JP2005187399A - Cationic surfactant and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a highly pure cationic surfactant having good appearance and excellent properties on handling, useful as a base for a softening agent for clothes, a conditioning agent for the hair, or the like, and containing an ester bond; and to provide an efficient method for producing the cationic surfactant. <P>SOLUTION: The method for producing the cationic surfactant involves reacting a reaction raw material containing at least one kind of a compound represented by structural formula (1), with a dialkyl sulfate without a solvent. The hydroxy value of the reaction raw material is ≤110 (mg KOH/g), and each of A, B and C in the structural formula (1) contains ≤55 mass% compound having an ester group based on the whole amount of the reaction raw material. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention is a cationic surfactant having high purity, good appearance, excellent physical properties in handling, and useful as a base for clothing softeners and hair conditioning agents, and an efficient production method thereof About.

  Conventionally, a dialkyl quaternary ammonium salt type cationic surfactant having two long-chain alkyl groups in one molecule has been used as a compound capable of imparting flexibility to fibers, hair, and the like. There was a problem that the base material itself was poorly biodegradable and had a great influence on the natural world. Therefore, in recent years, a cationic surfactant having an ester bond that has improved the influence on the environment and the biodegradability of the substrate itself has attracted attention. As a method for producing this cationic surfactant, first, triethanolamine, methyldiethanolamine, 3- (N, N-dimethylamino) -1,2-propylene glycol and N-methyl-N- (2- Hydroxyethyl) -1,3-propanediamine or the like is acylated with a long-chain fatty acid or fatty acid methyl at high temperature to synthesize an intermediate alkanolamine fatty acid ester, and then quaternary such as methyl chloride, dimethyl sulfate and diethyl sulfate. A method of converting to a cationic compound with an agent has been proposed (see Patent Document 1).

  Among the quaternizing agents in this proposal, organic halides such as methyl chloride have low reactivity, and in particular, in the quaternization reaction of alkanolamine fatty acid ester derived from triethanolamine, the reaction rate is insufficient. Therefore, a dialkyl sulfate such as dimethyl sulfate having higher reactivity is used as a quaternizing agent. However, when dialkyl sulfuric acid is used as a quaternizing agent, dialkyl sulfuric acid undergoes side reactions with lower alcohols such as ethanol and isopropyl alcohol, which are usually used as a dilution solvent during the quaternization reaction, and changes to monoalkyl sulfuric acid. As a result, there is a problem that a large amount of monoalkyl sulfate of alkanolamine fatty acid ester as an impurity is produced. Therefore, in order to prevent this side reaction, a quaternization reaction without a solvent has been proposed (see Patent Document 2). However, even if the quaternization reaction is carried out in the absence of a solvent, it is difficult to prevent the by-production of a small amount of monoalkyl sulfate, and there is a problem that the purity of the target cation activator is lowered. is there.

  In addition, in order to obtain a high-purity cationic surfactant, a alkanolamine fatty acid ester having a lower content of alkanolamine not acylated with a long-chain fatty acid or the like is used in the quaternization reaction. It is preferable to do. For this purpose, for example, a method is known in which unreacted alkanolamine is reduced by increasing the raw material charge ratio of fatty acid and alkanolamine when acylating alkanolamine. However, in practice, the ratio is often selected from the viewpoint of the physical properties of the resulting cationic surfactant and the performance such as flexibility, for example, in the case of triethanolamine fatty acid ester A range of 1.3 to 2.2 has been proposed (see Patent Document 4). However, in the case of triethanolamine fatty acid ester, the larger the ratio, the more the trifatty acid ester content increases and the melting point becomes higher, resulting in inconvenience in handling, and in the case of quaternization without solvent There is a problem that the reaction becomes difficult due to an increase in viscosity during the quaternization reaction.

  In order to obtain a higher purity cationic activator, the molar ratio of the quaternizing agent dialkyl sulfuric acid and the alkanolamine fatty acid ester (dialkyl sulfuric acid / alkanolamine fatty acid ester) in the quaternization reaction is increased, It is preferable to reduce the amount of unreacted alkanolamine fatty acid ester. However, there is a problem that the amount of monoalkyl sulfate by-products increases as the molar ratio increases. Moreover, since the quantity of unreacted alkanolamine fatty acid ester decreases, there exists a problem that pH when it is set as aqueous dispersion like a softening agent composition will fall more than necessary. Furthermore, the cationic surfactant having an ester bond is excellent in biodegradability, but is susceptible to hydrolysis, and it is necessary to maintain the pH at a desired value for hydrolysis stability. is there.

  Specifically, when triethanolamine fatty acid ester is quaternized with dialkylsulfuric acid, it has a low pH when used as an aqueous dispersion and exhibits strong acidity. For example, when used as a softener, a perfume It is necessary to control the pH more strictly from the influence on the stability of other components such as. However, in reality, the pH changes due to manufacturing errors such as slight charging errors of raw materials during the acylation reaction or quaternization reaction, and as a result, the composition of the softener It is a problem that the efficiency of industrial continuous production is lowered, such as the necessity of adjusting the pH sometimes and the quality of each product lot becoming unstable.

  Therefore, high-purity, good appearance, excellent physical properties in handling, and a cationic surfactant containing an ester bond, which is useful as a base for a softener for clothes, a conditioning agent for hair, and the like, and its efficiency Such a manufacturing method has not yet been provided, and the development of these is urgently desired.

JP 2003-12471 A JP 2003-252838 A JP 63-6168 (page 4-5) JP 2001-181973 A

  An object of the present invention is to solve the conventional problems and achieve the following objects. That is, the present invention is a cationic surfactant containing an ester bond, having high purity, good appearance, excellent physical properties in handling, and useful as a base for a softener for clothes, a conditioning agent for hair, etc. And it aims at providing the efficient manufacturing method.

