JPH10251972A - Hydrolysis inhibitor for cationic surfactant and cationic surfactant composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a softening agent composition that causes little environmental pollution and has excellent performance in both of its functions and costs by providing a hydrolysis inhibitor for cationic surfactant bearing ester linkage. SOLUTION: This cationic surfactant composition contains 65-80wt.% of a cationic surfactant bearing ester linkage and 2-12wt.% of water and includes 100-500ppm of a hydrolysis inhibitor for a cationic surfactant bearing ester linkage and having at least one of watersoluble alkali metal salt and water-soluble alkaline earth metal salt. This composition contains a lower alcohol as a solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a hydrolysis inhibitor for a cationic surfactant having an ester bond, and a cationic surfactant composition having an ester bond containing the hydrolysis inhibitor.

[0002]

2. Description of the Related Art Conventionally, a dialkyl cation surfactant having a long chain has been used as a fabric softener base, but the surfactant has poor biodegradability and may contaminate the discharged environment. Was high. For this reason, cationic surfactants having an ester bond have come to be used as a fabric softener base. The cationic surfactant includes, for example, diester quaternary ammonium compounds listed as softening compounds in JP-A-1-249129, U.S. Pat. No. 4,767,547, and JP-T-8-507766. There is. However, a cationic surfactant having an ester bond is easily hydrolyzed at an ester bond site.
It is necessary to maintain quality until it is used, and there is a disadvantage that when hydrolysis occurs, fatty acids are produced as by-products, which adversely affects the storage stability of the softener.

[0003] For this reason, it is necessary to handle the cationic surfactant having an ester bond after its production until the use thereof until the time of use. Therefore, the following two methods have been used. (1) First, this is a method in which the water content of a composition containing a cationic surfactant is extremely reduced, and a lower alcohol is used as a solvent. However, in this method, a lower alcohol is used as a solvent in place of water, so that the cost is high. Further, since the flammability of the composition is high, predetermined equipment is required in both production and handling, and as a result, the cost is further increased. Increase. (2) There is also a method of suppressing hydrolysis by handling at a low temperature from the time of manufacture to the time of use. However, in addition to the cost caused by handling at low temperature, there is a problem that the flexibility performance is reduced because the cationic surfactant is produced using an alkylating raw material having a high iodine value. As described above, when a cationic surfactant having an ester bond is used in the softener composition, problems have occurred in both the function and the cost of the softener composition.

[0004]

The present invention solves the problems of the prior art as described above by providing a hydrolysis inhibitor of a cationic surfactant having an ester bond in a softener composition. It is an object of the present invention to provide a softener composition which is less likely to cause environmental pollution and has excellent performance in both function and cost.

[0005]

Means for Solving the Problems The present inventors have studied to solve the above problems. As a result, it is considered that water contained in the cationic surfactant composition having an ester bond hydrates to a cation and causes hydrolysis of the ester bond. When a neutral salt having excellent solubility in water was added, it was found that the neutral salt deprives the cation of water of hydration and suppresses hydrolysis. And it was found that by adding at least one of a water-soluble alkali metal salt and a water-soluble alkaline earth metal salt, hydrolysis of a cationic surfactant having an ester bond can be efficiently suppressed.
The present invention has been made based on this finding. Accordingly, the present invention provides a hydrolysis inhibitor for a cationic surfactant having an ester bond, comprising at least one of a water-soluble alkali metal salt and a water-soluble alkaline earth metal salt. The present invention further provides a cationic surfactant composition comprising 65 to 80% of a cationic surfactant having an ester bond and 2 to 12% of water, wherein the hydrolysis inhibitor 100
The present invention provides a cationic surfactant composition, characterized in that the composition comprises about 500 ppm. In this specification, "%"
Means% by weight unless otherwise specified.

