JP4124524B2 - Method for producing N-substituted β-alanine or salt thereof and surfactant composition containing N-substituted β-alanine or salt thereof - Google Patents

Description

【００１７】
（式中、Ｒ¹ は置換基を含んでいても良い炭素数６〜２４の炭化水素基を示し、Ｍは水素原子、アルカリ金属イオン、アンモニウムイオン、炭素数２〜３のアルカノール基を有するモノ、ジもしくはトリアルカノールアンモニウムイオン、炭素数１〜５のアルキル基置換アンモニウムイオン又は塩基性アミノ酸基を示し、ＸはＣＯＯＭで表されるカルボン酸（塩）基、ＣＯＯＲ² で表されるエステル基又はシアノ基を示し、Ｒ² は炭素数１〜８、好ましくは１〜４の炭化水素基を示す）
【００１８】
本発明の製造方法で使用する脂肪族第一アミンは下記の一般式（II）で表される。
【００１９】
Ｒ¹ＮＨ₂ （II）
（式中、Ｒ¹ は置換基を含んでいても良い炭素数６〜２４の炭化水素基を示す）
【００２０】
上記の一般式（II）中のＲ¹ において、炭化水素基としては、直鎖でも分岐鎖でもよく、飽和でも不飽和でもよく、ヒドロキシル基のような置換基を任意に含んでよい。炭素数は６〜２４であり、好ましくは１０〜２２である。これらの中でも、直鎖又は分岐鎖の炭素数６〜２４のアルキル基又はアルケニル基が好ましく、直鎖又は分岐鎖の炭素数１０〜２２のアルキル基又はアルケニル基が特に好ましい。具体的には、Ｒ¹ としては、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、ベヘン酸、エルカ酸、椰子脂肪酸、牛脂脂肪酸に由来する炭化水素基等が挙げられる。この脂肪族第一アミンは対応する脂肪酸又はアルコールを原料にして製造される。
【００２１】
本発明の製造方法においては、最初に、上記脂肪族第一アミンを水素反応処理する。脂肪族第一アミンの水素反応処理は水素化触媒存在下に水素と反応させるか、あるいは水素化化合物を用いる方法によって行うことができる。
【００２２】
水素化触媒としては公知の水素化反応触媒であり、例えば、ニッケル系触媒、銅系触媒、貴金属系触媒等が挙げられる。特に、操作性、経済性等の面から担体に担持されたニッケル系触媒、例えば、ニッケル−珪藻土触媒、ニッケル−アルミナ触媒、ニッケル−シリカアルミナ触媒等が好ましい。触媒使用量は脂肪族第一アミン１００重量部に対して０．０５〜３．０重量部が適当であり、好ましくは０．１〜１．０重量部である。また、触媒は対応する脂肪酸又はアルコールを原料にして１級アミン化反応を行った後、使用した触媒をそのまま使用して、連続して水素反応処理を行うこともできる。反応温度は１００〜１８０℃、水素圧力は１〜２０ｋｇ／ｃｍ²（ゲージ圧） が好ましい。反応時間は０．１〜４時間が好ましい。
【００２３】
また、水素化化合物としては水素化ホウ素ナトリウム、水素化ホウ素リチウム等が挙げられ、特に水素化ホウ素ナトリウムが好ましい。使用量は脂肪族第一アミン１００重量部に対して０．０１〜５．０重量部が適当であり、好ましくは０．１〜３．０重量部である。反応温度は５０〜１５０℃が好ましい。反応時間は０．１〜４時間が好ましい。
【００２４】
次に、上記水素反応処理を行った脂肪族第一アミンをアクリル酸誘導体と反応させ、上記一般式(III) で表される付加反応生成物とする。アクリル酸誘導体は上記の式ＣＨ₂＝ＣＨＸ で表され、アクリル酸もしくはその塩、アクリル酸エステル又はアクリロニトリルである。
【００２５】
この付加反応は通常２０〜１００℃、望ましくは４０〜９０℃の温度で、アクリル酸誘導体を脂肪族第一アミンに対してモル比１〜２で反応させる。温度が２０℃より低いと反応が長時間かかり、１００℃より高いとＮ置換βアラニンの臭い及び色相が悪くなる。アクリル酸誘導体の脂肪族第一アミンに対するモル比は、多くなると未反応のアクリル酸誘導体が多く残り、しかも２モル付加体が多く副生するので好ましくない。また、モル比が少ないと未反応の脂肪族第一アミンが多くなり好ましくない。反応時間はアクリル酸誘導体を０．１〜２時間かけて滴下し、１〜１２時間熟成することが好ましい。
【００２６】
さらに、反応を促進させるためにメチルアルコール、エチルアルコール、プロピルアルコール、イソプロピルアルコール、ブチルアルコール等の低級アルコール又は水を添加してもよい。この低級アルコール又は水は付加反応物から必要により減圧下に留去してもよく、また残してもよい。低級アルコール又は水の使用量は付加生成物１００重量部に対して１〜１００重量部が好ましい。
【００２７】
アクリル酸誘導体としてアクリル酸エステル又はアクリロニトリルを使用した場合は、さらに、生成したＮ置換アミノプロピオン酸エステル又はＮ置換アミノプロピオニトリルをアルカリや酸で加水分解することによって、一般式（Ｉ）で表されるＮ置換βアラニンが得られる。
【００２８】
