JP4230004B2 - Quaternary ammonium salt and softener composition - Google Patents

Description

【０００７】
（式中、R¹及びR²は同一又は異なって炭素数１〜６のアルキル基又はヒドロキシアルキル基を示し、R³は炭素数２〜６のアルキレン基又はヒドロキシアルキレン基を示し、X はOH又はNH₂ を示す。）
で表される第３級アミノアルコール又は第３級アミノアルキルアミンと、(b) 一般式（II）
【０００８】
【化５】

【０００９】
（式中、R⁴及びR⁵は同一又は異なって炭素数１〜６のヒドロキシアルキル基又はアミノアルキル基を示す。）
で表される第２級アミノアルコール又は第２級アミノアルキルアミン、あるいはポリオールと、(c) 炭素数３〜10のポリカルボン酸と、(d) 炭素数８〜36の脂肪酸又はそのエステルとを反応させて得られるアミノ化合物を４級化剤で４級化してなる第４級アンモニウム塩、その製造方法並びにそれを含有した柔軟剤組成物である。
【００１０】
また、本発明は、一般式(III) 又は (IV) で表される第４級アンモニウム塩からなる界面活性剤である。
【００１１】
【化６】

【００１２】
（式中、R¹, R²及びR³は前記の意味を示す。R⁶は炭素数３〜10のポリカルボン酸からカルボキシル基を除いた残基、R⁷及びR⁸は同一又は異なって、炭素数１〜６のアルキレン基、R⁹は炭素数８〜36の脂肪酸からカルボキシル基を除いた残基、R¹⁰ は炭素数１〜３のアルキル基、A, B¹ 及びB²は同一又は異なって -O-CO- 又は -NH-CO-、Z はポリオールから水酸基を除いた残基、n はポリオールの水酸基の数より１少ない数、 Y^- は陰イオン基を示す。）
【００１３】
【発明の実施の形態】
本発明の一般式（Ｉ）で表される第３級アミノアルコール又は第３級アミノアルキルアミンにおいて、R¹及びR²は同一又は異なって炭素数１〜６のアルキル基又はヒドロキシアルキル基を示すが、好ましくは炭素数１〜２のアルキル基又はヒドロキシアルキル基であり、更に好ましくはメチル基である。R³は炭素数２〜６のアルキレン基又はヒドロキシアルキレン基を示すが、好ましくは炭素数２〜３のアルキレン基である。X はOH又はNH₂ を示す。
【００１４】
一般式（Ｉ）で表される第３級アミノアルコール又は第３級アミノアルキルアミンとしては、例えば、２−（ジメチルアミノ）エタノール、２−（ジメチルアミノ）プロパノール、メチルジエタノールアミン、トリエタノールアミン、３−（ジメチルアミノ）プロピルアミン、Ｎ−（２−ヒドロキシエチル）−Ｎ−メチルプロパンジアミン、Ｎ，Ｎ−ジ（２−ヒドロキシエチル）プロパンジアミン等が挙げられる。
【００１５】
一般式（II）で表される第２級アミノアルコール又は第２級アミノアルキルアミンにおいて、R⁴及びR⁵は同一又は異なって炭素数１〜６のヒドロキシアルキル基又はアミノアルキル基を示すが、好ましくは炭素数２〜３のヒドロキシアルキル基又はアミノアルキル基である。
【００１６】
一般式（II）で表される第２級アミノアルコール又は第２級アミノアルキルアミンとしては、例えば、ジエタノールアミン、アミノエチルエタノールアミン、アミノプロピルエタノールアミン等が挙げられる。
【００１７】
ポリオールとしては、分子内に３個以上のヒドロキシル基を含むものが好ましく、グリセリン、トリメチロールプロパン、ペンタエリスリトール、ソルビトール等が挙げられる。
【００１８】
炭素数３〜10のポリカルボン酸としては、コハク酸、マレイン酸、フタル酸、テレフタル酸、アジピン酸等が好ましい。本発明においてポリカルボン酸には、それから誘導されるものでアルコールやアミンとの反応性の誘導体、例えばその低級アルキルエステル、酸無水物、酸塩化物等も含まれる。
【００１９】
炭素数８〜36の脂肪酸又はそのエステルのアルキル基としては、直鎖でも分岐鎖でも、また飽和でも不飽和でも良い。好ましくは炭素数12〜22の直鎖又は分岐鎖の飽和又は不飽和脂肪酸であり、牛脂脂肪酸、硬化牛脂脂肪酸、パーム脂肪酸、硬化パーム脂肪酸、パームステアリン酸、硬化パームステアリン酸及びこれらのメチルエステルなどが好ましい。反応に際してはグリセリンエステル、すなわち油脂の状態で用いてもよい。
【００２０】
本発明において上記(a)〜(d) 成分の反応モル比は、特に限定されないが、(c)成分１モルに対し、(a) 成分を0.1〜10モル、特に 0.5〜２モル、(b) 成分を0.1〜10モル、特に 0.5〜２モル、および(d) 成分を(b) 成分１モルに対して 0.5〜３モル、特に１〜2.5 モル反応させるのが好ましい。
【００２１】
