JP4714457B2 - Amylase-containing granular detergent composition - Google Patents

Description

  The present invention relates to a granular detergent composition for use in textile products such as clothing, and more particularly to a granular detergent composition containing a specific amylase and having a high effect of cleaning a composite soil.

Dirt that adheres to clothing during work at a factory or construction site, during agricultural work, etc. contains inorganic sludge such as clay and organic sludge such as oil and fat components. On the other hand, starchy stains derived from laundry or food may remain invisible in clothing, and are mixed with the aforementioned stains on the clothing. Such a composite soil is difficult to remove by ordinary washing using a washing machine because starchy material serves as a binder. For this reason, a pretreatment such as applying a high-concentration washing liquid to dirt and washing in advance is necessary.
Therefore, there has been a demand for a granular detergent composition that can effectively remove composite dirt without such pretreatment.
So far, there has been a detergent composition having both amylase and an inorganic ion exchanger having a specific composition, and a detergent composition having both amylase and two specific builders in a specific ratio (Patent Documents 1 and 2). Although known, the former is excellent in enzyme stability during storage and aims to provide a detergent composition suitable for concentration, and the latter is a detergent composition particularly suitable for laundry. As a result, a satisfactory cleaning effect could not be obtained with respect to the composite soil as intended in the present invention.

JP-A-6-116590 Japanese National Patent Publication No. 11-507989

  In view of the above circumstances, an object of the present invention is to provide a cleaning composition that is highly effective in removing composite dirt even in normal washing.

As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by combining amylase, surfactant and crystalline silicate, and to complete the present invention. It came.
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 (1) of 40% or more,
(B) crystalline silicate and (C) surfactant.

  According to the present invention, it is possible to effectively and easily remove composite soil containing inorganic sludge derived from starch, clay, etc. and organic sludge derived from fats and oils derived from food, laundry glue, etc., cleaning effect It is possible to obtain an excellent detergent composition. The composition of the present invention is also excellent in the effect of preventing recontamination of inorganic sludge such as clay.

(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., and stirred and dissolved at 90 ± 2 ° C. for 1 hour, then at 5 ° C. for 12 hours. 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 vibratory 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. . Then, 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 (1).
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-4-500756 (13) described in JP-A-6-14775 (2) Alkaline isoamylase of the genus Bacillus (14) Alkaline amylase of the genus Bacillus described in JP-A-8-56662 (15) Alkaline α-amylase of the genus Bacillus described in JP-A-9-206073 (16) Α-Amylase variant described in Table 10-10504197 (17) Alkaline amylase described in JP 2000-023665 (18) Alkaline amylase described in JP 2000-023666 (19) JP 2000-023667 No. 20 Alkaline Amylase (20) Mutation α described in JP-A No. 2002-112792 -Amylase

(21) Pyrococcus-origin α-amylase described in JP-A-4-503757 (22) Bacillus-origin α-amylase (23) JP-T 8-504586 Α-amylase of the genus Bacillus or asparagillus described (24) Starch-degrading enzyme of the genus Pyrococcus described in JP-T 8-506673 (25) Origin of Bacillus in JP-T 9-503916 Α-amylase (26) α-amylase of the genus Bacillus described in JP-T 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 publication 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 component (A) of the present invention, in order to effectively remove composite dirt, starch contained in the composite dirt is more effectively decomposed, and it is easy to remove with a preferable t that reduces the viscosity of the dirt. An amylase having an excellent effect is preferable. Specifically, an amylase having a viscosity reduction rate of 50% or more is preferable, an amylase having a viscosity reduction rate of 70% or more is more preferable, and an amylase having a viscosity reduction rate of 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 spilled dirt. It is considered a thing. 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. 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.
In addition, the amount of enzyme protein in the detergent composition is determined by obtaining a crude enzyme by separation means such as a salting-out method, a precipitation method, an ultrafiltration method or the like, and then purifying and crystallizing by a known method. Alternatively, the band formed by SDS-polyacrylamide gel electrophoresis is stained by a known staining method, and the degree of staining is compared with a known enzyme purified product.

Component (B) The crystalline silicate used in the present invention is preferably an alkali metal of silicic acid (SiO ₂ ), and in particular, an alkali metal silicate of SiO ₂ / M ₂ O (where M represents an alkali metal). Is preferably 0.5 to 2.6. For example, Japanese Patent Laid-Open No. 11-507989 discloses a crystalline silicate having a SiO ₂ / Na ₂ O ratio of 1.9 to 4.0. In view of the poor builder effect, it may be unsuitable for blending into the granular detergent that is the subject of the present invention.
What is suitable as a crystalline silicate used for this invention has the following composition.
_{x (M 2 O) · y} (SiO 2) · z (Me m O n) · w (H 2 O) (II)
[Wherein M represents a group Ia element of the periodic table, and Me represents one or more selected from group IIa, IIb, IIIa, IVa, or VIII elements of the periodic table. The combination of y / x = 0.5 to 2.6, z / x = 0.01 to 1.0, w = 0 to 20, and n / m = 0.5 to 2.0. ]
M ₂ O · x ′ (SiO ₂ ) · y ′ (H ₂ O) (III)
[In the formula, M represents a group Ia element in the periodic table, and x ′ = 1.5 to 2.6 and y ′ = 0 to 20. ]

