JP2012087216A - Granular detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To dramatically improve suppressing effects on malodors when clothes are allowed to stand in a wet state.SOLUTION: This granular detergent composition includes: (A) an aluminosilicate compound in which the molar ratio SiO:MO:AlOof oxides in the aluminosilicate compound is 5-80:5-65:1-60 (wherein, M represents at least one metal selected from among zinc, copper, silver, cobalt, nickel, iron, titanium, barium, tin and zirconium; and n represents a mole-weighted average atomic valence of metal M); (B) a percarbonate; (C) a bleaching activator; and (D) a surfactant.

Description

  The present invention relates to a granular detergent composition.

  Conventionally, when laundry is dried indoors after washing, malodor is likely to occur, and for detergent compositions, percarbonate, percarbonate and bleach activator are used to suppress malodor. Blends, antibacterial agents, antioxidants, enzymes and the like are blended, and masking agents such as fragrances are blended for deodorizing the generated bad odors (for example, Patent Document 1). .

In general, the following reasons can be given as main causes of bad odor.
1) The residue of dirt is decomposed by the action of various bacteria.
2) Unsaturated compounds in sebum contained in the residue of soil are oxidatively decomposed.

International Publication No. 2010/103833 Pamphlet

  However, in recent years, the proportion of people who do laundry at night has increased, and after washing, the items to be washed may be left as they are in the washing tub. A further effect of suppressing the generation of malodor has been demanded. In addition, the present state is that the malodor control effect has reached its peak even if the bleach activator is simply increased.

  SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a granular detergent composition that exhibits an excellent effect of suppressing the generation of bad odor even in a situation where an object to be washed is left as it is in a washing tub after washing.

As a result of various investigations on the above problem, when a percarbonate, a bleach activator, and an aluminosilicate having a specific composition are blended in a specific ratio in the detergent composition, the clothes become wet. As a result, it was found that the effect of suppressing bad odor when left untreated was drastically improved, resulting in the present invention.

  The granular detergent composition of the present invention is excellent in the effect of suppressing the generation of bad odor in an object to be washed left wet.

The granular detergent composition of the present invention comprises:
(A) The aluminosilicate compound in which the molar ratio of the oxide in the aluminosilicate compound is SiO ₂ : MO _{n / 2} : Al ₂ O ₃ = 5 to 80: 5 to 65: 1 to 60 (provided that M Is at least one metal selected from zinc, copper, silver, cobalt, nickel, iron, titanium, barium, tin and zirconium, and n is the molar weighted average valence of metal M) (hereinafter referred to as “(A) Ingredients ”),
(B) percarbonate (hereinafter referred to as “component (B)”);
(C) Bleach activator (hereinafter referred to as “component (C)”) and (D) surfactant (hereinafter referred to as “component (D)”)
Containing.
<(A) component: aluminosilicate compound having specific composition>
The aluminosilicate compound (A) having a specific composition is added for the purpose of further improving the effect of the bleach activator and suppressing bad odor when the clothes are left in a wet state after washing.

As the composition of the aluminosilicate compound, the molar ratio of the oxide is SiO ₂ : MO _{n / 2} : Al ₂ O ₃ = 5 to 80: 5 to 65: 1 to 60, and SiO ₂ : MO _{n / 2.} : Al ₂ O ₃ = 10 to 70:10 to 60: 1 to 50 is preferable.
Here, M is at least one metal selected from zinc, copper, silver, cobalt, nickel, iron, titanium, barium, tin, and zirconium, and n is a molar weighted average valence of M. Preferably M is zinc.
As zinc aluminosilicate particles, Lionite SF (product name) manufactured by Lion Corporation or the like can be used.

  Alumino zinc silicate particles are obtained as a white to light powder, and water-soluble silicate and water-soluble zinc salt, water-soluble aluminum salt and / or water-soluble aluminate, etc. are reacted in the presence of water, If necessary, the resulting precipitate can be produced by heating in the presence of water.

  This reaction proceeds easily by the so-called metathesis method. That is, an alkali silicate such as sodium silicate is used as the silica component, a water-soluble zinc salt such as chloride, nitrate, or sulfate is used as the zinc oxide component, and an aqueous solution such as aluminum chloride and aluminum sulfate is used as the alumina component. Using a basic aluminum salt and / or sodium aluminate, these are mixed in the presence of moisture and allowed to react by metathesis.

  In order to perform this metathesis reaction homogeneously, it is preferable to carry out the reaction while simultaneously adding an aqueous silicate solution, a zinc salt aqueous solution and an aqueous solution containing an alumina component into water in which silica is dispersed in advance. The reaction by metathesis is sufficient at room temperature, but it can also be carried out under heating. For example, the reaction under heating up to about 95 ° C. is possible. The pH of the reaction system at the time of simultaneous injection is preferably maintained in the range of 5 to 10, particularly 6 to 8. If necessary, it is preferable to add acid or alkali to the reaction system to maintain the pH of the reaction solution within the above range.

  By simultaneous pouring, a precipitate of zinc aluminosilicate having a composition almost corresponding to the composition of the aqueous solution is formed. The precipitate is separated or heated in the presence of moisture as necessary to obtain a white or light-colored fine powder.

