JP2002265998A - Detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent composition having high detergent efficiency, particularly a detergent composition which is suited in the dip washing in hot water having a higher concentration than the normally used concentration to be conducted against remarkable stains. SOLUTION: The detergent composition comprises a surface active agent, a builder, and cellulase-containing granules having an anti-soil redeposition effect at 40 deg.C of >=110% provided that the anti-soil redeposition effect is obtained from the formulae: Anti-soil redeposition ratio (%)=(Reflectance of cotton white cloth after examination)/[(Reflectance of cotton white cloth before examination)]×100 and Anti-soil redeposition effect (%)=[(Anti-soil redeposition ratio of addition of cellulase granules)/(Anti-soil redeposition ratio of nonaddition of cellulase granules)]×100) according to the evaluation method of detergency described in JIS K3362: 1998.

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 When lipophilic stains such as collar sleeves and yellowishness of underwear and yellowishness of underwear and spills from foods are severe, ordinary washings cannot sufficiently remove stains or remain as stains. For this reason, conventionally, clothing has been immersed in an aqueous solution having a higher concentration than the normal use concentration of the detergent composition, and washing with warm water has been performed.

[0003] In particular, in immersion cleaning performed in a hot water having a concentration higher than a normal use concentration, which is performed for remarkable dirt, a part of the dirt separated from the object to be cleaned is deposited on the object to be cleaned again and the cleaning efficiency is increased. There is a problem that lowers. In order to prevent this redeposition, compounding of a cellulosic redeposition inhibitor such as carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxybutylmethylcellulose, and a nonionic polymer redeposition inhibitor such as polyethylene glycol, polyvinyl alcohol and polyvinylpyrrolidone. Although studies are being conducted, sufficient effects have not been obtained.

Japanese Patent Application Laid-Open No. 7-216084 discloses an amino acid polymer, Japanese Patent Application Laid-Open No. 6-330084 describes an α-sulfo fatty acid derivative, and Japanese Patent Application Laid-Open No. 10-505874 discloses ethylene tetraacetic acid (EDTA) and diethylene triamine. Derivatives of aminoacetic acids such as pentamethylenephosphoric acid and diethylenetriaminepentaacetic acid, homopolymers of acrylic acid or methacrylic acid, or methacrylic acid, methacrylamide or acrylamide, methacrylic acid esters or copolymers of acrylic acid and acrylic acid, and Copolymers of maleic acid and vinyl esters of styrene or vinyl ether have been disclosed as anti-redeposition agents, but have not been effective enough.

On the other hand, it has long been practiced to incorporate enzymes such as protease, lipase, cellulase and amylase into detergents as detergents. Cellulase acts on the amorphous region of cotton single fiber, It has been found that sebum stains within a single fiber are effectively removed and detergency is improved. However, most of the conventionally known cellulases have low heat resistance and have activity from acidic to near neutral, so-called acidic or neutral cellulases, and are stably incorporated in detergents for clothing. Was unsuitable for

Accordingly, a detergent composition having an excellent detergency against stains and stains derived from sebum such as collars and cuffs, and more specifically, washing suitable for high concentration immersion washing and washing with warm water. An agent composition has been desired.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a cleaning composition having high cleaning efficiency. In particular,
It is an object of the present invention to provide a cleaning composition suitable for immersion cleaning in warm water having a concentration higher than a normal use concentration, which is performed for remarkable soiling.

[0008]

That is, the gist of the present invention is as follows.
Surfactant, builder, effect of preventing re-contamination at 40 ° C is 11
Detergent composition containing 0% or more cellulase granules
, [However, the effect of preventing re-contamination is JIS K3362: 1.
998 based on the detergency evaluation method described below.
Do the price. Indicator detergent for detergency determination (without addition of fluorescent whitening agent)
1.33 g (in terms of anhydride) of water (CaCl 2)_Two: 5
5.42 mg / L, MgCl_Two・ 6H_TwoO: 43.51
mg / L) in 1000 mL, and then add
Add 0.25 g of carbon black selected by the Chemical Society,
Irradiate ultrasonic wave of 26 ± 1.5KHz for 5 minutes to carbon
Disperse black evenly. Then at 40 ° C
Transfer to a sample cup of a mixing type detergency tester, 6cm x 6
cm cotton white cloth (for making contaminated cloth selected by the Japan Oil Chemical Association)
Standard product) Add 5 sheets and 2 mg of cellulase granules or
Stir at 100 ± 5 rpm for 10 minutes with no addition
You. Next, the white cloth was taken out and the water content was 200% by weight.
% By hand, and then use water at 40 ° C.
(CaCl_Two: 55.42 mg / L, MgCl_Two・ 6H
_TwoO: 43.51 mg / L)
Use a mixing-type detergency tester (rotational speed 100 ± 5 rpm)
Rinsing for 3 minutes, and this rinsing operation is performed twice in total. Then wind
After drying, ironing is performed, and the
Measure the emissivity. The re-contamination prevention effect is calculated by the following formula.
You. Recontamination prevention rate (%) = [(Reflection of cotton white cloth after test
Rate) / (reflectance of cotton white cloth before test)] × 100 Anti-soil re-contamination effect (%) = [(re-addition of cellulase granule addition)
Pollution prevention rate / (Prevention of re-contamination without adding cellulase granules)
Rate)] × 100].