First, the crystalline silicate represented by the general formula (II) will be described.
In the general formula (II), examples of M include Na and K. Na is preferred. These may constitute M ₂ O alone or in combination with, for example, Na ₂ O and K ₂ O.
Examples of Me include Mg, Ca, Zn, Y, Ti, Zr, and Fe, and Mg and Ca are preferable from the viewpoint of safety. Further, it may be mixed alone or two or more, for example MgO, CaO or the like may constitute the Me _m O _n component are mixed.
y / x is 0.5 to 2.6, preferably 1.0 to 2.2, and more preferably 1.5 to 2.0. It is preferable that y / x is 0.5 or more because good water resistance, caking property, solubility, and powder physical properties of the detergent composition are exhibited. On the other hand, it is preferable that y / x is 2.6 or less because it sufficiently acts as an alkali agent and exhibits high ion exchange ability.
z / x is 0.01 to 1.0, preferably 0.02 to 0.9, and more preferably 0.1 to 0.5. When z / x is 0.01 or more, good water resistance is exhibited, and when z / x is 1.0 or less, high ion exchange ability is exhibited, which is preferable.
When x (M ₂ O) is, for example, x ′ (Na ₂ O) · x ″ (K ₂ O), x is x ′ + x ″. This relationship is the same in the z in the case where z (Me _m O _n) component consists of two or more.
n / m represents the number of oxygen ions coordinated with the element, and is substantially selected from the values of 0.5, 1.0, 1.5, and 2.0.

In order to produce the crystalline silicate represented by the general formula (II), a known compound is appropriately used as a raw material. For example, M ₂ O component, the Me _m O _n component, alone or oxides of the composite of each of the elements, hydroxides, salts, the element-containing minerals is used. Specifically, for example, as a raw material of M ₂ O _{component, NaOH, KOH, Na 2 CO} 3, K 2 CO 3, Na 2 SO 4 and the like, as a material of Me _m O _{n component,} CaCO 3, MgCO ₃ , Ca (OH) ₂ , Mg (OH) ₂ , MgO, ZrO ₂ , dolomite and the like. As the SiO ₂ component, silica, kaolin, talc, fused silica, sodium silicate and the like are used.
In the method for preparing the crystalline silicate represented by the general formula (II), the raw material components are mixed at a predetermined quantitative ratio so that x, y, and z of the target crystalline silicate are obtained. In the range of 600 to 900 ° C., a method of crystallization by baking in air for about 1 hour is exemplified.
The crystalline silicate represented by the general formula (II) thus obtained has a pH of 11 or more in a 0.1% by mass aqueous dispersion, and exhibits excellent alkaline ability. Further, the alkali buffering effect is also particularly excellent, and the alkali buffering effect is excellent even when compared with sodium carbonate or potassium carbonate.

The crystalline silicate represented by the general formula (II) preferably has an ion exchange capacity of at least 100 CaCO ₃ mg / g, more preferably 200 to 500 CaCO ₃ mg / g, and has an ion trapping ability. . The amount of Si dissolved in water is usually 110 mg / g or less in terms of SiO ₂ and is substantially insoluble in water. In the present invention, “substantially insoluble in water” means that when 2 g of sample is added to 100 g of ion-exchanged water and stirred for 30 minutes at 25 ° C., the amount of Si elution is usually less than 110 mg / g in terms of SiO _2. In the present invention, it is more preferable that the Si elution amount is 100 mg / g or less in terms of SiO _{2 in} order to satisfy this effect.
As described above, the crystalline silicate represented by the general formula (II) has an alkali ability and an alkali buffering effect, and further has an ion exchange ability. Conditions can be suitably adjusted.
The crystalline silicate represented by the general formula (II) preferably has an average particle size of 0.1 to 100 μm, more preferably 1 to 60 μm. If the average particle size exceeds 100 μm, the rate of ion exchange tends to be slow, resulting in a decrease in detergency. On the other hand, if the thickness is less than 0.1 μm, the hygroscopicity and CO ₂ absorption increase due to the increase in specific surface area, and the quality tends to deteriorate significantly. Here, the average particle diameter is the median diameter of the particle size distribution.
The crystalline silicate having such an average particle size and particle size distribution can be prepared by pulverization using a pulverizer such as a vibration mill, a hammer mill, a ball mill, or a roller mill. For example, it can be easily obtained by grinding with an HB-O type vibration mill (manufactured by Chuo Kako Co., Ltd.).