反応温度は 150〜250 ℃が好ましく、 170〜220 ℃が更に好ましい。反応圧力は常圧から減圧で行われ、好ましくは27〜2.7kPaである。反応中、窒素ガスやスチームなどの不活性ガスを反応液に流通させると更に好ましい。
(d) 成分として脂肪酸の低級アルキルエステルを用いる場合には、反応温度は 100〜200 ℃が好ましく、 120〜170 ℃が更に好ましい。また触媒としてナトリウムメチラート、水酸化ナトリウム、水酸化カリウムなどの塩基性物質が用いられる。
本発明において、上記(a) 〜(d) 成分は一度に混合してから反応させても良いし、順次反応させても良い。
【００２２】
得られたアミノ化合物は、有機溶媒に溶解し、アミノ化合物に対して0.8〜1.5当量、好ましくは 0.9〜1.2 当量の４級化剤を用いて４級化される。
用いられる有機溶媒は、低級アルコール、グリコール、ポリオール類が好ましく、エタノール、イソプロパノール、エチレングリコール、プロピレングリコール、グリセリン等が特に好ましい。４級化剤としては、メチルクロライド、ジメチル硫酸、ジエチル硫酸が好ましい。
４級化の反応温度は50〜120 ℃が好ましく、70〜100 ℃が更に好ましい。
【００２３】
４級化剤としてメチルクロライドを用いた場合、反応終了後、常圧又は減圧下で未反応のメチルクロライドを除去するのが好ましい。窒素などの不活性ガスを流通させると効果的である。
【００２４】
上記のような製造法により得られる本発明の第４級アンモニウム塩としては、上記一般式(III) 又は (IV) で表される化合物が挙げられる。
本発明で提供される第４級アンモニウム塩は界面活性剤、特に繊維用柔軟基剤として有用である。
【００２５】
本発明の柔軟剤組成物は、上記のようにして得られる第４級アンモニウム塩を必須成分として含有するが、更に柔軟性能を向上させるために高級アルコール、高級脂肪酸を、保存安定剤としてエタノール、イソプロパノールなどの低級アルコール、グリコール、ポリオール、又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、公知のカチオン界面活性剤、ノニオン界面活性剤、無機塩、ｐＨ調製剤、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。
本発明の柔軟剤組成物中の上記第４級アンモニウム塩の含有量は３〜50重量％が好ましい。
【００２６】
【実施例】
実施例１
攪拌機、脱水管、温度計、窒素吹き込み管をつけた４つ口フラスコにジエタノールアミン84.1ｇ、アジピン酸116.9 ｇ、２−（ジメチルアミノ）エタノール71.3ｇ、硬化牛脂脂肪酸436.8 ｇを仕込み、 180℃で７時間、反応水を系外に除きながら反応させた。ジエタノールアミン：アジピン酸：２−（ジメチルアミノ）エタノール：硬化牛脂脂肪酸の反応モル比は 1.0：1.0：1.0：2.0 である。アミノ化合物が652.5 ｇ得られた。このアミノ化合物はアミン価67.3、酸価 4.8、水酸基価 4.5、けん化価 275.2であり、反応の進行したことを確認した。
次に、上記アミノ化合物 308.7ｇ、イソプロパノール84.5ｇをオートクレーブに仕込み、メチルクロライド38.0ｇを反応させ、第４級アンモニウム塩を得た。アミン価は 0.1であり４級化が進行したことを確認した。
【００２７】
実施例２〜５
反応原料及びそれらのモル比を表１の様に変更した以外は実施例１と同様に反応させて、アミノ化合物及び第４級アンモニウム塩を得た。アミノ化合物及び第４級アンモニウム塩の分析値を表２に示す。
【００２８】
実施例６
実施例１と同様の４つ口フラスコにジエタノールアミン85.6ｇ、アジピン酸 119.0ｇを仕込み、 140℃で１時間反応させた。続いて、３−（ジメチルアミノ）プロピルアミン83.2ｇ、硬化牛脂脂肪酸 428.9ｇを仕込み、 180℃で７時間、反応水を系外に除きながら反応させた。ジエタノールアミン：アジピン酸：３−（ジメチルアミノ)プロピルアミン：硬化牛脂脂肪酸の反応モル比は1.0：1.0：1.0：1.9 である。アミノ化合物が 676.5ｇ得られた。このアミノ化合物はアミン価68.5、酸価 3.4、水酸基価12.9、けん化価 203.1であり、反応の進行したことを確認した。
次に、アミノ化合物 332.3ｇ、イソプロパノール89.3ｇをオートクレーブに仕込み、メチルクロライド33.4ｇを反応させ、第４級アンモニウム塩を得た。アミン価は 0.1であり４級化が進行したことを確認した。
【００２９】
実施例７〜10
反応原料及びそれらのモル比を表１の様に変更した以外は実施例６と同様に反応させて、アミノ化合物及び第４級アンモニウム塩を得た。アミノ化合物及び第４級アンモニウム塩の分析値を表２に示す。
【００３０】
【表１】