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION <Cleaning Composition> The cleaning composition of the present invention contains a surfactant, a builder, and a cellulase granule having an effect of preventing recontamination at 40 ° C. of 110% or more. It becomes.

In the present invention, the use of the cellulase granules having a high anti-recontamination effect as described above in combination with a surfactant and a builder enables high cleaning efficiency, especially for remarkable stains. An excellent effect of being able to obtain a detergent composition suitable for immersion cleaning in warm water having a concentration higher than the normal use concentration is exhibited.

The effect of preventing recontamination of the cellulase granules is evaluated as follows based on the cleaning power evaluation method described in JIS K3362: 1998. Detergent indicator detergent (without optical brightener) 1.33 g (anhydrous equivalent)
Using water (CaCl ₂ : 55.42 mg / L, MgC
_{l 2 · 6H 2 O: 43.51mg} / L) is dissolved in 1000 mL. Next, 0.25 g of carbon black selected by the Japan Oil Chemicals Association (Asahi Carbon Co., Ltd., preferably carbon black for Asahi cleaning) is added, and 26 ± 1.5 KHz is added.
For 5 minutes to uniformly disperse the carbon black. Next, this was transferred to a sample cup of a stirring type detergency tester (Terg-O-Tometer is preferable) at 40 ° C., and a 6 cm × 6 cm cotton white cloth (standard for making a contaminated cloth selected by the Japan Oil Chemical Association). Article, # 2023 cloth sold by Laundry Science Association) 5 sheets, and 2mg of cellulase granules with or without addition, rotation speed 100 ± 5r
Stir at pm for 10 minutes. Next, the white cloth is taken out and squeezed by hand so that the water content becomes 200% by weight or less.
Working water at 40 ° C. (CaCl ₂ : 55.42 mg / L, M
_{gCl 2 · 6H 2 O: 43.51mg} / L) 1000m
L, stir-in type detergency tester (rotation speed 100 ±
(5 rpm) for 3 minutes, and this rinsing operation is performed twice in total. Next, after air drying, ironing is performed, and 550
The reflectance in nm is measured (for example, 300A manufactured by Nippon Denshoku Industries Co., Ltd.). The re-contamination prevention effect is obtained by the following equation. Recontamination prevention rate (%) = [(reflectivity of cotton white cloth after test) / (reflectance of cotton white cloth before test)] × 100 Recontamination prevention effect (%) = [(addition of cellulase granules) Prevention rate of recontamination) / (Prevention rate of recontamination without adding cellulase granules)] × 100

The water used in the present invention (CaCl ₂ :
55.42 mg / L, MgCl ₂ .6H ₂ O: 43.5
1 mg / L) refers to CaCl ₂ per 1 L of deionized water.
55.42 mg and 43.5 mg of MgCl ₂ .6H ₂ O
1 mg dissolved.

The effect of preventing recontamination at 40 ° C. of the cellulase granules obtained by the above method is 110% or more, preferably 112% or more, more preferably 114%, from the viewpoint of excellent detergency at high temperatures. Above, more preferably 11
6% or more.

The cleaning composition of the present invention is JIS K336 in terms of convenience and reduction of waste (eg, boxes).
2: The apparent density measured by the method specified by 1998 is preferably 600 g / L or more, and 700 g / L.
/ L or more, more preferably 800 g / L or more. In terms of solubility, the apparent density is 1600 g /
L or less, more preferably 1300 g / L or less, and even more preferably 1000 g / L or less.

From the viewpoint of solubility, the average particle size of the detergent composition obtained by vibrating for 5 minutes using a standard sieve of JIS Z 8801 and obtained from the weight fraction depending on the size of the sieve is 150 to 150%.
700 μm is preferred, and more preferably 150 to 600
μm, and more preferably 180 to 400 μm.

The detergent composition of the present invention preferably has a surfactant release rate of 60% or more after 1 minute at 20 ° C. from the viewpoint of low damageability and cleaning performance of the object to be cleaned. %
The above is more preferable, and 80% or more is further preferable. The surfactant release rate can be measured based on the surfactant quantification method described in JIS K3362: 1998.

The cleaning composition of the present invention may be packaged in a single use amount in view of portability and simplicity, or may be packaged in a tablet form by compression molding. . At this time, it is preferable that the packaging material is water-soluble.

Next, the surfactant and builder used in the cleaning composition of the present invention have an effect of preventing re-contamination at 40 ° C. of 11%.
Various components such as a cellulase granulated material of 0% or more will be described.

<Surfactant> Examples of the surfactant include one or a combination of an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, and a cationic surfactant. Preferred are anionic surfactants and nonionic surfactants.

