JP2007302787A - Amylase-containing granular detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a granular detergent composition which has high food stain-removing effects also in ordinary laundries using washing machines. <P>SOLUTION: This granular detergent composition is characterized by comprising (A) an amylase whose viscosity-lowering rate calculated according to the following expression (I) is ≥40%, (B) a nonionic surfactant, and (C) an anionic surfactant, wherein (B)/(C) mass ratio is 5 to 30. (I): The viscosity-lowering rate (%)=ä[(initial viscosity)-(viscosity after 60 minutes)]/(initial viscosity)}×100. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a granular detergent composition used for textile products such as clothing, and more particularly to a granular detergent composition containing a specific amylase having a high effect of removing food stains.

Food stains caused by dropping food on clothes during meals are caused by various components such as pigments and fats and oils, and thus are difficult to remove by ordinary washing using a washing machine. For this reason, a pretreatment such as applying a high-concentration washing liquid to dirt and washing in advance is necessary.
Therefore, a granular detergent composition that can effectively remove food stains without such pretreatment has been desired.
So far, there have been known a bleaching detergent composition containing both amylase and a bleaching activator having a specific structure, and a detergent composition containing both amylase and a specific builder (Patent Documents 1 and 2).
In addition, even when washing clothes with food stains using the remaining hot water in the bath, the number of bacteria remaining in the clothes can be significantly reduced without using bleach, enabling a hygiene-friendly laundry finish. As a detergent composition, a detergent composition containing a specific ratio of an anionic surfactant, an inorganic reducing agent, a protease, and amylase (Patent Document 3), and in a washing process, it is difficult to remove by ordinary washing As a detergent composition capable of effectively removing stains derived from food stains, surfactants containing linear alkylbenzene sulfonate and / or alkyl sulfate, specific acrylic acid and maleic acid A detergent composition (Patent Document 4) containing a copolymer of the above or a salt thereof and amylase in a specific ratio has been proposed.
In addition, a nonionic surfactant, an α-sulfo fatty acid ester salt, a peroxide that generates hydrogen peroxide in water, a peracid precursor that reacts with hydrogen peroxide to generate an organic peracid, an alkali A bleach-containing detergent composition (Patent Document 5) containing a specific amount of an agent has been proposed as exhibiting excellent cleaning performance against stains such as food stains and yellowing stains such as sebum stains.
None of the above techniques has provided a satisfactory cleaning effect on food stains.

JP-A-10-95996 Japanese National Patent Publication No. 11-507989 JP 2001-64695 A JP 2001-64693 A JP 2005-29587 A

  In view of the above circumstances, an object of the present invention is to provide a granular detergent composition that is highly effective in removing food stains even in normal washing using a washing machine.

As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by using a specific amount of nonionic surfactant and anionic surfactant together with a specific amylase. The headline and the present invention were completed. That is, this invention provides the granular detergent composition characterized by containing the following components:
(A) an amylase having a viscosity reduction rate calculated by the following formula (I) of 40% or more;
(B) nonionic surfactant,
(C) an anionic surfactant,
And (B) / (C) = 5 to 30 (mass ratio).

  In the present invention, food stains can be effectively and easily removed by using a specific amylase with high activity and using a nonionic surfactant and an anionic surfactant in a specific ratio. .

The granular detergent composition of the present invention is a generic name for powder detergents and high bulk density granular detergents (high bulk density detergents), and among these, it is more suitable when prepared as a high bulk density detergent. The high bulk density detergent generally means a granular detergent having a bulk density of 0.6 g / mL or more.

(A) component (A) component of this invention is an amylase whose viscosity reduction rate computed by Formula (1) mentioned above is 40% or more.
Specifically, 25 g of corn starch (manufactured by Kanto Chemical Co., Inc.) was added to 475 g of an aqueous alkali (sodium carbonate 4000 ppm) solution at 90 ± 2 ° C., stirred and dissolved at 90 ± 2 ° C. for 1 hour, and then 12 hours at 5 ° C. Cooling. Then, it is allowed to stand at room temperature, and after the temperature of the solution becomes equal to room temperature, the temperature is adjusted to 25 ° C. Next, the viscosity (mPa · s) of 40 g of the solution adjusted to 25 ° C. was measured using a vibration viscometer (CJV5000 manufactured by A & D Co., Ltd., vibrator material: stainless steel SUS304-CSP-H, vibrator Shape and size: disk shape, measured at t (thickness) = 0.1 mm, φ (diameter) = 13 mm) and set as initial viscosity (measurement condition: set amplitude value 50 mV, vibration frequency: 30 Hz, sample amount) : 40 g (as 5% aqueous solution), measurement temperature: 25 ° C.). Thereafter, 0.004 mg of amylase as the amount of enzyme protein is quickly added and stirred to 40 g of the starch aqueous solution whose initial viscosity is measured, and the viscosity is measured in the same manner as the initial viscosity 10 seconds after the addition, and then the temperature is adjusted at 25 ° C. . Next, after 10 minutes, 30 minutes and 60 minutes, the viscosity is measured in the same manner as the initial viscosity.
The viscosity reduction rate (%) can be calculated by substituting the obtained initial viscosity and the value of the viscosity after 60 minutes into the above formula (I).
Amylase satisfying the specific viscosity reduction rate can be appropriately selected by a simple screening method using the above-described commercially available apparatus (CJV5000 manufactured by A & D Co., Ltd.).

