JPWO2003102104A1 - Gelling agent - Google Patents

Abstract

[PROBLEMS] To provide a gelling agent that can be dissolved in a composition at a relatively low temperature when preparing an oily gel-like composition and that can prepare a gel-like composition that is stable at a high temperature. [Solution] The following general formula (1): (wherein R1 and R2 each independently represents a hydrocarbon group having 1 to 26 carbon atoms, R3 represents a hydrocarbon group having 7 to 10 carbon atoms, at least one N-acyl-L-acidic amino acid dialkylamide such as N-2-ethylhexanoyl-L-glutamic acid dibutylamide and 3-methoxy-3-methylbutanol represented by An oily base gelling agent containing at least one monohydric lower alcohol. [Effect] When preparing an oily gel-like composition, it is possible to prepare a stable gel-like composition that can be dissolved at a low temperature of 100 ° C. or less and that does not release even at high temperatures. The obtained gel composition is excellent in appearance such as transparency, and can be suitably used for uses such as fragrances.

Description

（式中、Ｒ^１及びＲ^２はそれぞれ独立に炭素原子数１〜２６の炭化水素基を示し、Ｒ^３は炭素原子数７〜１０の炭化水素基を示し、ｎは１または２を示す）で表わされるＮ−アシル−Ｌ−酸性アミノ酸ジアルキルアミドの少なくとも１種と１価の低級アルコールの少なくとも１種とを含有するゲル化剤を提供するものである。本発明のゲル化剤は油性基剤のゲル化のために用いることができる。
この発明の好ましい態様によれば、Ｒ^１及びＲ^２がそれぞれ独立に炭素原子数１〜２６の直鎖又は分枝鎖のアルキル基であり、Ｒ^３が炭素原子数７〜１０の直鎖又は分枝鎖のアルキル基である上記のゲル化剤；ｎが２である上記のゲル化剤が提供される。さらに好ましい態様によれば、Ｒ^１及びＲ^２がそれぞれ独立に炭素原子数３〜５の直鎖又は分枝鎖のアルキル基であり、Ｒ^３が炭素原子数７〜９の直鎖又は分枝鎖のアルキル基であり、ｎが２である上記のゲル化剤が提供される。
本発明のさらに好ましい態様によれば、上記一般式（Ｉ）で表されるＮ−アシル−Ｌ−酸性アミノ酸ジアルキルアミドの総重量と低級アルコールの総重量との比が１：１００〜１００：１である上記のゲル化剤が提供される。本発明の特に好ましい態様によれば、上記一般式（Ｉ）で表されるＮ−アシル−Ｌ−酸性アミノ酸ジアルキルアミドがＮ−２−エチルヘキサノイル−Ｌ−グルタミン酸ジブチルアミドである上記のゲル化剤が提供される。また、低級アルコールが３−メトキシ−３−メチルブタノール、又はプロピレングリコールメチルエーテルである上記のゲル化剤も本発明の好ましい態様として提供される。
別の観点からは、（ａ）上記のゲル化剤及び（ｂ）油性基剤の少なくとも１種を含有するゲル状組成物が本発明により提供される。このゲル状組成物の好ましい態様によれば、油性基剤が揮発性テルペン炭化水素である上記のゲル状組成物；芳香剤として用いる上記のゲル状組成物；実質的に透明の組成物である上記のゲル状組成物；及び高温において実質的に離漿のない上記のゲル化剤が提供される。
さらに本発明により、油性基剤をゲル化する方法であって、上記一般式（Ｉ）で表される化合物の少なくとも１種及び低級アルコールの少なくとも１種を含むゲル化剤を油性基剤の少なくとも１種に混合する行程を含む方法；油性基剤を含むゲル状組成物の製造方法であって、上記のゲル化剤を油性基剤の少なくとも１種に混合する行程を含む方法；油性基剤の少なくとも１種を含むゲル状組成物の製造のための上記ゲル化剤の使用が提供される。
発明を実施するための最良の形態
一般式（Ｉ）において、Ｒ^１及びＲ^２はそれぞれ独立に炭素原子数１〜２６の炭化水素基を示す。Ｒ^１及びＲ^２が示す炭化水素基は、直鎖状、分枝鎖状、環状、又はそれらの組み合わせのいずれであってもよい。炭化水素基としては不飽和結合を含む炭化水素基を用いることもできるが、アルキル基を用いることがより好ましい。好ましくは炭素原子数１〜１０、より好ましくは炭素原子数２〜６の直鎖状又は分枝鎖状のアルキル基を用いることができ、さらに好ましいのは炭素原子数３〜５の直鎖状又は分枝鎖状のアルキル基である。最も好ましくはｎ−ブチル基を用いることができる。
Ｒ^３は炭素原子数７〜１０の炭化水素基を示す。Ｒ^３が示す炭化水素基は、直鎖状、分枝鎖状、環状、又はそれらの組み合わせのいずれであってもよい。炭化水素基としては不飽和結合を含む炭化水素基を用いることもできるが、アルキル基を用いることがより好ましい。アルキル基としては直鎖状又は分枝鎖状のアルキル基が好ましい。より好ましくはＲ^３は炭素原子数７〜９の直鎖状又は分枝鎖状のアルキル基を示す。Ｒ^３−ＣＯ−で表される基の例としては、例えば、ｎ−オクタノイル基、ｎ−ノナノイル基、ｎ−デカノイル基、ｎ−ウンデカノイル基、２−エチルヘキサノイル基などを挙げることができ、これらのうちオクタノイル基、デカノイル基、２−エチルヘキサノイル基が好ましく、ゲル化能の高さの観点で２−エチルヘキサノイル基がもっとも好ましい。Ｒ^３−ＣＯ−で表される基が２−エチルヘキサノイル基の場合、原料である２−エチルヘキサノイルクロライドの入手のし易さの観点から、２−（Ｒ，Ｓ）−エチルヘキサノイル基を用いることが好ましい。