As the anionic surfactant, a compound having 10 carbon atoms
To 18 alcohol sulfates, alcohol sulfates of 8 to 20 carbon alcohols, alkylbenzene sulfonates, alkyl sulfates, paraffin sulfonates, α-olefin sulfonates,
α-Sulfo fatty acid salts, α-sulfo fatty acid alkyl ester salts or fatty acid salts are preferred. In the present invention, a linear alkylbenzene sulfonate having 10 to 14 carbon atoms, more preferably 12 to 14 carbon atoms in the alkyl chain is particularly preferred. As a counter ion of these salts, alkali metal salts and amines are preferable, and sodium and / or potassium, monoethanolamine and diethanolamine are particularly preferable.

Examples of the nonionic surfactant include polyoxyalkylene alkyl (C 8-20) ether, alkyl polyglycoside, polyoxyalkylene alkyl (C 8-20) phenyl ether, polyoxyalkylene sorbitan fatty acid (carbon (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].

The total amount of the surfactant used in the present invention is preferably 10 to 10 in the detergent composition from the viewpoint of detergency and solubility.
It is preferably 60% by weight, more preferably 15 to 50% by weight, and still more preferably 20 to 45% by weight. The amount of the anionic surfactant is preferably 1 to 60% by weight in the detergent composition,
50% by weight is more preferable, and 3 to 40% by weight is particularly preferable. The amount of the nonionic surfactant in the detergent composition is preferably 1 to 45% by weight, more preferably 1 to 35% by weight, and particularly preferably 4 to 25% by weight. The anionic surfactant and the nonionic surfactant can be used alone, but preferably, they are used in combination. Further, an amphoteric surfactant or a cationic surfactant can be used in combination depending on the purpose.

<Builder> In the present invention, a builder by itself has no or little if any detergency, but when incorporated into a detergent composition, it significantly improves detergent performance. This is to improve the cleaning ability of a surfactant which is a main component. It has at least one of a polyvalent metal cation trapping action, a soil dispersing action, and an alkali buffering action. Examples of such builders include water-soluble inorganic compounds, water-insoluble inorganic compounds, and organic compounds.

Examples of the water-soluble inorganic compound include phosphates (tripolyphosphate, pyrophosphate, metaphosphate, trisodium phosphate, etc.), silicates, carbonates, sulfates and the like. Of these, phosphates are preferred because they have all three functions.

Examples of the water-insoluble inorganic compound include aluminosilicate (A-type zeolite, P-type zeolite, X-type zeolite, amorphous aluminosilicate, etc.), crystalline silicate and the like. Among them, A-type zeolite having a particle size of 3 μm or less (more preferably 1 μm or less) is preferable.

Examples of the organic compound include carboxylate (aminocarboxylate, hydroxyaminocarboxylate, hydroxycarboxylate, cyclocarboxylate, maleic acid derivative, oxalate, etc.), organic carboxylic acid (salt) polymer (Acrylic acid polymers and copolymers, polyvalent carboxylic acid polymers and copolymers, glyoxylic acid polymers, polysaccharides and salts thereof, etc.). Among them, an organic carboxylic acid (salt) polymer is preferable.

In the builder salt, the counter ion is preferably an alkali metal salt or an amine, particularly preferably sodium and / or potassium, monoethanolamine or diethanolamine.

In the present invention, these builders can be used alone or in combination of two or more. In particular, in the present invention, it is preferable to contain the water-soluble inorganic compound as a builder, it is more preferable to use a water-soluble inorganic compound and an organic compound in combination, a water-soluble inorganic compound,
More preferably, an organic compound and a water-insoluble inorganic compound are used in combination.

In the present invention, the total amount of the builder in the detergent composition is preferably from 20 to 80% by weight, more preferably from 30 to 70% by weight, even more preferably from 35 to 60% by weight. Further, the water-soluble inorganic compound builder in the detergent composition is preferably 10 to 50% by weight, more preferably 15 to 45% by weight, and still more preferably 20 to 40% by weight, and the water-insoluble inorganic compound builder in the detergent composition. It is preferably 5 to 50% by weight, more preferably 10 to 45% by weight, and 15 to 4% by weight.
0% by weight is more preferable, and the organic compound builder is preferably 0.1 to 20% by weight in the detergent composition, and 0.3 to 15% by weight.
% By weight, more preferably 0.5 to 10% by weight.

<Cellulase Granules> The cellulase granules used in the present invention are those having an effect of preventing recontamination at 40 ° C. of 110% or more as described above. Where 40 ° C
In the present invention, the effect of preventing the recontamination of the conventional cellulase is usually 100 to 102%, whereas the effect of the present invention is 110 to 102%.
%, And has an advantage of being excellent in cleaning efficiency in a high temperature region because of having a high effect of preventing re-contamination of not less than%.

From the viewpoint of low-temperature washing performance, the effect of preventing re-contamination of the cellulase granules at 10 ° C. is preferably 104% or more, more preferably 106% or more, still more preferably 108% or more, and 110%. The above is particularly preferred. In addition,
The effect of preventing re-contamination at 10 ° C. can be measured in the same manner as in the above-described method for measuring the effect of preventing re-contamination at 40 ° C., except that the measurement temperature is changed from 40 ° C. to 10 ° C.