  Alternatively, an aqueous solution containing a zinc salt and an aluminum salt can be coprecipitated under alkaline conditions, and the resulting precipitate and silica can be hydrothermally reacted under pressure to produce zinc aluminosilicate.

  The zinc aluminosilicate produced in this way can be adjusted for average particle size by wet grinding or dry grinding after drying. Examples of the pulverization method include jet mill pulverization and ball mill pulverization, but are not particularly limited.

  The average particle size of the aluminosilicate is preferably 10 μm to 0.01 μm, more preferably 5 to 0.1 μm. By setting the particles within the above range, the surface area is increased, and a good reaction or adhesion occurs. If the average particle size exceeds 10 μm, the malodor control effect may be weakened. If the average particle size is less than 0.01 μm, the particles become fine and problems such as fine powder flying easily occur, and the above range is preferable.

In the present invention, it is necessary to previously adjust the average particle size of the raw material aluminosilicate to 0.01 to 3 μm. For example, it must be used after being pulverized once by wet pulverization or dry pulverization. Examples of the pulverization method at this time include jet mill pulverization and ball mill pulverization, but are not particularly limited.
The blending amount is preferably 0.1% to 10%, more preferably 0.2% to 5%, and still more preferably 0.5 to 3% with respect to the whole detergent composition.
The blending ratio of the component (A) to the component (C) is a mass ratio, and (A) / (C) (mass ratio) = 0.1 to 10 is preferable.
<(B) component: percarbonate>
The percarbonate (B) is used for the purpose of generating hydrogen peroxide in an aqueous solution and activating the bleach activator.

  The percarbonate in the present invention is not particularly limited, and any of the percarbonates used in general granular detergent compositions can be suitably used. Inorganic peroxides that generate hydrogen peroxide when dissolved in can be used. Usually, one or both of sodium percarbonate and sodium perborate are used. In particular, sodium percarbonate is preferred from the viewpoint of stability over time. When moisture or other detergent components come into contact with the surface of the inorganic peroxide particles, the inorganic peroxide may be decomposed. Therefore, it is preferable to perform a treatment such as coating to prevent this. As the particles having a coated form, SPCC of JINKE, NAPOX-C1, NAPOX-C2 of Nippon Chemical Co., Ltd., PC-NK of Nippon Peroxide, and the like can be used.

The percarbonate is preferably 1 to 25% by mass, more preferably 3 to 20% by mass, based on the whole granular detergent composition.
<(C) component: bleach activator>
The bleaching activator (C) exhibits a bactericidal effect by reacting with hydrogen peroxide and generating an organic peracid, and further, as described above, synergistically suppresses malodors by using it together with the component (A).
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 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 represented by POE) is 1 to 10, preferably 1 to 5, and particularly sodium polyoxyethylene lauryl ether sulfate (POE = 2 to 5). ), Sodium polyoxyethylene myristyl ether sulfate (POE = 2 to 5) is good.

  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 is hydrolyzed during storage due to the presence of percarbonate or an alkaline component and water in the bleach detergent, and the bleaching and sterilizing effects are lost. 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 bleach activator is preferably 0.1 to 10% by mass, more preferably 0.3 to 8% by mass, and 0.5 to 7% by mass with respect to the whole granular detergent composition. Is more preferable. The effect of this invention is acquired by being 0.1 mass% or more. Even if 10% or more is blended, the malodor control effect may reach its peak.

Further, the blending ratio of the percarbonate (B) and the bleach activator (C) is preferably (B) / (C) = 1 to 100, and the organic peracid is efficiently generated and the odor control effect is enhanced. . If it is less than 1, the amount of bleach activator becomes excessive and the malodor control effect may be reduced. If it exceeds 100, the malodor control effect tends to decrease.
<(D) component: surfactant>
As the surfactant (D), a known surfactant can be appropriately used as a component of the granular detergent composition. Surfactant can be used individually by 1 type or in combination of 2 or more types as appropriate.
[Anionic surfactant]
Examples of anionic surfactants include the following.
(1) A methyl, ethyl or propyl ester (α-SF or MES) 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.
(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.

Among these anionic surfactants, from the viewpoint of detergency and odor control, (1) methyl, ethyl or propyl esters of saturated or unsaturated α-sulfo fatty acids having 8 to 20 carbon atoms are contained in the surfactant particles. It is preferable to use (α-SF or MES) salts. As for content with respect to the whole granular detergent composition, 5-30 mass% is preferable.
[Nonionic surfactant]
Examples of nonionic surfactants include the following.
(1) Polyoxyalkylene alkyl (or alkenyl) 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 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) Fatty acid alkyl ester alkoxylate represented by, for example, the following general formula (I) in which alkylene oxide is added between ester bonds of long chain fatty acid alkyl ester
R1CO (OA) nOR2 (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 oxide having 2 to 4 carbon atoms such as ethylene oxide or propylene oxide, preferably 2 to 3 carbon atoms. N represents the average number of moles of alkylene oxide added, and is generally a number of 3 to 30, preferably 5 to 20. R2 is a lower group which may have a substituent of 1 to 3 carbon atoms ( C1-4 represents an alkyl group.)
(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 above nonionic surfactants, The nonionic surfactant of (1) described above is preferred, and in particular, a polyoxyalkylene alkyl (or alkenyl) ether 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. 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.