加水分解温度は通常５０〜１００℃、好ましくは６０〜９０℃である。加水分解の時間としては、アルカリや酸を０．５〜２時間かけて滴下し、１〜６時間熟成することが好ましい。加水分解後、必要に応じて生成物のｐＨを酸で６〜１２に調整してもよい。使用する酸は一般的に使用される無機酸又は有機酸であり、塩酸、硫酸、安息香酸、パラトルエンスルホン酸等が挙げられる。温度は２０〜９０℃で行うのが好ましい。加水分解後、ｐＨ調整する場合は、使用する無機酸又は有機酸に対応して無機塩又は有機塩が生成するが、必要により電気透析などの脱塩方法によって除去してもよい。
【００２９】
このようにして得られる一般式（Ｉ）で表されるＮ置換βアラニンは、異臭の原因となる成分を含有せず、しかも保存しても着色がなく、当初の目的を達成した化合物であるため、種々の用途に供される界面活性剤として極めて好適である。
【００３０】
なかでも、身体用洗浄剤、台所用洗浄剤、硬表面用洗浄剤等、種々の洗浄剤としての利用は、Ｎ置換βアラニンの特性である高洗浄力、高マイルド性等の長所を積極的に活用できるので非常に好ましい。
【００３１】
洗浄剤として使用する場合、本発明の製造方法によって得られるＮ置換βアラニンは、単独であっても、他の界面活性剤と混合してもどちらでも好適に使用できる。混合する場合は、アルキル硫酸エステル塩、アルキルエトキシ硫酸エステル塩、α−スルホ脂肪酸エステル塩、アルキルベンゼンスルホン酸塩、石鹸、アルキルエーテルカルボン酸塩、アルキルスルホコハク酸塩、アルキルリン酸エステル塩、アルキルアラニネートやアルキルタウレート等のアミノ酸誘導体等に代表されるアニオン性界面活性剤や、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルエステル、脂肪酸アルカノールアミド、アルキルポリグルコシド、短鎖アルキルグルコシド長鎖脂肪酸エステル、アルキルメチルグルカミド、ショ糖脂肪酸エステル等に代表されるノニオン性界面活性剤や、アルキルアミンオキシド、アルキルカルボベタイン、アルキルアミドアルキルカルボベタイン、アルキルスルホベタイン、アルキルヒドロキシスルホベタイン、アルキルイミダゾリン又はその誘導体等に代表される両性及び双性界面活性剤等が好適である。これらの界面活性剤の中でも、特に高洗浄力、泡性能の点でアニオン性界面活性剤が好ましい。これら界面活性剤の配合割合はＮ置換βアラニン１００重量部に対して１０〜１０００重量部が好ましい。
【００３２】
また、洗浄剤として使用するに当たっては、一般の洗浄剤に通常用いられる界面活性剤以外の成分、即ち、低級アルコールやポリアルキレングリコール類等のアルコール系ハイドロトロープ剤や、トルエンスルホン酸、キシレンスルホン酸、キュメンスルホン酸、安息香酸、サリチル酸等のハイドロトロープ剤や抗菌剤として供される低分子芳香族化合物、クエン酸、リンゴ酸、ＥＤＴＡ等のキレート剤、色素、香料、粘度調整剤、無機化合物等の機能性物質等を好適に混合することができる。
【００３３】
【実施例】
次に実施例により本発明を詳細に説明するが、本発明の範囲はこれらによって限定されるものではない。尚、以下の例における「％」は「重量％」である。
【００３４】
実施例１
１リットルの誘導回転式オートクレーブに、ラウリルアミン３００ｇとニッケル−珪藻土触媒１．５ｇを仕込んだ後、水素をアミン液中に供給し、反応圧力を１０ｋｇ／ｃｍ²（ゲージ圧）まで加え、１５０℃の反応温度で１時間攪拌した。その後、６０℃まで冷却し、触媒を濾過により分離した。
【００３５】
次に、２リットル容−四つ口フラスコに、上記水素反応処理したラウリルアミン１８５ｇ（１．０モル）とエチルアルコール２０ｇを仕込んだ後、６０℃で加熱攪拌しながら、アクリル酸エチル１２０ｇ（１．２モル）を滴下漏斗より１時間かけて滴下した後、同温度で４時間熟成を行った。次に、未反応のアクリル酸エチルを６０℃で２０ｍｍＨｇの減圧下除去して、Ｎ−ラウリルアミノプロピオン酸エチルエステル８９．５％、Ｎ−ラウリルイミノジプロピオン酸エチルエステル１０．０％、未反応ラウリルアミン０．５％の付加反応生成物を得た。
【００３６】
この付加反応生成物に水６００ｇを加えて、攪拌しながら、７０℃へ昇温した。４０％ＮａＯＨ水溶液１２０ｇを同温度で１時間かけて滴下した後、３時間熟成を行った。反応終了後、塩酸によりｐＨ１０に調整し、Ｎラウリルβアラニンを得た。
【００３７】
実施例２
ニッケル−珪藻土触媒の添加量を０．０３ｇ、水素反応処理の反応時間を２時間とする以外は実施例１と同様の方法で、Ｎラウリルβアラニンを得た。
【００３８】
実施例３
１リットル容−四つ口フラスコに、水素化触媒としてニッケル−アルミナ触媒を用いる以外は実施例１と同様の方法で水素反応処理したラウリルアミン１８５ｇ（１．０モル）とエチルアルコール２０ｇを仕込んだ後、６０℃で加熱攪拌しながら、アクリロニトリル６４ｇ（１．２モル）を滴下漏斗より１時間かけて滴下した後、同温度で４時間熟成を行った。次に、未反応のアクリル酸エチルを６０℃で２０ｍｍＨｇの減圧下除去して、Ｎ−ラウリルアミノプロピオニトリル９８．９％、Ｎ−ラウリルイミノジプロピオニトリル０．７％、未反応ラウリルアミン０．４％の付加反応生成物を得た。
【００３９】