一般式（Ｉ）において、分子中の酸性アミノ酸残基はｎが１の場合にはＬ−アスパラギン酸残基、ｎが２の場合にはＬ−グルタミン酸残基を示す。一般式（Ｉ）においてｎが２であることが好ましい。一般式（Ｉ）で表されるＮ−アシル−Ｌ−酸性アミノ酸ジアルキルアミドは、Ｒ^１、Ｒ^２、及び／又はＲ^３の種類により１以上の不斉炭素を有する場合があるが、本発明のゲル化剤には、このような不斉炭素に基づく光学異性体又はジアステレオマーなどの立体異性体、任意の立体異性体の混合物、あるいはラセミ体を用いてもよい。また、Ｒ^１、Ｒ^２、及び／又はＲ^３がオレフィン性二重結合を有する場合には、その配置はＺ又はＥのいずれでもよく、本発明のゲル化剤には純粋な形態の幾何異性体又は任意の幾何異性体の混合物を用いてもよい。さらに、本発明のゲル化剤には、上記一般式（Ｉ）で表されるＮ−アシル−Ｌ−酸性アミノ酸ジアルキルアミドの任意の水和物又は溶媒和物を用いてもよい。
一般式（Ｉ）で表されるＮ−アシル−Ｌ−酸性アミノ酸ジアルキルアミドは、例えば塩基性触媒下に長鎖脂肪酸ハライドとＬ−グルタミン酸又はＬ−アスパラギン酸とをショッテン・バウマン反応で反応させることによりＮ−アシル化グルタミン酸又はＮ−アシル化アスパラギン酸を製造し、さらにアルキルアミンなどのアミン誘導体を酸触媒の存在下又は無触媒下に加熱反応することにより製造することができる。あるいは、酸触媒の存在下又は無触媒下にグルタミン酸又はアスパラギン酸とアルキルアミンなどのアミン誘導体とを反応させて得られるグルタミン酸アミド又はアスパラギン酸アミドを脂肪酸ハライド等のアシル化剤でＮ−アシル化することにより製造できる。
一般式（Ｉ）で表されるＮ−アシル−Ｌ−酸性アミノ酸ジアルキルアミドの製造例は本明細書の実施例に具体的かつ詳細に説明されているので、その製造例を参照しつつ、出発原料、試薬、反応条件などを適宜選択し、必要に応じてそれらの方法に適宜の修飾や改変を加えることにより、当業者は一般式（Ｉ）で表されるＮ−アシル−Ｌ−酸性アミノ酸ジアルキルアミドをいずれも製造することが可能である。
本発明のゲル化剤において、一般式（Ｉ）で表されるＮ−アシル−Ｌ−酸性アミノ酸ジアルキルアミドとして１種類の化合物を用いてもよいが、一般式（Ｉ）で表される化合物から選ばれる２種以上の化合物を組み合わせて用いてもよい。本発明のゲル化剤における一般式（Ｉ）で表されるＮ−アシル−Ｌ−酸性アミノ酸ジアルキルアミドの使用量は油性基剤がゲル化する量であれば特に制限はないが、通常、ゲル化させるべき油性基剤１００重量部に対し０．１〜１５重量部、好ましくは０．５〜１０重量部程度である。０．１重量部より少ない場合は十分なゲル強度を得ることができない場合があり、１５重量部より多い場合は油性基剤に溶解できず、得られるゲル化油性基剤の外観が損なわれる場合がある。
本発明のゲル化剤の成分として用いられる低級アルコール化合物の種類は特に限定されない。低級アルコール化合物としては１種類の化合物を用いてもよいが、２種以上の低級アルコール化合物を用いてもよい。本明細書において「低級」という用語は、ある化合物分子内に有する炭素原子の合計が一般的には１０以下であることを意味している。また、「アルコール化合物」とは１価のアルコール化合物を意味しており、２価又は３価の多価アルコールは包含されない。低級アルコール化合物は任意の官能基を有していてもよい。官能基の種類、個数、置換位置は特に限定されないが、例えば、アルコキシ基、アリール基、オキソ基などを１又は２個以上有していてもよい。分子内の炭素原子の合計が１１以上のアルコール化合物は揮発性が低く、ゲル状組成物を芳香剤として用いた場合には、使用時又は使用後に高級アルコールが残渣として残ってしまう場合がある。
低級アルコール化合物としては、例えば、メタノール、エタノール、イソプロピルアルコール、ｎ−ブタノール、２−ブタノール、ｔ−ブタノール、３−メトキシブタノール、３−メトキシ−３−メチルブタノール、ペンタノール、ヘキサノール、シクロヘキサノール、シス−３−ヘキセノール、リナロール、β−フェニルエチルアルコール、エチレングリコールメチルエーテル、エチレングリコールエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールメチルエーテル，ジプロピレングリコールメチルエーテル、プロピレングリコールメチルエーテルアセテートなどを挙げることができる。その中でも、３−メトキシブタノール、３−メトキシ−３−メチルブタノール、ヘキサノール、シクロヘキサノール、エチレングリコールメチルエーテル、エチレングリコールエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールメチルエーテル，ジプロピレングリコールメチルエーテル、プロピレングリコールメチルエーテルアセテートが好ましい。さらに好ましいのは、３−メトキシ−３−メチルブタノール、エチレングリコールメチルエーテル、エチレングリコールエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールメチルエーテル，ジプロピレングリコールメチルエーテルである。これらのうち、適度なゲル化能を保持したまま溶解温度を下げることができる点で３−メトキシ−３−メチルブタノール、又はプロピレングリコールメチルエーテルが特に好ましい。低級アルコール化合物の使用量は特に限定されないが、例えばゲル化させるべき油性基剤１００重量部に対して約０．１〜５０重量部で用いられ、より好ましくは１〜２０重量部である。０．１重量部よりも少ない場合、ゲル化剤の溶解温度が高くなる場合があり、５０重量部よりも多い場合は十分なゲル強度を得られない場合がある。
本発明のゲル化剤は、一般式（Ｉ）で表されるＮ−アシル−Ｌ−酸性アミノ酸ジアルキルアミドから選ばれる１種又は２種以上の化合物と、低級アルコール化合物の１種又は２種以上を含んでいる。このゲル化剤を用いると、ゲル強度及び透明度が高く、高温でも安定で実質的に離漿がないゲル状組成物を製造することができる。一般式（Ｉ）で表されるＮ−アシル−Ｌ−酸性アミノ酸ジアルキルアミドの総重量（本明細書において、「総重量」とは１種類の化合物を用いる場合にはその化合物の重量であり、２種以上の化合物を含む場合にはそれらの合計重量を意味する）と低級アルコール化合物の総重量の割合は所望の性能に応じて適宜選択可能であるが、一般的には１：１００〜１００：１であることが好ましい。
本発明のゲル状組成物の製造に用いられる油性基材としては、加熱により上記ゲル化剤を充分に溶解させ、室温に冷却したときにゲルを形成するものであれば特に制限はないが、具体例としては、シクロメチコン、ジメチコン等のシリコーン油；セチルアルコール、イソステアリルアルコール、ラウリルアルコール、ヘキサデシルアルコール、オクチルドデカノール等の高級アルコール；イソステアリン酸、ウンデシレン酸、オレイン酸等の脂肪酸；ミリスチン酸ミリスチル、ラウリン酸ヘキシル、オレイン酸デシル、ミリスチン酸イソプロピル、ジメチルオクタン酸ヘキシルデシル、モノステアリン酸グリセリン、フタル酸ジエチル、モノステアリン酸エチレングリコール、オキシステアリン酸オクチル等のエステル類；ｄ−リモネン、α−ピネン、流動パラフィン、ワセリン、スクワラン等の炭化水素；ラノリン、還元ラノリン、カルナバロウ等のロウ；ミンク油、カカオ油、ヤシ油、パーム核油、ツバキ油、ゴマ油、ヒマシ油、オリーブ油等の油脂等が挙げられる。