In view of the cleaning performance and the low damage property of the object to be cleaned, the cellulase release rate in the cellulase granule after 1 minute at 20 ° C., which is determined as follows, is preferably 50% or more,
% Or more, more preferably 70% or more, and 8% or more.
0% or more is particularly preferred.

The cellulase release rate was determined by adding 100 mL of a 0.9% by weight aqueous solution of sodium chloride at 20 ° C. to a 100 mL beaker (50 mm in inner diameter), and stirring with a stirrer (length 35 mm,
While stirring at a rotation speed of 100 rpm (diameter: 8 mm), 100 mg of the cellulase granule was put in, the cellulase activity released after 1 minute was divided by the cellulase activity at the time of complete dissolution, and the obtained value was multiplied by 100. Means something. 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.

With respect to the cellulase granule, the apparent density measured by the method specified in JIS K 3362: 1998 is preferably from 500 to 1600 g / L, more preferably from 600 to 1500 g / L, particularly from the viewpoint of non-classification. Preferably it is 700 to 1400 g / L.

Further, in terms of high-speed dissolution, low dust generation, and non-classification, after oscillating using a standard sieve of JIS Z 8801 for 5 minutes, the average particle diameter obtained from the weight fraction based on the sieve size is used. Is preferably 150 to 1200 μm, more preferably 150 to 1000 μm, and particularly preferably 200 to 1200 μm.
It is 500 μm. In addition, in terms of dust generation and solubility,
25 to 710 μm particles constitute 80% of the whole cellulase granulation.
% By weight or more, and more preferably 90% by weight or more.

The cellulase granule is preferably contained in the detergent composition in an amount of 0.1 to 10% by weight in terms of washing performance and economy.
0.2 to 8% by weight is more preferred, and 0.3 to 5% by weight is even more preferred.

The cellulase used for the cellulase granulated product is preferably 80% in terms of washing performance, washing effect under hot water or high temperature, heat history at the time of production of enzyme particles, and storage stability after granulation or product blending. At 40 ° C for 10 minutes
% Of the carboxymethylcellulose decomposition activity is preferably 7.5 or more.

The retained cellulase activity is more preferably at least 50%, further preferably at least 60%. The activity of these cellulases was measured according to JP-A-10-3.
It can be determined by the method described in JP-A-13859. Here, the treatment at 80 ° C. for 10 minutes means that the enzyme is treated at 0.
5M glycine-sodium hydroxide buffer (pH 9.0)
Incubation 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. Where the optimal reaction pH
The term “pH conditions” under which the carboxymethylcellulose degrading activity of the enzyme is maximized in a 40 mM Britton-Robinson broad-range buffer.

The source of such a cellulase is not particularly limited, but a cellulase obtained from the genus Bacillus is preferred. In particular, the cellulase is named Bacillus sp. Strain KSM-S237 and deposited as FERM P-16067. Cellulase produced from the obtained strain, its mutant, or a transformant having a gene encoding the enzyme is preferable in terms of washing performance. In addition, Bacillus sp .
rus sp. ) KSM-S237 strain (FERMP
-16067) and a method for producing cellulase from the strain include the method described in JP-A-10-313859. 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-10-229879.
And Japanese Patent Application Laid-Open No. 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 desirable to use an enzyme powder.

The content of the cellulase in the cellulase granule is preferably 0.5 to 20% by weight, more preferably 0.8 to 15% by weight in terms of granulation, solubility and washing performance.
More preferred is 1 to 10% by weight.

As the cellulase granules of the present invention, known granules can be used, but the granules of the following (I) and / or (II) are preferred, It is more preferable that the granulated product is (II) in view of low dust generation.

The granulated product (I) is obtained by granulating cellulase 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. Is 1 of the average particle size of the nuclear material.
It is a granulated product that is up to twice as large.

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 substance is preferably from 30 to 80% by weight in the granulated product of (I) from the viewpoint of granulating property 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. From the viewpoint of productivity, the amount of the water-soluble organic binder is preferably 5 to 60 parts by weight based on 100 parts by weight of the core material.

The melting point of the water-soluble organic binder is 35 to 7
It 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.

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.

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

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

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, and barium sulfate.
Inorganic substances are preferred, and zeolite and kaolin are particularly preferred from the viewpoint of dispersibility. From the viewpoint of uniformity, the water-insoluble substance preferably has an average primary particle diameter of 20 μm or less.
0 μm or less is more preferable, and 0.1 to 5 μm is particularly preferable. The content of the water-insoluble substance in the granulated product (II) is preferably 45% by weight or more, and more preferably 50% by weight or more, from the viewpoint of prompt elution of the enzyme. 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,
Potassium salts and ammonium salts are preferred. The addition of the water-soluble binder is preferable from the viewpoint of improving the particle strength and rapidly disintegrating the particles. 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, and
The above is more preferred. 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 3% by weight or less.
0 wt% or less is more preferable.

