JP2007197712A - Detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a detergent composition having deodorization action and giving excellent hand feel to hydrophobic chemical fibers such as acryl/polyester and the like. <P>SOLUTION: The detergent composition comprises (A) an anionic surfactant, (B) a hydroxypropylmethylcellulose having ≥100,000 weight average molecular weight, (C) a bleaching activator expressed by following formula (I) or (II), and(D) a bleaching agent. RCOO-C<SB>6</SB>H<SB>4</SB>-COOM (I), RCOO-C<SB>6</SB>H<SB>4</SB>-SO<SB>3</SB>M (II), wherein R expresses a straight chain or branched chain 9-11C alkyl or alkenyl; M expresses H or a salt forming cation. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a detergent composition, and more particularly to a detergent composition for textile products such as clothing that has a deodorizing action and can impart excellent flexibility (texture) to hydrophobic chemical fibers such as polyester. .

Up to now, various detergent compositions that can be used for clothing and the like have been known. For example, Patent Document 1 discloses a granular detergent composition excellent in cleaning performance by a combination of a powder composed of an α-sulfo fatty acid alkyl ester salt and soap and a nonionic water-soluble cellulose ether. Patent Document 2 discloses a detergent composition for clothing using a combination of endo-type cellulase and methylcellulose in order to sufficiently exhibit the effect of preventing redeposition of dirt and to suppress the deactivation of cellulase even in an alkali. Patent Document 3 discloses a detergent composition comprising a combination of surfactant + nonionic polysaccharide ether + cellulase. Patent Document 4 discloses a detergent composition that has an effect of antifouling and prevention of redeposition and combines a nonionic polysaccharide ether having a polymerization degree of 100 or more and an SR agent. Patent Document 5 discloses a detergent composition that improves antifouling performance by a combination of nonionic polysaccharide ether and nonsoap anionic surfactant. Patent Document 6 discloses a garment care treatment composition containing a polysaccharide.
However, flexibility (texture) with respect to hydrophobic chemical fibers such as acrylic and polyester is not satisfactory, and a pleasant feeling when touching the skin and hands is desired.

Japanese Patent Laid-Open No. 9-302395 Japanese Patent No. 3612414 Japanese National Patent Publication No. 10-512904 JP 10-510003 Gazette Japanese National Patent Publication No. 11-501965 Japanese translation of PCT publication No. 2002-543302

  Accordingly, an object of the present invention is to provide a detergent composition that has a deodorizing action and gives excellent softness (texture) to hydrophobic chemical fibers such as acrylic polyester.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have synergistically combined with anionic surfactant and specific hydroxypropylmethylcellulose synergistically excellent flexibility (texture) on hydrophobic chemical fibers such as polyester. The present invention has been completed.
That is, the present invention comprises (A) an anionic surfactant, (B) hydroxypropyl methylcellulose having a weight average molecular weight of 100,000 or more, (C) a bleach activator represented by the following formula (I) or (II): (D) A detergent composition comprising a bleaching agent is provided.
_{RCOO-C 6 H 4 -COOM (} I)
_{RCOO-C 6 H 4 -SO 3} M (II)
(In formulas (I) and (II), R represents a linear or branched alkyl group or alkenyl group having 7 to 11 carbon atoms, and M represents hydrogen or a salt-forming cation.)

  ADVANTAGE OF THE INVENTION According to this invention, the detergent composition which can give the outstanding softness | flexibility (texture) with respect to hydrophobic chemical fibers, such as polyester, while having a deodorizing effect can be provided. The composition of the present invention also has an excellent recontamination inhibiting effect.

(A) Anionic surfactant The anionic surfactant is not particularly limited as long as it is conventionally used as a detergent, and various anionic surfactants can be used. For example, the following can be mentioned.
(1) Linear or branched alkylbenzene sulfonate having an alkyl group having 8 to 18 carbon atoms (2) Alkyl sulfate (AS) salt or alkenyl sulfate having 10 to 20 carbon atoms (3) 10 to 20 carbon atoms Α-olefin sulfonic acid (AOS) salt of (4) C10-20 alkane sulfonate

(5) Alkyl ether added with ethylene oxide, propylene oxide, butylene oxide or a mixture thereof having a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms and an average addition mole number of 10 moles or less Sulfuric acid (AES) salt or alkenyl ether sulfate (6) Ethylene oxide, propylene oxide, butylene having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and an average addition mole number of 10 moles or less Alkyl ether carboxylate or alkenyl ether carboxylate to which oxide or a mixture thereof is added (7) Alkyl polyhydric alcohol ether sulfate such as alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms (8) C10 to 20 carbon atoms Higher fatty acid salt (soap),
(9) C8-20 saturated or unsaturated α-sulfo fatty acid (α-SF) salts or methyl, ethyl or propyl esters thereof.

Examples of the anionic surfactant include alkali metal salts of linear alkylbenzene sulfonic acid (LAS) (for example, sodium or potassium salt), AS salts, AOS, α-SF, and alkali metal salts of AES (for example, sodium or potassium salt) Etc.) and alkali metal salts of higher fatty acids (for example, sodium or potassium salts). These anionic surfactants can be used singly or in appropriate combination of two or more.
Among these, LAS sodium salt (LAS-Na) having an alkyl group having 10 to 14 carbon atoms, LAS potassium salt (LAS-K), AS salt having an alkyl group having 10 to 20 carbon atoms, 20 higher fatty acid salts, particularly primary soaps and sodium salts of α-SF having 12 to 18 carbon atoms (α-SF-Na) are preferred. A mixture of two or more of these is more preferred. Most preferred are mixtures of LAS-Na, LAS-K, α-SF-Na and higher fatty acid salts. Primary soap refers to a fatty acid salt in which one alkyl group is bonded to the carbon atom to which the carboxylic acid group is bonded.
The form of the composition of the present invention may take any conventional form, and may be granular, solid (tablet, briquette, bar, etc.) or liquid. From the viewpoint of compatibility between the surfactant and the component (B), a granular or solid form is preferable. When the composition of the present invention is in a particulate form, the anionic surfactant is preferably included in the form of particles containing an anionic surfactant (hereinafter, sometimes referred to as “surfactant-containing particles”). When the composition of the present invention is in a liquid form, the anionic surfactant is preferably contained in a form dissolved or solubilized in water or an organic solvent.
The compounding amount of the anionic surfactant in the composition of the present invention is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 10 to 25% by mass based on the total mass of the composition. . The blending amount of the surfactant in the surfactant-containing particles is preferably 10 to 50% by mass, more preferably 15 to 40% by mass in the surfactant-containing particles from the viewpoint of fluidity and solubility during production. It is. If it exceeds 50% by mass, the fluidity may deteriorate, and if it is less than 10% by mass, the solubility may deteriorate. When a higher fatty acid salt is used as the anionic surfactant, the amount of the higher fatty acid salt in the composition is preferably less than 10% by mass and more preferably 1 to 9% by mass from the viewpoint of solubility.

When the composition of the present invention is in a granular form, the average particle size of the surfactant-containing particles is not particularly limited, but is preferably 200 to 1500 μm, more preferably from the viewpoint of powder handling and solubility. Is 250 to 1000 μm, more preferably 300 to 700 μm. The bulk density is weighability, in terms of usability, preferably 0.4~1.2g / cm ^3, more preferably 0.5 to 1.0 g / cm ^3. The angle of repose is preferably 60 ° or less, particularly preferably 50 ° or less from the viewpoint of fluidity. The water content of the surfactant-containing particles is preferably 4 to 10% by mass, more preferably 5 to 9% by mass, and further preferably 5 to 8% by mass from the viewpoints of solubility and storage stability. These characteristic values can be measured by the method described in Examples described later.