The water-soluble salts used in the present invention are alkali metal salts and alkaline earth metal salts of inorganic acids, and alkali metal salts and alkaline earth metal salts of lower organic acids having 1 to 4 carbon atoms. These salts can be used alone or in combination. Preferred examples of these water-soluble salts include lithium chloride, sodium chloride, potassium chloride, lithium sulfate, sodium sulfate, potassium sulfate, lithium, sodium and potassium salts of phosphoric acid and its homologs, magnesium chloride, calcium chloride, and the like. Inorganic salts of
There are organic salts such as lithium, potassium, sodium, calcium and magnesium such as acetic acid, propionic acid, butyric acid, succinic acid, maleic acid, tartaric acid and citric acid.
The salt of the organic acid is considered to cause double decomposition with the cation of the active ingredient, but there is no particular problem. The addition amount of the water-soluble salt is 50 to 100 with respect to the cationic surfactant composition.
0 ppm, preferably 100-500 ppm, particularly preferably 150-450 ppm. The reason why the lower limit of the addition amount is set to 50 ppm or more is to exhibit a suppressing effect, and the upper limit is set to 1000 ppm, because the upper limit of the solubility in the cation composition causes the salt to be precipitated if added more. It is.

In the present invention, water is added as a component of the cationic surfactant composition in an amount of 2 to 12%, preferably 3 to 9%, particularly preferably 4 to 7%. In the present invention, by adding a predetermined amount of water to the composition, the amount of lower alcohol to be added can be reduced and the cost can be reduced, the flammability of the composition can be reduced and handling can be performed safely and easily, and There is an effect that the viscosity can be easily adjusted. In addition, since the cation is an amphipathic substance, it becomes difficult to crystallize when an appropriate amount of water is added, and the solubility increases, so that handling at a lower temperature becomes possible.

[0008] The amount of water to be added is specified because if it is lower than 2%, the hydrolysis of the ester bond is reduced and it is not necessary to suppress the hydrolysis. This is because the composition becomes difficult to handle. The lower alcohol used in the present invention is a monohydric or dihydric alcohol having 1 to 5 carbon atoms. Examples of the lower alcohol include methanol, ethanol,
There are isopropyl alcohol, propylene glycol, ethylene glycol, and mixtures thereof. The lower alcohol is the balance of the other components as it is used as a solvent and is approximately 10 to 40% of the composition. Also, examples of stabilizers added as needed to the composition of the present invention,
Ascorbic acid, propyl gallate, butylated hydroxytoluene, tertiary butylhydroquinone, natural tocopherols, butylated hydroxyanisole, sodium borohydride, hypophosphorous acid, isopropyl citrate, gallic acid and C ₈ -C ₂₂ alkanols And esters.

The cationic surfactant having an ester bond used in the present invention refers to a biodegradable quaternary ammonium compound having at least one ester bond. Among these compounds, quaternary ammonium salts of alkanolamine esters disclosed in Japanese Patent Application Laid-Open No. Hei 7-138221 and Japanese Patent Application No. 8-323660 filed by the present applicant are particularly preferable. In the following description, a quaternary ammonium salt of an alkanolamine ester is referred to as a quaternary ammonium salt unless otherwise specified. Next, the quaternary ammonium salt will be described. The quaternary ammonium salt is a product obtained by transesterification of an alkanolamine with a lower alkyl ester of an unsaturated or saturated fatty acid, and is produced, for example, by the method disclosed in Japanese Patent Application Laid-Open No. 7-138221. can do. The alkanolamine used for producing the quaternary ammonium salt is usually
As long as it is used for producing a quaternary ammonium salt, it can be used without any particular limitation. In the present invention, alkanolamines of the following formulas (1) to (4) are preferred.