但し、前記構造式（１）中、Ａは、アルキル基、Ｒ^１ＯＨ、又はＲ^２ＯＣＯＲ^３を表し、Ｂは、アルキル基、Ｒ^４ＯＨ、又はＲ^５ＯＣＯＲ^６を表し、Ｃは、Ｒ^７ＯＣＯＲ^８を表す。Ｒ^１、Ｒ^２、Ｒ^４、Ｒ^５及びＲ^７は、互いに同一であってもよく、異なっていてもよく、アルキレン基、又はアルケニレン基を表し、Ｒ^３、Ｒ^６及びＲ^８は、互いに同一であってもよく、異なっていてもよく、アルキル基、又はアルケニル基を表す。
＜２＞ 反応原料が、アルカノールアミンを該反応原料全量に対して１．５質量％以下含有する前記＜１＞に記載のカチオン性界面活性剤の製造方法である。
＜３＞ 少なくとも１種の構造式（１）で表される化合物及びアルカノールアミンの総量と、ジアルキル硫酸とのモル比が、１：０．９７〜１：１である前記＜１＞から＜２＞のいずれかに記載のカチオン性界面活性剤の製造方法である。
＜４＞ アルカノールアミンが、下記構造式（２）で表される前記＜１＞から＜３＞のいずれかに記載のカチオン性界面活性剤の製造方法である。

但し、前記構造式（２）中、Ｄは、アルキル基、又はＲ^９ＯＨを表し、Ｅは、アルキル基、又はＲ^１０ＯＨを表し、Ｆは、Ｒ^１１ＯＨを表す。Ｒ^９、Ｒ^１０及びＲ^１１は、互いに同一であってもよく、異なっていてもよく、アルキレン基、又はアルケニレン基を表す。
＜５＞ 前記＜１＞から＜４＞のいずれかに記載のカチオン性界面活性剤の製造方法により製造されることを特徴とするカチオン性界面活性剤である。 Means for solving the problems are as follows. That is,
<1> A method for producing a cationic surfactant in which at least one reaction raw material containing a compound represented by the following structural formula (1) and a dialkyl sulfuric acid are reacted in the absence of a solvent,
The reaction raw material has a hydroxyl value of 110 (mgKOH / g) or less, and in the structural formula (1), A is represented by R ² OCOR ³ and B is represented by R ⁵ OCOR ^6. Is contained in an amount of 55% by mass or less based on the total amount of the reaction raw material.

However, the structural formula (1), A is an alkyl ^group, an R 1 OH, or ^R 2 OCOR ^3, B represents an alkyl ^group, R 4 OH, or ^R 5 OCOR ^6, C is R ⁷ represents OCOR ⁸ . R ¹ , R ² , R ⁴ , R ⁵ and R ⁷ may be the same or different from each other, each represents an alkylene group or an alkenylene group, and R ³ , R ⁶ and R ⁸ are It may be the same or different and represents an alkyl group or an alkenyl group.
<2> The method for producing a cationic surfactant according to <1>, wherein the reaction raw material contains alkanolamine in an amount of 1.5% by mass or less based on the total amount of the reaction raw material.
<3> The above-mentioned <1> to <2 wherein the molar ratio of the total amount of the compound represented by the structural formula (1) and the alkanolamine to the dialkyl sulfate is 1: 0.97 to 1: 1. > A method for producing a cationic surfactant according to any one of the above.
<4> The method for producing a cationic surfactant according to any one of <1> to <3>, wherein the alkanolamine is represented by the following structural formula (2).

In Structural Formula (2), D represents an alkyl group or R ⁹ OH, E represents an alkyl group or R ¹⁰ OH, and F represents R ¹¹ OH. R ⁹ , R ¹⁰ and R ¹¹ may be the same as or different from each other, and represent an alkylene group or an alkenylene group.
<5> A cationic surfactant produced by the method for producing a cationic surfactant according to any one of <1> to <4>.

  Highly pure, good appearance, excellent physical properties in handling, and useful as a base for clothing softeners, hair conditioning agents, etc., cationic surfactants containing ester bonds, and efficient production thereof A method can be provided.

但し、前記構造式（１）中、Ａは、アルキル基、Ｒ^１ＯＨ、又はＲ^２ＯＣＯＲ^３を表し、Ｂは、アルキル基、Ｒ^４ＯＨ、又はＲ^５ＯＣＯＲ^６を表し、Ｃは、Ｒ^７ＯＣＯＲ^８を表す。Ｒ^１、Ｒ^２、Ｒ^４、Ｒ^５及びＲ^７は、互いに同一であってもよく、異なっていてもよく、アルキレン基、又はアルケニレン基を表し、Ｒ^３、Ｒ^６及びＲ^８は、互いに同一であってもよく、異なっていてもよく、アルキル基、又はアルケニル基を表す。 (Method for producing cationic surfactant)
The method for producing a cationic surfactant of the present invention comprises at least one reaction raw material containing a compound represented by the following structural formula (1) (hereinafter sometimes referred to as “alkanolamine fatty acid ester”); The dialkyl sulfate is reacted with no solvent.
The cationic surfactant of the present invention will be clarified through the description of the method for producing the cationic surfactant of the present invention.