    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).

Further, 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 product”.
[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 polyalkyl having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms. Oxyalkylene groups are preferred.
[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 ingredients>
In the granular detergent composition of the present invention, in addition to the components (A) to (D), other components can be appropriately blended as necessary within a range not impairing the effects of the present invention.

  Examples of other components include detergency builders, fluorescent brighteners, polymers, enzymes, enzyme stabilizers, anti-caking agents, reducing agents, metal ion scavengers, pH adjusters, fragrances, and dyes.

Examples of these are given below.
[Detergency Builder]
Detergency builders include inorganic builders and organic builders.

  Examples of inorganic builders 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 [eg, manufactured by Clariant Japan Ltd. "Crystalline alkali metal silicates such as Na-SKS-6" (δ-Na2O · 2SiO2)], amorphous alkali metal silicates; sulfates such as sodium sulfate and potassium sulfate; sodium chloride and potassium chloride Alkali metal chlorides such as orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate, phytate, etc .; crystalline aluminosilicate, amorphous aluminosilicate, sodium carbonate And amorphous alkali metal silicate complex (eg, Rhod a trade name "NABION15"), 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 those having the effect of improving solubility.

  As the aluminosilicate other than the component (A), either crystalline or amorphous (amorphous) can be used, and crystalline aluminosilicate is preferred 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 is preferably 1 to 40% by mass, and particularly preferably 2 to 30% by mass from the viewpoint of powder properties such as cleaning performance and fluidity with respect to the entire cleaning composition.

  As a commercial item, the product name ZEOLITE 4A made by HAIING CHEMICAL CO., LTD. OF DONGYING CITY; the product name 4AZEOL made by FUJIAN RISHENG CL., LTD. Product name: 4A Zeolite manufactured by Shanxi Yuchi Chang-High-Tech Co., Ltd .; China ■ Industrial Co., Ltd. ALUMINUM CORPORATION OF CHINA. , LTD. Product name 4A ZEOLITE; product name 4A Zeolite; Thai silicate chemical (Thai Silicate Chemicals Co., Ltd. , LTD.) Product name COLITE-P; PQ Chemicals Limited product name VALFOR 100 Zeolite NaA;

  When mix | blending potassium carbonate, the content is from the point of the effect of a solubility improvement, Preferably it is 1-15 mass% with respect to the whole cleaning composition, 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 thereof is preferably 0.5 to 40% by mass, more preferably 1 to 25% by mass, based on the entire cleaning composition, from the viewpoint of cleaning performance. More preferably, it is 3-20 mass%, Most preferably, it is 5-15 weight%.

  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 and hydroxymethylcellulose.

  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 acid copolymer having a weight average molecular weight of 1000-80000 Salts, polyacrylates, 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-54-52196), polysaccharides Derivatives are preferred.

  As the polysaccharide derivative, carboxymethylcellulose or a salt thereof (hereinafter sometimes referred to as CMC) is preferable.

  Examples of the salt of carboxymethyl cellulose include alkali metal salts such as sodium and potassium, ammonium salts, and the like, and a mixture of these salts may be used. Of the above, carboxymethylcellulose sodium salt is preferred.

  Preferable examples of CMC include an anionic water-soluble and water-insoluble cellulose ether obtained by reacting monochloroacetic acid after treating pulp with caustic soda as a raw material.

  The weight average molecular weight of CMC is 100,000 or more, preferably 300,000 or more, more preferably 800,000 or more. As an upper limit, Preferably it is 1200000 or less, More preferably, it is 1000000 or less. If the weight average molecular weight of CMC is not less than the above lower limit, the effect of preventing recontamination can be remarkably improved. On the other hand, if the weight average molecular weight of CMC is not more than the above upper limit value, the solubility in the washing liquid will be good.

  The weight average molecular weight of CMC can be measured by gel filtration chromatography (GPC) -differential refractive index detector (RI) system, eluent: 0.1 M NaNO3, flow rate: 1 mL / min, sample: It means a value obtained by calculating the weight average molecular weight as a numerical value in terms of PEG under the operating conditions of 0.02 to 0.3% by mass, solvent: 0.1M NaNO 3, injection amount: 200 μL. For the above measurement, for example, a liquid feed pump: Shodex DS-4 (manufactured by Showa Denko KK), a degasser: ERC3115 (manufactured by ERC KK), a column: Shodex SB-806MHQ (manufactured by Showa Denko KK) ), A differential refractive index detector: Shodex RI-71 (manufactured by Showa Denko KK) and the like can be used.

  The degree of etherification of CMC is preferably 0.2 to 1.3, more preferably 0.2 to 0.8. In the present invention, 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 of the glucose ring, how many are carboxymethyl groups or It indicates whether or not it has been replaced by a salt, and is a maximum of 3).

  The average particle diameter of CMC is preferably 10 to 1500 μm, more preferably 10 to 500 μm, and still more preferably 10 to 100 μm. When the average particle diameter is in such a range, it is preferable in terms of solubility and solidification. The average particle size of CMC can be calculated from the particle size distribution by sieving, as in the granular detergent composition.