この付加反応生成物にエタノール３００ｇと水１００ｇを加えて、攪拌しながら、７０℃へ昇温した。４０％ＮａＯＨ水溶液１２０ｇを同温度で１時間かけて滴下した後、反応液に窒素を流通させ、副生するアンモニアを追い出しながら５時間熟成を行った。反応終了後、塩酸によりｐＨ１０に調整し、Ｎラウリルβアラニンを得た。
【００４０】
実施例４
１リットル容−四つ口フラスコに、実施例１の方法で水素反応処理したラウリルアミン１８５ｇ（１．０モル）とエチルアルコール１００ｇと水５００ｇとを仕込んだ後、６０℃で加熱攪拌しながら、アクリル酸８６ｇ（１．２モル）を滴下漏斗より１時間かけて滴下した後、同温度で７時間熟成を行い、Ｎラウリルβアラニンを得た。
【００４１】
実施例５
１リットルの誘導回転式オートクレーブに、ラウリルアミン３００ｇと水素化ホウ素ナトリウム３．０ｇを仕込んだ後、１２０℃の反応温度で１時間攪拌した。その後、窒素をオートクレーブ内に流通させ、６０℃まで冷却し、水素化ホウ素ナトリウムを濾過により分離した。
【００４２】
上記処理したラウリルアミンを原料として用いる以外は実施例１と同様の方法で付加反応、加水分解反応及びｐＨ調整を行い、Ｎラウリルβアラニンを得た。
【００４３】
実施例６
水素化ホウ素ナトリウムを０．０１５ｇ、水素反応処理の反応時間を２時間とする以外は実施例５と同様の方法で、Ｎラウリルβアラニンを得た。
【００４４】
実施例７
ラウリルアミンの代わりにヤシ脂肪酸由来のアミン（ヤシアミンと略する）を用いる以外は、実施例１の方法で水素反応処理、付加反応、加水分解反応及びｐＨ調整を行い、Ｎヤシβアラニンを得た。
【００４５】
実施例８
ラウリルアミンの代わりにステアリルアミンを用い、水素反応処理の反応温度を１８０℃、反応圧力を１５ｋｇ／ｃｍ² （ゲージ圧）、反応時間を０．５時間とする以外は実施例１と同様の方法で、Ｎステアリルβアラニンを得た。
【００４６】
比較例１
原料アミンとして水素反応処理を行わないラウリルアミンを用いる以外は、実施例１と同様に付加反応、加水分解反応及びｐＨ調整を行って、Ｎラウリルβアラニンを得た。
【００４７】
比較例２
原料アミンとして水素反応処理を行わないラウリルアミンを用いる以外は、実施例４と同様に付加反応、加水分解反応及びｐＨ調整を行って、Ｎラウリルβアラニンを得た。
【００４８】
評価実験
実施例１〜８及び比較例１〜２で製造したＮ置換βアラニンの臭気及び５０℃で１ヶ月保存後の色相を次の評価基準に従って評価した。結果を表１に示す。
【００４９】
（臭気評価）
官能検査を行い、以下の基準で臭気を評価した。
○：異臭がなく臭気がよい。
△：若干異臭があり臭気が悪い。
×：異臭が強く著しく臭気が悪い。
【００５０】
（色相評価）
視覚により、以下の基準で色相を評価した。
○：色相の変化がわずかである。
△：色相の変化があり着色が認められる。
×：色相の変化が著しく明らかに着色が認められる。
【００５１】
【表１】

【００５２】
表１から明らかなように、本発明の方法で製造したＮ置換βアラニン（実施例１〜８）は臭気及び５０℃、１ヶ月保存後の色相が良いのに対し、比較例（比較例１〜２）はいずれも臭気及び５０℃、１ヶ月保存後の色相が悪いという問題点を有している。
【００５３】
次に上記実施例及び比較例によって製造されたＮ置換βアラニンを洗浄剤として用いた例を示す。
【００５４】
実施例９〜１３及び比較例３〜４
表２に示す液体洗浄剤組成物を調製し、組成物の臭気、皮膚刺激性、洗浄力及び１カ月保存後の色相を評価した。その結果を表２に示す。臭気及び色相については上記と同様の方法で評価し、皮膚刺激性及び洗浄力の評価方法については下記に示す。尚、表２中の配合量はすべて重量％であり、組成物はｐＨを６．５に調製したものである。
【００５５】
（皮膚の刺激性評価）
界面活性剤組成物１％水溶液（３５℃）を用いてテスター１０名の手による浸漬試験により評価を行った。即ち、１分毎の浸漬−乾燥操作を１５回行い、２４時間後の手の皮膚荒れの程度を以下の基準で視覚判定した。
【００５６】
○：皮膚荒れが殆どない。
△：皮膚の角質表面の一部に乾燥落屑性や赤斑変化等の手荒れ症状らしき兆候が認められる。
×：乾燥落屑性や赤斑変化等の手荒れ症状が明確に認められる。
【００５７】
（洗浄力評価）
日本薬局方に規定された大豆油と牛脂各１０ｇを６０ｍｌのクロロホルムに溶解した後、オイルレッド０．１ｇを加えて良く混合し、汚垢溶液を調製する。この溶液にガラスプレートを浸して汚染し、２５℃の温度で３０分以上風乾してクロロホルムを除去し、汚染片を作成する（汚染量２０〜３０ｍｇ／枚）。この汚染片６枚を２５℃、７００ｍｌの０．１５％の洗浄剤液中で２０ｒｐｍの回転速度で３分間かき混ぜて洗浄した後、風乾して重量を測定し、洗浄後の油除去率を下記の数式（１）により算出して洗浄力とした。
【００５８】
洗浄力（％）＝｛１−（Ｗ₂−Ｗ₀）／（Ｗ₁−Ｗ₀）｝×１００ （１）
（上記数式（１）中、Ｗ₀ はガラスプレートの重量を、Ｗ₁ は汚染後のガラスプレートの重量を、Ｗ₂ は洗浄風乾後のガラスプレートの重量を示す）
【００５９】
【表２】

【００６０】