However, the structural formula (1), A is an alkyl ^group, an R 1 OH, or ^R 2 OCOR ^3, B represents an alkyl ^group, R 4 OH, or ^R 5 OCOR ^6, C is R ⁷ represents OCOR ⁸ . R ¹ , R ² , R ⁴ , R ⁵ and R ⁷ may be the same or different from each other, each represents an alkylene group or an alkenylene group, and R ³ , R ⁶ and R ⁸ are It may be the same or different and represents an alkyl group or an alkenyl group.

As said alkyl group, a linear or branched C1-C4 alkyl group etc. are mentioned suitably, for example.
Examples of R ¹ , R ² , R ⁴ , R ^5, and R ⁷ include —CH ₂ —CH ₂ —, — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, —CH ₂ —CH ( _{CH 3) -, - CH =} CH -, - CH = CH-CH 2 -, - CH = CH-CH 2 CH 2 -, and the like. among _them, -CH 2 -CH ₂ - is preferably Can be mentioned.
Examples of R ³ , R ⁶ and R ⁸ include linear or branched alkyl groups or alkenyl groups having 7 to 23 carbon atoms. Among these, alkyl groups or alkenyl groups having 11 to 21 carbon atoms are preferable. It is mentioned in.

-Reaction raw materials-
The reaction raw material contains at least one compound represented by the structural formula (1). In the structural formula (1), A is represented by R ² OCOR ³ and B is R ⁵ OCOR ⁶ . The compound represented (hereinafter sometimes referred to as “tri-fatty acid ester”) is contained in an amount of 55% by mass or less based on the total amount of the reaction raw materials, and contains other components appropriately selected.
Moreover, the hydroxyl value of the said reaction raw material is 110 (mgKOH / g) or less.

As content of the said tri-fatty acid ester, it is 55 mass% or less with respect to the said reaction raw material whole quantity, 50 mass% or less is preferable, and 45 mass% or less is more preferable.
When the content of the tri-fatty acid ester exceeds 55% by mass, the melting point of the cationic surfactant increases, so that the compound containing the surfactant thickens or precipitates over time. There may be a problem in handling.

  Moreover, the said reaction raw material may contain alkanolamine, As this alkanolamine, what is represented by following Structural formula (2) is mentioned, for example.

但し、前記構造式（２）中、Ｄは、アルキル基、又はＲ^９ＯＨを表し、Ｅは、アルキル基、又はＲ^１０ＯＨを表し、Ｆは、Ｒ^１１ＯＨを表す。Ｒ^９、Ｒ^１０及びＲ^１１は、互いに同一であってもよく、異なっていてもよく、アルキレン基、又はアルケニレン基を表す。

In Structural Formula (2), D represents an alkyl group or R ⁹ OH, E represents an alkyl group or R ¹⁰ OH, and F represents R ¹¹ OH. R ⁹ , R ¹⁰ and R ¹¹ may be the same as or different from each other, and represent an alkylene group or an alkenylene group.

As said alkyl group, a linear or branched C1-C4 alkyl group etc. are mentioned suitably, for example.
Examples of R ⁹ , R ¹⁰ and R ¹¹ include —CH ₂ —CH ₂ —, — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, —CH ₂ —CH (CH ₃ ) —, — _{CH = CH -, - CH =} CH-CH 2 -, - CH = CH-CH 2 CH 2 -, and the like. among _them, -CH 2 -CH ₂ - is preferably exemplified.

  Specific examples of the alkanolamine include triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-methyldiisopropanolamine, N-methyl-N- (2-methyl-2-hydroxyethyl) ethanolamine, N- Examples include methyl-N- (2-hydroxyethyl) propanediamine, N, N-dimethyl, 2,3-dihydroxypropylamine, N, N-dimethylmonoethanolamine, and among these, triethanolamine, N- Preferable examples include methyldiethanolamine, N-methyl-N- (2-hydroxyethyl) propanediamine, N, N-dimethyl-2, 3-dihydroxypropylamine, N, N-dimethylmonoethanolamine and the like.

The content of the alkanolamine is preferably 1.5% by mass or less, more preferably 1.0% by mass or less, still more preferably 0.5% by mass or less, and particularly preferably 0% by mass with respect to the total amount of the reaction raw materials. preferable.
When the content of the alkanolamine exceeds 1.5% by mass, the content of the cation of the alkanolamine fatty acid ester in the cationic surfactant decreases, and the amount used must be increased to obtain the desired effect. It may not be.

-Production method of reaction raw materials-
There is no restriction | limiting in particular as a manufacturing method of the said reaction raw material, Although it can select suitably according to the objective, For example, (1) The method of making a fatty acid and an alkanolamine react in the absence of an catalyst or an acid catalyst, 2) A method of transesterification by reacting a lower alkyl ester of a fatty acid and an alkanolamine in the presence of a transesterification catalyst.

  There is no restriction | limiting in particular as said fatty acid, It can select suitably from well-known fatty acids, For example, the C8-C24 fatty acid etc. which were derived from natural fats and oils or were synthesized chemically are mentioned. These may be used alone or in combination of two or more.

The fatty acid lower alkyl ester is not particularly limited, and may be any one of a saturated fatty acid lower alkyl ester and an unsaturated fatty acid lower alkyl ester, and is a known fatty acid lower alkyl usually used in the production of a cationic surfactant. The alkyl ester can be appropriately selected from, for example, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, dimethyloctanoic acid, butylheptylnonanoic acid, methylheneico Sanic acid, Octenoic acid, Decenoic acid, Dodecenoic acid, Palmitoleic acid, Oleic acid, Elaidic acid, Linoleic acid, Linolenic acid, Arachidonic acid, Eicosenic acid, Erucic acid, Arachidic acid, Tallow fatty acid, Palm oil fatty acid, Palm fatty acid, Palm Fats such as nuclear oil fatty acids and fish oil fatty acids Methyl ester, ethyl ester, isopropyl ester, n- propyl ester, glyceride, and glycol esters. These may be used alone or in combination of two or more.
In the unsaturated fatty acid lower alkyl ester, the unsaturated fatty acid may be either a cis isomer or a trans isomer, or a mixture thereof.
As the fatty acid lower alkyl ester, for example, methyl stearate, methyl oleate, methyl palmitate and the like are particularly preferable. These may be used alone or in combination of two or more.