【００３１】
注）
略号はそれぞれ次の意味を示す。
【００３２】
DMAE：２−（ジメチルアミノ）エタノール
MDEA：メチルジエタノールアミン
TEA ：トリエタノールアミン
DMAPA：３−（ジメチルアミノ）プロピルアミン
HEMPDA：Ｎ−（２−ヒドロキシエチル）−Ｎ−メチルプロパンジアミン
DHEPDA：Ｎ，Ｎ−ジ（２−ヒドロキシエチル）プロパンジアミン
DEA ：ジエタノールアミン
AEEA：アミノエチルエタノールアミン
ADPA：アジピン酸
SA ：コハク酸
TPA ：テレフタル酸
HT ：硬化牛脂脂肪酸
T ：牛脂脂肪酸
HP ：硬化パーム脂肪酸
HPS ：硬化パームステアリン酸
DMS ：ジメチル硫酸
【００３３】
【表２】

【００３４】
実施例11
実施例１と同様の４つ口フラスコにグリセリン73.6ｇ、アジピン酸 116.9ｇ、２−（ジメチルアミノ）エタノール71.3ｇ、硬化牛脂脂肪酸 436.8ｇを仕込み、 180℃で７時間、反応水を系外に除きながら反応させた。グリセリン：アジピン酸：２−（ジメチルアミノ）エタノール：硬化牛脂脂肪酸の反応モル比は 1.0：1.0：1.0：2.0 である。アミノ化合物が 642.3ｇ得られた。このアミノ化合物はアミン価68.6、酸価 5.2、水酸基価 4.5、けん化価 275.2であり、反応の進行したことを確認した。
次に、アミノ化合物 310.5ｇ、イソプロパノール84.0ｇをオートクレーブに仕込み、メチルクロライド28.0ｇを反応させ、第４級アンモニウム塩を得た。アミン価は 0.1であり４級化が進行したことを確認した。
【００３５】
実施例12〜15
反応原料及びそれらのモル比を表３の様に変更した以外は実施例11と同様に反応させてアミノ化合物及び第４級アンモニウム塩を得た。アミノ化合物及び第４級アンモニウム塩の分析値を表４に示す。
【００３６】
実施例16
実施例１と同様の４つ口フラスコに３−（ジメチルアミノ）プロピルアミン81.7ｇ、アジピン酸 116.9ｇを仕込み、 140℃で１時間反応させた。続いて、グリセリン73.6ｇ、硬化牛脂脂肪酸 416.5ｇを仕込み、180 ℃で７時間、反応水を系外に除きながら反応させた。３−（ジメチルアミノ）プロピルアミン：アジピン酸：グリセリン：硬化牛脂脂肪酸の反応モル比は 1.0：1.0：1.0：1.9 である。アミノ化合物が654.1ｇ得られた。このアミノ化合物はアミン価70.7、酸価 3.5、水酸基価11.0、けん化価 207.3であり、反応が進行したことを確認した。
次に、アミノ化合物 345.3ｇ、イソプロパノール90.9ｇをオートクレーブに仕込み、メチルクロライド25.6ｇを反応させ、第４級アンモニウム塩を得た。アミン価は 0.1であり、４級化が進行したことを確認した。
【００３７】
実施例17〜20
反応原料及びそれらのモル比を表３の様に変更した以外は実施例16と同様に反応させて第４級アンモニウム塩を得た。アミノ化合物及び第４級アンモニウム塩の分析値を表４に示す。
【００３８】
【表３】