Examples of amylases that can be used in the present invention include α-amylase, β-amylase, α-glucosidase, and glucoamylase, α-1,6 bonds such as starch and glycogen, which hydrolyze α-1,4 bonds such as starch and glycogen. Glucoamylase, pullulanase, isoamylase, amylo-1,6 glucosidase / 4-alpha glucanotransferase, oligo-1,6-glucosidase and the like are included. It is not particularly limited as long as it is an enzyme that hydrolyzes starch, and one kind or a combination of two or more kinds can be used.
Examples of amylases that can be used in the present invention are given below. However, the following examples do not limit the present invention. Examples of commercially available enzymes include the following. Termamyl, Duramil, Stainzyme, Promozyme 200L (above, Novozymes), Maxamyl (Genencore), Amano Pharmaceutical's DB-Ranama 250, Pullulanase derived from Aerobacter aerogenes ATCC 9621 (crude or crystallized product released from Seikagaku Corporation).

In addition to the amylase described above, examples of the amylase described in the patent publication include the following.
(1) Alkaline amylase derived from Bacillus described in JP-A-48-91271 (2) Alkaline amylase derived from Streptomyces described in JP-A-61-209588 (3) JP-A-62-208278 Bacillus-origin alkaline amylase described in the publication (4) Bacillus genus-origin alkali amylase described in JP-A-2-49584 (5) Bacillus-origin alkali pullulanase described in JP-A-3-87176 (6) Bacillus-origin alkaline pullulanase described in JP-A-3-87177 (7) Bacillus-origin amylase described in JP-A-3-103177 (8) Bacillus-origin alkaline amylase described in JP-A-3-108482 (9) ) Alkaline amylase of the genus Bacillus described in JP-A-4-23983 (10) Alkaline amylase Bacillus origin of 4-58885 JP

(11) Alkaline amylase derived from Natronococcus described in JP-A-4-21369 (12) α-amylase derived from Bacillus described in JP-A-4-50076 (13) JP-A-6-14775 Bacillus-origin alkaline isoamylase described in (14) Bacillus genus alkaline amylase described in JP-A-8-56662 (15) Bacillus genus-origin alkaline α-amylase (16) described in JP-A-9-206073 Α-Amylase variant described in JP-A-10-504197 (17) Alkaline amylase described in JP-A-2000-023665 (18) Alkaline amylase described in JP-A-2000-023666 (19) JP-A-2000- No. 023667 Alkaline amylase (20) Mutation α described in JP-A No. 2002-112792 -Amylase

(21) α-amylase derived from Pyrococcus described in JP-T-4-503757 (22) α-amylase derived from Bacillus described in JP-A-8-500003 (23) No. 8-504586 Α-amylase of the genus Bacillus or Asparagillus described in the publication (24) Starch-degrading enzyme of the genus Pyrococcus described in JP-A-8-506731 (25) The genus Bacillus described in JP-A-9-503916 Α-amylase of origin (26) α-amylase of the genus Bacillus described in JP-A-9-510617 (27) α-amylase variant described in JP-T 2001-520006 (28) JP-A 2001-521739 Α-amylase variant (29) described in Japanese Patent Publication No. 2002-504323 Alkaline Bacillus amylase (30) Special Table 2002-530 Α-Amylase variant (31) described in Japanese Patent No. 072 (alpha) -Amylase variant (32) described in Japanese translation of PCT International Publication No. 2002-540785 (32) Alkaline Bacillus amylase (33) described in JP-T 2003-507059 Α-Amylase Mutant

  These amylases can be used alone or in combination of two or more. When two or more types are used in combination, even if the viscosity reduction rate for each amylase is less than 40%, if the viscosity reduction rate when used in combination is 40% or more, it is used as the component (A) of the present invention. can do. As the component (A) of the present invention, an amylase having a viscosity reduction rate of 70% or more is preferable, and an amylase having 80% or more is more preferable. Although not bound by any theory, if the viscosity reduction rate of amylase is 40% or more, the adhesion between clothes and dirt can be weakened, so it exhibits a high removal effect against food stains it is conceivable that. By selecting an amylase having a high viscosity reducing effect or by selecting an amylase mutated to increase the viscosity reducing effect, the viscosity reduction rate of the amylase can be increased. In particular, the amylases described in the above patent publications (21) to (33) are preferable. In particular, a stainzyme is preferable.

