JP4672164B2 - Production of quaternary ammonium salts - Google Patents
Production of quaternary ammonium salts Download PDFInfo
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- JP4672164B2 JP4672164B2 JP2001093069A JP2001093069A JP4672164B2 JP 4672164 B2 JP4672164 B2 JP 4672164B2 JP 2001093069 A JP2001093069 A JP 2001093069A JP 2001093069 A JP2001093069 A JP 2001093069A JP 4672164 B2 JP4672164 B2 JP 4672164B2
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- quaternary ammonium
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Description
【０００１】
【発明の属する技術分野】
本発明は柔軟基剤として有用な第４級アンモニウム塩の製法、及びその製法により得られた第４級アンモニウム塩並びにそれを含有する優れた柔軟性を有する柔軟剤組成物に関する。
【０００２】
【従来の技術及び発明が解決しようとする課題】
近年、繊維用柔軟剤として市販されている商品はほとんどがジ（長鎖アルキル）ジメチルアンモニウム クロライドに代表される1分子中に2つの長鎖アルキル基を有する第４級アンモニウム塩を含む組成物である。しかし、このような第４級アンモニウム塩は、処理後の残存物が河川等の自然界に放出された場合、殆どが生分解されずに蓄積されるという問題点がある。
【０００３】
この問題点の改良品としてN-メチル-N,N-ビス（長鎖アルカノイルオキシエチル）-N-（2-ヒドロキシエチル）アンモニウム メチルサルフェート等が上市されている。このものは、上記第４級アンモニウム塩に比べ、生分解性は改善されているものの柔軟性が充分満足できる基剤ではない。また、係る第４級アンモニウム塩は、対応する第３級アミンを４級化剤と反応させ製造されており、この４級化反応の時イソプロピルアルコールやエタノールなどのアルコール系溶媒を用いるのが一般的であった。このようなアルコール系溶媒は、引火点が低く火災の危険性があり、特有の匂いを有し、これらの基剤が配合された製品の匂いに悪影響を与え、布及び毛髪等の柔軟化有効成分として働かないので、その分余分なコストがかかるなどの問題点を有する。しかし、このような溶媒を用いない場合は、第４級アンモニウム塩の融点が高く、取り扱いが難しいという問題点を有する。
【０００４】
従って、本発明の課題は、柔軟基剤として優れ、生分解性が良好な第４級アンモニウム塩の効率的な製造法、並びに優れた柔軟性を有する柔軟剤組成物を提供することである。
【０００５】
【課題を解決するための手段】
本発明は、一般式（Ｉ）
【０００６】
【化２】
（式中、R1、R2及びR3は、同一又は異なって、炭素数１〜６のアルキル基、アルケニルもしくはヒドロキシアルキル基、あるいはR4を示し、R4はエーテル基、エステル基又はアミド基で分断されていても良い総炭素数８〜40の長鎖アルキル基又はアルケニル基を示し、R1、R2及びR3のうち少なくとも１つはR4である。）
で表される第３級アミン（以下第３級アミン（Ｉ）という）を４級化剤と反応させ、第４級アンモニウム塩を製造するに際し、反応溶媒として、ケトン化合物、炭化水素化合物、複素環式化合物及び一般式(II)で表される化合物から選ばれる少なくとも１種の非プロトン性溶媒を用いる第４級アンモニウム塩の製法、及びこの製法により得られる第４級アンモニウム塩、並びにこの第４級アンモニウム塩を含有する柔軟剤組成物を提供する。
【０００８】
R5O-(AO)n-R6 （II）
（式中、R5及びR6は、同一又は異なって、炭素数１〜30のアルキル基、アルケニル基又はアシル基を示し、Aは炭素数２〜４のアルキレン基、nは平均値で１〜40の数を示し、n個のAは同一でも異なっていても良い。）
【０００９】
【発明の実施の形態】
［非プロトン性溶媒］
本発明に用いられる非プロトン性溶媒は、ケトン化合物、炭化水素化合物、複素環式化合物及び一般式(II)で表される化合物から選ばれ、４級化反応時に液体であれば室温（２５℃）で液体であっても固体であってもよい。具体的にはアセトン、メチルエチルケトン等のケトン化合物、ペンタン、ヘキサン、ヘプタン、オクタン、ノナン、デカン等の炭化水素化合物、テトラヒドロフラン、ジオキサン等の複素環式化合物、一般式(II)で表される化合物が挙げられるが、水との混和性が良好で、得られる第４級アンモニウム塩の匂いが良好である点から、一般式（II）で表される化合物が好ましい。
【００１０】
一般式(II)において、アシル基は、牛脂脂肪酸、硬化牛脂脂肪酸、パームステアリン酸、硬化パームステアリン酸又はそれらから選ばれる２種以上の混合物のような炭素数8〜30、好ましくは12〜24の長鎖脂肪酸から誘導されるアシル基が好ましい。Aは、エチレン基又はプロピレン基が好ましく、エチレン基が更に好ましい。nは１〜30が好ましく、５〜30が更に好ましい。
【００１１】
一般式(II)で表される化合物としては、下記一般式(III)〜(VII)で表される化合物が挙げられ、水との混和性が良好で、得られる第４級アンモニウム塩の匂いが良好で、更に柔軟剤の分散剤としても兼用できる点から、一般式(III)又は(IV)で表される化合物が好ましく、一般式(III)で表される化合物が特に好ましい。
【００１２】
R7COO-(AO)n-R8 (III）
R7COO-(AO)n-COR9 (IV）
R10O-(AO)n-R11 (Ｖ）
R12COO-(AO)n-R8 (VI）
R12COO-(AO)n-COR13 (VII）
（式中、R7及びR9は、同一又は異なって、炭素数７〜29、好ましくは11〜23のアルキル基又はアルケニル基を示し、R8、R10及びR11は、同一又は異なって、炭素数１〜６、好ましくは１〜５のアルキル基又はアルケニル基を示し、R12及びR13は、同一又は異なって、炭素数１〜５、好ましくは１〜４のアルキル基又はアルケニル基を示し、A及びnは前記の意味を示す。）
