JPH06166898A - Production of high-bulk-density detergent composition - Google Patents

Abstract

PURPOSE:To mass-produce a high-quality high-bulk-density grainy detergent good in color tone on an industrial scale. CONSTITUTION:A slurry contg. a salt of a linear alkylbenzene-sulfonic acid (LAS-salt) is prepared either by using the LAS-salt or by neutralizing LAS-H, admixed with at least one of an alkali builder and zeolite, and then admixed with a sulfonic acid salt of a lower alkyl ester of a fatty acid, followed by spray-drying. The resulting powder is granulated to produce the objective high- bulk-density detergent grains.

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 which is excellent in manufacturability and can be mass-produced.

[0002]

2. Description of the Related Art Conventional laundry detergents contain an extender (usually Glauber's salt) which hardly contributes to cleaning performance, and are spray-dried to a bulk density of 0.00.
It was manufactured as bead-like hollow particles of about 3 g/cc.

[0003] However, since such detergents have a low specific gravity and a low active agent concentration, they are not only expensive to transport, but also require a considerable amount of space for storage and display. It was difficult to measure. Therefore, recently, a method for producing a high bulk density granular detergent that can be washed with a small amount of detergent has been proposed (JP-A-60-9
6698), and is also on the market. On the other hand, sulfonates of fatty acid lower alkyl esters are derived from natural raw materials and are surfactants with excellent detergency, particularly hard water resistance, and high bulk density detergent compositions containing them have been reported ( JP-A-62-597). High-bulk-density detergents are usually produced by kneading, mixing, crushing, and granulating detergent raw materials.
-69897-69900, JP-A-1-3180
97, 2-14297, 2-2950
No. 0, No. 2-86700, No. 2-17309
No. 9, No. 2-245100, No. 2-2867
99, 2-38497, 2-1456
99, 2-169696, 2-232
No. 299, No. 2-232300, No. 3-33
Various methods have been proposed in Japanese Patent Laid-Open No. 199 and the like.

[0004] Among these conventional methods, crushing and granulation of a type in which a spray-dried detergent composition containing a surfactant and a builder is compacted and then pulverized by impact and shear force with a knife cutter rotating at high speed. A method of granulating with a machine (Japanese Patent Application Laid-Open No. 61-69899), a mixer having a vertical stirring shaft in the interior of a vertical mixing tank and attaching stirring blades to this shaft to mix the powder. A method of agitating and granulating a spray-dried detergent composition containing a surfactant and a builder in the presence of a surface modifier and a binder (JP-A-61-69897); After grinding the spray-dried composition of detergent containing
A stirring granulation process is performed in the presence of a surface modifier and a binder by a mixer that has a stirring shaft protruding from the bottom inside a vertical mixing tank, and a stirring blade is attached to this shaft to mix the powder. method (JP-A-61-698
98) and a method using a horizontal mixing tank (JP-A-61-69900), a slurry containing a surfactant and a builder is spray-dried to once form a low-density spray-dried composition. A method of obtaining high-bulk-density detergent granules by granulating the obtained detergent particles is regarded as a promising industrial production method.

[0005] On the other hand, in the case of straight-chain alkylbenzene sulfonate, which is a representative surfactant, a method is known in which straight-chain alkylbenzene sulfonic acid is neutralized with an alkali when preparing a slurry for spraying and then introduced into the slurry. It is However, when the sulfonate of a fatty acid lower alkyl ester, an alkali builder and zeolite, which are excellent surfactants as described above, are added to a linear alkylbenzene sulfonate slurry and spray-dried, a spray-dried product is obtained. has a poor color tone, and the color tone of the high bulk density detergent particles obtained by using this as a raw material is further deteriorated. there were.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to produce a high-bulk-density detergent composition containing a fatty acid lower alkyl ester sulfonate and a linear alkylbenzene sulfonate and having excellent product properties. .

[0007]

SUMMARY OF THE INVENTION The process for producing a high bulk density detergent composition of the present invention comprises spraying a spray slurry containing a fatty acid lower alkyl ester sulfonate, a linear alkylbenzene sulfonate, an alkali builder and a zeolite. After drying, in the method for producing a detergent composition in which the obtained spray-dried powder is granulated to form high-bulk-density detergent particles, a liquid composition containing a linear alkylbenzene sulfonate is used when preparing the slurry for spraying. A sulfonate of a fatty acid lower alkyl ester is added after at least one of an alkali builder and a zeolite is added to the product.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, first, a spray-drying slurry containing at least fatty acid lower alkyl ester sulfonate, linear alkylbenzene sulfonate, alkali builder and zeolite is prepared and then spray-dried to A dry powder is obtained. Further, when preparing the slurry for spray drying, each treatment is performed in the order shown in the following methods A to C. The liquid composition containing LAS-salt (linear alkylbenzene sulfonate) may use LAS-salt slurry generally provided industrially, or LAS-salt slurry may be used.
It may also be prepared by neutralizing -H (linear alkyl benzene sulfonic acid).

