JPH04359099A - Production of high-bulk density detergent composition - Google Patents

Abstract

PURPOSE:To stably produce the subject composition having respectively improved particle size and product quality without adhesion to a crusher by crushing and granulating a uniform solid matter mixture containing an aliphatic acid lower alkyl ester sulfonic acid salt in a specified condition. CONSTITUTION:A uniform solid matter mixture containing an aliphatic lower alkyl ester sulfonic acid such as an alpha-sulfoaliphatic acid ester sodium salt, together with a cooling air of <=20 deg.C and 90-100% relative humidity, is supplied into a crusher. A fine powder containing a fatty acid lower alkyl ester sulfonic acid salt is further added thereto and the resultant mixture is then crushed, thus giving the objective composition.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a high bulk density detergent composition that has excellent manufacturability and can be mass-produced at a high yield.

0002

BACKGROUND OF THE INVENTION Conventional laundry detergents have a bulk density of 0.0 by adding an extender (usually mirabilite is used), which hardly contributes to cleaning performance, to the composition, and then spray drying this to achieve 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).

[0005] In this production, cleaning ingredients such as a sulfonate of a fatty acid lower alkyl ester, an alkali builder, and zeolite are kneaded in a kneader, and the resulting homogeneous kneaded product is pelletized and quantitatively fed to a crusher. This kneaded product is crushed by supplying cold air at 15° C. to a crusher to obtain high bulk density detergent particles. It is also known to add a crushing aid such as sodium carbonate during the crushing process.

[0006] However, homogeneous mixtures containing sulfonate salts of fatty acid lower alkyl esters tend to adhere to the inside of the equipment during the crushing process, leading to a decrease in productivity, and "variation" in the particle size of the resulting detergent particles. This has caused problems such as deterioration of product properties and reduction of yield.

[0007]

[Problems to be Solved by the Invention] An object of the present invention is to produce, with high productivity and yield, a high bulk density detergent containing a sulfonate of a fatty acid lower alkyl ester and having excellent product properties. shall be.

[0008]

[Means for Solving the Problems] The method for producing a high bulk density detergent composition of the present invention involves crushing and granulating a homogeneous solid mixture containing a sulfonate of fatty acid lower alkyl ester in a crusher to obtain a high bulk density detergent composition. When manufacturing detergent particles, the temperature is 20℃
Hereinafter, cooling air with a relative temperature of 90 to 100% is supplied into the crusher, and fine powder containing a sulfonate of a fatty acid lower alkyl ester is added for crushing.

[0009]

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.

0010

[Formula 1] (R1: alkyl group or alkenyl group R2: lower alkyl group M: counter ion)

Water-soluble salts are used as counterions, but alkali metal salts, particularly sodium salts, are preferred.

[0012] 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.

[0015] 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 Japanese Patent Application Laid-open No. 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.

[0017] 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.

[0018] 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.

[0020] The fatty acid residue (R1CHCOO) of the fatty acid lower alkyl ester sulfonate has 8 to 22 carbon atoms.
is suitable, preferably 12-18. The lower alkyl group (R2) preferably has 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.

[0021] Furthermore, as the sulfonate of fatty acid lower alkyl ester, those having a specific carbon number as shown in (a) and (b) below are used with (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. (b) Fatty acid residues with carbon numbers of 12 to 14 (b) Fatty acid residues with carbon numbers of 16 to 18

002
2] The sulfonic acid salt of fatty acid lower alkyl ester 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.

[0024] The high bulk density detergent composition of the present invention is produced by first obtaining a homogeneous solid mixture containing a sulfonate of fatty acid lower alkyl ester and other detergent components, and crushing this into high bulk density detergent particles. It is manufactured by powder mixing or spraying other detergent ingredients depending on the situation.

The homogeneous solid mixture is preferably obtained as a kneaded product by kneading with a kneader or the like, and is suitable for the method of the present invention. In addition, each component is mixed by stirring granulation, etc.
It can also be obtained through integration.

Sulfonic acid salts of fatty acid lower alkyl esters are generally provided industrially as an aqueous slurry, and other detergent components are added thereto to adjust the ingredients and water content to prepare a slurry for spraying. It is desirable to spray-dry this, add a binder substance and other detergent components (if necessary) to the obtained spray-dried product, and knead it uniformly.