Next, the crystalline silicate represented by the general formula (III) will be described. This crystalline silicate has the general formula (III)
M ₂ O · x ′ (SiO ₂ ) · y ′ (H ₂ O) (III)
[Wherein M represents an alkali metal, and x ′ = 1.5 to 2.6 and y ′ = 0 to 20. ]
In the general formula (III), x ′ and y ′ are preferably 1.7 ≦ x ′ ≦ 2.2 and y ′ = 0, and the cation exchange capacity is 100 to 400 CaCO. ₃ mg / g can be used, and is one of the substances having ion trapping ability in the present invention. The crystalline silicate represented by the general formula (III) has an alkali ability and an alkali buffering effect as described above, and further has an ion exchange ability. Can be suitably adjusted.
The manufacturing method of the crystalline silicate represented by the general formula (III) is described in JP-A-60-227895, and generally amorphous glassy sodium silicate is fired at 200 to 1000 ° C. To obtain crystallinity. Details of the synthesis method are described in, for example, Phys. Chem. Glasses. 7, 127-138 (1966), Z.M. Kristallogr. , 129, 396-404 (1969) and the like. In addition, the crystalline silicate represented by the general formula (III) is, for example, in the form of powder or granule as a trade name “SKS-6” (δ-Na ₂ Si ₂ O ₅ ) from Clariant Tokuyama. Available. In the present invention, the crystalline silicate represented by the general formula (III) preferably has an average particle diameter of 0.1 to 100 μm, like the crystalline silicate represented by the general formula (II). More preferably, it is 1-60 micrometers.
In the present invention, the crystalline silicate represented by the general formula (II) and the crystalline silicate represented by the general formula (III) can be used alone or in combination of two or more. The crystalline silicate represented by II) and the crystalline silicate represented by the general formula (III) can be used in combination. Moreover, it is desirable to occupy 30-100 mass% among the alkaline agents mix | blended in a composition, More preferably, 40-80 mass% is occupied. In addition, in this specification, what is generally used as an alkali cleaning builder is mention | raise | lifted with an alkali agent. Such compounds include carbonates, bicarbonates and sesquicarbonates, sulfites, phosphates and polycondensed phosphates, silicates, nitrites and the like.
In the present invention, the crystalline silicate of component (B) is blended in the composition in an amount of 1 to 20% by mass, preferably 5 to 10% by mass. When the blending amount of the component (B) is less than 1% by mass, the detergency is lowered, and even if it exceeds 20% by mass, the contribution to the cleaning performance is saturated and it is not economical.

Component (C) Examples of surfactants include anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants, and these may be used alone or in combination of two or more. it can.

(I) Nonionic surfactant Examples of the nonionic surfactant 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
R ¹ CO (OA) _n OR ² (I)
(In the formula, R ¹ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms, and OA is an alkylene having 2 to 4 carbon atoms such as ethylene oxide and propylene oxide, preferably 2 to 3 carbon atoms. Represents an oxide addition unit, and n represents the average number of moles of alkylene oxide added, and is generally a number of 3 to 30, preferably 5 to 20. R ² may have a substituent of 1 to 3 carbon atoms. A good lower (C1-C4) alkyl group is shown.)
(4) Polyoxyethylene sorbitan fatty acid ester (5) Polyoxyethylene sorbite fatty acid ester (6) Polyoxyethylene fatty acid ester (7) Polyoxyethylene hydrogenated castor oil (8) Glycerin fatty acid ester

Among the above nonionic surfactants, the above-described nonionic surfactant (1) is preferable, and an average of 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms is added to an aliphatic alcohol having 12 to 16 carbon atoms. Polyoxyalkylene alkyl (or alkenyl) ether is preferred. A polyoxyethylene alkyl (or alkenyl) ether having a melting point of 50 ° C. or less and an HLB of 9 to 16, a polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether, a fatty acid methyl ester ethoxylate obtained by adding ethylene oxide to a fatty acid methyl ester, A fatty acid methyl ester ethoxypropoxylate obtained by adding ethylene oxide and propylene oxide to a fatty acid methyl ester is preferably used. Moreover, these nonionic surfactants can be used individually by 1 type or in combination of 2 or more types as appropriate.
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”.

(Ii) Anionic surfactant The anionic surfactant is not particularly limited as long as it is conventionally used in detergents, and various anionic surfactants 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 Number 10 to 20 of the higher fatty acid salt (9) saturated or unsaturated α- sulfofatty acid having 8 to 20 carbon atoms (alpha-SF) salt or a methyl, ethyl or propyl ester

As the anionic surfactant, a linear alkylbenzene sulfonic acid (LAS), an alkyl sulfate (AS), AOS, α-SF, and an alkali metal salt of a higher fatty acid (for example, a sodium or potassium salt) are particularly preferable. Alkyl benzene sulfonic acid (LAS) and alkali metal salts of alkyl sulfate (AS) are preferred.
(I) As for the compounding quantity of the nonionic surfactant of a component, 5-18 mass% is preferable, More preferably, it is 8-17 mass%. (Ii) As for the compounding quantity of the anionic surfactant of a component, 1-20 mass% is preferable, More preferably, it is 3-15 mass%.
From the viewpoint of cleaning performance, an anionic surfactant and a nonionic surfactant are preferred, and a combination of an anionic surfactant and a nonionic surfactant is more preferred.
The total amount ((i) + (ii)) of the nonionic surfactant component and the anionic surfactant component is preferably 10 to 25% by mass, more preferably 15 to 25% by mass. If the component (i) + (ii) is less than 10%, sufficient cleaning performance cannot be obtained, and even if it exceeds 25%, the cleaning performance is saturated and it is not economical.
The ratio (i) / (ii) (mass ratio) of the component (i) to the component (ii) is preferably 0.3 to 17, more preferably 0.5 to 8.0, and still more preferably 0.7 to 4. .0. When (i) / (ii) is less than 0.3 or exceeds 17, a desirable cleaning effect cannot be obtained.