R ¹ R ² N-CH ₂ C (R ³ ) HOH ...... (1) R ¹ N (CH ₂ C (R ³ ) HOH) ₂ ...... (2) N (CH ₂ C (R ³ ) HOH) ₃ ...... (3) R ¹ R ² N-CH ₂ C (OH) HC (OH) H ₂ ...... (4) Wherein R ¹ and R ² are hydrogen, an alkyl group, an alkenyl group, a hydroxyalkyl group, an alkoxyalkyl group, an aminoalkyl group, an N-substituted aminoalkyl group, an amidoalkyl group or an N-substituted amidoalkyl group, R ¹ and R ² may be the same or different, and at least one is a substituent other than hydrogen, and R ³ is hydrogen or a methyl group.

Specific examples of the alkanolamine include triethanolamine, methyldiethanolamine, ethyldiethanolamine, propyldiethanolamine, butyldiethanolamine, octyldiethanolamine, decyldiethanolamine, dodecyldiethanolamine, tetradecyldiethanolamine,
Hexadecyldiethanolamine, stearyldiethanolamine, oleyldiethanolamine, dimethylethanolamine, diethylethanolamine, dipropylethanolamine, dibutylethanolamine, diisobutylethanolamine, dioctylethanolamine, didecylethanolamine, didodecylethanolamine, ditetradecylethanolamine , Dihexadecyldiethanolamine, distearylethanolamine, dioleylethanolamine, N-methyl, N-
(2-Hydroxyethyl) propylenediamine, N-methyl, N- (2-hydroxyethyl) ethylenediamine, 3-dimethylaminopropyleneglycol, 3-diethylaminopropyleneglycol and the like.

The unsaturated or saturated fatty acid or fatty acid lower alkyl ester used for producing the quaternary ammonium salt is not particularly limited as long as it is usually used for producing a quaternary ammonium salt. can do. Specific examples of fatty acids or lower alkyl esters of fatty acids include caprylic acid, capric acid, lauric acid, myristic acid, stearic acid, arachidonic acid,
Behenic acid, dimethyloctanoic acid, butylheptylnonanoic acid, methylheneicosanoic acid, octenoic acid, decenoic acid,
Methyl esters of dodecenoic acid, octadecenoic acid, oleic acid, linoleic acid, linoleic acid, elaidic acid, eicosenoic acid, erucic acid, docosenoic acid, tallow fatty acid, coconut oil fatty acid, palm oil fatty acid, palm kernel oil fatty acid, fish oil fatty acid and fatty acid , Ethyl ester, isopropyl ester, n-propyl ester, glyceride, glycol ester and the like. The unsaturated fatty acid may be either a cis-form or a trans-form, or a mixture of both.

The quaternary ammonium salt of the present invention is produced as follows. First, the fatty acid is reacted with an alkanolamine without a catalyst to obtain an amine. The fatty acid lower alkyl ester and the alkanolamine are subjected to a transesterification reaction in the presence of an alkaline catalyst, and the obtained transesterification reaction product is added with an acidic substance to neutralize the alkaline catalyst in the transesterification reaction product. . The obtained amine is quaternized in an alcohol solvent. The production of the quaternary ammonium salt can be performed by a known method disclosed in Japanese Patent Application Laid-Open No. 7-138221. In addition, among the quaternary ammonium salts produced by the above production method,
Preferred for the composition of the present invention are compounds of the following formulas (6) to (9). ^{R 6 R 7 R 8 N-} CH 2 C (R 9) H-OCOR 10 + · X - ...... (6) R 6 R 8 N (CH 2 C (R 9) H-OCOR 10) _{^{2 + · X - ...... (7}} ) R 8 N (CH 2 C (R 9) H-OCOR 10) 3 + · X - ...... (8) R 6 R 7 R 8 ^{_{N-CH 2 C (OCOR 10}} ) H-OCOR 11 + · X - .... (9)