表２から明らかなように、調製した洗浄剤組成物はいずれも優れたマイルド性及び洗浄性能を示すが、本発明の洗浄剤組成物（実施例９〜１３）は臭気及び５０℃で１ヶ月保存後の色相が良いのに対し、比較品の洗浄剤組成物（比較例３〜４）はいずれも臭気及び５０℃で１ヶ月保存後の色相が悪いという問題点を有している。
【発明の効果】
本発明の製造方法によって得られるＮ置換βアラニン又はその塩は、有臭成分などの不純物を含まないため、高起泡力、高洗浄力、低皮膚刺激性等の優れた特性を有する界面活性剤であり、しかも、液体洗浄剤として製剤化した場合にも臭気が良好で保存した場合にも着色や異常な臭気の発生を起こさない優れた基材であり、特に、台所用洗浄剤、毛髪用洗浄剤、皮膚用洗浄剤として極めて好適である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing N-substituted β-alanine or a salt thereof and a surfactant composition containing N-substituted β-alanine or a salt thereof obtained by this production method.
[0002]
[Prior art]
Recently, amino surfactants have been used as mild surfactants. N-substituted β-alanine represented by the following general formula (I) or a salt thereof is classified as an amino acid-based amphoteric activator, and is disclosed in US Pat. No. 2,787,633, JP-A-6-116596, and JP-A-9-3485. In particular.
[0003]
R ¹ NHCH ₂ CH ₂ COOM (I)
(In the formula, R ¹ represents a hydrocarbon group having 6 to 24 carbon atoms which may contain a substituent, and M represents a monovalent compound having a hydrogen atom, an alkali metal ion, an ammonium ion or an alkanol group having 2 to 3 carbon atoms. , Di- or trialkanol ammonium ion, C1-C5 alkyl group-substituted ammonium ion or basic amino acid group)
[0004]
As described in US Pat. No. 2,787,633, N-substituted β-alanine allows Michael addition of acrylic acid, acrylic acid ester, acrylonitrile, etc. to an aliphatic primary amine and hydrolyzes the resulting addition product. It is known that it can be manufactured.
[0005]
JP-A-6-116596 discloses a detergent composition comprising a combination of an N-substituted β-alanine activator and a hydroxycarboxylic acid, and JP-A-9-3485 discloses an N-substituted β-alanine activator and an ether carboxyl. A detergent composition in combination with an acid activator is described.
[0006]
[Problems to be solved by the invention]
However, the N-substituted β-alanine-based activator produced by the conventional method has a problem that when used as a cleaning agent or a surfactant composition, it has a bad odor and gives color over time. In particular, when used as a kitchen cleaning agent, a hair cleaning agent, or a skin cleaning agent, an unpleasant odor and coloring become problems, and the value as a product is remarkably impaired.
