JPS6051520B2 - Method for producing light-colored surfactant aqueous solution or slurry - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for bleaching sulfate ester salts of higher alcohols or ethoxylates thereof.

More specifically, it relates to a method for obtaining a light-colored surfactant aqueous solution or slurry by reacting hydrogen peroxide or a hydrogen peroxide generating substance with a carboxylic acid anhydride on a sulfuric ester salt aqueous solution or slurry of a higher alcohol or its ethoxylate. It is something. Sulfate ester salts of higher alcohols or their ethoxylates have excellent detergency and foaming power, and are widely used as raw materials for kitchen detergents, clothing detergents, and shampoos, but at the same time, these products have unique colorful colors. Because of this, its light color and inertness with pigments are important factors in terms of commercial value. Industrially produced sulfate ester salts of higher alcohols or their ethoxylates have a pale yellow color and are normally used as is, but they can be used as raw materials for high-end products with a cosmetic-like color tone. In such cases, bleaching is applied.

In this case, bleaches are broadly classified into chlorine-based and oxygen-based bleaches. Hypochlorous acid, chlorous acid, or their salts have traditionally been used as chlorine bleaches due to their bleaching effects, but skin sensitization has been pointed out, and the industry is moving towards self-regulation. The current situation is as follows. On the other hand, hydrogen peroxide, which is a typical oxygen bleaching agent, has a low bleaching effect and must be used in large quantities to lighten the color, which is economically disadvantageous and leaves a large amount of hydrogen peroxide remaining. There were problems such as dryness and generation of a pungent odor in the slurry. The present inventors have repeatedly conducted various studies regarding the bleaching of sulfate ester salts of higher alcohols or their ethoxylates, and found that by using hydrogen peroxide together with a specific carbonic acid anhydride, the above-mentioned hydrogen peroxide and chlorine bleaching The present inventors have discovered that the drawbacks of conventional bleaching agents can be overcome and a bleaching product with high commercial value can be obtained, leading to the completion of the present invention.

That is, according to the present invention, hydrogen peroxide or a hydrogen peroxide generating substance is added to a surfactant aqueous solution or slurry obtained by sulfonating a higher alcohol or its ethoxylate with sulfur trioxide or chlorosulfonic acid and then neutralizing it. Provided is a method for producing a light-colored aqueous surfactant solution or slurry, which is characterized by reacting succinic anhydride or benzoic anhydride with succinic anhydride or benzoic anhydride.

In the present invention, the carboxylic anhydride used together with hydrogen peroxide or a hydrogen peroxide generating substance is succinic anhydride or benzoic anhydride (hereinafter also simply referred to as carboxylic anhydride).
The products obtained using benzoic anhydride and succinic anhydride according to the present invention do not produce fatty acid odor even under acidic conditions, and therefore can be applied under a wide range of acidic, neutral and alkaline conditions.

The benzoic anhydride used in the present invention is hardly soluble in an aqueous solution or slurry of a higher alcohol or its sulfate salt of ethoxylate 1, but its good dispersibility makes it possible to shorten the bleaching time. In addition, the by-product benzoate exhibits an antibacterial effect against common bacteria, and has the advantage of providing a product with antibacterial properties.

The higher alcohols used as raw materials to be treated in the present invention include higher alcohols obtained by reducing natural animal and vegetable oils,
Alternatively, it may be a synthetic higher alcohol having 6 to 20 carbon atoms and having a straight or branched chain obtained by the Ziegler method, the oxo method, the direct oxidation method of paraffin, or the like.

Further, the ethoxylate of a higher alcohol used as a raw material to be treated in the present invention is obtained by adding ethylene oxide to the higher alcohol in an average addition mole number of 0 to 10. Ru. These higher alcohols or ethoxylates are sulfonated, neutralized and applied in the form of sulfate ester salts in order to make them surfactants with increased detergency and foaming power; in this case, sulfonated - Sulfur trioxide or chlorosulfonic acid is used as the agent, and conventional alkaline substances such as hydroxides, oxides, and carbonates of alkali metals and alkaline earth metals are used as the neutralizing agent. , ammonia and alkanolamines are also applicable.

Examples of the hydrogen peroxide generating substance used in the present invention include peroxocarbonate, peroxoborate, and sodium peroxide, and any substance can be used as long as it can generate hydrogen peroxide in the reaction system.

