JPH04359098A - Production of high-bulk density detergent composition - Google Patents

Abstract

PURPOSE:To produce the subject composition by mixing a surfactant powder containing an aliphatic lower alkyl ester sulfonic acid salt with an alkaline builder powder and granulating the resultant mixture while preventing hydrolysis of the sulfonic acid salt. CONSTITUTION:(A) A surfactant powder containing an aliphatic acid lower alkyl ester sulfonic acid salt such as an alpha-sulfoaliphatic acid ester sodium salt, capable of providing 1wt.% aqueous solution showing <=pH10 (preferably <=9) and substantially free from an alkaline builder is blended with (B) a powdery alkaline builder. A binder substance is added thereto and the resultant mixture is kneaded, e.g. by a kneader. The resultant kneaded material is granulated, e.g. by the crushing-granulation method, thus giving the objective composition.

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for producing high bulk density detergent compositions by preventing hydrolysis of sulfonate salts of fatty acid lower alkyl esters. BACKGROUND OF THE INVENTION Conventional laundry detergents include a bulking agent (usually mirabilite is used) that hardly contributes to cleaning performance, and the bulking agent is spray-dried to a bulk density of 0.
It was produced as bead-like hollow particles of about 3 g/cc. [0003] However, such detergents have a low specific gravity and a low concentration of active agent, which increases transportation costs and requires a considerable amount of space for storage and display.Furthermore, even in ordinary households, it is difficult to store them. It was difficult to measure. Therefore, recently, a method for manufacturing high bulk density granular detergent that can be cleaned with a small amount of detergent has been proposed (Japanese Patent Laid-Open No. 60-9
No. 6698) is also on the market. On the other hand, sulfonic acid salts of fatty acid lower alkyl esters are derived from natural raw materials and are surfactants with excellent detergency, especially hard water resistance, and high bulk density detergent compositions containing them have been reported. (Japanese Unexamined Patent Publication No. 1982-597). However, when sulfonate salts of fatty acid lower alkyl esters come into contact with alkaline agents in the presence of water, they are hydrolyzed and the ester bonds are broken, resulting in di-salt compounds (neutralization of sulfonated fatty acids) with poor cleaning performance. It changes into a salt (having a carboxylic acid group and a sulfonic acid group). On the other hand, in heavy detergents mainly used for clothing, alkaline builders are essential in order to exhibit the required cleaning power. SUMMARY OF THE INVENTION The present invention aims to prevent the decomposition of the sulfonate of fatty acid lower alkyl ester, which is an excellent surfactant, and to prepare high bulk density detergent compositions containing this active agent. The purpose is to manufacture. Means for Solving the Problems The method for producing a high bulk density detergent composition of the present invention comprises: (a) containing a sulfonate of a fatty acid lower alkyl ester, the pH of an aqueous solution of the sulfonate having a concentration of 1% by weight is 10 or less and substantially no alkali builder, and (
b) Mix powder with alkali builder (c
) It is characterized by adding a binder substance and granulating it. Embodiments of the Invention The sulfonate of fatty acid lower alkyl ester is typically represented by the following formula 1, which is α-
Also called sulfo fatty acid ester salt. ##STR1## (R1: Alkyl group or alkenyl group R2: Lower alkyl group M: Counter ion) Water-soluble salts are used as the counter ion, but alkali metal salts, particularly sodium salts are preferred. [0011] Sulfonic acid salts of saturated fatty acid lower alkyl esters are obtained by sulfonating fatty acid lower alkyl esters of the general formula R1CH2COOR2 obtained by transesterification or esterification of fatty acids, and if necessary, ripening,
Obtained by bleaching and then neutralizing. It can also be obtained by converting a sulfonated fatty acid into a lower alkyl ester. Sulfonic acid salts of lower alkyl esters of unsaturated fatty acids are also used, and are produced in the same manner as above using the same unsaturated fatty acids or lower alkyl esters thereof as starting materials. Sulfonation of fatty acid lower alkyl esters can be carried out using a sulfonating agent such as sulfuric anhydride diluted with an inert gas in a molar ratio of 1 to 2, for example, by the method described in JP-A-58-157763. Usually 50
It can be carried out at temperatures of -100°C. As the sulfonation method, any method such as a thin film sulfonation method or a tank sulfonation method can be adopted. [0014] The sulfonated product is aged to complete the sulfonation, but this aging is carried out at 50 to 100°C for 5 to 1 hour.
It is preferable to stir for 20 minutes. The sulfonated product of fatty acid lower alkyl ester thus obtained was then disclosed in JP-A-50-77.
Publication No. 317, Publication No. 59-25369, Publication No. 59-1
Bleaching can be performed by the method described in Japanese Patent No. 6870. Bleaching can be carried out by first mixing the sulfonated product of fatty acid lower alkyl ester and alcohol, and then immediately adding hydrogen peroxide after both are mixed uniformly. In this case, the amount of alcohol added is 100% of the sulfonated fatty acid lower alkyl ester.