  Such CMCs are sold under the trade name “CMC Daicel” by Daicel Chemical Industries, Ltd. 1110, 1120, 1130, 1140, 1160, 1180, 1190, 1220, 1240, 1260, 1280, 1290, 1380. 2200, 2260, 2280, 2450, 2340, etc., and Sun, such as F10LC, F600LC, F1400LC, F10MC, F150MC, F350HC, F1400MC, F1400MG, etc., sold by Nippon Paper Chemical Co., Ltd. under the trade name “Sunrose” Rose F series, Sunrose A series such as A02SH, A20SH, A200SH, SLD-F1 (above, trade name), Serogen (trade name) F-BSH-6, F- sold by Daiichi Kogyo Seiyaku Co., Ltd. 6HS9 And the like. Among the above, CMC Daicel 1130, 1180, 1190, Sunrose F1400LC, F1400MC, Sunrose SLD-F1, and Serogen F-6HS9 are particularly preferable. CMC can be used individually by 1 type or in combination of 2 or more types.

1-20 mass% is preferable with respect to the whole cleaning composition, More preferably, it is 1-10 mass%, More preferably, it is 2-5 mass% with respect to the whole cleaning composition.
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 a salt of a polymer, a salt of polyacetal carboxylic acid, an organic builder such as carboxymethyl cellulose and hydroxymethyl cellulose, and an inorganic builder such as zeolite. There are various grades of detergency builders available in commercial products, but these grades do not limit the use of the present invention. For example, impurities mixed in the production of commercial products and quality stability It may contain a storage stabilizer and an antioxidant added for the purpose of conversion.

The content of the detergency builder in the granular detergent composition 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 above-mentioned optical brighteners can be used alone or in combination of two or more.

  The content of the optical brightener is preferably 0.001 to 1% by mass with respect to the entire granular detergent composition.

Specific examples of commercially available products include Whiteex SA, Whitetex SKC (above, product; manufactured by Sumitomo Chemical Co., Ltd.); Chino Pearl AMS-GX, Chino Pearl DBS-X, and Chino Pearl CBS-X (above, trade name: Ciba Specialty Chemicals); Lemonite CBUS-3B (above, trade name: manufactured by Khyati Chemicals) and the like are preferable. Of these, Tinopearl CBS-X and Tinopearl AMS-GX are more preferable.
[Polymers]
In the present invention, an average molecular weight of 200 is used as a binder or powder physical property modifier 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 1000 to 100,000, cellulose derivatives such as polyvinyl alcohol, hydroxypropylmethylcellulose (HPMC), and the like can be blended.

  In addition, a copolymer of a repeating unit derived from terephthalic acid and a repeating unit derived from ethylene glycol and / or propylene glycol, a terpolymer, or the like 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.

As for content of the said polymers with respect to the whole granular detergent composition, 0.05-5 mass% is preferable.
[enzyme]
Enzymes are classified according to the reactivity of the enzyme, 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.

  Specific 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.

  Commercially available products include 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; Genencor) A protease K-14 or K-16 (protease described in JP-A-5-25492), and the like.

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

  Specific 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, cell cleans, and carezymes (trade names, manufactured by Novozymes); alkaline cellulase K, alkaline cellulase K-344, alkaline cellulase K-534, alkaline cellulase K-539, and alkaline cellulase K-577. 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).

  Examples of amylases include commercially available stainzymes, termamyls, duramils (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 granulated as separate stable particles in a state of being dry blended with detergent dough (particles).
[Enzyme stabilizer]
As the enzyme stabilizer, for example, calcium salt, magnesium salt, polyol, formic acid, boron compound and the like can be blended. 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.

As for content of an enzyme stabilizer with respect to the whole granular detergent composition, 0.05-2 mass% is preferable.
[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 is preferably from 0.1 to 5 mass%, more preferably from 0.5 to 3 mass%, based on the entire granular detergent composition. 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 granular detergent composition of the present invention is not particularly limited, but from the viewpoint of cleaning performance, the pH in a 1% by mass aqueous solution of the granular detergent composition is preferably 8 or more, and the 1 mass It is more preferable that pH in a 9% aqueous solution is 9-11. When the pH is 8 or more, the cleaning effect is easily exhibited.

  As a technique for controlling the pH of the granular detergent composition, the pH is usually adjusted with an alkaline agent. In addition to the alkaline agent described in the detergency builder, monoethanolamine, diethanolamine, triethanolamine, etc. Examples include 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.

  Moreover, in order to prevent that the pH of a granular detergent composition becomes high too much, it can also adjust to the said pH range using an acid etc.

  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.

  Further, it is 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.
[Defoaming agent]
Examples of the antifoaming agent include conventionally known ones such as silicone / silica-based ones. Moreover, you may use this antifoamer as the following antifoamer granulated material.
(Method for producing antifoam granulated product)
First, 100 g of maltodextrin (trade name, manufactured by Nissho Chemical Co., Ltd .; enzyme-modified dextrin) 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 mass% of the obtained homogeneous mixture, polyethylene glycol (PEG-6000, melting point 58 ° C.) 25 mass%, and neutral anhydrous sodium sulfate 25 mass% at 70-80 ° C., an extrusion granulator ( Granulate by model EXKS-1, manufactured by Fuji Paudal Co., Ltd. to obtain a defoamer granulated product (see JP-A-3-186307).
[Fragrance]
The fragrance | flavor in this invention is a mixture (fragrance | flavor composition) which consists of a fragrance | flavor component, a solvent, a fragrance | flavor stabilizer, etc.