[0007]
An object of this invention is to provide the manufacturing method of N substituted beta-alanine with favorable odor and hue.
[0008]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have found that a method of using an aliphatic primary amine by reacting with hydrogen achieves the object of the present invention, and completing the present invention. It came.
[0009]
That is, the present invention is a method for producing an N-substituted β-alanine represented by the following general formula (I) or a salt thereof, and in the reaction between an aliphatic primary amine and an acrylic acid derivative, the aliphatic primary amine As a method characterized by using an aliphatic primary amine treated with a hydrogen reaction.
[0010]
R ¹ NHCH ₂ CH ₂ COOM (I)
(In the formula, R ¹ represents a hydrocarbon group having 6 to 24 carbon atoms which may contain a substituent, and M represents a monovalent compound having a hydrogen atom, an alkali metal ion, an ammonium ion or an alkanol group having 2 to 3 carbon atoms. , Di- or trialkanol ammonium ion, C1-C5 alkyl group-substituted ammonium ion or basic amino acid group)
[0011]
In the method of the present invention, the hydrogen reaction treatment is preferably performed in the presence of a hydrogenation catalyst, or the hydrogen reaction treatment is preferably performed using sodium borohydride.
[0012]
The present invention also relates to a surfactant composition containing N-substituted β-alanine or a salt thereof produced by the above method.
[0013]
Moreover, this invention relates to the cleaning composition containing said surfactant composition. .
[0014]
Furthermore, this invention relates to the cleaning composition containing said surfactant and anionic surfactant.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
The production method of the present invention is specifically shown by the following formula.
[0016]
[Chemical 1]

[0017]
(In the formula, R ¹ represents a hydrocarbon group having 6 to 24 carbon atoms which may contain a substituent, and M represents a monovalent compound having a hydrogen atom, an alkali metal ion, an ammonium ion or an alkanol group having 2 to 3 carbon atoms. , A di- or trialkanol ammonium ion, an alkyl group-substituted ammonium ion having 1 to 5 carbon atoms, or a basic amino acid group, wherein X is a carboxylic acid (salt) group represented by COOM, an ester group represented by COOR ² , or A cyano group, and R ² represents a hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms)
[0018]
The aliphatic primary amine used in the production method of the present invention is represented by the following general formula (II).
[0019]
R ¹ NH ₂ (II)
(In the formula, R ¹ represents a hydrocarbon group having 6 to 24 carbon atoms which may contain a substituent)
[0020]
In R ¹ in the general formula (II), the hydrocarbon group may be linear or branched, may be saturated or unsaturated, and may optionally contain a substituent such as a hydroxyl group. Carbon number is 6-24, Preferably it is 10-22. Among these, a linear or branched alkyl group or alkenyl group having 6 to 24 carbon atoms is preferable, and a linear or branched alkyl group or alkenyl group having 10 to 22 carbon atoms is particularly preferable. Specific examples of R ¹ include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, erucic acid, coconut fatty acid, and a hydrocarbon group derived from beef tallow fatty acid. The aliphatic primary amine is produced from the corresponding fatty acid or alcohol.
[0021]
In the production method of the present invention, first, the aliphatic primary amine is subjected to a hydrogen reaction treatment. The hydrogenation treatment of the aliphatic primary amine can be carried out by reacting with hydrogen in the presence of a hydrogenation catalyst or by a method using a hydrogenated compound.
[0022]
The hydrogenation catalyst is a known hydrogenation reaction catalyst, and examples thereof include a nickel-based catalyst, a copper-based catalyst, and a noble metal-based catalyst. In particular, a nickel-based catalyst supported on a carrier, for example, a nickel-diatomaceous earth catalyst, a nickel-alumina catalyst, a nickel-silica alumina catalyst, or the like is preferable in terms of operability and economy. The amount of the catalyst used is suitably 0.05 to 3.0 parts by weight, preferably 0.1 to 1.0 parts by weight, based on 100 parts by weight of the aliphatic primary amine. In addition, the catalyst may be subjected to a primary amination reaction using the corresponding fatty acid or alcohol as a raw material, and then the hydrogenation treatment may be continuously performed using the catalyst used as it is. The reaction temperature is preferably 100 to 180 ° C., and the hydrogen pressure is preferably 1 to ²⁰ kg / cm ² (gauge pressure). The reaction time is preferably 0.1 to 4 hours.
[0023]
Examples of the hydride compound include sodium borohydride and lithium borohydride, and sodium borohydride is particularly preferable. The amount used is suitably 0.01 to 5.0 parts by weight, preferably 0.1 to 3.0 parts by weight, based on 100 parts by weight of the aliphatic primary amine. The reaction temperature is preferably 50 to 150 ° C. The reaction time is preferably 0.1 to 4 hours.
[0024]
Next, the aliphatic primary amine subjected to the hydrogen reaction treatment is reacted with an acrylic acid derivative to obtain an addition reaction product represented by the general formula (III). The acrylic acid derivative is represented by the above formula CH ₂ = CHX and is acrylic acid or a salt thereof, an acrylic ester or acrylonitrile.