  Amylase is preferably used as a granulated product with a stabilizer, a filler, a filler, a whitening agent, a binder, a coating agent and the like based on a normal granulation method. It is because it is excellent in stability and solubility in water. From the viewpoint of stability and solubility in water, it is desirable that the average particle size measured by the method described in Examples below be 200 to 700 μm. In addition, when granulating two or more kinds of enzymes, they may be granulated separately, or the enzymes may be mixed to form the same granulated product. As a compounding quantity of the enzyme granule containing the amylase in the composition of this invention, it is preferable that it is 0.1-3 mass%, and it is more preferable that it is 0.2-2 mass%. Usually, the amount of amylase in the enzyme granulated product is about 0.1 to 10% by mass, preferably 0.5 to 5% by mass, more preferably 1 to 3% by mass as the amount of enzyme protein. . As methods for granulating enzyme-containing particles, JP-A No. 53-6484, JP-A No. 60-262900, JP-A No. 62-257990, JP-A No. 1-112983, JP-A No. 3-129, No. 503775, JP-A-4-503369, JP-A-2000-178593, and the like.

In the composition of the present invention, the amount of (A) amylase is preferably 0.001% by mass or more, more preferably 0.002% by mass or more, particularly preferably 0.003 as the amount of enzyme protein, based on the total amount of the composition. It is preferably contained in an amount of not less than 0.05% by weight, preferably not more than 0.05% by weight, more preferably not more than 0.03% by weight, particularly preferably not more than 0.02% by weight. When the amount is less than 0.001% by mass, the effect of the present invention may be reduced. When the amount is more than 0.05% by mass, the effect may reach a peak.
The amount of enzyme protein in the detergent composition can be determined by obtaining a crude enzyme by separation means such as salting-out method, precipitation method, ultrafiltration method, etc. Alternatively, it is possible to stain a band formed by SDS-polyacrylamide gel electrophoresis by a known staining method and compare the degree of staining with a known enzyme purified product.

(B) Nonionic surfactant As a nonionic surfactant which is (B) component of this invention, the following can be mentioned, for example.
(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) An alkylene oxide added between the ester bonds of a long-chain fatty acid alkyl ester, for example, a fatty acid alkyl ester alkoxylate represented by the following general formula (II)
R1CO (OA) nOR2 (II)
(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 (9) Polyoxyalkylene alkyl (or Alkenyl) amine (10) polyoxyalkylene alkyl (or alkenyl) amide (11) alkyl polyglycoside

  Among the above nonionic surfactants, polyoxyethylene alkyl (or alkenyl) ether, polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether having a melting point of 50 ° C. or less and 9 to 16 HLB, ethylene oxide and fatty acid methyl ester Suitable examples include fatty acid methyl ester ethoxylates having added thereto, fatty acid methyl ester ethoxypropoxylates having ethylene oxide and propylene oxide added to fatty acid methyl esters, and the like. Of these, an ethylene oxide average 4 to 18 mol adduct of alcohol having an alkyl group having 12 to 16 carbon atoms is preferable, and an ethylene oxide average 6 to 15 mol adduct of alcohol having an alkyl group having 12 to 16 carbon atoms is particularly preferable. . 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). 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”.
The nonionic surfactant is preferably contained in an amount of 16% by mass or more, more preferably 17% by mass or more, preferably 28% by mass or less, more preferably 25% by mass or less, based on the total amount of the composition. Preferably. When the amount is less than 15% by mass, the effect of the present invention may be reduced. When the amount is more than 30% by mass, an amylase-containing granular detergent composition having good solubility and fluidity after long-term storage is prepared. May be difficult, and the effect may reach its peak.

