無水物を使用した易溶性アシル化ポリリジンを提供することにある。
【0004】
【課題を解決する手段】
即ち本発明は、ポリリジンを脂肪酸無水物でアシル化して得られる下記の一般式(1)
【0005】
【化2】

Figure 0004089841
【0006】
(式中、Rはアシル基、R'は水素原子を表わし、nは2以上を表わす。)で表わされるアシル化度40mol%以下の易溶性アシル化ポリリジンからなる界面活性剤を含む洗浄剤である。
【0007】
【発明の実施の形態】
本発明の易溶性アシル化ポリリジンの原料として使用することができるポリリジンとしては例えば、D−リジン又はL−リジンから通常のペプチド合成で得られるポリリジンや、微生物が産出するε−ポリリジン又はそれを酸、アルカリ又は酵素等で適当な分子量に分解したε−ポリリジン等が挙げられる。本発明に使用するポリリジンの好ましい分子量は1,000〜5,000である。
又、アシル化剤である脂肪酸無水物としては例えば、酢酸、プロピオン酸、酪酸、吉草酸、イソ吉草酸、カプロン酸、カプリル酸、カプリン酸、ウンデシレン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、イソステアリン酸、アラキン酸、ベヘン酸、リグノセリン酸、ゾーマリン酸、オレイン酸、リノール酸、リノレン酸、ガドレン酸、エルカ酸、セラコレイン酸等の脂肪酸の無水物が挙げられる。これらの中でも、炭素数8〜22の脂肪酸の無水物が好ましい。ここで使用した脂肪酸無水物に対応するアシル基がRに対応する。
【0008】
本発明の易溶性アシル化ポリリジンは、上記のポリリジンと脂肪酸無水物を溶媒中で反応させて得られるものである。アシル化度は、ポリリジンに対する脂肪酸無水物の仕込み比で制御することができる。例えば、アシル化度が40mol%以下であると本発明の易溶性アシル化ポリリジンは水溶性を示す。
反応に使用する溶媒は、ポリリジン及び脂肪酸無水物が共に溶解する溶媒であれば特に限定されないが、例えば、水−メタノール混合溶媒、水−エタノール混合溶媒、水−アセトン混合溶媒、水−ジメチルホルムアミド混合溶媒、水−酢酸混合溶媒等が挙げられる。反応温度は好ましくは室温〜100℃程度であり、特に高温であることは要求されない。反応時間は好ましくは2〜48時間程度である。
本発明の易溶性アシル化ポリリジンは、水又は様々な有機溶媒に溶解可能である。これは、アシル化剤として脂肪酸無水物を使用した本発明特有の効果である。先行技術である特開平5−246963号公報にもアシル化ポリリジンが開示されており見かけ上は同一の化学式で表現されるが、本発明の易溶性アシル化ポリリジンはポリリジンと脂肪酸無水物との反応によって得られる種々の混合物であるため、このような製法の相違によって前記のアシル化ポリリジンとは異なった性質のものとなると考えられる。
【0009】
本発明のアシル化ポリリジンは易溶性であるため、界面活性剤としての性質を示し、その性質を利用し今まで困難であったアシル化ポリリジンの種々の用途への利用が可能となった。具体的な用途としては例えば、洗浄剤、乳化剤、消泡剤、分散剤、繊維処理剤、帯電防止剤、抗菌剤等が挙げられる。
【0010】
【実施例】
以下、実施例により本発明を更に具体的に説明する。尚、以下の実施例中、部及び%は特に記載がない限り重量基準である。
【0011】
(製造例1)
ε−ポリリジン2.97g(1mmol)を20%酢酸水溶液とメタノールの1:5混合溶媒に溶解し、室温でラウリン酸無水物4.40g(11.5mmol)と24時間反応させた。生成物をアセトンによって3回再結晶を行い、目的物を得た。該化合物の1H−NMRスペクトルにおいて、0.9ppm付近に脂肪酸残基のメチルプロトン由来のピークa、3.3ppm付近にリジンのメチレン基由来のb、cのピークが検出された。目的物のアシル化度(アシル化されたアミノ基/全アミノ基)は9.8mol%であった。
【0012】
【化3】
Figure 0004089841
【0013】
以下、脂肪酸無水物の種類及び使用量を変えて同様にして反応を行い、ラウロイル化ε−ポリリジン(アシル化度16.4mol%)、デシロイル化ε−ポリリジン(アシル化度10.0mol%)、デシロイル化ε−ポリリジン(アシル化度21.9mol%)、オクチロイル化ε−ポリリジン(アシル化度10.0mol%)を得た。
【0014】
(評価)
製造例1で得られた種々のアシル化ε−ポリリジンは何れも水及びメタノール及びエタノールに対して良好な溶解性を示した。又、これらのアシル化ε−ポリリジンについて、以下に示す方法により表面張力、起泡力及び生分解性を評価した。
【0015】
「表面張力」
製造例1で合成したアシル化ポリリジンの種々の濃度の水溶液について、その25℃の表面張力をウイルヘルミ法によって測定した。その結果を表1に示す。いずれのアシル化ポリリジンも十分な表面活性能を示す。
【0016】
【表1】
Figure 0004089841
【0017】
「起泡力及び泡安定性」