これらのうち炭化水素油が好ましく、得られる油性ゲル状組成物の外観の透明性といった観点からテルペン炭化水素がより好ましく、揮発性テルペン炭化水素が特に好ましい。揮発性テルペン炭化水素としては、例えば、フェランドレン、テルピノレン、ミルセン、α−ピネン、ｄ−リモネンあるいはこれらの混合物、またはこれらの化合物を主成分とする天然製油、例えばα−ピネンを主成分とするテレピン油、ｄ−リモネンを主成分とするオレンジ油などを挙げることができる。
油性基剤は、好ましくはゲル状組成物の全重量に対して約１０〜９９重量％の割合で用いられる。油性基剤の配合量が１０重量％よりも少ない場合、または９９重量％よりも多い場合は、十分なゲル強度を得ることができない場合がある。なお、油性基剤としては２種以上の油性基剤を組み合わせて用いてもよい。
本発明のゲル状組成物の製造方法は特に限定されないが、例えば、Ｎ−アシル−Ｌ−酸性アミノ酸ジアルキルアミド、低級アルコール化合物、及び油性基剤を混合物が均一な溶液を形成するまで撹拌しながら約５０〜１００℃に加熱し、その後室温まで冷却して目的のゲル状組成物を得ることができる。より低い温度でゲル化剤を溶解させるために、先にＮ−アシル−Ｌ−酸性アミノ酸ジアルキルアミドと低級アルコールとを加熱溶解しておいて、均一溶液になったところに油性基材を添加して室温まで冷却するか、あるいはＮ−アシル−Ｌ−酸性アミノ酸ジアルキルアミドと低級アルコールとを加熱溶解した後、得られた混合物の溶液を油性基材に添加してゲル化させてもよい。
本発明のゲル状組成物の製造には、上記のゲル化剤に加えて他のゲル化剤を用いてもよい。例えば、油性基材のゲル化剤として用いられているポリアミド樹脂、１２−ヒドロキシステアリン酸、ステアリン酸ナトリウム、オクタン酸アルミニウム、ジベンジリデン−Ｄ−ソルビトール、Ｎ−ラウロイル−Ｌ−グルタミン酸ジブチルアミド等のゲル化剤を用いてもよい。また、ゲル化剤補助剤として１，２−ポリブタジエン等を用いることもできる。
本発明のゲル状組成物には、香料、界面活性剤、各種添加剤、各種粉体等などを必要に応じて配合することができる。これらの成分の種類は特に限定されず、ゲル状組成物の用途や所望の性能に応じて、適宜選択することが可能である。これらの成分の２種以上を組み合わせて用いてもよい。
香料としては、例えば、バラ油、ジャスミン油、ネロリ油、ラベンダー油といった天然植物性香料やムスク油、シベット油、カストリウム油などの天然動物性香料、リモネン、β−カリオフィレンなどの合成炭化水素、シス−３−ヘキセノール、リナロールなどの合成アルコール、２，６−ノナジエナール、シトラールなどの合成アルデヒド、β−イオノン、シクロペンタデカノンなどの合成ケトン、リナリルアセテートなどの合成エステル、γ−ウンデカラクトンなどの合成ラクトン、オイゲノールなどの合成フェノール、ローズオキサイドなどの合成オキサイド、インドールなどの合成含窒素化合物、フェニルアセトアルデヒドジメチルアセタールなどの合成アセタール、オーランチオールなどの合成シッフ塩基などが挙げられる。
界面活性剤としては、例えば、Ｎ−長鎖アシル酸性アミノ酸塩やＮ−長鎖アシル中性アミノ酸塩などのＮ−長鎖アシルアミノ酸塩、Ｎ−長鎖脂肪酸アシル−Ｎ−メチルタウリン塩、アルキルサルフェートおよびそのアルキレンオキシド付加物、脂肪酸アミドエーテルサルフェート、脂肪酸の金属塩および弱塩基塩、スルホコハク酸系界面活性剤、アルキルフォスフェートおよびそのアルキレンオキシド付加物、アルキルエーテルカルボン酸、等のアニオン界面活性剤；グリセリンエーテルおよびそのアルキレンオキシド付加物などのエーテル型界面活性剤、グリセリンエステルおよびそのアルキレンオキシド付加物などのエステル型界面活性剤、ソルビタンエステルおよびそのアルキレンオキシド付加物などのエーテルエステル型界面活性剤、ポリオキシアルキレン脂肪酸エステル、グリセリンエステル、脂肪酸ポリグリセリンエステル、ソルビタンエステル、ショ糖脂肪酸エステルなどのエステル型界面活性剤、アルキルグルコシド類、硬化ヒマシ油ピログルタミン酸ジエステルおよびそのエチレンオキシド付加物、ならびに脂肪酸アルカノールアミドなどの含窒素型の非イオン性界面活性剤、等の非イオン性界面活性剤；アルキルアンモニウムクロライド、ジアルキルアンモニウムクロライドなどの脂肪族アミン塩、それらの４級アンモニウム塩、ベンザルコニウム塩などの芳香族４級アンモニウム塩、脂肪酸アシルアルギニンエステル、等のカチオン界面活性剤；並びにカルボキシベタインなどのベタイン型界面活性剤、アミノカルボン酸型界面活性剤、イミダゾリン型界面活性剤等の両性界面活性剤等が挙げられる。
各種添加剤としては、例えば、グリシン、アラニン、セリン、スレオニン、アルギニン、グルタミン酸、アスパラギン酸、ロイシン、バリンなどのアミノ酸類；グリセリン、エチレングリコール、１，３−ブチレングリコール、プロピレングリコール、イソプレングリコールなどの多価アルコール；ポリグルタミン酸、ポリアスパラギン酸を含むポリアミノ酸およびその塩、ポリエチレングリコール、アラビアゴム類、アルギン酸塩、キサンタンガム、ヒアルロン酸、ヒアルロン酸塩、キチン、キトサン、水溶性キチン、カルボキシビニルポリマー、カルボキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルトリメチルアンモニウムクロライド、ポリ塩化ジメチルメチレンピペリジウム、ポリビニルピロリドン誘導体四級アンモニウム、カチオン化プロテイン、コラーゲン分解物およびその誘導体、アシル化タンパク、ポリグリセリンなどの水溶性高分子；マンニトールなどの糖アルコールおよびそのアルキレンオキシド付加物等の他、動植物抽出物、核酸、ビタミン、酵素、抗炎症剤、殺菌剤、防腐剤、抗酸化剤、紫外線吸収剤、キレート剤、制汗剤、顔料、色素、酸化染料、有機及び無機粉体、ｐＨ調整剤、パール化剤、湿潤剤等を挙げることができる。
各種粉体としては、例えば、ナイロンビーズ、シリコーンビーズ等の樹脂粉体、ナイロンパウダー、金属脂肪酸石鹸、黄酸化鉄、赤色酸化鉄、黒酸化鉄、酸化クロム、酸化コバルト、カーボンブラック、群青、紺青、酸化亜鉛、酸化チタン、酸化ジルコニウム、酸化珪素、酸化アルミニウム、酸化セリウム、雲母チタン、窒化ホウ素、硫酸バリウム、炭酸カルシウム、炭酸マグネシウム、珪酸アルミニウム、珪酸マグネシウム、炭化珪素、色素、レーキ、セリサイト、マイカ、タルク、カオリン、板状硫酸バリウム、バタフライ状硫酸バリウム、微粒子酸化チタン、微粒子酸化亜鉛、微粒子酸化鉄、アシルリジン、アシルグルタミン酸、アシルアルギニン、アシルグリシン等のアシルアミノ酸等が挙げられ、更にシリコーン処理、フッ素化合物処理、シランカップリング剤処理、シラン処理有機チタネート処理、アシル化リジン処理、脂肪酸処理、金属石鹸処理、油剤処理、アミノ酸処理等の表面処理が施してあっても構わない。
