JPS6187657A - Preparation of alpha-sulfo-fatty acid ester salt - Google Patents

Abstract

PURPOSE:To prepare the titled compound useful as a detergent and resistant to the lowering of the ester-content with time, with little hydrolysis of the product, easily, by mixing and neutralizing a liquid alpha-sulfo-fatty acid ester with powdery solid carbonate and/or bicarbonate. CONSTITUTION:A liquid alpha-sulfo-fatty acid ester is mixed and neutralized with (A) a powdery solid carbonate and/or (B) bicarbonate to obtain an alpha-sulfo-fatty acid ester salt. The amount of the component A and/or B is 1-150mol, preferably 4-60mol per 1mol of the alpha-sulfo-fatty acid ester. The component A or B is e.g. Na2CO3, K2CO3, NaHCO3, etc. A detergent composition having high hydrolysis resistance and cleaning property can be prepared by mixing the alpha-sulfo-fatty acid ester salt produced by the present process with other detergent components (e.g. spray-dried powder).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing an α-sulfo fatty acid ester salt. More specifically, the present invention relates to a simple and resource-saving method for producing a solid α-sulfo fatty acid ester salt which has a high ester retention rate and whose ester retention group hardly decreases even when added to detergents and stored.

[Conventional technology and its problems]

Although α-sulfo fatty acid ester salts have traditionally had distinctive performance as surfactants for powder detergents, it is well known that they have poor hydrolysis resistance. That is, sulfonated fatty acid esters undergo hydrolysis through a neutralization step with an aqueous alkali solution, detergent slurry formation, and spray drying steps, and furthermore, hydrolysis proceeds orally in spray-dried products.

As a result, α-sulfo fatty acid salt is produced as a by-product, but since α-sulfo fatty acid salt has poor surface activity, it is not preferable for it to be contained in a large amount in the α-sulfo fatty acid ester salt.

In order to prevent hydrolysis, the use of a specific alkaline virgoo (Japanese Patent Publication No. 52-28507), the combination of hindered phenol compounds and hydroxycarboxylic acid salts (Japanese Patent Publication No. 52-28507),
-28163) has been proposed, but it is not sufficiently effective.Also, in the spray drying process, a slurry of α-sulfo fatty acid ester salt and a slurry containing a strong alkaline component are simultaneously sprayed into the space of the same line. However, a method for preventing hydrolysis has also been proposed (Japanese Unexamined Patent Publication No. 58-4-09a). However, this method requires complicated operations, is not resource-saving, and its stability over time is not necessarily satisfactory.

Under these circumstances, we developed a simple and resource-saving method for producing a solid powdered α-sulfo fatty acid ester salt, which has a high ester retention rate and does not hydrolyze over time, as shown by the formula below. was desired.

((M): indicates molar concentration) [Means for solving the problem] In order to solve the above-mentioned problems, the present inventors have conducted extensive research and have developed a liquid α-sulfo fatty acid ester. Mix and neutralize with solid powdered carbonate and/or bicarbonate.

It has been discovered that a solid α-sulfo fatty acid ester salt can be obtained that has a high ester retention rate immediately after neutralization and is resistant to hydrolysis over time.

The present invention has been completed.

Although such dry neutralization techniques for alkylbenzenesulfonic acids have already been known, dry neutralization of α-sulfo fatty acid esters has never been attempted. This was because it was believed that hydrolysis was the biggest problem with α-sulfofatty acid esters, and that hydrolysis was unavoidable in dry neutralization in which α-sulfofatty acid esters were directly neutralized with alkali.

However, if the present inventors directly mixed and neutralized α-sulfo fatty acid ester with solid powdered carbonate and/or bicarbonate within a relatively short period of time, surprisingly little hydrolysis occurred. More surprisingly, K has completed the present invention by discovering that the ester retention rate hardly decreases over time. Furthermore, the method of the present invention is not only simple but also extremely excellent in terms of resource saving, which has been in increasing demand in recent years.

Examples of the α-sulfo fatty acid ester according to the present invention include compounds represented by the following general formula (1).

(In formula (1), R has 8 to 24 carbon atoms, preferably 10 to 24 carbon atoms.
20 straight-chain or branched-chain alkyl groups, and R2 represents a straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. ) The α-sulfo fatty acid ester can be prepared by preparing the fatty acid ester using a known method 1, e.g. 80. It is easily obtained by sulfonation with gas. The fatty acid ester used is a compound represented by the general formula OR10H200R2 (wherein R1 and R2 are as defined above). This fatty acid ester is beef tallow.

It is derived from animal fats and oils such as lard, bone oil, fish oil, and lanolin, and vegetable fats and oils such as coconut oil, palm oil, palm kernel oil, and soybean oil.