In the above formulas (6) to (9), R ⁶ and R ⁷ are
Hydrogen, an alkyl group, an alkenyl group, a hydroxyalkyl group, an alkoxyalkyl group, an aminoalkyl group, an N-substituted aminoalkyl group, an amidoalkyl group or an N-substituted amidoalkyl group, wherein R ⁶ and R ⁷ are the same or different And at least one is a substituent other than hydrogen, and R ⁹ is hydrogen or a methyl group. Also, R ¹⁰ and R
¹¹ is a linear or branched alkyl or alkenyl group having 1 to 21 carbon atoms, which may be the same or different, and R ⁸ is a methyl group or ethyl introduced with a quaternizing agent. X is Cl, CH ₃ SO ₄ or the like. Further, among these quaternary ammonium salts of formulas (6) to (9), a compound derived from N-methyldiethanolamine (formula (10)) and a compound derived from triethanolamine (1
1) is particularly preferred as the cationic surfactant having an ester bond of the present invention.

[0015] _{(CH 3) 2 N (CH} 2 CH 2 -OCOR 12) (CH 2 CH 2 -OCOR 13) + · X - ... (10) (CH 3) N (CH 2 CH 2 -OCOR 12 ^{_{) (CH 2 CH 2 -OCOR 13}} ) (CH 2 CH-OCOR 14) + · X - ... ( in 11) (10) and (11) in, R ^12, R ¹³ and R ¹⁴ is a linear Or a branched alkyl or alkenyl group having 1 to 21 carbon atoms. The content of the cationic surfactant is 60 to 90%, preferably 70 to 90%, of the composition.
-80%, particularly preferably 65-75%. The reason why the lower limit is set to 60% is that if the amount is less than this, the amount of the solvent must be increased, so that the economical efficiency is deteriorated. This is because the composition becomes high and the composition becomes difficult to handle. In addition, various by-products generated in the process of producing the cationic surfactant are also included as components constituting the composition of the present invention.

[0016]

Next, the present invention will be described in detail with reference to examples and comparative examples. In addition, this invention is not limited to a following example. [Example 1] N, N ditaloyloxy-N, N-dimethylammonium chloride was used as a cationic surfactant having an ester bond. Cationic surfactant solution 1 consisting of 73.3% of this surfactant, 1.03% of tallow fatty acid, 1.0% of free amine and amine salt and about 24% of ethanol
To 00 g, 1% aqueous sodium chloride, 1% aqueous potassium chloride, 0.6% aqueous sodium sulfate, 0.6% aqueous potassium sulfate, 0.6% aqueous magnesium sulfate, 0.6% aqueous magnesium chloride, 0.6% calcium chloride Aqueous solution, 0.6% sodium phosphate aqueous solution, 1
A 5% aqueous solution of sodium acetate, a 1% aqueous solution of sodium succinate, and a 1% aqueous solution of sodium citrate were each added in an amount of 5 g and uniformly dissolved, and then subjected to a hydrolysis test at 55 ° C. for 4 weeks. The hydrolysis amount was determined by fatty acid analysis. Table 1 shows the content of fatty acids before and after the test. The results show that the amount of fatty acid produced is smaller than that of Comparative Example 1, and the hydrolysis inhibitory effect of the hydrolysis inhibitor of the present invention is shown.

Comparative Example 1 N, N Ditaloyloxy-
N, N-dimethylammonium chloride was used as the cationic surfactant. 5 g of water was added to 100 g of a cation solution comprising 73.3% of the surfactant, 1.03% of tallow fatty acid, 1.6% of free amine and amine salt and about 24% of ethanol.
Was added and uniformly dissolved, and then subjected to a hydrolysis test under the same conditions as in Example 1. Table 1 shows the results of fatty acid analysis before and after the test. Also, 1.5 g of water (about 1.
48%) to prepare a composition. As a result, there was a problem that the flammability was increased and the dissolution concentration was high. Also,
When 15 g (about 13.04%) of water was added to 100 g of the cation solution, the viscosity of the composition increased, and the problem of gelation of the composition occurred.