  When the fatty acid is used, if the purification is insufficient, the resulting alkanolamine fatty acid ester may be colored to produce an unpleasant odor, and the quality of the obtained cationic surfactant may be deteriorated. On the other hand, the fatty acid lower alkyl ester is particularly preferably used as a raw material because the fatty acid lower alkyl ester is easily and inexpensively purified.

  There is no restriction | limiting in particular as said transesterification catalyst, According to the objective, it can select suitably, For example, alkali metals (for example, sodium etc.), alkaline earth metals (for example, magnesium etc.), these, Examples thereof include alkaline compounds. These may be used alone or in combination of two or more.

  The alkali compound is not particularly limited as long as it contains alkali metal or alkaline earth metal, and examples thereof include alkoxide, hydroxide, oxide, carbonate, fatty acid salt and the like. These may be used alone or in combination of two or more. Furthermore, the metal species to be used is not limited to one, and can be used without limitation.

  There is no restriction | limiting in particular as the usage-amount of the said transesterification catalyst, According to the objective, it can select suitably.

The method of setting the content of the alkanolamine in the total amount of the reaction raw material to 1.5% by mass or less and the content of the trifatty acid ester to 55% by mass or less is not particularly limited and is appropriately selected depending on the purpose. For example, when triethanolamine is used as a starting material, the esterification reaction molar ratio (reaction mole number of fatty acid lower alkyl ester to 1 mole of triethanolamine) is preferably 1.8 or more. 8-2.5 are more preferable, and 1.8-2.2 are particularly preferable.
When the esterification molar ratio is too large, a large amount of the tri-fatty acid ester is generated, and the resulting cationic surfactant has a high melting point and is likely to precipitate, or gelates and exits from the container due to high viscosity. It may cause deterioration of physical properties.

  The product obtained here contains triethanolamine mono-fatty acid ester, di-fatty acid ester, tri-fatty acid ester and unreacted triethanolamine, and the unreacted triethanolamine content and hydroxyl value should be within the desired range. Can do.

  The alkanolamine having a low boiling point may be removed by distillation or the like. Further, even if a part of the triethanolamine to be reacted is replaced with an alkanolamine having a hydroxyl value smaller than that of triethanolamine, such as methyldiethanolamine, the hydroxyl value of the alkanolamine fatty acid ester obtained with the same esterification molar ratio is obtained. Is effective as means for achieving the present invention.

-Dialkyl sulfate-
In the present invention, after obtaining the alkanolamine fatty acid ester (or a mixture thereof), it is cationized by a quaternization reaction using dialkyl sulfuric acid to produce the cationic surfactant of the present invention.
There is no restriction | limiting in particular as said dialkyl sulfuric acid, For example, a dimethyl sulfuric acid, diethyl sulfuric acid, etc. are preferable from a reactive viewpoint.

  Cationization reaction molar ratio between the total amount of the compound represented by the structural formula (1) and the alkanolamine and the dialkyl sulfuric acid (the dialkyl sulfuric acid relative to 1 mole of the compound represented by the structural formula (1)) The number of moles is not particularly limited and may be appropriately selected depending on the purpose. For example, it is preferably 1: 0.97 to 1: 1, and 1: 0.975 to 1: 0.99. More preferably, 1: 0.975 to 1: 0.985 is particularly preferable.

The quaternization reaction is performed without a solvent. Usually, water or lower alcohol used as a solvent in the quaternization reaction causes a side reaction with the dialkyl sulfuric acid to increase the amine monoalkyl sulfate, and the resulting cationic surfactant is reddish or has a pH value. It may be lowered to promote ester bond hydrolysis.
For the same reason, the water and lower alcohol content in the alkanolamine fatty acid ester (or mixture thereof) is preferably 0.5% (5000 ppm) in total, and 0.4% or less in total. It is more preferable to use those. If desired, it can be used after adjusting the amount, for example, by topping an excess amount.

  In the method for producing the cationic surfactant of the present invention, the dialkyl sulfate is added little by little to the alkanolamine fatty acid ester (or a mixture thereof) without solvent, and then the dialkyl sulfate is completely consumed. It is preferable to perform aging.

The reaction temperature in the quaternization reaction is not particularly limited as long as it is equal to or higher than the melting point of the alkanolamine fatty acid ester (or a mixture thereof), but the reaction product viscosity tends to increase as the reaction proceeds. The final temperature needs to be set at least above the temperature at which the reactants flow, specifically 50 to 105 ° C. is preferable, from the viewpoint of reducing the amount of by-produced amine monoalkyl sulfate as an impurity. -90 degreeC is more preferable.
If the temperature of the reaction is less than 50 ° C., the reaction proceeds slowly and the viscosity of the reaction product becomes too high as the cationization reaction proceeds. In this case, the amount of by-products increases, cation decomposition may occur, and the degree of cationization may decrease.

  After the quaternization reaction, a lower alcohol (dilution solvent) is added to adjust the concentration to 5 to 40% by mass. The lower alcohol is added to improve the handleability of the cationic surfactant, and is preferably a monovalent or divalent alcohol having 1 to 5 carbon atoms, specifically, methanol, ethanol, isopropanol, n -Propanol, propylene glycol, ethylene glycol and the like and mixtures thereof are preferred.

