JP2003105372A - Powdery detergent and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high-quality powdery detergent capable of providing detergent slurry mainly composed of soap, having low viscosity, not causing aggregation of sodium carbonate and having good stability and to provide a method for producing the high-quality powdery detergent in industrially high productivity. SOLUTION: This powdery detergent comprises (A) a fatty acid soap, (B) sodium carbonate, (C) a water-soluble polymer and (D) a sulfonate type anion surfactant and/or an ether type or ester type nonionic surfactant having >=12 average addition number of moles and the detergent is obtained by spraying and drying these components under conditions in which the content of components (A) and (D) is 8-60 wt.% and a weight ratio of the component (A) to the component (D) is (100/1) to (100/8).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a powder detergent having a soap-based detergent slurry having a low viscosity and good stability in which sodium carbonate does not aggregate, and a method for producing a powder detergent having high industrial productivity.

[0002]

2. Description of the Related Art Japanese Unexamined Patent Publication No. 2001-115198 and Japanese Unexamined Patent Publication No. 5-295399 propose a detergent containing a fatty acid soap as a main surfactant and sodium carbonate.

However, the slurries proposed by these are generally high in viscosity and difficult to handle, and sodium carbonate aggregates to clog nozzles during spray drying, which is a serious problem in operation.

[0004]

SUMMARY OF THE INVENTION Under such circumstances, it is an object of the present invention to solve various problems in the prior art and achieve the following objects. That is, the present invention is, among the surfactants, a soap-based detergent slurry having a low viscosity, and a detergent slurry having good stability in which sodium carbonate does not aggregate can be obtained, which has high industrial productivity and high quality. An object of the present invention is to provide a powder detergent and a method for producing the same.

[0005]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that a water-soluble polymer and a specific amount are used in spray-drying a slurry containing a fatty acid soap and sodium carbonate. By adding the above non-soap surfactant to the slurry, it is possible to obtain a detergent slurry that has a low viscosity of soap-based detergent slurry and that does not aggregate with sodium carbonate, and that has good stability, and that has high industrial productivity. It was found that a high-quality powder detergent can be obtained in the above, and the present invention has been completed.

[0006] That is, the present invention provides the following powder detergent and its manufacturing method in order to solve the above problems.

The invention of claim 1 is (A) fatty acid soap,
(B) sodium carbonate, (C) water-soluble polymer,
(D) contains a sulfonate type anionic surfactant and / or an ether type or ester type nonionic surfactant having an average addition mole number of alkylene oxide of 12 or more,
The component (A) + the component (D) is 8 to 60 mass%,
Moreover, the component (A) / the component (D) is 100/1 to 10
A powder detergent obtained by spray drying under the condition of 0/18 (mass ratio).

The invention of claim 2 is a powder detergent obtained by granulating the powder detergent of claim 1 together with a non-soap surfactant and a detergent builder.

The invention of claim 3 is (A) fatty acid soap,
(B) sodium carbonate, (C) water-soluble polymer, (D)
A sulfonate type anionic surfactant and / or an ether type or ester type nonionic surfactant having an average addition mole number of alkylene oxide of 12 or more, wherein (A) component + (D) component is 8 to 60 mass%. And, the component (A) / the component (D) is 100/1 to 100/18
It is a method for producing a powder detergent, which comprises spray-drying under conditions of (mass ratio).

The invention of claim 4 is a method for producing a powder detergent, which comprises granulating the powder detergent obtained by the production method according to claim 3 together with a non-soap-based surfactant and a detergent builder. .

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. The powder detergent of the present invention comprises (A) fatty acid soap,
(B) sodium carbonate, (C) water-soluble polymer,
(D) A sulfonate type anionic surfactant and / or an ether type or ester type nonionic surfactant having an average addition mole number of alkylene oxide of 12 or more.

The fatty acid soap as the component (A) preferably has a carbon chain length of fatty acid of generally 8 to 20, preferably 12 to 18. As the counter ion, an alkali metal is generally used, preferably Na or K.

The content of this fatty acid soap is generally 5 to 30% by mass, preferably 8 to 25% by mass, based on the slurry DM.

As the component (B), sodium carbonate, which is a heavy type or a light type, is commercially available, but either may be used. The content of this sodium carbonate is
Generally, it is 5 to 40% by mass, preferably 10 to 30% by mass, based on the slurry DM.

As the water-soluble polymer as the component (C),
Carboxylic acid-based polymers, polymers such as polyglyoxylate and polyglycidylate, cellulose derivatives such as carboxymethyl cellulose, aminocarboxylic acid-based polymers such as polyaspartate, vinyl-based polymers such as polyvinylpyridone, polyethylene glycol, etc. And the like, and one of these may be used alone, or two or more thereof may be used in combination. Among them, carboxylic acid-based polymers are preferable, and as the carboxylic acid-based polymers, homopolymers or copolymers of acrylic acid, methacrylic acid, itaconic acid, etc., and those obtained by copolymerizing the above monomers with maleic acid are preferable. It is preferable that the molecular weight is 1,000 to 100,000.

The content of the water-soluble polymer as the component (C) is generally 0.1 to 10% by mass, preferably 0.5 to 8% by mass, based on the slurry DM. If the content of the water-soluble polymer is less than 0.1% by mass, sodium carbonate may be aggregated. On the other hand, if it exceeds 10% by mass, there may occur a problem that the drying efficiency is lowered.

Examples of the sulfonate type anionic surfactant as the component (D) include straight chain or branched alkyl (average carbon chain length 8 to 18) benzene sulfonate, long chain alkyl (average carbon chain length 10 to 20) sulfone. Acid salts, long-chain olefins (average carbon chain length 10 to 20) sulfonates, α-sulfo fatty acid alkyl ester salts (average carbon chain length 12 to 20 of fatty acid residues), etc. It can be used as a mixture of the above. These sulfonate type anionic surfactants can be used as alkali metal salts such as sodium and potassium, amine salts and ammonium salts. Further, particularly preferred sulfonate type anionic surfactants are alpha sulfo fatty acid ester salts, linear alkylbenzene sulfonates, alpha olefin sulfonates, and alkane sulfonates.

As the ether type or ester type nonionic surfactant as the component (D), the following are used. (I) An aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms and an alkylene oxide having 2 to 4 carbon atoms on average 1
2 to 30 mol, preferably 13 to 25 mol of polyoxyalkylene alkyl (or alkenyl) ether added. Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable. As the aliphatic alcohol used here, a primary alcohol and a secondary alcohol are used. The alkyl group may have a branched chain. A primary alcohol is used as a preferable aliphatic alcohol. (Ii) Polyoxyethylene alkyl (or alkenyl) phenyl ether (iii) An alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester, for example, a fatty acid alkyl ester alkoxylate represented by the following general formula (I). . R ¹ CO (OA) _n OR ² ... (I) (R ¹ CO is a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms, OA is 2 to 4 carbon atoms such as ethylene oxide and propylene oxide, Preferably 2 to 3 alkylene oxide addition units, n is the average number of moles of alkylene oxide addition, generally 12 to 30, preferably 13 to 2
It is a number of 5. R ² represents a lower alkyl group which may have a substituent having 1 to 3 carbon atoms) As such a fatty acid alkyl ester alkoxylate, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, Examples thereof include polyoxyethylene fatty acid ester, polyoxyethylene hydrogenated castor oil, and glycerin fatty acid ester.

Among the nonionic surfactants as the component (D), polyoxyethylene alkyl (or alkenyl) ethers and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ethers having a melting point of 40 ° C. or less and an HLB of 9 to 16 are used. A fatty acid methyl ester ethoxylate obtained by adding ethylene oxide to a fatty acid methyl ester, a fatty acid methyl ester ethoxypropoxylate obtained by adding ethylene oxide and propylene oxide to a fatty acid methyl ester, and the like are preferably used. Further, these nonionic surfactants may be used as a mixture.