本発明のゲル状組成物の用途は特に限定されないが、例えば、芳香剤、ゲル状化粧料、パック化粧料、粒状化粧料、又はロウソクなどとして用いることができ、それらの目的に応じて適宜の形状の組成物として調製することができる。
［実施例］
以下、本発明を実施例によりさらに具体的に説明するが、本発明の範囲は下記の実施例に限定されることはない。比較例で用いたラウロイルグルタミン酸ジブチルアミドとしては、味の素株式会社製のアミノ酸系ゲル化剤「ＧＰ−１」を用いた。例１；Ｎ−２−（Ｒ，Ｓ）−エチルヘキサノイル−Ｌ−グルタミン酸ジアルキルアミドの製造
グルタミン酸ナトリウム−水和物１１０ｇを水１４０ｇ、２７％水酸化ナトリウム水溶液７８ｇに溶解させて、１０℃に冷却した。アセトン１１０ｇを加えた後、２−エチルヘキサノイルクロライド８７ｇと２７％水酸化ナトリウム水溶液７８ｇを滴下した。アシル化反応液を１００ｇの水で希釈し、９５％硫酸６３ｇで中和し、油状分離させた。水層を除去し油層を減圧濃縮して油状物質を得た。この油状物質をメタノール７４２ｇに溶解し、９５％硫酸６．２ｇを加え９時間還流させた。反応液を３５℃まで放冷し、ｎ−ブチルアミン８．８ｇで中和後メタノールを留去し、油状物質をえた。この油状物質をトルエン６４３ｇと、ｎ−ブチルアミン２７１ｇを加えて、９０℃で１０時間加熱撹拌した。これに温水５０６ｇ、９５％硫酸１３０ｇを加えて、油状分離させ、水層を除去した。油層に温水１２００ｇを加えて、常圧で溶媒を除去して白色固体のスラリー液を得た。この固体をろ過し、５０℃で真空乾燥して２−エチルヘキサノイルグルタミン酸ジブチルアミドを得た。
（ａ）^１３Ｃ−ＮＭＲピーク（溶媒ＣＤＣｌ_３）：１２．０４、１２．０７、１３．７４、１３．９６、１３．９９、２０．０８、２０．１１、２２．７０、２２．７４、２６．０１、２９．８３、３１．５６、３１．６０、３２．３７、３３．０５、３９．２９、３９．５３、４９．３７、５２．５３、５２．５６、１７１．２９、１７３．０３、１７６．６６（ｐｐｍ）
（ｂ）^１Ｈ−ＮＭＲピーク（ＣＤＣｌ_３） δ：３．２４８（ｍ，４Ｈ）、４．３７３（ｍ，１Ｈ）、６．１９９（ｂｒｓ，１Ｈ）、７．０７９（ｂｒｓ，１Ｈ）、７．１６９（ｂｒｓ，１Ｈ）
（ｃ）赤外線吸収スペクトルの波数：３２９１．７、２９６１．０、２９３２．５、１６３８．２、１５５１．２、１４５２．６（ｃｍ^−１）
（ｄ）ＭＳスペクトル：３８２．３（Ｍ−Ｈ）⁻
例２；Ｎ−２−（Ｒ，Ｓ）−エチルヘキサノイル−Ｌ−グルタミン酸ジブチルアミドの製造
グルタミン酸ナトリウム−水和物５７．６ｇを水９２．６ｇ、ＩＰＡ７２．９ｇ、２７％水酸化ナトリウム水溶液４１ｇに溶解させて、１０℃に冷却した。ｐＨ１１（±０．２）、湿度１０（±５）℃を保持したまま、２−エチルヘキサノイルクロライド５０．１ｇと２７％水酸化ナトリウム水溶液４９．６ｇを１．５時間かけて同時滴下し、その後３０℃まで昇温して、１時間攪拌した。得られたアシル化反応液を、温度を４０℃以下に保持した状態で、７５％硫酸４１．２ｇを用いて中和し、ｐＨを１．９に調整し、油状分離させた。水層を除去し油層を減圧濃縮（５０℃、減圧）して油状物質を得た。この油状物質に水１５１．９ｇ、ｎ−ブタノール９１．３ｇ、トルエン４９６．１ｇを添加し、４０℃にて油状分離させた。得られた油層に酸化ホウ素２１．４ｇとブチルアミン６１．９ｇを添加し、オイルバスを用いて（バス温度１３５℃）還流し、生成した水の共沸脱水を１３時間かけて行った。これに希硫酸（約６％）４４４ｇを添加し、８５℃で油状分離を行った。得られた油層に水４１９ｇを添加し、再度油状分離を行った。得られた油層を、水１０００ｇを徐々に滴下しながら減圧下で共沸させ、ｎ−ブタノールとトルエンを除去すると、白色固体の水スラリーが得られた。その白色固体をろ過し、減圧乾燥してＮ−２−（Ｒ，Ｓ）−エチルヘキサノイル−Ｌ−グルタミン酸ジブチルアミド１０５ｇ（収率８９％）を得た。
例３：ゲル状組成物の製造
表１に示す組成に従って例１で得られたＮ−アシルグルタミン酸ジブチルアミド０．１ｇを油性基材に入れて、オイルバスで加熱溶解し、そのまま室温まで放冷し、ゲル状組成物を得た。また得られたゲル状組成物を０℃、室温、５０℃に１ヶ月間保存し、それぞれの外観の様子を目視で確認した。表１には、ゲル化剤を溶解させるのに要する温度及びゲル状組成物の外観を示した。ゲル状組成物の外観に関しては、透明な固体ゲルを○、透明なゲルだが一部離漿しているものを△、ゲルが白濁しているもの又は完全に液化しているものを×とした。

表１に示された結果から、本発明のゲル化剤は油性ゲル状組成物の調製の際に油性基剤中に比較的低い温度で溶解でき、かつ得られたゲル状組成物は高温状態においても離漿することなく安定であることが分かる。また、得られたゲル状組成物は透明性にも優れ、外観が良好であることがわかる（組成物１）。一方、低級アルコール化合物を用いない場合にはゲル化剤の溶解温度が１００℃を超えており（組成物２）、低級アルコールに替えて高級アルコールを用いた場合には特に高温保存後の外観の悪化が顕著であった（組成物３）。また、低級アルコール化合物に替えて三価のグリセリンを用いた場合にはゲル状組成物に分層が認められた（組成物４）。また、一般式（１）に包含されないＮ−ラウロイルグルタミン酸ジブチルアミドを用いた場合にはゲル状組成物の外観の悪化が認められた（組成物５及び６）。
産業上の利用可能性
本発明のゲル化剤は油性ゲル状組成物を調製する際に１００℃以下の低い温度で溶解することができ、かつ高温状態においても離漿することのない安定なゲル状組成物を調製可能である。また、得られたゲル状組成物は透明性などの外観に優れており、芳香剤などの用途に好適に使用できる。Technical field
The present invention relates to a gelling agent. More specifically, the present invention relates to a gelling agent that can be dissolved in a composition at a relatively low temperature when preparing an oily gel-like composition and that can prepare a gel-like composition that is stable at high temperatures.