(Iii) Other surfactants Examples of the cationic surfactant include the following.
(1) Di long 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 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 and amide betaines.
0.1-10 mass% is preferable and the compounding quantity in the case of using a cationic surfactant and an amphoteric surfactant is 0.2-7% more preferably.

In the present invention, the surfactant can be blended in the composition of the present invention as it is, or can be blended as particles containing a cleaning builder, a dissolution accelerator, etc. described later. From the viewpoint of improving the solubility, it is preferable to blend as particles containing a cleaning builder.
In the present invention, (A), (B), and (C) are preferably blended in a mass ratio of (A) :( B) = 1: 20 to 1: 20000. It is more preferable to blend at a ratio of ˜1: 10000. Moreover, it is preferable to mix | blend (A) :( C) in the ratio of 1: 200-1: 25000, and it is more preferable to mix | blend in the ratio of 1: 750-1: 25000. The amount of (A) is shown as the amount of enzyme protein. Within such a range, it is preferable because the dispersibility of the composite soil can be increased while maintaining a pH suitable for the enzyme.

The granular detergent composition of the present invention may contain the following optional components in addition to the above essential components. Each of these optional components can be used alone or in combination of two or more.
(1) Cleaning Builder (B) Examples of the builder other than the crystalline silicate as the component include the following inorganic and organic builders.
(1-1) Inorganic builder Examples of the inorganic builder include neutral salts such as sodium carbonate, potassium carbonate, sodium bicarbonate, sodium sulfite, sodium sesquicarbonate, sodium silicate, and amorphous layered sodium silicate, and sodium sulfate. Salts, orthophosphates, pyrophosphates, tripolyphosphates, metaphosphates, hexametaphosphates, phosphates such as phytate, the following general formula (II)
_{^{x 1 (M 2 O) ·}} Al 2 O 3 · y 1 (SiO 2) · w 1 (H 2 O) (II)
(In the formula, M represents an alkali metal atom such as sodium or potassium, x ¹ , y ¹ and w ¹ represent the number of moles of each component, and generally x ¹ is 0.7 to 1.5, y ^1. Is a number from 0.8 to 6, and w ¹ is an arbitrary positive number.)
A crystalline aluminosilicate represented by the following general formulas (III) and (IV)
_{^{x 2 (M 2 O) ·}} Al 2 O 3 · y 2 (SiO 2) · w 2 (H 2 O) (III)
(In the formula, M represents an alkali metal atom such as sodium or potassium, x ² , y ² and w ² represent the number of moles of each component. In general, x ² is 0.7 to 1.2, y ^2. 1.6 to 2.8, w ² represents 0 or any positive number.)
_{^{x 3 (M 2 O) ·}} Al 2 O 3 · y 3 (SiO 2) · z 3 (P 2 O 5) · w 3 (H 2 O)
(IV)
(In the formula, M represents an alkali metal atom such as sodium or potassium, x ³ , y ³ , z ³ and w ³ represent the number of moles of each component, and generally x ³ is 0.2 to 1.1. , y ³ is 0.2 to 4.0, z ³ is 0.001 to 0.8, w ³ represents 0 or any positive number.)
Amorphous aluminosilicate represented by the following. Among inorganic builders, sodium carbonate, potassium carbonate, sodium silicate, sodium tripolyphosphate, and sodium aluminosilicate are preferable.

In addition, inorganic builder can also be mix | blended in the composition of this invention by forming particle | grains with surfactant as stated above, and can also mix | blend separately from surfactant containing particle | grains. . When blending (powder mixing) separately from the surfactant-containing particles, from the viewpoint of solubility at a low water temperature, an inorganic or builder is used as the core particle, and the core particle is an organic or inorganic water solution that is the first surface treatment agent. The surface treated inorganic builder particles (component (D)) are preferably blended with a surface treatment with a functional polymer compound and the treated surface treated with a poorly water-soluble compound as a second surface treatment agent. In this case, the inorganic builder is preferably a water-soluble alkaline inorganic compound, and more preferably a carbonate. As the first surface treating agent, a carboxylic acid polymer is preferable, an acrylic acid polymer is more preferable, and a sodium salt of a copolymer of acrylic acid and maleic acid is most preferable. As the second surface treatment agent, a higher fatty acid having 12 to 16 carbon atoms is preferable, and lauric acid is more preferable.
As an optimal example of the surface-treated inorganic builder particles, the surface of sodium carbonate particles was treated with a sodium salt of a copolymer of acrylic acid and maleic acid as a first surface treating agent and lauric acid as a second surface treating agent. And surface-treated sodium carbonate particles.