［第３級アミン（Ｉ）］
第３級アミン（Ｉ）において、R1、R2及びR3のうち少なくとも１つはR4であるが、R4としては、それぞれ、式(VIII)又は（IX）で表される基が好ましい。
【００１３】
【化３】
（式中、R14及びR15は同一又は異なって、炭素数2〜6、好ましくは2〜3のアルキレン基を示し、R16COは炭素数8〜30、好ましくは12〜24の脂肪酸から水酸基を除いた残基を示す。）
また、R1、R2及びR3で示される炭素数１〜６アルキル基、アルケニル基もしくはヒドロキシアルキル基としては、炭素数1〜３のアルキル基又はヒドロキシアルキル基が好ましく、メチル基、エチル基、ヒドロキシエチル基が更に好ましい。
【００１５】
第３級アミン（Ｉ）としては、R1、R2及びR3が全てR4であるトリ長鎖アルキル第３級アミンを多く含有するほど、得られる第４級アンモニウム塩の柔軟性効果は大きく、第３級アミン（Ｉ）中のトリ長鎖アルキル第３級アミンの割合が20重量％以上、更に50重量％以上、特に70重量％以上のものが好ましい。トリ長鎖アルキル第３級アミンとしては以下に示すものが特に好ましい。
【００１６】
【化４】
（R16COは前記の意味を示し、ｍは２又は３を示す。）
これらのトリ長鎖アルキル第３級アミンは、例えば、トリエタノールアミン等のトリアルカノールアミンをトリエステル化する方法、N-アミノプロピル-N,N-ヒドロキシエチルアミンの様な分子内にアミノ基を持つアルカノールアミン類をトリアシル化する方法等により得られる。この時、トリエステル化、トリアシル化反応に用いる脂肪酸又はそのエステルとしては、牛脂脂肪酸、硬化牛脂脂肪酸、パームステアリン酸、硬化パームステアリン酸又はそれらから選ばれる２種以上の混合物のような炭素数8〜30、好ましくは12〜24の長鎖脂肪酸、及びその低級アルキルエステル、又は油脂等が挙げられる。
【００１８】
［４級化反応］
本発明において、４級化反応は、第３級アミン（Ｉ）に、非プロトン性溶媒を加え４級化剤で４級化することにより行う。非プロトン性溶媒は、第３級アミン（Ｉ）に対して、好ましくは５〜90重量％、更に好ましくは９〜70重量％用いる。４級化反応に用いる４級化剤としては、ジメチル硫酸、ジエチル硫酸、メチルクロライド等が挙げられる。４級化反応時の温度は30〜150℃が好ましく、50〜120℃が更に好ましい。
【００１９】
非プロトン性溶媒として、ヘキサン等の水との混和性が低い溶媒を用いる場合や、アセトンやテトラヒドロフラン等の匂いのある溶媒を用いる場合には、４級化後、溶媒を留去し、イソプロパノール等の低級アルコール溶液として、柔軟剤に用いることが好ましい。非プロトン性溶媒として一般式(II)で表される化合物を用いる場合には、溶媒を留去せず、そのまま柔軟剤に用いることができる。
【００２０】
本発明により得られる第４級アンモニウム塩（以下第４級アンモニウム塩（Ｉ）という）としては、第４級アンモニウム塩（Ｉ）中のトリ長鎖アルキル体の割合が20重量％以上、更に50重量％以上、特に70重量％以上のものが好ましい
［柔軟剤組成物］
本発明の柔軟剤組成物中の第４級アンモニウム塩（Ｉ）の含有量は、３〜50重量％が好ましく、４〜30重量％が更に好ましい。
【００２１】
本発明の柔軟剤組成物には、更に柔軟性能や保存安定性を向上させるために、非イオン界面活性剤（炭素数８〜24のアルコールのアルキレンオキサイド付加物等）、高級アルコール（炭素数８〜24）、高級脂肪酸（炭素数８〜24）、エタノール、イソプロパノール等の低級アルコール、グリコール、ポリオール、更にはそれらのエチレンオキサイド、プロピレンオキサイド付加物等を添加することができ、また無機塩、pH調整剤、ハイドロトロープ剤、香料、消泡剤、顔料等を必要に応じて添加することができる。
【００２２】
【実施例】
例中の％は、特記しない限り重量基準である。
【００２３】
実施例１
トリエタノールアミン149gと硬化牛脂脂肪酸821gを用いて、200℃、窒素雰囲気下で10時間エステル化反応を行い、N,N,N-トリ（硬化牛脂アルカノイルオキシエチル）アミンを得、ついでヘキサン458gを加え、ジメチル硫酸126gを用いて、70℃、10時間かけて４級化反応を行った。反応後、減圧で溶媒を留去した後、イソプロパノール184g を加えて、第４級アンモニウム塩のイソプロパノール溶液を得た。４級化率及びその組成を表１に示した。
【００２４】
尚、４級化率及び組成は、VARIAN製、MERCURY400を用いて1Ｈ−ＮＭＲ手法による内部標準法で測定した。
【００２５】
実施例２
N,N-ジ（ヒドロキシエチル）アミノプロピルアミン162gと硬化牛脂脂肪酸821gを用いて実施例１と同様の反応を行い、N,N-ジ（硬化牛脂アルカノイルオキシエチル）-N-硬化牛脂アルカノイルアミノプロピルアミンを得、ついでヘキサン465gを加えジメチル硫酸126gを用いて実施例１と同様に４級化反応を行い、溶媒留去後、イソプロパノール186gを加えて、第４級アンモニウム塩のイソプロパノール溶液を得た。４級化率及び組成を表１に示した。
【００２６】
実施例３
N,N-ジ（ヒドロキシエチル）-N-硬化牛脂アルカノイルアミノエチルアミン404gと硬化牛脂脂肪酸547gを用い、実施例１と同様にエステル化反応を行い、N,N-ジ（硬化牛脂アルカノイルオキシエチル）-N-硬化牛脂アルカノイルアミノエチルアミンを得、ついでヘキサン458gを加えジメチル硫酸126gを用いて実施例１と同様に４級化反応を行い、溶媒留去後、イソプロパノール184gを加えて、第４級アンモニウム塩のイソプロパノール溶液を得た。４級化率及び組成を表１に示した。
【００２７】
実施例４
N,N-ジ（ヒドロキシエチル）-N-硬化牛脂アルキルアミン299gと硬化牛脂脂肪酸547gを用い実施例１と同様にエステル化反応を行い、N,N-ジ（硬化牛脂アルカノイルオキシエチル）-N-硬化牛脂アルキルアミンを得、ついでヘキサン405gを加えジメチル硫酸126gを用いて実施例１と同様に４級化反応を行い、溶媒留去後、イソプロパノール165gを加えて、第４級アンモニウム塩のイソプロパノール溶液を得た。４級化率及び組成を表１に示した。
【００２８】
実施例５