The hydrogen peroxide or hydrogen peroxide generating substance and the carbonic anhydride used in the present invention can be added after the neutralization reaction described above, but in some cases,
After sulfonation, it is also possible to add hydrogen peroxide or a hydrogen peroxide generating substance and then, after neutralization, to add the carboxylic acid anhydride.

The amount of carboxylic anhydride used in the present invention is 0.5 mol or more per hydrogen peroxide or 1 mol of H2O2 of the hydrogen peroxide generating substance. 1. When by-product carboxylic acid is not required.
The amount is preferably in the range of 0 to 2 moles. The bleaching effect does not differ much depending on the order in which hydrogen peroxide or a hydrogen peroxide-generating substance and carboxylic anhydride are added first, but carboxylic anhydride gradually becomes hydrated when kept in an aqueous solution for a long time. Since it decomposes and changes into a carboxylic acid that has poor reactivity with hydrogen peroxide, it is preferable to add it after adding hydrogen peroxide or a hydrogen peroxide-generating substance in order to use this substance effectively.

The amount of hydrogen peroxide or hydrogen peroxide generating substance used varies depending on the desired color tone of the surfactant aqueous solution or slurry, but is usually 0.001 to 1.0% by weight (H2O
2 conversion).

The bleaching temperature is 20 to 90°C, preferably 60 to 70°C from the viewpoint of bleaching effect, workability, and product quality. The longer the bleaching time, the better the bleaching effect, but 20 to 4 powders is appropriate. If it is shorter than this range, the bleaching effect will be small.
Bleaching according to the present invention is achieved via the carboxylic acid peroxide produced by the reaction of hydrogen peroxide with a carboxylic acid anhydride, but heretofore, in bleaching of this type of surfactant,
There is no known method that utilizes the reaction between rubonic acid anhydride and hydrogen peroxide. When bleaching is carried out according to the present invention, the resulting aqueous solution or slurry of a sulfuric ester salt of a higher alcohol or its ethoxylate is light in color and has significantly increased commercial value. When bleaching according to the present invention, it is possible to obtain a higher bleaching effect than when using hydrogen peroxide alone, so the amount of hydrogen peroxide used can be significantly reduced, and the bleaching time can also be significantly shortened. Furthermore, when residual peroxide is removed by reaction with pentasulfite, the amount of sulfite used can be significantly reduced.

Furthermore, when higher alcohols or their ethoxylates are sulfonated using a continuous sulfonation apparatus, first a predetermined amount of hydrogen peroxide or a hydrogen peroxide generating substance is continuously added and mixed to the obtained sulfuric ester. It is best to bleach with hydrogen peroxide under acidic conditions, then neutralize it, add carboxylic anhydride, react with the remaining hydrogen peroxide, and bleach with the resulting organic peroxide. One.

By adopting such a bleaching method, the bleaching efficiency can be significantly increased, and the amount of hydrogen peroxide or hydrogen peroxide-generating substances used can be significantly reduced compared to the conventional case of using hydrogen peroxide alone. and a significant reduction in bleaching time can be achieved. Next, the present invention will be explained in more detail with reference to Examples, in which the color tone and bleaching rate are based on the following measuring method. That is, the color tone is determined by adding the test solution to 10×2 Cyfr$L.
Using a spectrophotometer with pure water in a quartz cell as a control,
It is shown as the 100@ value of the absorbance (-10 gT) measured under the conditions of a wavelength of 420 mμ and a slit width of 0.15 Tnm.

Incidentally, the bleaching rate is calculated using the following formula.

Example 1 An oxo alcohol having 12 to 13 carbon atoms (product name: Dovanol 2) was prepared using an industrial-scale sulfuric acid anhydride continuous flow thin film sulfonation equipment with an average number of added moles of ethylene oxide of 3.01 and a carbon number of 12 to 13.
After sulfonating the higher alcohol ethoxylate in 3),
Further, it was continuously neutralized with an aqueous sodium hydroxide solution to give an active ingredient of 28.0% and a pH of 7.5. Color tone 120 (7) AES-N
An aqueous solution was obtained.