【００３９】
注）
略号のうち、DMAE, MDEA，TEA, DMAPA, HEMPDA, DHEPDA, ADPA, SA, TPA, HT, T, HP, HPS, DMSは前記の意味を示し、その他は次の意味を示す。
GLY ：グリセリン
TMP ：トリメチロールプロパン
PEL ：ペンタエリスリトール
SOL ：ソルビトール
【００４０】
【表４】

【００４１】
応用例
実施例１〜20で得られた第４級アンモニウム塩を用い、以下の方法で柔軟性の評価を行なった。結果を表５に示す。
【００４２】
＜柔軟性の評価方法＞
▲１▼ 実施例で製造した第４級アンモニウム塩、及び比較対照としてジ硬化牛脂アルキルジメチルアンモニウムクロライドを用い、それぞれ融解したものを、攪拌しながら水中に滴下し、固形分濃度が５重量％になるようにして、それぞれの分散液を調製した。
【００４３】
▲２▼ 処理方法
市販の木綿タオル２kgを、30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、上記第４級アンモニウム塩分散液を25ml投入し、25℃、１分間攪拌下で処理した。
【００４４】
▲３▼ 柔軟性評価方法
上記方法で処理した布を室温で風乾後、25℃、65％RHの恒温、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。評価はジ硬化牛脂アルキルジメチルアンモニウムクロライドで処理した布を対照にして一対比較を行った。評価は次の基準で表す。
【００４５】
３；対照よりかなり柔らかい
２；対照より柔らかい
１；対照よりやや柔らかい
０；対照と柔らかさが同等
【００４６】
【表５】

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel quaternary ammonium salt, a process for producing the same, a surfactant comprising the same, and a fabric softener composition containing the same.
[0002]
[Prior art and problems to be solved by the invention]
Currently, most of the products marketed as fabric softeners contain quaternary ammonium salts having two long-chain alkyl groups in one molecule, as typified by di (long-chain alkyl) dimethylammonium chloride. It is a composition.
However, when the quaternary ammonium salt is released to the natural world such as a river, most of the quaternary ammonium salt is accumulated without being biodegraded.
[0003]
N-methyl-N, N-bis (long-chain alkanoyloxyethyl) -N- (2-hydroxyethyl) ammonium methyl sulfate and N, N-dimethyl-N, N-bis are improved products for such problems. Although (alkanoyloxyethyl) ammonium chloride and the like are commercially available, the biodegradability is improved as compared with the quaternary ammonium salt, but it cannot be said that the base is sufficiently satisfactory in flexibility.
[0004]
Therefore, an object of the present invention is to provide a flexible base having excellent flexibility and good biodegradability.
[0005]
[Means for Solving the Problems]
The present invention relates to (a) the general formula (I)
[0006]
[Formula 4]

[0007]
(In the formula, R ¹ and R ² are the same or different and each represents an alkyl group or hydroxyalkyl group having 1 to 6 carbon atoms; R ³ represents an alkylene group or hydroxyalkylene group having 2 to 6 carbon atoms; Or NH _2. )
A tertiary amino alcohol or a tertiary aminoalkylamine represented by formula (b):
[0008]
[Chemical formula 5]