４級化溶媒としてヘキサンの代わりにアセトン458gを用いる以外は実施例１と同様な操作を行い、第４級アンモニウム塩のイソプロパノール溶液を得た。４級化率及び組成を表１に示した。
【００２９】
実施例６
４級化溶媒としてヘキサンの代わりにテトラヒドロフラン458gを用いる以外は実施例１と同様な操作を行い、第４級アンモニウム塩のイソプロパノール溶液を得た。４級化率及び組成を表１に示した。
【００３０】
実施例７
トリエタノールアミン149gと硬化牛脂脂肪酸821gを用いて200℃、窒素雰囲気下で10時間エステル化反応を行い、N,N,N-トリ（硬化牛脂アルカノイルオキシエチル）アミンを得、ついで４級化溶媒として硬化牛脂脂肪酸メチルエステルのエチレンオキサイド12モル付加物417gを加え、ジメチル硫酸126gを用いて100℃、10時間かけて４級化反応を行い、第４級アンモニウム塩の硬化牛脂脂肪酸メチルエステルエチレンオキサイド12モル付加物溶液を得た。４級化率及び組成を表１に示した。
【００３１】
実施例８
４級化溶媒として硬化牛脂脂肪酸メチルエステルのエチレンオキサイド12モル付加物の代わりにエチレングリコールジメチルエーテル417gを用いる以外は実施例７と同様な操作を行い、第４級アンモニウム塩のエチレングリコールジメチルエーテル溶液を得た。４級化率及び組成を表１に示した。
【００３２】
実施例９
４級化溶媒としてエチレングリコールジメチルエーテルの代わりにエチレングリコールジアセテート417gを用いる以外は実施例８と同様な操作を行い、第４級アンモニウム塩のエチレングリコールジアセテート溶液を得た。４級化率及び組成を表１に示した。
【００３３】
実施例１０
N,N-ジ（ヒドロキシエチル）アミノプロピルアミン162gと硬化牛脂脂肪酸821gを用いて実施例１と同様の反応を行い、N,N-ジ（硬化牛脂アルカノイルオキシエチル）-N-硬化牛脂アルカノイルアミノプロピルアミンを得、ついで４級化溶媒として硬化牛脂脂肪酸メチルエステルのエチレンオキサイド12モル付加物422gを加え、実施例７と同様の４級化反応を行い、第４級アンモニウム塩の硬化牛脂脂肪酸メチルエステルエチレンオキサイド12モル付加物溶液を得た。４級化率及び組成を表１に示した。
【００３４】
実施例１１
N,N-ジ（ヒドロキシエチル）-N-硬化牛脂アルカノイルアミノエチルアミン404gと硬化牛脂脂肪酸547gを用いて実施例１と同様のエステル化反応を行い、N,N-ジ（硬化牛脂アルカノイルオキシエチル）-N-硬化牛脂アルカノイルアミノエチルアミンを得、ついで４級化溶媒として硬化牛脂脂肪酸メチルエステルのエチレンオキサイド12モル付加物416gを加え、実施例７と同様の４級化反応を行い、第４級アンモニウム塩の硬化牛脂脂肪酸メチルエステルエチレンオキサイド12モル付加物溶液を得た。４級化率及び組成を表１に示した。
【００３５】
実施例１２
トリエタノールアミン149gと硬化牛脂脂肪酸547gを用いて200℃、窒素雰囲気下で10時間エステル化反応を行い、N,N-ビス（硬化牛脂アルカノイルオキシエチル）-N-(2-ヒドロキシエチル)アミンを得、ついで４級化溶媒としてヘキサン330gを用いて実施例１と同様な操作を行い、第４級アンモニウム塩のイソプロパノール溶液を得た。４級化率及びその組成を表１に示した。
【００３６】
比較例１
４級化溶媒としてヘキサンの代わりにイソプロピルアルコール184gを用いる以外は実施例１と同様な操作を行い、第４級アンモニウム塩のイソプロパノール溶液を得た。４級化率及びその組成を表１に示した。
【００３７】
比較例２
４級化溶媒として硬化牛脂脂肪酸メチルエステルのエチレンオキサイド12モル付加物の代わりにステアリルアルコールエチレンオキサイド13モル付加物417gを用いる以外は実施例７と同様の操作を行い、第４級アンモニウム塩のステアリルアルコールエチレンオキサイド13モル付加物溶液を得た。４級化率及び組成を表１に示した。
【００３８】
比較例３
４級化溶媒としてヘキサンの代わりイソプロピルアルコール184gを用いる以外は実施例１２と同様な操作を行い、第４級アンモニウム塩のイソプロパノール溶液を得た。４級化率及びその組成を表１に示した。
【００３９】
【表１】
実施例１〜６、実施例８、９、１２及び比較例１〜３で得られた第４級アンモニウム塩の溶液を第4級アンモニウム塩の合計が5ｇとなるような量とり、ステアリルアルコールエチレンオキサイド13モル付加物2ｇと混合し、60℃に加熱後、溶解した状態で60℃の水に滴下し、柔軟剤組成物100ｇを調製した。また、実施例７、１０、１１で得られた第4級アンモニウム塩の溶液を、第4級アンモニウム塩含量の合計が5ｇとなるような量とり、60℃に加熱後、溶解した状態で60℃の水に滴下し、柔軟剤組成物100ｇを調製した。これらの柔軟剤組成物の柔軟性を下記方法で評価した。結果を表２に示す。
【００４１】
＜柔軟性の評価法＞
▲１▼ 柔軟仕上げ処理
市販の木綿タオル又はアクリルジャージ１kgを、15リットル洗濯機を用い、3.5°DH硬水にて市販洗剤アタック（花王株式会社製、登録商標）で5回繰り返し洗濯した後、上記柔軟剤組成物を25mL投入し、25℃、1分間攪拌下で処理した。
【００４２】
▲２▼ 柔軟性評価
上記柔軟仕上げ処理した布を温室で乾燥後、25℃、65％RH恒温、恒湿室にて24時間放置した。これらの布について柔軟性の評価を行った。評価は前記比較例３で調製した柔軟剤組成物で処理した布を対照にして、10人の熟練試験者が一対比較を行い、次の基準で評価し、10人の評価の平均値を小数点以下１桁で四捨五入して評価値とした。
【表２】
BACKGROUND OF THE INVENTION
The present invention relates to a process for producing a quaternary ammonium salt useful as a soft base, a quaternary ammonium salt obtained by the process, and a softener composition having excellent flexibility containing the quaternary ammonium salt.
[0002]
[Prior art and problems to be solved by the invention]