The granulated product (II) has a structure in which more water-soluble binder is present near the surface than inside the particles. For example, the above-mentioned cellulase, water-insoluble substance, and water-soluble binder are mixed. , Preferably a water content of 30 to
It is obtained by spray-drying the slurry after making it a slurry of 60% by weight. The temperature of the hot air at the time of spray drying is preferably 140 to 180 ° C. from the viewpoint of enzyme stability and productivity. The other spray drying conditions are not particularly limited. The uneven distribution of the water-soluble binder in the cellulase granule can be confirmed by, for example, a method (FT-IR / PAS) using Fourier transform infrared spectroscopy (FT-IR) or photoacoustic spectroscopy (PAS). It can be performed using:
These are Applied Spectroscopy
vol. 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 particle, whereby the uneven distribution of a water-soluble component can be confirmed.

The granulated product (II) is JIS Z 880 in terms of high-speed dissolution, low dust generation, and non-classification.
After shaking for 5 minutes using the standard sieve of No. 1, the average particle size determined from the weight fraction according to the size of the sieve is 150 to 5
00m is preferable, and more preferably 150 to 450 μm.
m, particularly preferably 200 to 400 μm. In addition, from the viewpoints of dust generation and solubility, the content of particles having a particle size of 125 to 710 μm is preferably 80% by weight or more, and more preferably 90% by weight or more of the whole granulated product of (II).

<Other Components> The detergent composition includes a bleaching agent (percarbonate, perborate, bleaching activator, etc.), a re-staining agent (carboxymethylcellulose, etc.), a softening agent (dialkyl type Quaternary ammonium salts, clay minerals, etc.), reducing agents (sulfites, etc.), optical brighteners (biphenyl type, aminostilbene type, etc.), foam control agents (silicone, etc.), fragrances, and other enzymes (protease, pectinase, Additives such as amylase and lipase). These may be contained in the detergent particles or may be added as separate particles.

Among them, in terms of cleaning performance, particles releasing hydrogen peroxide in an aqueous solution and 100 g of water (20 ° C., pH
It is preferable to contain bleach activator-containing particles having a solubility in 6) of 5 g or less (preferably 3 g or less). In particular,
The particles releasing hydrogen peroxide at 20 ° C., the hydrogen peroxide release rate after 1 minute, and the bleach activator-containing particles at 20 ° C.
It is more preferable that the release rate of the bleaching activator after 1 minute is higher in terms of cleaning performance and low damage to the object to be cleaned. The value obtained by dividing the hydrogen peroxide release rate by the bleaching activator release rate is 2 or more. Is more preferable, 4 or more is further preferable, and 6 or more is particularly preferable.

The hydrogen peroxide release rate was 100 m of water at 20 ° C.
L was added to 0.1 g of a sample (particles releasing hydrogen peroxide) under stirring with a stirrer at 100 rpm, and the amount of hydrogen peroxide released after 1 minute was divided by the amount of hydrogen peroxide at the time of complete dissolution to obtain a value of 100. Multiplied by. The amount of hydrogen peroxide can be measured based on a titration method using an aqueous solution of potassium permanganate.

The bleaching activator release rate was 100 ° C. water at 20 ° C.
0.1 mL of the sample (bleaching activator-containing particles) was added to the mL under stirring with a stirrer at 100 rpm, and the bleaching activator released after 1 minute was divided by the bleaching activator at the time of complete dissolution. The value is multiplied by 100. Incidentally, the amount of the bleaching activator can be measured based on a known method.

Examples of the component that releases hydrogen peroxide in an aqueous solution include inorganic peroxide salts such as percarbonate, perborate and perphosphate, and among them, percarbonate is preferred. . Specifically, sodium percarbonate, sodium tripolyphosphate / hydrogen peroxide adduct, sodium pyrophosphate / hydrogen peroxide adduct, urea / hydrogen peroxide adduct, or 4Na ₂ SO ₄ .2H ₂ O ₂ .NaCl; Examples thereof include sodium perborate monohydrate, sodium perborate tetrahydrate, sodium peroxide, calcium peroxide and the like. Of these, sodium percarbonate, sodium perborate monohydrate and sodium perborate tetrahydrate are particularly preferred.

The particles releasing hydrogen peroxide in the aqueous solution are:
Particles coated with a water-soluble substance are preferred in terms of stability. Examples of the water-soluble substance include boric acid or a salt thereof, polyalkylene glycol, water glass No. 1 alkali metal salt, and the like. Among them, metaboric acid, orthoboric acid, borax, sodium salt of tetraborate, polyethylene glycol, and water glass No. 1 alkali metal salt are preferred. As a method of coating with a water-soluble substance, a method of spraying an aqueous solution of a water-soluble substance onto a peroxide that generates hydrogen peroxide in an aqueous solution can be selected, but is not particularly limited.

In terms of cleaning performance, the particles releasing hydrogen peroxide in an aqueous solution are shaken with a standard sieve of JIS Z 8801 for 5 minutes, and then the average particle size determined from the weight fraction based on the size of the sieve is It is preferably from 200 to 500 μm, more preferably from 250 to 400 μm.

The amount of particles releasing hydrogen peroxide in the aqueous solution is 0.1 to 30% by weight in the cleaning composition in terms of cleaning performance.
Is preferred, and 0.3 to 25% by weight is more preferred.
5-20% by weight is more preferred.

As the bleaching activator, those having high lipophilicity are preferred from the viewpoint of the detergency of lipophilic stains, and tetraacetylethylenediamine, acetoxybenzenesulfonate, glucose pentaacetate, and JP-A-59-229 are available.
No. 99, JP-A-63-258647 and JP-A-6-316700, an organic peracid precursor, or a metal catalyst in which a transition metal is stabilized with a sequestering agent can also be used. In particular, the following general formula (I) or general formula (II):

[0065]

Embedded image

Wherein R is an alkyl group having 10 to 13 carbon atoms;
R 'is an alkyl group having 7 to 11 carbon atoms, and M represents a hydrogen atom or an alkali metal, an alkaline earth metal, ammonium or an alkanolamine] from the viewpoint of washing performance. Among them, sodium alkanoyl (10 to 13 carbon atoms) oxybenzenesulfonate is more preferable.

The content of the bleach activator in the bleach activator-containing particles is preferably from 1 to 90% by weight, more preferably from 10 to 70% by weight, and still more preferably from 30 to 70% by weight.

In order to improve the solubility of the bleaching activator in the washing bath, anionic surfactants, especially alkyl sulfates or polyoxyethylene alkyl ether sulfates, are added to the bleach activator-containing particles. Alternatively, the mixture is preferably blended in the bleach activator-containing particles in an amount of 0 to 50% by weight, more preferably 5 to 45% by weight, and still more preferably 10 to 50% by weight.
~ 40% by weight. Alkyl sulfates have 10 to 10 carbon atoms
In 18, an alkali metal salt such as a sodium salt is preferred, and sodium lauryl sulfate or sodium myristyl sulfate is particularly preferred. As the alkyl ether sulfate, a polyoxyethylene alkyl ether sulfate having 10 to 18 carbon atoms is preferable, and an alkali metal salt such as a sodium salt is preferable. The average number of moles of ethylene oxide added (hereinafter referred to as EOP) is preferably 1 to 10, particularly 1 to 5. Particularly, sodium polyoxyethylene lauryl ether sulfate and sodium polyoxyethylene myristyl ether sulfate having EOP of 2 to 5 are preferable.

The bleach activator-containing particles can be formulated using a binder selected from polyethylene glycol or fatty acids. The average molecular weight of the polyethylene glycol is preferably from 2,000 to 20,000, more preferably from 4000 to 10,000, even more preferably from 4,000 to 8,000. The fatty acid has 8 to 20, preferably 10 to 18, and more preferably 12 to 18 carbon atoms, and these may be in the form of sodium or potassium soap. It is desirable that such a binder substance is incorporated in the bleach activator-containing particles in an amount of 0.5 to 30% by weight, preferably 1 to 20% by weight, more preferably 5 to 20% by weight.

For the purpose of improving the stability of the bleaching activator, an acidic substance may be incorporated into the bleaching activator-containing particles, if desired. Carboxylic acids are preferred as the acidic substance,
In particular, at least one selected from succinic acid, maleic acid, fumaric acid, citric acid, glycolic acid, and p-hydroxybenzoic acid is preferred. The amount of the acidic substance is preferably 0 to 20% by weight, preferably 1 to 15% by weight, more preferably 1 to 10% by weight in the bleach activator-containing particles.

The bleach activator-containing particles can be obtained by mixing and granulating the above components by any method. In particular, the bleach activator and a part or all of the anionic surfactant are mixed first. Then, a method of adding a binder substance and an acidic substance is preferable. Further, it is preferable to add the binder substance after melting it in advance. Binder material 40 ~ 100
C., preferably at 50 to 100.degree. C., more preferably at 50 to 90.degree. These are stirred and mixed until they become uniform, and then formulated by a usual granulator. Extrusion granulation can be mentioned as a preferable granulation method, and the average particle diameter is 200 to 800 μm, preferably 250 to 500 μm.
m is preferred. Further, as another granulation method, a granulation method using a briquette machine and the like can be mentioned.

The amount of the bleach activator-containing particles is preferably from 0.1 to 10% by weight, particularly preferably from 0.5 to 5% by weight, in the cleaning composition from the viewpoint of cleaning performance.

The detergent composition of the present invention can be produced by adding and mixing the above-mentioned surfactant, builder, granulated cellulase, and if necessary, other components by a known method. For example, after preparing a slurry containing the builder (preferably having a water content of 30 to 60% by weight), spray drying is performed, a surfactant is added thereto, and a granulating operation is performed. A detergent composition can be prepared by adding and mixing.

In particular, it is preferable to use particles obtained by preparing a slurry containing the builder and then spray-drying as a core substance of the detergent particles from the viewpoint of solubility and cleaning performance. In this case, the temperature of the hot air at the time of spray drying is preferably 200 to 300 ° C. from the viewpoint of solubility.

Further, in terms of fluidity and non-caking properties,
It is preferable to perform a surface modification by mixing the detergent particles and a part of various builder components. Various builder components used for surface modification are preferably 1 to 30% by weight, more preferably 2 to 25% by weight, even more preferably 5 to 25% by weight in the detergent particles.