Background art
Conventionally, hydrated gel fragrances and hydrophobic gel fragrances having a relatively low water content have been reported as gel-like fragrances, and these are provided as products on the market. Water-containing gel fragrances have been known for a long time, and water-containing gels such as agar and carrageenan as well as polyvinyl- and polyacrylate-based polymer water-containing gels have recently been used. These are used as fragrances by gradually allowing the perfume to ooze onto the gel surface as the water evaporates. However, these hydrated gel fragrances are easy to separate water. In particular, natural polymer gels have a problem that, when thawed after freezing, a large amount of water is separated and the commercial value is remarkably lowered. In addition, the polymer-based water-containing gel has a problem that the gel strength is small and the retention is inferior. Moreover, these hydrated gel fragrances have poor heat resistance, and are unsuitable for applications that are exposed to high temperature conditions, such as fragrances for automobiles.
Hydrophobic gel fragrances, on the other hand, can be easily gelled with higher fatty acid salts, especially sodium stearate, such as ethanol, ethylene glycol monoethyl ether, petroleum solvents, and natural hydrocarbon solvents. (Japanese Patent Publication No. 56-6783 and Japanese Patent Publication No. 57-50502). However, these hydrophobic gel fragrances contain water or a solvent such as glycols or alcohols as an essential component in order to dissolve sodium stearate as a gel forming agent. For this reason, these hydrophobic gel fragrances are vulnerable to heat, and the resulting gel has a drawback of reducing the value as a product, such as a large amount of residue at the end of preparation and poor appearance such as transparency. . Other hydrophobic gel fragrances include solid gel fragrances of hydrogenated castor oil and hydrocarbon compounds such as d-limonene, and solid gel fragrances of 12-hydroxystearic acid and hydrocarbon compounds such as d-limonene. There are agents. However, these hydrophobic gel fragrances have the disadvantage of being inferior in heat resistance as compared with the sodium stearate-based gel fragrances.
On the other hand, it is disclosed that an amine salt of an N-acylamino acid, or an ester or amide derivative thereof has a gelling performance with respect to an oily base (Japanese Patent Publication No. 53-13434). Japanese Patent Publication No. 3-80025 teaches that a gel-like composition having excellent transparency can be obtained from these amide derivatives and volatile terpene hydrocarbons. However, these methods require a large amount of gelling agent to solidify fragrances and the like, and require a high temperature of 100 ° C. or higher to dissolve the gelling agent. It is not satisfactory as a method for producing a composition.
[Problems to be solved by the invention]
This inventor makes it the subject to provide the gelatinizer which eliminated said fault. More specifically, when preparing an oily gel-like composition, the gel-like composition that can be dissolved at a low temperature of 100 ° C. or less and is stable even at high temperatures, particularly that it can be separated at high temperatures. It is an object of the present invention to provide a gelling agent capable of preparing a non-gel composition. Another object of the present invention is to provide a gelling agent capable of preparing a gel composition having excellent appearance such as transparency. Still another object of the present invention is to provide a gel-like composition that can be used as a fragrance, does not release in a high temperature state, and has excellent appearance such as transparency.
[Means for solving problems]
As a result of intensive studies to solve the above problems, the present inventors have found that a gelling agent containing a specific N-acyl-L-acidic amino acid dialkylamide and a lower alcohol is excellent as a gelling agent for an oily base. It was found that when preparing an oily gel-like composition, the gel-like composition can be dissolved at a low temperature of 100 ° C. or lower and stable even at high temperatures. Moreover, the obtained gel-like composition was excellent in transparency, and it discovered that it was a composition which can be utilized as an aromatic. The present invention has been completed based on the above findings.
Disclosure of the invention
That is, the present invention provides the following general formula (1):

(Wherein R¹And R²Each independently represents a hydrocarbon group having 1 to 26 carbon atoms, R³Represents a hydrocarbon group having 7 to 10 carbon atoms, and n represents 1 or 2, and at least one of N-acyl-L-acidic amino acid dialkylamides and at least one monovalent lower alcohol, It is intended to provide a gelling agent containing The gelling agent of the present invention can be used for gelation of an oily base.
According to a preferred embodiment of the present invention, R¹And R²Each independently represents a linear or branched alkyl group having 1 to 26 carbon atoms, and R³The above gelling agent wherein n is 2 is a linear or branched alkyl group having 7 to 10 carbon atoms; According to a further preferred embodiment, R¹And R²Each independently represents a linear or branched alkyl group having 3 to 5 carbon atoms, and R³Is a linear or branched alkyl group having 7 to 9 carbon atoms, and n is 2.
According to a further preferred embodiment of the present invention, the ratio of the total weight of the N-acyl-L-acidic amino acid dialkylamide represented by the general formula (I) to the total weight of the lower alcohol is 1: 100 to 100: 1. The above gelling agent is provided. According to a particularly preferred embodiment of the present invention, the gelation described above, wherein the N-acyl-L-acidic amino acid dialkylamide represented by the general formula (I) is N-2-ethylhexanoyl-L-glutamic acid dibutylamide. An agent is provided. Moreover, said gelling agent whose lower alcohol is 3-methoxy-3-methylbutanol or propylene glycol methyl ether is also provided as a preferable aspect of the present invention.
From another point of view, the present invention provides a gel composition containing at least one of (a) the above gelling agent and (b) an oily base. According to a preferred embodiment of the gel composition, the gel composition in which the oil base is a volatile terpene hydrocarbon; the gel composition to be used as a fragrance; the substantially transparent composition There is provided a gel composition as described above; and a gelling agent as described above that is substantially free of separation at elevated temperatures.
Further, according to the present invention, there is provided a method for gelling an oily base, wherein the gelling agent comprising at least one compound represented by the general formula (I) and at least one lower alcohol is used as an oily base. A method comprising a step of mixing with one type; a method for producing a gel composition containing an oily base, the method comprising a step of mixing the above gelling agent with at least one type of oily base; There is provided the use of the gelling agent for the preparation of a gel composition comprising at least one of the following.
BEST MODE FOR CARRYING OUT THE INVENTION
In general formula (I), R¹And R²Each independently represents a hydrocarbon group having 1 to 26 carbon atoms. R¹And R²The hydrocarbon group represented by may be linear, branched, cyclic, or a combination thereof. As the hydrocarbon group, a hydrocarbon group containing an unsaturated bond can be used, but an alkyl group is more preferably used. Preferably, a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably 2 to 6 carbon atoms can be used, and more preferably a linear chain having 3 to 5 carbon atoms. Or it is a branched alkyl group. Most preferably, an n-butyl group can be used.
