JP2002265997A - Detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent composition having excellent solubility and the low damageability of materials to be washed and excellent detergency against the stains derived from sebum at collars, cuffs and the like. SOLUTION: The detergent composition comprises (A) particles comprising (a) 10-50 wt.% surface active agent, (b) 10-50 wt.% water soluble salts, and (c) 5-50 wt.% water insoluble inorganic substance with a sum of component (a) and component (b) of 40-70 wt.%, (B) cellulase-containing particles having a cellulase release ratio at 20 deg.C after one minute of >=50%, maintaining an activity of the cellulase in the treatment at 80 deg.C for 10 minutes of >=40%, and having an optimum reaction pH of >=7.5, and (C) protease-containing particles having a protease release ratio at 20 deg.C after one minute of 20-98%, the protease being insusceptible to the inhibition of the casein decomposition activity by oleic acid, and the cellulase release ratio of the particles (B) at 20 deg.C after one minute being not smaller than the protease release ratio of the particles (C) at 20 deg.C after one minute.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a cleaning composition. Particularly preferably, it relates to a detergent composition for clothing.

[0002]

2. Description of the Related Art Granular detergent compositions are strongly directed to higher bulk densities and lower usage amounts from the convenience of consumers. However, it is known that a high bulk density detergent composition tends to have a higher surfactant content than a low bulk density detergent composition, and thus tends to have a lower dissolution rate of detergent particles constituting the composition. Have been. In addition, washing machines in recent years
In response to energy issues and economics, high bath ratio (clothing /
There is a tendency to (wash water), to shorten the operation time, to use low power agitation, and the like. All of these recent trends are responsible for the slow dissolution rate of detergent compositions. Significant improvement in the dissolution rate of detergent compositions due to a significant decrease in the cleaning ability due to a delay in the dissolution rate of the detergent composition, or damage to clothing due to local increase in concentration due to adhesion of the detergent composition to clothing. Is eagerly awaited.

[0003] For remarkable stains, clothes are usually immersed in an aqueous solution (warm water) having a higher concentration than a normal use concentration of a detergent composition. The conventionally known cellulase has low heat resistance and, in a high-concentration aqueous detergent solution, has a reduced enzyme activity, so that a sufficient effect cannot be obtained.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a detergent composition which is excellent in solubility and low damage to an object to be washed, and has excellent detergency against stains derived from sebum such as collars and cuffs. It is to provide.

[0005]

That is, the gist of the present invention is as follows.
Detergent composition containing the following (A) particles, (B) particles and (C) particles: (A) particles: (a) 10 to 50% by weight of a surfactant,
(B) particles containing 10 to 50% by weight of a water-soluble salt and (c) 5 to 50% by weight of a water-insoluble inorganic substance,
And (c) a total of 40 to 70% by weight of particles,
(B) Particles: Cellulase release rate after 1 minute at 20 ° C. is 50
% Or more, wherein the cellulase retains an activity of 40% or more after treatment at 80 ° C. for 10 minutes, and has an optimal reaction pH of 7.5 or more.
(C) Particles: protease release rate after 1 minute at 20 ° C. is 2
0 to 98%, wherein the protease is a protease-containing particle that is not inhibited by casein degradation activity by oleic acid, wherein the particle (B) has a cellulase release rate after 1 minute at 20 ° C. C) A detergent composition having a protease release rate of 20 ° C. or more after 1 minute of the particles.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS <Cleaning composition> The cleaning composition of the present invention contains (A) particles, (B) particles and (C) particles, and if necessary, (D) particles. It is.

[0007] The apparent density of the detergent composition of the present invention measured by the method specified in JIS K 3362: 1998 is 600 g / L or more from the viewpoint of convenience and reduction of waste (eg, boxes). Preferably, it is 700 g / L or more, more preferably 800 g / L or more.
In terms of solubility, the apparent density is preferably 1600 g / L or less, more preferably 1300 g / L or less, and
00g / L or less is more preferable.

[0008] Using a standard sieve of JIS Z 8801, 5
After shaking for minutes, the average particle size of the cleaning composition of the present invention determined from the weight fraction based on the sieve size is preferably 150 to 700 μm, more preferably 150 to 600 μm, and more preferably 150 to 600 μm, from the viewpoint of excellent solubility. Preferably 180-4
00 μm.

[0009] The detergent composition is portable and easy to use.
A single use amount may be divided and packaged, or may be compressed and molded into a tablet form and packaged. At this time, the packaging material is preferably water-soluble.

<(A) Particles> The (A) particles comprise (a) 10 to 50% by weight of a surfactant, preferably 15 to 45% by weight.
And (b) 10 to 50% by weight, preferably 2% by weight of water-soluble salts.
0 to 40% by weight and (c) 5 to 50% by weight, preferably 10 to 40% by weight, of a water-insoluble inorganic substance, wherein the total of (b) and (c) is 40 to 70% by weight. (Preferably 45 to 65% by weight).

As the surfactant (a), one or a combination of an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, and a cationic surfactant can be mentioned, but it is preferable. Is an anionic surfactant and a nonionic surfactant. The addition of the surfactant is preferable from the viewpoint of cleaning oily soils.

As the anionic surfactants, those having 10 carbon atoms
-18 alcohol sulfate, alkoxylated alcohol sulfate having 8 to 20 carbon atoms, alkylbenzene sulfonate, paraffin sulfonate, α
-Olefin sulfonate, α-sulfo fatty acid salt, α-
Sulfo fatty acid alkyl ester salts or fatty acid salts are preferred. In the present invention, particularly, the alkyl chain has 10 to 14 carbon atoms,
More preferably, a linear alkylbenzene sulfonate of 12 to 14 is preferable, and as a counter ion, alkali metal salts and amines are preferable, and sodium and / or potassium, monoethanolamine, and diethanolamine are particularly preferable.

Examples of nonionic surfactants include polyoxyalkylene alkyl (C 8-20) ether, alkyl polyglycoside, polyoxyalkylene alkyl (C 8-20) phenyl ether, polyoxyalkylene sorbitan fatty acid (C (8 to 22) esters, polyoxyalkylene glycol fatty acid (8 to 22 carbon atoms) esters, and polyoxyethylene polyoxypropylene block polymers are preferred. In particular, as a nonionic surfactant, an alkylene oxide such as ethylene oxide or propylene oxide is added to an alcohol having 10 to 18 carbon atoms to form a 4- to 10-alkyl alcohol.
After adding 20 mol [HLB value (calculated by Griffin method) is 10.5
-15.0, preferably 11.0-14.5].