  As such a fragrance, for example, those described in JP-A Nos. 2002-146399 and 2003-89800 can be used.

0.001-2 mass% is preferable and, as for content of a fragrance | flavor with respect to the whole granular detergent composition, 0.01-1 mass% is more preferable.
[Dye]
In the present invention, various dyes such as dyes and pigments can be used to improve the appearance of the granular detergent composition. Of these, pigments are preferable from the viewpoint of storage stability, and those having oxidation resistance are particularly preferable.

Examples of such a dye include oxides, and preferable examples include titanium oxide, iron oxide, copper phthalocyanine, cobalt phthalocyanine, ultramarine blue, bitumen, cyanine blue, and cyanine green.
<Method for producing granular detergent composition>
The manufacturing method of the granular detergent composition of this invention is not restrict | limited in particular, It can manufacture with the manufacturing method generally used. For example, when the granular detergent composition is in powder form, a method of dispersing and dissolving a surfactant or other raw material in water and spray drying, kneading / extrusion, stirring granulation, rolling granulation, etc. It can be manufactured by a method in which it is subjected to kneading, granulation, compression molding and the like, and further pulverized as necessary.

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. In the following, “%” means “mass%” unless otherwise specified.
<Used raw materials>
The following raw materials were used.
Aluminosilicate compound A-1: Lion Corporation, Lionite SF (SiO ₂ : ZnO: Al ₂ O ₃ molar ratio = 52: 32: 16), aluminosilicate zinc particles having an average particle size of 3.5 μm object.
A-2: 14 g of lionite SF of A-1 was dispersed in 686 g of ion-exchanged water, and an aqueous dispersion was adjusted to 2% by mass. This aqueous dispersion was subjected to a condition of a peripheral speed of 10 m / sec (rotor rotation speed: 4,300 rpm) using 0.1 mm diameter zirconia beads with a bead mill (Ultra Apex Mill: UAM-015) manufactured by Kotobuki Kogyo Co., Ltd. Was pulverized for 10 minutes to obtain a zinc aluminosilicate particle dispersion. This was suction filtered, washed with water, and dried at 100 ° C. The obtained cake was pulverized by a jet mill to obtain Lionite SF having an average particle size of 0.42 μm.
A-3: Synthesis Example The SiO ₂ : ZnO: Al ₂ O ₃ molar ratio of zinc aluminosilicate was adjusted as follows to be 31:54:15.

No. 3 sodium silicate (Fuji Chemical, SiO ₂ : 29% by weight, Na ₂ O: 9.5% by weight) 82.6g and sodium hydroxide (manufactured by Kanto Chemical Co., Ltd., special grade) 94g are dissolved in ion-exchanged water. Is 1 L, and this is designated as liquid A. On the other hand, 95 g of zinc chloride (manufactured by Kanto Chemical Co., Ltd., special grade) and 97 g of aluminum chloride hexahydrate (manufactured by Kanto Chemical Co., Ltd., special grade) are dissolved in ion-exchanged water to make the total volume 1 L, and this is designated as B liquid. 1 L of ion-exchanged water was put into a 5 L beaker, and A liquid and B liquid were simultaneously added at a rate of about 25 mL / min with stirring. After completion of the addition, the pH of the reaction solution was 6.9. The mixture was further stirred and aged for 30 minutes, and then heated at 85 to 90 ° C. for 2 hours in a water bath. The reaction solution was suction filtered, washed with water, and dried at 100 ° C. The obtained cake was pulverized by jet mill to obtain a zinc aluminosilicate granule as a granule having an average particle size of 3.5 μm.
-Percarbonate: Zhejiang JINKE CHEMICALS, Inc. Product name: SPCC, effective oxygen amount 13.8%, average particle size 870 μm
Bleach activator C-1: Synthesis of sodium 4-dodecanoyloxybenzenesulfonate as bleach activator, sodium 4-hydroxybenzenesulfonate (reagent manufactured by Kanto Chemical Co., Inc.), N, N-dimethylformamide as raw materials (Reagent manufactured by Kanto Chemical Co., Inc.), lauric acid chloride (reagent manufactured by Tokyo Chemical Industry Co., Ltd.), and reagent manufactured by acetone (Kanto Chemical Co., Ltd.) were used in the following manner.
3000 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.
70 parts by mass of sodium 4-dodecanoyloxybenzenesulfonate synthesized by the above method, 20 parts by mass of PEG (trade name: Polyethylene glycol # 6000M (manufactured by Lion Corporation)), sodium α-olefin sulfonate having 14 carbon atoms Product (trade name: Liporan PJ-400 (manufactured by Lion Corporation)) into Hosokawa Micron's Extrude Ohmic EM-6 (trade name) so that the total amount is 5000 g at a ratio of 5 parts by mass, and kneaded and extruded. As a result, a noodle-like extruded product having a diameter of 0.8 mmφ was obtained. This extruded product (60 ° C.) was introduced into Fitzmill DKA-3 (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 granulate was obtained.
Bleach activator C-2: 70 parts by mass of 4-decanoyloxybenzoic acid (manufactured by Mitsui Chemicals) as a bleach activator, 20 parts by mass of PEG (trade name: polyethylene glycol # 6000M (manufactured by Lion Corporation)) Parts, carbon alpha 14 sodium olefin sulfonate powder product (trade name: Lipolane PJ-400 (manufactured by Lion Corporation)) at a ratio of 5 parts by mass, a total of 5000 g, manufactured by Hosokawa Micron Extrude Ohmics EM A noodle-like extruded product having a diameter of 0.8 mmφ was obtained by charging into -6 type (trade name) and kneading and extruding. This extruded product (60 ° C.) was introduced into Fitzmill DKA-3 (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 granulate was obtained.
Bleach activator C-3: Synthesis of sodium 4-nonanoyloxybenzenesulfonate as a bleach activator, sodium p-phenolsulfonate (reagent manufactured by Kanto Chemical Co., Inc.), N, N-dimethylformamide ( Using Kanto Chemical Co., Ltd. reagent), pelargonic acid chloride (Tokyo Kasei Kogyo Co., Ltd. reagent), and acetone (Kanto Chemical Co., Ltd. reagent), synthesis was performed by the following method.
100 g (0.51 mol) of sodium p-phenolsulfonate dehydrated in advance was dispersed in 300 g of N, N-dimethylformamide, and 90 g (0.51 mol) of pelargonic acid chloride was mixed at 50 ° C. with stirring with a magnetic stirrer. It was added dropwise over a period of minutes. 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 solvent of water / acetone = 1/1 (mol ratio) to obtain 146 g of crystals of sodium nonanoyloxybenzenesulfonate.