(C) Anionic surfactant The anionic surfactant that is the component (C) of the present invention is not particularly limited as long as it is conventionally used in detergents, and various anionic surfactants are used. Can be used. For example, the following can be mentioned.
(1) Linear or branched alkylbenzene sulfonate (LAS) having an alkyl group having 8 to 18 carbon atoms
(2) C10-20 alkyl sulfate (AS) or alkenyl sulfate (3) C10-20 α-olefin sulfonate (AOS)
(4) Alkanesulfonate having 10 to 20 carbon atoms (5) Ethylene oxide or propylene 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 sulfate (AES) or alkenyl ether sulfate to which oxide, butylene oxide or a mixture thereof is added (6) having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and an average addition mole Alkyl ether carboxylate or alkenyl ether carboxylate to which ethylene oxide, propylene oxide, butylene oxide or a mixture thereof having a number of 10 moles or less is added (7) Alkyl polycarboxylic acid such as alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms Monohydric alcohol ether sulfate (8) charcoal The number of 8 to 20 saturated or unsaturated α- sulfofatty acids (alpha-SF) salt or a methyl, ethyl or propyl ester (9) secondary alkane sulfonates of 10 to 20 carbon atoms (SAS)
(10) C10-20 higher fatty acid salt (soap)

As the anionic surfactant, LAS, AS, AOS, AES, methyl ester of α-SF, and an alkali metal salt of soap (for example, sodium or potassium salt) are preferable.
The anionic surfactant is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, particularly preferably 1% by mass or more, and preferably 20% by mass or less, based on the total amount of the composition. More preferably, it is contained in an amount of 10% by mass or less, particularly preferably 5% by mass or less. When the amount is less than 0.1% by mass, the effect of the present invention may be reduced. When the amount is more than 20% by mass, the effect may reach a peak.

  In the present invention, the mass ratio of (B) nonionic surfactant to (C) anionic surfactant ((B) / (C)) is 5 or more, preferably 7 or more, based on the total amount of the composition. Preferably it is 8 or more, 30 or less, preferably 20 or less, more preferably 15 or less. When (B) / (C) is less than 5, the effect of the present invention may be reduced. When it is greater than 30, stains may occur when washing clothes including hydrophobic fibers such as polyester fibers. Reattachment may occur, and the effect may reach a peak.

When the granular detergent composition of the present invention further contains (D) a carboxylic acid polymer, it is preferable in terms of the effect of cleaning food stains.
(D) Carboxylic acid polymer The carboxylic acid polymer as the component (D) of the present invention is usually used as an organic builder. In the present invention, as the carboxylic acid polymer, acrylic acid polymer compound, polyacetal carboxylate, cellulose polymer compound, itaconic acid, fumaric acid, tetramethylene-1,2-dicarboxylic acid, succinic acid, aspartic acid, etc. Polymers, copolymers, polysaccharide oxides such as starch, cellulose, amylose and pectin, and polysaccharides such as carboxymethyl cellulose, and acrylic acid polymer compounds are preferred. As the acrylic acid polymer compound, an acrylic acid polymer and an acrylic acid / maleic acid copolymer are preferable, and in particular, a salt of an acrylic acid / maleic acid copolymer having a weight average molecular weight of 1,000 to 80,000, Acrylic acid polymer salts are preferred. Examples of the polyacetal carboxylate include polyacetal carboxylates such as polyglyoxylic acid having a weight average molecular weight of 800 to 1,000,000, preferably 5,000 to 200,000 described in JP-A No. 54-52196. Is preferred. As the cellulose polymer compound, carboxymethyl cellulose (CMC) is preferable. The weight average molecular weight of the cellulosic polymer compound is preferably 1,000 to 1,000,000, and more preferably 1,000 to 100,000. Carboxylic acid builder can be used individually by 1 type or in combination of 2 or more types.
The carboxylic acid polymer as the component (D) is 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, particularly preferably 4% by mass, based on the total amount of the composition. It is preferable that it is contained in an amount of 20% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less, and particularly preferably 7% by mass or less. When the amount is less than 0.1% by mass, the effect of the present invention may be reduced. When the amount is more than 20% by mass, the effect may reach a peak.

The granular detergent composition of the present invention can be blended with the following various components that are usually blended in the detergent composition, as long as the effects of the present invention are not hindered, in addition to the above essential components.
(1) Surfactant other than component (B) and component (C) Examples of the surfactant other than the component (B) and component (C) of the present invention include cationic surfactants and amphoteric surfactants.
Examples of the cationic surfactant include the following.
(I) Di long chain alkyl dishort chain alkyl type quaternary ammonium salt (ii) Mono long chain alkyl tri short chain alkyl type quaternary ammonium salt (iii) Tri long chain alkyl mono short chain alkyl type quaternary ammonium salt The chain alkyl is an alkyl group having 12 to 26 carbon atoms, preferably 14 to 18 carbon atoms, and the short chain alkyl is an alkyl group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, a benzyl group, and 2 to 4 carbon atoms, preferably 2 to 2 carbon atoms. 3 represents a hydroxyalkyl group or a polyoxyalkylene group.)
Examples of amphoteric surfactants include amphoteric surfactants such as imidazolines, amide betaines, and amine oxides.