[0018]

Table 1 Hydrolysis test (55 ° C, 4 weeks) and effects of additives Example No. Additives Fatty acid content before and after hydrolysis test (%) % before test% after test Example 1 Sodium chloride 0.99 1.68 Potassium chloride 1.02 1.71 Sodium sulfate 0.97 2.03 Potassium sulfate 1.01 2.08 Magnesium sulfate 0.98 1.94 Magnesium chloride 0.97 2.12 Calcium chloride 0. 99 2.73 Sodium phosphate 0.98 2.65 Sodium acetate 1.00 3.02 Sodium succinate 0.98 3.09 Sodium citrate 1.02 2.97 Comparative Example 1 Blank 0.97 7.54 Water 1.5g 0.99 1.59

Example 2 N, N Ditaloyloxy-N
Methyl-N hydroxyethyl ammonium methosulfate was used as the cationic surfactant. The surfactant
73.8%, tallow fatty acid 1.25%, free amine and amine salt 1.
To 100 g of a cationic solution consisting of 95% and about 23% of ethanol, 1% aqueous solution of sodium chloride, 1% aqueous solution of potassium chloride, 0.6% aqueous solution of sodium sulfate, 0.6%
Potassium sulfate aqueous solution, 0.6% magnesium sulfate aqueous solution, 0.6% magnesium chloride aqueous solution, 0.6% calcium chloride aqueous solution, 0.6% sodium phosphate, 1% sodium acetate aqueous solution, 1% sodium succinate aqueous solution, 1% Of sodium citrate was added and dissolved uniformly, and then subjected to a hydrolysis test at 55 ° C. for 4 weeks. The hydrolysis amount was determined by fatty acid analysis. Table 2 shows the fatty acid contents before and after the test. The results show that the amount of fatty acid produced is smaller than that of Comparative Example 1, indicating the hydrolysis inhibiting effect of the hydrolysis inhibitor of the present invention.

Comparative Example 2 N, N ditaroyloxy-Nmethyl-Nhydroxyethylammonium methosulfate was used as a cationic surfactant. 5 g of water was added to 100 g of a cation solution consisting of 73.8% of the surfactant, 1.25% of tallow fatty acid, 1.95% of free amine and amine salt, and about 23% of ethanol, and the mixture was uniformly dissolved.
A hydrolysis test was performed under the same conditions as described above. Table 2 shows the results of fatty acid analysis before and after the test. The cation solution 1
When the composition was prepared by adding 1.5 g (about 1.48%) of water to 00 g, there was a problem that the flammability was increased and the dissolution temperature was increased. Further, when 15 g (about 13.04%) of water was added to 100 g of the cation solution, the viscosity of the composition became high and the problem of gelation of the composition occurred.

[0021]

Table 2 Hydrolysis test (55 ° C., 4 weeks) and fatty acid content (%) before and after additive effect hydrolysis test Example No. Additives Before test% After test% Example 2 Sodium chloride 1 .21 1.98 Potassium chloride 1.18 1.91 Sodium sulfate 1.17 2.33 Potassium sulfate 1.23 2.19 Magnesium sulfate 1.20 2.14 Magnesium chloride 1.19 2.42 Calcium chloride 1.20 2.93 sodium phosphate 1.22 3.12 sodium acetate 1.18 3.33 sodium succinate 1.19 3.28 sodium citrate 1.22 3.97 Comparative Example 2 blank 1.20 8.13 water 1 0.5g 1.18 2.02

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Claims (3)

[Claims] 1. A hydrolysis inhibitor for a cationic surfactant having an ester bond, comprising at least one of a water-soluble alkali metal salt and a water-soluble alkaline earth metal salt. 2. A cationic surfactant composition comprising 65 to 80% of a cationic surfactant having an ester bond and 2 to 12% of water, wherein the hydrolysis inhibitor 1 according to claim 1 is used.
A cationic surfactant composition comprising from 0.00 to 500 ppm. 3. The cationic surfactant composition according to claim 2, further comprising a lower alcohol as a solvent.