For example, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid.

Methyl lignoceric acid, cerotic acid, indecanoic acid, neodecanoic acid, Kundecene rJ:1, indoridecanoic acid, invalmitic acid, isostearic acid, hydrogenated beef tallow fatty acid, coconut oil fatty acid, palm oil fatty acid, palm kernel oil fatty acid, hydrogenated fish oil fatty acid, etc. , ethyl, propyl, isopropyl, butyl, isobutyl, BeC-butyl, tert-
Butyl, pentyl, impentyl, neopentyl, te
Examples include esters such as rt-pentyl, hexyl, inhexyl and the like.

The iodine value (IV) of the fatty acid ester is preferably 1 or less.

In carrying out the present invention, other sulfonic acids and sulfuric esters may be mixed with α-sulfo fatty acid XX til and used for neutralization. Examples of other sulfonic acids and sulfuric esters include
-Sulfo fatty acids, alkyl sulfate esters, alkyl polyoxyethylene sulfate esters, and the like.

Examples of the carbonate and/or hydrogen carbonate as a neutralizing agent used in the present invention include charcoal alkali metal salts and alkaline earth metal carbonates.

Ammonicum carbonate salt, alkanolamine carbonate salt, etc.
Examples of the hydrogen carbonate include alkali metal hydrogen carbonate salts, alkaline earth metal hydrogen carbonate salts, 77monicum hydrogen carbonate salts, and alkanolamine hydrogen carbonate salts. (preferably carbonate), potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, anhydrous salts or aqueous salts, or mixtures thereof.

The amount of carbonate and/or bicarbonate used is α-
The amount is 1 to 150 mol, preferably 4 to 60 mol, per 1 mol of sulfo fatty acid ester. If it is less than 1 mole, the reactivity is poor and the reaction takes a long time, and the neutralized product also becomes a solid lump, making it difficult to granulate it by pulverization.

If the amount exceeds 150 moles, the effect on the reaction will not change, but the amount of carbonate or hydrogen carbonate relative to the α-sulfo fatty acid ester salt is extremely large, and when combining other detergent ingredients to form a detergent composition, it may be difficult to clean. This will cause performance problems.

It is preferable to mix and neutralize liquid α-sulfo fatty acid ester and solid powder carbonate and/or hydrogen carbonate under strong stirring. When the proportion of salt is in the range of 1730 to 1/1 (molar ratio), it is desirable to mix and neutralize under strong shearing force.

In carrying out the present invention, it is also possible to add other components other than α-sulfo fatty acid ester and carbonate and/or hydrogen carbonate within a range that does not impair the effects of the present invention. As for these other ingredients.

Water, sodium hydroxide aqueous solution, sodium silicate or its aqueous solution, high molecular weight organic polymer containing carboxyl group and/or hydroxyl group and its aqueous solution, nonionic surfactant, foam powder stabilizer, bleach, zeolite, Examples include phosphates, sodium sulfate, polyalkylene glycols or aqueous solutions thereof, fragrances, fluorescent dyes, pigments, enzymes, ultraviolet absorbers, and other substances that can effectively act as detergent ingredients.

These other components also include components that facilitate the pulverization of the neutralized product after neutralization or components that have the effect of promoting the neutralization reaction.

Examples of components that facilitate the pulverization of the neutralized product after neutralization include zeolite, phosphate, sodium sulfate, and the like.

In addition, examples of components that have the effect of promoting the neutralization reaction include water, a small amount of hydroxide, IJ cum, and silicic acid.
IJum aqueous solution is mentioned. During the neutralization reaction, the amount of water added is 1 to 6 per mole of α-sulfo fatty acid ester.
0 mol is preferred.

If the amount of water is less than 1 mol, the effect of promoting neutralization is small.

On the other hand, if the amount of water is 60 moles or more, the neutralized product will become paste-like and cannot be crushed, or problems will occur, such as causing hydrolysis of the α-sulfo fatty acid salt. During the neutralization reaction, the number of moles of water added to the α-sulfo fatty acid ester is a value that includes water added alone as well as water contained in other components.

The apparatus used for the neutralization reaction in the present invention is as follows.

It is a strong shearing device similar to a cross-wire type, and can be used in both continuous and batch types. For example, the Honda Continuous Kneader (Honda Iron Works Co., Ltd.) is a continuous kneader.
Multi-purpose continuous mixer (BAKII
: RPKRK NS [0,), KRO kneader (Kurimoto Iron Works Co., Ltd.), Nesco kneader (Fuji Sangyo Co., Ltd.), and the like. All of the above-mentioned crosstalk machines have a mechanism that increases the chance of contact between unneutralized substances, carbonates, and hydrogen carbonates, and are characterized by having a continuous self-cleaning mechanism.