[0009]
(In the formula, R ⁴ and R ⁵ are the same or different and each represent a hydroxyalkyl group or aminoalkyl group having 1 to 6 carbon atoms.)
A secondary amino alcohol or a secondary aminoalkylamine or polyol represented by: (c) a polycarboxylic acid having 3 to 10 carbon atoms; and (d) a fatty acid having 8 to 36 carbon atoms or an ester thereof. A quaternary ammonium salt obtained by quaternizing an amino compound obtained by reaction with a quaternizing agent, a production method thereof, and a softener composition containing the same.
[0010]
The present invention also provides a surfactant comprising a quaternary ammonium salt represented by the general formula (III) or (IV).
[0011]
[Chemical 6]

[0012]
(Wherein R ¹ , R ² and R ³ are as defined above. R ⁶ is a residue obtained by removing a carboxyl group from a polycarboxylic acid having 3 to 10 carbon atoms, and R ⁷ and R ⁸ are the same or different. , An alkylene group having 1 to 6 carbon atoms, R ⁹ is a residue obtained by removing a carboxyl group from a fatty acid having 8 to 36 carbon atoms, R ¹⁰ is an alkyl group having 1 to 3 carbon atoms, and A, B ¹ and B ² are the same Or -O-CO- or -NH-CO-, where Z is a residue obtained by removing a hydroxyl group from a polyol, n is a number one less than the number of hydroxyl groups of the polyol, and Y ^- is an anionic group.)
[0013]
DETAILED DESCRIPTION OF THE INVENTION
In the tertiary amino alcohol or tertiary aminoalkylamine represented by the general formula (I) of the present invention, R ¹ and R ² are the same or different and each represents an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group. Is preferably an alkyl group having 1 to 2 carbon atoms or a hydroxyalkyl group, and more preferably a methyl group. R ³ represents an alkylene group having 2 to 6 carbon atoms or a hydroxyalkylene group, preferably an alkylene group having 2 to 3 carbon atoms. X represents OH or NH ₂ .
[0014]
Examples of the tertiary amino alcohol or tertiary aminoalkylamine represented by the general formula (I) include 2- (dimethylamino) ethanol, 2- (dimethylamino) propanol, methyldiethanolamine, triethanolamine, 3 -(Dimethylamino) propylamine, N- (2-hydroxyethyl) -N-methylpropanediamine, N, N-di (2-hydroxyethyl) propanediamine and the like.
[0015]
In the secondary amino alcohol or secondary aminoalkylamine represented by the general formula (II), R ⁴ and R ⁵ are the same or different and represent a hydroxyalkyl group or aminoalkyl group having 1 to 6 carbon atoms, Preferably it is a C2-C3 hydroxyalkyl group or an aminoalkyl group.
[0016]
Examples of the secondary amino alcohol or secondary aminoalkylamine represented by the general formula (II) include diethanolamine, aminoethylethanolamine, aminopropylethanolamine, and the like.
[0017]
As the polyol, those containing three or more hydroxyl groups in the molecule are preferable, and examples thereof include glycerin, trimethylolpropane, pentaerythritol, and sorbitol.
[0018]
As the polycarboxylic acid having 3 to 10 carbon atoms, succinic acid, maleic acid, phthalic acid, terephthalic acid, adipic acid and the like are preferable. In the present invention, the polycarboxylic acid includes derivatives derived therefrom and reactive with alcohols and amines, such as lower alkyl esters, acid anhydrides, acid chlorides and the like.
[0019]
The alkyl group of the fatty acid having 8 to 36 carbon atoms or its ester may be linear or branched, saturated or unsaturated. Preferably it is a C12-22 straight or branched chain saturated or unsaturated fatty acid, beef tallow fatty acid, hardened beef tallow fatty acid, palm fatty acid, hardened palm fatty acid, palm stearic acid, hardened palm stearic acid and their methyl esters, etc. Is preferred. You may use in the state of glycerol ester, ie, fats and oils, in the case of reaction.
[0020]
In the present invention, the reaction molar ratio of the above components (a) to (d) is not particularly limited, but 0.1 mol to 10 mol, particularly 0.5 to 2 mol, It is preferable to react 0.1 to 10 mol, particularly 0.5 to 2 mol of the component, and 0.5 to 3 mol, particularly 1 to 2.5 mol, of the component (d) with respect to 1 mol of the component (b).
[0021]
The reaction temperature is preferably 150 to 250 ° C, more preferably 170 to 220 ° C. The reaction pressure is from normal pressure to reduced pressure, and is preferably 27 to 2.7 kPa. More preferably, an inert gas such as nitrogen gas or steam is passed through the reaction solution during the reaction.
When a fatty acid lower alkyl ester is used as the component (d), the reaction temperature is preferably 100 to 200 ° C, more preferably 120 to 170 ° C. As the catalyst, a basic substance such as sodium methylate, sodium hydroxide or potassium hydroxide is used.