(2) Examples of builder builders include inorganic builders and organic builders (excluding component (D)).
Examples of inorganic builders include, for example, alkaline salts such as sodium carbonate, potassium carbonate, sodium bicarbonate, sodium sesquicarbonate, sodium silicate, crystalline layered sodium silicate, and amorphous layered sodium silicate, sodium sulfate, potassium sulfate, Neutral salts such as sodium chloride, potassium chloride, phosphates such as orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate, phytate,
The following general formula (III)
_{^{x 1 (M 2 O) ·}} Al 2 O 3 · y 1 (SiO 2) · w 1 (H 2 O) ··· (III)
(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.)
The following general formula (IV), (V)
_{^{x 2 (M 2 O) ·}} Al 2 O 3 · y 2 (SiO 2) · w 2 (H 2 O) ··· (IV)
(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) ··· (V)
(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 the inorganic builders, sodium carbonate, potassium carbonate, sodium silicate, and sodium aluminosilicate are preferable.
In addition, from the viewpoint of solubility, among the inorganic builders, it is preferable to blend those showing an effect of improving low-temperature solubility such as potassium carbonate, sodium chloride, potassium chloride and the like in the granular detergent composition of the present invention. It is suitable to mix 15% by mass, more preferably 3 to 10% by mass.

  When water-soluble inorganic compound particles such as sodium carbonate are used in a powder blend with particles constituting other granular detergent compositions, surface treatment is performed for the purpose of preventing poor dissolution at low water temperature. The surface-treated water-soluble inorganic compound particles are preferably used. As the surface-treated water-soluble inorganic compound particles, for example, the surface-treated water-soluble inorganic compound particles described on pages 3 to 25 of WO 2004/094313 are suitably used. It is preferable that the surface-treated water-soluble inorganic compound particles are incorporated in the granular detergent composition in an amount of 3 to 30% by mass, more preferably 7 to 20% by mass, and particularly preferably 10 to 15% by mass.

  Examples of the organic builder include aminocarboxylates such as nitrilotriacetate, ethylenediaminetetraacetate, β-alanine diacetate, aspartate diacetate, methylglycine diacetate, and iminodisuccinate; serine diacetate, hydroxyimino Hydroxyaminocarboxylates such as disuccinate, hydroxyethylethylenediaminetriacetate, dihydroxyethylglycine; Hydroxycarboxylates such as hydroxyacetate, tartrate, citrate, gluconate; pyromellitic acid salt, Cyclocarboxylates such as benzopolycarboxylates and cyclopentanetetracarboxylates; ether carboxylates such as carboxymethyltaltronate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid mono- or disuccinate Polyethylene glycol, polyvinyl alcohol, undissociated polymer compounds such as polyvinyl pyrrolidone, and the like. Among these organic builders, citrate, aminocarboxylate, and hydroxyaminocarboxylate are preferable.

  The said builder is normally used individually or in mixture of 2 or more types. The amount of the builder is preferably 10 to 70% by mass, particularly preferably 20 to 50% by mass in the detergent composition in order to impart sufficient detergency.

(3) As a fluorescent brightening agent, bis (triazinylaminostilbene) disulfonic acid derivative [Tinopearl AMS-GX], bis (sulfostyryl) biphenyl salt [Tinopearl CBS-X] and the like.
(4) As a surface modifier, fine calcium carbonate, fine zeolite, granular zeolite, polyethylene glycol and the like.
(5) Cellulose derivatives such as carboxymethylcellulose, polyvinylpyrrolidone and derivatives thereof as anti-staining agents.
(6) As a porous oil absorbent, amorphous anhydrous silicic acid, calcium silicate and the like.
(7) As a flexibility-imparting agent, cationic surfactants such as dialkyl quaternary ammonium salts, clay minerals such as smectite, and the like.
(8) As a bleaching agent, sodium percarbonate, sodium perborate and the like.
(9) Tetraacetylethylenediamine (TAED), decanoyloxybenzoic acid, sodium dodecanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, sodium decanoyloxybenzenesulfonate, and the like as bleach activators.
(10) Bleach activation catalyst (11) As an enzyme, protease, lipase, cellulase, amylase other than component (A), and the like.
(12) Silicone oil or the like as an antifoaming agent.
(13) Fragrance (14) Coloring agents such as water-soluble dyes and pigments (15) Examples of reducing agents include sodium sulfite and potassium sulfite.
The reducing agent is usually used alone or in combination of two or more, but sodium sulfite is preferred. The amount of the reducing agent is preferably 0.3% by mass or more, more preferably 0.00% or more in the detergent composition from the viewpoint of the stability of the enzyme in the washing liquid for imparting sufficient detergency. It is preferable that the amount is 5% by mass or more, preferably 3% by mass or less, and more preferably 2% by mass or less.
(16) Enzymes other than component (A) As the enzyme, protease, amylase, lipase, cellulase, etc. other than component (A) can be used. It is preferably contained in an amount of 0.01 to 10%, more preferably 0.2 to 1.5% by mass with respect to the granular detergent composition of the present invention.