70 parts by mass of sodium 4-nonanoyloxybenzenesulfonate synthesized by the above method, 20 parts by mass of PEG (trade name: polyethylene glycol # 6000M (manufactured by Lion Corporation)), sodium α-olefin sulfonate powder having 14 carbon atoms Product (trade name: Liporan PJ-400 (manufactured by Lion Corporation)) into Hosokawa Micron's Extrude Ohmic EM-6 (trade name) so that the total amount is 5000 g at a ratio of 5 parts by mass, and kneaded and extruded. As a result, a noodle-like extruded product having a diameter of 0.8 mmφ was obtained. This extruded product (60 ° C.) was introduced into Fitzmill DKA-3 (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 granulate was obtained.
Zinc oxide: manufactured by Kanto Chemical Co., Inc., zinc oxide 3N5, average particle size of 5 to 10 μm.
-Copper sulfate: manufactured by Kanto Chemical Co., Ltd., copper sulfate (II) pentahydrate-Silver sulfate: reagent grade, manufactured by Toyo Chemical Industry Co., Ltd.-MES (α-sulfo fatty acid methyl ester salt) -containing composition:
(Sulfonation process)
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). Furthermore, the fatty acid methyl ester mixture was purified by reducing the iodine value to 0.2 by a hydrogenation treatment by a conventional method, and the mixture was subjected to 7% with dehumidified air using a falling film reactor. Was sulfonated with a SO3 gas diluted to a reaction molar ratio (SO3 / saturated fatty acid ester) = 1.18 and a reaction temperature of 80 ° C. to obtain 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. In order to connect three loop aging tubes in succession, average residence time is 60 minutes, and in order to maintain sufficient stirring and constant temperature, the loop aging tubes are allowed to flow at a linear speed of 0.16 m / s. The actual temperature was controlled at 78 to 82 ° C. with respect to 80 ° C., and the aging reaction was performed to complete the sulfonation to obtain α-sulfo fatty acid methyl ester.
(Esterification / bleaching process)
After introducing 20% by mass of methanol (Methanol manufactured by Sumitomo Chemical Co., Ltd .: industrial grade moisture 500 ppm or less) to 100 parts by mass of the α-sulfo fatty acid methyl ester obtained, this mixture and 35% hydrogen peroxide (Mitsubishi Gas) Chemical Co., Ltd. 35% industrial hydrogen peroxide (industrial grade) 5.7% by mass was introduced into a continuous loop reactor equipped with a mixing mixer and heat exchanger to perform bleaching, and α-sulfo fatty acid methyl ester bleaching A treated product was obtained.
(Neutralization process)
Next, with respect to 125 parts by mass of the obtained 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), nonionic surfactant (nonionic surfactant described later) Agent (A)) 25 parts by mass, water 69 parts by mass, methanol (Sumitomo Chemical Co., Ltd. methanol: industrial grade) 24 parts by mass, linear alkylbenzene sulfonic acid (LAS-H) 5 parts by mass in the neutralization line Continuously fed.