In the present invention, the above components (a) to (d) may be mixed and reacted at the same time, or may be reacted sequentially.
[0022]
The obtained amino compound is dissolved in an organic solvent and quaternized with a quaternizing agent in an amount of 0.8 to 1.5 equivalents, preferably 0.9 to 1.2 equivalents relative to the amino compound.
The organic solvent used is preferably a lower alcohol, glycol or polyol, and particularly preferably ethanol, isopropanol, ethylene glycol, propylene glycol or glycerin. As the quaternizing agent, methyl chloride, dimethyl sulfate, and diethyl sulfate are preferable.
The reaction temperature for quaternization is preferably 50 to 120 ° C, more preferably 70 to 100 ° C.
[0023]
When methyl chloride is used as the quaternizing agent, it is preferable to remove unreacted methyl chloride under normal pressure or reduced pressure after completion of the reaction. It is effective to distribute an inert gas such as nitrogen.
[0024]
Examples of the quaternary ammonium salt of the present invention obtained by the above production method include compounds represented by the above general formula (III) or (IV).
The quaternary ammonium salt provided in the present invention is useful as a surfactant, particularly as a flexible base for fibers.
[0025]
The softening agent composition of the present invention contains the quaternary ammonium salt obtained as described above as an essential component, but in order to further improve softening performance, higher alcohol, higher fatty acid, ethanol as a storage stabilizer, Lower alcohols such as isopropanol, glycols, polyols, or their ethylene oxide, propylene oxide adducts, known cationic surfactants, nonionic surfactants, inorganic salts, pH adjusters, hydrotropes, fragrances, antifoaming agents, A pigment etc. can be added as needed.
The content of the quaternary ammonium salt in the softener composition of the present invention is preferably 3 to 50% by weight.
[0026]
【Example】
Example 1
A four-necked flask equipped with a stirrer, dehydration tube, thermometer, and nitrogen blowing tube was charged with 84.1 g of diethanolamine, 116.9 g of adipic acid, 71.3 g of 2- (dimethylamino) ethanol, and 436.8 g of hardened tallow fatty acid, and 7 at 180 ° C. The reaction was carried out while removing the reaction water from the system for a period of time. The reaction molar ratio of diethanolamine: adipic acid: 2- (dimethylamino) ethanol: cured tallow fatty acid is 1.0: 1.0: 1.0: 2.0. 652.5 g of amino compound was obtained. This amino compound had an amine value of 67.3, an acid value of 4.8, a hydroxyl value of 4.5, and a saponification value of 275.2, and it was confirmed that the reaction had proceeded.
Next, 308.7 g of the above amino compound and 84.5 g of isopropanol were charged into an autoclave and reacted with 38.0 g of methyl chloride to obtain a quaternary ammonium salt. The amine value was 0.1 and it was confirmed that quaternization proceeded.
[0027]
Examples 2-5
The reaction was carried out in the same manner as in Example 1 except that the reaction raw materials and their molar ratios were changed as shown in Table 1, to obtain an amino compound and a quaternary ammonium salt. The analytical values of the amino compound and the quaternary ammonium salt are shown in Table 2.
[0028]
Example 6
The same 4-necked flask as in Example 1 was charged with 85.6 g of diethanolamine and 119.0 g of adipic acid and reacted at 140 ° C. for 1 hour. Subsequently, 83.2 g of 3- (dimethylamino) propylamine and 428.9 g of cured beef tallow fatty acid were charged and reacted at 180 ° C. for 7 hours while removing the reaction water from the system. The reaction molar ratio of diethanolamine: adipic acid: 3- (dimethylamino) propylamine: cured tallow fatty acid is 1.0: 1.0: 1.0: 1.9. 676.5 g of amino compound was obtained. This amino compound had an amine value of 68.5, an acid value of 3.4, a hydroxyl value of 12.9, and a saponification value of 203.1, and it was confirmed that the reaction had proceeded.
Next, 332.3 g of an amino compound and 89.3 g of isopropanol were charged into an autoclave and reacted with 33.4 g of methyl chloride to obtain a quaternary ammonium salt. The amine value was 0.1 and it was confirmed that quaternization proceeded.
[0029]
Examples 7-10
The reaction was conducted in the same manner as in Example 6 except that the reaction raw materials and their molar ratios were changed as shown in Table 1, to obtain an amino compound and a quaternary ammonium salt. The analytical values of the amino compound and the quaternary ammonium salt are shown in Table 2.
[0030]
[Table 1]