  Furthermore, in the method for producing the cationic surfactant of the present invention, a step of adding an antioxidant, a chelating agent or the like may be provided as desired in order to prevent deterioration of odor and color tone due to aging. Examples of the antioxidant and chelating agent include phenol derivatives, hydroxycarboxylic acids, and phosphoric acid compounds that are usually used as antioxidants or chelating agents for cationic surfactants. These may be used alone or in combination of two or more.

  Hereinafter, although the Example of this invention is described, this invention is not limited to this Example at all.

(Example 1)
-Preparation of reaction raw materials-
A mixture of methyl stearate derived from palm oil 40% by mass, methyl oleate 40% by mass (cis / trans ratio = 75/25), and methyl palmitate 20% by mass (produced by Lion Oleo Chemical Co., Pastel) M180, a mixture of pastel M181 and pastel M16) 927 g (3.2 mol) and 250 g (1.7 mol) of triethanolamine using 2.5 g of 48% by weight NaOH aqueous solution as an alkali catalyst, A 2 l four-necked flask equipped with a condenser, condenser, thermometer and nitrogen inlet tube was charged. In addition, the reaction molar ratio of the mixture of the fatty acid methyl ester and the triethanolamine is 1.9.

Next, nitrogen was allowed to flow in at a rate of 0.51 / min, and by-produced methanol was distilled out of the system, while the temperature was raised to 190 ° C. at a rate of 1.5 ° C./min. I let you. After the reaction, the reaction was stopped after confirming that the unreacted fatty acid methyl ester was 1% by mass or less by gas chromatographic analysis.
The reaction raw material containing the alkanolamine fatty acid ester mixture which is an intermediate was prepared as described above. When the reaction raw material was analyzed, the trifatty acid ester represented by the following structural formula (1) contained in the alkanolamine fatty acid ester mixture and the content (mass%) of the triethanolamine with respect to the total amount of the reaction raw material, The hydroxyl value of the prepared reaction raw material and the average molecular weight of the alkanolamine fatty acid ester mixture were measured. The results are shown in Table 1.

但し、前記構造式（１）中、Ａ、Ｂ及びＣは、互いに同一であっても、異なっていてもよく、Ｃ_１５Ｈ_３１ＣＯＯ（ＣＨ_２）_２、Ｃ_１７Ｈ_３５ＣＯＯ（ＣＨ_２）_２、及びＣ_１７Ｈ_３３ＣＯＯ（ＣＨ_２）_２のいずれかである。

However, the structural formula (1), A, B and C are identical to each other or _{different, C 15 H 31 COO (CH} 2) 2, C 17 H 35 COO (CH 2) ₂ and C ₁₇ H ₃₃ COO (CH ₂ ) ₂ .

<Hydroxyl value>
The analysis of the hydroxyl value was measured according to the method described in Reference Oil Analysis Method 2.3.6.2-1996.

<Content>
The reaction raw material was diluted to about 10 ml of isopropanol and heated moderately to completely dissolve the reaction raw material. This was used as a measurement sample, analyzed by liquid chromatography under the following analysis conditions, and the content of the tri-fatty acid ester and the alkanolamine was measured with respect to the total amount of the reaction raw material.
-Analysis conditions-
Column: Nucleosil 5SB 4.6φ × 250 mm, eluent: 0.3% -sodium perchlorate / 0.175% monochloroacetic acid-methanol solution, flow rate: 1.0 ml / min, detector: RI (differential refractometer) Sample injection volume: 100 μl

<Average molecular weight>
Using an automatic potentiometric titrator (Hiranuma, Titstation TS-980 type), the sample dissolved in isopropanol / methanol = 50/50 (v / v) solvent was titrated with 0.2 N HCl-IPA normal solution, and the amine value was determined. When measured by obtaining, the average molecular weight was 644.

-Production of cationic surfactants-
300 g of the prepared reaction raw material was charged into a 1 l separable flask equipped with a thermometer, a dropping funnel and a condenser, and purged with nitrogen. Then, it heated at 90 degreeC and 57.6 g (0.457 mol: The ratio with respect to 1 mol of said alkanolamine fatty acid ester mixture is 0.98 mol) was dripped over 2 hours. After completion of dropping, the mixture was further stirred for 1 hour. Next, the solution was cooled while dropping about 65 g of ethanol to prepare an ethanol solution having a solid content of 85% by mass.
The cationic surfactant was manufactured by the above. About the produced cationic surfactant, the content (mass%) of impurities (cations of free amine, amine monomethyl sulfate, and triethanolamine), pH measurement, and appearance evaluation were performed as follows. Went. The results are shown in Table 3.

<Impurity>
The content of each of the free amine, amine monomethyl sulfate, and triethanolamine cation was measured. The free amine was measured by the same method as the method for measuring the average molecular weight. The amine monoethyl sulfate is titrated with a 0.1 N KOH normal solution by using an automatic potentiometric titrator (manufactured by Hiranuma, Titstation TS-980) and titrated with 0.1 N KOH normal solution in an isopropanol solvent. The amount was measured. The cation of the triethanolamine was measured by the same method as that used for the liquid chromatography.

<PH>
In a 100 ml beaker, 5.9 g of the above-mentioned cationic surfactant was collected, and 70 ° C. ion-exchanged water that had been boiled and degassed in advance was added to a total amount of 50 g. The obtained sample was stirred with a high-speed mixer to obtain a uniform aqueous dispersion, cooled to 25 ° C., and then measured with a pH meter (manufactured by Toa Denpa Kogyo Co., Ltd., HM-30V).