Add 0.03% (H2O2) 35% hydrogen peroxide aqueous solution to this.
After adding (converted) and stirring uniformly, 0.2% of a specified carboxylic acid anhydride was immediately added, and the color tone after stirring at 60° C. for 1 hour was evaluated. In the test whose results are shown in Table 1, Experiment No. In the case of the carboxylic acid anhydrides shown in Nos. 6 to 9, the bleaching rate was only slightly improved;
l), propionic anhydride (Experiment No. 2), and isovaleric anhydride (Experiment No. 3) generate odor under acidic conditions, whereas succinic anhydride (Experiment No. 4) and benzoic anhydride In the case of acid (Experiment No. 5), it does not have the above-mentioned disadvantages and gives a good product with a high bleaching rate and no odor. Example 2 Using the sulfonation equipment shown in Example 1, after sulfonating higher alcohol ethoxylate of oxo alcohol (trade name: Dovanol 25) with an average number of added moles of ethylene oxide of 3.01 and 12 to 15 carbon atoms. , processed in the same manner as in Example 1, containing 28% of active ingredient and PHLO. 5. An AES-Na aqueous solution with a color tone of 133 was obtained.

To this was added 0.06% of 35% hydrogen peroxide (H2O2 equivalent) and 0.4% of succinic anhydride or benzoic anhydride, and after stirring for 70'Cl2, the amount of residual peroxide determined by iodometry was On the other hand, after removing residual peroxide by adding 1.02 times mol of acidic sulfite sorter,
The color tone and mirabilite content were measured. The results are shown in Table 2. Comparative Example 1 35% hydrogen peroxide was added to the AES-Na aqueous solution obtained in Example 2 at 0.06% or 0.15% (both H2O).

After stirring at 70° C. for 1 hour, residual hydrogen peroxide was removed according to Example 2, and the color tone and mirabilite content were measured. The results are shown in Table 3. In the case of bleaching alone with hydrogen peroxide, the color tone was poorer than in Example 2, and the amount of mirabilite was significantly large due to the large amount of hydrogen peroxide remaining after bleaching.

Example 3 After sulfating coconut oil reduced alcohol using 1.02 times the molar amount of chlorosulfonic acid, the obtained sulfuric ester was added dropwise to an aqueous sodium hydroxide solution to give PHLO. 30% tuna ingredients,
An AS-Na aqueous solution with a color tone of 200 was obtained.

To this, add 35% hydrogen peroxide to 0.06% (H2O. conversion)
,． Bleaching and residual peroxide were removed according to Example 2 using 0.4% benzoic anhydride, and comparison was made with the case where benzoic anhydride was not used. Example 4 Using the sulfonation equipment shown in Example 1, higher alcohol ethoxylate of oxo alcohol (trade name: Dovanol 25) having an average number of added moles of ethylene oxide of 3.01 and 12 to 15 carbon atoms was sulfonated. Thereafter, 35% hydrogen peroxide and 0.1% (calculated as H2O2) are continuously added to the sulfuric ester for acid bleaching.

Subsequently, after neutralization with aqueous sodium hydroxide solution using a jet mixer, a final slurry containing 0.3% dibasic sodium phosphate, 0.5% sodium benzoate, EDTAO. l%
and succinic anhydride to an aqueous solution containing each at a concentration of 0.05%. 2 at 70'C after preparing the specified amount.
After stirring for 0 minutes, an extremely light-colored slurry with no residual peroxide, 64% active ingredient, 1.27% mirabilite content, and color tone 4 (measured when diluted 2 times) was obtained in accordance with Example 2. In addition, when the remaining peroxide was removed according to Example 2 after production under the same conditions without using succinic anhydride, the mirabilite content and color tone in the slurry were 1.32% and 35 (2 times), respectively. (measured upon dilution).

Claims (1)

[Claims] 1. H_2O
0.001 to 1.0% by weight of hydrogen peroxide or a hydrogen peroxide generating substance in terms of _2, and 0.5 mol or more of succinic anhydride or benzoic anhydride per mol of H_2O_2 of the hydrogen peroxide or hydrogen peroxide generating substance. A method for producing a light-colored aqueous surfactant solution or slurry, characterized by reacting with an acid. 2 0.001 in terms of H_2O_2 for the sulfuric ester obtained by sulfonating higher alcohol or its ethoxylate with sulfur trioxide or chlorosulfonic acid.
After acting with ~1.0% by weight of hydrogen peroxide or hydrogen peroxide-generating substance, it is neutralized, and the neutralized product is treated with 0.5% by weight per mole of hydrogen peroxide or hydrogen peroxide-generating substance. 1. A method for producing a light-colored aqueous surfactant solution or slurry, characterized by reacting with succinic anhydride or benzoic anhydride in a molar or more amount.