[0031]
note)
Each abbreviation has the following meaning.
[0032]
DMAE: 2- (dimethylamino) ethanol
MDEA: Methyldiethanolamine
TEA: Triethanolamine
DMAPA: 3- (dimethylamino) propylamine
HEMPDA: N- (2-hydroxyethyl) -N-methylpropanediamine
DHEPDA: N, N-di (2-hydroxyethyl) propanediamine
DEA: Diethanolamine
AEEA: Aminoethylethanolamine
ADPA: Adipic acid
SA: Succinic acid
TPA: terephthalic acid
HT: Hardened beef tallow fatty acid
T: Tallow fatty acid
HP: Hardened palm fatty acid
HPS: Hardened palm stearic acid
DMS: Dimethyl sulfate [0033]
[Table 2]

[0034]
Example 11
The same four-necked flask as in Example 1 was charged with 73.6 g of glycerin, 116.9 g of adipic acid, 71.3 g of 2- (dimethylamino) ethanol, and 436.8 g of hardened tallow fatty acid, and the reaction water was removed from the system at 180 ° C. for 7 hours. It was made to react, removing. The reaction molar ratio of glycerin: adipic acid: 2- (dimethylamino) ethanol: cured tallow fatty acid is 1.0: 1.0: 1.0: 2.0. 642.3 g of amino compound was obtained. This amino compound had an amine value of 68.6, an acid value of 5.2, a hydroxyl value of 4.5, and a saponification value of 275.2, and it was confirmed that the reaction had proceeded.
Next, 310.5 g of an amino compound and 84.0 g of isopropanol were charged into an autoclave and reacted with 28.0 g of methyl chloride to obtain a quaternary ammonium salt. The amine value was 0.1 and it was confirmed that quaternization proceeded.
[0035]
Examples 12-15
An amino compound and a quaternary ammonium salt were obtained by reacting in the same manner as in Example 11 except that the reaction raw materials and their molar ratios were changed as shown in Table 3. The analytical values of the amino compound and the quaternary ammonium salt are shown in Table 4.
[0036]
Example 16
A 4-necked flask similar to that in Example 1 was charged with 81.7 g of 3- (dimethylamino) propylamine and 116.9 g of adipic acid, and reacted at 140 ° C. for 1 hour. Subsequently, 73.6 g of glycerin and 416.5 g of hardened beef tallow fatty acid were added and reacted at 180 ° C. for 7 hours while removing the reaction water from the system. The reaction molar ratio of 3- (dimethylamino) propylamine: adipic acid: glycerin: cured tallow fatty acid is 1.0: 1.0: 1.0: 1.9. 654.1g of amino compounds were obtained. This amino compound had an amine value of 70.7, an acid value of 3.5, a hydroxyl value of 11.0, and a saponification value of 207.3, confirming that the reaction had proceeded.
Next, 345.3 g of an amino compound and 90.9 g of isopropanol were charged into an autoclave and reacted with 25.6 g of methyl chloride to obtain a quaternary ammonium salt. The amine value was 0.1, and it was confirmed that quaternization had progressed.
[0037]
Examples 17-20
A quaternary ammonium salt was obtained by reacting in the same manner as in Example 16 except that the reaction raw materials and their molar ratios were changed as shown in Table 3. The analytical values of the amino compound and the quaternary ammonium salt are shown in Table 4.
[0038]
[Table 3]