[0025]
In this addition reaction, the acrylic acid derivative is reacted with the aliphatic primary amine in a molar ratio of 1 to 2 at a temperature of usually 20 to 100 ° C., preferably 40 to 90 ° C. When the temperature is lower than 20 ° C., the reaction takes a long time, and when it is higher than 100 ° C., the smell and hue of the N-substituted β-alanine are deteriorated. When the molar ratio of the acrylic acid derivative to the aliphatic primary amine is increased, a large amount of unreacted acrylic acid derivative remains and a large amount of 2-mol adduct is by-produced, which is not preferable. On the other hand, if the molar ratio is small, the amount of unreacted aliphatic primary amine increases, which is not preferable. As for the reaction time, it is preferable that the acrylic acid derivative is added dropwise over 0.1 to 2 hours and aged for 1 to 12 hours.
[0026]
Furthermore, in order to accelerate the reaction, lower alcohol such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol or water may be added. The lower alcohol or water may be distilled off from the addition reaction product under reduced pressure as necessary, or may be left. The amount of the lower alcohol or water used is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the addition product.
[0027]
When acrylic acid ester or acrylonitrile is used as the acrylic acid derivative, the resulting N-substituted aminopropionic acid ester or N-substituted aminopropionitrile is further hydrolyzed with an alkali or an acid, thereby being represented by the general formula (I). N-substituted β-alanine is obtained.
[0028]
The hydrolysis temperature is usually 50 to 100 ° C, preferably 60 to 90 ° C. As the hydrolysis time, it is preferable to drop an alkali or an acid over 0.5 to 2 hours and age for 1 to 6 hours. After the hydrolysis, the pH of the product may be adjusted to 6 to 12 with an acid as necessary. The acid to be used is a generally used inorganic acid or organic acid, and examples thereof include hydrochloric acid, sulfuric acid, benzoic acid, and paratoluenesulfonic acid. The temperature is preferably 20 to 90 ° C. When the pH is adjusted after hydrolysis, an inorganic salt or an organic salt is produced corresponding to the inorganic acid or organic acid to be used, but it may be removed by a desalting method such as electrodialysis if necessary.
[0029]
The N-substituted β-alanine represented by the general formula (I) thus obtained does not contain a component that causes off-flavors and is not colored even when stored, and is a compound that has achieved the original purpose. Therefore, it is extremely suitable as a surfactant used for various applications.
[0030]
In particular, the use of various cleaning agents such as body cleaners, kitchen cleaners, and hard surface cleaners positively emphasizes the advantages of N-substituted β-alanine such as high detergency and high mildness. It is very preferable because
[0031]
When used as a cleaning agent, the N-substituted β-alanine obtained by the production method of the present invention can be suitably used either alone or mixed with other surfactants. When mixing, alkyl sulfate ester salt, alkyl ethoxy sulfate ester salt, α-sulfo fatty acid ester salt, alkyl benzene sulfonate, soap, alkyl ether carboxylate, alkyl sulfosuccinate, alkyl phosphate ester salt, alkyl alaninate And anionic surfactants typified by amino acid derivatives such as alkyl taurates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, fatty acid alkanolamides, alkyl polyglucosides, short chain alkyl glucoside long chain fatty acid esters, alkyls Nonionic surfactants such as methyl glucamide and sucrose fatty acid esters, alkylamine oxides, alkylcarbobetaines, alkylamidoalkylcarbobetaines, alkylsulfobetas Emissions, alkyl hydroxy sulfobetaine, amphoteric and zwitterionic surfactants such as represented by alkyl imidazolines or its derivatives and the like. Among these surfactants, anionic surfactants are particularly preferable in terms of high detergency and foam performance. The blending ratio of these surfactants is preferably 10 to 1000 parts by weight with respect to 100 parts by weight of N-substituted β-alanine.
[0032]
In addition, when used as a cleaning agent, components other than surfactants usually used in general cleaning agents, that is, alcohol-based hydrotropes such as lower alcohols and polyalkylene glycols, toluenesulfonic acid, xylenesulfonic acid , Low molecular weight aromatic compounds used as hydrotropes and antibacterial agents such as cumene sulfonic acid, benzoic acid and salicylic acid, chelating agents such as citric acid, malic acid and EDTA, dyes, fragrances, viscosity modifiers, inorganic compounds, etc. These functional substances can be suitably mixed.
[0033]
【Example】
EXAMPLES Next, although an Example demonstrates this invention in detail, the scope of the present invention is not limited by these. In the following examples, “%” is “wt%”.
[0034]
Example 1
Into a 1 liter induction rotating autoclave, 300 g of laurylamine and 1.5 g of nickel-diatomaceous earth catalyst were charged, then hydrogen was supplied into the amine solution, the reaction pressure was increased to 10 kg / cm ² (gauge pressure), and 150 ° C. The mixture was stirred at the reaction temperature of 1 hour. Then, it cooled to 60 degreeC and isolate | separated the catalyst by filtration.