The cleaning composition of the present invention has a high cleaning efficiency against dirt and stains derived from sebum such as collars and cuffs, and is particularly suitable for immersion cleaning in warm water having a concentration higher than a normal use concentration. Therefore, it can be used for clothing, textiles such as curtains and carpets, and can be suitably used especially as a detergent composition for clothing.

[0077]

EXAMPLES Examples 1 to 7 and Comparative Examples 1 to 3 Builders (excluding 5% by weight of zeolite, crystalline silicate and amorphous aluminosilicate) based on the detergent composition shown in Table 1. ) Was prepared by spray drying at a hot air temperature of 250 ° C., and a granulation operation was carried out by adding a surfactant and the like. This has spices,
5% by weight of zeolite, crystalline silicate and amorphous aluminosilicate are added to perform surface modification to obtain detergent particles,
The cellulase granules and other components were added thereto to obtain a detergent composition. Each of the obtained detergent compositions has an apparent density of 800 to 1000 g / L and an average particle size of 180 to 4
It was 00 μm. The value obtained by dividing the hydrogen peroxide release rate of the compositions described in Examples 5 to 7 by the bleach activator release rate is as follows:
6 or more.

[0078]

[Table 1]

The compounds described in Table 1 are as follows. The properties of each compound such as the average particle size and the apparent density were determined based on the above-described methods.

LAS-Na: straight-chain sodium alkylbenzene sulfonate having 10 to 14 carbon atoms LAS-K: straight-chain potassium alkylbenzene sulfonate having 10 to 14 carbon atoms AS-Na: straight-chain having 10 to 13 carbon atoms Sodium alkyl sulfate ester ・ AOS-K: α-olefin sulfonate potassium having 14 to 18 carbon atoms ・ Fatty acid Na: sodium fatty acid having 14 to 18 carbon atoms ・ Nonionic surfactant 1: secondary alcohol having 12 to 14 carbon atoms Polyoxyalkylene alkyl ether obtained by adding 6 mol of ethylene oxide (EO) on average to non-ionic surfactant 2: Non-ionic surfactant having 10 to 14 carbon atoms
Polyoxyalkylene alkyl ether obtained by block addition of EO to tertiary alcohol in an average of 5 mol, propylene oxide in an average of 2 mol, and EO in an average of 3 mol ・ Zeolite: 4A zeolite (average particle size 1 μm) Salt: Al ₂ O ₃ = 29.6% by weight, SiO ₂ = 52.4% by weight, Na ₂ O = 18.0% by weight (1.0Na ₂ O · Al ₂ O ₃ · 3.1SiO ₂ )
(Based on atomic absorption analysis and plasma emission analysis) Crystalline silicate: Powder SKS-6 (produced by Hoechst Tokuyama Co., Ltd.) AA / MA copolymer: Acrylic acid-maleic acid copolymer sodium salt (70 Mol% neutralized), monomer ratio is acrylic acid / maleic acid = 3/7 (molar ratio), weight average molecular weight 50,000. Sodium polyacrylate: average molecular weight 10,000.

[0081] - granulated product 1: Bacillus sp. (Bac
illus sp. ) 2% by weight of cellulase (25000 U / g) produced from the strain named KSM-S237 and deposited as FERM P-16067, nuclear material (sodium chloride with an average particle size of 250 μm) 4
5% by weight, water-soluble organic binder (polyethylene glycol 6000, melting point 63 ° C.) 15% by weight, titanium oxide 5
% By weight, 1% by weight of calcium chloride and 32% by weight of sodium sulfate were granulated under the conditions described in Example 1 of JP-A-62-257990 to obtain a granulated product having an average particle size of 350 μm. 125-
The content of particles having a particle size of 710 μm was 90% by weight or more, and the apparent density was 830 g / L. Also, 20
The cellulase release rate after 1 minute at 68 ° C. was 68%. 40
The effect of preventing re-contamination at 110 ° C was 116% or more, and the effect of preventing re-contamination at 10 ° C was 110% or more. Also, FT-IR / P
As measured by AS, a large amount of the water-soluble organic binder was present near the surface of the obtained granulated product.

[0082]-granules 2: Bacillus sp. (Bac
illus sp. 2) 2 parts by weight of cellulase (25000 U / g) produced from a strain named KSM-S237 and deposited as FERM P-16067, water-insoluble substance (zeolite: average particle size 3 μm) 65
A slurry having a water content of 55 parts by weight, which is 25 parts by weight, a water-soluble binder (polyacrylic acid / multit = 1/1 (weight ratio)), and 4 parts by weight of sodium sulfate 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. 125-710μ
The content of particles having a particle size of m was 90% by weight or more, and the apparent density was 810 g / L. Also, FT-IR / P
As measured by AS, a large amount of the water-soluble binder was present near the surface of the obtained granulated product. Also, at 20 ° C, 1
The cellulase release after 80 minutes was 80%. The effect of preventing re-contamination at 40 ° C was 116% or more, and the effect of preventing re-contamination at 10 ° C was 110% or more. Further, as measured by FT-IR / PAS, a large amount of the water-soluble organic binder was present near the surface of the obtained granulated product.