Since sulfonic acid salts of fatty acid lower alkyl esters tend to undergo hydrolysis in an alkaline atmosphere, it is desirable to adjust the pH of the above slurry for spraying to 10 or less, preferably 9 or less, and the slurry contains Preferably, substantially no alkali builder is blended. In addition, the slurry for spraying is preferably sprayed with a neutral builder blended, and the following components (a) to (c) are mixed in a weight ratio of (a)/(b) = 1/0.5 to 1. /5 (preferably 1
/0.6~1/3), (a)/(c)=1/0.3~1
/3 (preferably 1/0.4 to 1/2). This prevents the hydrolysis of the sulfonate of fatty acid lower alkyl ester, and provides a detergent raw material with good powder physical properties.

(a) Sulfonate of fatty acid lower alkyl ester (b) Zeolite (c) Sodium sulfate

Furthermore, 70% of the solid component of the slurry for spraying is
At least 80% by weight (preferably at least 80% by weight) of the above (a)
, (b), and (c).

The spray-dried product is uniformly mixed and kneaded with an alkali builder and a binder substance to form a kneaded product. Further, at this time, other detergent components may be mixed and kneaded. The spray-dried material preferably accounts for 15 to 80% by weight of the kneaded raw material. Note that instead of the spray drying method, a raw material powder containing a sulfonate of fatty acid lower alkyl ester can also be obtained by combining vacuum drying and pulverization.

[0031] The binder substance is 5 to 20% of the kneading raw materials.
Suitably, it is used in amounts of % by weight. As the alkali builder, carbonates such as sodium carbonate and potassium carbonate, silicates such as sodium silicate and potassium silicate, etc. can be used.In particular, carbonates etc. that contain water as stable crystal water can be used. It is desirable that the free water in the binder can be maintained as stable water of crystallization.

[0032] 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.

[0033] Examples of the above-mentioned anionic surfactants include the following. 1) Straight chain alkylbenzene sulfonate having an alkyl group having an average carbon number of 8 to 16,

2) an α-olefin sulfonate having an average carbon number of 10 to 20; 3) an alkyl sulfate having an average carbon number of 10 to 20;

0
4) Alkyl ether sulfate or alkenyl ether sulfate having a linear or branched alkyl group or alkenyl group having an average carbon number of 10 to 20 and to which an average of 0.5 to 8 moles of ethylene oxide is added, 5
) Lower alkyl fatty acids having an average carbon number of 8 to 22 (C
1-C3) ester sulfonate,

6) Saturated or unsaturated fatty acid salt having an average carbon number of 10 to 22. As the counter ion in these anionic surfactants, alkali metal salts such as sodium and potassium are usually suitable.

[0037] 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.

The obtained kneaded product (uniform solid mixture) is crushed by a crusher to give a bulk density of 0.5 to 1.1 g/
cc, and is granulated as particles with an average particle diameter of about 200 to 800 μm. During this crushing, air at a temperature of 20° C. or less and a relative temperature of 90 to 100% and fine powder containing a sulfonate of fatty acid lower alkyl ester are supplied together with the kneaded material. The properties of the sulfonate of fatty acid lower alkyl ester in the fine powder are the same as described above.

[0040] By crushing and granulating the kneaded material together with the above-mentioned fine powder under predetermined temperature and humidity conditions, the added fine powder and the crushed particles are agglomerated and granulated, and the powder particle size of the resulting high bulk density detergent particles increases. This improves product yield by reducing the generation of particles with particle sizes that are too large or too small compared to the set particle size. Additionally, there is less adhesion to the crusher, allowing for smooth operation.

The fine powder containing the sulfonate of fatty acid lower alkyl ester may be produced separately, or the fine powder may be prepared from the above-mentioned spray-dried product, or the fine powder in the final crushed product may be prepared from the above-mentioned spray-dried product. It may be collected and recovered and used. That is, the fine powder contains a sulfonate of fatty acid lower alkyl ester, and can further contain detergent components such as a neutral builder and an alkali builder. The sulfonate of fatty acid lower alkyl ester is preferably contained in the fine powder in an amount of 5 to 40% by weight, more preferably 7 to 30% by weight.
Weight%.