In recent years, most of the products marketed as fabric softeners are compositions containing a quaternary ammonium salt having two long-chain alkyl groups in one molecule represented by di (long-chain alkyl) dimethylammonium chloride. is there. However, when such a quaternary ammonium salt is released into the natural world such as a river after treatment, most of it is accumulated without being biodegraded.
[0003]
As an improved product of this problem, N-methyl-N, N-bis (long-chain alkanoyloxyethyl) -N- (2-hydroxyethyl) ammonium methyl sulfate has been put on the market. This is a base that is sufficiently satisfactory in flexibility, although the biodegradability is improved as compared with the quaternary ammonium salt. The quaternary ammonium salt is produced by reacting a corresponding tertiary amine with a quaternizing agent. In this quaternization reaction, an alcohol solvent such as isopropyl alcohol or ethanol is generally used. It was the target. Such alcohol-based solvents have a low flash point and a fire hazard, have a unique odor, adversely affect the odor of products containing these bases, and are effective in softening fabrics and hair Since it does not work as a component, there is a problem that an extra cost is required. However, when such a solvent is not used, there is a problem that the quaternary ammonium salt has a high melting point and is difficult to handle.
[0004]
Accordingly, an object of the present invention is to provide an efficient method for producing a quaternary ammonium salt which is excellent as a softening base and has good biodegradability, and a softening agent composition having excellent softness.
[0005]
[Means for Solving the Problems]
The present invention relates to general formula (I)
[0006]
[Chemical 2]
Wherein R 1 , R 2 and R 3 are the same or different and each represents an alkyl group, alkenyl or hydroxyalkyl group having 1 to 6 carbon atoms, or R 4 , and R 4 represents an ether group, an ester group or an amide A long-chain alkyl group or an alkenyl group having a total carbon number of 8 to 40 which may be interrupted by a group, at least one of R 1 , R 2 and R 3 is R 4 )
In the production of a quaternary ammonium salt by reacting a tertiary amine represented by the following formula (hereinafter referred to as tertiary amine (I)) with a quaternizing agent, a ketone compound, a hydrocarbon compound, a complex is used as a reaction solvent. A process for producing a quaternary ammonium salt using at least one aprotic solvent selected from a cyclic compound and a compound represented by formula (II), a quaternary ammonium salt obtained by this process, and A softener composition containing a quaternary ammonium salt is provided.