[0035]
Next, 185 g (1.0 mol) of laurylamine treated with the hydrogen reaction and 20 g of ethyl alcohol were charged into a 2 liter-four-necked flask, and then 120 g of ethyl acrylate (1 2 mol) was dropped from the dropping funnel over 1 hour, and then aging was performed at the same temperature for 4 hours. Next, unreacted ethyl acrylate was removed at 60 ° C. under reduced pressure of 20 mmHg, and N-laurylaminopropionic acid ethyl ester 89.5%, N-lauryliminodipropionic acid ethyl ester 10.0%, unreacted An addition reaction product of 0.5% laurylamine was obtained.
[0036]
600 g of water was added to this addition reaction product, and the temperature was raised to 70 ° C. while stirring. After 120 g of 40% NaOH aqueous solution was dropped at the same temperature over 1 hour, aging was performed for 3 hours. After completion of the reaction, the pH was adjusted to 10 with hydrochloric acid to obtain N lauryl β-alanine.
[0037]
Example 2
N lauryl β-alanine was obtained in the same manner as in Example 1 except that the amount of the nickel-diatomite catalyst added was 0.03 g and the reaction time of the hydrogen reaction treatment was 2 hours.
[0038]
Example 3
A 1-liter four-necked flask was charged with 185 g (1.0 mol) of laurylamine and 20 g of ethyl alcohol that had been subjected to a hydrogen reaction in the same manner as in Example 1 except that a nickel-alumina catalyst was used as the hydrogenation catalyst. Thereafter, 64 g (1.2 mol) of acrylonitrile was dropped from the dropping funnel over 1 hour while stirring at 60 ° C., followed by aging at the same temperature for 4 hours. Next, unreacted ethyl acrylate was removed at 60 ° C. under a reduced pressure of 20 mmHg, and N-laurylaminopropionitrile 98.9%, N-lauryliminodipropionitrile 0.7%, unreacted laurylamine 0 .4% addition reaction product was obtained.
[0039]
Ethanol 300g and water 100g were added to this addition reaction product, and it heated up to 70 degreeC, stirring. After 120 g of 40% NaOH aqueous solution was dropped at the same temperature over 1 hour, nitrogen was passed through the reaction solution, and aging was carried out for 5 hours while expelling ammonia as a by-product. After completion of the reaction, the pH was adjusted to 10 with hydrochloric acid to obtain N lauryl β-alanine.
[0040]
Example 4
Into a 1-liter four-necked flask was charged 185 g (1.0 mol) of laurylamine treated with hydrogen by the method of Example 1, 100 g of ethyl alcohol and 500 g of water, and then heated and stirred at 60 ° C., After 86 g (1.2 mol) of acrylic acid was added dropwise from the dropping funnel over 1 hour, the mixture was aged at the same temperature for 7 hours to obtain N lauryl β-alanine.
[0041]
Example 5
A 1 liter induction rotating autoclave was charged with 300 g of laurylamine and 3.0 g of sodium borohydride, and then stirred at a reaction temperature of 120 ° C. for 1 hour. Thereafter, nitrogen was passed through the autoclave, cooled to 60 ° C., and sodium borohydride was separated by filtration.
[0042]
An addition reaction, hydrolysis reaction and pH adjustment were carried out in the same manner as in Example 1 except that the treated laurylamine was used as a raw material to obtain N lauryl β-alanine.
[0043]
Example 6
N lauryl β-alanine was obtained in the same manner as in Example 5 except that 0.015 g of sodium borohydride was used and the reaction time of the hydrogen reaction treatment was 2 hours.
[0044]
Example 7
Except for using coconut fatty acid-derived amine (abbreviated as coconut amine) in place of laurylamine, hydrogen reaction treatment, addition reaction, hydrolysis reaction and pH adjustment were carried out by the method of Example 1 to obtain N coconut β-alanine. .
[0045]
Example 8
The same method as in Example 1 except that stearylamine is used instead of laurylamine, the reaction temperature of the hydrogen reaction treatment is 180 ° C., the reaction pressure is 15 kg / cm ² (gauge pressure), and the reaction time is 0.5 hours. N stearyl β-alanine was obtained.
[0046]
Comparative Example 1
N lauryl β-alanine was obtained by performing addition reaction, hydrolysis reaction and pH adjustment in the same manner as in Example 1 except that laurylamine not subjected to hydrogen reaction treatment was used as a raw material amine.
[0047]
Comparative Example 2
N lauryl β-alanine was obtained by carrying out addition reaction, hydrolysis reaction and pH adjustment in the same manner as in Example 4 except that laurylamine not subjected to hydrogen reaction treatment was used as a raw material amine.
[0048]
Evaluation Experiments The odor of the N-substituted β-alanine produced in Examples 1 to 8 and Comparative Examples 1 and 2 and the hue after storage at 50 ° C. for 1 month were evaluated according to the following evaluation criteria. The results are shown in Table 1.
[0049]
(Odor evaluation)
A sensory test was performed and the odor was evaluated according to the following criteria.