Method A: Prepare liquid composition containing LAS-salt → Add alkali builder → Add zeolite Method B: Prepare liquid composition containing LAS-salt → Add zeolite → Add alkali builder C Method: Prepare liquid composition containing LAS-salt → Simultaneous addition of alkali builder and zeolite

[0010] Thus, in the present invention, after first obtaining a liquid composition containing linear alkylbenzene sulfonic acid, an alkali builder and zeolite are added thereto. Furthermore, the sulfonate of a fatty acid lower alkyl ester is always added after adding at least one of the alkali builder and the zeolite to the liquid composition in the methods A to C described above. That is, for example, in the case of A method,
(1) addition of the alkali builder prior to the zeolite, (2) addition of the alkali builder followed by the zeolite, or (3) addition of the alkali builder and the zeolite followed by the sulfonate of the fatty acid lower alkyl ester. Add last.

[0011] When the sulfonate of fatty acid lower alkyl ester is added before or immediately after neutralization of linear alkylbenzene sulfonic acid, or when the slurry containing linear alkylbenzene sulfonate is added prior to alkali builder and zeolite. When the sulfonate of fatty acid lower alkyl ester is added, the color tone of the dry powder obtained by spray-drying the prepared slurry is remarkably poor. The product color tone of bulk density detergent particles is also poor, and a high-quality detergent composition cannot be obtained. A sulfonate of a fatty acid lower alkyl ester is typically represented by Chemical Formula 1 below, and is also called an α-sulfo fatty acid ester salt.

[0012]

[Chemical 1] (R ¹ : alkyl group or alkenyl group R ² : lower alkyl group M: counter ion)

Water-soluble salts are used as counterions, but alkali metal salts, especially sodium salts, are preferred. Sulfonates of saturated fatty acid lower alkyl esters can be obtained by sulfonating fatty acid lower alkyl esters by, for example, the method described in Japanese Patent Application No. 3-159735, aging and bleaching if necessary, and then neutralizing. can get.

The fatty acid residue (R ¹ CHCOO) of the fatty acid lower alkyl ester sulfonate has 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms. lower alkyl group
(R ² ) preferably has 1 to 6 carbon atoms, preferably 1 to
3. Also, as the sulfonate of fatty acid lower alkyl ester, the following (a) and (b) having specific carbon numbers (a)/(b) = 1/9 to 6/4, especially 2/
From the viewpoint of the solubility of the detergent composition, it is preferable to combine them in a weight ratio of 8 to 5/5. (a) Fatty acid residue with 12 to 14 carbon atoms (b) Fatty acid residue with 16 to 18 carbon atoms

The sulfonates of fatty acid lower alkyl esters generally include α-sulfo fatty acid disalts (R ² =M in Chemical Formula 1 above), lower alkyl fatty acid salts or esters, and higher alkyl fatty acid salts. Or including esters, mirabilite, various ethers, which are industrial post-treatments,
For example, it can result from hydrolysis of ester bonds upon bleaching or neutralization with H ₂ O ₂ . This di-salt is usually contained in industrial products in amounts of 1 to 10% by weight, without impairing the effectiveness of the product. The sulfonate of fatty acid lower alkyl ester is 2-30% by weight, preferably 2.5-20% by weight in the final detergent composition.
Blended into the slurry so as to be included.

The straight-chain alkylbenzene sulfonate has an average C8-16 alkyl group and is incorporated in the final composition in an amount of 1-30% by weight, preferably 3-20% by weight. As the salt, sodium salt, potassium salt and the like are used.

In addition to the essential component surfactants of the present invention, other anionic and nonionic surfactants can be blended in the slurry. Specific examples of anionic surfactants are given below. can. (1) an α-olefin sulfonate having an average carbon number of 10 to 20, (2) an alkyl sulfate having an average carbon number of 10 to 20, (3) a linear or branched alkyl group having an average carbon number of 10 to 20, or Have an alkenyl group, average 0.5
~8 moles of ethylene oxide adduct alkyl ether sulfate or alkenyl ether sulfate, (4)
A saturated or unsaturated fatty acid salt having an average of 10 to 22 carbon atoms. Alkali metal salts such as sodium and potassium are generally suitable as counter ions in the above anionic surfactants.

[0018] As the nonionic surfactant, the following are preferable. (1) An EO addition type nonionic surfactant obtained 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) A primary or secondary alcohol having 8 to 18 carbon atoms, an average of 4 to 25 moles of EO, propylene oxide (P
EO-PO addition type nonionic surfactant to which O) is added in an average of 3 to 15 mol. (3) Ester-type nonionic surfactants of Formula 2, in which 4 to 25 mols on average of EO are added to lower alkyl esters of fatty acids having 6 to 20 carbon atoms.

[0019]

##STR2## RCO(OCH ₂ CH ₂ )nOR' (R: alkyl or alkenyl group having 5 to 19 carbon atoms, R': alkyl group having 1 to 3 carbon atoms, n: 4 to 25)

[0020] These other surfactants may be added to the slurry at any time and in any amount, but preferably within a range that does not interfere with the effects of the present invention. As zeolites, commercially available zeolites, for example A-type, X-type or amorphous synthetic zeolites, can be used, and are present in the final detergent composition in an amount of 5-35% by weight, preferably 10-30% by weight.
The slurry contains 5 of them.
It is preferable to mix 0 to 90%.

Known alkali bilters include
For example, sodium silicate, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium sodium carbonate, potassium hydrogencarbonate, sodium sulfite, sodium sesquicarbonate, powdered sodium silicate and the like can be used, and carbonate is particularly preferably used. The alkali builder is 5-60% by weight, preferably 8-50%, in the final detergent composition.
It is blended so that it is contained in weight %, and it is preferable to blend 50 to 90% of it in the aqueous slurry. An aqueous slurry is prepared in the above-described order using the above-mentioned components or other optional components, and a common method is used, for example, using a countercurrent spray drying tower with a hot air temperature of 200 to 300 ° C.
to obtain a dry powder.

Next, in the production method of the present invention, the spray-dried powder thus obtained is mixed with other detergent ingredients, such as zeolite, alkali builder, etc., which are optionally used.
It is granulated together with a binder component and the like.

[0023] The granulation method is not particularly limited, and either stirring granulation or crushing granulation can be used.
For example, in stirring granulation, as a mixer using stirring blades,
A horizontal stirring mixer that mixes by attaching stirring blades inside a horizontal mixing tank, a vertical stirring mixer that has stirring blades at the bottom of the vertical type and mixes by rotating the stirring blades, etc. is preferably used. Specifically, horizontal stirring mixers such as Loedige mixers, ribbon mixers, Spartanreusers, Pagmills and turbulizers, and vertical stirring mixers such as high speed mixers and Henschel mixers are preferably used. The stirring and mixing conditions are not particularly limited, and normal stirring and mixing conditions can be used.

In the case of crushing and granulation, the method of crushing and kneading, and the method of crushing and granulating the obtained compacted body can be carried out by adopting usual methods and conditions. Specifically, for powder compaction and kneading, a continuous kneader or screw extruder with a strong shearing function is used. Those of the formula are preferably used. The dry powder is preferably used in an amount of 40 to 80% by weight, particularly 50 to 70% by weight, of the entire detergent composition. As the zeolite and alkali builder, the same ones as described above can be used, and the blending amounts of these components are also as described above.

As the binder component, a high-concentration aqueous solution of an anionic surfactant, a nonionic surfactant or its aqueous solution, a polymer aqueous solution such as polyethylene glycol, polyacrylic acid, polyacrylate, polyvinyl alcohol, water, or the like is used. be able to. Here, as the anionic surfactant and the nonionic surfactant, those similar to those of the present invention and other surfactants described above are used. The binder component is preferably 5 to 20% by weight in the kneaded product composition. 0.5 to 1.2 by powder blending enzymes, softening agents, bleaching agents, etc., or by spraying fragrances to the detergent particles obtained by granulation, if necessary.
A final detergent composition with a bulk density on the order of g/cc is obtained.

In addition to the components described above, the detergent composition of the present invention further contains inorganic builders such as sodium tripolyphosphate, sodium pyrophosphate and sodium sulfate; sodium citrate, sodium ethylenediaminetetraacetate and nitrilotriacetate. , sodium polyacrylate, sodium acrylate-sodium maleic anhydride copolymer, calcium ion-trapping builders such as polyacetal carboxylate; anti-soil redeposition agents such as carboxymethylcellulose and polyethylene glycol; para-toluenesulfonate, toluenesulfonate , xylene sulfonate, viscosity modifiers such as urea; proteases, lipases,
Enzymes such as cellulase and amylase; softening agents such as quaternary ammonium salts and bentonite; bleaching agents, fluorescent agents, fragrances, dyes and the like can be used. The timing of blending these components is arbitrary, and various modifications are possible.

[0027]

According to the present invention, after preparing a liquid composition containing linear alkylbenzene sulfonate, at least one of zeolite and alkali builder is added, and then sulfonate of fatty acid lower alkyl ester is added. an aqueous slurry containing a fatty acid lower alkyl ester sulfonate, a linear alkylbenzene sulfonate, a zeolite and an alkali builder is prepared to obtain a spray-dried powder, and the spray-dried powder is granulated into high bulk density detergent particles. By forming a detergent composition as a detergent composition, the color tone of the spray-dried powder is good, and the color tone of the high bulk density detergent composition is also good, and high-quality granular detergent can be industrially mass-produced.

[0028]

[Embodiment] The flowchart shown in FIGS.
A detergent slurry was prepared according to -C). Here, in flows A and B, water, fluorescent agent, potassium hydroxide, α-
A liquid composition containing potassium linear alkylbenzene sulfonate (LAS-K) obtained by adding linear alkylbenzene sulfonic acid (LAS-H) to an aqueous alkaline composition containing potassium olefin sulfonate (AOS-K) for neutralization and then soap according to flow A or B,
A detergent slurry was prepared by sequentially adding alkali builder and zeolite. On the other hand, in flow C, LAS-K
was used to prepare a slurry, to which soap, alkali builder and zeolite were added in sequence. At this time, in each example and comparative example, the sodium salt of α-sulfo fatty acid methyl ester (α-SF-Na) was added at the times shown in FIGS.

The obtained detergent slurry (adjusted to have a water content of 50%) was spray-dried using a countercurrent spray dryer at a hot air temperature of 230° C., and dried to a moisture content of 5%.
A spray-dried product having the composition shown in was obtained. Next, each component shown in the kneaded product composition in Table 2 was added to this spray-dried product, and KRC
The mixture was kneaded with a kneader (manufactured by Kurimoto Iron Works Co., Ltd.) and made into pellets of about 10 mmφ×20 mm with an extruder (manufactured by Fuji Paudal Co., Ltd.). This pellet product is placed in a speed mill (Okada Seiko Co., Ltd.) equipped with a screen with an opening of 2 mm.
(manufacturer) to obtain a high bulk density granular detergent. The b values of the spray-dried product and the high-bulk-density granular detergent in the comparative examples of the above examples were measured with a reflectometer, and the measurement results are shown in Table 3. In addition, each example,
In the comparative example, both the spray-dried product and the final granular detergent have the same composition, and differ only in the timing of addition of α-SF-Na and the order of addition of zeolite and alkali builder.

[0030]

Table 1: Spray-dried product composition Surfactant: α-SF-Na* ¹ 10 parts by weight AOS-K* ² 2 parts by weight LAS-K* ³ 15 parts by weight Soap 4 parts by weight Alkali builder: Potassium carbonate 5 parts by weight Sodium carbonate 12.8 parts by weight Sodium sulfite 2 parts by weight Zeolite 14 parts by weight Other components: Fluorescent agent 0.2 parts by weight Water 5 parts by weight *1) Sodium salt of α-sulfo fatty acid methyl ester (fatty acid residue with 14/C16-C18=
3/7 (weight ratio) mixture) * ₂ ) Potassium C14- _C18 α-olefin sulfonate *3) Potassium linear alkyl ₍ C10 _- C14) benzene sulfonate

[0031]

[Table 2] Table 2: Kneaded product composition spray-dried product 70 parts by weight Nonionic surfactant* ¹ 4 parts by weight Potassium carbonate 8 parts by weight Sodium carbonate 12 parts by weight Zeolite 4 parts by weight Added water 2 parts by weight *1) Carbon Ethylene oxide 25 mol adduct of primary alcohol of number 12-13

[0032]

Table 3: Color (b value) Color of spray-dried product (b value)* ¹ Color of high bulk density detergent (b value)* ¹ Comparative example 1 12 14 Comparative example 2 7 9 Comparative example 3 6 8 Example 1 5 5 Example 2 4.5 4.5 Example 3 5 5 Example 4 4.5 4.5 Example 5 5 5 Example 6 4.5 4.5 *1) b value was measured using a reflectometer.

[Brief description of the drawing]

FIG. 1 is a flow chart showing the manufacturing process of detergent slurries in Examples and Comparative Examples of the present invention;

FIG. 2 is a flow chart showing the manufacturing process of detergent slurries in Examples and Comparative Examples of the present invention;

continuation of the front page (72) Inventor Seiji Abe Rio, 1-3-7 Honjo, Sumida-ku, Tokyo within N Co., Ltd.

Claims (1)

[Claims] 1. After spray-drying a spray slurry containing fatty acid lower alkyl ester sulfonate, linear alkylbenzene sulfonate, alkali builder and zeolite, the obtained spray-dried powder is granulated to obtain high bulk. In the method for producing a detergent composition with high-density detergent particles, when preparing the slurry for spraying, after adding at least one of an alkali builder and a zeolite to the liquid composition containing the linear alkylbenzene sulfonate, A method for producing a high bulk density detergent composition, characterized by adding a sulfonate of a fatty acid lower alkyl ester.