The residence time in these devices depends on the conditions, but is usually
Approximately 5 to 10 minutes is sufficient.

The temperature during neutralization is 30 to 90°C, preferably 40 to 90°C.
The temperature is 70°C.

The cooled neutralized product is a granular or lumpy solid. This neutralized product is ground either alone or mixed with a detergent formulation of Glauber's salt or zeolite fat. Usually 1,500μ or less, preferably 8
Grind to 00μ or less.

When the α-sulfo fatty acid ester salt obtained in the present invention is mixed with other detergent components, a detergent composition with good hydrolysis resistance and cleaning performance can be obtained. Other detergent ingredients may be powder products obtained by separate spray drying. Other detergent ingredients include
Examples include various surfactants, virgoos, and various additives.

As the surfactant, various anionic surfactants, nonionic surfactants, amphoteric surfactants can be used alone or in combination. Preferred examples of such surfactants are shown below.

(1) Anionic surfactant - Straight chain or branched alkylbenzene sulfonate having an alkyl group with an average carbon number of 10 to 16 - Straight chain or branched alkyl group or alkyl group having an average carbon number of 8 to 20 Alkyl or alkenyl ethoxy sulfate or phosphorus is a salt having an average of 0.5 to 8 moles of ethylene oxide added to each molecule.Alkyl or alkenyl sulfate having an alkyl or alkenyl group with an average carbon filo to 20 Salt or phosphate - Olefin sulfonate having an average of 10 to 20 carbon atoms in one molecule - Alkane sulfonate salt having an average of 10 to 20 carbon atoms in one molecule - An average of 10 to 2 carbon atoms Saturated or unsaturated fatty acid salt in one molecule - Alkyl or alkenyl ethoxy carbon having an alkyl group or alkenyl group with an average carbon number of 1 to 2 o, and an average of 0.5 to 8 moles of ethylene oxide added to each molecule Acid acid salt (11) Nonionic surfactant - Polyoxyethylene alkyl or alkyl having a primary or secondary alkyl group or alkenyl group with an average carbon number of 8 to 2 o and to which 3 to 12 moles of ethylene oxide are added. Polyoxyethylene alkylphenyl ether having an alkyl group with an average carbon number of 8 to 12 and added with 3 to 12 moles of ethylene oxide.Higher fatty acid alkanolamide represented by the following formula or its alkylene oxide adduct ( IIO amphoteric surfactant - Alkylamine oxide represented by the following formula R, - N→0 (wherein R is an alkyl group or alkenyl group having 10 to 20 carbon atoms, R6 and R7 are carbon atoms 1 to 20) 3, which may be the same or different) - Alkylbetaine or sulfobetaine RQ represented by the following formula (in the formula, R8 represents an alkyl group or alkenyl group having 10 to 20 carbon atoms, and R91RlG represents a carbon alkyl group of numbers 1 to 4; p is an integer;
Condensed phosphates such as tripolyphosphate, pyrophosphate, metaphosphate, aminopolyacetic acid such as nitrilotriacetate, ethylenediaminetetraacetate, diethylenetriaminepentaacetate, citrate, malate, glycolate, etc. Examples include polymer electrolytes such as oxycarboxylic acid salts, polyacrylic acid, and alkali hydrolyzed salts of vinyl acetate-maleic anhydride copolymers.

Furthermore, sodium silicate, sodium sulfate, etc. may be added as an alkaline agent or inorganic electrolyte, and polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, etc. may be added as a re-staining prevention agent.

In addition, bleaching agents such as soda percarbonate, and fluorescent whitening agents.

Additives such as fragrances, pigments, enzymes, bluing agents, fabric softeners, foam control agents, etc. can also be blended. [Effects of the Invention] The ester retention rate is high immediately after addition, and even when stored in a moisture-proof carton container in a thermostatic chamber at 35° C., oral hydrolysis is hardly observed or, if at all, minimal.

Furthermore, even if the detergent composition containing the α-sulfo fatty acid ester salt obtained by the method of the present invention is stored in a thermostatic chamber at 35° C. in a moisture-proof carton container, the oral hydrolysis of the α-sulfo fatty acid ester salt will not occur. Almost no or only a small amount was observed, and no deterioration in cleaning performance was observed.

〔Example〕

Examples are shown below to further explain the present invention in detail. Production Example 1
(Production of α-sulfo fatty acid ester) Hardened beef tallow fatty acid methyl was reacted with SO in a thin film type sulfonation apparatus at a molar ratio of 1.2 and a reaction temperature of 50 to 60°C. This sulfonated product was immediately introduced into a cyclone for gas-liquid separation, and then passed through a heat exchanger and aged at 100°C for 30 minutes. After cooling the sulfonated product to 55°C, 5% by weight of methanol was added to the sulfonated product, and the product was aged at 60°C for 30 minutes (this is referred to as α-sulfofatty acid ester color).