(B) As the water-soluble salts, water 1 at 25 ° C.
A solubility of at least 0.5 g and a molecular weight of less than 1,000, for example, an alkali metal salt such as carbonate, hydrogencarbonate, sulfate, sulfite, hydrogensulfate, hydrochloride, or phosphate; Examples include water-soluble inorganic salts such as ammonium salts and amine salts, and low-molecular-weight water-soluble organic acid salts such as citrate and fumarate. It is preferable to mix the water-soluble salts from the viewpoint of solubility.

(C) The water-insoluble inorganic substance is a solid having a solubility of less than 0.5 g in 100 g of water at 25 ° C., particularly preferably having an average primary particle diameter of 0.1 to 20 μm. For example, there are crystalline or amorphous aminosilicates, silicon dioxide, hydrated silicate compounds, clay compounds such as perlite and bentonite, etc., and crystalline or amorphous aluminosilicates, silicon dioxide, water, etc. Sulfosilicate compounds are preferred, and crystalline aluminosilicates are particularly preferred in terms of sequestering ability and supporting ability of a surfactant. Mixing the water-insoluble inorganic substance is preferable from the viewpoint of solubility.

The particles (A) preferably further contain (d) a water-soluble polymer in an amount of 0.5 to 20% by weight, more preferably 1 to 15% by weight, and more preferably 3 to 1 from the viewpoint of cleaning performance.
0% by weight is more preferred.

(D) The water-soluble polymer has a solubility of 0.5 g or more in 100 g of water at 25 ° C. and a molecular weight of 1
It is an organic polymer of 1,000 or more and includes, for example, polyalkylene glycol, carboxylic acid polymer, carboxymethyl cellulose, soluble starch, saccharides and the like. Among them, a carboxylic acid-based polymer and a polyethylene glycol having a molecular weight of several thousands to 100,000 are preferable in terms of sequestering ability of metal ions, dispersing ability of solid dirt / particle dirt, and prevention of re-contamination. In particular,
Salts of acrylic acid-maleic acid copolymers, polyacrylates and polyethylene glycols are preferred. here,
Salts include sodium, potassium and ammonium salts.

The particles (A) are preferably subjected to surface modification with a surface coating agent in view of fluidity and non-caking properties. The surface coating agent is preferably 1 to 30% by weight, more preferably 2 to 25% by weight, even more preferably 5 to 25% by weight in the particles (A). As the surface coating agent, for example, silicate compounds such as aluminosilicate, calcium silicate, silicon dioxide, bentonite, talc, clay, amorphous silica derivative, crystalline silicate compound, metal soap, powdered surfactant, etc. Fine powder, carboxymethyl cellulose, polyethylene glycol, sodium polyacrylate,
Water-soluble polymers such as polycarboxylates such as copolymers of acrylic acid and maleic acid or salts thereof; and fatty acids. Among them, silicate compounds are preferred, and crystalline aluminosilicates, amorphous aluminosilicates, and crystalline silicate compounds are particularly preferred.

(A) The method for producing the particles is not particularly limited.
100 parts by weight of base granules obtained by spray-drying a slurry containing (b) water-soluble salts, (c) a water-insoluble inorganic substance and, if necessary, (d) a water-soluble polymer,
(A) 5 to 80 parts by weight of a surfactant (preferably 12 to 8 parts by weight)
0 parts by weight, more preferably 15 to 65 parts by weight, and still more preferably 20 to 60 parts by weight), and then the surface is modified by a surface coating agent. ,preferable.

The base granules are (b) water-soluble salts,
Particles obtained by spray-drying a slurry containing (c) a water-insoluble inorganic substance and, if necessary, (d) a water-soluble polymer. As the base granules, those having a structure in which many water-soluble components are unevenly distributed in the vicinity of the surface are preferable from the viewpoint of solubility.

The confirmation of the uneven distribution of the water-soluble component in the structure of the base granules can be performed by, for example, Fourier transform infrared spectroscopy (FT).
-IR) and photoacoustic spectroscopy (PAS) (F
T-IR / PAS). These are Applied Spectroscopy vo
l. 47, 1311-1316 (1993), which is a method for analyzing the distribution state of a substance in the depth direction from the surface of a base granule, whereby the uneven distribution of a water-soluble component can be confirmed.

The base granules may contain, in addition to the above components, a surfactant and auxiliary components such as fluorescent dyes, pigments and dyes suitable for the detergent composition.

The base granules are obtained by mixing various components to form a slurry having a water content of preferably 30 to 60% by weight, and then spray-drying the slurry. The temperature of the hot air at the time of spray drying is preferably from 200 to 300C from the viewpoint of solubility. The other spray drying conditions are not particularly limited. In addition, there are no particular limitations on the physical properties such as the apparent density and the average particle size of the base granules.

As a method for supporting the surfactant on the base granules, a granulator may be used, but it is preferable to mix the base granules and the surfactant using a stirrer in view of solubility. It is particularly preferable to perform the mixing under mild conditions so as not to crush the pores of the (A) particles described below. Also,
The granulator and the stirrer are not particularly limited as long as they are known.

In terms of solubility, the particles (A) are preferably at least 1/10, more preferably at least 1/5, further preferably at least 1/4, particularly preferably at least 1/4 of the particle diameter in the process of dissolving in water. Emit bubbles of 1/3 or more in diameter. When the bubbles are dissolved in water (20 ° C.) in a state of being left standing, bubbles of a predetermined size are preferably generated within 120 seconds, more preferably within 60 seconds, and preferably within 45 seconds. More preferred. In order to release bubbles, it is only necessary to have pores (single or plural) capable of releasing bubbles of a predetermined size, and the form and structure of the particles are not particularly limited. The pores can be confirmed by, for example, cutting the particles and observing the cut surface with a scanning electron microscope (FT-IR / PAS).

(A) From the viewpoint of convenience and waste reduction, the particles (A) preferably have an apparent density of 600 g / L or more, more preferably 700 g / L or more, as measured by the method specified in JIS K 3362: 1998. 800 g / L or more is more preferable. In terms of solubility, the apparent density is preferably 1600 g / L or less, more preferably 1300 g / L or less, and even more preferably 1000 g / L or less.

(A) The particles are JIS Z in terms of solubility.
After oscillating for 5 minutes using a standard sieve of 8801, the average particle size determined from the weight fraction according to the size of the sieve is 150 to
700 μm is preferred, and more preferably 150 to 600
μm, and more preferably 180 to 400 μm. From the viewpoint of solubility, the content of the particles having a particle size of 177 to 350 μm is preferably 40% by weight or more, more preferably 50% by weight or more in the particles (A).