The water-soluble polymer compound as the first surface treatment agent is preferably used in an amount of 0.1 to 10% by mass, particularly 0.5 to 8% by mass, based on the core particles. If the amount is less than 0.1% by mass, the effect of the surface treatment may not be obtained. If the amount exceeds 10% by mass, the amount of the core particles may be too small.
The poorly water-soluble compound as the second surface treatment agent is preferably used in an amount of 0.5 to 10% by mass, particularly 1 to 8% by mass, based on the core particles surface-treated with the first surface treatment agent. If the amount is less than 0.5% by mass, the effect of the surface treatment may not be obtained. If the amount exceeds 10% by mass, the amount of the core particles may be too small.
When the surface-treated sodium carbonate particles are used, 1 to 50% by mass, more preferably 5 to 30% by mass, and most preferably 10 to 20% by mass is blended in the cleaning composition of the present invention. .
When the present invention further contains a component (D), (B) and (D) are blended at a mass ratio of (B) :( D) = 1: 50 to 20: 1. Is preferable, and it is more preferable to mix in a ratio of 1: 6 to 2: 1. Within such a range, the solubility in cold water is improved, which is preferable.

(1-2) Organic builder Examples of the organic builder include aminocarboxylates such as nitrilotriacetate, ethylenediaminetetraacetate, β-alanine diacetate, aspartate diacetate, methylglycine diacetate, and iminodisuccinate; Hydroxyaminocarboxylates such as serine diacetate, hydroxyiminodisuccinate, hydroxyethylethylenediamine triacetate, dihydroxyethylglycine; hydroxycarboxylates such as hydroxyacetate, tartrate, citrate, gluconate A cyclocarboxylic acid salt such as pyromellitic acid salt, benzopolycarboxylic acid salt, cyclopentanetetracarboxylic acid salt; an agent such as carboxymethyl tartronate, carboxymethyloxysuccinate, oxydisuccinate, monotartaric acid or disuccinate Polymers or copolymers of itaconic acid, fumaric acid, tetramethylene-1,2-dicarboxylic acid, succinic acid, aspartic acid, etc .; polysaccharide oxides such as starch, cellulose, amylose, pectin, and carboxymethyl cellulose And the like.
Among these organic builders, citrate, aminocarboxylate, hydroxyaminocarboxylate, and hydroxyiminodisuccinate are preferable.
The compounding amount of the organic builder is preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass in the granular detergent composition.
In addition, citrates, aminocarboxylates, hydroxyaminocarboxylates, polyacrylates, acrylic acid-maleic acid copolymers, polyacetal carboxyls are used for the purpose of improving detergency and soil dispersibility in washing liquids. It is preferable to use an organic builder such as an acid salt in combination with an inorganic builder such as zeolite.
The said cleaning builder is normally used individually or in mixture of 2 or more types. The amount of the cleaning 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.

(2) Dissolution accelerator (A) Examples of the dissolution accelerator blended in the surfactant-containing particles include potassium carbonate, inorganic ammonium salts such as ammonium sulfate and ammonium chloride, sodium p-toluenesulfonate, and xylenesulfone. Water such as sodium benzene sulfonate, sodium benzoate, sodium benzene sulfonate, sodium chloride, citric acid, D-glucose, urea, sucrose, etc. Substances. Of these, potassium carbonate and sodium chloride are preferred, and potassium carbonate is particularly preferred from the standpoint of improving solubility and cost.
When potassium carbonate is blended, the blending amount is preferably 1 to 15% by mass, more preferably 2 to 12% by mass, and still more preferably 5 to 10% by mass in the granular detergent composition, from the viewpoint of improving solubility. It is. When sodium chloride is blended, the blending amount thereof is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, and further preferably 3 to 7% by mass in the granular detergent composition from the viewpoint of improving the solubility. It is.

(3) Swellable water-insoluble substance (A) Examples of the swellable water-insoluble substance blended in the surfactant-containing particles include powdered cellulose, crystalline cellulose, bentonite and the like.
(4) Fluorescent agent: bis (triazinylaminostilbene) disulfonic acid derivative (Tinopal AMS-GX), bis (sulfostyryl) biphenyl salt [Tinopearl CBS-X], etc. (5) Antistatic agent: Dialkyl type quaternary ammonium Cationic surfactants such as salts (6) Recontamination inhibitors: Cellulose derivatives such as carboxymethyl cellulose (7) Bulking agents: Sodium sulfate, potassium sulfate, etc. (8) Reducing agents: Sodium sulfite, potassium sulfite, etc. (9) Fragrance (10) Dye (11) Bleach: Sodium percarbonate, sodium perborate, etc. (12) Bleach activator: 4-decanoyloxybenzoic acid, 4-nonanoyloxybenzene sodium sulfonate, 4-dodecanoyl Sodium oxybenzene sulfonate, etc. (13) Bleach activation catalyst

(14) Enzymes other than Component (C) Commercially available enzyme particles that are currently used in granular laundry detergents can be used as they are for the enzymes other than amylase (C).
Examples of the amylase other than the component (C) include the enzymes described in JP-A-2001-64695 [0011]. Examples of commercially available enzymes include Novozymes Termamyl, Duramil and Genencor. And maxamyl.
Enzymes other than amylase (which are enzymes that inherently perform enzyme action during the washing process) are classified according to the reactivity of the enzyme, such as hydrolases, oxidoreductases, lyases, transferases, and isomerases. However, any can be applied to the present invention. Particularly preferred are protease, esterase, lipase, nuclease, cellulase and pectinase.