(B) Hydroxypropylmethylcellulose In the present invention, hydroxypropylmethylcellulose is a compound having a cellulose skeleton and is a derivative in which part of the hydrogen atoms of the hydroxyl group is substituted with a methyl group or a hydroxypropyl group. Among celluloses, hydroxypropylmethylcellulose is excellent in terms of improving the flexibility (texture) of chemical fibers.
The weight average molecular weight of the component (B) of the present invention is at least 100,000, preferably 300,000 or more, more preferably 350,000 or more. From the viewpoint of solubility, the upper limit of the weight average molecular weight is preferably 1,000,000. When the weight average molecular weight is less than 100,000, the adsorptivity to the chemical fiber is lowered, and a desired flexibility (texture) may not be obtained. The component (B) is preferably 19 to 30% by mass of methoxyl group, 4 to 12% by mass of hydroxyproposyl group, more preferably 25 to 30% by mass of methoxyl group, and 4 to 4 of hydroxypropoxyl group. 12% by mass, most preferably 28-30% by mass of methoxyl group, and 7-12% by mass of hydroxypropoxyl group. The degree of substitution of the component (B) is 1.5 to 2.3, preferably 1.8 to 2.2, and more preferably 2.0 to 2.2. In addition, the said substitution degree is the sum total of the average added mole number of the methoxyl group added per glucose ring unit of a cellulose, and a hydroxypropoxyl group. The average number of hydroxyl groups substituted with methoxyl groups per glucose ring unit of cellulose is 1.4 to 2.0, preferably 1.7 to 2.0, and most preferably 1.9 to 2.0. . Since the hydrophilic / hydrophobic balance changes depending on the structure, the adsorptivity decreases when the structure deviates from this structure, and the desired flexibility (texture) may not be obtained. Specific examples of hydroxypropylmethylcellulose that can be used in the present invention include 60SH4000, 60SH10000, 60SH30000, 65SH400, 65SH1500, 65SH4000, 65SH15000, 90SH400, 90SH4000, and 90SH15000 sold by Shin-Etsu Chemical Co., Ltd. , 90SH30000, 90SH100000 can be used. Among these, 60SH series and 65SH series are particularly preferable.

<Calculation method of molecular weight>
The molecular weight of hydroxypropyl methylcellulose can be measured by gel filtration chromatography (GPC) -multi-angle laser light scattering detector (MALLS) system. (This measurement is carried out by using a liquid feed pump: Shodex DS-4 (manufactured by Showa Denko), a degasser: ERC3115 (manufactured by ERC), a column: Shodex SB-806MHQ (manufactured by Showa Denko), and a light scattering detector: DOWN. (Manufactured by Wyat Technology), concentration detector: Shodex RI-71 (manufactured by Showa Denko), and operating conditions were eluent: 0.1 M NaNO ₃ 1.0 ml / min, sample: 0.02 0.3 wt% The solvent was 0.1 M NaNO ₃ injection amount: 200 μm)

  Moreover, the compounding quantity in a composition becomes like this. Preferably it is 0.01-10.0 mass%, More preferably, it is 0.01-5.0 mass%, More preferably, it is 0.1-3.0 mass%, Especially 0.1 to 2.5% by mass. If the amount exceeds 10.0% by mass, the effect of imparting flexibility (texture) to the chemical fiber may be reduced, and if it is less than 0.01% by mass, a sufficient effect may not be obtained.

  When the composition of the present invention is in a granular form, it is preferable that hydroxypropylmethylcellulose is contained in the surfactant-containing particles in terms of uniform blending. Hydroxypropyl methylcellulose can be added to the slurry or kneaded product obtained in the surfactant-containing particle production process, or can be added after the surfactant-containing particles are obtained. When the composition of the present invention is in a liquid form, it is preferable to dissolve hydroxypropyl methylcellulose in water in advance.

(C) Bleach activator The bleach activator used in the present invention is represented by the following formula (I) or (II).
_{RCOO-C 6 H 4 -COOM (} I)
_{RCOO-C 6 H 4 -SO 3} M (II)
In formulas (I) and (II), R represents a linear or branched alkyl group or alkenyl group having 7 to 11, preferably 9 to 11 carbon atoms, and M is hydrogen or a salt-forming cation such as sodium. Represents a salt-forming cation such as an alkali metal such as potassium, or an amine such as ammonium or alkanolamine.
Specific examples of the bleach activator of the formula (I) include octanoyloxybenzoic acid, nonanoyloxybenzoic acid, decanoyloxybenzoic acid, undecanoyloxybenzoic acid, dodecanoyloxybenzoic acid and the like.
Specific examples of the bleach activator of the formula (II) include sodium octanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, sodium decanoyloxybenzenesulfonate, sodium undecanoyloxybenzenesulfonate, And sodium dodecanoyloxybenzenesulfonate.
In particular, it is preferable to use 4-decanoyloxybenzoic acid, sodium 4-decanoyloxybenzenesulfonate, or sodium 4-dodecanoyloxybenzenesulfonate.
From the viewpoint of storage stability during storage, it is preferably blended as a granulated product or a molded product. The content of the bleach activator in the granulated product or molded product is preferably 30 to 95% by mass, more preferably 50 to 90% by mass. If the content is outside this range, the effect of granulation may not be sufficiently obtained.
These are preferably made into a granulated product or a molded product using a binder compound selected from polyethylene glycol, a saturated fatty acid having 12 to 20 carbon atoms, polyacrylic acid having a weight average molecular weight of 1,000 to 1,000,000 and salts thereof. The polyethylene glycol is preferably polyethylene glycol 1000 to 20000 (average molecular weight 500 to 25000), more preferably an average molecular weight 2600 to 9300, particularly preferably an average molecular weight 5000 to 9300. In addition, the saturated fatty acid having 12 to 20 carbon atoms is preferably a saturated fatty acid having 14 to 20 carbon atoms, and more preferably 14 to 18 carbon atoms. In addition, the average molecular weight of the polyethylene glycol in this invention shows the average molecular weight of cosmetic raw material reference | standard (2nd edition comment) description. The weight average molecular weight of polyacrylic acid and its salt is a value measured by gel permeation chromatography using polyethylene glycol as a standard substance. Such a binder substance is preferably used in the granulated product in an amount of 0.5 to 30% by mass, more preferably 1 to 20% by mass, more preferably 5 to 20% by mass.

  In addition, the granulated product may contain polyoxyalkylene alkyl ether, olefin sulfonate, alkyl benzene sulfonate, alkyl sulfate ester salt or polyoxyethylene alkyl to improve the solubility of the bleach activator in the washing bath. It is preferably used in combination with a surfactant such as an ether sulfate ester salt or a mixture thereof, and the content in the granulated product is preferably 0 to 50% by mass, more preferably 3 to 40% by mass, and particularly preferably 5%. -30 mass%. As polyoxyalkylene alkyl ether, the alkyl group preferably has 10 to 15 carbon atoms, and is preferably an adduct of ethylene oxide (hereinafter abbreviated as EO) and / or propylene oxide (hereinafter abbreviated as PO). The average added mole number is preferably 4 to 30, more preferably 5 to 15 in total in any case of EO, PO, or a mixture of EO and PO, and the molar ratio of EO / PO is preferably 5 / 0 to 1/5, more preferably 5/0 to 1/2. The olefin sulfonate is preferably a sodium or potassium salt of an α-olefin sulfonic acid having an alkyl group with 14 to 18 carbon atoms. The alkylbenzene sulfonate is preferably a sodium or potassium salt of a linear alkylbenzene sulfonic acid having 10 to 14 carbon atoms in the alkyl group. Further, as the alkyl sulfate ester salt, the alkyl group has 10 to 18 carbon atoms, and an alkali metal salt such as a sodium salt is preferable, and sodium lauryl sulfate ester or myristyl sulfate ester sodium is particularly preferable. Moreover, as a polyoxyethylene alkyl ether sulfate ester salt, the polyoxyethylene alkyl ether sulfate ester salt which has a C10-C18 alkyl group is preferable, and a sodium salt is favorable. Here, the average degree of polymerization of the oxyethylene group (hereinafter, the average degree of polymerization is indicated by POE) is 1 to 10, preferably 1 to 5, particularly sodium polyoxyethylene lauryl ether sulfate (POE = 2 to 5). ), Sodium polyoxyethylene myristyl ether sulfate (POE = 2 to 5).