In the present invention, from the viewpoint of cleaning performance,
(A) It is preferable to use particles. (A) The particles are:
From the viewpoint of cleaning performance, 50 to 99.5% by weight in the detergent composition is preferable, 50 to 98% by weight is more preferable, and 60 to 9% by weight.
6% by weight is more preferred, and 70-94% by weight is particularly preferred.

<(B) Particles>
The cellulase release rate after 50 minutes is 50% or more, the cellulase retains 40% or more activity at 80 ° C. for 10 minutes, and the optimal reaction pH for carboxymethyl cellulose decomposition activity is 7.5 or more. Cellulase-containing particles.

Cellulase is 40% or more after treatment at 80 ° C. for 10 minutes from the viewpoint of the washing effect in hot water or high temperature, the heat history during the production of enzyme particles, and the storage stability after granulation or after compounding the product. , Preferably at least 45%, more preferably at least 50% activity. The activity of these cellulases can be determined by the method described in JP-A-10-313859.

Here, the treatment at 80 ° C. for 10 minutes means that the enzyme is treated with a 0.5 M glycine-sodium hydroxide buffer solution (pH
9.0) at 80 ° C. for 10 minutes.

Cellulase is required to exhibit a sufficient effect in a weakly alkaline washing liquid.
Is 7.5 or more, preferably 8.0 or more, and more preferably 8.5 or more.

Here, the optimum reaction pH means a pH condition under which the carboxymethylcellulose degrading activity of the enzyme is maximized in a 40 mM Britton-Robinson broad-range buffer.

The cellulase is not particularly limited as long as it retains an activity of 40% or more after treatment at 80 ° C. for 10 minutes and has an optimum reaction pH of 7.5 or more, but it is not limited to Bacillus sp. .) KSM-
A cellulase named S237 strain and deposited as FERM P-16067, a mutant thereof, or a transformant having a gene encoding the enzyme is preferable in terms of washing performance. As a method for producing cellulase from the strain, a method described in JP-A-10-313859 can be mentioned. Further, mutants of the above-mentioned strains, transformants having a gene encoding the enzyme and methods for producing cellulase from these strains are described in JP-A-6-343461 and JP-A-10-22.
9879 and JP-A-2000-210081. The cellulase used in the present invention is supplied in the form of a concentrated solution obtained by filtering and concentrating a culture solution and / or an enzyme powder obtained by drying the concentrated solution. In a granulation method using a nuclear substance described later, it is preferable to use an enzyme powder.

In terms of granulation, solubility, and washing performance, the content of the cellulase in the (B) particles is preferably 0.5 to 20% by weight, more preferably 0.8 to 15% by weight, and 1 to 10% by weight.
% By weight is more preferred.

(B) The cellulase release rate of the particles is 100
100 mL of a 0.9% by weight aqueous NaCl solution at 20 ° C. was placed in a mL melt beaker (inner diameter: 50 mm), and a stirrer (length 35 mm) was added.
mm, diameter 8 mm) with stirring at 100 rpm.
(B) 100 mg of particles are added, the cellulase activity released after 1 minute is divided by the cellulase activity at the time of complete dissolution, and the obtained value is multiplied by 100. The released cellulase activity was determined according to the method described in JP-A-10-313859.
It is measured by the method described in Japanese Patent Application Publication No. The release rate is 5
It is 0% or more, preferably 60% or more, more preferably 70% or more, even more preferably 80% or more from the viewpoint of cleaning performance.

In order to achieve such a release rate,
The particles (B) are preferably the following granules (I) and / or (II), and the granules (II) are more preferable from the viewpoint of high-speed dissolution and low dust generation.

(I) is a method in which the cellulase has an average particle size of 200 to
Nuclear substance composed of 1200 μm water-soluble particles and melting point 35
A granulated product obtained by granulating with a water-soluble organic binder at a temperature of up to 70 ° C. and having an average particle size of 1 to 2 times the average particle size of the core material.

Examples of the core substance include water-soluble particles such as sodium chloride, potassium chloride, sodium sulfate, sodium carbonate, and sugar. Among them, sodium chloride is preferable. The average particle size of the core material is preferably from 200 to 1200 μm, from the viewpoint of solubility, beauty of appearance when the desired final enzyme particles are mixed with detergent particles, and non-classification, and from 250 to 1200 μm.
00 μm is more preferred. The average particle size is determined according to JIS
After shaking for 5 minutes using a standard sieve of Z8801, it can be determined from the weight fraction depending on the sieve size.

The content of the core material is preferably from 30 to 80% by weight in the granulated product of (I) from the viewpoint of granulation properties and solubility.
40-70% by weight is more preferred.

Examples of the water-soluble organic binder include polyethylene glycol, nonionic surfactants (polyoxyethylene-polyoxypropylene glycol, polyoxyethylene alkyl ether, etc.), among which polyethylene glycol is preferred. In terms of productivity, the water-soluble organic binder is 5 to 6 parts by weight based on 100 parts by weight of the core material.
0 parts by weight is preferred.

The melting point of the water-soluble organic binder is 35 to 7
The temperature is preferably 0 ° C, more preferably 40 to 70 ° C, and still more preferably 45 to 68 ° C. The melting point is JIS
It can be measured by a visual method defined in K0064: 1992.

The average particle size of the granulated product (I) obtained as described above is 1 to 2 times the average particle size of the core material from the viewpoint of solubility and non-classification, and is 1.05 to 1.05. 1.5 times is more preferable.

A method for producing a granulated product (I) by granulating cellulase together with a nuclear substance and a water-soluble organic binder is as follows.
Any known method may be used.
The granulation method described in Japanese Patent Application Laid-Open No. 990 is preferable.

(II) is a cellulase, a water-insoluble substance 45
It is a granulated material having a structure containing at least 5% by weight of a water-soluble binder and 5 to 40% by weight of a water-soluble binder, and having a larger amount of a water-soluble binder near the surface than inside the granulated material.

Examples of the water-insoluble substance include organic substances such as cellulose powder, and inorganic substances such as zeolite, talc, clay, alumina, kaolin, titania, calcium carbonate, barium sulfate, and the like.
Inorganic substances are preferred, and zeolite and kaolin are particularly preferred in terms of dispersibility. From the viewpoint of uniformity, the water-insoluble substance preferably has an average primary particle size of 20 μm or less,
The following is more preferable, and 0.1 to 5 μm is particularly preferable.
The content of the water-insoluble substance in the granulated product of (II) is preferably 45% by weight or more, from the viewpoint of prompt elution of the enzyme.
0% by weight or more is more preferable. On the other hand, from the viewpoint of preventing undissolved residue, the content is preferably 90% by weight or less, more preferably 80% by weight or less, and particularly preferably 70% by weight or less.