[0008]
R 5 O- (AO) nR 6 (II)
(In the formula, R 5 and R 6 are the same or different and each represents an alkyl group, alkenyl group or acyl group having 1 to 30 carbon atoms, A is an alkylene group having 2 to 4 carbon atoms, and n is 1 on average. Represents a number of ˜40, and n A's may be the same or different.)
[0009]
DETAILED DESCRIPTION OF THE INVENTION
[Aprotic solvent]
The aprotic solvent used in the present invention is selected from a ketone compound, a hydrocarbon compound, a heterocyclic compound and a compound represented by the general formula (II), and is room temperature (25 ° C.) if it is liquid during the quaternization reaction. ) May be liquid or solid. Specifically, ketone compounds such as acetone and methyl ethyl ketone, hydrocarbon compounds such as pentane, hexane, heptane, octane, nonane and decane, heterocyclic compounds such as tetrahydrofuran and dioxane, and compounds represented by the general formula (II) The compound represented by the general formula (II) is preferable from the viewpoint of good miscibility with water and good odor of the resulting quaternary ammonium salt.
[0010]
In the general formula (II), the acyl group has 8 to 30 carbon atoms, preferably 12 to 24, such as beef tallow fatty acid, hardened beef tallow fatty acid, palm stearic acid, hardened palm stearic acid or a mixture of two or more selected from them. An acyl group derived from a long-chain fatty acid is preferred. A is preferably an ethylene group or a propylene group, and more preferably an ethylene group. n is preferably from 1 to 30, and more preferably from 5 to 30.
[0011]
Examples of the compound represented by the general formula (II) include compounds represented by the following general formulas (III) to (VII), which have good miscibility with water and the odor of the resulting quaternary ammonium salt. Are preferable, and the compound represented by the general formula (III) or (IV) is preferable, and the compound represented by the general formula (III) is particularly preferable.
[0012]
R 7 COO- (AO) nR 8 (III)
R 7 COO- (AO) n-COR 9 (IV)
R 10 O- (AO) nR 11 (V)
R 12 COO- (AO) nR 8 (VI)
R 12 COO- (AO) n-COR 13 (VII)
(In the formula, R 7 and R 9 are the same or different and each represents an alkyl group or an alkenyl group having 7 to 29 carbon atoms, preferably 11 to 23, and R 8 , R 10 and R 11 are the same or different. Represents an alkyl group or alkenyl group having 1 to 6 carbon atoms, preferably 1 to 5 carbon atoms, and R 12 and R 13 are the same or different and each represents an alkyl group or alkenyl group having 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms. A and n have the above-mentioned meanings.)
[Tertiary amine (I)]
In the tertiary amine (I), at least one of R 1 , R 2 and R 3 is R 4 , and R 4 is a group represented by the formula (VIII) or (IX), respectively. preferable.
[0013]
[Chemical 3]
(In the formula, R 14 and R 15 are the same or different and each represents an alkylene group having 2 to 6 carbon atoms, preferably 2 to 3 carbon atoms, and R 16 CO is from a fatty acid having 8 to 30 carbon atoms, preferably 12 to 24 carbon atoms. Indicates a residue excluding a hydroxyl group.)
Further, R 1, R 2 and the number 6 alkyl group having a carbon represented by R 3, the alkenyl group or hydroxyalkyl group, preferably an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, a methyl group, an ethyl group Further, a hydroxyethyl group is more preferable.
[0015]
As the tertiary amine (I), the more the tri-long-chain alkyl tertiary amine in which R 1 , R 2 and R 3 are all R 4 , the more flexible the resulting quaternary ammonium salt is. The ratio of the tri-long chain alkyl tertiary amine in the tertiary amine (I) is preferably 20% by weight or more, more preferably 50% by weight or more, and particularly preferably 70% by weight or more. As the tri-long-chain alkyl tertiary amine, those shown below are particularly preferable.
[0016]
[Formula 4]
(R 16 CO represents the above meaning, and m represents 2 or 3.)
These tri-long alkyl tertiary amines have, for example, a method of triesterizing trialkanolamines such as triethanolamine, and an amino group in the molecule such as N-aminopropyl-N, N-hydroxyethylamine. It can be obtained by a method of triacylating alkanolamines. At this time, as the fatty acid or ester thereof used in the triesterification and triacylation reaction, the number of carbon atoms such as beef tallow fatty acid, hardened beef tallow fatty acid, palm stearic acid, hardened palm stearic acid, or a mixture of two or more selected from them. -30, preferably 12-24 long chain fatty acids, and their lower alkyl esters or oils.
[0018]
[Quaternization reaction]
In the present invention, the quaternization reaction is performed by adding an aprotic solvent to the tertiary amine (I) and quaternizing with a quaternizing agent. The aprotic solvent is preferably used in an amount of 5 to 90% by weight, more preferably 9 to 70% by weight, based on the tertiary amine (I). Examples of the quaternizing agent used in the quaternization reaction include dimethyl sulfate, diethyl sulfate, and methyl chloride. The temperature during the quaternization reaction is preferably 30 to 150 ° C, more preferably 50 to 120 ° C.