It is preferably 5 to 30 parts by weight, more preferably 10 to 20 parts by weight. If this amount is less than 5 parts by weight, the bleaching effect may not be sufficient;
If the amount exceeds 1 part by weight, it may cause a decrease in the purity of the sulfonated fatty acid lower alkyl ester obtained. Note that alcohols having 1 to 6 carbon atoms are preferably used, and specific examples include methanol, ethanol, isopropyl alcohol, and butanol. These alcohols preferably have a low water content and a purity of 95% by weight or more. [0016] After adding alcohol and stirring to mix uniformly, H2O2 is added for bleaching, and the amount of H2O2 added is as follows:
Preferably 0.2 to 10 parts by weight per 00 parts by weight,
More preferably, it is 1 to 5 parts by weight. If this amount is less than 0.2 parts by weight, the bleaching effect may not be sufficient;
Even if the amount exceeds 0 parts by weight, the bleaching effect remains unchanged and economic benefits are unlikely to occur. [0017] The bleaching temperature is preferably 50 to 100°C, and if bleaching is carried out at this temperature, the bleaching can be completed in 5 to 120 minutes. If it is lower than 50°C, bleaching will take a long time, while if it is higher than 100°C, the color tone may return after bleaching and the color tone may deteriorate. In this way, a light-colored sulfonated product of fatty acid lower alkyl ester was obtained, which was disclosed in JP-A-57-
If neutralized with an alkaline aqueous solution according to the method described in Publication No. 7462, the sulfonate of fatty acid lower alkyl ester (α
-sulfofatty acid alkyl ester salt) can be obtained. [0019] The number of carbon atoms in the fatty acid residue (R1CHCOO) of the fatty acid lower alkyl ester sulfonate is 8 to 22.
is suitable, preferably 12-18. The lower alkyl group (R2) preferably has 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. [0020] As the sulfonate of fatty acid lower alkyl ester, those having a specific carbon number as shown in (a) and (b) below are also used (a)/(b) = 1/9 to 6/4, especially 2 /
It is preferable to combine them in a weight ratio of 8 to 5/5 from the viewpoint of solubility of the detergent composition. (a) Fatty acid residues have 12 to 14 carbon atoms (b) Fatty acid residues have 16 to 18 carbon atoms 002
1] This fatty acid lower alkyl ester sulfonate generally contains α-sulfo fatty acid disalt (R2=M in the above formula 1) in a subordinate amount, which can be subjected to industrial post-treatment, e.g. with H2O2. It can result from hydrolysis of ester bonds during bleaching or neutralization. This di-salt is usually present in industrial products in amounts of 1 to 10% by weight, without impairing the effectiveness of the product. The fatty acid lower alkyl ester sulfonate is incorporated in the final detergent composition in an amount of 3 to 30% by weight, preferably 5 to 20% by weight. Sulfonic acid salts of fatty acid lower alkyl esters are industrially obtained as 50 to 70% aqueous solutions containing some impurities such as sodium sulfate. When attempting to powderize this aqueous solution as a single sulfonate of fatty acid lower alkyl ester, it is necessary to remove water to 5% or less, preferably 3% or less. Therefore, it is possible to add a neutral builder such as zeolite or sodium sulfate to a sulfonate slurry of fatty acid lower alkyl ester, and remove water from this slurry by vacuum drying, spray drying, etc. to obtain active agent powder. desirable. This makes it possible to obtain active agent powder that is easy to handle even with a relatively large amount of moisture, is advantageous in terms of energy, and prevents decomposition of the sulfonate of fatty acid lower alkyl ester due to severe heating. The above neutral builder is preferably added to the slurry in an amount of 20 to 90% by weight, more preferably 30 to 70% by weight. [0024] Furthermore, since the sulfonate of fatty acid lower alkyl ester undergoes hydrolysis in an alkaline atmosphere,
It is necessary that the active agent powder does not substantially contain an alkali builder, and that the pH of a 1% by weight aqueous solution of the active agent powder is 10 or less, preferably pH 9 or less. [0025] Next, the activator powder and the alkali builder are powder-mixed, and a binder substance is added and granulated to give a bulk density of 0.5 to 1.1 g/cc and an average particle diameter of 200 to 800 μm. The detergent particles have a high bulk density. According to this granulation process, the contact between the sulfonate of fatty acid lower alkyl ester and the alkali builder is carried out as a mixture of far fewer powders than in a solution system. Hydrolysis of is prevented. Regarding the order of addition, the binder substance is added after mixing the activator powder and the alkali builder, but it is preferable to mix these three substances almost simultaneously. If an alkali builder is added after adding a binder substance to the activator powder and making it into a paste, the chances of the fatty acid lower alkyl ester sulfonate coming into contact with the alkali will increase, and the fatty acid lower alkyl ester sulfonate will come into contact with the alkali. Decomposition of increases. [0026] Furthermore, by increasing the bulk density of the particles,