  Specific examples of the protease include savinase, alcalase, evalase, cannase, esperase (above, manufactured by Novozymes), API21 (produced by Showa Denko KK), and maxatase. (Maxtaze), Maxacal, Purefect, Purafect, Maxapem (manufactured by Genencor Corp.), KAP (manufactured by Kao Corporation), Protease K-14 and K- described in JP-A-5-25492 16 etc. can be mentioned. Specific examples of the esterase include gastric lipase, buncreatic lipase, plant lipase, phospholipase, cholinesterase and phosphotase. Specific examples of the lipase include commercially available lipases such as lipolase, lipolase ultra, lipex (manufactured by Novozymes), and liposome (manufactured by Showa Denko KK). Examples of the cellulase include commercially available cellzymes, carezymes (manufactured by Novozymes), KAC500 (manufactured by Kao Corporation), and cellulase according to claim 4 of JP-A 63-264699. These enzymes can be used alone or in combination of two or more. The enzyme is preferably granulated as a separate stable particle and used in a dry blended state with a detergent dough (particle). As a method for granulating the enzyme-containing particle, JP-A-53-6484 is disclosed. JP-A-60-262900, JP-A-62-257990, JP-A-1-112983, JP-T-3-503775, JP-A-4-503369, JP-A-2000-178593. And the method described in the Japanese Patent Publication. The average particle size of the enzyme-containing particles is preferably 200 to 1,000 μm, more preferably 300 to 700 μm, from the viewpoints of solubility and storage stability.

  The granular detergent composition of the present invention 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.

  Although the physical property value of the granular detergent composition of the present invention is not particularly limited, the water content is preferably 10% by mass or less, more preferably 4-9% by mass, from the viewpoint of solubility and storage stability. More preferably, it is 5 to 8% by mass. The bulk density is usually 0.3 g / mL or more, preferably 0.5 to 1.2 g / mL, more preferably 0.6 to 1.1 g / mL. The average particle diameter is preferably 200 to 1,500 μm, more preferably 250 to 1,000 μm, and still more preferably 280 to 700 μm. When the average particle size is less than 200 μm, dust may be easily generated or handling properties may be deteriorated. On the other hand, when the average particle size is more than 1,500 μm, it may be difficult to obtain the target solubility. Furthermore, the fluidity of the granular detergent composition is preferably 60 ° or less, particularly 50 ° or less as an angle of repose. Furthermore, after storage (when stored in a highly permeable container such as a paper container for a long period of time), the fluidity is preferably 60 ° or less, more preferably 50 ° or less as the angle of repose from the viewpoint of usability. .

The granular detergent composition of the present invention can be filled into a suitable container to form a granular detergent article in a container. As a material for the container, in terms of storage stability, the moisture permeability is preferably 30 g / m ² · 24 hours (40 ° C., 90% RH) or less, and 25 g / m ² · 24 hours (40 ° C., 90% RH) or less. Is more preferable. These can be achieved by a combination of general packaging materials and a change in thickness. In addition, the water vapor transmission rate in the present invention is measured by a method defined in JIS Z0208-1976. The granular detergent composition of the present invention can be further used as a compression molding detergent such as a tablet detergent or a briquette detergent after further mixing with a disintegrant and the like.

Preferable formulation examples of the composition of the present invention include the following:
(A) Amylase having a viscosity reduction rate calculated by the above formula (1) of 90% or more: 0.001 to 0.05% by mass as the amount of enzyme protein,
(B) Crystalline silicate represented by formula (III) wherein M is sodium, x ′ = 1.7 to 2.2, y ′ = 0: 5 to 10% by mass, and (C) As a surfactant, a mixture of an anionic surfactant and a nonionic surfactant; Here, as an anionic surfactant, an alkali metal salt of a higher fatty acid having 12 to 18 carbon atoms and an alkyl group having 10 to 14 carbon atoms. Alkali metal salt of linear alkylbenzene sulfonic acid (LAS): 3 to 10% by mass,
As a nonionic surfactant, 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: 8 to 17% by mass
A granular detergent composition containing
Furthermore, it is particularly preferable to contain 0.001 to 0.05% by mass of protease as the amount of enzyme protein and 0.001 to 0.03% by mass of lipase as the amount of enzyme protein.
Furthermore, the surface treatment sodium carbonate particle | grains which processed the surface of sodium carbonate particle | grains using the sodium salt of the copolymer of acrylic acid and maleic acid as a 1st surface treatment agent, and lauric acid as a 2nd surface treatment agent are 10-20. Most preferably, it is contained in an amount of mass%.