The neutralization method employs the neutralization method described in JP-A No. 2001-64248, and a 48% sodium hydroxide aqueous solution is quantitatively fed between the premixer and the neutralization mixer, and the medium is continuously added. I was able to sum up. Then, the neutralized product of the esterified product that had been neutralized in advance and the esterified product were thoroughly mixed with a premixer, and then mixed with an aqueous sodium hydroxide solution to obtain a neutralized product.
(Concentration process)
Furthermore, using the above neutralized product as a raw material surfactant aqueous solution, recycling flash evaporation described in JP-A-2004-210807 is performed, lower alcohol is removed and concentrated, and α-sulfo fatty acid alkyl ester salt-containing composition (MES 62 mass%, LAS-Na 3.5 mass%, nonionic surfactant (A) 16.8 mass%, moisture 10.8 mass%, impurities, by-products, etc. 6.9 mass%).
Soap: 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 11.7% by mass, C14 0.4% by mass, C16 29 2% by mass, C18F0 (stearic acid) 0.7% by mass, C18F1 (oleic acid) 56.8% by mass, C18F2 (linoleic acid) 1.2% by mass; molecular weight: 289).
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%).
LAS-Na: linear alkyl (10 to 14 carbon atoms) benzene sulfonic acid [manufactured by Lion Co., Ltd., Rypon LH-200 (LAS-H pure content: 96% by mass)] was added at the time of preparation of the surfactant composition. What mixed the compound neutralized with the mass% sodium hydroxide aqueous solution and the compound neutralized with 48 mass% potassium hydroxide aqueous solution instead of neutralizing with the said sodium hydroxide by 2: 1 mass ratio. The compounding quantity in a table | surface shows the value (mass%) as these mixtures.
MA agent: Acrylic acid / maleic anhydride copolymer sodium salt (trade name: Aqualic TL-400, manufactured by Nippon Shokubai Co., Ltd .; 40% by weight pure water solution).
Zeolite: A-type zeolite Silton B (trade name, manufactured by Mizusawa Chemical Co., Ltd .; pure content: 80% by mass).
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 diameter 490 μm, bulk density 1.30 g / cm 3).
Sodium sulfate: neutral anhydrous sodium sulfate (manufactured by Nippon Chemical Industry Co., Ltd.)
・ Sodium chloride: Sodium chloride (manufactured by Kanto Chemical Co., Inc.)
Layered sodium silicate: crystalline layered sodium silicate SKS-6 (Hoechst)
Bentonite: Landrosyl DGA Powder (manufactured by Zudchemi).
・ Enzyme: Sabinase 12T (Novozymes Japan)
Fragrance: Fragrance composition A shown in [Table 11] to [Table 18] of JP-A-2002-146399
Fluorescent whitening agent: Cinopearl CBS-X (trade name, Ciba Japan Co., Ltd.) / Cinopearl AMS-GX (trade name, Ciba Japan Co., Ltd.) = 3/1 (mass ratio).
-Dye: Ultramarine (Daiichi Seika Kogyo Co., Ltd., Ultramarine Blue)
<Preparation of granular detergent composition>
By the preparation method shown below, the surfactant-containing particles shown in Table 1 were prepared, and granular detergent compositions were prepared according to the compositions shown in Tables 2-5. Next, the prepared granular detergent composition was used, and the effect of suppressing leftover odor and the cleaning performance were evaluated. In the following examples, unless otherwise specified, “%” of the composition indicates mass%.
(Examples 1-20)
Process (A)
Water was put into a jacketed mixing tank equipped with a stirrer, and the temperature was adjusted to 60 ° C. A surfactant (except for the MES-containing composition and nonionic surfactant) was added thereto, and the mixture was stirred for 10 minutes. Subsequently, a polymer (MA agent or sodium polyacrylate) was added. After further stirring for 10 minutes, a part of the powder A-type zeolite (1.0% for addition at the time of kneading, 5.0% for grinding aid, 1.5% surface from the addition amount shown in Table 1) Sodium carbonate, potassium carbonate, sodium sulfate, and sodium chloride were added in amounts excluding each type A zeolite for 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.
Process (B)
Spray dried particles obtained in step (A), MES-containing composition, 1.0% powder A-type zeolite, remaining nonionic surfactant except 0.5% nonionic surfactant for spray addition, fluorescent whitening Agent, bentonite, layered sodium silicate, and water were added to a continuous kneader (Kurimoto Kokoro Co., Ltd., KRC-S4 type) and kneaded under conditions of a kneading capacity of 120 kg / hr and a temperature of 60 ° C. A kneaded material containing 6% of water and containing an agent was obtained.
Process (C)
The kneaded product obtained in the step (B) was cut with a cutter while extruding it using a pelleter double (Fuji Powder Co., Ltd., EXDFJS-100 type) equipped with a die with a hole diameter of 10 mm (the cutter peripheral speed was 5 m / s) A pellet having a length of about 5 to 30 mm was obtained.