The particle size of this fine powder is preferably 150 μm or less, more preferably 100 μm or less. The amount of fine powder added is preferably 1 to 15 parts by weight, more preferably 3 to 10 parts by weight, per 100 parts by weight of the kneaded material.

[0043] The high bulk density detergent particles obtained by crushing are
A final high bulk density detergent composition can be obtained by powder-blending enzymes, softeners, etc. or spraying fragrances, if necessary.

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. Furthermore, various modifications can be made to the timing of blending, such as blending an anionic surfactant or chelating agent other than the sulfonate of fatty acid lower alkyl ester into the slurry for spray drying.

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.

[0046]

According to the present invention, when a homogeneous solid mixture (detergent raw material) containing a sulfonate of fatty acid lower alkyl ester is crushed and granulated into high bulk density detergent particles,
By supplying fine powder containing a sulfonate of fatty acid lower alkyl ester together with air at a specified temperature and humidity, the particle size of the resulting detergent particles is improved and a high bulk density detergent with excellent product properties can be obtained at a high yield. be able to.

[0047] Furthermore, there is no trouble such as adhesion to the crusher, and stable production is possible, making it an excellent method for industrial mass production of high bulk density detergents.

[0048]

【Example】

Example 1 A slurry with a solid content concentration of 60% by weight containing α-SF, sodium fatty acid, A-type zeolite, and sodium sulfate among the compositions shown in Table 1 below was prepared and spray-dried. The pH of this slurry was 7.6.

AOS, nonionic (surfactant) active agent, sodium carbonate, potassium carbonate, and water were added to the obtained spray-dried product, and the mixture was kneaded uniformly with a kneader. long).

[0050] The obtained pellets were heated at a temperature of 20°C and a humidity of 90°C.
% of cooling air (twice the amount by mass) into a crusher (Fitzmill DKA-6 manufactured by Hosokawa Micron Co., Ltd.). At the same time, 3% by weight of fine powder containing α-SF and having a particle size of 150 μm or less (recovered fine powder generated in Comparative Example 3 was used) was added.

[0051] The crusher rotates at 3000 rpm, the screen is made of 180° punching metal, and the crushers are connected in three consecutive stages, and the crushed material from the first stage crusher is transferred to the second stage crusher, and then in the same manner. It was supplied to the third stage crusher and crushed in three stages. Hole diameter of punching metal is 1st stage: 12mmφ
, second stage: 6 mmφ, and third stage: 2 mmφ.

[0052] The pulverized product that had passed through the crusher in three stages was separated from the cooling air, sprayed with perfume, and added with enzymes to obtain a high bulk density detergent composition (product). The composition, manufacturability, product properties and performance are shown in Table 1.

Examples 2 and 3, Comparative Examples 1 and 2 Production was carried out in the same manner as in Example 1, except that the conditions of the cooling air of the crusher and the amount of α-SF-containing fine powder added were changed as shown in Table 1. The manufacturability, product properties and performance are shown in Table 1.

Examples 4 and 5 The spray-dried product of Example 1 was crushed and used as the α-SF-containing fine powder added to the crusher. In Example 4, the fine powder was crushed to have an average particle size of 50 μm or less, and in Example 5, the average particle size was adjusted to 100 μm or less under the following crushing conditions.

[0055] The crusher (manufactured by Okada Seiko Co., Ltd., Speed Mill D30 type) has four stages of cross crushing blades with a diameter of 15 cm, rotates at 3000 rpm, and has a screen of 1.5 mm.
A punching metal with a diameter of φ and a porosity of 20% was used. The rest was manufactured in the same manner as in Example 1. Its manufacturability, product properties and performance are shown in Table 1.

Comparative Example 3 Production was carried out in the same manner as in Example 1 except that no fine powder was added during crushing. Its manufacturability, product properties and performance are shown in Table 1.