<Appearance>
The bottle containing the cationic surfactant (solid content: 85%) was placed in a thermostatic bath at 60 ° C. and allowed to stand for 1 hour, and then the appearance of the cationic surfactant was visually confirmed and evaluated according to the following evaluation criteria. .
-Evaluation criteria-
○ Appearance is uniform and transparent.
X Turbidity, precipitation, and solidified parts were observed.

(Example 2)
-Preparation of reaction raw materials-
In Example 1, the mixture of fatty acid methyl esters (Lion Oleochemical, Pastel M180, Pastel M181, Pastel M16) was replaced with 1073 g (3.7 moles), and 48% NaOH aqueous solution as an alkali catalyst The reaction raw material containing the alkanolamine fatty acid ester mixture of Example 2 was prepared in the same manner as in Example 1 except that 2.8 g was replaced by the same measurement as in Example 1. The results are shown in Table 1.

-Production of cationic surfactants-
300 g (average molecular weight 722, 0.416 mol) of the prepared reaction raw material was charged into a 1-liter separable flask equipped with a thermometer, a dropping funnel and a condenser, and purged with nitrogen. Thereafter, the mixture was heated to 90 ° C., and 51.4 g of dimethyl sulfate (0.407 mol: the ratio of 1 mol of the alkanolamine fatty acid ester mixture was 0.98 mol) was added dropwise over 2 hours. After completion of dropping, the mixture was further stirred for 1 hour. Next, the solution was cooled while dropping about 62 g of ethanol to prepare an ethanol solution having a solid content of 85%.
Thus, the cationic surfactant of Example 2 was produced. About the produced cationic surfactant, the content (mass%) of impurities (cations of free amine, amine monomethyl sulfate, and triethanolamine), pH measurement, and appearance evaluation were performed as follows. Went. The results are shown in Table 3.

(Example 3)
-Preparation of reaction raw materials-
In Example 1, 976 g (3.4 mol) of the mixture of fatty acid methyl esters (Lion Oleochemical Co., Ltd., pastel M180, pastel M181, pastel M16) was replaced by 976 g (48 mol NaOH aqueous solution as an alkali catalyst) The reaction raw material containing the alkanolamine fatty acid ester mixture of Example 3 was prepared in the same manner as in Example 1 except that 2.6 g was changed to 2.6 g, and the same measurement as in Example 1 was performed. The results are shown in Table 1.

-Production of cationic surfactants-
300 g (average molecular weight 670, 0.448 mol) of the prepared reaction raw material was charged into a 1 liter separable flask equipped with a thermometer, a dropping funnel and a condenser, and purged with nitrogen. Thereafter, the mixture was heated to 90 ° C., and 55.4 g of dimethyl sulfate (0.439 mol: 0.98 mol with respect to 1 mol of the alkanolamine fatty acid ester mixture) was added dropwise over 2 hours. After completion of dropping, the mixture was further stirred for 1 hour. Next, the solution was cooled while dropping about 63 g of ethanol to prepare an ethanol solution having a solid content of 85%.
Thus, the cationic surfactant of Example 3 was produced. About the produced cationic surfactant, the content (mass%) of impurities (cations of free amine, amine monomethyl sulfate, and triethanolamine), pH measurement, and appearance evaluation were performed as follows. Went. The results are shown in Table 3.

Example 4
-Preparation of reaction raw materials-
In Example 1, the mixture of fatty acid methyl esters (Lion Oleo Chemical Co., pastel M180, pastel M181, pastel M16) was replaced with 927 g (3.2 mol), and 48% NaOH aqueous solution as an alkali catalyst The reaction raw material containing the alkanolamine fatty acid ester mixture of Example 3 was prepared in the same manner as in Example 1 except that the amount was changed to 2.5 g, and the same measurement as in Example 1 was performed. The results are shown in Table 1.

-Production of cationic surfactants-
300 g (average molecular weight 644, 0.466 mol) of the prepared reaction raw material was charged into a 1 liter separable flask equipped with a thermometer, a dropping funnel and a condenser, and purged with nitrogen. Thereafter, the mixture was heated to 90 ° C., and 57.0 g of dimethylsulfuric acid (0.452 mol: 0.97 mol with respect to 1 mol of the alkanolamine fatty acid ester mixture) was added dropwise over 2 hours. After completion of dropping, the mixture was further stirred for 1 hour. Next, the solution was cooled while dropping about 63 g of ethanol to prepare an ethanol solution having a solid content of 85%.
Thus, the cationic surfactant of Example 4 was produced. About the produced cationic surfactant, the content (mass%) of impurities (cations of free amine, amine monomethyl sulfate, and triethanolamine), pH measurement, and appearance evaluation were performed as follows. Went. The results are shown in Table 3.

(Example 5)
-Preparation of reaction raw materials-
In Example 1, the mixture of fatty acid methyl esters (Lion Oleochemical, Pastel M180, Pastel M181, Pastel M16) was replaced with 1073 g (3.7 moles), and 48% NaOH aqueous solution as an alkali catalyst The reaction raw material containing the alkanolamine fatty acid ester mixture of Example 5 was prepared in the same manner as in Example 1 except that 2.8 g was changed to 2.8 g, and the same measurement as in Example 1 was performed. The results are shown in Table 1.