Examples of the water-soluble binder include polyethylene glycol and its derivatives, polyvinyl alcohol and its derivatives, water-soluble cellulose derivatives, carboxylic acid polymers, starch, and saccharides. As derivatives,
Ether compounds and the like. Among them, carboxylic acid-based polymers and saccharides are preferable in terms of productivity and high-speed solubility, and acrylic acid-maleic acid copolymer salts and polyacrylates are more preferable. As the salt, a sodium salt, a potassium salt, and an ammonium salt are preferable. The content of the water-soluble binder in the granulated product of (II) is preferably 5% by weight or more, more preferably 10% by weight or more from the viewpoint of low dust generation.
It is more preferably at least 15% by weight. Further, from the viewpoint of high-speed dissolution, the content is preferably 40% by weight or less, more preferably 35% by weight or less, and still more preferably 30% by weight or less.

The granulated product (B) of the particle (II) has a structure in which a water-soluble binder is present more in the vicinity of the surface than in the inside of the particle. For example, the cellulase, the water-insoluble substance, and the water-soluble It is obtained by mixing a binder to form a slurry having a water content of preferably 30 to 60% by weight, and then spray-drying the slurry. The method and conditions of the spray drying may be the same as in the case of producing the particles (A), but the temperature of the hot air at the time of the spray drying is 140 to 180 ° C. in consideration of the stability and productivity of the enzyme. It is preferable to carry out. The uneven distribution of the water-soluble binder in the particles can be confirmed using the FT-IR / PAS.

(B) Regarding the granulated product of the particle (II),
The apparent density measured by the method specified in JIS K 3362: 1998 is 500 to 1 in terms of non-classification.
000 g / L is preferable, and more preferably 600 to 10 g / L.
00 g / L, particularly preferably 700 to 950 g / L. In addition, in terms of high-speed dissolution, low dust generation, and non-classification,
After shaking for 5 minutes using a standard sieve of IS Z 8801, the average particle size determined from the weight fraction according to the sieve size is preferably 150 to 500 μm, more preferably 1 to 500 μm.
50 to 450 μm, particularly preferably 200 to 400 μm
It is. In addition, in terms of dust generation and solubility, 125 to 71
The content of particles having a particle size of 0 μm is (II) 8
0 wt% or more is preferable, and 90 wt% or more is more preferable.

In the present invention, (B) particles are preferably 0.1 to 10% by weight, more preferably 0.2 to 8% by weight, and more preferably 0.3 to 8% by weight in the detergent composition from the viewpoint of cleaning performance and economy. ~
5% by weight is more preferred.

<(C) Particles> The (C) particles were prepared at 20 ° C.,
Protease release rate after 20 minutes is 20 to 98%, and the protease is a protease-containing particle in which the casein degradation activity is not inhibited by oleic acid.

The protease is stable at a pH of 6 to 11 when treated at 40 ° C. for 30 minutes, and has a pH of 4 to 13
The activity value at pH 6 to 12 is 80% or more of the optimum pH activity value, the isoelectric point is 8.9 to 9.1, and the casein decomposition activity is not inhibited by oleic acid. Are preferred.

The protease is preferably stable at a pH of 6 to 11 after treatment at 40 ° C. for 30 minutes in order to exert a sufficient effect even in immersion washing using warm water.
Here, “stable” means not deactivated. The activity of these proteases can be determined by the method described in WO99 / 18218 (casein method).

Here, the treatment at 40 ° C. for 30 minutes means that the enzyme is dissolved in Britton-Robinson buffer (20 mM) for 4 minutes.
This means to incubate at 0 ° C. for 30 minutes.

Since the protease needs to exhibit a sufficient effect in a weakly alkaline washing liquid, the pH of the protease is adjusted to pH 6-1.
The activity value at 2 is preferably at least 80%, more preferably at least 82%, even more preferably at least 84% of the optimum pH activity value.

"Protease is not affected by the inhibition of casein degrading activity by oleic acid" means that casein is 1%
(W / v) containing 50 mM phosphate buffer (pH 7.0)
It means that the activity is not lost at all even if oleic acid is present at 1 to 10 mM in the reaction system.

[0057] As the protease is not particularly limited as long as it does not undergo inhibition of caseinolytic activity by oleate, Bacillus sp. (Bacillus
sp. ) Named KSM-KP43 strain, FERM
A strain deposited as BP-6532, Bacillus sp. KSM-KP17
It named 90 strain deposited strains as FERM BP-6533, Bacillus sp. (Bacillus
sp. ) KSM-KP9860 strain, named FE
Proteases produced from strains deposited as RMBP-6534, mutants thereof, or transformants having a gene encoding the enzyme are preferable in that they can exert sufficient effects even in a washing liquid containing a bleaching agent. As a method for producing a protease from the above-mentioned strain, its mutant or a transformant having a gene encoding the enzyme, WO99 / 18218, Agric. Biol. Che
m., 55 (9), 2387-2391, 1991.

In terms of granulation, solubility and washing performance, the content of the protease is preferably 1 to 30% by weight, more preferably 2 to 25% by weight, and more preferably 5 to 2% by weight in the particles (C).
5% by weight is more preferred.

The protease release rate was determined by placing 100 mL of a 2 mM CaCl ₂ aqueous solution at 20 ° C. in a 100 mL beaker (inner diameter: 50 mm), and stirring with a stirrer (length 35 mm, diameter 8 mm).
(C) particles 1 with stirring at a rotation speed of 100 rpm (mm).
00 mg was added, the protease activity released after 1 minute was divided by the protease activity at the time of complete dissolution, and the resulting value was multiplied by 100. The release rate is 20 to
It is 98%, preferably 50-98%, more preferably 70-98%, even more preferably 80-98% in terms of cleaning performance. Here, the protease activity amount is determined by WO99 /
It is measured by the method described in JP 18218 (casein method).

In order to achieve such a release rate,
The (C) particles are preferably the following (III) and / or (IV) granules, and the (IV) granules are more preferable in terms of high-speed dissolution and low dust generation.

(III) Protease having an average particle size of 200 to
Nuclear substance composed of 1200 μm water-soluble particles and melting point 35
A granulated product obtained by granulating with a water-soluble organic binder at a temperature of up to 70 ° C. and having an average particle size of 1 to 2 times the average particle size of the core material.

(IV) Protease, water-insoluble substance 45
A granulated material containing at least 5% by weight of a water-soluble binder and 5 to 40% by weight of a water-soluble binder, and having a structure in which a larger amount of a water-soluble binder is present near the surface than inside.