Comparative Example 4 Fine powder containing α-SF was not added during crushing, and instead fine powder of sodium carbonate (average particle size 20
Production was carried out in the same manner as in Example 1 except that 6 parts by weight of 6 parts by weight of .mu.m) were added when introducing the pellets.

The manufacturability, product properties and performance are shown in Table 1. The above results are summarized in Table 1. In addition, the dissolved residue was measured as follows and was used as a measure of the solubility of detergent particles.

Dissolved residue 10 g of each detergent composition shown in Table 1 was placed in a 1 liter beaker containing 50 ml of water at 5° C. After leaving for 2 minutes, 950 ml of water at 5° C. was added and stirred using a constant speed stirrer for 2 minutes.
After stirring for 8 minutes at a speed of 50 rpm, it is filtered through a nylon cloth, and the dissolved residue is dried at 80° C. for 1 hour and weighed. The percentage of this remaining dissolved amount is determined and is defined as the dissolved residue.

[0060]

[Table 1]
Comparative example 1 Example 1 Example 2
Example 3 composition (wt%):

Mixture:


α-SF*1
16 16
16 16
Fatty acids (C16-C18)
2 2 2
2 Sodium


A type zeolite
18 18 18
18 Sodium sulfate
Balance AOS*2
2
2 2
2 Nonionic activator *3
3 3
3 3 Potassium carbonate 9
9 9
9 Sodium carbonate
10 10
10 10 Water *4

6 6 6
6 Addition during crushing:

Sodium carbonate fine powder -
− − −
α-SF containing fine powder
5 3 5
10 Rating:


Cooling air condition: Temperature (℃)
15 20 15
10
Humidity (%) 85
90 95 100
Manufacturability: Operating status No problem No problem No problem No problem
Product yield (%) *5
86 92 93
94 Product properties:


Particle size (%) 16# on
5 5 5
6 100#
pass 14
10 9 8
Average particle size (μm)
390 400 410
430 Product performance: Dissolved residue (%)
3 2
2 2 *1) Sodium salt of α-sulfo fatty acid (C14-C16) methyl ester *2) Potassium α-olefin (C14-C18) sulfonate *3) EO of C13 alcohol (p=20)
Additives *4) Also includes moisture derived from other additives *5) Product yield when products are made from particles with particle sizes from 12#pass to 200#on

[0061]

[Table 2]


Comparative example 2
Example 4 Example 5 Comparative Example 3 Comparative Example 4 Composition (wt%):

Mixture:


α-SF*1
16 16
16 16 16
Fatty acids (C16-C18)
2 2 2
2 2
sodium

A type zeolite
18 18
18 18 18
sodium sulfate
balance
AOS*2
2 2
2 2
2 Nonionic activator *3
3 3 3
3 3
potassium carbonate 9
9 9 9
8 Sodium carbonate
10 10
10 10 5
Water *4
6 6 6
6 6
Added during grinding:

Sodium carbonate fine powder − −
− − 6
α-SF containing fine powder 5
4 8 -
− Evaluation:


Cooling air conditions: Temperature (℃) 25
10 15
15 15
Humidity (%) 100
95 100 100
100 Manufacturability: Operating status
Adhesion occurs No problem No problem Adhesion occurs
No problem Product yield (%) *5
82 93 94
80 85 Product properties:

Particle size (%) 1
6# on 10 5
6 8
5 100# pass
7 9 8
14 15
Average particle size 460
410 420
410 390 Product performance: Dissolved residue (%) 6 2
2 5 10
*1) Sodium salt of α-sulfo fatty acid (C14-C16) methyl ester *2) Potassium α-olefin (C14-C18) sulfonate *3) EO of C13 alcohol (p=20)
Additives *4) Also includes moisture derived from other additives *5) Product yield when products are made from particles with particle sizes from 12#pass to 200#on

Claims (1)

[Claims] Claim 1: A homogeneous solid mixture containing a sulfonate of fatty acid lower alkyl ester is crushed and granulated in a crusher to produce high bulk density detergent particles at a temperature of 20°C or less and a relative temperature of 90 to 100%. 1. A method for producing a high bulk density detergent composition, which comprises supplying cooling air into a crusher, and adding and crushing fine powder containing a sulfonate of fatty acid lower alkyl ester.