The amount of the sulfonate type anionic surfactant and / or the ether type or ester type nonionic surfactant having an average addition mole number of alkylene oxide of 12 or more as the component (D) is generally 0.1 based on the slurry DM.
The content is 1 to 10% by mass, preferably 0.2 to 8% by mass. If the amount of the component (D) surfactant is too small, the sodium carbonate may aggregate. On the other hand, if the amount is too large, there may occur a problem that the drying efficiency is lowered.

In this case, the compounding ratio of component (A) / component (D) is generally 100/1 to 100/18 (mass ratio), preferably 100/2 to 100/15 (mass ratio).
Is. As (D) component is less than 100/1, As
h is aggregated. On the other hand, when the amount of the component (D) is more than 100/18, the viscosity becomes too high and the productivity decreases. In addition, (A) component + (D) component is slurry D
It is 8 to 60% by mass, preferably 1 based on M.
It is 0 to 40% by mass. (A) component fatty acid soap +
(D) Component sulfonate type anionic surfactant and /
Alternatively, if the ether type or ester type nonionic surfactant having an average added mole number of alkylene oxide of 12 or more is less than 8% by mass, the cleaning performance is deteriorated. On the other hand, (A)
If the content of the component + (D) is more than 60% by mass, the drying efficiency will be reduced.

The slurry preparation conditions in the present invention are such that the water content of the slurry is generally 30 to 50%, preferably 35 to 50%.
45%. The slurry temperature is generally 50-9.
The temperature is 0 ° C, preferably 60 to 85 ° C. As a device for producing the slurry, any general stirring and mixing device may be used, but a stirring and mixing device as shown in FIG. 1 is particularly preferable. In FIG. 1, 1 is a mixing tank, 2 is a stirring blade, and 3 is a slurry.

The powder detergent of the present invention includes the above (A) to
In addition to the component (D), a non-soap-based surfactant, a detergent builder, and other additive components can be optionally blended.
The optional components are not particularly limited.

The non-soap surfactant is not particularly limited as long as it is a non-soap surfactant, and an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a mixture thereof are appropriately selected according to the purpose. can do.

The anionic surfactant is not particularly limited as long as it has been conventionally used in detergents, and various anionic surfactants can be used. Examples of the anionic surfactant include the following.

(1) A linear or branched alkylbenzene sulfonate having an alkyl group having 8 to 18 carbon atoms (L
AS or ABS). (2) Alkane sulfonate having 10 to 20 carbon atoms. (3) an α-olefin sulfonate (AOS) having 10 to 20 carbon atoms. (4) Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms. (5) Having a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms, and having an average of 0.5 to 10 mol of ethylene oxide, propylene oxide, butylene oxide or ethylene oxide / propylene oxide = 0.1. Alkyl ether sulfate or alkenyl ether sulfate (AES) added at a ratio of /9.9 to 9.9 / 0.1. (6) Having a linear or branched alkylphenyl group or alkenylphenyl group having 10 to 20 carbon atoms, and having an average of 3
~ 30 moles of ethylene oxide, propylene oxide, butylene oxide or ethylene oxide / propylene oxide = 0.1 / 9.9 to 9.9 / 0.1 alkyl phenyl ether sulfate or alkenyl phenyl ether sulfate salt. (7) It has a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms and has an average of 0.5 to 10 mol of ethylene oxide, propylene oxide, butylene oxide or ethylene oxide / propylene oxide = 0.1. Alkyl ether carboxylate or alkenyl ether carboxylate added at a ratio of /9.9 to 9.9 / 0.1. (8) Alkyl polyhydric alcohol ether sulfate such as alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms. (9) A saturated or unsaturated α-sulfofatty acid salt having 8 to 20 carbon atoms or its methyl, ethyl or propyl ester (α-SF or MES). (10) Long-chain monoalkyl, dialkyl or sesquialkyl phosphate. (11) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphate. (12) A higher fatty acid salt having 10 to 20 carbon atoms.

These anionic surfactants can be used as alkali metal salts such as sodium and potassium, amine salts, ammonium salts and the like. Further, these anionic surfactants may be used as a mixture. Particularly preferred anionic surfactants include, for example, straight-chain alkylbenzene sulfonic acid (LAS) alkali metal salts (eg, sodium or potassium salts).
Examples thereof include alkali metal salts of AOS, α-SF, and AES (for example, sodium or potassium salt) and alkali metal salts of higher fatty acids (for example, sodium or potassium salt).

The cationic surfactant is not particularly limited as long as it has been conventionally used in detergents, and various cationic surfactants can be used. Examples of the cationic surfactant include the followings.

(1) Di-long chain alkyl Di-short chain alkyl type 4
Grade ammonium salt ^{[R 1 R 2 R 3 R} 4 N] + · X - ( wherein, ^{R 1} and ^{R 2} are usually carbon atoms 12 to 26, .R ³ preferably represents an alkyl group of 14 to 18 And R ⁴
Is usually an alkyl group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, a benzyl group, usually 2 to 4 carbon atoms, preferably 2
3 shows a hydroxyalkyl group or a polyoxyalkylene group. X is halogen, CH ₃ SO ₄ , C ₂ H ₅ S
_{O 4, 1 / 2SO 4,} OH, showing a HSO 4, _CH 3 CO ₂ or _{CH 3 -C 6 H 4 -SO 3} . )

Specific examples of the di-long-chain alkyldi-short-chain alkyl-type quaternary ammonium salt include distearyldimethylammonium salt, dihydrogenated beef tallow alkyldimethylammonium salt, dihydrogenated beef tallow alkylbenzenemethylammonium salt, and dihydrate. Stearylmethylbenzylammonium salt, distearylmethylhydroxyethylammonium salt, distearylmethylhydroxypropylammonium salt, distearyldihydroxyethylammonium salt, dioleyldimethylammonium salt, dicoconutalkyldimethylammonium salt and the like can be mentioned. Further, specific examples of the halogen which is X include a chlorine atom and a bromine atom.

(2) Mono long chain alkyl tri short chain alkyl
Type quaternary ammonium salt [R¹R^TwoR^ThreeR^FourN]⁺・ X⁻ (In the formula, R¹Usually has 12 to 26 carbon atoms, preferably
Represents an alkyl group of 14-18. R^Two, R^ThreeAnd R^Four
Is usually an alkyl group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms.
Group, benzyl group, usually having 2 to 4 carbon atoms, preferably 2
~ 3 hydroxyalkyl group or polyoxyalkyle
Group. X is halogen, CH_ThreeSO _Four, C_TwoH₅
SO_Four, 1 / 2SO_Four, OH, HSO_Four, CH_ThreeCO_Two
Or CH_Three-C₆H_Four-SO_ThreeIndicates. )

Specific examples of the mono-long-chain alkyltri-short-chain alkyl-type quaternary ammonium salt include lauryltrimethylammonium salt, stearyltrimethylammonium salt, hydrogenated beef tallow alkyltrimethylammonium salt, and hydrogenated beef tallow alkylbenzenedimethylammonium salt. Examples thereof include salts, stearyl dimethyl benzyl ammonium salts, stearyl dimethyl hydroxyethyl ammonium salts, stearyl dimethyl hydroxy propyl ammonium salts, stearyl trihydroxy ethyl ammonium salts, oleyl trimethyl ammonium salts, coconut alkyl trimethyl ammonium salts. Further, specific examples of the halogen which is X include a chlorine atom and a bromine atom.

(3) Tetra short chain alkyl type quaternary ammonium salt [R ¹ R ² R ³ R ⁴ N] ⁺ · X ⁻ (In the formula, R ¹ , R ² , R ³ and R ⁴ are usually carbon. An alkyl group having a number of 1 to 4, preferably 1 to 3, a benzyl group,
Usually, it has 2 to 4 carbon atoms, preferably 2 to 3 hydroxyalkyl groups or polyoxyalkylene groups. X is
_{Halogen, CH 3 SO 4, C 2} H 5 SO 4, 1 / 2SO
₄ , OH, HSO ₄ , CH ₃ CO ₂ or CH ₃ -C ₆ H
_4- SO ₃ is shown. )

Specific examples of the tetra short-chain alkyl type quaternary ammonium salt include tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydroxide tetrabutylammonium hydrogensulfate and benzyltrimethylammonium chloride. , Benzyltrimethylammonium hydroxide, benzyltriethylammonium chloride, benzyltributylammonium bromide, benzyltributylammonium chloride, trimethylphenylammonium chloride and the like.

(4) Tri long chain alkyl mono short chain alkyl quaternary ammonium salt [R ¹ R ² R ³ R ⁴ N] ⁺ · X ⁻ (wherein R ¹ , R ² and R ³ are usually 12 to 12 carbon atoms
26, preferably 14 to 18 alkyl groups are shown. R ⁴
Is usually 1 to 4 carbon atoms, preferably 1 to 2 alkyl groups, benzyl group, usually 2 to 4 carbon atoms, preferably 2
3 to 3 hydroxyalkyl groups or polyoxyalkylene groups. X is halogen, CH ₃ SO ₄ , C ₂ H ₅ S
_{O 4, 1 / 2SO 4,} OH, showing a HSO 4, _CH 3 CO ₂ or _{CH 3 -C 6 H 4 -SO 3} . )

Specific examples of the tri-long-chain alkylmono-short-chain alkyl-type quaternary ammonium salts include trilaurylmethylammonium chloride, tristearylmethylammonium chloride trioleylmethylammonium chloride and tricoconut alkylmethylammonium chloride. Can be mentioned.

The amphoteric surfactant is not particularly limited as long as it has been conventionally used in detergents, and various amphoteric surfactants can be used. Examples of the amphoteric surfactant include the following.

(1) Betaines Lauric acid amidopropyl betaine, stearic acid amidoethyl betaine, carbobetaine, sulfobetaine and the like can be mentioned. (2) Imidazoline derivatives 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, N-coconut oil fatty acid acyl-N-carboxyethyl-N-hydroxyethylethylenediamine sodium and the like can be mentioned. (3) Phosphate-type phosphate-type lecithin (phosphatidylcholine, etc.) and the like can be mentioned.

The amount of the above-mentioned non-soap-based surfactant compounded is generally 0.1 to 10% by mass, preferably 0.2 to 8% by mass, based on the slurry DM.

Next, as a cleaning builder, a chelate builder (metal ion sequestering agent) for ^capturing alkaline earth metal ions (Ca ²⁺ , Mg ²⁺ ) in tap water, an alkali builder having an alkaline buffering capacity, a neutral builder Builders and mixtures thereof can be used, whether inorganic or organic.

As the chelate builder, various kinds of the following (1) to (3) can be used. (1) Aluminosilicate A-type zeolite, P-type zeolite, X-type zeolite, amorphous zeolite and the like can be mentioned. (2) Condensed Phosphate An alkali metal salt of tripolyphosphoric acid, an alkali metal salt of pyrophosphoric acid and the like can be mentioned. (3) Organic builders Citric acid alkali metal salts, ethylenediaminetetraacetic acid alkali metal salts (EDTA), nitrilotriacetic acid alkali metal salts (NTA), polyacrylic acid alkali metal salts,
Examples thereof include alkali metal salts of copolymers of acrylic acid and maleic anhydride, polyacetal carboxylates, and alkali metal salts of hydroxyiminodisuccinic acid.

As the alkali builder, the following various types (1) to (2) can be used. (1) Alkali metal carbonate sodium carbonate, potassium carbonate, sodium hydrogen carbonate,
Examples thereof include potassium hydrogen carbonate and sodium potassium carbonate. (2) Examples include alkali metal silicate sodium silicate (water glass) and layered sodium silicate.

As the neutral builder, the following (1)
Various types of (2) to (2) can be used. (1) Sulfate Sodium sulfate, potassium sulfate and the like can be mentioned. (2) Chlorides Sodium chloride, potassium chloride and the like can be mentioned.

The amount of the washing builder compounded is generally 30 to 90% by mass, preferably 40 to 85% by mass based on the slurry DM.
It is% by mass.

The other detergent components are not particularly limited as long as they are optional components usually blended with detergent raw materials, and various components can be used in combination. Examples of such components include the following components.

(1) Anti-redeposition agent Carboxymethyl cellulose, polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone and the like can be mentioned. (2) Viscosity modifiers Paratoluene sulfonate, toluene sulfonate, xylene sulfonate, urea and the like can be mentioned. (3) Softeners Quaternary ammonium salts, smectite minerals such as montmorillonite, saponite, hectorite, and stevensite. (4) Reducing agents Sodium sulfite, sodium hydrogen sulfite and the like can be mentioned. (5) Bleaching agents Sodium percarbonate, sodium perborate, sodium sulfate hydrogen peroxide adduct and the like can be mentioned. (6) Bleach activator ethylenediaminetetraacetate, sodium octanoyloxybenzenesulfonate, sodium dodecanoyloxybenzenesulfonate, decanoyloxybenzenecarboxylic acid, and the like (7) Optical brightener 4,4′- Bis- (2-sulfostyryl) -biphenyl salt, 4,4'-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, 2- (styrylphenyl) naphthothiazole derivative, 4,4'-bis ( Triazole-2
Examples include -yl) stilbene derivatives and bis (triazinylamino) stilbene disulfonic acid derivatives. (8) Fragrance C10 to C15 alcohol, C7 to C10 aromatic alcohol, C8 to C17 formic acid ester or acetate, C10 to C15 hydrocarbon, C7 to C1
Examples thereof include aromatic aldehydes having 5 carbon atoms, aliphatic aldehydes having 8 to 14 carbon atoms, and phenolic fragrances. (9) Enzymes such as protease, lipase, cellulase and amylase can be mentioned. (10) Examples include dye ultramarine. (11) Oil absorbing carrier Amorphous silicic acid, white carbon, amorphous calcium silicate, amorphous aluminosilicate, magnesium silicate, magnesium carbonate, calcium carbonate, spinel, cordierite, mullite, decomposed product of starch, etc. To be (12) Surface modifier Examples include finely divided calcium carbonate, finely divided zeolite, finely divided silica, finely divided alumina, finely modified starch, clay mineral, and polyethylene glycol. (13) Foam suppressor Silicone, silicone compound, wax and the like can be mentioned. (14) Antioxidant tert-butyl hydroxytoluene, 4,4′-butylidene bis- (6-tert-butyl-3-methylphenol),
2,2'-butylidene bis- (6-tert-butyl-4-methylphenol), monostyrenated cresol, distyrenated cresol, monostyrenated phenol, distyrenated phenol, 1,1'-bis- (4-hydroxyphenyl) ) Cyclohexane and the like. (15) Photoactivated bleaching agent Sulfonated aluminum phthalocyanine, sulfonated zinc phthalocyanine and the like can be mentioned.

The following is a method for granulating the slurry. Detergent slurry → Spray drying → Agitation granulation → Granular detergent detergent slurry → Spray drying → Kneading (doughing) → Crush granulation → Granular detergent detergent slurry → Spray drying → Fluid bed granulation → Granular detergent

The method of pulverizing after kneading is a step of kneading (kneading) a detergent raw material and spray-dried particles to prepare a solid detergent. Detergent raw materials and spray-dried particles are introduced into a kneading (kneading) device and transported, compacted, while applying shearing force.
Stepwise mixed with kneading to form a solid detergent.

Various devices can be used as a kneading (kneading) device. Specifically, a closed type consolidation apparatus, and more preferably a horizontal continuous kneader can be preferably mentioned. In addition to the kneader, a single or twin screw extruder can be used. These devices may be either batch type or continuous type.

When a continuous kneading (kneading) device is used, the arrangement of the paddles involved in kneading (kneading) is particularly important in terms of the quality of the resulting detergent. JP 2000-14
As disclosed in Japanese Patent No. 4194, when a kneading (kneading) machine having a stirring blade is continuously supplied with a detergent component, a kneading (kneading) is performed when a kneaded (kneading) product of the detergent component is manufactured.
Inside the machine, each of the functions of (a) transporting the detergent component from the supply port of the kneading machine toward the discharge port, (b) the function of consolidating the detergent component, and (c) the function of kneading the detergent component are provided. Stirring blades are sequentially arranged from the supply port of the kneading (kneading) machine toward the discharge port side to continuously knead (knead). Also,
In order to prevent abrasion after long-time operation, it is desirable to subject the screw, paddle and body (casing) to treatment such as stellite or tungsten carbide.

The following can be used as a continuous kneading device. Example 1: KRC Kneader [Kurimoto Steel Co., Ltd.] Example 2: Extruded Omics [Hosokawa Micron Co., Ltd.] Example 3: Fine Luther [Fuji Paudal Co., Ltd.] Example 4: Continuous Kneader [manufactured by Dalton Co., Ltd.] Example 5: JP-A-63-242334 and JP-A-6-2
No. 3251, No. 6-23252, No. 7-26
Device Example 6 described in Japanese Patent No. 5679: Twin Dome Gran [manufactured by Fuji Paudal Co., Ltd.] Example 7: Dome Gran [manufactured by Fuji Paudal Co., Ltd.]

The following may be used as a batch type kneading (kneading) device. Example 1: Kneader [Dalton Co., Ltd.] Example 2: Universal mixing stirrer [Dalton Co., Ltd.]

The kneading (kneading) conditions are as shown below. It is suitable to operate at a temperature of generally 30 to 80 ° C, preferably 35 to 75 ° C, more preferably 40 to 70 ° C. If the temperature is lower than 30 ° C., the load on the kneading (kneading) device tends to be excessive, which is not preferable. On the other hand, the temperature is 8
If the temperature is higher than 0 ° C., on the contrary, the kneaded (kneaded) product tends to adhere to a device used in a subsequent step such as a crusher, which is not preferable.

Treatment time In the case of the batch type, the treatment time is usually 1 to 20 minutes, preferably 2 to 15 minutes, more preferably 3 to 10 minutes. The treatment time in the case of the continuous system is usually 10 to 120 seconds, preferably 20 to 90 seconds, more preferably 30 to 60 seconds.

Pressure As disclosed in JP-A-61-118500, the internal pressure of the kneader is controlled to 0.01 to 5 kg / cm ² · G to continuously knead (knead).

Binder As a binder at the time of kneading (kneading), generally, water,
Anionic surfactant aqueous solutions, nonionic surfactants, nonionic surfactant aqueous solutions, and mixtures thereof are used, and nonionic surfactants, nonionic surfactant aqueous solutions and mixed aqueous solutions of anionic surfactants and nonionic surfactants are used. It is suitable.

In order to suppress the temperature rise of the detergent solids due to cooling kneading (kneading), it is desirable to carry out kneading (kneading) while passing the refrigerant through the jacket of the kneading (kneading) device. As the refrigerant, an aqueous solution of ethylene glycol is suitable and its concentration is 1
5 to 30%, preferably 20 to 25% is used.

The physical properties of the kneading (kneading) are as follows. Bulk density Generally 0.5-1.2 g / mL, preferably 0.6-
It is 1.0 g / mL. The size is generally 10 to 500 mm, but is not particularly limited as long as it is smaller than the pitch of the screw of the extruder for introducing the kneaded (kneaded) product.

The crushing step is a step of crushing a mixture of detergents, a kneaded product, pellets or a granulated product with a crushing granulator to prepare a desired particle size. As a particularly preferable grinding method, a detergent mill consisting of a surfactant and a builder (mixture, kneaded material, pellets or granulated material) is crushed and granulated, and a cutter mill type crusher having a classification screen is used. It is particularly preferable that the crusher having a large screen hole diameter is successively supplied to a crusher having a small screen hole diameter to perform multistage crushing.

The crushing granulator is as follows. Granulator Generally, a crushing granulator equipped with a rotating body and a screen inside, preferably an impact crusher such as a hammer mill, atomizer or palpelizer, a cutting / shear crusher such as a cutter mill or a feather mill. Used. Example 1: Fitzmill [manufactured by Hosokawa Micron Co., Ltd.] Example 2: Speed mill [manufactured by Okada Seiko Co., Ltd.] Example 3: Crushing granulator Power Mill [Fuji Paudal Co., Ltd.]
Example 4: Atomizer [Fuji Paudal Co., Ltd.] Example 5: Pulverizer [Hosokawa Micron Co., Ltd.] Example 6: Comminator [Fuji Paudal Co., Ltd.] Although it does not matter, there is a rotary crushing blade in the crushing chamber, crushed by the rotary crushing blade,
The thing which discharges the crushed detergent granules from the screen of a predetermined hole diameter etc. is used suitably.

The screen is not particularly limited to a wire mesh type, a herringbone type, a punching metal type, etc. However, considering the screen strength and the shape of the crushed material, punching metal is preferable.

A rotary hammer or a cutter is used, but a cutter type is preferable in order to avoid generation of fine powder due to impact crushing. However,
Treatment with stellite, tungsten carbide, etc. is desirable to prevent the blade of the cutter from becoming worn during long-term operation.

The crushing conditions are as shown below. Peripheral speed of the rotating body Generally, it is set according to the pulverizability of the object to be pulverized (crushed material) and the desired particle size. Usually, in the case of detergent, it can be used in the range of 10 to 70 m / s. When the crushed material is brittle or has strong adhesion, crushing at 50 m / s or less is preferable, and 40 m / s
s or less is more preferable. On the contrary, when viscoelasticity is strong and adhesion is weak, pulverization at 50 m / s or more is preferable from the viewpoint of productivity and particle size control.

Introduction of cold air In general, it is desirable to introduce cold air into the crusher in order to prevent the crushed material from being softened by the crushing heat and attached to the crusher. The cold air temperature is suitably 5 to 30 ° C, preferably 10 to 25 ° C. In addition, the amount of cold air is 0.1
5 m ³ / kg (crushed material) is suitable. If the amount of cold air is too large, the temperature of the crushed product is remarkably lowered, and the crushed product becomes hard and brittle, resulting in over-pulverization and increase in fine powder and deterioration in shape. As a method of introducing the cold air, either a batch introduction of a necessary amount into the first stage or a divided introduction into each stage may be adopted. In addition, it is economically advantageous to recycle the cold air discharged from the crusher after separating it from the powder.

When crushing the crushing aid, it is preferable to add a crushing aid.
Grinding aids are generally grinding aids.
It is known as d), and when added in a small amount to the crusher, it has the effects of reducing the crushing power, improving the crushing particle size, and improving the properties of the crushed product. Particle size of crushing aid is 50
The thickness is preferably not more than μm, more preferably not more than 20 μm. Moreover, the addition amount is 0.5 to 10% by mass with respect to the crushing amount.
Is preferred. Examples of the crushing aid include stearates, aluminosilicates such as A-type zeolite, calcium carbonate, magnesium carbonate, alkaline earth metal carbonates, amorphous silica, calcium silicate, magnesium silicate, and other silicic acids. Clay minerals such as salt, talc and bentonite, silicon dioxide, titanium dioxide, finely divided sodium carbonate and sodium sulfate are preferable. These crushing aids adhere to the surface of the crushed material and reduce the surface activity of the crushed material, thereby preventing adhesion to the crusher, reducing the crushing power associated with this, and improving the fluidity of the crushed material. To be As a method for adding the auxiliary agent, a method of mixing before crushing in advance and a method of multi-step crushing 1
There are a method of adding all the required amount to the stage at once, and a method of dividing and adding each stage. Any of them may be selected, but it is preferable to add them all at once from the viewpoint of the effect of the auxiliary agent and the economical efficiency.
Furthermore, by connecting the crushers directly to each other and sealing each stage (closed direct connection type), the loss of the auxiliary agent is reduced,
It is possible to work effectively with a small amount of auxiliary agent added.

Milling material temperature The milling material temperature is generally 5 to 50 ° C., preferably 10 to 40.
It is suitable to carry out at 0 ° C, more preferably 10 to 30 ° C. The temperature and flow rate of the cold air are set so as to fall within this temperature range. When the temperature is lower than 5 ° C, dew condensation is likely to occur, which is not preferable. On the other hand, when the temperature is higher than 50 ° C., on the contrary, the adhesion to the crusher easily occurs, which is not preferable.

Processing time is usually 1 to 30 seconds, preferably 3 to 30 seconds. Screen pore size Generally, it is set according to the pulverizability of the object to be pulverized (crushed material) and the desired particle size. Generally, in the case of detergent, a screen having a pore size of 3.0 to 30.0 times, preferably 4.0 to 25.0 times the desired average particle size can be used. Average particle size 500μm
In order to obtain the detergent particles, the screen having a hole diameter of 1.5 to 15 mm may be selected and used according to the size of the crushed material.

Multistage crushing It is preferable that the crushing capacity in the multistage crushing of the high-bulk density detergent has a large capacity and is common to all stages because the crushers are connected in series. In order to realize this, it was found that there is an optimum value for the ratio of the average particle size of the crusher inlet and outlet obtained by selecting the screen hole diameter. When the average particle size at the start of the crushing process and the desired average particle size of the crushed granulated product are set, the number of crushing stages is naturally determined accordingly. At that time, it is more effective if the relationship between the screen hole diameter and the average particle diameter of the obtained crushed material can be predicted in advance.

Further, since the surface area of the powder is small and the load applied to the crusher is small when the particle size is large, the ratio of the average particle size at the inlet to the outlet can be widened. Therefore, in multistage crushing, it is desirable to reduce the crushed particle size as much as possible with the upper crusher. For multi-stage crushing, it is possible to install a sieve at the outlet of the crusher for each stage and supply only the desired level of crushed material to the crusher of the next stage, but clogging of the sieve, complication of the system, installation It is disadvantageous in terms of area increase. Therefore, it is preferable to use a direct connection type in which the discharged material (crushed material) from the first-stage crusher is directly supplied to the second-stage (further, the third and subsequent stages) crushers.

Regarding the properties of the crushed granules, the average particle size of the crushed granules is preferably 300 to 1500 μm, preferably 500 to 1.
It is 000 μm. If the particle size is large, the solubility in the laundry will be delayed, causing problems of cloth adhesion and detergency. Conversely, if the particle size is small, the amount of fine particles will increase and the crushing yield will decrease.
It leads to deterioration of liquidity.

The stirring and granulating apparatus for stirring and granulating has a stirring shaft equipped with stirring blades at the center of the inside thereof and forms a clearance between the stirring blades and the vessel wall when the stirring blades rotate. Is important. Average clearance is 1
-30 mm is preferable.

Examples of the stirring type mixer having such a structure include a Henschel mixer [manufactured by Mitsui Miike Kakoki Co., Ltd.] and a high speed mixer [Fukae Industry Co., Ltd.].
Device), a vertical granulator (manufactured by Paulec Co., Ltd.), etc., and particularly preferably a horizontal mixing tank having a stirring shaft at the center of the cylinder, and stirring powder is attached to this shaft by stirring blades. Examples of the mixer include a Loedige mixer [manufactured by Matsubo Co., Ltd.] and a broche mixer [manufactured by Taiheiyo Kiko Co., Ltd.].

The average clearance is 1 to 30 m
m, preferably 3-10 mm. If it is less than 1 mm, the adhering layer tends to cause the mixer to be overpowered. If it exceeds 30 mm, the compaction efficiency decreases and the particle size distribution becomes broad. Further, the granulation time becomes long and the productivity is lowered.

The granulation conditions are as follows. Froude number (Fr number) The Froude number defined by the following formula is preferably 1 to 4, and more preferably 1.2 to 3. If the Froude number is less than 1, consolidation is not promoted, which is not preferable. On the other hand, when it exceeds 4, the particle size distribution becomes wide, which is not preferable. Fr = V / (R × g) ^0.5 V: peripheral speed [m / s] of tip of stirring blade R: radius of rotation of stirring blade [m] g: acceleration of gravity [m / s ² ]

Granulation time In order to obtain a suitable granulated product, the granulation time in batch granulation and the average residence time in continuous granulation are 0.5
It is preferably -20 minutes, more preferably 3-10 minutes. If it is less than 0.5 minutes, the granulation time is too short to control the granulation to obtain a suitable average particle size and bulk density, and the particle size distribution becomes broad. On the other hand, when it exceeds 20 minutes, the granulation time is too long and the productivity is lowered.

Filling Rate of Detergent Raw Material The filling rate (feeding amount) of the detergent raw material into the granulator is preferably 70% by volume or less, more preferably 15 to 40% by volume of the total internal volume of the mixer. If it exceeds 70% by volume, the mixing efficiency of the detergent raw material in the mixer is lowered, so that suitable granulation cannot be performed.

The temperature granulator preferably has a structure having a jacket, and the temperature of the medium passed through the jacket is preferably 5 to 40 ° C.
More preferably, it is 10 to 20 ° C. Within this temperature range, the granulation time for obtaining a suitable granulated product is shortened, the productivity is improved, and the particle size distribution is sharpened. Further, among the detergent raw materials, the powder raw material may be supplied at room temperature and the nonionic activator may be supplied at a melting temperature, and it is not necessary to control the temperature in the mixer. The temperature of the granulated product is usually 30 to 60 ° C depending on the temperature of the feed material, the heat of stirring, and the like.

Additives In order to accelerate the granulation during granulation, a binder may be added. Examples of the binder, carboxymethyl cellulose, polyethylene glycol, water-soluble polymer solution such as polycarboxylic acid salts such as sodium polyacrylate,
Examples thereof include nonionic substances such as polyoxyethylene alkyl ether, fatty acid monoethanolamide and fatty acid diethanolamide, fatty acid, aqueous sodium silicate solution and water. The amount of the binder to be blended is 10
0.1 to 10 parts by mass is preferable with respect to 0 parts by mass, and more preferably 0.5 to 5 parts by mass.

[0079]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

The raw materials used in this example are shown below together with their abbreviations.

"Α-SF": sodium alphasulfofatty acid having a C _14-16 alkyl chain (purity 65.6% and others, methyl sulfate 3.28%, sodium sulfate 1. 31%, sodium salt of alpha sulfo fatty acid 3.08%, methanol 1.51%, unreacted methyl ester 1.21%, water 24.01%, provided that this sodium alpha sulfo fatty acid is a detergent composition. During the process, 7% equivalent may be changed to a di-salt of sodium alphasulfofatty acid during long-term storage of the detergent composition, and 25% equivalent may be changed. (Manufacturing method) Thin film reactor (single tube, inner diameter = 10 m
m, reactor length = 2.5 m) as a raw material compound methyl myristate (manufactured by Lion Corporation, Pastel M-
14) and methyl palmitate (Lion Co., Ltd., Pastel M-16) were mixed at a mass ratio of 2: 8, and a fatty acid methyl ester (iodine value 0.40, molecular weight 264) was used.
Liquid SO ₃ was used as the SO ₃ gas system equipment, nitrogen gas was used as the dilution gas, and an inert gas containing 8% SO ₃ was used, and the gas absorption reaction was performed at a reaction molar ratio (SO ₃ / methyl ester) = 1.2. Perform in a thin film reactor, and after gas-liquid separation,
An aging reaction was performed at 0 ° C. for 60 minutes to obtain a sulfonic acid having a reaction rate of 97%. Then 20% by weight of methanol to sulfonic acid,
35% hydrogen peroxide water (2% as hydrogen peroxide pure content against sulfonic acid) was added, and after uniform mixing, a bleaching reaction was carried out at 80 ° C. for 180 minutes. Then, a neutralization reaction is performed with an aqueous sodium hydroxide solution to obtain a neutralized product having a concentration of 47% (surfactant concentration), and methanol (recycled by rectification in the subsequent step) by recycle flash concentration and water evaporated to 65.6. A concentrated neutralized product having a concentration of 10% (surfactant concentration) was obtained. Color tone (5% by mass ethanol solution 40 mm optical path length, measured with a Klett photoelectric photometer using No. 42 blue filter) is 30.
Met.

"Soap": sodium palmitate and me
Sodium innate and TMD (C₁₀~ ₂₀Ester system
Compound: 1: 3: 1 (mass ratio) mixture. 40-60 ° C fatty acid methyl ester (pastel MC
* O, Lion Oreo Chemical Co., Ltd.) 1576kg
/ H, 445 kg of 40% NaOH aqueous solution at 40-60 ° C
/ H, water (Lion Chiba factory middle water) 336 kg / h
Continuously introduced into mixing pump, shell & tube type
While keeping the temperature at 110 to 130 ° C with the supplementary heat and preheater,
The saponification reaction was allowed to proceed for 9 to 10 minutes (reaction rate 99.5 to
99.8%). Then, the column top pressure is 0.2 to 0.6 kPa,
Introduced to a flash evaporator with a tower top temperature of 98-100 ° C.
Then, the reaction product methanol was added at a residence time of 40 minutes.
Evaporated. Finally, pad the soap with the methanol removed.
Introduced into a stirring tank with le-type stirring blades, residence time 140
Add 80 ° C warm water while maintaining 98 ° C while stirring for 5 minutes
Adjust the soap concentration to 66-67%.
It was. The soap thus obtained has an AI of 66-67%
Yes, as impurities, about 0.01% fatty acid, about 0.2
% Unreacted fatty acid ester, about 0.2% NaOH, about
Contains 0.4% methanol.

"AAO": CH ₃ (CH ₂ ) _11-12 O
(CH ₂ CH ₂ O) ₁₅ H (manufactured by Lion Chemical Co., Ltd.) 40 diadol 13 (manufactured by Mitsubishi Chemical Co., Ltd.) in a 4-liter autoclave (manufactured by Pressure Resistant Glass Industry Co., Ltd.)
0 g and 2.3 g of a 30% NaOH aqueous solution were charged, the inside of the autoclave was replaced with nitrogen, and the temperature was raised with stirring (in the middle, dehydration was performed at a temperature of 100 ° C. for 30 minutes). Then, while maintaining the temperature at 180 ° C. and the pressure at 300 kPa, ethylene oxide (EO: manufactured by Mitsubishi Chemical Corporation) 1320
g (average number of added moles: 15) was introduced, and Diadol 1
The reaction between 3 and EO was performed. Finally, it was aged for 30 minutes to obtain a nonionic surfactant. Impurities in the nonionic surfactant were about 2.0% PEG and about 0.7% unreacted alcohol.

"AAEP15030": CH ₃ (CH ₂ )
_11-12 O (CH ₂ CH ₂ O) ₁₅ (CH ₂ CH ₂ CH
₂ O) ₃ H (manufactured by Lion Chemical Co., Ltd.) 40 diadol 13 (manufactured by Mitsubishi Chemical Co., Ltd.) in a 4-liter autoclave (manufactured by Pressure Resistant Glass Industry Co., Ltd.)
0 g and 2.3 g of a 30% NaOH aqueous solution were charged, the inside of the autoclave was replaced with nitrogen, and the temperature was raised with stirring (in the middle, dehydration was performed at a temperature of 100 ° C. for 30 minutes). Then, while maintaining the temperature at 180 ° C. and the pressure at 3 atm, 1320 g of ethylene oxide (EO: manufactured by Mitsubishi Chemical Corporation)
(Average number of moles added: 15)
Was reacted with EO and aged for 30 minutes. After that, the reaction liquid is cooled to a temperature of 120 ° C., and the temperature is 120 ° C.
While maintaining Pa, propylene oxide (PO: manufactured by Asahi Glass Co., Ltd.) (350 g) was added and the reaction was carried out. Finally, it was aged for 30 minutes to obtain a nonionic surfactant. PE is the impurity in the nonionic surfactant.
G was about 2.0% and unreacted alcohol was about 0.7%.

"MEE (C ₁₂ EO ₉ )": CH ₃ (C
_{H 2) 10 CO (OCH 2} CH 2) 9 OCH 3 ( Lion Chemical Co., Ltd.) _"MEE (C 12 _{EO 12)": CH 3 (CH 2) 10} C
_{O (OCH 2 CH 2) 1} 2 OCH 3 ( manufactured by Lion Chemical Co.) _"MEE (C 12 _{EO 15)": CH 3 (CH 2) 10} C
_{O (OCH 2 CH 2) 1} 5 OCH 3 ( manufactured by Lion Chemical Co.) "MEE _(C 16 EO _{9)": CH 3 (CH 2) 14} CO
(OCH ₂ CH ₂ ) ₉ OCH ₃ (Lion Chemical Co., Ltd.
"MEE (C ₁₆ EO ₁₂ )": CH ₃ (CH ₂ ) ₁₄ C
_{O (OCH 2 CH 2) 1} 2 OCH 3 ( manufactured by Lion Chemical Co.) _"MEE (C 16 _{EO 15)": CH 3 (CH 2) 14} C
_{O (OCH 2 CH 2) 1} 5 OCH 3 ( manufactured by Lion Chemical Co.) _{"MEE (C 180/181 = 10} /90 EO 9) ":
_{(CH 3 (CH 2) 16} CO / C 17 H 33 = 10/9
0) (OCH ₂ CH ₂ ) ₉ OCH ₃ (manufactured by Lion Chemical Co., Ltd.) “MEE (C 180/181 _{= 10/90} E
O _{12) ":( CH 3 (CH 2) 16} CO / C 17 H 33
= 10/90) (OCH ₂ CH ₂ ) ₁₂ OCH ₃ (manufactured by Lion Chemical Co., Ltd.) “MEE (C 180/181 _{= 10/90} E
O _{15) ":( CH 3 (CH 2) 16} CO / C 17 H 33
_{= 10/90) (OCH 2} CH 2) 15 OCH 3 ( Lion Chemical Co., Ltd.) The MEE was prepared as follows. Description will be made by taking C ₁₂ EO ₉ as an example. (Production method) 400 g of Pastel M-12 (manufactured by Lion Oreo Chemical Co., Ltd.) and a catalyst (composite hydroxide of magnesium / aluminum / manganese in nitrogen) were placed in a 4-liter autoclave (manufactured by Pressure Resistant Glass Co., Ltd.). 1.2 g of 40% KOH aqueous solution and 0.12 g of 40% KOH aqueous solution were charged, and the autoclave was purged with nitrogen.
The temperature was raised with stirring (in the middle, dehydration was performed at a temperature of 100 ° C. for 30 minutes). Next, the temperature is 180 ° C. and the pressure is 300.
While maintaining at kPa, 696 g (average added mole number: 15) of ethylene oxide (EO: manufactured by Mitsubishi Chemical Co., Ltd.) was introduced and the reaction between Pastel M-12 and EO was performed. Finally, it was aged for 30 minutes to obtain a nonionic surfactant. Impurities in the nonionic surfactant were about 2.0% PEG and about 1.0% unreacted methyl ester. Other MEEs are produced in the same manner by changing the raw material (pastel) used and the ethylene oxide introduced. It is summarized in Table 1 below.

[0086]

[Table 1] (* 1) Pastel M-12, Pastel M-16, Pastel M-181 are all manufactured by Lion Oreo Chemical Co., Ltd.
All were reacted at 400 g.

"PEG # 1500": average molecular weight 15
00 polyethylene glycol (Lion Chemical Co.) _"LAS": sodium dodecylbenzenesulfonate of C 10 _{-C 14} (Raibon LH-200, manufactured by Lion Corporation)

"AOS-K": carbon number 14: 16: 18 = 15: 50: 35 obtained by the following production method.
A mixture of potassium α-olefin sulfonate and potassium hydroxyalkyl sulfonate (purity 70%, the ratio of potassium α olefin sulfonate: potassium hydroxyalkyl sulfonate is 7: 3, the balance is unreacted α-olefin, sodium sulfate, Sultone, sodium hydroxide,
(Water, etc.) (Production method) α-olefin (Dialen 14
8. Mitsubishi Chemical Co., Ltd., TO reactor (TO-500, Lion Co., Ltd.) with a capacity of 970 kg / hr continuously.
Manufactured, film-type reactor) and subjected to sulfonation reaction by contacting with SO ₃ gas inside to obtain a sulfonated product containing α-olefinsulfonic acid and impurities (mainly sultone) at about 35 ° C. It was This sulfonate 1370k
Caustic potash 630 kg / hr against g / hr (water content 52%
Aqueous solution) is added to carry out a neutralization reaction, and α-
Obtained potassium olefin sulfonate. In order to hydrolyze the sultone in the impurities, the temperature was heated to 140 ° C. through a shell-and-tube heat exchanger, and steam of 1.4 MPa was passed through the reaction coil to keep the temperature at 170 ° C. to accelerate the hydrolysis. After that, flash concentration and dehydration were performed at a pressure of 1 MPa to make the water content about 27%. The net content of AOS-K thus obtained is usually 66 to 74%.
The main component is potassium α-olefin sulfonate (about 7
0%) and potassium hydroxyalkyl sulfonate (about 3%)
0%), the color is (10% solution LK value) 70,
It is 1.8% of free alkali content (KOH) (vs. AOS-K pure content).

"Fine powder zeolite": 4A type zeolite,
Average particle size 3 μm (manufactured by Mizusawa Chemical Co., Ltd.) “Granular zeolite”: 4A type zeolite, average particle size 2
00 μm (manufactured by Cosmo, Korea) “Zeolite slurry”: 4A type zeolite aqueous solution, 47% water (Nippon Kagaku Co., Ltd.) “Potassium carbonate”: Food grade (manufactured by Asahi Glass Co., Ltd.) “Sodium sulfite”: Anhydrous sulfite Soda (manufactured by Shinshu Chemical Co., Ltd.) "Sodium carbonate": Granulated ash (manufactured by Asahi Glass Co., Ltd.) "MA agent": Acrylic acid-maleic acid copolymer, Aqualic TL-400 (manufactured by Nippon Shokubai) "CMC" : Carboxymethyl cellulose (CMC Daicel 1360, manufactured by Daicel Chemical Industries) "PAA": Polyacrylic acid, Junron PW150
(Nippon Pure Chemical)

[Examples 1 to 17 and Comparative Examples 1 to 5] Table 2
~ As shown in Table 5, the composition tank (D = 0.60 m,
H = 0.70m) and the temperature is 75 ° C by the following method.
The B-type viscosity and the Ash aggregation rate were measured. In addition,
The compounding time was 30 to 40 minutes. The results are shown in Table 2 to Table 5.
Also described in.

<Method of measuring Ash aggregation rate> 32 Mesh
(Opening: 500 μm) sieve (TOKYO SCREE
NZ, JIS Z 8801) was prepared. After putting about 500 g of the slurry and shaking it, washing with MeOH,
The organic components were washed off using a brush. Then, after drying in a dryer and a constant temperature bath of 80 ° C., the weight of the sieve is weighed, and the weight of the empty sieve is subtracted from the following formula to obtain A
The sh aggregation rate was calculated. The Ash aggregation rate (%) is the ratio of the Ash aggregation amount to the slurry put in the sieve. Y = (X−W) × 100 / Z (where Y is the agglomeration rate, X is the mass of the slurry and sieve after drying, W is the mass of the empty sieve, and Z is the mass of the sieved slurry).

<Viscosity Measuring Method> A B8H viscometer (manufactured by Tokyo Keiki Co., Ltd.) was used for measurement. Rotor used: No. 4, rotation speed is 20 rpm.

[0093]

[Table 2] Slurry composition and properties

[0094]

[Table 3] Slurry composition and properties

[0095]

[Table 4] Slurry composition and properties

In Tables 2 to 4, similar results were obtained even when "water-soluble polymer" was replaced with CMC, PEG # 1500, and PAA. Also, "α-SF" is AOS-K, L
Similar results were obtained even when AS-Na was used instead. Furthermore, "AA
"O" and "C ₁₂ EO ₁₂ " as C ₁₂ EO ₁₅ , C
₁₆ EO ₁₂ , C ₁₆ EO ₁₅ , C _{180/181 = 1
0/90} EO ₁₂ , C _{180/181 = 10/90} EO
Similar results were obtained even when the "MEE" of ₁₅ was replaced.

[0097]

[Table 5] Slurry composition and properties

In Table 5, "water-soluble polymer" is
Similar results can be obtained by replacing CMC, PEG # 1500, and PAA.
The fruit was obtained. Also, "α-SF" is AOS-K, LA
Similar results were obtained even when S-Na was used instead. Furthermore, "A
AO "to C₁₂EO₁₂, C ₁₂EO₁₅, C₁₆EO
₁₂, C₁₆EO₁₅, C_{180/181 = 10/9 0}
EO₁₂, C_{180/181 = 10/90}EO₁₅of
Even if it replaces with "MEE" and "AAEP15030"
Results were obtained.

Next, the detergent slurry was sprayed using a countercurrent spray drying tower (tower diameter: 2 m, effective length 5 m) with a pressure nozzle system at a spray pressure of 0.3 MPa and a hot air temperature of 260 ° C. (hot air outlet temperature of 90 ° C.). ), The dried product was dried to a water content of 5%. The spray-dried product has an average particle size of 400 μm and a bulk density of 0.3.
The fluidity was also good with 5 g / ml and the angle of repose of 45 °.

(In addition, ・ Slurry water content: 35-50%, dry product can be produced ・ Slurry temperature: 50-80 ° C, dry product can be produced ・ Hot air temperature: 200-300 ° C, dry product can be produced ・ Atomization method: Dry product production is possible with the two-fluid nozzle system and high-speed rotating disc system. ・ Dry product production is possible even with a spraying pressure of 0.2 to 0.4 MPa. ・ Dry product moisture: 2 to 10% can be granulated. ・ Dry product average particle size: Granulation is possible even at 150-500 μm-Bulk density: Granulation is possible even at 0.10-0.50 g / ml-Angle at repose angle is 30-60 °.

[Examples 18 to 35 and Comparative Examples 6 to 11]
The dry powder thus obtained was continuously kneaded with the composition shown in Tables 6 to 11 (KRC Kneader 4 type, manufactured by Kurimoto Iron Works).
Introduced into, to obtain a dense and uniform kneaded product. Kneading ability 177k
Homogenization was performed under the conditions of g / hr and a kneading temperature of 60 ° C. (rotation speed: 134 rpm). The homogenized kneaded product was continuously supplied to a pelletizer double (EXD-100 type (manufactured by Fuji Paudal Co., Ltd.)) and extruded from a 10 mmφ die (die thickness: 10 mm) and simultaneously cut (pelletter). (Cutter) peripheral speed: 5 m / s), and a pellet-like solid substance (pellet size: diameter 10 mmφ, length 20 mm).
At this time, the pressure applied to the pelletizing die is 0.93MP
It was a.

Then, the obtained pellet solids and a granulation aid of 8 kg / hr of zeolite granules (average particle diameter: 100 μm) were made into a solid-gas two-phase flow in a Fitzmill (D).
KASO-6 type (manufactured by Hosokawa Micron Co., Ltd.) so that the average particle diameter becomes 500 μm (rotary crushing blade peripheral speed: 30 m / s, ratio of wind (ki) to pellet (solid) (ki /
(Solid) = 2.3 m / kg) was continuously pulverized in 3 stages (1
Step screen diameter 6 mmφ, rotation speed 1880 rpm, 2
Stage screen diameter 4mmφ, rotation speed 2350rpm, 3
Stage screen diameter 2 mmφ, rotation speed 3760 mmφ).
At this time, the temperature of the gas phase was 16 ° C and the temperature of the powder was 25 ° C. Then, 1% zeolite and 1% nonionic surfactant having the final composition were mixed with the obtained granules in a rolling drum (horizontal cylindrical rolling granulator (diameter: 60 cm, height: 48 cm), mixing and stirring time: 2 min (Froude number:
0.14)) The operation was performed. The pulverizer adhesion, T90 and solubility were evaluated by the following methods. The results are shown in Tables 6 to 11.
Shown in.

<Measurement of crusher adhesion> After crushing for 5 minutes, the amount adhered to the crusher was measured and calculated by substituting it in the following formula and evaluated according to the following criteria. Crusher adhesion rate (%) = 100 x adhesion amount / feed amount <Evaluation criteria> ◎: 0% ≤ adhesion rate ≤ 0.03% ◯: 0.03% ≤ adhesion rate <0.05% △: 0.05 % ≦ adhesion rate <0.1% x: 0.1% <adhesion rate

<Measurement method of T90> A constant speed stirrer (MAZELA Z-1300, manufactured by Tokyo Rikakikai Co., Ltd.) and a conductivity meter (manufactured by Toa Kagaku, pH /) were placed in a 3 liter beaker containing tap water at 5 ° C. EC METERWM-50
EG) was set. Detergent particles (710-1000μ
m) 0.5 g was prepared and stirred in a beaker (250 rp)
Conductivity was measured while m). The time at which the conductivity became 90% was calculated from the conductivity by calculating the time at which the conductivity became constant as the time at which the conductivity was completely dissolved.

<Measurement of Solubility> Prepare 30 liters of tap water at 10 ° C in a tub-type washing machine (Mitsubishi Electric; CW-225), and use 2 navy blue cotton skin shirts, 2 black acrylic sweaters, and black nylon strip. A total of 1.5 kg (a bath ratio of 20 times) of 2 sheets and 5 skin shirts as a charge cloth was put in to form a hollow in the center of the cloth to be washed, and 30 g of detergent was intensively put therein. After allowing the detergent to soak in water for 2 minutes, it was washed with a weak water flow for 5 minutes. It was naturally drained and dehydrated for 1 minute, and the amount of detergent adhering to the cloth was visually evaluated according to the following criteria. <Evaluation Criteria> 0 point: No adhesion at all 1 point: Very slight adhesion, but improved by rinsing Level 2 points: Partial adhesion is observed 3 points: Adhesion to the entire cloth is large Unsatisfactory level after rinsing 4 points: Adhered much to the entire cloth 5 points: Violently adhered to the entire cloth

(In addition, kneading ability: 100 to 300 kg
Manufacture is possible with / hr. Kneading temperature: Manufacture is possible even at 40-80 ° C.・ Rotation speed: 100-150 rpm can be manufactured ・ Die diameter: 0.3-50 mmφ ・ Die thickness: 5-50 mm ・ Pellet size: Diameter 0.3-50 mmφ, length 0.5-
100mm ・ Pellettor-Peripheral speed: 1-10m / s can also be manufactured. ・ Pelletter die pressure: 0.5-1.5MP
Can be manufactured with a. • Grinding aid: Can be manufactured with 20 to 200 μm. • Grinding aid: Can be manufactured with 2 to 18 kg / hr. • Average particle size can be 300 to 1000 μm. • Rotating crushing blade peripheral speed is 20. ～60M / s even manufacturability, gas / solid = 1.0~5m ³ / kg even manufacturability-blast temperature: 10 to 40 ° C. even manufacturable and mixing stirring time: 0.5～5Min even be produced. )

[0107]

[Table 6]

[0108]

[Table 7]

[0109]

[Table 8]

[0110]

[Table 9] In Tables 7 to 9, it was possible to granulate using the dry powders of Examples 6 to 17. In addition, "AAO" is changed to C _{12
EO 9, C 12 EO 12,} C 16 EO 9, C 1 2 EO
₁₅ , C ₁₆ EO ₁₂ , C ₁₆ EO ₁₅ , C
_{180/181 = 10/90} EO ₁₂ , C
_{180/181 = 10/90} EO ₉ , C
"MEE" of _{180/181 = 10/9 0} EO 15,
Similar results were obtained even when "AAEP15030" was used.

[0111]

[Table 10]

[0112]

[Table 11]

In Tables 10 and 11, Comparative Examples 2 to 2
Similar results were obtained with the dry powder of No. 5. In addition, "AA
O "to C₁₂EO₉, C₁₂EO₁₂, C₁₂E
O₁₅, C ₁₆EO₁₂, C₁₆EO₁₅, C
_{180/181 = 10/90}EO₉, C_{18
0/181 = 10/90}EO₁₂, C
_{180/181 = 10/90}EO₁₅"MEE",
Similar results were obtained even when "AAEP15030" was used.

[0114]

EFFECTS OF THE INVENTION According to the present invention, it is possible to obtain a detergent slurry having a low viscosity of soap-based detergent slurry and good stability in which sodium carbonate does not aggregate, and which is industrially highly productive and of high quality. A powder detergent is obtained.

[Brief description of drawings]

FIG. 1 is a schematic view showing an example of a stirring and mixing apparatus of the present invention.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C11D 11/00 C11D 11/00 11/02 11/02 17/06 17/06 (72) Inventor Hiromichi Horie Tokyo, Sumida-ku, Tokyo 1-3-7, Lion Co., Ltd. (72) Inventor, Akitomo Morita 1-3-3, Sumida-ku, Tokyo Tokyo, F-term (reference) 4H003 AB03 AB21 AC08 AC12 BA09 CA20 CA21 DA01 EA12 EA16 EA28 EB32 ED02 FA40

Claims (4)

[Claims] 1. An average number of moles of addition of (A) fatty acid soap, (B) sodium carbonate, (C) water-soluble polymer, and (D) sulfonate type anionic surfactant and / or alkylene oxide is 12 or more. And an ether type or ester type nonionic surfactant of
(D) component is 8 to 60 mass%, and (A)
Powder detergent characterized by being obtained by spray drying under the condition that the ratio of component / (D) component is 100/1 to 100/18 (mass ratio). 2. A powder detergent obtained by granulating the powder detergent according to claim 1 together with a non-soap surfactant and a detergent builder. 3. The average addition mole number of (A) fatty acid soap, (B) sodium carbonate, (C) water-soluble polymer, and (D) sulfonate type anionic surfactant and / or alkylene oxide is 12 or more. An ether type or ester type nonionic surfactant, wherein (A) component + (D) component is 8 to 60% by mass, and (A) component / (D)
A method for producing a powder detergent, comprising spray-drying under the condition that the components are 100/1 to 100/18 (mass ratio). 4. A method for producing a powder detergent, which comprises granulating the powder detergent obtained by the production method according to claim 3 together with a non-soap surfactant and a detergent builder.