同様に、製造例1で合成した下記のアシル化ポリリジン及び典型的な非イオン性界面活性剤であるポリオキシエチレンモノラウリルエーテルについて、起泡力及び泡安定性を測定した。測定は、各試料の臨海ミセル濃度の水溶液を調製し、25℃にて起泡力計を用いて半微量TK法により起泡力を求め、その5分後泡の容積より泡安定性を求めた。その結果を表2に示す。本発明の易溶性アシル化ポリリジンは、起泡力ではポリオキシエチレンモノラウリルエーテルのような起泡力はなく、低泡性の界面活性剤である。
【0018】
【表2】
Figure 0004089841
【0019】
「生分解性」
同様に合成したアシル化ポリリジンおよび原料のε−ポリリジンの生分解性を測定した。測定は、活性汚泥を使用したOECD−301D法によって行った。その結果を表3に示す。本発明の易溶性アシル化ポリリジンは、良好な生分解性を示した。
【0020】
【表3】
Figure 0004089841
【0021】
(比較製造例1)
ε−ポリリジン2.97g(1mmol)水溶液に、室温でラウリン酸クロライド5.03g(23mmol)と水酸化ナトリウム0.96g(23mmol)水溶液を徐々に添加した。1時間反応後、生じた結晶をろ別し、エタノール及び水で洗浄後、凍結乾燥により目的物を得た。
この精製物は、水、メタノール、エタノール、アセトン及びトルエンには全く溶解しなかった。
【0022】
【発明の効果】
本発明の効果は、水及び様々な溶媒に溶解するアシル化ポリリジン及びその製造方法を提供したことにある。これにより、安全性と生物分解性の高いアシル化ポリリジンの界面活性剤としての利用が可能となった。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a detergent containing a surfactant composed of a readily soluble acylated polylysine useful as a surfactant .
[0002]
[Prior art]
In recent years, attention has been focused on products that are friendly to humans and the earth due to the growing concern about global environmental conservation and human safety. As surfactants, highly safe products with little irritation to the human body and highly biodegradable products with low environmental impact are desired, and interfaces with high safety and biodegradability are mainly used in toiletry products. Active agent development is underway.
An amino acid is used as a raw material for a highly safe surfactant. Amino acids are structural units of proteins and are important substances for constituting living tissues. An amino acid derivative-type surfactant using such an amino acid as a raw material is expected to have a safe and high function. Examples of conventionally known amino acid derivative-type surfactants include acylated peptides and acylated glutamic acids. An acylated peptide is a product obtained by acylating a polypeptide obtained by hydrolyzing animal and plant proteins, and is blended in toiletry products such as shampoos.
Polyglutamic acid, polyaspartic acid, etc., which are condensates of single amino acids, are known to be used in synthetic leather, surface treatment agents, fiber raw materials, fiber processing, paper processing, films, paints, electrical parts, etc. It has been. Similar polylysines are used as food preservatives, hair cosmetics, water-absorbing polymers, and the like.