The surface area per weight of detergent particles is reduced, the amount of moisture absorbed during storage is reduced, and decomposition of fatty acid lower alkyl ester sulfonate due to long-term storage can also be prevented. Furthermore, if a builder (alkali builder, neutral builder) that can contain water as stable water of crystallization is coexisting, the free water in the binder can be maintained as stable water of crystallization when the binder substance is added, and lower fatty acids Hydrolysis of the sulfonate of alkyl ester can be more effectively prevented. [0028] In the above granulation process, for example, the active agent powder and the alkali builder are mixed, a binder substance is added thereto, the mixture is kneaded with a kneader, etc., and the resulting kneaded product is crushed and granulated. This can be done by Alternatively, by spraying a binder substance onto a mixture of active agent powder and alkali builder and stirring and granulating it, or by stirring and granulating relatively large particles, which are further crushed and granulated. It can also be obtained by The binder material is preferably used in an amount of 5 to 20% by weight in the resulting granulated particles. As the alkali builder, carbonates such as sodium carbonate and potassium carbonate, silicates such as sodium silicate and potassium silicate, etc. can be used. It is desirable to be able to contain the free water in the binder as water and to maintain the free water in the binder as stable water of crystallization. Silicates are slightly less effective because they retain water as bound water. [0031] As the binder substance, a highly concentrated aqueous solution of an anionic surfactant, a nonionic surfactant or its aqueous solution, an aqueous solution of a polymer such as polyethylene glycol, polyacrylic acid, polyacrylate, polyvinyl alcohol, or water may be used. Can be done. [0032] Examples of the above-mentioned anionic surfactants include the following. 1) Linear alkylbenzene sulfonate having an alkyl group having an average of 8 to 16 carbon atoms, 2) α-olefin sulfonate having an average of 10 to 20 carbon atoms, 3) Alkyl sulfate having an average of 10 to 20 carbon atoms, [ 4) Alkyl ether sulfate or alkenyl ether sulfate having a linear or branched alkyl group or alkenyl group having an average of 10 to 20 carbon atoms, and to which an average of 0.5 to 8 moles of ethylene oxide is added; 5) Sulfonates of lower alkyl (C1-C3) esters of fatty acids having an average of 8 to 22 carbon atoms; 6) Salts of saturated or unsaturated fatty acids having an average of 10 to 22 carbon atoms. As the counter ion in these anionic surfactants, alkali metal salts such as sodium and potassium are usually suitable. [0036] As the above-mentioned nonionic surfactant, the following are suitable. (1) An EO-added nonionic surfactant prepared by adding an average of 4 to 50 moles of ethylene oxide (EO) to a primary or secondary alcohol having 8 to 18 carbon atoms. (2) EO-P, which is obtained by adding an average of 4 to 25 moles of EO and an average of 3 to 15 moles of propylene oxide (PO) to a primary or secondary alcohol having 8 to 18 carbon atoms.
O-added nonionic surfactant. In addition to the above-mentioned components, the detergent composition of the present invention further contains surfactants, zeolites (aluminosilicate), inorganic builders such as sodium tripolyphosphate and sodium pyrophosphate; sodium citrate, and ethylenediamine. Calcium ion scavenging builders such as sodium tetraacetate, nitrilotriacetate, sodium polyacrylate, sodium acrylate-sodium maleate anhydride copolymer, polyacetal carboxylate; carbonate;
Alkali builders such as silicates; anti-recontamination agents such as carboxymethyl cellulose and polyethylene glycol; viscosity modifiers such as para-toluene sulfonate, toluene sulfonate, xylene sulfonate, and urea; protease, lipase, cellulase, amylase, etc. enzyme; fourth
Softeners such as grade ammonium salts and bentonite; bleaches, fluorescent agents, perfumes, pigments, etc. can be used. The timing of blending these additional ingredients is not particularly limited; for example,
It can be blended during the granulation process, during the production of active agent powder, or by powder blending with high bulk density detergent particles. The final high bulk density detergent composition of the present invention preferably contains 10 to 50% by weight (preferably 15 to 30% by weight) of alkali builder. According to the present invention, when producing a detergent composition containing a sulfonate of a fatty acid lower alkyl ester and an alkali builder, the detergent composition containing the sulfonate of a fatty acid lower alkyl ester and substantially no alkali builder can be used. By preparing a powder containing no active agent, mixing the active agent powder with an alkali builder, adding a binder substance, and granulating it into high bulk density detergent particles, lower alkyl fatty acids can be prepared. Heavy detergent can be obtained by effectively preventing the hydrolysis of ester sulfonates. [Example] Example 1 Sodium neutralized product of α-sulfo fatty acid methyl ester (
Zeolite powder and sodium sulfate are added to active ingredients (65%, solid content concentration 71%), dried in a vacuum dryer to a moisture content of 5%, and ground in a tabletop grinder to produce the following composition with good fluidity and white color. Activator powder (average particle size: 280 μm) was obtained. α-Sulfo fatty acids (C14-C16)