The granules (III) and (IV) are obtained by using the granules (I) or (II) of the particles (B) by using protease instead of cellulase, respectively. The components other than the protease used in these granules, the method for producing the granules, and the like may be the same as those of the particles (B).

(C) Regarding the granulated product of (IV) of the particles,
The apparent density measured by the method specified in JIS K 3362: 1998 is 500 to 1 in terms of non-classification.
000 g / L is preferable, and more preferably 600 to 10 g / L.
00 g / L, particularly preferably 700 to 950 g / L. In addition, in terms of high-speed dissolution, low dust generation, and non-classification,
After shaking for 5 minutes using a standard sieve of IS Z 8801, the average particle size determined from the weight fraction according to the sieve size is preferably 150 to 500 μm, more preferably 1 to 500 μm.
50 to 450 μm, particularly preferably 200 to 400 μm
It is. In addition, in terms of dust generation and solubility, 125 to 71
The content of particles having a particle size of 0 μm is (IV) 8
0 wt% or more is preferable, and 90 wt% or more is more preferable.

In the present invention, (C)
Preferably, particles are used. (C) Particles are preferably 0.1 to 10% by weight, more preferably 0.2 to 8% by weight, even more preferably 0.3 to 5% by weight in the detergent composition from the viewpoint of cleaning performance.

In the present invention, there is one great feature in using the particles (B) and (C) having the above-mentioned constitutions in combination, and the use of the particles (B) and (C) has a major feature. As compared with the case where the enzyme particles themselves are simply blended as in the conventional case, the action of the enzyme can be maximized, and the synergistic effect of the combined use can be significantly increased, so that the solubility is good. There is an advantage that the object to be cleaned is excellent in low damage property and has an excellent detergency against dirt derived from sebum such as collars and cuffs.

<(D) Particles> The (D) particles comprise a slurry containing (c) a water-insoluble inorganic substance and one or more water-soluble components selected from (d) a water-soluble polymer and (b) a water-soluble salt. The particles are obtained by supporting (a) less than 10 parts by weight of a surfactant (preferably from 0 parts by weight to less than 5 parts by weight) on 100 parts by weight of base granules obtained by spray drying. The components (a) to (d) may be the same as those described in the description of the particles (A).

(D) The particles are preferably surface-modified with a surface coating agent in view of fluidity and non-caking properties. The surface coating agent is preferably 1 to 30% by weight, more preferably 2 to 25% by weight, even more preferably 5 to 25% by weight in the particles (D). The surface coating agent may be any one as long as it is the same as that used for the particles (A), and among them, a silicate compound is preferable, and a crystalline aluminosilicate, an amorphous aluminosilicate, and a crystalline silicate compound are particularly preferable. .

The method for granulating the particles (D) may be any known method, and for example, the granulation method used for producing the particles (A) is preferable.

(D) In terms of solubility, the particles are preferably at least 1/10, more preferably at least 1/5, further preferably at least 1/4, particularly preferably at least 1/4 of the particle diameter in the process of dissolving in water. Emit bubbles of 1/3 or more in diameter. The release of bubbles is 120 when dissolved in water.
Preferably, bubbles of a predetermined size are generated within seconds, more preferably within 60 seconds, even more preferably within 45 seconds. In order to release bubbles, it is only necessary to have pores (single or plural) capable of releasing bubbles of a predetermined size, and the form and structure of the particles are not particularly limited. The confirmation of the pores can be performed in the same manner as the confirmation of the pores of the particles (A).

(D) Particles are JIS based on non-classification.
The apparent density measured by the method specified by K 3362: 1998 is preferably 500 g / L or more, and 600 g / L.
/ L or more, more preferably 700 g / L or more. In terms of non-classification and solubility, the apparent density is preferably 1500 g / L or less, more preferably 1200 g / L or less, and even more preferably 900 g / L or less.

(D) In terms of non-classification and solubility, the particles were shaken for 5 minutes using a standard sieve according to JIS Z 8801, and the average particle size determined from the weight fraction based on the sieve size was 150. To 700 μm, more preferably 150 to 600 μm, and still more preferably 180 to 400 μm.
m. Further, from the viewpoint of solubility, the particle diameter of 177 to 350 μm is preferably 40% by weight or more, more preferably 50% by weight or more in the particles (D).

The addition of the particles (D) is preferable from the viewpoint of suppressing the formation of a paste and dissolving the paste. More preferably, it is 1 to 40% by weight in the detergent composition, and still more preferably 3 to 30% by weight.
%, Particularly preferably 5 to 20% by weight.

<Other Ingredients> The detergent composition includes builders, bleaching agents (percarbonate, perborate, bleach activator, etc.) and re-staining inhibitors (carboxymethylcellulose) known in the field of clothing detergents. Etc.), softening agents, reducing agents (sulfites, etc.), optical brighteners, foam inhibitors (silicone, etc.), fragrances, and other enzymes (pectinase, amylase, lipase, etc.)
And the like. They are,
(A) to (D) may be contained in the particles or may be added as separate particles.

The cleaning composition of the present invention comprises the particles (A), (B) and (C), optionally (D),
It can be produced by adding and mixing various additives by a known method.

Since the detergent composition of the present invention is excellent in solubility, damageability of an object to be washed, and cleanability, it can be used for textiles such as clothing, curtains, carpets, and the like. Among them, it can be suitably used as a detergent composition for clothing. Further, since the detergent composition of the present invention has excellent detergency, it can be suitably used particularly for dirt derived from sebum such as collars and cuffs.

[0077]

【Example】

<(A) Particles> A-1 14% by weight of potassium linear alkylbenzene sulfonate (C10 to 14), 12% by weight of potassium α-olefin sulfonate (C14 to C18), based on the final detergent particles,
Polyoxyethylene alkyl ether (C12-14,
EO12) 8% by weight, polyethylene glycol (average molecular weight = 8500) 1% by weight, zeolite 18% by weight, acrylic acid-maleic acid copolymer (average molecular weight = 70,000)
0.5% by weight, fatty acid potassium (derived from palm kernel oil) 4% by weight, No. 1 silicate 4% by weight, potassium carbonate 8% by weight,
2% by weight of sodium sulfate, 1% by weight of sodium sulfite,
And a slurry comprising 0.3% by weight of a fluorescent dye (solid content 5
0% by weight) and spray dried to obtain a spray-dried composition. To this, 13% by weight of sodium carbonate based on the weight of the final detergent particles was charged into a ribbon mixer and mixed. The obtained mixture was extruded into a cylindrical shape having a diameter of 10 mm by a pre-extrusion type twin-screw extrusion granulator (pelleter double: manufactured by Fuji Paudal Co., Ltd.) and compacted. The obtained pellets were pulverized and granulated with a flash mill (manufactured by Fuji Paudal Co., Ltd.) together with 5% by weight of zeolite to perform surface coating. After removing coarse substances from the granules, the granules were transferred to a V blender and mixed with 5% by weight of zeolite to obtain detergent particles having a water content of 4.2% by weight.