[0039]
note)
Among the abbreviations, DMAE, MDEA, TEA, DMAPA, HEMPDA, DHEPDA, ADPA, SA, TPA, HT, T, HP, HPS, and DMS have the above-mentioned meanings, and the others have the following meanings.
GLY: Glycerin
TMP: Trimethylolpropane
PEL: Pentaerythritol
SOL: Sorbitol [0040]
[Table 4]

[0041]
Application Example Using the quaternary ammonium salts obtained in Examples 1 to 20, flexibility was evaluated by the following method. The results are shown in Table 5.
[0042]
<Flexibility evaluation method>
(1) Using the quaternary ammonium salt produced in the examples and di-cured tallow alkyldimethylammonium chloride as a comparative control, each melted solution was dropped into water with stirring to a solid content concentration of 5% by weight. Thus, each dispersion was prepared.
[0043]
(2) Treatment method After washing 2 kg of a commercially available cotton towel 5 times with a commercial detergent attack (registered trademark, Kao Co., Ltd.) in 3.5 ° DH hard water using a 30 liter washing machine, the above quaternary ammonium 25 ml of the salt dispersion was added and treated with stirring at 25 ° C. for 1 minute.
[0044]
(3) Flexibility evaluation method The cloth treated by the above method was air-dried at room temperature, and then allowed to stand 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 as a pair comparison using a cloth treated with di-cured tallow alkyldimethylammonium chloride as a control. Evaluation is expressed by the following criteria.
[0045]
3; considerably softer than the control 2; softer than the control 1; slightly softer than the control 0; soft equal to the control
[Table 5]

Claims (4)

(a) General formula (I)

(In the formula, R ¹ and R ² are the same or different and each represents an alkyl group or hydroxyalkyl group having 1 to 2 carbon atoms, R ³ represents an alkylene group or hydroxyalkylene group having 2 to ³ carbon atoms, and X is OH. Or NH _2. )
A tertiary amino alcohol or a tertiary aminoalkylamine represented by formula (b):

(In the formula, R ⁴ and R ⁵ are the same or different and represent a C2-C3 hydroxyalkyl group or aminoalkyl group.)
Or a polyol selected from glycerin, trimethylolpropane, pentaerythritol and sorbitol, and (c) succinic acid, maleic acid, phthalic acid, terephthalic acid and adipine A general formula (III) or (IV) obtained by quaternizing an amino compound obtained by reacting a dicarboxylic acid selected from acids with a fatty acid having 8 to 36 carbon atoms or an ester thereof with a quaternizing agent. A quaternary ammonium salt represented by the general formula (III) wherein R ⁶ is a residue obtained by removing a carboxyl group from terephthalic acid, A, B ¹ And B ² is —O—CO— , and in general formula (IV), R ¹ , R ² and R ¹⁰ are methyl groups, R ³ is an ethylene group, and R ⁶ is a carboxyl from succinic acid. A quaternary ammonium salt in which A is —O—CO—, Z is a residue obtained by removing a hydroxyl group from glycerin, and R ⁹ is a residue obtained by removing a carboxyl group from oleic acid).

(Wherein R ¹ , R ² and R ³ have the above-mentioned meanings. R ⁶ is a residue obtained by removing a carboxyl group from a dicarboxylic acid selected from succinic acid, maleic acid, phthalic acid, terephthalic acid and adipic acid, R ⁷ and R ⁸ are the same or different, an alkylene group having 2 to 3 carbon atoms, R ⁹ is a residue obtained by removing a carboxyl group from a fatty acid having 8 to 36 carbon atoms, and R ¹⁰ is an alkyl group having 1 to 3 carbon atoms. A, B ¹ and B ² are the same or different and are —O—CO— or —NH—CO—, Z is a residue obtained by removing a hydroxyl group from a polyol selected from glycerin, trimethylolpropane, pentaerythritol and sorbitol, n number one less than the number of hydroxyl groups of the polyol, Y ^- represents an anion group).   (c) 0.1 to 10 mol of component (a), 0.1 to 10 mol of component (b), and 0.5 to 3 mol of component (d) to 1 mol of component (b) per 1 mol of component The manufacturing method of the quaternary ammonium salt of Claim 1.   A surfactant comprising a quaternary ammonium salt represented by the general formula (III) or (IV) according to claim 1.   A fabric softener composition comprising a quaternary ammonium salt represented by the general formula (III) or (IV) according to claim 1.