In the present invention, the granulated product of the bleach activator can be produced by any method. In addition, a preferable result can be obtained by adding the binder substance after being melted in advance. The binder material is added after being melted at 40 to 100 ° C, preferably 50 to 100 ° C, more preferably 50 to 90 ° C. These are agitated and mixed until uniform, and then formulated with a normal granulator. Extrusion granulation can be mentioned as a preferable granulation method, and it is preferable to make a granulated product having an average particle size of 500 to 5000 μm, preferably 500 to 3000 μm. As another granulation method, a tablet shape by a briquetting machine can be cited as a preferable granulation method.
Here, it is known that the bleach activator causes hydrolysis during storage due to the presence of alkali components and moisture in the bleach or bleach detergent, and loses the bleaching and sterilizing effects. Therefore, in the present invention, in order to prevent such decomposition, the bleach activator is mixed with a film-forming polymer, zeolite, etc. in addition to the binder and surfactant, and blended as a granulated product. Is more preferable.
The blending ratio of the granulated product containing the bleach activator in the bleach detergent composition is preferably 0.1 to 20% by mass, more preferably 0.5 to 5% by mass in the bleach detergent composition ( The content of component C) is preferably 0.1 to 5% by mass, and more preferably 0.3 to 4% by mass. Even if it exceeds the above range, the deodorizing effect and the bleaching effect may not increase any more, and if it is less than the above range, the sufficient deodorizing effect and bleaching effect may not be obtained.

(D) Bleach The bleaching agent that can be used in the present invention can be used without particular limitation as long as it is usually used as a bleaching agent for clothing, but a peroxide is preferred. Hydrogen peroxide, percarbonate or perborate is more preferred. Of these, percarbonate is particularly preferred, and sodium percarbonate is most preferred.
Although the compounding quantity of (D) component in this invention is not restrict | limited in particular, 1 to 20 mass% is preferable in the composition of this invention, More preferably, 2 to 10 mass% is more preferable. It is.

Optional Component Nonionic Surfactant In the present invention, it is preferable to add a nonionic surfactant because the cleaning performance is improved.
Examples of nonionic surfactants that can be used in the present invention include the following.
1) Polyoxyalkylene alkyl (or alkenyl) ether obtained by adding an average of 3 to 30 moles, preferably 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms 2) Polyoxyethylene alkyl (or alkenyl) phenyl ether 3) Fatty acid alkyl ester alkoxylate represented by the following general formula (I), for example, having an alkylene oxide added between the ester bonds of a long-chain fatty acid alkyl ester
R ¹ CO (OA) _n OR ² (I)
(In the formula, R ¹ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms, and OA is an alkylene having 2 to 4 carbon atoms such as ethylene oxide and propylene oxide, preferably 2 to 3 carbon atoms. Represents an oxide addition unit, and n represents the average number of moles of alkylene oxide added, and is generally a number of 3 to 30, preferably 5 to 20. R ² may have a substituent of 1 to 3 carbon atoms. A good lower (C1-C4) alkyl group is shown.)
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 the nonionic surfactants described above, the above-mentioned 1) nonionic surfactant is preferable, and in particular, a polysiloxane obtained by adding an average of 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 12 to 16 carbon atoms. Oxyalkylene alkyl (or alkenyl) ether is 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 can be used individually by 1 type or in combination of 2 or more types as appropriate.

In this invention, it is preferable that the compounding quantity of nonionic surfactant is 0-30 mass% on the basis of the total mass of a composition, and it is more preferable that it is 1-20 mass%. When the amount of the nonionic surfactant is within such a range, the cleaning performance is excellent.
(E) When the HLB contains a nonionic surfactant having 13 or less, the mass ratio (A) / (E) of the component (A) to the component (E) is preferably 60/40 or more, preferably 100/0. Less than, more preferably 70/30 or more, more preferably 90/10 or less, still more preferably 75/25 or more, and still more preferably 80/20 or less. When the mass ratio is in such a range, it is preferable from the viewpoint of not reducing the softness (texture) of the chemical fiber and the cleaning performance.

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”.

-Cleaning builder As a cleaning builder mix | blended in surfactant-containing particle | grains, an inorganic and organic builder is mentioned.
Inorganic builder Examples of inorganic builders include alkaline salts such as sodium carbonate, potassium carbonate, sodium bicarbonate, sodium sulfite, sodium sesquicarbonate, sodium silicate, sodium metasilicate, crystalline layered sodium silicate, and amorphous layered sodium silicate, Neutral salts such as sodium sulfate, orthophosphates, pyrophosphates, tripolyphosphates, metaphosphates, hexametaphosphates, phosphates such as phytate, the following general formula (II)
_{^{x 1 (M 2 O) ·}} Al 2 O 3 · y 1 (SiO 2) · w 1 (H 2 O) (II)
(In the formula, M represents an alkali metal atom such as sodium or potassium, x ¹ , y ¹ and w ¹ represent the number of moles of each component, and generally x ¹ is 0.7 to 1.5, y ^1. Is a number from 0.8 to 6, and w ¹ is an arbitrary positive number.)
A crystalline aluminosilicate represented by the following general formulas (III) and (IV)
_{^{x 2 (M 2 O) ·}} Al 2 O 3 · y 2 (SiO 2) · w 2 (H 2 O) (III)
(In the formula, M represents an alkali metal atom such as sodium or potassium, x ² , y ² and w ² represent the number of moles of each component. In general, x ² is 0.7 to 1.2, y ^2. 1.6 to 2.8, w ² represents 0 or any positive number.)
_{^{x 3 (M 2 O) ·}} Al 2 O 3 · y 3 (SiO 2) · z 3 (P 2 O 5) · w 3 (H 2 O)
(IV)
(In the formula, M represents an alkali metal atom such as sodium or potassium, x ³ , y ³ , z ³ and w ³ represent the number of moles of each component, and generally x ³ is 0.2 to 1.1. , y ³ is 0.2 to 4.0, z ³ is 0.001 to 0.8, w ³ represents 0 or any positive number.)
Amorphous aluminosilicate represented by the following. Among inorganic builders, sodium carbonate, potassium carbonate, sodium silicate, sodium tripolyphosphate, and sodium aluminosilicate are preferable.
The compounding amount of the inorganic builder in the surfactant-containing particles is 10 to 80% by mass, preferably 20 to 70% by mass. If the blending amount of the inorganic builder is too small, the fluidity may be deteriorated, and if it is too much, dust generation may occur.