The method for preparing the granular detergent composition of the present invention is not particularly limited, and the detergent particles containing the components (A) to (C) can be prepared according to a conventional method.
Specifically, the detergent particles can be obtained by the following granulation method. The raw powder and binder components (surfactant, water, liquid polymer component, etc.) are kneaded and kneaded, then extruded and granulated by extruding, kneaded and kneaded, and the resulting solid detergent is crushed Kneading and crushing granulation method, granulating by adding binder component to raw material powder and stirring granulation by stirring with stirring blade, spraying binder component while rolling raw material powder And a fluidized bed granulation method in which a liquid binder is sprayed and granulated while fluidizing the raw material powder. Specific devices and conditions that can be used in these granulation methods are as described in JP-A-2003-105400, JP-A-2003-238998, edited by Japan Powder Technology Association, granulation handbook first edition, and the like. is there.

  The bulk density of the composition of the present invention is 0.5 g / mL or more, preferably 0.6 g / mL or more, more preferably 0.7 g / mL or more, particularly preferably 0.8 g / mL or more, 1.3 g / mL or less, preferably 1.2 g / mL or less, more preferably 1.1 g / mL or less, and particularly preferably 1.0 g / mL. When the bulk density is less than 0.5 g / mL, the bulk may become bulky, resulting in a large packaging form and may be uneconomical. When the bulk density is greater than 1.3 g / mL, the solubility may deteriorate.

In terms of solubility and stability, the granular detergent composition of the present invention has an average particle size of 200 μm or more, preferably 250 μm or more, more preferably 300 μm or more, 1000 μm or less, preferably 700 μm or less, more preferably 600 μm or less. This is preferable. When the average particle size is smaller than 200 μm, powdering may occur during use, and when it is larger than 1000 μm, the solubility may deteriorate.
The water content of the granular detergent composition of the present invention is preferably 4 to 10% by mass, more preferably 5 to 9% by mass, and 6 to 8% in terms of solubility and storage stability. Is most preferred. In addition, the moisture content in this invention can be measured by the heating loss method prescribed | regulated to JISK3622-1998.

  The granular detergent composition of the present invention is suitably used as a detergent for clothing, and its usage is not particularly limited and can be used in a conventional manner.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following examples, unless otherwise specified, “%” indicates mass%, and the ratio indicates mass ratio.

(1) (A) Measurement of viscosity reduction rate of amylase 25 g of corn starch (manufactured by Kanto Chemical Co., Inc.) was added to 475 g of an aqueous alkali (sodium carbonate 4000 ppm) solution at 90 ± 2 ° C. and stirred and dissolved at 90 ± 2 ° C. for 1 hour. And then cooled at 5 ° C. for 12 hours. Thereafter, the solution was allowed to stand at room temperature, and after the temperature of the solution became equal to room temperature, the temperature was adjusted to 25 ° C. Next, the viscosity of 40 g of the solution adjusted to 25 ° C. was measured using a vibration viscometer (CJV5000 manufactured by A & D Co., Ltd., vibrator material: stainless steel SUS304-CSP-H, vibrator shape and size: Disk shape, t (thickness) = 0.1 mm, φ (diameter) = 13 mm) were used as initial viscosity (measurement condition: set amplitude value 50 mV, vibration frequency: 30 Hz, sample amount: 40 g (5% As aqueous solution), measuring temperature: 25 ° C.). Thereafter, 0.004 mg of amylase as an enzyme protein amount was rapidly added to 40 g of an aqueous starch solution and stirred, and 10 seconds after the addition, the viscosity was measured in the same manner as the initial viscosity, and then the temperature was adjusted at 25 ° C. Then, after 10 minutes, 30 minutes and 60 minutes, the viscosity was measured in the same manner as the initial viscosity. The initial viscosity and the viscosity value after 60 minutes were obtained. Next, the viscosity reduction rate was calculated according to the above-described formula (1).
When the viscosity reduction ratios of Stainzyme (manufactured by Novozymes), Termamyl (manufactured by Novozymes) and Duramil (manufactured by Novozymes) were measured by the above method, they were 91%, 20% and 23%, respectively. These values are average values of three experiments. Moreover, the fluctuation range of the measured value was about 10 mPa · s. The relationship between time and viscosity for each enzyme is shown in FIG.