30wt% Sodium salt of methyl ester (α-SF-Na)
zeolite

30wt% sodium sulfate

35wt% moisture


5wt% [0043] 1wt of this active agent powder
% concentration aqueous solution was 6.8. Also, α-S
The amount of di-salt (disodium salt) in F-Na is
The I content was 4% and remained the same after powdering. Next, this powder and alkali builder were placed in a Σ-type tabletop kneader (inner capacity: 1 liter) in the proportions shown in the table below, a binder substance was added, and the mixture was kneaded at a temperature of 50° C. for 10 minutes. [Table 1]

Activator powder (contains α-SF-Na)
36
0gr Alkali Builder Sodium Carbonate (Average Particle Size 50μ)

90g potassium carbonate (average particle size 50
μ)
50gr Binder material α-olefin (C14-C18) potassium sulfonate (AI70%) 20gr
Nonionic surfactant (AI84%)

20gr (25 moles of ethylene oxide adduct of C13 alcohol) Water


25gr Other Sodium Sulfite

24gr fluorescent agent (Tinopal CBS)
1 gr
[0046] After shredding this kneaded material into approximately 1/cm square pieces,
The mixture was cooled to a temperature of 20° C. and ground using a speed mill. 10g of zeolite powder was added as a surface modifier to the pulverized product, and a 16-100 mesh product was sieved to obtain a high bulk density detergent composition (sample). [0047] This sample has a bulk density of 0.90 g/cc
, showed good powder properties with an angle of repose of 40 degrees, and α-SF-N
The decomposition of a into di-salt was hardly observed at 6% of AI, and the cleaning performance and solubility were equivalent to or better than commercially available detergents. Comparative Example 1 When producing the active agent powder in Example 1, an alkali builder was added instead of sodium sulfate, and on the other hand, during kneading, sodium sulfate was added instead of the alkali builder. Samples were prepared in the same manner. Note that the final composition of the sample is the same as in Example 1. The pH of the 1% aqueous solution of the active agent powder was 11.4, and the amount of di-salt was 25% relative to AI. Further, the amount of di-salt in the sample was 32% relative to AI. Example 2 A high bulk density detergent composition of the present invention was prepared using an agitation granulation method. Redige Mixer (manufactured by Matsusaka Trading Co., Ltd., FM13)
0D type) in the same manner as in Example 1. The activator powder and alkali builders of potassium carbonate and sodium carbonate were charged into a mixer and mixed for 10 minutes. Thereafter, the same binder substances of α-olefin sulfonate, nonionic surfactant, and water as in Example 1 were sprayed and added using a pressure nozzle, and the mixture was stirred and mixed for 3 minutes. At this time, the rotation speed of the main shaft is 160 rpm, and the rotation speed of the chopper is 3600 rpm.
I did it with m. The resulting granulated product was a spherical powder with good fluidity and an average particle diameter of 2500 μm. This granulated product was processed into a 2% zeolite powder using a speed mill (manufactured by Okada Seiko Co., Ltd.).
The sample was sieved with a size of 16 to 100 mesh. The bulk density of this sample is 0.85 g/cc, the angle of repose is 40
The di-salt content was 5% relative to AI.

Claims (1)

[Claims] Claim 1: (a) an active agent powder containing a sulfonate of a fatty acid lower alkyl ester, whose aqueous solution has a pH of 10 or less and does not substantially contain an alkali builder; (b) While mixing powder with alkali builder (
c) A method for producing a high bulk density detergent composition, which comprises adding a binder substance and granulating the composition.