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. 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 an 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. Method for producing surface-treated sodium carbonate particles (cleaning builder) Proshear mixer (Ohira) with 85.5 parts by weight of sodium carbonate (granular ash manufactured by Asahi Glass Co., Ltd.) equipped with a blade-shaped shovel and a clearance between the shovel and the wall surface of 5 mm The mixture was put into Yoki Co., Ltd. (filling rate: 30% by volume), and stirring was started at a spindle of 150 rpm (chopper rotation speed: 1015 rpm, blade tip speed (circumferential speed): 6.9 m / s). Later, 7.5 parts by weight of sodium salt of acrylic acid / maleic acid copolymer (Nippon Shokubai Aqualic TL-400, 40% solid content aqueous solution) is sprayed for 180 seconds with a pressure nozzle (flat nozzle) with a spray angle of 115 degrees. After adding, granulation and coating operations were performed.
Subsequently, 7 parts by weight of lauric acid was sprayed and added for 180 seconds with a pressure nozzle (full cone nozzle) having a spray angle of 60 degrees while continuing to stir the plow shear mixer. Stirring was continued for 30 seconds to obtain particles.
Next, the obtained particles are filled into a fluidized bed (Glatt-POWREX, model number FD-WRT-20, manufactured by Paulex Co., Ltd.), and after filling, 15 ° C. wind (air) is sent into the fluidized bed, The cooling operation was performed to obtain particles cooled to 20 ° C. The air velocity in the fluidized bed was adjusted in the range of 0.2 to 10.0 m / s while confirming the fluidized state. The obtained particles are classified using a sieve having an opening of 2,000 μm, and surface-treated sodium carbonate particles having an average particle diameter of 350 μm and a bulk density of 1.14 g / mL passing through a sieve having an opening of 2,000 μm are obtained. It was.

3. 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. Sodium sulfate and a fluorescent brightening agent were added thereto, and after stirring for 10 minutes, sodium carbonate was added, and then an acrylic acid polymer was added. After further stirring for 10 minutes, sodium chloride and a part of powdered zeolite were 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 and an anionic surfactant 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 surfactant composition was added to the mixture for 2 minutes, and then stirred for 5 minutes. Then, a layered silicate and a part (10% by mass) of the powdered zeolite were added to perform a surface coating treatment for 2 minutes. A detergent composition was obtained.
After mixing a part of the powdered zeolite (2% by mass) and the surface-treated sodium carbonate particles in this detergent composition with a V blender, the enzyme is mixed with a V blender, and further, a dye 20% aqueous dispersion and a fragrance are added. Spray addition was performed to obtain a granular detergent composition.

About the obtained granular detergent composition, the washing | cleaning performance with respect to composite dirt, an average particle diameter, and a bulk density were evaluated in accordance with the following evaluation method. The results are also shown in Table 1.
(1) Evaluation of cleaning performance against composite soil using artificial soil cloth (i) Method for preparing artificial soil evaluation fabric Clay composed mainly of crystalline minerals such as kaolinite and vermiculite is dried at 200 ° C. for 30 hours. The product was used as inorganic dirt. Disperse 3.5 g of gelatin and 0.5 g of potato starch (manufactured by Kanto Chemical Co., Ltd.) in 950 cc of room temperature water, dissolve at about 90 ° C., and then add 0. 0. with Polytron (manufactured by KINEMATICA, Switzerland). 25 g of carbon black was dispersed in water. Next, 14.9 g of inorganic dirt was added and emulsified with Polytron, and further 31.35 g of organic dirt was added and emulsified and dispersed with Polytron to form a stable dirt bath. A predetermined 10 cm × 20 cm clean cloth (No. 60 cotton cloth designated by the Japan Oil Chemistry Association) was immersed in this dirt bath, and water was squeezed with two rubber rolls to uniformize the amount of dirt adhered. The soiled cloth was dried at 105 ° C. for 30 minutes, and then rubbed on both sides of the soiled cloth 25 times each side. This was cut into 5 cm × 5 cm, and the one having a reflectance in the range of 42 ± 2% was used as a dirty cloth. The dirt composition of the artificial dirt cloth thus obtained is as follows.

(Ii) Evaluation of Cleaning Performance of Granular Detergent Composition Using Terg-O-meter of Testing USA as a cleaning tester, 10 artificial dirt cloths, sebum cloth and washing knitted cloth are put, and the granularity shown in Table 1 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.

(2) Measurement of average particle diameter For each sample and a mixture thereof, a 9-stage sieve and a saucer having openings of 1,680 μm, 1,410 μm, 1,190 μm, 1,000 μm, 710 μm, 500 μm, 350 μm, 250 μm, and 149 μm Classification operation was performed using. In the classification operation, a sieve with a small opening and a sieve with a large opening are stacked in the order of the sieve, and a base sample of 100 g / time is put on the top of the top sieve of 1,680 μm, and the lid is covered and a low-tap type sieve shaker Attached to (made by Iida Seisakusho, tapping: 156 times / minute, rolling: 290 times / minute), and vibrated for 10 minutes, the samples remaining on each sieve and the saucer were collected for each sieve mesh. The mass of the sample was measured. When the mass frequency of the tray and each sieve is integrated, the opening of the first sieve where the integrated mass frequency is 50% or more is set to a μm, and the opening of the sieve that is one step larger than a μm is set to b μm. The average particle size (weight: 50%) was calculated by the following equation, where c% was the cumulative mass frequency from the sieve to the aμm sieve and d% was the mass frequency on the aμm sieve.