(2) Preparation method of granular detergent composition About the detergent composition shown in Table 1, it prepared by the following procedures.
Water was put into a jacketed mixing tank equipped with a stirrer, and the temperature was adjusted to 50 ° C. To this was added sodium sulfate, sodium sulfite, and a fluorescent brightening agent. After stirring for 10 minutes, sodium carbonate was added and then a carboxylic acid polymer was added. After further stirring for 10 minutes, sodium chloride and a part of the powdered zeolite ( The amount obtained by subtracting 12% by mass from the amount shown in Table 1 was added. The mixture was further stirred for 30 minutes to prepare a slurry for spray drying. The temperature of the resulting slurry for spray drying was 60 ° C. This slurry is spray-dried in a counter-current spray dryer equipped with a pressure spray nozzle, the volatile content (105 ° C., reduced for 2 hours) is 3%, the bulk density is 0.50 g / mL, and the average particle size is 250 μm spray-dried particles were obtained.
Next, a nonionic surfactant, an anionic surfactant, and soap were added under mixing at 80 ° C. to prepare a surfactant composition having a water content of 10% by mass. Next, spray-dried particles were put into a Redige mixer M20 type (manufactured by Matsuzaka Giken Co., Ltd.), and stirring of the main shaft (150 rpm) and chopper (4000 rpm) was started. Warm water at 80 ° C. was passed through the jacket at a flow rate of 10 L / min. The above surfactant composition was charged there over 2 minutes and then stirred for 5 minutes. Then, layered sodium silicate and a part (10% by mass) of the above powdered zeolite were added to perform surface coating treatment for 2 minutes. A detergent composition was obtained.
After mixing a part (2% by mass) of the powdered zeolite with this detergent composition with a V blender, the enzyme and the surface-treated water-soluble inorganic compound particles are mixed with a V blender, and further, a dye 20% aqueous dispersion and Perfume was added by spraying to obtain a granular detergent composition. The resulting granular detergent composition had a bulk density of 0.75 g / mL and an average particle size of 300 μm. About the granular detergent composition, the washing | cleaning performance with respect to food stain | pollution | contamination was evaluated in accordance with the following evaluation method. The results are also shown in Table 1.

(3) Food dirt cleaning performance evaluation (i) Preparation method of food dirt evaluation cloth No. 60 cotton plain weave cloth was cut into 20cm x 30cm, and Kagome Co., Ltd.'s pasta sauce "Mokuto Umami Napolitan sauteed onion & butter “After immersing one can (with 295 g) in a stainless steel bat for about 1 hour, remove the solid matter attached to the surface and air-dry it overnight in a dark and constant temperature and humidity chamber at 20 ° C. and 40% RH. A food soil evaluation cloth was used.
(Ii) Evaluation of Cleaning Performance of Granular Detergent Composition Using Terg-O-meter of Testing USA as a cleaning tester, 10 pieces of the above-mentioned food dirt evaluation cloth, sebum cloth, and cleaning knitted cloth are put. The detergent composition was added so that the detergent concentration would be 0.067%, and washed at 120 rpm and 20 ° C. for 10 minutes in accordance with the bath ratio of 30 times. The water used was 4 ° DH, the amount of the cleaning solution was 900 mL, and the rinse was washed with 900 mL of water for 3 minutes. After rinsing, the evaluation fabric was dried, and the washing rate was calculated by the following equation.

  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.

(4) Measurement of bulk density The bulk density was measured according to JIS K3362-1998.
(5) Measurement of average particle diameter It measured according to the measurement of (2) average particle diameter of Paragraph [0095] of Unexamined-Japanese-Patent No. 2005-239865.
(6) Measurement of moisture content The moisture content was measured using the heat loss method defined in JISK3362-1998.