R³Represents a hydrocarbon group having 7 to 10 carbon atoms. R³The hydrocarbon group represented by may be linear, branched, cyclic, or a combination thereof. As the hydrocarbon group, a hydrocarbon group containing an unsaturated bond can be used, but an alkyl group is more preferably used. As the alkyl group, a linear or branched alkyl group is preferable. More preferably R³Represents a linear or branched alkyl group having 7 to 9 carbon atoms. R³Examples of the group represented by —CO— include, for example, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, 2-ethylhexanoyl group, etc. Of these, an octanoyl group, a decanoyl group, and a 2-ethylhexanoyl group are preferable, and a 2-ethylhexanoyl group is most preferable from the viewpoint of high gelling ability. R³When the group represented by —CO— is a 2-ethylhexanoyl group, a 2- (R, S) -ethylhexanoyl group is selected from the viewpoint of easy availability of 2-ethylhexanoyl chloride as a raw material. It is preferable to use it.
In the general formula (I), an acidic amino acid residue in the molecule represents an L-aspartic acid residue when n is 1 and an L-glutamic acid residue when n is 2. In general formula (I), n is preferably 2. N-acyl-L-acidic amino acid dialkylamide represented by the general formula (I) is R¹, R²And / or R³May have one or more asymmetric carbons, but the gelling agent of the present invention includes optical isomers based on such asymmetric carbons, stereoisomers such as diastereomers, and any stereoisomers. Mixtures of racemates or racemates may be used. R¹, R²And / or R³In the case of having an olefinic double bond, the arrangement may be either Z or E, and the gelling agent of the present invention may be a pure form geometric isomer or a mixture of arbitrary geometric isomers. Good. Furthermore, any hydrate or solvate of N-acyl-L-acidic amino acid dialkylamide represented by the above general formula (I) may be used for the gelling agent of the present invention.
The N-acyl-L-acidic amino acid dialkylamide represented by the general formula (I) is obtained by, for example, reacting a long-chain fatty acid halide with L-glutamic acid or L-aspartic acid by a Schotten-Baumann reaction under a basic catalyst. Can be produced by producing N-acylated glutamic acid or N-acylated aspartic acid, and further subjecting an amine derivative such as alkylamine to a heat reaction in the presence or absence of an acid catalyst. Alternatively, glutamic acid amide or aspartic acid amide obtained by reacting glutamic acid or aspartic acid with an amine derivative such as alkylamine in the presence or absence of an acid catalyst is N-acylated with an acylating agent such as a fatty acid halide. Can be manufactured.
Examples of the production of N-acyl-L-acidic amino acid dialkylamides represented by the general formula (I) are described specifically and in detail in the examples of the present specification. By appropriately selecting raw materials, reagents, reaction conditions, and the like, and adding appropriate modifications and alterations to those methods as necessary, those skilled in the art can obtain N-acyl-L-acidic amino acids represented by the general formula (I). Any dialkylamide can be produced.
In the gelling agent of the present invention, one type of compound may be used as the N-acyl-L-acidic amino acid dialkylamide represented by the general formula (I), but from the compound represented by the general formula (I) Two or more selected compounds may be used in combination. The amount of the N-acyl-L-acidic amino acid dialkylamide represented by the general formula (I) in the gelling agent of the present invention is not particularly limited as long as the oily base is gelled. The amount is 0.1 to 15 parts by weight, preferably about 0.5 to 10 parts by weight, based on 100 parts by weight of the oily base to be converted. When the amount is less than 0.1 part by weight, sufficient gel strength may not be obtained. When the amount is more than 15 parts by weight, it cannot be dissolved in the oil base, and the appearance of the resulting gelled oil base is impaired. There is.
The kind of lower alcohol compound used as a component of the gelling agent of the present invention is not particularly limited. As the lower alcohol compound, one kind of compound may be used, but two or more kinds of lower alcohol compounds may be used. In this specification, the term “lower” means that the total number of carbon atoms in a compound molecule is generally 10 or less. The “alcohol compound” means a monovalent alcohol compound, and does not include divalent or trivalent polyhydric alcohols. The lower alcohol compound may have any functional group. The type, number, and substitution position of the functional group are not particularly limited. For example, the functional group may have one or more alkoxy groups, aryl groups, oxo groups, and the like. Alcohol compounds having a total of 11 or more carbon atoms in the molecule have low volatility, and when a gel composition is used as a fragrance, higher alcohol may remain as a residue during or after use.
Examples of the lower alcohol compound include methanol, ethanol, isopropyl alcohol, n-butanol, 2-butanol, t-butanol, 3-methoxybutanol, 3-methoxy-3-methylbutanol, pentanol, hexanol, cyclohexanol, cis -3-hexenol, linalool, β-phenylethyl alcohol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, dipropylene glycol methyl List ethers, propylene glycol methyl ether acetate, etc. Can. Among them, 3-methoxybutanol, 3-methoxy-3-methylbutanol, hexanol, cyclohexanol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Propylene glycol methyl ether, dipropylene glycol methyl ether, and propylene glycol methyl ether acetate are preferred. More preferably, 3-methoxy-3-methylbutanol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, dipropylene glycol Methyl ether. Among these, 3-methoxy-3-methylbutanol or propylene glycol methyl ether is particularly preferable in that the dissolution temperature can be lowered while maintaining an appropriate gelling ability. Although the usage-amount of a lower alcohol compound is not specifically limited, For example, it is used at about 0.1-50 weight part with respect to 100 weight part of oil-based bases to be gelatinized, More preferably, it is 1-20 weight part. When the amount is less than 0.1 part by weight, the dissolution temperature of the gelling agent may increase. When the amount is more than 50 parts by weight, sufficient gel strength may not be obtained.
The gelling agent of the present invention is one or more compounds selected from N-acyl-L-acidic amino acid dialkylamides represented by the general formula (I) and one or more of lower alcohol compounds. Is included. When this gelling agent is used, a gel composition having high gel strength and transparency, stable even at high temperatures and substantially free from separation can be produced. The total weight of the N-acyl-L-acidic amino acid dialkylamide represented by the general formula (I) (in this specification, “total weight” is the weight of the compound when one compound is used, The ratio of the total weight of the lower alcohol compound and the lower alcohol compound can be appropriately selected according to the desired performance, but generally it is 1: 100-100. : 1 is preferred.
The oily substrate used in the production of the gel composition of the present invention is not particularly limited as long as the gelling agent is sufficiently dissolved by heating and forms a gel when cooled to room temperature, Specific examples include silicone oils such as cyclomethicone and dimethicone; higher alcohols such as cetyl alcohol, isostearyl alcohol, lauryl alcohol, hexadecyl alcohol and octyldodecanol; fatty acids such as isostearic acid, undecylenic acid and oleic acid; myristic acid Esters such as myristyl, hexyl laurate, decyl oleate, isopropyl myristate, hexyl decyl dimethyloctanoate, glyceryl monostearate, diethyl phthalate, ethylene glycol monostearate, octyl oxystearate; d-limonene, α Hydrocarbons such as pinene, liquid paraffin, petrolatum, squalane; waxes such as lanolin, reduced lanolin, carnauba wax; oils and fats such as mink oil, cacao oil, coconut oil, palm kernel oil, camellia oil, sesame oil, castor oil, olive oil, etc. Can be mentioned.