[0003]
[Problems to be solved by the invention]
By the way, acylated polylysine obtained by acylating such a polylysine condensate is known. For example, JP-A-5-246963 discloses emulsifiers, antibacterial agents, food additives and the like using acylated polylysine. However, since the acylated polylysine described in JP-A-5-246963 is not dissolved in water or an organic solvent, its use as a surfactant has been limited. This is thought to be due to the use of acid chloride as the acylating agent.
In view of such a current situation, improvement in the solubility of acylated polylysine in water and various organic solvents has been demanded as a surfactant with high safety and biodegradability. Therefore, the present inventors have found that in the production of acylated polylysine, when a fatty acid anhydride is used as an acylating agent, a compound having clearly different physical properties from that obtained when acid chloride is used can be obtained.
Accordingly, an object of the present invention is to provide a readily soluble acylated polylysine using a fatty acid anhydride as an acylating agent.
[0004]
[Means for solving the problems]
That is, the present invention provides the following general formula (1) obtained by acylating polylysine with a fatty acid anhydride.
[0005]
[Chemical 2]
Figure 0004089841
[0006]
(Wherein R represents an acyl group, R ′ represents a hydrogen atom, and n represents 2 or more.) A detergent containing a surfactant composed of a readily soluble acylated polylysine having an acylation degree of 40 mol% or less. is there.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the polylysine that can be used as a raw material for the readily soluble acylated polylysine of the present invention include, for example, polylysine obtained by normal peptide synthesis from D-lysine or L-lysine, ε-polylysine produced by microorganisms or an acid thereof. Ε-polylysine decomposed to an appropriate molecular weight with an alkali or an enzyme. The preferred molecular weight of the polylysine used in the present invention is 1,000 to 5,000.
Examples of the fatty acid anhydride as an acylating agent include acetic acid, propionic acid, butyric acid, valeric acid, isovaleric acid, caproic acid, caprylic acid, capric acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, stearic acid. Examples thereof include anhydrides of fatty acids such as acid, isostearic acid, arachidic acid, behenic acid, lignoceric acid, zomarinic acid, oleic acid, linoleic acid, linolenic acid, gadrenic acid, erucic acid, and ceracoleic acid. Among these, an anhydride of a fatty acid having 8 to 22 carbon atoms is preferable. The acyl group corresponding to the fatty acid anhydride used here corresponds to R.
[0008]
The readily soluble acylated polylysine of the present invention is obtained by reacting the above polylysine with a fatty acid anhydride in a solvent. The degree of acylation can be controlled by the ratio of fatty acid anhydride to polylysine charged. For example, when the acylation degree is 40 mol% or less, the readily soluble acylated polylysine of the present invention exhibits water solubility.
The solvent used in the reaction is not particularly limited as long as it dissolves both polylysine and the fatty acid anhydride. For example, water-methanol mixed solvent, water-ethanol mixed solvent, water-acetone mixed solvent, water-dimethylformamide mixed Examples thereof include a solvent and a water-acetic acid mixed solvent. The reaction temperature is preferably about room temperature to about 100 ° C., and is not particularly required to be a high temperature. The reaction time is preferably about 2 to 48 hours.
The readily soluble acylated polylysine of the present invention can be dissolved in water or various organic solvents. This is an effect unique to the present invention using a fatty acid anhydride as an acylating agent. Prior art Japanese Patent Application Laid-Open No. 5-246963 discloses acylated polylysine, which is apparently expressed by the same chemical formula, but the readily soluble acylated polylysine of the present invention is a reaction between polylysine and a fatty acid anhydride. Therefore, it is considered that the acylated polylysine has different properties due to the difference in the production method.
[0009]
Since the acylated polylysine of the present invention is easily soluble, it exhibits properties as a surfactant, and it has become possible to use the acylated polylysine, which has been difficult until now, for various uses. Specific applications include cleaning agents, emulsifiers, antifoaming agents, dispersants, fiber treatment agents, antistatic agents, antibacterial agents and the like.
[0010]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples. In the following examples, parts and% are based on weight unless otherwise specified.