Next, Fitzmill in which 5.0% of powder A-type zeolite (average particle size 180 μm) as a grinding aid was added to the obtained pellets and arranged in three stages in series in the presence of cold air (10 ° C., 15 m / s) (Screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12 mm / 6 mm / 3 mm, rotation speed: 1st stage / 2nd stage / In each of the third stages, 4700 rpm), surfactant-containing particles listed in Table 1 were obtained.
Process (D)
Horizontal cylindrical rolling mixer comprising the surfactant-containing particles obtained above, sodium percarbonate as component (B), and aluminosilicate as component (A) having a specific composition so as to have the compositions shown in Tables 2 to 4 (With a cylindrical diameter of 585 mm, a cylindrical length of 490 mm, a drum inner wall surface of the container 131.7L having two baffle plates with a clearance of 20 mm and a height of 45 mm with respect to the inner wall surface), a filling rate of 30% by volume, a rotational speed of 22 rpm, Under the condition of 25 ° C., 1.5% powder A-type zeolite was added, and sprayed with 0.5% nonionic surfactant, tumbled for 1 minute, and (B) component bleach activator, 0.5% of enzyme was added and mixed for 5 minutes to obtain granular detergent compositions described in Tables 2-4.
(Comparative Examples 1-3)
The granular detergents described in Table 5 were prepared in the same manner as in the Examples except that the (A) component (Comparative Example 1), (B) component (Comparative Example 2), and (C) component (Comparative Example 3) were not blended. A composition was obtained.
(Comparative Examples 4-7)
A granular detergent composition described in Table 5 was obtained in the same manner as in Example except that (A) ′ component was blended in place of (A) component.

<Evaluation method>
[Leaving odor control evaluation method]
Using each detergent composition, the fibers were washed according to the following washing method and left in the washing tub, and then the smell of the fibers was sniffed, and the effect of suppressing the generation of malodor was evaluated according to the following evaluation criteria. In general, the relationship between odor intensity and substance concentration is expressed by Y = a log X + b (X is the amount of stimulation (ppm), Y is sensory intensity, and a and b are idiosyncratic constants) according to Weber-Fechner's law. It is said that when the odor intensity decreases by 1, the concentration decreases in log units, and a one-step change in the malodor level is a great deodorizing effect.
(Laundry / Evaluation method)
After using 20 new 100% cotton hand towels for about 1 day each in normal life, put them in a fully automatic washing machine (NA-F70AP, manufactured by Matsushita Electric Industrial Co., Ltd.), tap water with a temperature of about 20 ° C and a hardness of about 3 ° DH. Water was poured and washing was performed 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 allowed to stand at room temperature of about 25 ° C. and humidity of 100% RH for 18 hours, and then the odor was evaluated by five specialist panels.
(Evaluation criteria)
A: No odor is felt.
○: Almost no odor is felt.
Δ: A slight odor is felt.
X: A bad odor is felt.
[Method for Measuring Average Particle Diameter of Component (A)]
(Measurement method of average particle size)
The average particle diameter of the component (A) in the present invention is a value measured by the following method.

  Samples to be measured (zinc oxide particles, zinc aluminosilicate particles) are dispersed in an ethanol solution of 99% or more using a homogenizer capable of rotating at a rotation speed of 10,000 rpm or more, air-dried on a sample stage, and then several It is measured with a scanning electron microscope or a transmission electron microscope that can be used at a magnification of 100,000 times.

More specifically, 200 mL of 99.5% ethanol was added to 5 g of the sample, and after stirring and dispersing for 5 minutes at a rotational speed of 1000 rpm using a powerful homogenizer DIAX900 (shaft generator 18F) manufactured by Heidorf, several samples were immediately placed on the sample stage. Drip and air dry. The air-dried sample is vapor-deposited with platinum palladium, preferably platinum, and the particles are photographed at a magnification of 50,000 to 100,000 times using a Hitachi scanning transmission electron microscope apparatus H-8010.
In the case of 50,000 times, 20 particles are measured, and in the case of 100,000 times, the particle diameter of 10 particles is measured, and the average value is obtained.
[Evaluation of cleaning performance]
Using each granular detergent composition, the fibers were washed according to the following washing method, and the washing performance was evaluated.
(Laundry / Evaluation method)
Using a Teg-O-tometer as a washing tester in the United States of America, put 10 wet artificial soiled cloths (purchased from the Laundry Science Association) (2g) and a washed knitted cloth (28g) (bath ratio 30 times), detergent concentration The plate was washed with 0.067% washing solution at 120 rpm and 20 ° C. for 10 minutes. The water used was 4 ° DH, the amount of the washing solution was 900 mL, and the rinse was washed with 900 mL of water for 3 minutes. After rinsing, the evaluation cloth was dried, the washing rate was calculated by the following formula, the following evaluation criteria were set, and ◎◎, ◎, and ○ were accepted. In the formula, R is a reflectance measured using a color meter Σ-9000 made by Nippon Denshoku. The reflectance was measured using a 460 nm filter. The evaluation of the washing rate was carried out by the average value of 10 test cloths.
(Evaluation criteria)
◎: 80% or more ◎: 75% or more and less than 80% ○: 70% or more and less than 75% △: 65% or more and less than 70% ×: less than 65%

Claims (2)

(A) The aluminosilicate compound in which the molar ratio of the oxide in the aluminosilicate compound is SiO ₂ : MO _{n / 2} : Al ₂ O ₃ = 5 to 80: 5 to 65: 1 to 60 (provided that M Represents at least one metal selected from zinc, copper, silver, cobalt, nickel, iron, titanium, barium, tin and zirconium, and n represents the molar weighted average valence of metal M).
(B) percarbonate,
(C) a bleach activator;
(D) A granular detergent composition comprising a surfactant. The granular detergent composition according to claim 1, wherein the mass ratio of the component (A) to the component (C) is (A) / (C) = 0.1 to 10.