Of these, hydrocarbon oils are preferred, terpene hydrocarbons are more preferred, and volatile terpene hydrocarbons are particularly preferred from the viewpoint of transparency of the appearance of the resulting oily gel composition. Examples of the volatile terpene hydrocarbon include, for example, ferrolandrene, terpinolene, myrcene, α-pinene, d-limonene, a mixture thereof, or a natural oil mainly containing these compounds, for example, α-pinene. Examples thereof include turpentine oil and orange oil mainly composed of d-limonene.
The oily base is preferably used in a proportion of about 10 to 99% by weight based on the total weight of the gel composition. If the amount of the oily base is less than 10% by weight or more than 99% by weight, sufficient gel strength may not be obtained. In addition, as an oily base, you may use combining 2 or more types of oily bases.
Although the manufacturing method of the gel composition of this invention is not specifically limited, For example, stirring N-acyl-L-acidic amino acid dialkylamide, a lower alcohol compound, and an oily base until the mixture forms a uniform solution. The target gel composition can be obtained by heating to about 50 to 100 ° C. and then cooling to room temperature. In order to dissolve the gelling agent at a lower temperature, the N-acyl-L-acidic amino acid dialkylamide and the lower alcohol are first heated and dissolved, and the oily base material is added to the homogeneous solution. The mixture may be cooled to room temperature, or N-acyl-L-acidic amino acid dialkylamide and a lower alcohol may be heated and dissolved, and then the resulting mixture solution may be added to an oily base material for gelation.
In the production of the gel composition of the present invention, other gelling agents may be used in addition to the above gelling agents. For example, gels such as polyamide resin, 12-hydroxystearic acid, sodium stearate, aluminum octoate, dibenzylidene-D-sorbitol, N-lauroyl-L-glutamic acid dibutylamide, which are used as gelling agents for oily substrates An agent may be used. Moreover, 1, 2-polybutadiene etc. can also be used as a gelatinizer adjuvant.
A fragrance | flavor, surfactant, various additives, various powders, etc. can be mix | blended with the gel-like composition of this invention as needed. The kind of these components is not specifically limited, It can select suitably according to the use and desired performance of a gel-like composition. Two or more of these components may be used in combination.
Examples of the fragrances include natural vegetable fragrances such as rose oil, jasmine oil, neroli oil, and lavender oil, natural animal fragrances such as musk oil, civet oil, and castrium oil, synthetic hydrocarbons such as limonene and β-caryophyllene, cis Synthetic alcohols such as -3-hexenol and linalool, synthetic aldehydes such as 2,6-nonadienal and citral, synthetic ketones such as β-ionone and cyclopentadecanone, synthetic esters such as linalyl acetate, and γ-undecalactone Examples include synthetic lactones, synthetic phenols such as eugenol, synthetic oxides such as rose oxide, synthetic nitrogen-containing compounds such as indole, synthetic acetals such as phenylacetaldehyde dimethyl acetal, and synthetic Schiff bases such as auranthiol.
Examples of the surfactant include N-long chain acyl amino acid salts such as N-long chain acyl acidic amino acid salts and N-long chain acyl neutral amino acid salts, N-long chain fatty acid acyl-N-methyl taurine salts, alkyls. Anionic surfactants such as sulfates and their alkylene oxide adducts, fatty acid amide ether sulfates, fatty acid metal salts and weak base salts, sulfosuccinic acid surfactants, alkyl phosphates and their alkylene oxide adducts, alkyl ether carboxylic acids, etc. Ether type surfactants such as glycerin ether and its alkylene oxide adduct, ester type surfactants such as glycerin ester and its alkylene oxide adduct, ether ester type surfactants such as sorbitan ester and its alkylene oxide adduct Ester-type surfactants such as polyoxyalkylene fatty acid ester, glycerin ester, fatty acid polyglycerin ester, sorbitan ester, sucrose fatty acid ester, alkyl glucoside, hydrogenated castor oil pyroglutamic acid diester and its ethylene oxide adduct, and fatty acid alkanolamide Nonionic surfactants such as nitrogen-containing nonionic surfactants; aliphatic amine salts such as alkylammonium chloride and dialkylammonium chloride; aromatics such as quaternary ammonium salts and benzalkonium salts thereof Cationic surfactants such as quaternary ammonium salts and fatty acyl arginine esters; betaine surfactants such as carboxybetaine, aminocarboxylic acid surfactants, imidazoline interfaces Amphoteric surfactants such as sexual agents.
Examples of various additives include amino acids such as glycine, alanine, serine, threonine, arginine, glutamic acid, aspartic acid, leucine, and valine; glycerin, ethylene glycol, 1,3-butylene glycol, propylene glycol, and isoprene glycol. Polyhydric alcohols; polyamino acids including polyglutamic acid and polyaspartic acid and salts thereof, polyethylene glycol, gum arabic, alginate, xanthan gum, hyaluronic acid, hyaluronic acid salt, chitin, chitosan, water-soluble chitin, carboxyvinyl polymer, carboxy Methylcellulose, hydroxyethylcellulose, hydroxypropyltrimethylammonium chloride, polydimethylmethylenepiperidinium chloride, polyvinylpyrrolidone derivatives Water-soluble polymers such as quaternary ammonium, cationized protein, collagen degradation products and derivatives thereof, acylated protein, polyglycerol, sugar alcohols such as mannitol and alkylene oxide adducts thereof, animal and plant extracts, nucleic acids, vitamins, Enzymes, anti-inflammatory agents, bactericides, antiseptics, antioxidants, UV absorbers, chelating agents, antiperspirants, pigments, dyes, oxidation dyes, organic and inorganic powders, pH adjusters, pearlizing agents, wetting agents Etc.
Various powders include, for example, resin powders such as nylon beads and silicone beads, nylon powder, metal fatty acid soap, yellow iron oxide, red iron oxide, black iron oxide, chromium oxide, cobalt oxide, carbon black, ultramarine, and bitumen , Zinc oxide, titanium oxide, zirconium oxide, silicon oxide, aluminum oxide, cerium oxide, titanium mica, boron nitride, barium sulfate, calcium carbonate, magnesium carbonate, aluminum silicate, magnesium silicate, silicon carbide, dye, lake, sericite, Examples include mica, talc, kaolin, plate-like barium sulfate, butterfly-like barium sulfate, fine particle titanium oxide, fine particle zinc oxide, fine particle iron oxide, acyl lysine, acyl glutamic acid, acyl arginine, acyl glycine and other acyl amino acids, and further silicone treatment , Fluorinated compounds Treatment, silane coupling agent treatment, silane treatment organic titanate process, acylated lysine treatment, fatty acid treatment, metal soap treatment, oil treatment, may be each other by subjecting the surface treatment of the amino acid treatment or the like.
The use of the gel composition of the present invention is not particularly limited. For example, it can be used as a fragrance, a gel cosmetic, a pack cosmetic, a granular cosmetic, a candle, etc. It can be prepared as a shaped composition.