[0011]
(Production Example 1)
2.97 g (1 mmol) of ε-polylysine was dissolved in a 1: 5 mixed solvent of 20% aqueous acetic acid and methanol, and reacted with 4.40 g (11.5 mmol) of lauric anhydride at room temperature for 24 hours. The product was recrystallized three times with acetone to obtain the desired product. In the 1 H-NMR spectrum of the compound, a peak a derived from the methyl proton of the fatty acid residue was detected in the vicinity of 0.9 ppm, and b and c peaks derived from the methylene group of lysine were detected in the vicinity of 3.3 ppm. The acylation degree of the target product (acylated amino group / total amino group) was 9.8 mol%.
[0012]
[Chemical 3]
Figure 0004089841
[0013]
Hereinafter, the reaction is carried out in the same manner while changing the type and amount of fatty acid anhydride, lauroylated ε-polylysine (acylation degree 16.4 mol%), desiloylated ε-polylysine (acylation degree 10.0 mol%), Decyloylated ε-polylysine (acylation degree 21.9 mol%) and octyroylated ε-polylysine (acylation degree 10.0 mol%) were obtained.
[0014]
(Evaluation)
The various acylated ε-polylysines obtained in Production Example 1 all showed good solubility in water, methanol and ethanol. Further, the surface tension, foaming power and biodegradability of these acylated ε-polylysines were evaluated by the following methods.
[0015]
"surface tension"
About the aqueous solution of the acylated polylysine of various density | concentrations synthesize | combined in manufacture example 1, the 25 degreeC surface tension was measured by the Wilhelmi method. The results are shown in Table 1. Any acylated polylysine exhibits sufficient surface activity.
[0016]
[Table 1]
Figure 0004089841
[0017]
"Foaming power and foam stability"
Similarly, foaming power and foam stability were measured for the following acylated polylysine synthesized in Production Example 1 and polyoxyethylene monolauryl ether, which is a typical nonionic surfactant. For measurement, prepare an aqueous solution of each micelle concentration of each sample, obtain the foaming force by a semi-trace TK method using a foaming force meter at 25 ° C, and obtain the foam stability from the foam volume after 5 minutes. It was. The results are shown in Table 2. The readily soluble acylated polylysine of the present invention does not have foaming power like polyoxyethylene monolauryl ether in foaming power and is a low foaming surfactant.
[0018]
[Table 2]
Figure 0004089841
[0019]
"Biodegradable"
Similarly, biodegradability of acylated polylysine synthesized and raw material ε-polylysine was measured. The measurement was performed by the OECD-301D method using activated sludge. The results are shown in Table 3. The readily soluble acylated polylysine of the present invention showed good biodegradability.
[0020]
[Table 3]
Figure 0004089841
[0021]
(Comparative Production Example 1)
To an aqueous solution of 2.97 g (1 mmol) of ε-polylysine, 5.03 g (23 mmol) of lauric acid chloride and 0.96 g (23 mmol) of sodium hydroxide were gradually added at room temperature. After reacting for 1 hour, the resulting crystals were filtered off, washed with ethanol and water, and then lyophilized to obtain the desired product.
This purified product did not dissolve at all in water, methanol, ethanol, acetone and toluene.
[0022]
【The invention's effect】
The effect of the present invention is to provide an acylated polylysine that is soluble in water and various solvents and a method for producing the same. As a result, it is possible to use acylated polylysine having high safety and high biodegradability as a surfactant.

Claims (1)

ポリリジンを脂肪酸無水物でアシル化して得られる下記の一般式(1)
Figure 0004089841
(式中、Rはアシル基、R’は水素原子を表し、nは2以上を表わす。)で表わされる、アシル化度40mol%以下の易溶性アシル化ポリリジンからなる界面活性剤を含む洗浄剤。
The following general formula (1) obtained by acylating polylysine with a fatty acid anhydride
Figure 0004089841
(Wherein R represents an acyl group, R ′ represents a hydrogen atom, and n represents 2 or more), a detergent comprising a surfactant comprising a readily soluble acylated polylysine having an acylation degree of 40 mol% or less. .
JP06121298A 1998-03-12 1998-03-12 Detergent containing a surfactant comprising a readily soluble acylated polylysine Expired - Fee Related JP4089841B2 (en)

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US7887838B2 (en) 2002-01-18 2011-02-15 Banner Pharmacaps, Inc. Non-gelatin film and method and apparatus for producing same

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