JP5154634B2 - Quaternary ammonium salt composition and softener composition - Google Patents
Quaternary ammonium salt composition and softener composition Download PDFInfo
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Description
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。 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.
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。 In recent years, most of the products marketed as fabric softeners are compositions containing quaternary ammonium salts 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.
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。 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 not a base that is sufficiently satisfactory in flexibility, although 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.
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。 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.
本発明は、一般式（Ｉ） The present invention relates to general formula (I)
（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、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反応溶媒として、４級化剤と反応させて得られる、第４級アンモニウム塩と一般式（II）で表される化合物を含有する第４級アンモニウム塩組成物、並びにこの第４級アンモニウム塩組成物を含有する柔軟剤組成物を提供する。
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 )
A quaternary amine (hereinafter referred to as a tertiary amine (I)) is quaternized with at least one aprotic solvent selected from compounds represented by the general formula (II) as a reaction solvent. A quaternary ammonium salt composition containing a quaternary ammonium salt and a compound represented by the general formula (II) obtained by reacting with the agent, and a softener composition containing the quaternary ammonium salt composition Offer things.
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。）
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.)
［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、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。一般式(II)で表される化合物は、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好ましい。
[Aprotic solvent]
The aprotic solvent used in the present invention is selected from the compounds represented by the general formula (II) and may be liquid at room temperature (25 ° C.) or solid as long as it is liquid during the quaternization reaction. Good. The compound represented by the general formula (II) is preferable in terms of good miscibility with water and good odor of the resulting quaternary ammonium salt.
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。 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.
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。 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.
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。
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.
（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。
(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.
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。 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.
（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。
(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.
［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。
[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.
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本発明では、溶媒を留去せず、そのまま柔軟剤に用いることができる。 In the present invention using the compound represented by the general formula (II) as an aprotic solvent, the solvent can be used as it is without removing the solvent.
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。
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.
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。 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.
例中の％は、特記しない限り重量基準である。 In the examples, “%” is based on weight unless otherwise specified.
参考例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。
Reference 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.
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。 The quaternization rate and composition were measured by an internal standard method using a 1 H-NMR technique using MERCURY400 manufactured by VARIAN.
参考例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を用いて参考例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を用いて参考例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。
Reference example 2
Using 162 g of N, N-di (hydroxyethyl) aminopropylamine and 821 g of hardened beef tallow fatty acid, the same reaction as in Reference Example 1 was performed, and N, N-di (hardened beef tallow alkanoyloxyethyl) -N-hardened beef tallow alkanoylamino was used. Propylamine is obtained, then 465 g of hexane is added, and quaternization reaction is carried out in the same manner as in Reference 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.
参考例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、参考例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を用いて参考例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。
Reference example 3
Using 404 g of N, N-di (hydroxyethyl) -N-cured beef tallow alkanoylaminoethylamine and 547 g of cured beef tallow fatty acid, an esterification reaction was performed in the same manner as in Reference 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 dimethyl sulfuric acid in the same manner as in Reference Example 1. After distilling off the solvent, 184 g of isopropanol was added to form quaternary ammonium. An isopropanol solution of the salt was obtained. The quaternization rate and composition are shown in Table 1.
参考例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を用い参考例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を用いて参考例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。
Reference example 4
Using 299 g of N, N-di (hydroxyethyl) -N-cured tallow alkylamine and 547 g of cured beef tallow fatty acid, an esterification reaction was performed in the same manner as in Reference 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 Reference Example 1 using 126 g of dimethyl sulfate. 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.
参考例５
４級化溶媒としてヘキサンの代わりにアセトン458gを用いる以外は参考例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。
Reference Example 5
The same operation as in Reference Example 1 was performed except that 458 g of acetone 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.
参考例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を用いる以外は参考例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。
Reference Example 6
The same operation as in Reference Example 1 was performed except that 458 g of tetrahydrofuran 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.
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。
Example 1
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. Add 417g of 12 mol adduct of hydrogenated beef tallow fatty acid methyl ester and quaternization reaction with 126g 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.
実施例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１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。
Example 2
The same operation as in Example 1 was carried out except that 417 g of ethylene glycol dimethyl ether was used as a quaternizing solvent instead of 12 mol of ethylene oxide 12 mol adduct of hardened tallow fatty acid methyl ester 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.