○: No odor and good odor.
Δ: Slightly off-flavor and bad odor
X: Strong odor and remarkably bad odor.
[0050]
(Hue evaluation)
The hue was visually evaluated according to the following criteria.
○: Slight change in hue.
(Triangle | delta): There exists a change of a hue and coloring is recognized.
X: The hue is remarkably changed and the coloring is clearly recognized.
[0051]
[Table 1]

[0052]
As is apparent from Table 1, the N-substituted β-alanine (Examples 1 to 8) produced by the method of the present invention has a good odor and hue after storage at 50 ° C. for 1 month, whereas the comparative example (Comparative Example 1). All of ˜2) have the problem of bad odor and hue after storage at 50 ° C. for 1 month.
[0053]
Next, an example in which N-substituted β-alanine produced by the above Examples and Comparative Examples is used as a cleaning agent will be shown.
[0054]
Examples 9-13 and Comparative Examples 3-4
The liquid detergent composition shown in Table 2 was prepared, and the odor, skin irritation, detergency and hue after storage for 1 month were evaluated. The results are shown in Table 2. The odor and hue are evaluated by the same method as described above, and the evaluation methods for skin irritation and cleaning power are shown below. In addition, all the compounding quantities in Table 2 are% by weight, and the compositions were prepared with a pH of 6.5.
[0055]
(Evaluation of skin irritation)
Evaluation was carried out by an immersion test of 10 testers using a surfactant composition 1% aqueous solution (35 ° C.). That is, the immersion-drying operation per minute was performed 15 times, and the degree of rough skin on the hands after 24 hours was visually determined according to the following criteria.
[0056]
○: There is almost no rough skin.
(Triangle | delta): The sign which seems to be rough hand symptoms, such as dry desquamation and a red spot change, is recognized in a part of keratinous surface of skin.
X: Rough hand symptoms such as dry desquamation and red spot change are clearly recognized.
[0057]
(Detergency evaluation)
After dissolving 10 g of soybean oil and beef tallow specified in Japanese Pharmacopoeia in 60 ml of chloroform, 0.1 g of oil red is added and mixed well to prepare a dirt solution. A glass plate is immersed in this solution to be contaminated, and air-dried at a temperature of 25 ° C. for 30 minutes or more to remove chloroform to produce a contaminated piece (contamination amount 20 to 30 mg / sheet). Six of these contaminated pieces were washed by stirring for 3 minutes at 25 ° C. in 700 ml of 0.15% detergent solution at a rotation speed of 20 rpm, then air-dried, weighed, and the oil removal rate after washing was as follows: The detergency was calculated by the following formula (1).
[0058]
Detergency (%) = {1− (W ₂ −W ₀ ) / (W ₁ −W ₀ )} × 100 (1)
(In the above formula (1), W ₀ represents the weight of the glass plate, W ₁ represents the weight of the glass plate after contamination, and W ₂ represents the weight of the glass plate after washing and air drying)
[0059]
[Table 2]

[0060]
As can be seen from Table 2, all of the prepared cleaning compositions exhibit excellent mildness and cleaning performance, but the cleaning compositions of the present invention (Examples 9 to 13) have an odor and a temperature of 1 month at 50 ° C. While the hue after storage is good, the comparative detergent compositions (Comparative Examples 3 to 4) all have the problem of bad odor and hue after storage at 50 ° C. for 1 month.
【The invention's effect】
The N-substituted β-alanine or salt thereof obtained by the production method of the present invention does not contain impurities such as odorous components, and thus has a surface activity having excellent properties such as high foaming power, high detergency, and low skin irritation. In addition, it is an excellent base material that does not cause coloring or abnormal odor generation even when formulated as a liquid cleaning agent or when it has a good odor and is stored, especially kitchen cleaning agents, hair It is extremely suitable as a cleaning agent for skin and a cleaning agent for skin.

Claims (6)

A method for producing an N-substituted β-alanine or a salt thereof represented by the following general formula (I), wherein a fat subjected to a hydrogen reaction treatment as an aliphatic primary amine in a reaction between an aliphatic primary amine and an acrylic acid derivative A method comprising using a primary amine.
R ¹ NHCH ₂ CH ₂ COOM (I)
(In the formula, R ¹ represents a hydrocarbon group having 6 to 24 carbon atoms which may contain a substituent, and M represents a monovalent compound having a hydrogen atom, an alkali metal ion, an ammonium ion or an alkanol group having 2 to 3 carbon atoms. , Di- or trialkanol ammonium ion, C1-C5 alkyl group-substituted ammonium ion or basic amino acid group) The method according to claim 1, wherein the hydrogen reaction treatment is performed in the presence of a hydrogenation catalyst. The method according to claim 1, wherein the hydrogen reaction treatment is performed using sodium borohydride. A surfactant composition containing N-substituted β-alanine or a salt thereof produced by the method according to claim 1. A cleaning composition comprising the surfactant composition according to claim 4. A cleaning composition comprising the surfactant according to claim 4 and an anionic surfactant.