Organic builder Examples of the organic builder include organic polymer builder and organic low molecular builder. Examples of organic polymer builders include polymers or copolymers such as acrylic acid polymer compounds, polyacetal carboxylates, itaconic acid, fumaric acid, tetramethylene-1,2-dicarboxylic acid, succinic acid, and aspartic acid. Can be mentioned. As the acrylic acid-based polymer compound, an acrylic acid polymer and an acrylic acid / maleic anhydride copolymer are preferable. In particular, a salt of an acrylic acid / maleic anhydride copolymer having a weight average molecular weight of 1000 to 80000, acrylic acid Polymer salts are preferred. In particular, sodium or potassium salt of acrylic acid / maleic anhydride copolymer is preferred. As the polyacetal carboxylate, a polyacetal carboxylate such as polyglyoxylic acid having a weight average molecular weight of 800 to 1000000, preferably 5000 to 200000 described in JP-A No. 54-52196 is suitable. The water-soluble polymer compound preferably has a weight average molecular weight of 1,000 to 1,000,000, more preferably 1,000 to 100,000. The organic polymer builder can be used singly or in appropriate combination of two or more.
Examples of the organic low molecular weight builder include aminocarboxylates such as nitrilotriacetate, ethylenediaminetetraacetate, β-alanine diacetate, aspartate diacetate, methylglycine diacetate, and iminodisuccinate; serine diacetate, Hydroxyaminocarboxylates such as hydroxyiminodisuccinate, hydroxyethylethylenediamine triacetate, dihydroxyethylglycine; hydroxycarboxylates such as hydroxyacetate, tartrate, citrate, gluconate; pyromellitic acid Cyclocarboxylates such as salts, benzopolycarboxylates, cyclopentanetetracarboxylates; ether carboxylic acids such as carboxymethyltaltronate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid mono- or disuccinate Etc. The.
Among these organic low molecular weight builders, citrate, aminocarboxylate, hydroxyaminocarboxylate, and hydroxyiminodisuccinate are preferable.
The compounding quantity of the organic builder in the surfactant-containing particles is 0.1 to 20% by mass, preferably 0.5% to 15% by mass, and more preferably 1 to 10% by mass. If the blending amount of the organic builder is too small, the effect of improving the cleaning performance may not be obtained, and if it is too large, the solubility of the surfactant-containing particles themselves may be deteriorated.
In addition, citrates, aminocarboxylates, hydroxyaminocarboxylates, polyacrylates, acrylic acid-maleic acid copolymers, polyacetal carboxyls are used for the purpose of improving detergency and soil dispersibility in washing liquids. It is preferable to use an organic builder such as an acid salt in combination with an inorganic builder such as zeolite.

-Solubilizers Examples of solubilizers incorporated in the surfactant-containing particles include, for example, potassium carbonate, inorganic ammonium salts such as ammonium sulfate and ammonium chloride, sodium p-toluenesulfonate, sodium xylenesulfonate, cumenesulfone. Examples thereof include water-soluble substances such as benzenesulfonate having a C1-C5 short chain alkyl such as sodium acid, sodium benzoate, sodium benzenesulfonate, sodium chloride, citric acid, D-glucose, urea, and sucrose. . Of these, potassium carbonate and sodium chloride are preferred, and potassium carbonate is particularly preferred from the standpoint of improving solubility and cost.
When potassium carbonate is blended, the blending amount is preferably 1 to 15% by mass, more preferably 2 to 12% by mass in the surfactant-containing particles, from the viewpoint of improving the solubility. When sodium chloride is blended, the blending amount is preferably 1 to 10% by mass, more preferably 2 to 8% by mass in the surfactant-containing particles from the viewpoint of improving the solubility.

・ Swellable water-insoluble substances such as bentonite
Fluorescent agent: bis (triazinylaminostilbene) disulfonic acid derivative (Tinopearl AMS-GX), bis (sulfostyryl) biphenyl salt [Tinopearl CBS-X], etc.
-Antistatic agent: cationic surfactants such as dialkyl quaternary ammonium salts, etc.
-Bulking agents: sodium sulfate, potassium sulfate, etc.
・ Reducing agent: sodium sulfite, potassium sulfite, etc.
-Photocatalyst such as Tinolux BMC (Ciba), Tinolux BBS (Ciba), etc.
・ Perfume, dye, bleach activation catalyst, especially transition metal atoms such as copper, iron, manganese, nickel, cobalt, chromium, vanadium, ruthenium, rhodium, palladium, rhenium, tungsten, molybdenum and ligands are nitrogen A complex is formed through an atom, an oxygen atom, or the like, and the transition metal contained is preferably copper, cobalt, manganese or the like, and particularly preferably copper or manganese.
Surface-treated water-soluble inorganic compound particles (hereinafter referred to as surface-treated inorganic particles): Examples of the surface-treated water-soluble inorganic compound particles include the surface treatment described in pages 3 to 25 of International Publication No. 2004/094313. Water-soluble inorganic compound particles are preferably used.

When the composition of the present invention is in a granular form, it is not particularly limited, but the average particle diameter is preferably 200 to 1500 μm, more preferably 250 to 1000 μm, and 280 to 700 μm. Further preferred. When the average particle diameter is out of such a range, handling and solubility may be deteriorated. The bulk density is usually 0.3 g / cm ³ or more in terms of the metering property and usability, preferably 0.5 to 1.2 g / cm ^3, more preferably a 0.6~1.1g / cm ^3. Furthermore, from the viewpoint of fluidity of the granular detergent composition, the angle of repose is preferably 60 ° or less, particularly preferably 50 ° or less. In addition, an average particle diameter, a bulk density, and a repose angle can be measured by the method as described in the Example mentioned later.

When the composition of the present invention is in a granular form, (A) an anionic surfactant, (B) hydroxypropylmethylcellulose, (C) a bleach activator represented by the following formula (I) or (II): (D) with peroxide
RCOO-C6H4-COOM (I)
RCOO-C6H4-SO3M (II)
(In formulas (I) and (II), R represents a linear or branched alkyl group or alkenyl group having 7 to 11 carbon atoms, and M represents hydrogen or a salt-forming cation), if necessary. It is kneaded together to obtain surfactant-containing particles, and if necessary, it can be produced by mixing with optional components.
In the liquid form, the composition of the present invention can be produced by a conventional method.
The composition of the present invention can be used by a method conventionally used in the art, but (A) an anionic surfactant, (B) hydroxypropyl methylcellulose having a weight average molecular weight of 100,000 or more, (C) the following formula (I ) Or (II) and a detergent composition comprising (D) a peroxide.
RCOO-C6H4-COOM (I)
RCOO-C6H4-SO3M (II)
(In formulas (I) and (II), R represents a linear or branched alkyl group or alkenyl group having 7 to 11 carbon atoms, and M represents hydrogen or a salt-forming cation). The laundry containing chemical fibers such as acrylic and polyester is treated at a bath ratio of 5 to 40 L (water) / Kg (laundry), preferably 10 to 30 L (water) / Kg (laundry). Is preferred. It is preferable from a practical viewpoint that the laundry is processed in such a range. Moreover, as a density | concentration of (A) component at the time of processing, Preferably it is 33-333 ppm, More preferably, it is 66-266 ppm, and as a density | concentration of (B) component, 0.66-66 ppm, More preferably, it is 0.66. The concentration of the component (C) is 0.66 to 33 ppm, more preferably 2 to 30 ppm, the concentration of the component (D) is 6 to 133 ppm, more preferably 13 to 133 ppm, The value of the component concentration ratio (A) / (B) is preferably 7 to 300, more preferably 10 to 250. It is preferable to treat the concentration and concentration ratio in such a range from the viewpoint of not reducing the effect of the present invention and from a practical viewpoint.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. Prior to this, the evaluation method used in the examples will be described.
(1) Fabric pre-treatment / washing and flexibility (texture) evaluation method Pre-treatment: Using a top (manufactured by Lion Corporation), Mitsubishi Electric Corporation two-tank washing machine (CW-C30A1- H _{1 type} ) using tap water of 50 ° C., washing for 15 minutes at standard bath concentration at 30 times the bath ratio, and then dewatering for 5 minutes, followed by washing and dewatering twice, and then rinsing with running water for 15 minutes The rinsing / dehydration operation of dehydrating for 5 minutes was repeated 5 times and hung at room temperature. Washing treatment: Using a fully automatic electric washing machine (JW-Z23A) manufactured by Haier as a washing machine, two pieces of polyester jersey (39 g / sheet), acrylic jersey 2 in tap water with a bath ratio of 28 times and a water temperature of 20 ° C. One sheet (41 g / sheet) and four cotton towels (68 g / sheet) (total 432 g) were treated in the same bath. In addition, the composition of each Example and comparative example (except comparative example 1) was added so that it might become 666 ppm in washing | cleaning liquid, and the washing process was performed. The washing treatment was repeated four times, and after hanging at room temperature, the following evaluation was performed.