Example 1 The α-sulfofatty acid ester color obtained in Production Example 1 and the components shown in Table 1 were supplied in quantitative amounts, mixed and neutralized using a Kurimoto KRO Nigu. The residence time was 5-7 minutes, and the temperature during neutralization was 40-65°C. After the neutralization was completed, the neutralized product was ground into granules.

The ester retention rate of the granules was as shown in Table 1.

Furthermore, the obtained granules were placed in a moisture-proof carton container at 35°C.
It was stored in a constant temperature room at 50°C. The ester retention rates after one month and after three months were as shown in Table 2.

The ester retention rates of all samples are as follows: Comparative Example 1 Sample X
(α-sulfofatty acid ester A, neutralized with a total of 2.5% NaOH water; sulfonation rate 97.5%, ester retention rate 95.6%).

Table 2 It can be seen that the hydrolysis of all samples is much smaller than that of Comparative Example 2 below.

Example 2 Samples F and G obtained in Example 1 were mixed with powder obtained by spray-drying other formulation component slurries in advance to form detergent compositions 2-1 and 2-2 shown below. was prepared. This detergent composition was placed in a moisture-proof carton container, -5°C, 40°C,
It was stored in a constant temperature room at 50°C, and the ester retention rate was measured after one month and after three months. The results are shown in Table 3.

Mixture 2-12-2 sample
F15 wt% - wt% sample
G-15 Dodecylbenzene Yuyaho 7 members soda 10 1゜zeo
light 20
20 Sodium carbonate -27 Sodium bicarbonate 27.55 - Moisture 55 Sodium silicate 55 Compound 2-12-2% by weight
Weight% mirabilite 17.35 1
8.7 Firefly light dye 0.3
0.4 Table 3 Comparative Example 1 Neutralized product K, detergent slurry 17-1, and spray-dried product M were prepared using α-sulfo fatty acid ester A obtained in Production Example 1.

・α-sulfo fatty acid ester A 2.5% Ha Oil for neutralization
Neutralized with a water-soluble ridge.

・Detergent slurry 17-L (solid content 45wt%, moisture 57
wt%) Solid content composition Na 2 s ox 25 Spray-dried product M Detergent slurry 17 L was spray-dried using a countercurrent spray transfer line device.

Table 4 shows the results of measuring the retention rates of the three types of esters mentioned above.

The diester retention rate was significantly reduced due to detergent slurry formation and spray transition, which shows the importance.0 Comparative Example 2 The spray-dried product M of Comparative Example 1 was heated to -5°C and 40°C.

Store in a moisture-proof carton container in a constant temperature room at 50°C.

Ester retention was measured. The results are shown in Table 5.

Table 5 At 40 to 50°C, hydrolysis occurs, resulting in the formation of α-sulfo fatty acid salts, and the cleaning performance is significantly reduced, indicating that this method is practically difficult to implement industrially.

Applicant's agent: Kaoru Furuya Proposed proceedings (self-proposal) November 16, 1980 1, Indication of the case Patent Application No. 1983-209293 2.51 Name of Ming Method for producing α-sulfo fatty acid ester salts 3. Relationship with the case of the person making the amendment Patent applicant (091) Kao Soap Co., Ltd. 4, Column 8 of the detailed explanation of the invention in the agent's specification, Contents of the amendment (1) "On page 21, line 12 of the specification" sample F” to “α−゛(1
) "Sample G" on page 21, line 13 is defined as [α-sulfolipid costate lu (in sample G)].

(1) In the third line of page 23, "in neutralized product" is corrected to "α-sulfo fatty acid ester salt in neutralized product".

Claims (1)

[Scope of Claims] 1. A method for producing an α-sulfo fatty acid ester salt, which comprises mixing and neutralizing a liquid α-sulfo fatty acid ester with a solid powdered carbonate and/or hydrogen carbonate. 2. The method for producing an α-sulfo fatty acid ester salt according to claim 1, wherein the amount of carbonate and/or hydrogen carbonate used is 1 to 150 mol per 1 mol of the α-sulfo fatty acid ester. 3. The method for producing an α-sulfo fatty acid ester salt according to claim 1, wherein the carbonate or hydrogen carbonate is sodium carbonate or sodium hydrogen carbonate. 4. Mixing α-sulfo fatty acid ester salt obtained by mixing and neutralizing liquid α-sulfo fatty acid ester with solid powder carbonate and/or hydrogen carbonate, and detergent component powder obtained by separate spray drying. A method for producing a detergent, characterized by: