JP5470022B2 - High bulk density granular detergent composition - Google Patents

Description

  The present invention relates to high bulk density granular detergent compositions.

  Conventionally, as a granular detergent composition, particularly a detergent for clothing, a detergent made of spray-dried particles produced by a spray-drying method and having voids inside the particles has been used. However, since the spray-dried particles are bulky, the volume used for one washing is large, and the spray-drying method has a large energy loss and is not economical. Therefore, in place of the above-mentioned spray-dried particles, a so-called compact detergent (high bulk density granular detergent composition) in which the density of the granular detergent is increased in recent years. This high bulk density granular detergent composition can be washed with a smaller apparent volume than before. In addition, the high bulk density granular detergent composition is produced by crushing and granulating a high bulk density detergent kneaded product obtained by closely kneading detergent components such as surfactants and builders with a kneader. A method for obtaining a high bulk density granular detergent composition is common. According to this production method, since it is compacted and granulated into high bulk density particles, drying by the spray drying method can be simplified or omitted, and there is an advantage that there is less energy loss than the spray dried particles. . On the other hand, since the high bulk density granular detergent composition has no voids inside the particles, there is a problem that the solubility is inferior compared with a detergent made of conventional spray-dried particles.

  In recent years, with the increase in capacity of washing machines and the widespread use of drum-type washing machines, the washing environment is an environment in which washing is performed with less water. For this reason, in addition to detergency, detergents are required to have improved solubility and prevent re-contamination (reattachment of dirt).

  Regarding re-contamination, by using carboxymethyl cellulose and / or a salt thereof (hereinafter sometimes referred to as CMC (salt) in general) as a re-contamination preventive agent, it is possible to apply dirt to the laundry to be washed. It is known that reattachment can be prevented (for example, Patent Document 1). It is known that CMC (salt) can be used as a coating agent for nonionic surfactants as well as being used as a recontamination preventing agent (for example, Patent Document 2). Patent Document 2 describes that by coating a nonionic surfactant with CMC (salt), elution of the nonionic surfactant can be prevented and solidification of the granular detergent composition can be prevented. In addition, for example, CMC (salt) is known to be usable as an aggregating agent for fine particle active agents in order to prevent classification of fine particle active agents (tetraacetylethylenediamine, etc.) (for example, patents). Reference 3).

Japanese National Patent Publication No. 11-509574 JP 2005-239786 A Japanese Translation of National Publication No. 08-510767

However, when blending CMC (salt) into a high bulk density granular detergent composition to prevent recontamination, CMC (salt) is added to the slurry or added in a kneading step with a surfactant or the like. Then, there exists a problem that a high bulk density granular detergent composition becomes difficult to melt | dissolve. In addition, when CMC (salt) is powdered with other detergent components, there is a problem that the high bulk density granular detergent composition is easily solidified during storage. As described above, detergents for clothing are required to improve solubility and prevent recontamination. In addition, laundry detergents are required to have excellent storage stability that does not solidify even during long-term storage. The conventional methods for adding CMC (salt) to granular detergent compositions such as Patent Documents 1 to 3 cannot exhibit recontamination prevention performance, excellent solubility, and excellent storage stability.
Therefore, the present invention aims at a high bulk density granular detergent composition that can prevent recontamination and is excellent in solubility and storage stability.

High bulk density granular detergent composition of the present invention, viewed contains at least a portion is coated with nonionic surfactant carboxymethylcellulose particles carboxymethylcellulose and / or the surface of the salt, the carboxymethyl cellulose particles, carboxymethyl cellulose and its The total salt is 70 to 99.5% by mass . The carboxymethyl cellulose particles preferably have a total of carboxymethyl cellulose and a salt thereof of 70 to 99.5% by mass and a nonionic surfactant of 0.1 to 30% by mass.
The high bulk density granular detergent composition of the present invention further contains surfactant-containing particles (excluding the carboxymethylcellulose particles), and the nonionic surfactant is sprayed onto the granular carboxymethylcellulose and / or a salt thereof. The carboxymethyl cellulose particles are prepared, and the carboxymethyl cellulose particles and the surfactant particles are mixed, or granular carboxymethyl cellulose and / or a salt thereof, and the surfactant particles. It is preferable to produce by mixing and spraying the nonionic surfactant on the mixture.

  The high bulk density granular detergent composition of the present invention can prevent recontamination and is excellent in solubility and storage stability.

The high bulk density granular detergent composition of the present invention is a carboxymethyl cellulose particle (hereinafter referred to as CMC particle) in which at least a part of the surface of carboxymethyl cellulose and / or a salt thereof (CMC (salt)) is coated with a nonionic surfactant. Is included). In the present invention, the “high bulk density granular detergent composition” means a known granulation method, for example, a method in which a surfactant or other raw material is dispersed and dissolved in water and spray-dried, or kneading / extrusion. It is obtained by a method such as kneading, granulation, compression molding, and the like, followed by pulverization as necessary, using an apparatus such as stirring granulation and rolling granulation, and a bulk density of 0.6 g / cm ^3. The granular detergent composition raised above is said.

  Although the moisture content of the high bulk density granular detergent composition of the present invention is not particularly limited, it is preferably 4 to 10% by mass, more preferably 5 to 9% by mass, and 6 to 8% by mass from the viewpoints of solubility and storage stability. % Is more preferable. In the present specification, the moisture content is a value measured with an infrared moisture meter (Kett Co., Ltd.) at a sample surface temperature of 165 ° C. for 20 minutes.

(Carboxymethylcellulose particles)
The carboxymethyl cellulose particles are particles in which the surface of CMC (salt) is coated with a nonionic surfactant (hereinafter, the nonionic surfactant used for coating the CMC particles may be referred to as a nonionic surfactant for coating). In the present invention, “coating” means not only a state in which the entire surface of CMC (salt) is covered with a nonionic surfactant, but also a state in which the surface of CMC (salt) is partially covered with a nonionic surfactant. including.

  The degree of coating with the nonionic surfactant for coating on the CMC particles is preferably 50% or more, more preferably 70% or more as a coating ratio with respect to the surface area of CMC (salt), and the entire surface of CMC (salt) is completely covered. A broken state (100% coverage) is particularly preferred. This is because if the coverage is 50% or more, the solubility of CMC (salt) itself is good and the solidification of CMC (salt) as a binder during storage to prevent detergent particles from coalescing can be prevented. .

  Although the compounding quantity of the CMC particle in a high bulk density granular detergent composition is not specifically limited, 0.1-3 mass% is preferable and 0.5-3 mass% is more preferable. This is because if it is less than the lower limit, it is difficult to obtain the effect of preventing recontamination, and if it exceeds the upper limit, it is difficult to improve the cleaning effect of the high bulk density granular detergent composition due to balance with other components. .

<Carboxymethyl cellulose and / or salt thereof>
CMC (salt) is blended as a granular detergent composition to obtain a recontamination preventing effect. Preferable examples of CMC (salt) include anionic water-soluble and water-insoluble cellulose ethers obtained by reacting monochloroacetic acid after treating pulp with caustic soda as a raw material.

  The CMC (salt) preferably has a weight average molecular weight of 100,000 or more, more preferably 300,000 or more, and even more preferably 800,000 or more. The upper limit is preferably 1,200,000 or less, more preferably 1,000,000 or less from the viewpoint of solubility. By setting the range of the weight average molecular weight of CMC (salt) as described above, the recontamination preventing effect can be remarkably improved. On the other hand, if the weight average molecular weight of CMC (salt) is 1.2 million or less, the solubility of CMC (salt) will be good.

Here, the weight average molecular weight can be measured by a method of analyzing with a gel filtration chromatography (GPC) -differential refractive index detector (RI) system using polyethylene glycol (PEG) as a standard substance. The measurement of the weight average molecular weight is an operation of eluent: 0.1 M NaNO ₃ , flow rate: 1 ml / min, sample: 0.02 to 0.3% by mass, solvent: 0.1 M NaNO ₃ , injection amount: 200 μl. In the conditions, the weight average molecular weight is a value calculated as a numerical value in terms of PEG. In addition, for the above measurement, as an apparatus, for example, a liquid feed pump: Shodex DS-4 (manufactured by Showa Denko KK), a degasser: ERC3115 (manufactured by RC Co., Ltd.), a column: Shodex SB-806MHQ (Showa Denko KK) Manufactured), differential refractive index detector: Shodex RI-71 (manufactured by Showa Denko KK) and the like can be used (hereinafter the same).

  The degree of etherification of CMC (salt) is preferably 0.2 to 1.3, more preferably 0.2 to 0.8. The degree of etherification refers to the average number of hydroxyl groups substituted with a carboxymethyl group or a salt thereof per glucose ring unit (of the three hydroxyl groups possessed by the glucose ring, how many are substituted with a carboxymethyl group or a salt thereof). Indicates a maximum of 3).

Preferable examples of CMC (salt) include anionic water-soluble cellulose ethers obtained by reacting monochloroacetic acid after treating pulp with caustic soda as cellulose as a raw material.
Specifically, a polymer compound having a repeating unit represented by the following formula (I) is exemplified.

[In Formula (I), n represents the number of repeating units, R ^{1 to} R ³ each independently represents a hydrogen group or a carboxymethyl group (—CH ₂ COO ⁻ Z ⁺ ; Z ⁺ represents a counter ion. ). ]

In R ^{1 to} R ³ , Z ⁺ is a counter ion, and examples of Z ⁺ include a hydrogen ion, a metal ion, and an ammonium ion. Examples of metal ions include alkali metal ions such as sodium ions and potassium ions. Among these, as Z ⁺ , a metal ion is preferable, an alkali metal ion is more preferable, and a sodium ion is more preferable. That is, CMC (salt) is preferably carboxymethylcellulose sodium salt. This is because carboxymethylcellulose sodium salt has better solubility in water.

  As CMC (salt), for example, CMC Daicel (trade name) 1110, 1120, 1130, 1140, 1160, 1180, 1190, 1220, 1240, 1260, 1280, 1290, 1380 sold by Daicel Chemical Industries, Ltd. 2200, 2260, 2280, 2450, 2340, etc .; Sunrose F series sold by Nippon Paper Chemical Co., Ltd. (trade names) F10LC, F600LC, F1400LC, F10MC, F150MC, F350HC, F1400MC, F1400MG, etc. Sunrose (trade name) A02SH, A20SH, A200SH, etc. Sunrose A series, Sunrose (trade name) SLD-F1; Cellogen (trade name) F-BSH-6 sold by Daiichi Kogyo Seiyaku Co., Ltd. -6HS9, and the like. Among these, CMC Daicel 1130, 1180, 1190, Sunrose F1400LC, F1400MC, Sunrose SLD-F1, and Serogen F-6HS9 are particularly preferable.

  The average particle size of CMC (salt) is preferably 10 to 1500 μm, more preferably 10 to 500 μm, and still more preferably 10 to 100 μm. When the average particle size is in the above range, the high bulk density granular detergent composition has good solubility and is difficult to solidify.

In this specification, the average particle diameter is a value determined by classification using a 9-stage sieve having a mesh opening of 1680 μm, 1410 μm, 1190 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm, and 149 μm and a tray. In the classification operation, a sieve with a small opening is stacked in the order of a sieve with a large opening, and a measurement sample of 100 g / time is placed on the top of the top 1680 μm sieve, and a lid is put on a low-tap type sieve shaker (stock) (Made by Iida Seisakusho, tapping: 156 times / minute, rolling: 290 times / minute), and after shaking for 10 minutes, the sample remaining on each sieve and the saucer was collected for each sieve. Measure the mass.
When the mass frequency of the tray and each sieve is integrated, the opening of the first sieve where the integrated mass frequency is 50% or more is set to a μm, and the opening of the sieve that is one step larger than a μm is set to b μm. The average particle diameter (mass 50%) can be obtained by the following equation (1), where c% is the total mass frequency from the sieve to the aμm sieve and d% is the mass frequency on the aμm sieve (the same applies hereinafter) ).

The content of CMC (salt) in the CMC particles is preferably 70 to 99.5% by mass, more preferably 80 to 99.5% by mass, and still more preferably 90 to 99.5% by mass. . By setting it as the said range, a high bulk density granular detergent composition has favorable solubility, it is hard to solidify, and can acquire the recontamination prevention effect.
CMC (salt) can be used individually by 1 type or in mixture of 2 or more types.

<Nonionic surfactant for coating>
Examples of nonionic surfactants contained in CMC particles include the following.
(1) An average of 3 to 30 mol, preferably 5 to 20 mol, more preferably 10 to 18 mol of an alkylene oxide having 2 to 4 carbon atoms is added to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. Polyoxyalkylene alkyl (or alkenyl) ether. Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable. Examples of the aliphatic alcohol used here include primary alcohols and secondary alcohols. The alkyl group may have a branched chain. As the aliphatic alcohol, a primary alcohol is preferable.
(2) Polyoxyethylene alkyl (or alkenyl) phenyl ether.
(3) A fatty acid alkyl ester alkoxylate represented by, for example, the following general formula (II) in which an alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester.

R ⁴ CO (OA) _m OR ⁵ (II)

[In the formula (II), R ⁴ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms, and OA represents 2 to 4 carbon atoms such as ethylene oxide and propylene oxide, preferably 2 to 3 represents an alkylene oxide addition unit, and m represents the average number of added moles of alkylene oxide, generally 3 to 30, preferably 5 to 20. R ⁵ represents a lower (carbon number 1 to 4) alkyl group which may have a substituent having 1 to 3 carbon atoms. ]

(4) Polyoxyethylene sorbitan fatty acid ester (5) Polyoxyethylene sorbite fatty acid ester (6) Polyoxyethylene fatty acid ester (7) Polyoxyethylene hydrogenated castor oil (8) Glycerin fatty acid ester

  Among these, as the nonionic surfactant for coating, the nonionic surfactant (1) described above is preferable, and in particular, an alkylene oxide having 2 to 4 carbon atoms in an average of 5 to 20 moles of an aliphatic alcohol having 12 to 16 carbon atoms. Added polyoxyalkylene alkyl (or alkenyl) ethers are preferred. A polyoxyethylene alkyl (or alkenyl) ether having a melting point of 50 ° C. or less and an HLB of 9 to 16, a polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether, 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 is preferably used. Moreover, these nonionic surfactants for coating can be used individually by 1 type or in combination of 2 or more types.

  The content of the nonionic surfactant for coating in the CMC particles is preferably 0.1 to 30% by mass, more preferably 0.3 to 15% by mass, and further preferably 0.3 to 5% by mass. It is. By setting it as the said range, the surface of CMC (salt) can be coat | covered moderately, and a high bulk density granular detergent composition has favorable solubility, and it becomes difficult to solidify.

The HLB of the nonionic surfactant in the present invention is a value determined by the Griffin method (Yoshida, Shindo, Ogaki, Yamanaka, edited by “New Edition Surfactant Handbook”, Kogyoshosho Co., Ltd., 1991). , Page 234).
The melting point in the present invention is a value measured by a melting point measurement method described in JIS K0064-1992 “Method for measuring melting point and melting range of chemical products”.

<Other components in CMC particles>
In addition to CMC (salt) and coating nonionic surfactant, CMC particles may contain builders described later.

<Method for producing CMC particles>
The method for producing CMC particles is not particularly limited. For example, CMC (salt) is placed in a horizontal cylindrical rolling mixer, and the nonionic surfactant for coating is sprayed on CMC (salt) while rotating the cylinder. CMC particles can be obtained by coating the surface of CMC (salt) with a nonionic surfactant for coating. In addition, for example, CMC (salt) is put into a horizontal cylindrical rolling mixer together with surfactant-containing particles excluding CMC particles and optional component powder, and the coating nonionic surfactant is sprayed while rotating the cylinder. May be. In this case, a high bulk density granular detergent composition can be obtained simultaneously with the CMC particles.

(Surfactant-containing particles)
In the high bulk density granular detergent composition of the present invention, in addition to CMC particles, a detergent component such as a surfactant is blended as surfactant particles excluding CMC particles (hereinafter sometimes referred to simply as surfactant particles). can do. By blending the surfactant particles, it is possible to improve the cleaning effect of the high bulk density granular detergent composition.

  70 mass% or more is preferable and, as for the compounding quantity of surfactant-containing particle | grains in a high bulk density granular detergent composition, 80 mass% or more is more preferable. It is because there exists a possibility that the improvement of a cleaning effect may not be aimed at that it is less than the said lower limit.

  The surfactant-containing particles are granular particles containing a surfactant. As the surfactant, any of an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant may be blended, and one or two or more of them may be used in combination. When the surfactant-containing particles include the following surfactant, the total amount of the surfactant in the surfactant-containing particles is preferably 10 to 30% by mass, and more preferably 15 to 30% by mass.

<Anionic surfactant>
(1) A methyl, ethyl or propyl ester salt of a saturated or unsaturated α-sulfo fatty acid having 8 to 20 carbon atoms.
(2) Alkali metal salts or alkaline earth metal salts of higher fatty acids having an average number of carbon atoms of 10 to 20 fatty acids.
(3) A linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms.
(4) Alkane sulfonate having 10 to 20 carbon atoms.
(5) α-olefin sulfonate (AOS) having 10 to 20 carbon atoms.
As the α-olefin that is a raw material of AOS, for example, linearene 148 (manufactured by Idemitsu Kosan Co., Ltd.), linear alpha olefins C14-18 (manufactured by SABIC) or the like is used.
(6) C10-20 alkyl sulfate or alkenyl sulfate (AS).
(7) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) with an average of 0.5 Alkyl (or alkenyl) ether sulfate (AES) having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added by 10 mol.
(8) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) on average 3 to 30 An alkyl (or alkenyl) phenyl ether sulfate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added in a mole form.
(9) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) with an average of 0.5 An alkyl (or alkenyl) ether carboxylate having 10 to 20 moles of a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms.
(10) Alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl ether sulfonic acids having 10 to 20 carbon atoms.
(11) Long chain monoalkyl, dialkyl or sesquialkyl phosphate.
(12) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphate.
These anionic surfactants can be used as alkali metal salts such as sodium and potassium, amine salts and ammonium salts. These anionic surfactants may be used as a mixture.

  When an anionic surfactant is blended in the surfactant-containing particles, it is preferably blended in an amount of 5 to 25% by mass, preferably 10 to 20% by mass, based on the total amount of surfactant in the surfactant-containing particles. It is preferable to mix. This is because the cleaning power is good within the above range.

<Nonionic surfactant>
The nonionic surfactant blended in the surfactant-containing particles is the same as the above-described nonionic surfactant for coating.

  When a nonionic surfactant is blended in the surfactant-containing particles, it is preferably blended in an amount of 1 to 20% by mass, preferably 3 to 15% by mass, based on the total amount of the surfactant in the surfactant-containing particles. It is preferable to mix. If it is the said range, it is because detergency is favorable and solidification of a high bulk density granular detergent composition can be suppressed.

<Cationic surfactant>
Examples of the cationic surfactant include the following.
(1) Dilong chain alkyl dishort chain alkyl type quaternary ammonium salt.
(2) Mono long chain alkyl tri short chain alkyl type quaternary ammonium salt.
(3) Tri long chain alkyl mono short chain alkyl type quaternary ammonium salt.
However, the above “long chain alkyl” represents an alkyl group having 12 to 26 carbon atoms, preferably 14 to 18 carbon atoms. The “short chain alkyl” includes a substituent such as a phenyl group, a benzyl group, a hydroxy group, and a hydroxyalkyl group, and may have an ether bond between carbons. Among them, an alkyl group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms; a benzyl group; a hydroxyalkyl group having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms; a polyoxy having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms An alkylene group is mentioned as a suitable thing.

<Amphoteric surfactant>
Examples of amphoteric surfactants include imidazoline-based amphoteric surfactants and amide betaine-based amphoteric surfactants. Specifically, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine and lauric acid amidopropyl betaine are preferable.

<Other components in surfactant-containing particles>
Detergent builders, fluorescent brighteners, polymers, enzyme stabilizers, anti-caking agents, reducing agents, metal ion scavengers, pH adjusters, etc. can be blended with the surfactant-containing particles as necessary. .

<Detergency Builder>
Detergency builders include inorganic builders and organic builders.
Examples of the inorganic builder include alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate, and sesquicarbonate; alkali metal sulfites such as sodium sulfite and potassium sulfite; crystalline layered sodium silicate (for example, manufactured by Clariant Japan Ltd.) Trade name "Na-SKS-6" (δ-Na ₂ O · 2SiO ₂ ) and other crystalline alkali metal silicates; amorphous alkali metal silicates; sulfates such as sodium sulfate and potassium sulfate; sodium chloride Alkali metal chlorides such as potassium chloride; phosphates such as orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate, phytate; crystalline aluminosilicate, amorphous aluminosilicate , A composite of sodium carbonate and amorphous alkali metal silicate (for example, manufactured by Rhodia) NABION15 (trade name)), and the like.

  Among the inorganic builders, sodium carbonate, aluminosilicate, or potassium salts (potassium carbonate, potassium sulfate, etc.) or alkali metal chlorides (potassium chloride, sodium chloride, etc.) are preferred as having the effect of improving solubility.

  As the aluminosilicate, either crystalline or amorphous (amorphous) can be used, and crystalline aluminosilicate is preferable from the viewpoint of cation exchange ability.

  As the crystalline aluminosilicate, A-type, X-type, Y-type, P-type zeolite and the like can be suitably blended, and the average primary particle size is preferably 0.1 to 10 μm. The content of the crystalline aluminosilicate in the surfactant-containing particles is preferably 1 to 40% by mass, and particularly preferably 2 to 30% by mass from the viewpoint of powder physical properties such as cleaning performance and fluidity.

  Commercially available crystalline aluminosilicates include ZEOLITE 4A (trade name) manufactured by HAIXING CHEMICAL CO., LTD. OF DONGYING CITY; FUJIAN RISHENG C. 4A ZEOLITE (trade name) manufactured by L., LTD.); 4A-Zeolite (trade name) manufactured by Shanxi Yuchi Changi High-Tech Co., Ltd .; 4A ZEOLITE (trade name) manufactured by ALUMINUM CORPORATION OF CHINA., LTD .; 4A Zeolite manufactured by Huying Chemical Products Co., LTD. Zeolite 4A Type (trade name) manufactured by Thai Silicate Chemicals Co., Ltd .; COLITE-P (trade name) manufactured by COSMO FINE CHEMICALS CO., LTD .; PQm (PQ chemical C) Suitable examples include VALFOR 100 Zeolite NaA manufactured by Limited; Shiruton B (trade name) manufactured by Mizusawa Chemical Co., Ltd., and the like.

  When mix | blending potassium carbonate, the content is from 1-15 mass% in surfactant-containing particle | grains from the point of the effect of a solubility improvement, More preferably, it is 2-12 mass%.

  When blending an alkali metal chloride, the content thereof is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, and still more preferably from the viewpoint of the effect of improving the solubility in the surfactant-containing particles. Is 3-7% by mass.

  When blending the crystalline alkali metal silicate, the content is preferably 0.5 to 40% by mass, more preferably 1 to 25% by mass in the surfactant-containing particles from the viewpoint of cleaning performance. Preferably it is 3-20 mass%, Most preferably, it is 5-15 mass%.

  Examples of the organic builder include aminocarboxylates such as nitrilotriacetate, ethylenediaminetetraacetate, β-alanine diacetate, aspartate diacetate, methylglycine diacetate, and iminodisuccinate; serine diacetate, hydroxyiminodia Hydroxyaminocarboxylates such as succinate, hydroxyethylethylenediamine triacetate, dihydroxyethylglycine; Hydroxycarboxylates such as hydroxyacetate, tartrate, citrate, gluconate; pyromellitic acid salt, benzoate Cyclocarboxylates such as polycarboxylates and cyclopentanetetracarboxylates; ether carboxylates such as carboxymethyltaltronate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid mono- or disuccinate; poly Crylate, acrylic acid-allyl alcohol copolymer salt, acrylic acid-maleic acid copolymer salt, polyacetal carboxylic acid salt such as polyglyoxylic acid; hydroxyacrylic acid polymer, polysaccharide-acrylic acid copolymer Salt of acrylic acid polymer or copolymer such as polymer; salt of polymer or copolymer such as maleic acid, itaconic acid, fumaric acid, tetramethylene 1,2-dicarboxylic acid, succinic acid, aspartic acid; starch, Examples thereof include polysaccharide oxides such as cellulose, amylose and pectin, and polysaccharide derivatives such as carboxymethylcellulose.

  Among the organic builders, citrate, aminocarboxylate, hydroxyaminocarboxylate, polyacrylate, salt of acrylic acid-maleic acid copolymer, and salt of polyacetal carboxylic acid are preferable. In particular, hydroxyiminodisuccinate, salt of acrylic acid-maleic acid copolymer having a weight average molecular weight of 1000-80000, polyacrylate, acrylic acid-maleic anhydride copolymer having a weight average molecular weight of 1000-80000 And polyacetal carboxylates such as polyglyoxylic acid having a weight average molecular weight of 800 to 1000000 (preferably 5000 to 200000) (for example, those described in JP-A No. 54-52196) are suitable.

The content of the organic builder is preferably 1 to 20% by mass, more preferably 1 to 10% by mass, and particularly preferably 1 to 5% by mass in the surfactant-containing particles.
The said detergency builder can be used individually by 1 type or in combination of 2 or more types as appropriate.

  Among the above detergency builders, the detergency and stain dispersibility in the washing liquid are improved, so that citrate, aminocarboxylate, hydroxyaminocarboxylate, polyacrylate, acrylic acid-maleic acid It is preferable to use an organic builder such as a polymer salt or a polyacetal carboxylic acid salt in combination with an inorganic builder such as zeolite.

  The content of the detergency builder in the surfactant-containing particles is preferably 10 to 80% by mass and more preferably 20 to 75% by mass from the viewpoint of imparting sufficient cleaning performance.

《Fluorescent brightener》
Examples of the optical brightener include 4,4′-bis- (2-sulfostyryl) -biphenyl salt, 4,4′-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, and 2- (styryl). Phenyl) naphthothiazole derivatives, 4,4′-bis (triazol-2-yl) stilbene derivatives, bis- (triazinylaminostilbene) disulfonic acid derivatives, and the like. The said fluorescent brightening agent can be used individually by 1 type or in combination of 2 or more types as appropriate.
The content of the fluorescent brightening agent in the surfactant-containing particles is preferably 0.001 to 1% by mass.

  Commercially available fluorescent brighteners include Whiteex SA, Whitetex SKC (trade name) manufactured by Sumitomo Chemical Co., Ltd .; Chino Pearl AMS-GX, Chino Pearl DBS-X, and Chino Pearl CBS manufactured by Ciba Specialty Chemicals. -X (trade name); Lemonite CBUS-3B (trade name) manufactured by Khyati Chemicals and the like are preferable. Of these, chinopearl CBS-X and chinopearl AMS-GX are more preferable.

<Polymers>
In the present invention, an average molecular weight of 200 is used as a binder or a powder physical property adjusting agent used when densifying the surfactant-containing particles or to impart a recontamination preventing effect on hydrophobic fine particles (dirt). Polyethylene glycol having a molecular weight of ˜200000, a salt of acrylic acid and / or maleic acid polymer having a weight average molecular weight of 1,000 to 100,000, cellulose derivatives such as polyvinyl alcohol, hydroxypropylmethylcellulose (HPMC), and the like can be blended.
Moreover, a copolymer or terpolymer of a repeating unit derived from terephthalic acid and a repeating unit derived from ethylene glycol and / or propylene glycol can be blended as a soil release agent.
Further, polyvinyl pyrrolidone or the like can be blended in order to impart an effect of preventing color transfer.
Among the above polymers, HPMC is preferable and HPMC having a weight average molecular weight of 20,000 or more is more preferable from the viewpoint of imparting flexibility to an object to be washed and preventing recontamination. Such polymers can be used singly or in appropriate combination of two or more.
The content of the polymers in the surfactant-containing particles is preferably 0.05 to 5% by mass.

《Enzyme stabilizer》
As an enzyme stabilizer, calcium salt, magnesium salt, a polyol, formic acid, a boron compound etc. can be mix | blended, for example. Of these, sodium tetraborate, calcium chloride and the like are preferable.
An enzyme stabilizer can be used individually by 1 type or in combination of 2 or more types as appropriate.
The content of the enzyme stabilizer in the surfactant-containing particles is preferably 0.05 to 2% by mass.

<Anti-caking agent>
As the anti-caking agent, paratoluenesulfonate, xylenesulfonate, acetate, sulfosuccinate, talc, fine powder silica, clay, magnesium oxide and the like can be blended.

《Reducing agent》
Examples of the reducing agent include sodium sulfite and potassium sulfite.

《Metal ion scavenger》
The metal ion scavenger captures trace metal ions and the like in tap water and has an effect of suppressing the adsorption of metal ions to the fiber (object to be washed).
As metal ion scavengers, in addition to those included in the detergency builder, aminopolyacetic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, glycolethylenediaminehexaacetic acid; 1-hydroxyethane-1,1-diphosphonic acid (HEDP) -H), ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, hydroxyethane-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic Acid, hydroxymethanephosphonic acid, ethylenediaminetetra (methylenephosphonic acid), nitrilotri (methylenephosphonic acid), 2-hydroxyethyliminodi (methylenephosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) ) Organic phosphonic acid Conductor or a salt thereof; diglycolic acid, citric acid, tartaric acid, oxalic acid, organic acids or salts thereof such as gluconic acid and the like.
The said metal ion trapping agent can be used individually by 1 type or in combination of 2 or more types as appropriate.

  The content of the metal ion scavenger in the surfactant-containing particles is preferably 0.1 to 5% by mass, and more preferably 0.5 to 3% by mass. If it is 0.1 mass% or more, the effect which capture | acquires the metal ion in tap water will improve. On the other hand, if it is 5 mass% or less, the effect of capturing metal ions is sufficiently obtained.

<PH adjuster>
The pH of the surfactant-containing particles is not particularly limited, but from the viewpoint of cleaning performance, the pH in a 1% by mass aqueous solution of the surfactant-containing particles is preferably 8 or more, and the 1% by mass The pH in the aqueous solution is more preferably 9-11. When the pH is 8 or more, the cleaning effect is easily exhibited.
As a technique for controlling the pH of the surfactant-containing particles, the pH is usually adjusted with an alkali agent. In addition to the alkali agent described in the detergency builder, monoethanolamine, diethanolamine, triethanolamine, etc. Alkanolamine, sodium hydroxide, potassium hydroxide and the like.
Specifically, for example, from the viewpoint of solubility in water and alkalinity, NABION15 (trade name, Rhodia Co., Ltd.), which is a mixture of sodium carbonate, sodium silicate, and water at a ratio of 55/29/16 (mass ratio). Are preferably used.
In order to prevent the pH of the surfactant-containing particles from becoming too high, the pH can be adjusted to the above range using an acid or the like. Examples of the acid include the metal ion scavenger, alkali metal dihydrogen phosphates such as potassium dihydrogen phosphate, lactic acid, succinic acid, malic acid, gluconic acid, or polycarboxylic acids thereof, citric acid, sodium hydrogen carbonate. , Sulfuric acid, hydrochloric acid and the like can be used.
In addition, it is also possible to use a buffering agent for preventing a decrease in pH due to an acid component derived from fiber dirt during washing.
The said pH adjuster can be used individually by 1 type or in combination of 2 or more types as appropriate.

  The water content in the surfactant-containing particles is preferably 4 to 10% by mass, more preferably 5 to 9% by mass, and 6 to 8% by mass from the viewpoints of solubility and storage stability. Most preferably.

  The average particle size of the surfactant-containing particles is preferably 200 to 1500 μm, more preferably 250 to 1000 μm, and particularly preferably 300 to 700 μm. This is because when the average particle size is in the above range, the solubility is excellent.

<Method for producing surfactant-containing particles>
The method for producing the surfactant-containing particles can be produced by a known production method. For example, powdery surfactant-containing particles can be obtained by dispersing and dissolving a surfactant and optional components in water and then spray drying. In addition, for example, the surfactant and optional components are subjected to kneading / extrusion, agitation granulation, rolling granulation, etc., and kneading, granulation, compression molding, etc. are performed, and if necessary, by pulverization Surfactant-containing particles having a desired form can be obtained.

(Other ingredients in high bulk density granular detergent composition)
In addition to CMC particles and surfactant-containing particles, high bulk density granular detergent composition contains bleaching agent, bleach activator, bleach activation catalyst, enzyme, antifoaming agent, fragrance, pigment, etc. can do.

<Bleaching agent>
As the bleaching agent, any of oxygen bleaching agents such as hydrogen carbonate and percarbonate such as sodium percarbonate, and chlorine bleaching agents such as sodium hypochlorite and thiourea dioxide can be used. Of these, oxygen bleaches are preferred, percarbonates are more preferred, and sodium percarbonate is most preferred. Commercial products of sodium percarbonate include SPC-D and SPC-HGD (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd .; PC-NK (trade name) manufactured by Nippon Peroxide Co., Ltd .; SPEC (trade name) manufactured by Zhejiang Jin Chemicals Co., Ltd .; sodium percarbonate manufactured by Zhejiang DC Chemical Co., Ltd. It is done.

  As for the compounding quantity of the bleaching agent in a high bulk density granular detergent composition, 1-20 mass% is preferable, More preferably, it is 2-10 mass%. This is because the bleaching effect may be saturated even if blended exceeding the above range, and if it is less than the above range, a sufficient bleaching effect may not be obtained.

<Bleaching activator>
As the bleach activator, a known compound can be used, but an organic peracid precursor is preferably used.
Examples of the organic peracid precursor include tetraacetylethylenediamine, alkanoyloxybenzenesulfonic acid having 8 to 12 carbon atoms, alkanoyloxybenzoic acid having 8 to 12 carbon atoms, and salts thereof, among which 4-decanoyloxy Benzoic acid, sodium 4-dodecanoyloxybenzenesulfonate, and sodium 4-nonanoyloxybenzenesulfonate are preferred. These may be used alone or in combination of two or more.

  The bleach activator can be formulated as particles containing a bleach activator. Particles containing the bleach activator can be produced by a known production method. As a manufacturing method, the granulation method by the extrusion granulation method and the tablet shape using a briquette machine is mentioned, for example. Specifically, the organic peracid precursor particles can be obtained by the following production method. PEG (weight average molecular weight 3000 to 20000, preferably 4000 to 6000) and other solid binder materials heated and melted at room temperature, organic peracid precursor and olefin sulfonate, alkylbenzene sulfonate, alkyl sulfate ester salt A surfactant powder such as is dispersed. Then, it extrudes with an extrusion molding machine etc., makes a noodle shape about 1 mm in diameter, and can further obtain a bleach activator particle | grain by grind | pulverizing to length about 0.5-3 mm. The bleach activator particles thus obtained can be suitably used from the viewpoint of preventing classification in a high bulk density granular detergent composition. As the surfactant powder, an α-olefin sulfonate having an alkyl chain length of 14 is preferred.

<Bleaching activation catalyst>
A known compound can be used as the bleach activating catalyst. Specific examples include transition metal atoms and ligands such as copper, iron, manganese, nickel, cobalt, chromium, vanadium, ruthenium, rhodium, palladium, rhenium, tungsten, and molybdenum via nitrogen atoms, oxygen atoms, etc. To form a complex. As the transition metal contained in the bleach activation catalyst, cobalt, manganese and the like are preferable, and manganese is more preferable. In particular, the bleach activating catalyst described in JP-A No. 2004-189893 is preferable.

  The bleach activation catalyst can be formulated as particles containing the bleach activation catalyst. Particles containing the bleach activating catalyst can be produced by a known granulation method. For example, it can be produced by an extrusion granulation method or a granulation method by a tablet shape using a briquette machine.

<Enzyme>
The enzymes are classified according to the reactivity of the enzymes, and include hydrolases, oxidoreductases, lyases, transferases and isomerases, and any of them can be applied in the present invention. Of these, protease, esterase, lipase, nuclease, cellulase, amylase, pectinase and the like are preferable.

  Examples of the protease include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin, papain, promeline, carboxypeptidase A or B, aminopeptidase, aspergillopeptidase A or B, and the like. As commercial products of protease, sabinase, alcalase, polarzyme, cannase, everase, deozyme (above, trade name, manufactured by Novozymes); API21 (trade name, manufactured by Showa Denko KK); Maxacal, Maxapem (above, trade name, Genencore); protease K-14 or K-16 (protease described in JP-A-5-25492), and the like.

  Examples of the esterase include gastric lipase, buncreatic lipase, plant lipase, phospholipase, cholinesterase, phosphotase and the like.

  Examples of the lipase include commercially available lipases such as lipolase, Lipex (trade name, manufactured by Novozymes), and liposum (trade name, manufactured by Showa Denko KK).

Examples of cellulases include commercially available cellzymes (trade name, manufactured by Novozymes); alkaline cellulase K, alkaline cellulase K-344, alkaline cellulase K-534, alkaline cellulase K-539, alkaline cellulase K-577, and alkaline cellulase K. -425, alkaline cellulase K-521, alkaline cellulase K-580, alkaline cellulase K-588, alkaline cellulase K-597, alkaline cellulase K-522, CMCase I, CMCase II, alkaline cellulase E-II, and alkaline cellulase E-III (the cellulase described in JP-A-63-264699) and the like.
Examples of amylase include commercially available stainzyme, termamyl, duramil (manufactured by Novozymes) and the like.

The said enzyme can be used individually by 1 type or in combination of 2 or more types as appropriate.
In addition, it is preferable to use the enzyme which was granulated as separate stable particles and dry-blended into a high bulk density granular detergent composition.

<Antifoaming agent>
Examples of antifoaming agents include silicone / silica-based ones. Moreover, you may use this antifoamer as the following antifoamer granulated material.

<< Production Method of Antifoam Granules >>
First, 100 g of maltodextrin (trade name, enzyme-modified dextrin, manufactured by Nissho Chemical Co., Ltd.) is added with 20 g of silicone (compound type, product name: PS Antifoam, manufactured by Dow Corning) as an antifoam component and mixed. To obtain a homogeneous mixture. Next, after mixing 50 parts by mass of the obtained homogeneous mixture, 25 parts by mass of polyethylene glycol (PEG-6000, melting point 58 ° C.) and 25 parts by mass of neutral anhydrous sodium sulfate at 70 to 80 ° C., an extrusion granulator (model) It can be granulated by EXKS-1, manufactured by Fuji Paudal Co., Ltd., and an antifoam granulated product can be obtained.

<Fragrance>
A fragrance | flavor is a mixture (fragrance | flavor composition) which consists of a fragrance | flavor component, a solvent, a fragrance | flavor stabilizer, etc. As this fragrance | flavor, the thing as described in Unexamined-Japanese-Patent No. 2002-146399 and Unexamined-Japanese-Patent No. 2003-89800 etc. can be used, for example.
0.001-2 mass% is preferable and, as for content of the fragrance | flavor in a high bulk density granular detergent composition, 0.01-1 mass% is more preferable.

<Dye>
Various pigments such as dyes and pigments can be blended with the high bulk density granular detergent composition in order to improve the appearance. Among these, pigments are preferable from the viewpoint of storage stability, and those having oxidation resistance are particularly preferable. Examples of the dye include oxides, and preferable examples include titanium oxide, iron oxide, copper phthalocyanine, cobalt phthalocyanine, ultramarine blue, bitumen, cyanine blue, and cyanine green.

<Surface treatment water-soluble inorganic compound particles>
As the surface-treated water-soluble inorganic compound particles, for example, the surface-treated water-soluble inorganic compound particles described on pages 3 to 25 of WO 2004/094313 are suitably used.

(Method for producing high bulk density granular detergent composition)
Surfactant-containing particles and CMC particles, together with optional components, are stirred and mixed in a mixer such as a horizontal cylindrical rolling mixer, ribbon mixer, V-type blender, Ladyge mixer and the like. You can get things. In addition, for example, the nonionic surfactant on the surface of CMC (salt) is coated by spraying the nonionic surfactant for coating while stirring the surfactant-containing particles and CMC (salt) together with optional components in the mixer. At the same time as the production of CMC particles, the high bulk density granular detergent composition of the present invention can be obtained.

  As described above, the high bulk density granular detergent composition contains CMC (salt), which is a recontamination preventive agent, as CMC particles obtained by coating the surface of CMC (salt) with a nonionic surfactant for coating. Solidification due to aggregation of CMCs (salts) can be prevented and storage stability can be improved. In addition, since the CMC particles are present independently of the surfactant-containing particles, the contact area with the washing liquid is ensured, and the solubility can be improved. And by including CMC (salt), the high bulk density granular detergent composition has the effect of preventing recontamination.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, it is not limited to an Example.

(Measurement of bulk density)
The bulk density of the granular detergent composition was measured according to JIS-K3362.

(Evaluation of solubility)
<Test method>
In the vicinity of the outer periphery of the pulsator of a washing machine (two-tank washing machine CW-C30A1, manufactured by Mitsubishi Electric Corporation), 30.0 g of a high bulk density granular detergent composition was installed in an assembled state. The installation position of the high bulk density granular detergent composition was such that the water to be poured did not drop directly onto the aggregate of the high bulk density granular detergent composition. Without destroying the aggregate state of this high bulk density granular detergent composition, 1.5 kg of clothing (cotton underwear: 50 mass%, polyester / cotton blend undergarment 50: mass%) was put into a washing tub. Next, 30 L of tap water at 5 ° C. was poured into the washing machine at a flow rate of 10 L / min. Stirring was started with a soft water flow 3 minutes after the start of water injection, and after stirring for 3 minutes, the water was drained, and the state of the high bulk density granular detergent composition remaining in the clothes and the washing tub was visually determined according to the following evaluation criteria. Evaluation criteria ◎◎, ◎, ○ were regarded as acceptable. The “aggregate” described below refers to a lump having a diameter of 3 mm or more in which detergent particles are aggregated.

<Evaluation criteria>
◎: No aggregate ◎: 1 to 3 aggregates ○: 4 to 6 aggregates ×: 7 or more aggregates

(Evaluation of storage stability)
<Test method>
Using paper consisting of three layers of coated cardboard (basis weight: 350 g / m ² ), wax sand paper (basis weight: 30 g / m ² ), and kraft pulp paper (basis weight: 70 g / m ² ) from the outside, A box 15 cm long × 9.3 cm wide × 18.5 cm high was prepared, and 1.1 kg of a high bulk density granular detergent composition was placed in the box. The box containing the high bulk density granular detergent composition was stored in a constant temperature and humidity room for 14 days. The constant temperature and humidity chamber was repeatedly operated at 45 ° C. and 85% RH for 8 hours and at 25 ° C. and 65% RH for 16 hours. After storage for 14 days, the box containing the high bulk density granular detergent composition was taken out of the constant temperature and humidity chamber and allowed to stand at a temperature of 20 ° C. and a relative humidity of 60% for 6 hours. Thereafter, the high bulk density granular detergent composition is gently transferred from the box onto a sieve having an opening of 5 mm, and the sieve is gently swung left and right 10 times, and then the residue on the sieve and the mass passing through the sieve are obtained. The solidification rate was calculated by the following formula (2).

  Solidification rate (%) = [mass of residue on sieve (g)] ÷ [mass of residue on sieve (g) + mass of sieve passage (g)] × 100 (2)

<Evaluation criteria>
From the calculated value of the solidification rate, storage stability was evaluated in the following four stages. Evaluation criteria ◎◎, ◎, ○ were regarded as acceptable.
◎: Less than 0 to 1% ◎: Less than 1 to 5% ○: Less than 5 to 10% ×: More than 10%

(Raw material)
-MES mixed concentrate The MES mixed concentrate was prepared by the method demonstrated below.
<Sulfonation step>
Methyl palmitate (product name: Pastel M-16, manufactured by Lion Corporation) and methyl stearate (product name: Pastel M-180, manufactured by Lion Corporation) were mixed at 80:20 (mass ratio). Further, by performing hydrogenation treatment by a conventional method, the iodine value was reduced to 0.2 and purified to obtain a purified fatty acid methyl ester. Using this flow-through type thin film reactor, this purified fatty acid methyl ester was reacted with SO ₃ gas diluted to 7% with dehumidified air at a reaction molar ratio (SO ₃ / saturated fatty acid ester) = 1.18 and a reaction temperature of 80 ° Sulfonation under conditions gave a sulfonated product.

<Aging process>
The resulting sulfonated product was introduced into a loop ripening tube with a double tube jacket having an average residence time of 20 minutes. Three loop type ripening tubes were connected in succession, and the average residence time was 60 minutes. In order to maintain sufficient stirring and constant temperature, the sulfonated product is allowed to flow through a loop aging tube at a linear speed of 0.16 m / s and controlled to 78 to 82 ° C. to complete the sulfonation by performing an aging reaction. -Sulfo fatty acid methyl ester was obtained.

<Esterification and bleaching process>
After introducing 20 parts by mass of methanol (manufactured by Sumitomo Chemical Co., Ltd .: industrial grade, moisture 500 ppm or less) with respect to 100 parts by mass of the obtained α-sulfo fatty acid methyl ester, this mixture and 35% hydrogen peroxide (Mitsubishi) 5.7 parts by mass of 35% industrial hydrogen peroxide manufactured by Gas Chemical Co., Ltd. (industrial grade) was introduced into a continuous loop reactor equipped with a mixing mixer and a heat exchanger for bleaching, and α-sulfo fatty acid methyl ester A bleached product was obtained.

<Neutralization process>
Next, with respect to 125 parts by mass of the α-sulfo fatty acid methyl ester bleached product, 28 parts by mass of 48% NaOH aqueous solution (Caustic soda manufactured by Daiso Corporation: industrial grade), 25 parts by mass of nonionic surfactant, 69 parts by mass of water, 24 parts by mass of methanol (manufactured by Sumitomo Chemical Co., Ltd .: industrial grade) and 5 parts by mass of linear alkylbenzene sulfonic acid (LAS-H) were continuously supplied to the neutralization line.
The neutralization method employs the neutralization method described in JP-A-2001-64248, and a 48% by mass aqueous solution of sodium hydroxide is quantitatively fed between the premixer and the neutralization mixer. I was able to neutralize. And after neutralizing the neutralized product of the α-sulfo fatty acid methyl ester bleached product previously neutralized and the α-sulfo fatty acid methyl ester bleached product with a premixer, an aqueous sodium hydroxide solution and A neutralized product was obtained by mixing.

<Concentration process>
Furthermore, using the neutralized product as a raw material surfactant aqueous solution, recycling flash evaporation described in Japanese Patent Application Laid-Open No. 2004-210807 is performed, lower alcohol is removed and concentrated, and MES concentration with a water content of 10.8% by mass is concentrated. A mixture (62% by mass of MES, 3.5% by mass of linear alkylbenzene sulfonate Na (LAS-Na), 16.8% by mass of nonionic surfactant) was obtained.

-LAS salt used for surfactant-containing particles a-1 to a-4, a-6 to a-10:
A compound neutralized with a 48% by mass aqueous sodium hydroxide solution during the preparation of linear alkyl (10 to 14 carbon atoms) benzene sulfonic acid [manufactured by Lion Corporation, Rypon LH-200 (LAS-H pure content 96% by mass)] ( LAS-Na) and a compound (LAS-K) neutralized with a 48% by mass aqueous potassium hydroxide solution in a mass ratio of 1: 2 instead of neutralizing with sodium hydroxide. The compounding quantity in a table | surface shows the total amount (mass%) as a mixture of LAS-Na and LAS-K in a MES concentrated mixture.

-LAS salt used for the surfactant-containing particles a-5:
LAS- neutralized with a 48% by weight aqueous sodium hydroxide solution during the preparation of linear alkyl (10 to 14 carbon atoms) benzenesulfonic acid [manufactured by Lion Corporation, Rypon LH-200 (LAS-H pure 96% by mass)] Na.

AOS used for the surfactant-containing particles a-8 to a-10:
Mixture of alkene sulfonic acid Na having 14 to 18 carbon atoms and hydroxyalkane sulfonic acid Na [manufactured by Lion Corporation, Lipolane LB-840 (pure content 38% by mass)]

A higher fatty acid salt having 10 to 20 carbon atoms (hereinafter sometimes simply referred to as a higher fatty acid salt):
Fatty acid sodium having 12 to 18 carbon atoms (manufactured by Lion Corporation, pure content: 67% by mass, titer: 40 to 45 ° C .; fatty acid composition: C12 = 1% by mass, C14 = 10% by mass, C16 = 24% by mass, C18F0 (Stearic acid) = 10 mass%, C18F1 (oleic acid) = 54 mass%, C18F2 (linoleic acid) = 1 mass%).

Nonionic surfactant (A): ECOROL26 (manufactured by ECOGREEN; alcohol having an alkyl group having 12 to 16 carbon atoms) average adduct of 15 moles of ethylene oxide (pure content 90% by mass, water 10%).
Nonionic surfactant (B): ECOROL26 (manufactured by ECOGREEN; alcohol having an alkyl group having 12 to 16 carbon atoms) average adduct of 7 moles of ethylene oxide (pure content 90% by mass, water 10%).
Nonionic surfactant (C): ECOROL26 (manufactured by ECOGREEN; alcohol having an alkyl group having 12 to 16 carbon atoms) average 3 mol of ethylene oxide adduct (pure content 90% by mass, water 10%).
Nonionic surfactant (D): ECOROL26 (manufactured by ECOGREEN; alcohol having an alkyl group having 12 to 16 carbon atoms) average 12-mole ethylene oxide adduct (pure content 90% by mass, water 10%).
Nonionic surfactant (E): Ethanol oxide average 20-mole adduct of ECOROL26 (manufactured by ECOGREEN; alcohol having an alkyl group having 12 to 16 carbon atoms) (pure content 90% by mass, water 10%).
In Table 2, the average number of moles of added ethylene oxide of the nonionic surfactants (A) to (E) is described as “EO”.

Enzyme: Sabinase 12T (Novozymes) / LIPEX100T (Novozymes) / Stainzyme 12GTS (Novozymes) / Cellzyme 0.7T (Novozymes) = 4/1/4/1 (mass ratio) mixture .
Zeolite: A-type zeolite (trade name: Shilton B, manufactured by Mizusawa Chemical Co., Ltd .; pure content 80% by mass, average particle size 180 μm)
MA agent: acrylic acid / maleic anhydride copolymer sodium salt (trade name: Aqualic TL-400, manufactured by Nippon Shokubai Co., Ltd .; pure 40% by weight aqueous solution)
-Sodium polyacrylate: Socaran PA30 (manufactured by BASF, weight average molecular weight 8000, solid content 50% by mass)
CMC: Carboxymethylcellulose sodium salt (trade name: CMC Daicel 1170, manufactured by Daicel Chemical Industries, average particle size 60 μm)
・ Sodium sulfite: anhydrous sodium sulfite (manufactured by Shinshu Chemical Co., Ltd.)
・ Sodium sulfate: neutral anhydrous sodium sulfate (manufactured by Nippon Chemical Industry Co., Ltd.)
Sodium carbonate: granular ash (Asahi Glass Co., Ltd., average particle size 320 μm, bulk density 1.07 g / cm ³ )
Potassium carbonate: Potassium carbonate (powder) (Asahi Glass Co., Ltd .; average particle size 490 μm, bulk density 1.30 g / cm ³ )
-Layered sodium silicate: SKS-6 (manufactured by Clariant)
・ Sodium chloride: Nissei Yaki salt C (manufactured by Nippon Salt Corporation)
NA type bentonite granulated product: Landrosil DGA (manufactured by SUD; Na / Ca mass ratio 2.7)
Fragrance: Fragrance composition A shown in [Table 11] to [Table 18] of JP-A-2002-146399
・ Fluorescent whitening agent: Chinopearl CBS-X (Ciba Specialty Chemicals) / Chinopearl AMS-GX (Ciba Specialty Chemicals) = 3/1 (mass ratio) mixture )

  -Coated sodium carbonate particles: 85% by mass of sodium carbonate, 3% by mass of acrylic acid / maleic anhydride copolymer sodium salt, 7% by mass of lauric acid, water, etc., prepared in the first to third steps shown below Surface treated inorganic particles consisting of the balance

<First step>
Sodium carbonate was charged into a plow shear mixer (manufactured by Taiheiyo Kiko Co., Ltd.) equipped with a blade-shaped shovel and a clearance between the shovel and the wall surface of 5 mm (filling rate: 30% by volume), and stirring was started at a main shaft of 150 rpm ( Chopper rotation speed: 1015 rpm, blade tip speed (peripheral speed): 6.9 m / s). Ten seconds after the start of stirring, the MA agent was sprayed and added for 180 seconds with a pressure nozzle (flat nozzle) having a spray angle of 115 degrees, and granulation and coating operations were performed. In addition, in the particle | grains prepared at the 1st process, when the moisture content with respect to this particle | grain whole quantity exceeded 10 mass%, hot air was introduce | transduced into the said apparatus and it dried, and the moisture content was adjusted to 10 mass% or less. .

<Second step>
Subsequently, lauric acid was sprayed and added for 180 seconds with a pressure nozzle (full cone nozzle) having a spray angle of 60 degrees, while continuing the stirring of the Proshear mixer. Subsequently, stirring was continued for 30 seconds to obtain particles.

<Third step>
Next, after the particles obtained in the second step are filled in a fluidized bed (product name: Glatt-POWREX, model number FD-WRT-20, manufactured by Paulex Co., Ltd.), 15 ° C. air is sent into the fluidized bed. Cooling particles cooled to 20 ° C. were obtained.
The air velocity in the fluidized bed was adjusted in the range of 0.2 to 10.0 m / s while confirming the fluidized state. The obtained cooled particles were classified using a sieve having an opening of 2000 μm to obtain coated sodium carbonate particles passing through a sieve having an opening of 2000 μm.

(Production Example 1) Production of surfactant-containing particles a-1 to a-4 According to the composition shown in Table 1, surfactant-containing particles a-1 to a-4 were obtained in the following production process.
<Process (A)>
Water was put into a jacketed mixing tank equipped with a stirrer, and the temperature was adjusted to 60 ° C. A higher fatty acid salt and a part of the LAS salt (amount excluding LAS-Na contained in the MES concentrated mixture added in the step (B)) were added thereto, followed by stirring for 10 minutes, and then the MA agent was added. After further stirring for 10 minutes, a part of the zeolite (2.0% by mass equivalent amount (for surfactant-containing particles, the same applies hereinafter)) during addition, 5.0% by mass equivalent amount of grinding aid 1), sodium carbonate, potassium carbonate, and sodium sulfate were added. The slurry was further stirred for 20 minutes to prepare a slurry for spray drying having a moisture content of 38% by mass, and then spray-dried using a counter-current spray drying tower at a hot air temperature of 280 ° C., with an average particle size of 320 μm and a bulk density of 0.30 g. / Cm ³ , 5% by mass moisture-dried particles were obtained.

<Process (B)>
Spray dried particles obtained in step (A), MES concentrated mixture, 2.0 mass% equivalent of zeolite, for spray addition (0.3 mass% equivalent) and the amount of nonionic surfactant contained in the MES concentrated mixture Nonionic surfactant (A), fluorescent whitening agent and water are added to a continuous kneader (KRC-S4, KRC-S4 type), and the kneading ability is 120 kg / hr and the temperature is 60 ° C. The mixture was kneaded to obtain a 6% by mass water-containing mixture containing a surfactant.

<Process (C)>
The mixture obtained in the step (B) was cut with a cutter while extruding it with a pelleter double (Fuji Paudal Co., Ltd., EXDFJS-100 type) equipped with a die having a hole diameter of 10 mm (cutter peripheral speed was 5 m / m). s) A pellet having a length of about 5 to 30 mm was obtained. Next, Fitzmill (manufactured by Hosokawa Micron Co., Ltd.) arranged in three stages in series under cold air (10 ° C., 15 m / s) was added zeolite equivalent to 5.0 mass% as a grinding aid to the obtained pellets. DKA-3) (screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12 mm / 6 mm / 3 mm, rotation speed: 1st stage / 2nd stage / 3rd stage are all 4700 rpm) . Thus, surfactant-containing particles a-1 to a-4 were obtained as the surfactant-containing particles.

Production Example 2 Production of Surfactant-Containing Particles a-5 According to the composition shown in Table 1, surfactant-containing particles a-5 were obtained in the following production process.
Water was put into a jacketed mixing tank equipped with a stirrer, and the temperature was adjusted to 50 ° C. In accordance with the composition described in Table 1, sodium sulfate, sodium sulfite, and a fluorescent brightening agent were added. After stirring for 10 minutes, sodium carbonate was added, and then sodium polyacrylate was added. After further stirring for 10 minutes, sodium chloride was added. A part of the powdered zeolite (amount obtained by subtracting an amount corresponding to 10% by mass from the amount shown in Table 1) was added. The slurry was further stirred for 30 minutes to prepare a slurry for spray drying. The temperature of the resulting slurry for spray drying was 60 ° C. This slurry is spray-dried in a counter-current spray dryer equipped with a pressure spray nozzle, the volatile content (105 ° C., reduced for 2 hours) is 3% by mass, the bulk density is 0.50 g / cm ³ , and the average particle Spray-dried particles having a diameter of 250 μm were obtained.

  Next, a nonionic surfactant (B), an LAS salt, and a higher fatty acid salt having 10 to 20 carbon atoms were added under a temperature condition of 80 ° C. to prepare a surfactant composition having a water content of 10% by mass. . Next, spray-dried particles were put into a Redige mixer M20 type (manufactured by Matsuzaka Giken Co., Ltd.), and stirring of the main shaft (150 rpm) and chopper (4000 rpm) was started. Warm water at 80 ° C. was passed through the jacket at a flow rate of 10 L / min. The entire amount of the surfactant composition was added thereto for 2 minutes and stirred for 5 minutes, and then a part of the layered sodium silicate and zeolite (equivalent to 10% by mass) was added to perform surface coating treatment for 2 minutes. Thus, surfactant-containing particles a-5 were obtained as the surfactant-containing particles.

(Production Example 3) Production of Surfactant-Containing Particles a-6 In the step (A), a surfactant-containing material is produced in the same manner as in Production Example 1 except that CMC is mixed in advance with sodium carbonate, potassium carbonate, and sodium sulfate. Particle a-6 was obtained.

(Production Example 4) Production of surfactant-containing particles a-7 In the step (B), surfactant-containing particles a-7 were obtained in the same manner as in Production Example 1 except that CMC was added to the continuous kneader. .

(Production Example 5) Production of surfactant-containing particles a-8 In step (A), part of higher fatty acid salt and LAS salt (excluding LAS-Na contained in the MES concentrated mixture added in step (B)) Surfactant-containing particles a-8 were obtained in the same manner as in Production Example 1 except that AOS was added in addition to (Amount).

(Production Example 6) Production of surfactant-containing particles a-9 In step (A), part of higher fatty acid salt and LAS salt (excluding LAS-Na contained in the MES concentrated mixture added in step (B)) Surfactant-containing particles a-9 were obtained in the same manner as in Production Example 1 except that AOS was added in addition to (Amount) and sodium carbonate, potassium carbonate, sodium sulfate and CMC were mixed in advance.

(Production Example 7) Production of surfactant-containing particles a-10 In step (A), part of higher fatty acid salt and LAS salt (excluding LAS-Na contained in the MES concentrated mixture added in step (B)) Surfactant-containing particles a-10 were obtained in the same manner as in Production Example 1 except that AOS was added in addition to (Amount) and CMC was added to the continuous kneader in Step (B).

(Production Example 8) Production of CMC particles b-1 to b-9 According to the composition of Table 2, CMC was put into a horizontal cylindrical rolling mixer A (cylinder diameter 137 mm, cylinder length 115 mm, container 1.7 L). . Next, rolling was performed for 1 minute while spraying any one of nonionic surfactants (A) to (E) on the CMC as a nonionic surfactant for coating under the conditions of a filling rate of 30% by volume, a rotational speed of 22 rpm, and 25 ° C. The coating nonionic surfactant was adsorbed on the surface of CMC. In this way, CMC particles b-1 to b-9 were obtained.

(Examples 1-14)
According to the composition of Tables 3-4, a horizontal cylindrical rolling mixer B (cylinder diameter 585 mm, cylinder length 490 mm, baffle plate with a clearance of 20 mm from the inner wall surface and a height of 45 mm on the drum inner wall surface of the container 131.7 L In the case of spraying perfume with surfactant-containing particles, predetermined amounts of CMC particles, sodium sulfite and zeolite in each production example under the conditions of a filling rate of 30% by volume, a rotational speed of 22 rpm, and 25 ° C. Rolled for 1 minute to obtain a particle mixture.
In order to color a part of the obtained particle mixture, the particle mixture was transferred on a belt conveyor at a speed of 0.5 m / s (the height of the surfactant-containing particle layer on the belt conveyor was 30 mm, the layer width). 300 mm) The surface was sprayed with 0.1% by weight of a 20% aqueous dispersion of the dye.
In the horizontal cylindrical rolling mixer B, the particles obtained above and the enzyme are mixed for 5 minutes under the conditions of a filling rate of 30% by volume, a rotational speed of 22 rpm, and 25 ° C. to obtain a high bulk density granular detergent composition. It was. The resulting high bulk density granular detergent composition had an average particle size of 500 μm. About the obtained high bulk density granular detergent composition, bulk density (g / cm < ³ >), solubility, and preservability were evaluated, and the result is shown to Tables 3-4. In addition, the manufacturing method of Examples 1-14 is described as "the CMC particle addition method" in a table | surface.

(Example 15)
In accordance with the composition of Table 5, surfactant-containing particles a-1, a predetermined amount of CMC particles b-5, with a horizontal cylindrical rolling mixer B under conditions of a filling rate of 30% by volume, a rotational speed of 22 rpm, and 25 ° C. A high bulk density granular detergent composition was obtained in the same manner as in Example 1 except that sodium sulfite, coated sodium carbonate and zeolite were rolled for 1 minute while spraying the fragrance to obtain a particle mixture. The resulting high bulk density granular detergent composition had an average particle size of 500 μm. About the obtained high bulk density granular detergent composition, bulk density (g / cm < ³ >), solubility, and preservability were evaluated, and the result is shown in Table 5. In addition, the manufacturing method of Example 15 is described as “CMC particle addition method” in the table.

(Example 16)
According to the composition of Table 5, the surfactant-containing particles a-5 and a predetermined amount of zeolite were mixed with a V blender, and then the CMC particles b-5 and the enzyme were mixed with a V blender. Thereafter, a 20% aqueous pigment dispersion and a fragrance were further added by spraying to obtain a high bulk density granular detergent composition. The resulting high bulk density granular detergent composition had an average particle size of 300 μm. About the obtained high bulk density granular detergent composition, bulk density (g / cm < ³ >), solubility, and preservability were evaluated, and the result is shown in Table 5. In addition, the manufacturing method of Example 16 is described as "V mixing" in a table | surface.

(Example 17)
In accordance with the composition in Table 5, the surfactant-containing particles a-1, sodium sulfite, CMC, and zeolite were mixed with a horizontal cylindrical rolling mixer B under the conditions of a filling rate of 30 vol%, a rotation speed of 22 rpm, and 25 ° C. did. The high bulk density granular detergent composition was prepared in the same manner as in Example 1 except that the particle mixture was obtained by rolling for 1 minute while spraying the nonionic surfactant (A) and the fragrance while mixing. Obtained. The resulting high bulk density granular detergent composition had an average particle size of 500 μm. About the obtained high bulk density granular detergent composition, bulk density (g / cm < ³ >), solubility, and preservability were evaluated, and the result is shown in Table 5. The manufacturing method of Example 17 is described as “CMC post-coating method” in the table.

(Examples 18 and 20)
According to the composition of Table 6, in the horizontal cylindrical rolling mixer B, the surfactant-containing particles a-8, a predetermined amount of CMC particles b-5, under the conditions of a filling rate of 30 vol%, a rotation speed of 22 rpm, and 25 ° C. A high bulk density granular detergent composition was obtained in the same manner as in Example 1 except that the coated sodium carbonate and zeolite were rolled for 1 minute while spraying the fragrance to obtain a particle mixture. The resulting high bulk density granular detergent composition had an average particle size of 500 μm. The resulting high bulk density granular detergent composition was evaluated for bulk density (g / cm ³ ), solubility, and storage stability, and the results are shown in Table 6. The production methods of Examples 18 and 20 are described as “CMC particle addition method” in the table.

(Example 19)
In accordance with the composition in Table 6, the surfactant-containing particles a-8, a predetermined amount of CMC particles b-5, and a predetermined amount of CMC particles b-5 and a horizontal cylindrical rolling mixer B under the conditions of a filling rate of 30 vol%, a rotation speed of 22 rpm, and 25 ° C. A high bulk density granular detergent composition was obtained in the same manner as in Example 1 except that zeolite was rolled for 1 minute while spraying the fragrance to obtain a particle mixture. The resulting high bulk density granular detergent composition had an average particle size of 500 μm. The resulting high bulk density granular detergent composition was evaluated for bulk density (g / cm ³ ), solubility, and storage stability, and the results are shown in Table 6. The production method of Example 19 is described as “CMC particle addition method” in the table.

(Example 21)
According to the composition of Table 6, after the surfactant-containing particles a-8 and a predetermined amount of coated sodium carbonate and zeolite were mixed in a V blender, the CMC particles b-5 and the enzyme were mixed in a V blender. A high bulk density granular detergent composition was obtained in the same manner as in Example 16. The resulting high bulk density granular detergent composition had an average particle size of 500 μm. The resulting high bulk density granular detergent composition was evaluated for bulk density (g / cm ³ ), solubility, and storage stability, and the results are shown in Table 6. In addition, the manufacturing method of Example 21 is described as "V mixing" in a table | surface.

(Example 22)
In accordance with the composition of Table 6, the surfactant-containing particles a-8, a predetermined amount of CMC, sodium sulfite and A high bulk density granular detergent composition was obtained in the same manner as in Example 17 except that zeolite was mixed. The resulting high bulk density granular detergent composition had an average particle size of 500 μm. The resulting high bulk density granular detergent composition was evaluated for bulk density (g / cm ³ ), solubility, and storage stability, and the results are shown in Table 6. The production method of Example 22 is described as “CMC post-coating method” in the table.

(Comparative Example 1)
According to the composition of Table 5, a high bulk density granular detergent composition was obtained in the same manner as in Example 17 except that the nonionic surfactant was not sprayed. The resulting high bulk density granular detergent composition had an average particle size of 500 μm. About the obtained high bulk density granular detergent composition, bulk density (g / cm < ³ >), solubility, and preservability were evaluated, and the result is shown in Table 5. In addition, the manufacturing method of the comparative example 1 is described as “without CMC coating” in the table.

(Comparative Example 2)
According to the composition of Table 5, a surfactant-containing particle a-6 was used as the surfactant-containing particle, and a high bulk density granular detergent composition was obtained in the same manner as in Example 1 except that CMC particles were not added. . The resulting high bulk density granular detergent composition had an average particle size of 500 μm. About the obtained high bulk density granular detergent composition, bulk density (g / cm < ³ >), solubility, and preservability were evaluated, and the result is shown in Table 5. In addition, the manufacturing method of Comparative Example 2 is described as “CMC slurry blending method” in the table.

(Comparative Example 3)
A high bulk density granular detergent composition was obtained in the same manner as in Comparative Example 2 except that the surfactant-containing particles a-6 were changed to the surfactant-containing particles a-7. The resulting high bulk density granular detergent composition had an average particle size of 500 μm. About the obtained high bulk density granular detergent composition, bulk density (g / cm < ³ >), solubility, and preservability were evaluated, and the result is shown in Table 5. In addition, the manufacturing method of the comparative example 3 is described as "CMC kneading method" in a table | surface.

(Comparative Example 4)
In accordance with the composition of Table 5, the surfactant-containing particles a-1, sodium sulfite, and zeolite were converted into a nonionic surface active material in a horizontal cylindrical rolling mixer B under the conditions of a filling rate of 30 vol%, a rotation speed of 22 rpm, and 25 ° C. While spraying the agent (A) and the fragrance, it was rolled for 1 minute to obtain a detergent composition precursor.
In order to color a part of the obtained detergent composition precursor, the particles are transferred on a belt conveyor at a speed of 0.5 m / s (the surfactant-containing particle layer on the belt conveyor is 30 mm high and the layer width is 300 mm). ), A 20% aqueous dispersion of the dye was sprayed on the surface.
Using a horizontal cylindrical rolling mixer B, a partially colored detergent composition precursor, CMC, and enzyme are mixed for 5 minutes under the conditions of a filling rate of 30% by volume, a rotational speed of 22 rpm, and 25 ° C., and a high bulk density. A granular detergent composition was obtained. The resulting high bulk density granular detergent composition had an average particle size of 500 μm. About the obtained high bulk density granular detergent composition, bulk density (g / cm < ³ >), solubility, and preservability were evaluated, and the result is shown in Table 5. The manufacturing method of Comparative Example 4 is described as “No CMC coating” in the table.

(Comparative Example 5)
According to the composition of Table 6, a high bulk density granular detergent composition was obtained in the same manner as in Example 22 except that the nonionic surfactant was not sprayed. The resulting high bulk density granular detergent composition had an average particle size of 500 μm. The resulting high bulk density granular detergent composition had an average particle size of 500 μm. The resulting high bulk density granular detergent composition was evaluated for bulk density (g / cm ³ ), solubility, and storage stability, and the results are shown in Table 6. In addition, the manufacturing method of Comparative Example 5 is described as “without CMC coating” in the table.

(Comparative Example 6)
According to the composition of Table 6, a surfactant-containing particle a-9 was used as the surfactant-containing particle, and a high bulk density granular detergent composition was obtained in the same manner as in Example 18 except that CMC particles were not added. . The resulting high bulk density granular detergent composition had an average particle size of 500 μm. The resulting high bulk density granular detergent composition was evaluated for bulk density (g / cm ³ ), solubility, and storage stability, and the results are shown in Table 6. In addition, the manufacturing method of Comparative Example 6 is described as “CMC slurry blending method” in the table.

(Comparative Example 7)
A high bulk density granular detergent composition was obtained in the same manner as Comparative Example 6 except that the surfactant-containing particles a-9 were changed to the surfactant-containing particles a-10. The resulting high bulk density granular detergent composition had an average particle size of 500 μm. The resulting high bulk density granular detergent composition was evaluated for bulk density (g / cm ³ ), solubility, and storage stability, and the results are shown in Table 6. In addition, the manufacturing method of the comparative example 7 is described as "CMC kneading method" in a table | surface.

(Comparative Example 8)
In accordance with the composition in Table 6, the surfactant-containing particles a-8, a predetermined amount of the coated sodium carbonate and zeolite were added in a horizontal cylindrical rolling mixer B under the conditions of a filling rate of 30 vol%, a rotation speed of 22 rpm, and 25 ° C. While spraying the nonionic surfactant (A) and the fragrance, the composition was rolled for 1 minute to obtain a detergent composition precursor.
In order to color a part of the obtained detergent composition precursor, the particles are transferred on a belt conveyor at a speed of 0.5 m / s (the surfactant-containing particle layer on the belt conveyor is 30 mm high and the layer width is 300 mm). ), A 20% aqueous dispersion of the dye was sprayed on the surface.
Using a horizontal cylindrical rolling mixer B, a partially colored detergent composition precursor, CMC, and enzyme are mixed for 5 minutes under the conditions of a filling rate of 30% by volume, a rotational speed of 22 rpm, and 25 ° C., and a high bulk density. A granular detergent composition was obtained. The resulting high bulk density granular detergent composition had an average particle size of 500 μm. The resulting high bulk density granular detergent composition was evaluated for bulk density (g / cm ³ ), solubility, and storage stability, and the results are shown in Table 6. The production method of Comparative Example 8 is described as “No CMC coating” in the table.

  As shown in Tables 3-6, Examples 1 to 16, which were produced by CMC particle addition method or V mixing, using CMC particles b-1 to b-9 in which the surface of CMC was coated with a nonionic surfactant for coating, The high bulk density granular detergent compositions of 18 to 21 were all excellent in solubility and storage stability. In addition, the high bulk density granular detergent compositions of Examples 17 and 22 manufactured by the CMC post-coating method were also excellent in solubility and storage stability. On the other hand, the high bulk density granular detergent compositions of Comparative Examples 1, 4, 5, and 8 produced without coating CMC with the coating nonionic surfactant had poor solubility but good solubility. there were. The high bulk density granular detergent compositions of Comparative Examples 2, 3, 6, and 7 produced by adding CMC to the slurry or kneading into the surfactant-containing particles had excellent storage stability but poor solubility. It was a thing. From the above results, the high bulk density granular detergent composition can prevent recontamination by using CMC particles having the CMC surface coated with a nonionic surfactant for coating, and has excellent solubility and storage stability. It was found that can be demonstrated.

Claims (3)

At least a portion is coated with nonionic surfactant carboxymethylcellulose particles carboxymethylcellulose and / or the surface of the salt seen including,
The said carboxymethylcellulose particle | grain is a high bulk density granular detergent composition whose sum total of carboxymethylcellulose and its salt is 70-99.5 mass% . The carboxymethyl cellulose particles, Roh anion surfactant is 0.1 to 30 wt%, high bulk density granular detergent composition according to claim 1. Further containing surfactant-containing particles (excluding the carboxymethyl cellulose particles),
It is manufactured by spraying the nonionic surfactant onto granular carboxymethyl cellulose and / or a salt thereof to prepare the carboxymethyl cellulose particles, and mixing the carboxymethyl cellulose particles and the surfactant particles, or
The high bulk density according to claim 1 or 2, which is produced by mixing granular carboxymethyl cellulose and / or a salt thereof and the surfactant particles, and spraying the nonionic surfactant on the mixture. Granular detergent composition.