<Flexibility (texture)>
A pair of comparisons by 10 professional panelists (the control was the same composition in each Example / Comparative Example, except that hydroxypropylmethylcellulose was removed). Evaluation of the softness (texture) of the chemical fiber was carried out by using a composition treated with hydroxypropylmethylcellulose as a control.
Better than control: +2
Slightly better than the control: +1
Equivalent to control: 0
Slightly worse than the control: -1
Bad compared to control: -2
When the total score of 10 people is 16-20, ◎◎ when 11-15, ◯ when 6-10, Δ when 1-5, and x when 0 or less. The evaluation results are as shown in Table 1.
(2) Evaluation method of deodorant effect (i) Washing method 5 people wear a new 100% cotton skin shirt (BVD), and after about 1 day in normal life, the skin shirt is fully automatic washing machine ( It was put into Matsushita Electric, NA-F70AP), and tap water having a temperature of about 20 ° C. and a hardness of about 3 ° DH was poured into it and was washed on a standard course. The amount of detergent input was in accordance with the amount of detergent displayed on the washing machine. After dehydration, the sample was dried in a room with a room temperature of about 25 ° C. and a humidity of 70% RH, and dried for 12 hours.
(Ii) Deodorizing effect evaluation method After washing and drying each detergent composition according to the following washing method, the smell of the clothing was sniffed, and the deodorizing effect was evaluated by 10 professional panelists.
0: No foul odor 1: No foul odor 2: No foul odor a little 3: A foul odor is felt, and when the total score of 10 people is 0-7, 8-15, ○, 16-23 When Δ, 24-30, x. The evaluation results are as shown in Table 1.

  Surfactant-containing particles and surface-treated inorganic particles were produced by the following production method, and compositions of Examples and Comparative Examples described in Table 1 were obtained. In the following, “%” unless otherwise specified is mass%. In addition, the numerical value in Table 1 shows the mass% on the basis of the total mass of a composition. However, the numerical value of a comparative example is a mass part (mass ratio). Moreover, the amount of each component in Table 1 indicates the blending amount as a pure component.

<Method 1 for preparing surfactant-containing particles>
According to the composition shown in Table 1 below, surfactant-containing particles 1 were prepared by the following procedure. First, water was put into a jacketed mixing tank equipped with a stirring device, and the temperature was adjusted to 60 ° C. To this, surfactant excluding α-SF-Na and nonionic surfactant was added and stirred for 10 minutes. Subsequently, MA agent (acrylic acid / maleic anhydride copolymer sodium salt, AQUALIC TL-400 (manufactured by Nippon Shokubai Co., Ltd.) (pure 40% aqueous solution)), hydroxypropylmethylcellulose and fluorescent agent (Tinopearl CBS-X (Ciba Specialty Chemicals) / Chino Pearl AMS-GX (Ciba Specialty Chemicals) = 3/1 (mass ratio) mixture). After further stirring for 10 minutes, a part of the powder A-type zeolite (2.0% equivalent amount (vs. each particle, the same applies hereinafter) for the addition during kneading, 3.2% equivalent amount for the grinding aid, Sodium carbonate, potassium carbonate, and sodium sulfite were added except 5% equivalent amount of each type A zeolite for surface coating. The slurry was further stirred for 20 minutes to prepare a slurry for spray drying having a moisture content of 38%, and then spray dried using a countercurrent spray drying tower at a hot air temperature of 280 ° C. to obtain an average particle size of 320 μm and a bulk density of 0.30 g / Spray dried particles with cm ³ and 5% moisture were obtained.
On the other hand, an aqueous slurry of α-SF-Na (moisture concentration 25%) obtained by sulfonating and neutralizing the fatty acid ester of the raw material was mixed with a part of the nonionic surfactant (25 relative to α-SF-Na). %) Was added and concentrated under reduced pressure with a thin film dryer until the water content was 11% to obtain a mixed concentrate of α-SF-Na and a nonionic surfactant.

The above-mentioned spray-dried particles, this mixed concentrate, 2.0% equivalent of type A zeolite, 0.5% equivalent of the remaining nonionic surfactant and water except for spray addition, and continuous kneader (Kurimoto Co., Ltd.) (Kakosho, KRC-S4 type) was kneaded under conditions of a kneading capacity of 120 kg / hr and a temperature of 60 ° C. to obtain a surfactant-containing kneaded product. This surfactant-containing kneaded product 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 / s) A pellet-shaped surfactant-containing molded product having a length of about 5 to 30 mm was obtained.
Next, 3.2% equivalent amount of particulate A-type zeolite (average particle size: 180 μm) as a grinding aid was added to the obtained pellet-shaped surfactant-containing molded product, and coexisting with cold air (10 ° C., 15 m / s) The powder was pulverized using a Fitz mill (manufactured by Hosokawa Micron Co., Ltd., DKA-3) arranged in series at the bottom (screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12 mm / 6 mm / 3 mm, rotation Number: 1st stage / 2nd stage / 3rd stage are all 4700 rpm). Finally, filled with a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, the inner wall surface of the drum of the container 131.7L has two baffle plates with a clearance of 20 mm from the inner wall surface and a height of 45 mm) Rolling for 1 minute while spraying 0.5% equivalent of nonionic surfactant and fragrance, adding 1.5% equivalent of fine powder A-type zeolite under the conditions of rate 30 volume%, rotation speed 22rpm, 25 ° C Then, the surface was modified to obtain particles.

In order to color a part of the obtained particles, the surfactant-containing particles are transported at a speed of 0.5 m / s on the belt conveyor (the height of the surfactant-containing particle layer on the belt conveyor is 30 mm, the layer width) 300 mm) A 20% aqueous dispersion of a pigment (Ultramarine Blue (manufactured by Dainichi Seika Kogyo Co., Ltd.)) was sprayed on the surface, and surfactant-containing particles 1 (average particle size 550 μm, bulk density 0.84 g / cm ³ , angle of repose 45 °).

<Preparation of granular detergent composition>
Filling rate of 30 with a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, inner wall surface of drum of container 131.7 L, clearance between inner wall surface: 20 mm, height: 45 mm) Surface-treated inorganic particles, surfactant-containing particles 1, bleach activator granulated product, sodium percarbonate, and enzyme are mixed for 5 minutes according to the composition shown in Table 1 under the conditions of volume%, rotational speed 22 rpm, 25 ° C. A composition was obtained.

<Method 2 for preparing surfactant-containing particles>
According to the composition shown in Table 1 below, surfactant-containing particles 2 were prepared by the following procedure. First, water was put into a jacketed mixing tank equipped with a stirring device, and the temperature was adjusted to 60 ° C. To this, surfactant excluding α-SF-Na and nonionic surfactant was added and stirred for 10 minutes. Subsequently, an MA agent (acrylic acid / maleic anhydride copolymer sodium salt) and a fluorescent agent were added. After further stirring for 10 minutes, a part of the powder A-type zeolite (2.0% equivalent amount (vs. each particle, the same applies hereinafter) for the addition during kneading, 3.2% equivalent amount for the grinding aid, Sodium carbonate, potassium carbonate, and sodium sulfite were added except 5% equivalent amount of each type A zeolite for surface coating. The slurry was further stirred for 20 minutes to prepare a slurry for spray drying having a moisture content of 38%, and then spray dried using a countercurrent spray drying tower at a hot air temperature of 280 ° C. to obtain an average particle size of 320 μm and a bulk density of 0.30 g / Spray dried particles with cm ³ and 5% moisture were obtained.
On the other hand, an aqueous slurry of α-SF-Na (moisture concentration 25%) obtained by sulfonating and neutralizing the fatty acid ester of the raw material was mixed with a part of the nonionic surfactant (25 relative to α-SF-Na). %) Was added and concentrated under reduced pressure with a thin film dryer until the water content was 11% to obtain a mixed concentrate of α-SF-Na and a nonionic surfactant.