[0019]
When using a solvent with low miscibility with water such as hexane as an aprotic solvent, or when using a solvent with odor such as acetone or tetrahydrofuran, the solvent is distilled off after quaternization and isopropanol or the like is used. The lower alcohol solution is preferably used as a softening agent. When the compound represented by the general formula (II) is used as the aprotic solvent, it can be used as it is for the softening agent without distilling off the solvent.
[0020]
As the quaternary ammonium salt obtained by the present invention (hereinafter referred to as quaternary ammonium salt (I)), the proportion of tri-long-chain alkyl in the quaternary ammonium salt (I) is 20% by weight or more, and further 50 It is preferable to have a weight percent of 70% by weight or more [softener composition]
The content of the quaternary ammonium salt (I) in the softener composition of the present invention is preferably 3 to 50% by weight, more preferably 4 to 30% by weight.
[0021]
In the softener composition of the present invention, a nonionic surfactant (an alkylene oxide adduct of an alcohol having 8 to 24 carbon atoms), a higher alcohol (8 carbon atoms) is used in order to further improve softness performance and storage stability. To 24), higher fatty acids (8 to 24 carbon atoms), lower alcohols such as ethanol and isopropanol, glycols, polyols, and ethylene oxide and propylene oxide adducts thereof, inorganic salts, pH A regulator, a hydrotrope agent, a fragrance | flavor, an antifoamer, a pigment, etc. can be added as needed.
[0022]
【Example】
In the examples, “%” is based on weight unless otherwise specified.
[0023]
Example 1
Using 149g of triethanolamine and 821g of hardened beef tallow fatty acid, esterification reaction was carried out at 200 ° C in a nitrogen atmosphere for 10 hours to obtain N, N, N-tri (hardened beef tallow alkanoyloxyethyl) amine, followed by 458g of hexane. In addition, quaternization reaction was carried out using 126 g of dimethyl sulfuric acid at 70 ° C. for 10 hours. After the reaction, the solvent was distilled off under reduced pressure, and then 184 g of isopropanol was added to obtain an isopropanol solution of a quaternary ammonium salt. The quaternization rate and its composition are shown in Table 1.
[0024]
The quaternization rate and composition were measured by an internal standard method using a 1 H-NMR technique using MERCURY400 manufactured by VARIAN.
[0025]
Example 2
The same reaction as in Example 1 was performed using 162 g of N, N-di (hydroxyethyl) aminopropylamine and 821 g of hardened beef tallow fatty acid, and N, N-di (hardened beef tallow alkanoyloxyethyl) -N-hardened beef tallow alkanoylamino was used. Propylamine is obtained, 465 g of hexane is added, and quaternization reaction is carried out in the same manner as in Example 1 using 126 g of dimethyl sulfate. After the solvent is distilled off, 186 g of isopropanol is added to obtain an isopropanol solution of a quaternary ammonium salt. It was. The quaternization rate and composition are shown in Table 1.
[0026]
Example 3
Using 404 g of N, N-di (hydroxyethyl) -N-cured tallow alkanoylaminoethylamine and 547 g of cured beef tallow fatty acid, an esterification reaction was performed in the same manner as in Example 1 to produce N, N-di (cured tallow alkanoyloxyethyl). -N-cured tallow alkanoylaminoethylamine was obtained, then 458 g of hexane was added and quaternization reaction was carried out using 126 g of dimethylsulfuric acid in the same manner as in Example 1. After distilling off the solvent, 184 g of isopropanol was added and quaternary ammonium was added. An isopropanol solution of the salt was obtained. The quaternization rate and composition are shown in Table 1.
[0027]
Example 4
Using 299 g of N, N-di (hydroxyethyl) -N-cured beef tallow alkylamine and 547 g of cured beef tallow fatty acid, an esterification reaction was carried out in the same manner as in Example 1, and N, N-di (cured tallow alkanoyloxyethyl) -N -Hard beef tallow alkylamine is obtained, then 405 g of hexane is added and quaternization reaction is carried out in the same manner as in Example 1 using 126 g of dimethyl sulfuric acid. After distilling off the solvent, 165 g of isopropanol is added to obtain isopropanol of a quaternary ammonium salt. A solution was obtained. The quaternization rate and composition are shown in Table 1.
[0028]
Example 5
The same operation as in Example 1 was carried out except that 458 g of acetone was used in place of hexane as the quaternization solvent to obtain an isopropanol solution of a quaternary ammonium salt. The quaternization rate and composition are shown in Table 1.
[0029]
Example 6
The same operation as in Example 1 was carried out except that 458 g of tetrahydrofuran was used in place of hexane as a quaternization solvent to obtain an isopropanol solution of a quaternary ammonium salt. The quaternization rate and composition are shown in Table 1.
[0030]
Example 7
An esterification reaction was performed using 149 g of triethanolamine and 821 g of hardened beef tallow fatty acid at 200 ° C. in a nitrogen atmosphere for 10 hours to obtain N, N, N-tri (hardened beef tallow alkanoyloxyethyl) amine, and then a quaternized solvent. 417 g of 12 mol adduct of hydrogenated beef tallow fatty acid methyl ester is added and quaternized with 100 g of dimethyl sulfuric acid at 100 ° C. for 10 hours to form quaternary ammonium salt hardened tallow fatty acid methyl ester ethylene oxide. A 12 molar adduct solution was obtained. The quaternization rate and composition are shown in Table 1.
[0031]
Example 8
The same operation as in Example 7 was carried out except that 417 g of ethylene glycol dimethyl ether was used in place of the 12 mol adduct of cured beef tallow fatty acid methyl ester as the quaternized solvent to obtain an ethylene glycol dimethyl ether solution of a quaternary ammonium salt. It was. The quaternization rate and composition are shown in Table 1.
[0032]
Example 9
The same operation as in Example 8 was carried out except that 417 g of ethylene glycol diacetate was used in place of ethylene glycol dimethyl ether as a quaternizing solvent to obtain an ethylene glycol diacetate solution of a quaternary ammonium salt. The quaternization rate and composition are shown in Table 1.
[0033]
Example 10
The same reaction as in Example 1 was performed using 162 g of N, N-di (hydroxyethyl) aminopropylamine and 821 g of hardened beef tallow fatty acid, and N, N-di (hardened beef tallow alkanoyloxyethyl) -N-hardened beef tallow alkanoylamino was used. Propylamine was obtained, and then 422 g of a 12-mole ethylene oxide adduct of hardened beef tallow fatty acid methyl ester was added as a quaternized solvent, and the same quaternization reaction as in Example 7 was carried out. An ester ethylene oxide 12 molar adduct solution was obtained. The quaternization rate and composition are shown in Table 1.
[0034]
Example 11
N, N-di (hydroxyethyl) -N-cured beef tallow alkanoylaminoethylamine and 547 g of cured beef tallow fatty acid were subjected to the same esterification reaction as in Example 1 to produce N, N-di (cured tallow alkanoyloxyethyl). -N-cured beef tallow alkanoylaminoethylamine was obtained, and then 416 g of ethylene oxide 12 mol adduct of cured beef tallow fatty acid methyl ester was added as a quaternized solvent, followed by quaternization similar to Example 7 to produce quaternary ammonium. A salt-cured tallow fatty acid methyl ester ethylene oxide 12 molar adduct solution was obtained. The quaternization rate and composition are shown in Table 1.
[0035]
Example 12
Perform esterification reaction using 149 g of triethanolamine and 547 g of hardened beef tallow fatty acid at 200 ° C. in a nitrogen atmosphere for 10 hours to obtain N, N-bis (hardened beef tallow alkanoyloxyethyl) -N- (2-hydroxyethyl) amine. Then, the same operation as in Example 1 was performed using 330 g of hexane as a quaternization solvent to obtain an isopropanol solution of a quaternary ammonium salt. The quaternization rate and its composition are shown in Table 1.
[0036]
Comparative Example 1
The same operation as in Example 1 was carried out except that 184 g of isopropyl alcohol was used instead of hexane as the quaternization solvent to obtain an isopropanol solution of a quaternary ammonium salt. The quaternization rate and its composition are shown in Table 1.
[0037]
Comparative Example 2
The same procedure as in Example 7 was followed, except that 417 g of stearyl alcohol ethylene oxide 13 mol adduct was used instead of the ethylene oxide 12 mol adduct of hardened beef tallow fatty acid methyl ester as the quaternization solvent, and stearyl of the quaternary ammonium salt. An alcohol ethylene oxide 13 molar adduct solution was obtained. The quaternization rate and composition are shown in Table 1.
[0038]
Comparative Example 3
The same operation as in Example 12 was carried out except that 184 g of isopropyl alcohol was used instead of hexane as a quaternization solvent to obtain an isopropanol solution of a quaternary ammonium salt. The quaternization rate and its composition are shown in Table 1.
[0039]
[Table 1]
The quaternary ammonium salt solutions obtained in Examples 1 to 6, Examples 8, 9, and 12 and Comparative Examples 1 to 3 were taken so that the total amount of the quaternary ammonium salt was 5 g, and stearyl alcohol ethylene was used. It was mixed with 2 g of an oxide 13 mol adduct, heated to 60 ° C., and then dropped into water at 60 ° C. in a dissolved state to prepare 100 g of a softener composition. In addition, the quaternary ammonium salt solutions obtained in Examples 7, 10 and 11 were taken in an amount so that the total quaternary ammonium salt content was 5 g, heated to 60 ° C., and dissolved in the solution. It was dripped in water at 0 ° C. to prepare 100 g of a softener composition. The softness | flexibility of these softening agent compositions was evaluated by the following method. The results are shown in Table 2.
[0041]
<Flexibility evaluation method>
(1) Soft finish treatment After washing 1 kg of a commercially available cotton towel or acrylic jersey with a 15 liter washing machine in 3.5 ° DH hard water repeatedly with a commercial detergent attack (registered trademark, Kao Corporation) 5 times, 25 mL of the softening agent composition was charged and treated under stirring at 25 ° C. for 1 minute.
[0042]
{Circle around (2)} Flexibility Evaluation The fabric subjected to the above-mentioned soft finish was dried in a greenhouse and then left in a constant temperature and humidity room at 25 ° C. and 65% RH for 24 hours. These fabrics were evaluated for flexibility. The evaluation was made using the fabric treated with the softener composition prepared in Comparative Example 3 above, and 10 skilled testers made a paired comparison, evaluated according to the following criteria, and the average value of 10 evaluations was the decimal point. The value was rounded off to the next decimal place.
[Table 2]
Claims (3)
で表される第３級アミンを４級化剤と反応させ、第４級アンモニウム塩を製造するに際し、反応溶媒として、ケトン化合物、炭化水素化合物、複素環式化合物及び一般式(II)で表される化合物から選ばれる少なくとも１種の非プロトン性溶媒を用いる第４級アンモニウム塩の製法。
R5O-(AO)n-R6 （II）
（式中、R5及びR6は、同一又は異なって、炭素数１〜30のアルキル基、アルケニル基又はアシル基を示し、Aは炭素数２〜４のアルキレン基、nは平均値で１〜40の数を示し、n個のAは同一でも異なっていても良い。）Formula (I)
In the production of a quaternary ammonium salt by reacting a tertiary amine represented by the following formula with a quaternizing agent, the reaction solvent is represented by a ketone compound, a hydrocarbon compound, a heterocyclic compound, and a general formula (II). A method for producing a quaternary ammonium salt using at least one aprotic solvent selected from the following compounds:
R 5 O- (AO) nR 6 (II)
(In the formula, R 5 and R 6 are the same or different and each represents an alkyl group, alkenyl group or acyl group having 1 to 30 carbon atoms, A is an alkylene group having 2 to 4 carbon atoms, and n is 1 on average. Represents a number of ˜40, and n A's may be the same or different.)
R7COO-(AO)n-R8 （III）
（式中、R7は炭素数７〜29のアルキル基又はアルケニル基を示し、R8は炭素数１〜６のアルキル基又はアルケニル基を示し、A及びnは前記の意味を示す。）The process according to claim 2, wherein the compound represented by the general formula (II) is a compound represented by the general formula (III).
R 7 COO- (AO) nR 8 (III)
(In the formula, R 7 represents an alkyl group or alkenyl group having 7 to 29 carbon atoms, R 8 represents an alkyl group or alkenyl group having 1 to 6 carbon atoms, and A and n have the above-mentioned meanings.)
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001093069A JP4672164B2 (en) | 2001-03-28 | 2001-03-28 | Production of quaternary ammonium salts |
| ES07018604T ES2340078T3 (en) | 2001-03-08 | 2002-03-04 | PROCEDURE TO PREPARE QUATERNARY AMMONIUM SALTS. |
| EP07018604A EP1884560B1 (en) | 2001-03-08 | 2002-03-04 | Method for preparing quaternary ammonium salts |
| EP02004360A EP1239024B1 (en) | 2001-03-08 | 2002-03-04 | Softener composition |
| ES02004360T ES2294054T3 (en) | 2001-03-08 | 2002-03-04 | SOFTENING COMPOSITION. |
| DE60235331T DE60235331D1 (en) | 2001-03-08 | 2002-03-04 | Process for the preparation of quaternary ammonium salts |
| DE60223614T DE60223614T2 (en) | 2001-03-08 | 2002-03-04 | softener composition |
| US10/092,983 US6855682B2 (en) | 2001-03-08 | 2002-03-08 | Softener composition |
| MXPA02002549A MXPA02002549A (en) | 2001-03-08 | 2002-03-08 | Softener composition. |
| US10/967,176 US7115779B2 (en) | 2001-03-08 | 2004-10-19 | Softener composition |
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| JP4773188B2 (en) * | 2005-12-05 | 2011-09-14 | ライオン株式会社 | Novel ether type compound and liquid softener composition containing the compound |
| JP4970019B2 (en) * | 2006-12-19 | 2012-07-04 | ライオン株式会社 | Hair cosmetics |
| JP5394215B2 (en) * | 2008-12-11 | 2014-01-22 | 花王株式会社 | Softener composition |
| JP6482829B2 (en) * | 2014-11-18 | 2019-03-13 | 花王株式会社 | Method for producing cationic surfactant |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH04506804A (en) * | 1989-07-17 | 1992-11-26 | ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチェン | Production method of quaternary ammonium compound |
| WO1999064661A1 (en) * | 1998-06-11 | 1999-12-16 | Kao Corporation | Softener composition |
| JP2000212132A (en) * | 1999-01-18 | 2000-08-02 | Sumitomo Seika Chem Co Ltd | Production of quaternary tetraethylammonium chloride |
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| JP2625068B2 (en) * | 1992-10-06 | 1997-06-25 | 花王株式会社 | Novel ammonium salt, process for preparing the same, intermediate amidoamine, and hair treatment agent |
| JP2951805B2 (en) * | 1992-11-26 | 1999-09-20 | 花王株式会社 | Novel ammonium salt, process for producing the same, intermediate amino ester, and hair treatment agent |
| JP3476555B2 (en) * | 1994-08-26 | 2003-12-10 | 花王株式会社 | Method for producing quaternary ammonium salt |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH04506804A (en) * | 1989-07-17 | 1992-11-26 | ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチェン | Production method of quaternary ammonium compound |
| WO1999064661A1 (en) * | 1998-06-11 | 1999-12-16 | Kao Corporation | Softener composition |
| JP2000212132A (en) * | 1999-01-18 | 2000-08-02 | Sumitomo Seika Chem Co Ltd | Production of quaternary tetraethylammonium chloride |
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| JP2011088905A (en) * | 2010-12-01 | 2011-05-06 | Kao Corp | Method for producing quaternary ammonium salt |
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