-Production of cationic surfactants-
300 g (average molecular weight 722, 0.416 mol) of the prepared reaction raw material was charged into a 1-liter separable flask equipped with a thermometer, a dropping funnel and a condenser, and purged with nitrogen. Thereafter, the mixture was heated to 90 ° C., and 50.9 g of dimethyl sulfate (0.403 mol: the ratio of the alkanolamine fatty acid ester mixture to 1 mol was 0.97 mol) was added dropwise over 2 hours. After completion of dropping, the mixture was further stirred for 1 hour. Next, the solution was cooled while dropping about 62 g of ethanol to prepare an ethanol solution having a solid content of 85%.
Thus, the cationic surfactant of Example 5 was produced. About the produced cationic surfactant, the content (mass%) of impurities (cations of free amine, amine monomethyl sulfate, and triethanolamine), pH measurement, and appearance evaluation were performed as follows. Went. The results are shown in Table 3.

(Comparative Example 1)
-Preparation of reaction raw materials-
In Example 1, the mixture of fatty acid methyl esters (made by Lion Oleo Chemical Co., pastel M180, pastel M181, pastel M16) was replaced with 586 g (2.0 mol), and 48% NaOH aqueous solution as an alkali catalyst The reaction raw material containing the alkanolamine fatty acid ester mixture of Comparative Example 1 was prepared in the same manner as in Example 1 except that was changed to 1.5 g, and the same measurement as in Example 1 was performed. The results are shown in Table 2.

-Production of cationic surfactants-
300 g (average molecular weight 462, 0.650 mol) of the prepared reaction raw material was charged into a 1 l separable flask equipped with a thermometer, a dropping funnel and a condenser, and purged with nitrogen. Then, it heated at 90 degreeC and the dimethyl sulfuric acid 80.3g (0.637 mol: The ratio with respect to 1 mol of said alkanolamine fatty-acid ester mixtures is 0.98 mol) was dripped over 2 hours. After completion of dropping, the mixture was further stirred for 1 hour. Next, the solution was cooled while dripping about 67 g of ethanol to prepare an ethanol solution having a solid content of 85%.
Thus, the cationic surfactant of Comparative Example 1 was produced. About the produced cationic surfactant, the content (mass%) of impurities (cations of free amine, amine monomethyl sulfate, and triethanolamine), pH measurement, and appearance evaluation were performed as follows. Went. The results are shown in Table 4.

(Comparative Example 2)
-Preparation of reaction raw materials-
In Example 1, the mixture of fatty acid methyl esters (produced by Lion Oleo Chemical Co., pastel M180, pastel M181, pastel M16) was replaced with 683 g (2.3 mol), and a 48% NaOH aqueous solution as an alkali catalyst The reaction raw material containing the alkanolamine fatty acid ester mixture of Comparative Example 2 was prepared in the same manner as in Example 1 except that was replaced with 1.9 g, and the same measurement as in Example 1 was performed. The results are shown in Table 2.

-Production of cationic surfactants-
300 g (average molecular weight 514, 0.584 mol) of the prepared reaction raw material was charged into a 1-liter separable flask equipped with a thermometer, a dropping funnel and a condenser, and purged with nitrogen. Then, it heated at 90 degreeC and 72.2 g (0.572 mol: The ratio with respect to 1 mol of said alkanolamine fatty-acid ester mixtures is 0.98 mol) was dripped over 2 hours. After completion of dropping, the mixture was further stirred for 1 hour. Next, cooling was performed while dropping about 66 g of ethanol to prepare an ethanol solution having a solid content of 85%.
Thus, the cationic surfactant of Comparative Example 2 was produced. About the produced cationic surfactant, the content (mass%) of impurities (cations of free amine, amine monomethyl sulfate, and triethanolamine), pH measurement, and appearance evaluation were performed as follows. Went. The results are shown in Table 4.

(Comparative Example 3)
-Preparation of reaction raw materials-
In Example 1, the mixture of fatty acid methyl esters (Lion Oleochemical, Pastel M180, Pastel M181, Pastel M16) was replaced with 1220 g (4.2 mol), and 48% NaOH aqueous solution as an alkali catalyst The reaction raw material containing the alkanolamine fatty acid ester mixture of Comparative Example 3 was prepared in the same manner as in Example 1 except that 3.1 g was changed to 3.1 g, and the same measurement as in Example 1 was performed. The results are shown in Table 2.

-Production of cationic surfactants-
300 g (average molecular weight 800, 0.375 mol) of the prepared reaction raw material was charged into a 1 liter separable flask equipped with a thermometer, a dropping funnel and a condenser, and purged with nitrogen. Then, it heated at 90 degreeC and the dimethyl sulfuric acid 46.4g (0.368 mol: The ratio with respect to 1 mol of said alkanolamine fatty-acid ester mixtures is 0.98 mol) was dripped over 2 hours. After completion of dropping, the mixture was further stirred for 1 hour. Next, the solution was cooled while dropping about 61 g of ethanol to prepare an ethanol solution having a solid content of 85%.
Thus, the cationic surfactant of Comparative Example 3 was produced. About the produced cationic surfactant, the content (mass%) of impurities (cations of free amine, amine monomethyl sulfate, and triethanolamine), pH measurement, and appearance evaluation were performed as follows. Went. The results are shown in Table 4.

(Comparative Example 4)
-Preparation of reaction raw materials-
In Example 1, the mixture of fatty acid methyl esters (Lion Oleochemical, Pastel M180, Pastel M181, Pastel M16) was replaced with 781 g (2.7 mol), and 48% NaOH aqueous solution as an alkali catalyst The reaction raw material containing the alkanolamine fatty acid ester mixture of Comparative Example 4 was prepared in the same manner as in Example 1 except that 2.1 g was changed to 2.1 g, and the same measurement as in Example 1 was performed. The results are shown in Table 2.