Continuous kneader of the above-mentioned spray-dried particles, this mixed concentrate, hydroxypropyl methylcellulose, 2.0% equivalent of A-type zeolite, 0.5% equivalent of the remaining nonionic surfactant and water except for spray addition ( The product was put into KRC-S4, manufactured by Kurimoto Seiko Co., Ltd., and kneaded under conditions of a kneading capacity of 120 kg / hr and a temperature of 60 ° C. to obtain a surfactant-containing kneaded material. This surfactant-containing kneaded product 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 / s) A pellet-shaped surfactant-containing molded product having a length of about 5 to 30 mm was obtained.
Next, 3.2% equivalent amount of particulate A-type zeolite (average particle size: 180 μm) as a grinding aid was added to the obtained pellet-shaped surfactant-containing molded product, and coexisting with cold air (10 ° C., 15 m / s) The powder was pulverized using a Fitz mill (manufactured by Hosokawa Micron Co., Ltd., DKA-3) arranged in series at the bottom (screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12 mm / 6 mm / 3 mm, rotation Number: 1st stage / 2nd stage / 3rd stage are all 4700 rpm). Finally, filled with a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, the inner wall surface of the drum of the container 131.7L has two baffle plates with a clearance of 20 mm from the inner wall surface and a height of 45 mm) Rolling for 1 minute while spraying 0.5% equivalent of nonionic surfactant and fragrance, adding 1.5% equivalent of fine powder A-type zeolite under the conditions of rate 30 volume%, rotation speed 22rpm, 25 ° C Then, the surface was modified to obtain particles.
In order to color a part of the obtained particles, the surfactant-containing particles are transported at a speed of 0.5 m / s on the belt conveyor (the height of the surfactant-containing particle layer on the belt conveyor is 30 mm, the layer width) 300 mm) A 20% aqueous dispersion of the pigment was sprayed on the surface to obtain surfactant-containing particles 23 (average particle size 550 μm, bulk density 0.84 g / cm ³ , angle of repose 45 °).

<Preparation of granular detergent composition>
Filling rate of 30 with a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, inner wall surface of drum of container 131.7 L, clearance between inner wall surface: 20 mm, height: 45 mm) A granular detergent composition in which surface-treated inorganic particles, surfactant-containing particles, bleach activator granules, sodium percarbonate, and enzyme are mixed for 5 minutes according to the composition shown in Table 1 under the conditions of volume%, rotation speed 22 rpm, and 25 ° C. I got a thing.

<Method 3 for preparing surfactant-containing particles>
According to the composition shown in Table 1 below, surfactant-containing particles 3 were prepared by the following procedure. First, water was put into a jacketed mixing tank equipped with a stirring device, and the temperature was adjusted to 60 ° C. To this, surfactant excluding α-SF-Na and nonionic surfactant was added and stirred for 10 minutes. Subsequently, an MA agent (acrylic acid / maleic anhydride copolymer sodium salt) and a fluorescent agent were added. After further stirring for 10 minutes, a part of the powder A-type zeolite (2.0% equivalent amount (vs. each particle, the same applies hereinafter) for the addition during kneading, 3.2% equivalent amount for the grinding aid, Sodium carbonate, potassium carbonate, and sodium sulfite were added except 5% equivalent amount of each type A zeolite for surface coating. The slurry was further stirred for 20 minutes to prepare a slurry for spray drying having a moisture content of 38%, and then spray dried using a countercurrent spray drying tower at a hot air temperature of 280 ° C. to obtain an average particle size of 320 μm and a bulk density of 0.30 g / Spray dried particles with cm ³ and 5% moisture were obtained.
On the other hand, an aqueous slurry of α-SF-Na (moisture concentration 25%) obtained by sulfonating and neutralizing the fatty acid ester of the raw material was mixed with a part of the nonionic surfactant (25 relative to α-SF-Na). %) Was added and concentrated under reduced pressure with a thin film dryer until the water content was 11% to obtain a mixed concentrate of α-SF-Na and a nonionic surfactant.

  Continuous kneader of the above-mentioned spray-dried particles, this mixed concentrate, hydroxypropyl methylcellulose, 2.0% equivalent of A-type zeolite, 0.5% equivalent of the remaining nonionic surfactant and water except for spray addition ( The product was put into KRC-S4, manufactured by Kurimoto Seiko Co., Ltd., and kneaded under conditions of a kneading capacity of 120 kg / hr and a temperature of 60 ° C. to obtain a surfactant-containing kneaded material. This surfactant-containing kneaded product was cut with a cutter while extruding it using 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-shaped surfactant-containing molded product having a length of about 5 to 30 mm was obtained.

Next, 3.2% equivalent amount of particulate A-type zeolite (average particle size: 180 μm) as a grinding aid was added to the obtained pellet-shaped surfactant-containing molded product, and coexisting with cold air (10 ° C., 15 m / s) The powder was pulverized using a Fitz mill (manufactured by Hosokawa Micron Co., Ltd., DKA-3) arranged in series at the bottom (screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12 mm / 6 mm / 3 mm, rotation Number: 1st stage / 2nd stage / 3rd stage are all 4700 rpm). Finally, filled with a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, the inner wall surface of the drum of the container 131.7L has two baffle plates with a clearance of 20 mm from the inner wall surface and a height of 45 mm) Rolling for 1 minute while spraying 0.5% equivalent of nonionic surfactant and fragrance, adding 1.5% equivalent of fine powder A-type zeolite under the conditions of rate 30 volume%, rotation speed 22rpm, 25 ° C Then, the surface was modified to obtain particles.
In order to color a part of the obtained particles, the surfactant-containing particles are transported at a speed of 0.5 m / s on the belt conveyor (the height of the surfactant-containing particle layer on the belt conveyor is 30 mm, the layer width) 300 mm) A 20% aqueous dispersion of the dye was sprayed on the surface to obtain surfactant-containing particles 3 (average particle size 550 μm, bulk density 0.84 g / cm ³ , angle of repose 45 °).

<Preparation of granular detergent composition>
Filling rate of 30 with a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, inner wall surface of drum of container 131.7 L, clearance between inner wall surface: 20 mm, height: 45 mm) Surface treated inorganic particles, surfactant-containing particles 3, hydroxypropylmethylcellulose, granulated bleach activator, sodium percarbonate, and enzyme for 5 minutes according to the composition shown in Table 1 under the conditions of volume%, rotational speed 22 rpm, 25 ° C. A granular detergent composition was obtained by mixing.

<Method 4 for preparing surfactant-containing particles>
According to the composition shown in Table 1 below, surfactant-containing particles 4 were prepared by the following procedure. First, water was put into a jacketed mixing tank equipped with a stirring device, and the temperature was adjusted to 50 ° C. To this, sodium sulfate, a fluorescent agent and hydroxypropylmethylcellulose were added and stirred for 10 minutes. Subsequently, after adding sodium carbonate, PAS (polyacrylic acid sodium salt) was added, and after stirring for another 10 minutes, sodium chloride and a part of the powder A-type zeolite were added. Furthermore, the slurry for spray drying was prepared by stirring for 30 minutes.
The temperature of the obtained slurry for spray drying was 50 ° C. This slurry was spray-dried with a counter-current spray dryer equipped with a pressure spray nozzle to obtain spray-dried particles having a moisture content of 3%, a bulk density of 0.50 g / cm ³ and an average particle size of 250 μm.
Separately, a nonionic surfactant, PEG # 6000, and an anionic surfactant were mixed at a temperature of 80 ° C. to prepare a surfactant composition having a water content of 10%. LAS-Na was used as a solution neutralized with an aqueous sodium hydroxide solution.