The raw materials used in the examples are shown below.
[amylase]
A-1: Stainzyme 12T (manufactured by Novozymes)
A′-2: Termamyl 120T (manufactured by Novozymes) (A′-2 is not the component (A) of the present invention)
In addition, the compounding quantity of Table 1 shows the quantity of the enzyme granulated material containing amylase.
[Nonionic surfactant]
B-1: Ethanol oxide average 6 mol adduct of ECOROL26 (alcohol having an alkyl group having 12 to 16 carbon atoms manufactured by ECOGREEN) (pure content 90%, HLB11.5, melting point 18 ° C.)
-B-2: An average of 15 moles of ethylene oxide adduct of ECOROL 26 (alcohol having an alkyl group having 12 to 16 carbon atoms manufactured by ECOGREEN) (pure content 90%, HLB 15.4, melting point 43 ° C.)
-B-3: Average 20-mole ethylene oxide adduct of Diadol 13 (manufactured by Mitsubishi Chemical Corporation) (90% pure, HLB16.3, melting point 45 ° C.)
[Anionic surfactant]
C-1: 14 carbon atoms: sodium salt of α-sulfo fatty acid methyl ester of carbon number 16 = 18: 82 (manufactured by Lion Corporation, AI = 70%, the remainder is unreacted fatty acid methyl ester, sodium sulfate, methyl Sulfate, hydrogen peroxide, water, etc.)
C-2: linear alkyl (10 to 14 carbon atoms) benzenesulfonic acid (Lypon LH-200 (LAS-H pure content 96%) manufactured by Lion Corporation) was neutralized with 48% aqueous sodium hydroxide during preparation Linear alkylbenzene sulfonate sodium (LAS-Na). The compounding quantity in Table 1 shows the mass% as LAS-Na.
C-3: Sodium α-olefin sulfonate having an alkyl group having 14 to 18 carbon atoms (manufactured by Lion Corporation)
C-4: Sodium alkyl ether sulfate (produced by Lion Co., Ltd.) obtained by converting a 2-mole ethylene oxide adduct of Neodol 23 (manufactured by Shell Co., Ltd.) into a sulfate ester and neutralizing with an aqueous sodium hydroxide solution
-C-5: Fatty acid sodium having 12 to 18 carbon atoms (manufactured by Lion Corporation, pure content: 67%, titer: 40-45 ° 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)
[Carboxylic acid polymer]
D-1: sodium polyacrylate, trade name Socaran PA30 (manufactured by BASF, weight average molecular weight 8,000, solid content 50% aqueous solution)
D-2: Sodium salt of acrylic acid / maleic acid copolymer (Nippon Shokubai Co., Ltd. Aquaric TL-400, weight average molecular weight 50,000, solid content 40% aqueous solution)

[Others]
・ Sodium carbonate: Heavy sodium carbonate (Soda Ash Japan Co., Ltd., soda ash)
-Potassium carbonate: Potassium carbonate (Asahi Glass Co., Ltd.)
・ Sodium sulfate: neutral anhydrous sodium sulfate (manufactured by Shikoku Chemicals Co., Ltd.)
・ Sodium sulfite: Sodium sulfite (Mitsui Chemicals)
・ Sodium chloride: Nissei Yaki Salt C (manufactured by Nippon Salt Co., Ltd.)
-Layered sodium silicate: SKS-6 (manufactured by Clariant)
・ Zeolite: Type A zeolite (Silton B manufactured by Mizusawa Chemical Co., Ltd.)
・ Optical brightener: Chinopearl CBS-X (manufactured by Ciba Specialty Chemicals) and Chinopearl AMS-GX (manufactured by Ciba Specialty Chemicals) at a mass ratio of 8/2 ・ Enzymes other than amylase: Sabinase 12T (manufactured by Novozymes) ), Lipex 100T (manufactured by Novozymes) and Cellzyme 0.7T (manufactured by Novozymes) in a 4: 1: 1 (mass ratio) surface treatment water-soluble inorganic compound particles: Table 1 of WO 2004/094313 Surface-treated water-soluble inorganic compound particles a9
-Dye A: Ultramarine (Daiichi Seika Kogyo, Ultramarine Blue)
-Dye B: Pigment Green 7 (manufactured by Dainichi Seika Kogyo)
Fragrance A: Fragrance composition A shown in JP-A-2002-146399, Tables 11-18
Fragrance B: Fragrance composition B shown in JP-A No. 2002-146399, Tables 11 to 18

FIG. 1 is a graph showing changes in viscosity over time for three types of amylases (Termamyl, Duramil and Steinzyme).

Claims (4)

(A) an amylase having a viscosity reduction rate calculated by the following formula (I) of 40% or more;

(B) nonionic surfactant,
(C) an anionic surfactant,
And (B) / (C) = 5 to 30 (mass ratio).   The granular detergent composition according to claim 1, comprising a carboxylic acid polymer as component (D).   The granular detergent composition according to claim 1 or 2, wherein the amylase as component (A) has a viscosity reduction rate of 50% or more.   The granular detergent composition according to any one of claims 1 to 3, wherein the amylase as component (A) is Steinzyme (registered trademark).

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