The obtained particles had an apparent density of 820 g /
L, the content of particles having an average particle size of 390 μm and 177 to 350 μm was 55% by weight. The apparent density was measured by a method defined by JIS K 3362: 1998 (the same applies hereinafter).

A-2 A slurry having a solid content of 50% by weight was spray-dried at a hot air temperature of 250 ° C. to obtain a base granule I having the following composition. In addition, when FT-IR / PAS was used for the base granule I, many water-soluble components were unevenly distributed near the surface thereof.

Sodium polyacrylate (average molecular weight 1
0000) 7% by weight, sodium carbonate 25% by weight, sodium sulfate 20% by weight, sodium sulfite 1% by weight, sodium chloride 3% by weight, fluorescent dye 0.5% by weight, zeolite 40% by weight, water 3.5% by weight.

As the fluorescent dye, Tinopearl CBS-X was used.
(Manufactured by Ciba Geigy). 4 for zeolite
A type zeolite (manufactured by Tosoh Corporation) was used.

Next, the base granules I were loaded with a surfactant or the like to obtain particles (A). That is, 100 parts by weight of the base granule I was charged into a Redige mixer (manufactured by Matsusaka Giken Co., Ltd., capacity 20 L, with a jacket), and the main shaft (15
0 rpm) under stirring, 20 parts by weight of a nonionic surfactant,
22 parts by weight of sodium linear alkyl (C12-14) benzenesulfonate, sodium fatty acid (C14-18) 4
Parts by weight, polyethylene glycol (average molecular weight 850)
0) A mixed solution of 2 parts by weight and 6 parts by weight of water was charged in 3 minutes, and then stirred for 5 minutes. Further, 20 parts by weight of the crystalline silicate and 10 parts by weight of the zeolite were added to the mixer to perform a surface modification.

The nonionic surfactant has 12 carbon atoms.
~ 16, polyoxyethylene alkyl ether having an average number of moles of added EO of 6.0 was used. As the crystalline silicate, powder SKS-6 (manufactured by Hoechst Tokuyama Co., Ltd.) was used.

The obtained particles had an apparent density of 820 g /
L, the content of particles having an average particle diameter of 250 μm and particles having a particle diameter of 177 to 350 μm was 55% by weight, and bubbles having a particle diameter of 1/3 or more were released from inside the particles during the process of dissolving in water.

A-3 A slurry having a solid content of 50% by weight was spray-dried at a hot air temperature of 250 ° C. to obtain a base granule II having the following composition. When FT-IR / PAS was used for the base granule II, many water-soluble components were unevenly distributed near the surface.

1% by weight of sodium linear alkyl (C12-14) benzenesulfonate, 5% by weight of sodium polyacrylate (average molecular weight 10,000), sodium carbonate 2
6% by weight, sodium sulfate 10% by weight, sodium sulfite 1% by weight, sodium chloride 3% by weight, fluorescent dye 0.5
Wt%, zeolite 50 wt%, water 3.5 wt%.

As the fluorescent dye, Tinopearl CBS-X is used.
(Manufactured by Ciba Geigy). 4 for zeolite
A type zeolite (manufactured by Tosoh Corporation) was used.

Then, particles (A) were obtained by supporting a surfactant or the like on the base granules II. That is, 100 parts by weight of the base granule I was charged into a Redige mixer (manufactured by Matsusaka Giken Co., Ltd., capacity 20 L, with a jacket), and the main shaft (15
0 rpm), 10 parts by weight of a nonionic surfactant,
Linear alkyl (C12-14) benzenesulfonate sodium 26 parts by weight, fatty acid (C14-18) sodium 4
Parts by weight, polyethylene glycol (average molecular weight 850)
0) A mixed solution of 2 parts by weight and 6 parts by weight of water was charged in 3 minutes, and then stirred for 5 minutes. Further, 20 parts by weight of the crystalline silicate and 10 parts by weight of the zeolite were added to the mixer to perform a surface modification.

The nonionic surfactant has 12 carbon atoms.
~ 16, polyoxyethylene alkyl ether having an average number of moles of added EO of 6.0 was used. As the crystalline silicate, powder SKS-6 (manufactured by Hoechst Tokuyama Co., Ltd.) was used.

The obtained particles had an apparent density of 840 g /
L, the content of particles having an average particle diameter of 280 μm and 177 to 350 μm was 55% by weight, and bubbles having a particle diameter of 1/3 or more were released from the inside of the particles during the process of dissolving in water.

<(B) Particles> B-1 Bacillus sp. K
FERM P-16067 named SM-S237 strain
Cellulase (25) produced from the strain deposited as
000 U / g) 2% by weight, nuclear material (average particle size 250 μm)
Sodium chloride) 45% by weight, water-soluble organic binder (polyethylene glycol 6000, melting point: 63 ° C.) 1
5% by weight, 5% by weight of titanium oxide, 1% by weight of calcium chloride and 32% by weight of sodium sulfate are granulated under the conditions described in Example 1 of JP-A No. 62-257990 to give a granulated product having an average particle size of 350 μm. Obtained. The content of particles having a particle size of 125 to 710 μm is 90% by weight or more, and the apparent density is 830 g / L.
Met. The cellulase release rate after one minute at 20 ° C. was 68%. The cellulase release rate was 10
In a 0 mL beaker (inner diameter: 50 mm), 100 mL of a 0.9% by weight NaCl aqueous solution at 20 ° C. is placed, and a stirrer (length 3
(B) 100 mg of particles were added under stirring at a rotation speed of 100 rpm (5 mm, diameter: 8 mm), and the amount of cellulase activity released after 1 minute was divided by the amount of cellulase activity at the time of complete dissolution. Was calculated. The cellulase activity was measured by the method described in JP-A-10-313859 (hereinafter the same).

B-2 Bacillus sp. K
FERM P-16067 named SM-S237 strain
Cellulase (25) produced from the strain deposited as
000 U / g) 2 parts by weight, water-insoluble substance (zeolite:
A slurry having an average particle size of 3 μm), 65 parts by weight, a water-soluble binder (polyacrylic acid / maltite = 1/1 (weight ratio)), 25 parts by weight, and 4 parts by weight of sodium sulfate, a water content of 55% by weight, was prepared. Next, this was spray-dried (spray temperature 150 ° C.) to obtain a granulated product having an average particle diameter of 250 μm and a water content of 4% by weight. The content of particles having a particle size of 125 to 710 μm was 90% by weight or more, and the apparent density was 810 g / L.
Further, as measured by FT-IR / PAS, a large amount of the water-soluble binder was present near the surface of the obtained granulated product. The cellulase release rate after one minute at 20 ° C. was 80%.
%Met.

<(C) Particles> C-1 Bacillus sp. K
SM-KP43 strain and FERM BP-653
6% by weight of protease (100 PU / g) produced from the strain deposited as No. 2 and nuclear material (mean particle size 2
45% by weight of 50 μm sodium chloride, water-soluble organic binder (polyethylene glycol 6000, melting point: 6)
(3 ° C.) 15% by weight, 5% by weight of titanium oxide, 1% by weight of calcium chloride, 28% by weight of sodium sulfate
No. 0, granulated under the conditions described in Example 1 and obtained an average particle size of 38.
A granule of 0 μm was obtained. The content of particles having a particle size of 125 to 710 μm is 90% by weight or more, and the apparent density is 81%.
It was 0 g / L. The protease release rate after one minute at 20 ° C. was 69%. The protease release rate was measured by the method (casein method) described in WO 99/18218 (hereinafter the same).

C-2 Bacillus sp. K
Named SM-KP43, FERM BP-6532
Protease (1) produced from the strain deposited as
00P. U. / G) 6 parts by weight, water-insoluble substance (zeolite: average particle size 3 μm) 65 parts by weight, water-soluble binder (polyacrylic acid / malt = 1/1 (weight ratio)) 2
A slurry having a water content of 55% by weight, which is 5 parts by weight and 4 parts by weight of sodium sulfate, was prepared. Next, this is spray-dried (spray temperature 150
C) to obtain a granulated product having a water content of 4% by weight and an average particle size of 260 µm. The content of particles having a particle size of 125 to 710 μm was 90% by weight or more, and the apparent density was 800 g / L. Further, as measured by FT-IR / PAS, a large amount of the water-soluble binder was present near the surface of the obtained granulated product. Further, the protease release rate after one minute at 20 ° C. was 79%.

[0096] C-3 Bacillus sp. (Bacillus sp.) K
SM-KP9860 strain and FERM BP-6
No. 534, 6 parts by weight of a protease (100 PU / g) produced from the strain deposited as No. 534, 65 parts by weight of a water-insoluble substance (zeolite: average particle size of 3 μm), a water-soluble binder (polyacrylic acid / malt = 1/1) 1 (weight ratio)), and a slurry having a water content of 55% by weight, which is 25 parts by weight and 4 parts by weight of sodium sulfate, was prepared. Next, this was spray-dried (spray temperature 150 ° C.) to give an average particle size of 260 μm with a water content of 4% by weight.
m was obtained. The content of particles having a particle size of 125 to 710 μm is 90% by weight or more, and the apparent density is 800 g.
/ L. Further, as measured by FT-IR / PAS, a large amount of the water-soluble binder was present near the surface of the obtained granulated product. Further, the protease release rate after one minute at 20 ° C. was 79%.

<(D) Particles> D-1 A slurry having a solid content of 50% by weight was spray-dried at a hot air temperature of 250 ° C. to obtain base granules III having the following composition. Acrylic acid-maleic acid copolymer 7% by weight, sodium carbonate 25% by weight, sodium sulfate 20% by weight, zeolite 45
Wt%, water 3 wt%.

The acrylic acid-maleic acid copolymer was a sodium salt (70 mol% neutralized), and the monomer ratio was acrylic acid / maleic acid = 3/7 (molar ratio). As the zeolite, 4A type zeolite (manufactured by Tosoh Corporation) was used.

Then, particles (D) were obtained by supporting a surfactant and the like on the base granules III. That is, 100 parts by weight of Base Granule III was charged into a Ladyge mixer (manufactured by Matsusaka Giken Co., Ltd., capacity 20 L, with jacket), and the main shaft (1
50 parts by weight of a nonionic surfactant under stirring at 50 rpm)
A mixed solution of 2 parts by weight of polyethylene glycol (average molecular weight: 13000) and 6 parts by weight of water was charged over 3 minutes, and then stirred for 5 minutes. Further, 10 parts by weight of zeolite was added to perform surface modification.

The nonionic surfactant has 12 carbon atoms.
~ 16, polyoxyethylene alkyl ether having an average number of moles of added EO of 6.0 was used.

The obtained particles had an apparent density of 760 g /
L, particles 5 having an average particle size of 220 μm and 177 to 350 μm
It was 5% by weight, and bubbles of 1/3 or more of the particle diameter were released from inside the particles during the process of dissolving in water.

<Detergent Particles> Based on the final detergent particles, 20 parts by weight of sodium tripolyphosphate, 22 parts by weight of sodium carbonate, 7 parts by weight of sodium sulfate, 1 part by weight of sodium sulfite, and 0.5 part by weight of a fluorescent agent were mixed with a Loedige mixer. FKM
It mixed using -130D (made by Matsubo). Next, while operating the mixer, 24 parts by weight of linear alkylbenzene sulfonic acid (C12-14) and 4 parts by weight of palm kernel oil fatty acid were added to carry out a neutralization reaction. While operating the mixer, 6 parts by weight of polyoxyethylene alkyl ether (C12-16, EO6), 5 parts by weight of polyethylene glycol (average molecular weight 13000), and 5 parts by weight of acrylic acid-maleic acid copolymer were added, and granulation was performed.
Subsequently, 3 parts by weight of zeolite was added to perform a surface modification treatment to obtain detergent particles having a water content of 2.5% by weight.

<Enzyme particles> E-1 Cellzyme 0.7T (manufactured by Novozymes). E-2 Savinase 12T (manufactured by Novozymes).

Examples 1 to 8 and Comparative Examples 1 to 3 The components were mixed in the combinations shown in Table 1 to obtain the cleaning compositions of Examples 1 to 8 and Comparative Examples 1 to 3. The solubility, damage and detergency of the obtained detergent composition were evaluated as follows. Table 1 shows the results.

[0105]

[Table 1]

<Evaluation of solubility> 1 L beaker (105 m inner diameter)
m) in 5 ° C. water (CaCl ₂ : 55.42 mg /
L, MgCl ₂ .6H ₂ O: 43.51 mg / L) 1 L
And rotate the stirrer (length 35mm, diameter 8mm) at 800rpm
Under stirring, add 1 g of the detergent composition and stir for 60 seconds.
It was passed through a standard sieve specified by JIS Z 8801 (mesh size: 74 μm). The condition on the screen at this time was visually determined according to the following criteria.

Evaluation criteria ◎: No residue at all ○: Very little residue can be confirmed X: Residue can be clearly confirmed

<Evaluation of Detergency> An oil / fat / carbon stain composed of the components shown in Table 2 was dyed on a cotton / gold cloth to prepare an artificially stained cloth (6 × 6 cm).

[0109]

[Table 2]

Then, use water (CaCl ₂ : 5) at 40 ° C.
5.42 mg / L, MgCl ₂ .6H ₂ O: 43.51
mg / L) 167 mL into a 1 L beaker (105 m inner diameter)
m), and 0.67 g of the cleaning composition shown in Table 1 was dissolved therein. Five pieces of the artificially contaminated cloth were put therein, and immersed at 40 ° C. for 1 hour. Next, hard water at 40 ° C. (same as above) 8
Add 33 mL, transfer the whole amount to a sample cup of a stirring type detergency tester (Targotometer), and rotate at 100 r.
Stirred at pm for 10 minutes. After the artificially stained cloth was rinsed under running water, it was iron-pressed and subjected to reflectance measurement.

The original cloth before and after the cleaning and the artificial cloth before and after the cleaning were used.
The reflectance at 550 nm was measured with a self-recording colorimeter (manufactured by Shimadzu Corporation), the cleaning rate (%) was determined by the following formula, and the measured average value of the five samples was evaluated according to the following criteria.

[0112]

(Equation 1)

Evaluation criteria ：: Cleaning rate of 70% or more Δ: Cleaning rate of 65% or more and less than 70% ×: Cleaning rate of less than 65%

From the results shown in Table 1, the cleaning compositions obtained in Examples 1 to 8 are all superior in solubility and detergency to the cleaning compositions obtained in Comparative Examples 1 to 3. It turns out to be something. Regarding the damage to the washed material after washing, in Examples 1 to 8, since the solubility is excellent, there is no problem such as a local increase in alkali concentration or damage due to an increase in cellulase activity. In the case of Comparative Example 1,
In the case of the locally high concentration of alkali and Comparative Example 2, there was damage due to the locally high concentration of enzyme activity.

[0115]

Since the detergent composition of the present invention is excellent in solubility, damageability of an object to be washed, and detergency, it can be used for stains on textiles such as clothes, curtains and carpets. In particular, an effect of having an excellent detergency on dirt derived from sebum such as a collar and a cuff is exerted.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C11D 3/386 ZAB C11D 3/386 ZAB 17/06 17/06 // C12N 9/42 C12N 9/42 9 / 54 9/54 (C12N 9/42 (C12N 9/42 C12R 1:07) C12R 1:07) (C12N 9/54 (C12N 9/54 C12R 1:07) C12R 1:07) (72) Hiroshi Nishimura 1334 Minato, Wakayama-shi Kao Corporation Research Laboratory F-term (reference) 4B050 CC07 DD02 JJ02 KK01 KK02 KK14 KK16 KK17 LL04 4H003 AB03 AB15 AB19 AC08 BA10 CA20 DA01 DA04 EA09 EA12 EA15 EA16 EA30 EB22 EB30 ED02 EE09 FA15 FA32

Claims (8)

[Claims] 1. The following (A) particles, (B) particles and (C)
Detergent composition containing particles: (A) particles: (a) 10 to 50% by weight of surfactant,
(B) particles containing 10 to 50% by weight of a water-soluble salt and (c) 5 to 50% by weight of a water-insoluble inorganic substance,
And (c) a total of 40 to 70% by weight of particles,
(B) Particles: Cellulase release rate after 1 minute at 20 ° C. is 50
% Or more, wherein the cellulase retains an activity of 40% or more after treatment at 80 ° C. for 10 minutes, and has an optimal reaction pH of 7.5 or more.
(C) Particles: protease release rate after 1 minute at 20 ° C. is 2
0 to 98%, wherein the protease is a protease-containing particle that is not inhibited by casein degradation activity by oleic acid, wherein the particle (B) has a cellulase release rate after 1 minute at 20 ° C. C) A detergent composition having a protease release rate of 20 ° C. or more after 1 minute of the particles. 2. A cellulase, Bacillus sp. (B
acillus sp. A cellulase produced from a strain named KSM-S237 strain and deposited as FERM P-16067, a mutant thereof, or a transformant having a gene encoding the enzyme.
The cleaning composition according to the above. 3. The protease is stable in the range of pH 6 to 11 after treatment at 40 ° C. for 30 minutes, and has a pH of 4 to 13.
The cleaning composition according to claim 1 or 2, wherein the activity at pH 6 to 12 is 80% or more of the optimum pH activity and the isoelectric point is 8.9 to 9.1. 4. A protease, a strain named Bacillus sp. KSM-KP43 and deposited as FERM BP-6532, Bacillus sp.
Named KSM-KP1790 strain, FERM BP
Bacillus sp. KSM-KP9860 deposited as strain -6533.
The detergent composition according to any one of claims 1 to 3, which is a protease produced from a strain named a strain and deposited as FERM BP-6534, a mutant thereof, or a transformant having a gene encoding the enzyme. object. 5. Granulation obtained by (B) granulating (I) a cellulase together with a core material composed of water-soluble particles having an average particle diameter of 200 to 1200 μm and a water-soluble organic binder having a melting point of 35 to 70 ° C. And / or (II) cellulase, at least 45% by weight of a water-insoluble substance, and 5 to 40% by weight of a water-soluble binder. The cleaning composition according to any one of claims 1 to 4, which is a granulated material having a structure in which a water-soluble binder is present nearer to the surface than in the interior. 6. The granulation obtained by granulating (C) particles together with (III) a nuclear substance comprising water-soluble particles having an average particle diameter of 200 to 1200 μm and a water-soluble organic binder having a melting point of 35 to 70 ° C. A granulated product having an average particle size of 1 to 2 times the average particle size of the nuclear material, and / or (IV) protease, at least 45% by weight of a water-insoluble substance, and 5 to 40% by weight of a water-soluble binder. The cleaning composition according to any one of claims 1 to 5, wherein the cleaning composition is a granulated product having a structure in which a water-soluble binder is present nearer to the surface than in the interior. 7. The cleaning composition according to claim 1, wherein (A) the particles are capable of releasing bubbles having a diameter of 1/10 or more from the inside of the particles during the process of dissolving in water. object. 8. Further, (c) a water-insoluble inorganic substance and
100 parts by weight of base granules obtained by spray-drying a slurry containing one or more water-soluble components selected from (d) a water-soluble polymer and (b) a water-soluble salt,
The cleaning composition according to any one of claims 1 to 7, further comprising (D) particles (a) supporting less than 10 parts by weight of a surfactant.