実施例３
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２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。
Example 3
The same operation as in Example 2 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.
実施例４
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を用いて参考例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１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。
Example 4
Using 162 g of N, N-di (hydroxyethyl) aminopropylamine and 821 g of hardened beef tallow fatty acid, the same reaction as in Reference Example 1 was performed, 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, followed by the same quaternization reaction as in Example 1, and the hardened tallow fatty acid methyl of a quaternary ammonium salt. An ester ethylene oxide 12 molar adduct solution was obtained. The quaternization rate and composition are shown in Table 1.
実施例５
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を用いて参考例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１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。
Example 5
N, N-di (hydroxyethyl) -N-cured beef tallow alkanoylaminoethylamine 404 g and hardened beef tallow fatty acid 547 g were subjected to the same esterification reaction as in Reference Example 1 to produce N, N-di (cured tallow tallow alkanoyloxyethyl). -N-cured beef tallow alkanoylaminoethylamine was obtained, and then 416 g of a 12-mole ethylene oxide adduct of cured beef tallow fatty acid methyl ester was added as a quaternization solvent, followed by the same quaternization reaction as in Example 1 to produce a 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.
参考例７
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を用いて参考例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。
Reference Example 7
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 Reference Example 1 was carried out 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.
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を用いる以外は参考例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。
Comparative Example 1
The same operation as in Reference Example 1 was performed except that 184 g of isopropyl alcohol was used in place 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.
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１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。
Comparative Example 2
The same procedure as in Example 1 was conducted except that 417 g of stearyl alcohol ethylene oxide 13 mol adduct was used in place of the ethylene oxide 12 mol adduct of cured beef tallow fatty acid methyl ester as a quaternized solvent, and stearyl of a quaternary ammonium salt was used. An alcohol ethylene oxide 13 molar adduct solution was obtained. The quaternization rate and composition are shown in Table 1.
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を用いる以外は参考例７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。
Comparative Example 3
The same operation as in Reference Example 7 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.
参考例１〜７、実施例２、３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１、４、５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。 The solutions of the quaternary ammonium salts obtained in Reference Examples 1-7, Examples 2, 3 and Comparative Examples 1-3 were taken so that the total amount of the quaternary ammonium salts was 5 g, and stearyl alcohol ethylene oxide 13 It was mixed with 2 g of a molar 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. Further, the solutions of the quaternary ammonium salts obtained in Examples 1, 4, and 5 were taken in an amount so that the total content of the quaternary ammonium salts was 5 g, heated to 60 ° C., and dissolved. 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.
＜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。
<Flexibility evaluation method>
(1) Flexible finishing treatment 1 kg of a commercially available cotton towel or acrylic jersey was washed 5 times with a commercial detergent attack (registered trademark, Kao Corporation) in 3.5 ° DH hard water using a 15 liter washing machine, and then the above 25 mL of the softening agent composition was charged and treated under stirring at 25 ° C. for 1 minute.
(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。
＋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
−１；対照よりややかたい
−２；対照よりかたい
(2) Flexibility evaluation After the above-mentioned soft finish was dried in a greenhouse, it was allowed to stand in a constant 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.
+2; softer than control +1; slightly softer than control 0; softer than control -1; slightly softer than control -2; harder than control
Claims (6)
で表され、R 1 、R 2 及びR 3 が全てR 4 であるトリ長鎖アルキル第３級アミンの割合が７０重量％以上である第３級アミンを、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反応溶媒として、４級化剤と反応させて得られる、第４級アンモニウム塩と一般式（II）で表される化合物を含有する第４級アンモニウム塩組成物。
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)
A tertiary amine in which the proportion of a tri-long-chain alkyl tertiary amine in which R 1 , R 2 and R 3 are all R 4 is 70% by weight or more is represented by the general formula (II) A quaternary salt containing a quaternary ammonium salt and a compound represented by the general formula (II) obtained by reacting with a quaternizing agent using at least one aprotic solvent selected from compounds as a reaction solvent. Ammonium salt composition.
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 quaternary ammonium salt composition according to any one of claims 1 to 4 , 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.)
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