[Example]
Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to the following examples. As the lauroyl glutamic acid dibutylamide used in the comparative example, an amino acid gelling agent “GP-1” manufactured by Ajinomoto Co., Inc. was used. Example 1 Preparation of N-2- (R, S) -ethylhexanoyl-L-glutamic acid dialkylamide
110 g of sodium glutamate-hydrate was dissolved in 140 g of water and 78 g of a 27% aqueous sodium hydroxide solution, and cooled to 10 ° C. After adding 110 g of acetone, 87 g of 2-ethylhexanoyl chloride and 78 g of 27% aqueous sodium hydroxide solution were added dropwise. The acylation reaction solution was diluted with 100 g of water, neutralized with 63 g of 95% sulfuric acid, and separated into oil. The aqueous layer was removed and the oil layer was concentrated under reduced pressure to obtain an oily substance. This oily substance was dissolved in 742 g of methanol, 6.2 g of 95% sulfuric acid was added, and the mixture was refluxed for 9 hours. The reaction solution was allowed to cool to 35 ° C., neutralized with 8.8 g of n-butylamine, and methanol was distilled off to obtain an oily substance. To this oily substance, 643 g of toluene and 271 g of n-butylamine were added, and the mixture was heated and stirred at 90 ° C. for 10 hours. To this, 506 g of warm water and 130 g of 95% sulfuric acid were added for oily separation, and the aqueous layer was removed. 1200 g of warm water was added to the oil layer, and the solvent was removed at normal pressure to obtain a white solid slurry. This solid was filtered and dried under vacuum at 50 ° C. to obtain 2-ethylhexanoylglutamic acid dibutylamide.
(A)¹³C-NMR peak (solvent CDCl₃): 12.04, 12.07, 13.74, 13.96, 13.99, 20.08, 20.21, 22.70, 22.74, 26.01, 29.83, 31.56, 31.60, 32.37, 33.05, 39.29, 39.53, 49.37, 52.53, 52.56, 171.29, 173.03, 176.66 (ppm)
(B)¹H-NMR peak (CDCl₃): Δ: 3.248 (m, 4H), 4.373 (m, 1H), 6.199 (brs, 1H), 7.079 (brs, 1H), 7.169 (brs, 1H)
(C) Wave number of infrared absorption spectrum: 3291.7, 2961.0, 2932.5, 1638.2, 1551.2, 1452.6 (cm^-1)
(D) MS spectrum: 382.3 (M-H)⁻
Example 2: Production of N-2- (R, S) -ethylhexanoyl-L-glutamic acid dibutylamide
57.6 g of sodium glutamate-hydrate was dissolved in 92.6 g of water, 72.9 g of IPA, and 41 g of 27% aqueous sodium hydroxide solution, and cooled to 10 ° C. While maintaining pH 11 (± 0.2) and humidity 10 (± 5) ° C., 50.1 g of 2-ethylhexanoyl chloride and 49.6 g of a 27% aqueous sodium hydroxide solution were simultaneously added dropwise over 1.5 hours, Thereafter, the temperature was raised to 30 ° C. and stirred for 1 hour. The obtained acylation reaction liquid was neutralized with 41.2 g of 75% sulfuric acid while maintaining the temperature at 40 ° C. or lower, pH was adjusted to 1.9, and oil separation was performed. The aqueous layer was removed, and the oil layer was concentrated under reduced pressure (50 ° C., reduced pressure) to obtain an oily substance. To this oily substance, 151.9 g of water, 91.3 g of n-butanol and 496.1 g of toluene were added, and oily separation was performed at 40 ° C. Boron oxide (21.4 g) and butylamine (61.9 g) were added to the obtained oil layer, and the mixture was refluxed using an oil bath (bath temperature: 135 ° C.), and azeotropic dehydration of the produced water was performed over 13 hours. To this was added 444 g of dilute sulfuric acid (about 6%), and oily separation was performed at 85 ° C. 419 g of water was added to the obtained oil layer, and oily separation was performed again. The obtained oil layer was azeotroped under reduced pressure while gradually adding 1000 g of water, and n-butanol and toluene were removed to obtain a white solid water slurry. The white solid was filtered and dried under reduced pressure to obtain 105 g (yield 89%) of N-2- (R, S) -ethylhexanoyl-L-glutamic acid dibutylamide.
Example 3: Production of a gel composition
According to the composition shown in Table 1, 0.1 g of N-acylglutamic acid dibutylamide obtained in Example 1 was put in an oily base material, heated and dissolved in an oil bath, and allowed to cool to room temperature as it was to obtain a gel composition. . Moreover, the obtained gel-like composition was preserve | saved for one month at 0 degreeC, room temperature, and 50 degreeC, and the mode of each external appearance was confirmed visually. Table 1 shows the temperature required to dissolve the gelling agent and the appearance of the gel composition. Regarding the appearance of the gel composition, a transparent solid gel is indicated by ◯, a transparent gel that is partially separated is indicated by △, and the gel is cloudy or completely liquefied is indicated by ×. .

From the results shown in Table 1, the gelling agent of the present invention can be dissolved in the oily base at a relatively low temperature during the preparation of the oily gel-like composition, and the obtained gel-like composition is in a high temperature state. It can be seen that it is stable without separation. Moreover, it turns out that the obtained gel-like composition is excellent also in transparency, and an external appearance is favorable (composition 1). On the other hand, when no lower alcohol compound is used, the melting temperature of the gelling agent exceeds 100 ° C. (Composition 2). When a higher alcohol is used instead of the lower alcohol, the appearance after storage at high temperature is particularly high. The deterioration was remarkable (Composition 3). In addition, when trivalent glycerin was used in place of the lower alcohol compound, a split layer was observed in the gel composition (Composition 4). In addition, when N-lauroyl glutamic acid dibutylamide not included in the general formula (1) was used, deterioration of the appearance of the gel composition was observed (Compositions 5 and 6).
Industrial applicability
The gelling agent of the present invention can be dissolved at a low temperature of 100 ° C. or lower when preparing an oily gel-like composition, and can prepare a stable gel-like composition that does not release even at high temperatures. It is. Moreover, the obtained gel composition is excellent in appearance such as transparency, and can be suitably used for uses such as fragrances.

Claims (7)

The following general formula (1):

(Wherein R ¹ and R ² each independently represents a hydrocarbon group having 1 to 26 carbon atoms, R ³ represents a hydrocarbon group having 7 to 10 carbon atoms, and n represents 1 or 2) An oily base gelling agent comprising at least one of N-acyl-L-acidic amino acid dialkylamides and at least one monovalent lower alcohol. R ¹ and R ² are each independently a linear or branched alkyl group having 3 to 5 carbon atoms, R ³ is a linear or branched alkyl group having 7 to 9 carbon atoms, The gelling agent according to claim 1, wherein n is 2. The gelling agent according to claim 1, wherein the N-acyl-L-acidic amino acid dialkylamide represented by the general formula (I) is N-2-ethylhexanoyl-L-glutamic acid dibutylamide. The gelling agent according to any one of claims 1 to 3, wherein the lower alcohol is 3-methoxy-3-methylbutanol or propylene glycol methyl ether. A gel composition containing the gelling agent according to any one of claims 1 to 4 and at least one of an oily base. The gel composition according to claim 5, wherein the oily base is a volatile terpene hydrocarbon. The gel composition according to claim 5 or 6, which is used as a fragrance.