(3) Measurement of bulk density The bulk density was measured according to JIS K3362-1998.

The raw materials used in the examples are shown below.
[enzyme]
Amylase A: Stainzyme 12T (Novozymes)
Amylase B: Termamyl 120T (manufactured by Novozymes)
Protease A: Sabinase 12T (Novozymes)
Protease B: Everase 8T (Novozymes)
Lipase: Lipex 50T (manufactured by Novozymes)
Cellulase: Cellzyme 0.7T (manufactured by Novozymes)
[Crystalline silicate]
Crystalline layered sodium silicate (SKS-6 manufactured by Clariant Tokuyama)
[Surfactant]
LAS-Na: linear alkyl (10 to 14 carbon atoms) benzenesulfonic acid (Lypon LH-200 (96% pure LAS-H) manufactured by Lion Co., Ltd. is neutralized with 48% aqueous sodium hydroxide during preparation) . The compounding quantity in Tables 1-3 shows the mass% as LAS-Na.
Soap: Fatty acid sodium having an alkyl group having 12 to 18 carbon atoms (manufactured by Lion Corporation)
Nonionic surfactant A: ECOROL26 (Ecogreen Co., Ltd. alcohol having an alkyl group having 12 to 16 carbon atoms) average 8 mol ethylene oxide adduct (pure 90%)
Nonionic surfactant B: Diadol 13 (Mitsubishi Chemical Co., Ltd.) ethylene oxide average 15 mol adduct (pure 90%)
[Optional ingredients]
Lauric acid: Lauric acid (NAA-12, manufactured by NOF Corporation)
Sodium carbonate: Heavy sodium carbonate (Asahi Glass 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 chloride: Nissei Yaki salt C (manufactured by Nippon Salt Co., Ltd.)
Zeolite: Type A zeolite (Silton B manufactured by Mizusawa Chemical Co., Ltd.)
Acrylic acid polymer A: sodium polyacrylate, trade name Socaran PA30 (BASF)
Acrylic acid polymer B: Sodium salt of acrylic acid / maleic acid copolymer (Aquaric TL-400 manufactured by Nippon Shokubai, 40% solids aqueous solution)
Optical brightener: Chinopearl CBS-X (manufactured by Ciba Specialty Chemicals) and Chinopearl AMS-GX (manufactured by Ciba Specialty Chemicals) in a mass ratio of 8/2 Surface treated sodium carbonate particles: The above surface treated sodium carbonate particles Treated Sodium Carbonate Particles Obtained by the Manufacturing Method of Dye A: Ultramarine Blue (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
Perfume B: Perfume composition B shown in JP-A-2002-146399, Tables 11-18

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

Claims (5)

A granular detergent composition comprising the following components:
(A) An amylase having a viscosity reduction rate calculated by the following formula (1) of 40% or more, which is Steinzyme (registered trademark),
(B) crystalline silicate, and (C) (i) 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 6 to 22 carbon atoms a nonionic surfactant is, contain and (ii) an anionic surfactant, the total amount of said nonionic surfactant and an anionic surfactant ((i) + (ii) ) is 10 to 25 wt% A surfactant having a ratio (i) / (ii) (mass ratio) of the component (i) to the component (ii) of 0.7 to 4.0.

  The granular detergent composition according to claim 1, wherein the amylase as component (A) is Steinzyme (registered trademark) 12T.   (Ii) The anionic surfactant is one or more anionic surfactants selected from linear alkylbenzene sulfonates, α-olefin sulfonates, α-sulfo fatty acid salts or methyl, ethyl or propyl esters thereof and higher fatty acid salts. The granular detergent composition according to claim 1 or 2, which is an agent. The granular detergent composition according to any one of claims 1 to 3, wherein the crystalline silicate of the component (B) has a composition represented by the following formula (II) or (III):

x (M ₂ O) · y (SiO ₂ ) · z (Me _m O _n ) · w (H ₂ O) (II)
M ₂ O · x ′ (SiO ₂ ) · y ′ (H ₂ O) (III)

(In Formula II, M represents a group Ia element of the periodic table, and Me represents one or two types selected from a group IIa element, a group IIb element, a group IIIa element, a group IVa element, or a group VIII element in the periodic table. The above combinations are shown, and y / x = 0.5 to 2.6, z / x = 0.01 to 1.0, w = 0 to 20, and n / m = 0.5 to 2.0.
In Formula III, M represents a group Ia element of the periodic table, and x ′ = 1.5 to 2.6 and y ′ = 0 to 20. )   Furthermore, the granular detergent composition of any one of Claims 1-4 containing sodium chloride.

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