-Production of cationic surfactants-
300 g (average molecular weight 566, 0.530 mol) of the prepared reaction raw material was charged into a 1 liter separable flask equipped with a thermometer, a dropping funnel and a condenser, and purged with nitrogen. Then, it heated at 90 degreeC and 65.6 g (0.520 mol: The ratio with respect to 1 mol of the said alkanolamine fatty acid ester mixture is 0.98 mol) was dripped over 2 hours. After completion of dropping, the mixture was further stirred for 1 hour. Next, the solution was cooled while dropping about 65 g of ethanol to prepare an ethanol solution having a solid content of 85%.
Thus, the cationic surfactant of Comparative Example 4 was produced. About the produced cationic surfactant, the content (mass%) of impurities (cations of free amine, amine monomethyl sulfate, and triethanolamine), pH measurement, and appearance evaluation were performed as follows. Went. The results are shown in Table 4.

(Comparative Example 5)
-Preparation of reaction raw materials-
In Example 1, the mixture of fatty acid methyl esters (produced by Lion Oleo Chemical Co., pastel M180, pastel M181, pastel M16) was replaced with 683 g (2.3 mol), and a 48% NaOH aqueous solution as an alkali catalyst The reaction raw material containing the alkanolamine fatty acid ester mixture of Comparative Example 5 was prepared in the same manner as in Example 1 except that was replaced with 1.9 g, and the same measurement as in Example 1 was performed. The results are shown in Table 2.

-Production of cationic surfactants-
300 g (average molecular weight 514, 0.584 mol) of the prepared reaction raw material was charged into a 1-liter separable flask equipped with a thermometer, a dropping funnel and a condenser, and purged with nitrogen. Thereafter, the mixture was heated to 90 ° C., and 71.5 g of dimethyl sulfate (0.567 mol: the ratio of 1 mol of the alkanolamine fatty acid ester mixture was 0.97 mol) was added dropwise over 2 hours. After completion of dropping, the mixture was further stirred for 1 hour. Next, cooling was performed while dropping about 66 g of ethanol to prepare an ethanol solution having a solid content of 85%.
Thus, the cationic surfactant of Comparative Example 5 was produced. About the produced cationic surfactant, the content (mass%) of impurities (cations of free amine, amine monomethyl sulfate, and triethanolamine), pH measurement, and appearance evaluation were performed as follows. Went. The results are shown in Table 4.

表１において、エステル化モル比は、脂肪酸メチルエステル混合物のモル数／トリエタノールアミンのモル数、で計算されるモル比である。

In Table 1, the esterification molar ratio is a molar ratio calculated by the number of moles of fatty acid methyl ester mixture / number of moles of triethanolamine.

表２において、エステル化モル比は、脂肪酸メチルエステル混合物のモル数／トリエタノールアミンのモル数、で計算されるモル比である。

In Table 2, the esterification molar ratio is a molar ratio calculated by the number of moles of fatty acid methyl ester mixture / number of moles of triethanolamine.

表３において、カチオン化モル比は、アルカノールアミン脂肪酸エステル混合物のモル数／ジメチル硫酸のモル数、で計算されるモル比である。

In Table 3, the cationization molar ratio is a molar ratio calculated by the number of moles of alkanolamine fatty acid ester mixture / number of moles of dimethyl sulfate.

表４において、カチオン化モル比は、アルカノールアミン脂肪酸エステル混合物のモル数／ジメチル硫酸のモル数、で計算されるモル比である。

In Table 4, the cationization molar ratio is a molar ratio calculated by the number of moles of alkanolamine fatty acid ester mixture / number of moles of dimethyl sulfate.

  From the results of Tables 1 to 4, the examples in which the alkanolamine content is 1.5% by mass or less and the trifatty acid ester content is 55% by mass or less are impurities as compared with the comparative example. It was found that the pH was substantially constant, and the appearance was also excellent.

The method for producing a cationic surfactant of the present invention can produce a surfactant with few impurities, and thus can be widely used in various fields, such as a high-quality softener for clothing and a hair conditioning agent. It can use suitably for manufacture of the base of this. Since the cationic surfactant of the present invention has few impurities, it can be widely used in various fields, and can be suitably used for a base such as a high-quality clothing softener and a hair conditioning agent.

Claims (4)

A method for producing a cationic surfactant comprising reacting at least one reaction raw material containing a compound represented by the following structural formula (1) with a dialkyl sulfuric acid in the absence of a solvent,
The reaction raw material has a hydroxyl value of 110 (mgKOH / g) or less, and in the structural formula (1), A is represented by R ² OCOR ³ and B is represented by R ⁵ OCOR ^6. A compound containing 55% by mass or less of the compound based on the total amount of the reaction raw materials.

However, the structural formula (1), A is an alkyl ^group, an R 1 OH, or ^R 2 OCOR ^3, B represents an alkyl ^group, R 4 OH, or ^R 5 OCOR ^6, C is R ⁷ represents OCOR ⁸ . R ¹ , R ² , R ⁴ , R ⁵ and R ⁷ may be the same or different from each other, each represents an alkylene group or an alkenylene group, and R ³ , R ⁶ and R ⁸ are It may be the same or different and represents an alkyl group or an alkenyl group.   The method for producing a cationic surfactant according to claim 1, wherein the reaction raw material contains alkanolamine in an amount of 1.5% by mass or less based on the total amount of the reaction raw material.   3. The molar ratio of the total amount of the compound represented by the structural formula (1) and the alkanolamine to the dialkyl sulfate is 1: 0.97 to 1: 1. A method for producing a cationic surfactant. A cationic surfactant produced by the method for producing a cationic surfactant according to claim 1.