Then, the obtained spray-dried particles were put into a Roedige mixer (M20 type, manufactured by Matsubo Co., Ltd.) equipped with a blade-shaped excavator and having a clearance between the shovel and the wall surface of 5 mm (filling rate 50% by volume). The stirring of the main shaft (150 rpm) and the chopper (4000 rpm) was started while flowing 80 ° C. warm water through the jacket at a flow rate of 10 L / min. The surfactant composition prepared above was added thereto over 2 minutes and then stirred for 5 minutes, and then a layered silicate (SKS-6, average particle size 5 μm) and a part of the powder A-type zeolite (10 % Equivalent amount) and stirred for 2 minutes to obtain particles.
In order to color a part of the surfactant-containing particles after mixing the obtained particles and a part (2% equivalent amount) of the powder A-type zeolite with a V blender and spraying a fragrance, A 20% aqueous dispersion of the dye was sprayed in the same manner as in Particle Preparation Method 1 to obtain surfactant-containing particles 4 (average particle size 300 μm, bulk density 0.75 g / cm ³ , angle of repose 35 °). .

<Preparation of granular detergent composition>
Filling rate of 30 with a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, inner wall surface of drum of container 131.7 L, clearance between inner wall surface: 20 mm, height: 45 mm) Surface treated inorganic particles, surfactant-containing particles 4, bleach activator granulated product, sodium percarbonate, and enzyme were mixed for 5 minutes according to the composition shown in Table 1 under the conditions of volume%, rotational speed 22 rpm, and 25 ° C. A detergent composition was obtained.
<Evaluation results in Preparation Method 5 and Comparative Examples 1, 5, 6, and 8>
Comparative Examples 1, 5, 6, and 8 were prepared by removing the anionic surfactant from the detergent composition of Example 2, and the component concentrations other than the anionic surfactant were treated with the composition of Example 2. The composition was added so as to have the same concentration in the washing liquid as in the case of preparing the washing liquid, and the washing liquid was prepared and evaluated in the same manner as in Example 2.
<Measurement of average particle diameter>
Each surfactant-containing particle and detergent composition particle were classified 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 on a tray in the order of a large opening, and a base sample of 100 g / time is placed on the top of the top 1680 μm sieve. Attached to Iida Seisakusho Co., Ltd., Tapping: 156 times / minute, Rolling: 290 times / minute), and after vibrating for 10 minutes, the sample remaining on each sieve and the saucer was collected for each sieve, The mass of was measured.
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 size (weight: 50%) was calculated by the following equation, where c% was the cumulative mass frequency from the sieve to the aμm sieve and d% was the mass frequency on the aμm sieve.

<Measurement of bulk density>
The bulk density was measured according to JIS K3362-1998.
<Measurement of repose angle>
The angle of repose was measured using a turntable type repose angle measuring instrument manufactured by Tsutsui Rika Instruments Co., Ltd.
<Measurement of water content>
The amount of water was measured by the heating loss method defined in JIS K3362-1998.

<Preparation of surface-treated inorganic particles>
Surface-treated inorganic particles such as sodium carbonate 85%, acrylic acid / maleic anhydride copolymer sodium salt 3%, lauric acid 7%, water and the rest were prepared in the following steps.
1st step Sodium carbonate was added to a pro-shear mixer (Daiyo Kiko Co., Ltd.) equipped with a blade-shaped shovel and a clearance between the shovel and the wall surface of 5 mm (filling ratio 30% by volume), and stirring was started at a spindle of 150 rpm. (Chopper rotation speed: 1015 rpm, blade tip speed (peripheral speed): 6.9 m / s). After 10 seconds from the start of stirring, an acrylic acid / maleic anhydride copolymer sodium salt aqueous solution (concentration: see MA agent described in raw material column below) is sprayed for 180 seconds with a pressure nozzle (flat nozzle) having a spray angle of 115 degrees. Then, granulation and coating operations were performed. Moreover, when the moisture content with respect to the whole particle | grain amount prepared at the 1st process exceeded 10 mass%, hot air was introduce | transduced into the said apparatus and it dried and adjusted the moisture content 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 to stir the Proshear mixer. Stirring was continued for 30 seconds to obtain particles.

Third Step Next, the obtained particles are filled into a fluidized bed (Glatt-POWREX, model number FD-WRT-20, manufactured by Paulex Co., Ltd.), and after filling, 15 ° C. wind (air) is put into the fluidized bed. Feeding and particle cooling operations were performed to obtain particles cooled to 20 ° C. 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 particles were classified using a sieve having an opening of 2000 μm to obtain surface-treated inorganic particles passing through a sieve having an opening of 2000 μm.

The raw materials used in the examples are shown below.
(A) Anionic surfactant (a-1) LAS-K: linear alkyl (C10-14) benzenesulfonic acid (Lypon LH-200 (manufactured by Lion Corporation) LAS-H pure 96%) Neutralize with 48% aqueous potassium hydroxide when preparing the surfactant composition). The compounding quantity in Table 1 shows the mass% as LAS-K.
(A-2) LAS-Na: linear alkyl (10 to 14 carbon atoms) benzenesulfonic acid (Lypon LH-200 (LAS-H pure 96%) manufactured by Lion Co., Ltd.) was used when preparing the surfactant composition. % Neutralized with aqueous sodium hydroxide). The compounding quantity in Table 1 shows the mass% as LAS-Na.
(A-3) α-SF-Na: Sodium salt of α-sulfo fatty acid methyl ester having 14 carbon atoms: 16 carbon atoms = 18: 82 (manufactured by Lion Corporation, AI = 70%, the remainder being unreacted fatty acid methyl ester) Ester, sodium sulfate, methyl sulfate, hydrogen peroxide, water, etc.)
(A-4) First grade soap: Fatty acid sodium having 12 to 18 carbon atoms (manufactured by Lion Corporation, pure content: 67%, titer: 40 to 45 ° C., fatty acid composition: C12: 11.7%, C14: 0 .4%, C16: 29.2%, C18F0 (stearic acid): 0.7%, C18F1 (oleic acid): 56.8%, C18F2 (linoleic acid): 1.2%, molecular weight: 289)

(B) Hydroxypropylmethylcellulose The following methoxyl group substitution degree is the average number of hydroxyl groups substituted with methoxyl groups per glucose ring unit of cellulose.
(B-1) Metroise 60SH4000 (manufactured by Shin-Etsu Chemical Co., Ltd. HPMC, weight average molecular weight of about 300,000, methoxyl group substitution degree of 1.9, methoxyl group mass% is 28-30%, hydroxypropoxyl group mass% 7-12 hydroxypropyl methylcellulose)
(B-2) Metrows 60SH10000 (manufactured by Shin-Etsu Chemical Co., Ltd. HPMC, weight average molecular weight of about 380,000, methoxyl group substitution degree of 1.9, methoxyl group mass% is 28-30%, hydroxypropoxyl group mass% 7-12 hydroxypropyl methylcellulose)
(B-3) Metrows 60SH30000 (manufactured by Shin-Etsu Chemical Co., Ltd. HPMC, weight average molecular weight of about 530,000, methoxyl group substitution degree of 1.9, methoxyl group mass% is 28-30%, hydroxypropoxyl group mass% 7-12 hydroxypropyl methylcellulose)
(B-4) Metroze 65SH1500 (manufactured by Shin-Etsu Chemical Co., Ltd. HPMC, weight average molecular weight of about 210,000, methoxyl group substitution degree of 1.8, methoxyl group mass% is 27 to 30%, hydroxypropoxyl group mass% is 4-7.5 hydroxypropylmethylcellulose)
(B-5) Metrows 65SH4000 (manufactured by Shin-Etsu Chemical Co., Ltd. HPMC, weight average molecular weight of about 300,000, methoxyl group substitution degree 1.8, methoxyl group mass% 27-30%, hydroxypropoxyl group mass% 4-7.5 hydroxypropylmethylcellulose)
(B-6) Metroise 90SH4000 (manufactured by Shin-Etsu Chemical Co., Ltd. HPMC, weight average molecular weight of about 300,000, methoxyl group substitution degree is 1.4, methoxyl group mass% is 19 to 24%, hydroxypropoxyl group mass% is 4-12 hydroxypropylmethylcellulose)
(B-1 ') Metrose 60SH3 (manufactured by Shin-Etsu Chemical Co., Ltd. HPMC, weight average molecular weight of about 20,000, methoxyl group substitution degree of 1.9, methoxyl group mass% is 28-30%, hydroxypropoxyl group mass% 7-12 hydroxypropyl methylcellulose)

(C) Bleach activator (c-1) Preparation method of bleach activator granulated product A As a bleach activator, 4-decanoyloxybenzoic acid (manufactured by Mitsui Chemicals, Inc.) 70 parts by mass, PEG (product) Name: Polyethylene glycol # 6000M (manufactured by Lion Corporation)) 20 parts by mass, sodium α-olefin sulfonate powder product having 14 carbon atoms (trade name: Lipolane PJ-400 (manufactured by Lion Corporation)) 5 parts by mass The mixture was put into Extrude Ohmic EM-6 (trade name) manufactured by Hosokawa Micron Corporation so that the total amount was 5000 g, and kneaded and extruded to obtain a noodle-like extruded product having a diameter of 0.8 mmφ. This extruded product (60 ° C.) was introduced into Fitzmill DKA-3 type (trade name) manufactured by Hosokawa Micron Co., Ltd., and 5 parts by mass of A-type zeolite powder was similarly supplied as an auxiliary agent, and pulverized to obtain an average particle size of about A 700 μm bleach activator granulated product A was obtained.

(C-2) Preparation Method of Bleach Activator Granule B First, synthesis of bleach activator sodium 4-decanoyloxybenzenesulfonate was used as a raw material, sodium 4-hydroxybenzenesulfonate (manufactured by Kanto Chemical Co., Inc.). Reagent), N, N-dimethylformamide (reagent manufactured by Kanto Chemical Co., Inc.), decanoic acid chloride (reagent manufactured by Tokyo Chemical Industry Co., Ltd.), acetone (reagent manufactured by Kanto Chemical Co., Ltd.) and the following method. went.
3000 g (15.3 mol) of sodium 4-hydroxybenzenesulfonate dehydrated in advance was dispersed in 9000 g of N, N-dimethylformamide, and 2918 g (15.3 mol) of decanoic acid chloride was stirred at 50 ° C. for 30 minutes. It was dripped over. Reaction was performed after completion | finish of dripping for 3 hours, and N, N- dimethylformamide was distilled off at 100 degreeC under pressure reduction (0.5-1 mmHg). After washing with acetone, the crystals were purified by recrystallization in a water / acetone (= 1/1 mol) solvent to obtain crystals of sodium 4-decanoyloxybenzenesulfonate. The yield was 91%.
As bleaching activator, except that 4-decanoyloxybenzenesulfonic acid sodium synthesized by the above method was used instead of 4-decanoyloxybenzoic acid, it was the same as bleaching activator granulated product A, Bleach activator granulation B was prepared.

(C-3) Preparation Method of Bleach Activator Granule C Firstly, synthesis of bleach activator sodium 4-dodecanoyloxybenzenesulfonate was used as a raw material, sodium 4-hydroxybenzenesulfonate (manufactured by Kanto Chemical Co., Inc.). Reagent), N, N-dimethylformamide (reagent manufactured by Kanto Chemical Co., Inc.), lauric acid chloride (reagent manufactured by Tokyo Chemical Industry Co., Ltd.), acetone (reagent manufactured by Kanto Chemical Co., Ltd.) and the following method. went.
3,000 g (15.3 mol) of sodium 4-hydroxybenzenesulfonate dehydrated in advance was dispersed in 9000 g of N, N-dimethylformamide, and 3347 g (15.3 mol) of lauric acid chloride was stirred at 50 ° C. for 30 minutes while stirring with a stirrer. It was dripped over. Reaction was performed after completion | finish of dripping for 3 hours, and N, N- dimethylformamide was distilled off at 100 degreeC under pressure reduction (0.5-1 mmHg). After washing with acetone, purification was performed by recrystallization in a water / acetone (= 1/1 mol) solvent to obtain crystals of sodium 4-dodecanoyloxybenzenesulfonate. The yield was 90%.
Next, a bleaching activator granulated product was prepared by the following method.
As the bleach activator granulated product A, except that sodium 4-dodecyloxybenzenesulfonate synthesized by the above method was used instead of sodium 4-decyloxybenzenesulfonate as the bleach activator. Thus, a bleaching activator granulated product C was prepared.
(D) Bleaching agent / sodium percarbonate: manufactured by Mitsubishi Gas Chemical Co., Inc., SPC-D, effective oxygen amount 13.2%, average particle diameter 760 μm
<Nonionic surfactant>
-BRE15: Nonionic surfactant-Ethanol oxide average 15 mol adduct of ECOROL26 (alcohol having 12 to 16 carbon atoms produced by ECOGREEN) (pure content: 90%, melting point: 43 ° C, HLB15.4)
-BRE7: Nonionic surfactant-Softanol 70 (manufactured by Nippon Shokubai Co., Ltd., secondary alcohol ethoxylate having 12 to 14 carbon atoms: ethylene oxide average 7 mol adduct, 100% pure, HLB 12.5)

<Inorganic compounds>
・ Zeolite: A-type zeolite ・ Silton B (manufactured by Mizusawa Chemical Co., Ltd., 80% pure) ・ Carbonate K: Potassium carbonate (powder) (manufactured by Asahi Glass Co., Ltd., average particle size 490 μm, bulk density 1.30 g / cm ³ )
・ Sulfuric acid Na: neutral anhydrous sodium sulfate (made by Nippon Chemical Industry Co., Ltd.)
・ Sulphite Na: anhydrous sodium sulfite (manufactured by Shinshu Chemical Co., Ltd.)
-Carbonic acid Na: granular ash (Asahi Glass Co., Ltd. average particle size 320 μm, bulk density 1.07 g / cm ³ )
<Organic>
MA agent: acrylic acid / maleic anhydride copolymer sodium salt, Aquaric TL-400 (manufactured by Nippon Shokubai Co., Ltd.) (pure 40% aqueous solution)
・ Lauric acid (manufactured by NOF Corporation, NAA-122, melting point 43 ° C.)
Enzyme: Sabinase 12T (Novozymes) / LIPEX100T (Novozymes) / Stainzyme 12T (Novozymes) = 5/4 (mass ratio) mixture <Others>
Fragrance A: Fragrance composition A shown in JP-A-2002-146399 [Table 11] to [Table 18]
Fragrance B: Fragrance composition B shown in JP-A-2002-146399 [Table 11] to [Table 18]
Fragrance C: Fragrance composition C shown in JP-A-2002-146399 [Table 11] to [Table 18]
Fragrance D: Fragrance composition D shown in JP-A-2002-146399 [Table 11] to [Table 18]

Claims (5)

(A) an anionic surfactant, (B) hydroxypropyl methylcellulose having a weight average molecular weight of 100,000 or more, (C) a bleach activator represented by the following formula (I) or (II), and (D) a bleach A detergent composition comprising:
_{RCOO-C 6 H 4 -COOM (} I)
_{RCOO-C 6 H 4 -SO 3} M (II)
(In formulas (I) and (II), R represents a linear or branched alkyl group or alkenyl group having 7 to 11 carbon atoms, and M represents hydrogen or a salt-forming cation.)   The detergent composition according to claim 1, wherein the component (D) is a peroxide.   The detergent composition according to claim 1 or 2, wherein (B) hydroxypropylmethylcellulose has a methoxyl group mass% of 19 to 30%, a hydroxypropoxyl group mass% of 4 to 12%, and a substitution degree of 1.5 to 2.3. .   Further, (E) a nonionic surfactant having an HLB of 13 or less is contained within a range where the mass ratio (A) / (E) of the component (A) to the component (E) is 60/40 or more and less than 100/0. The detergent composition according to any one of claims 1 to 3.   (A) A component is 1st grade soap, The detergent composition of any one of Claims 1-4.