Cellulase-containing particles: Cellzyme 0.7
T (Novozyme). The effect of preventing re-contamination at 40 ° C is 11
Less than 0%, the effect of preventing re-contamination at 10 ° C was less than 104%.

Bleach: 84% by weight of sodium percarbonate
The granules contained were surface-coated with water glass No. 1 sodium salt, and had an average particle size of 280 μm.

A bleach activator: alkanoyl (C 1
2) The granulated product was 70% by weight of sodium oxybenzenesulfonate, and the average particle size was 280 μm. The granulated product of the bleaching activator is prepared by mixing the bleaching activator and citric acid first, then adding a binder material (polyethylene glycol 6000) previously melted at 70 ° C. and stirring and mixing until uniform. After that, it was made into a formulation by a usual granulator and obtained.

Polyethylene glycol: average molecular weight 8
000 protease-containing particles: Bacillus sp. (Bac
illus sp. ) Named KSM-KP43;
6 parts by weight of a protease (100 PU / g) produced from the strain deposited as ERM BP-6532,
65 parts by weight of a water-insoluble substance (zeolite: average particle size of 3 μm), a water-soluble binder (polyacrylic acid / multit =
A slurry having a water content of 55% by weight, which was 25 parts by weight (1/1 (weight ratio)) and 4 parts by weight of sodium sulfate, was prepared. Next, this was 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. Also, FT-IR / PAS
As a result, 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%.

A fluorescent whitening agent: a mixture of Tinopearl CBS-X and Tinopearl AMS-GX (manufactured by Ciba Specialty Chemicals) at a weight ratio of 1/1.

Further, the surfactant release rate, recontamination prevention property and detergency of the obtained detergent composition were evaluated according to the following methods. Table 3 shows the results.

<Surfactant Release Rate of Cleaning Composition> The surfactant release rate can be measured based on the surfactant quantification method described in JIS K 3362: 1998.
The detergent compositions obtained in Examples 1 to 7 all had a surfactant release rate of 80% or more.

<Prevention of Recontamination of Cleaning Composition> JIS
K3362: 1998, it is carried out as follows based on the detergency evaluation method. 0.67 g of the obtained detergent composition
At 40 ° C. using water (CaCl ₂ : 55.42 mg /
L, MgCl ₂ .6H ₂ O: 43.51 mg / L) 10
Dissolve in 00 mL. Next, 0.25 g of carbon black selected by the Japan Oil Chemicals Association (Asahi Carbon Co., Ltd., preferably carbon black for Asahi cleaning) was added, and 26 ±
The carbon black is uniformly dispersed by irradiating ultrasonic waves of 1.5 KHz for 5 minutes. Next, this was stirred at 20 ° C. with a detergency tester (Tergotometer: Terg-O-To).
The sample was transferred to a sample cup, and 5 pieces of 6 cm × 6 cm cotton white cloth (a standard product selected by the Japan Oil Chemical Society, # 2023 cloth sold by the Washing Science Association) were put into the sample cup, and the rotation speed was 100 rpm.
Stir at ± 5 rpm for 10 minutes. Next, a cotton white cloth is taken out, lightly squeezed by hand so that the water content becomes 200% by weight or less, and then used water (CaCl ₂ : 55.42) at 40 ° C.
mg / L, MgCl ₂ .6H ₂ O: 43.51 mg /
L) Put in 1000 mL, rinse for 3 minutes using a stirring type detergency tester (rotational speed 100 ± 5 rpm), and perform this rinsing operation twice in total. Next, after air-drying, ironing is performed, and the reflectance at 550 nm is measured (300A manufactured by Nippon Denshoku Industries Co., Ltd.). The recontamination prevention rate was determined by the following equation, and evaluated according to the following criteria. Recontamination prevention rate (%) = [(reflectance of cotton white cloth after test) / (reflectance of cotton white cloth before test)] × 100 Evaluation criteria ：: Recontamination prevention rate of 116% or more ：: Re Contamination prevention rate of 110% or more and less than 116% ×: Recontamination prevention rate of less than 110%

<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). 40 ° C water (CaCl
₂ : 55.42 mg / L, MgCl ₂ .6H ₂ O: 4
(3.51 mg / L) 167 mL was placed in a 1 L beaker (inner diameter: 105 mm), and the detergent composition 0.6 shown in Table 2 was added.
7 g is dissolved, and the five artificially contaminated cloths are put therein.
It was immersed at 40 ° C. for 1 hour. Next, 833 mL of 40 ° C. hard water (same as above) was added, and the whole amount was transferred to a sample cup of a stirring type detergency tester (Targotometer) and stirred at a rotation speed of 100 ± 5 rpm for 10 minutes. After rinsing the artificially contaminated cloth under running water, iron press and measure the reflectance at 550 nm (Nippon Denshoku Industries Co., Ltd. 300A)
Then, the cleaning rate (%) was determined by the following formula, and the measured average value of the five sheets was evaluated according to the following criteria.

[0092]

[Table 2]

[0093]

[Table 3]

[0094] As shown in Table 3, the cleaning compositions obtained in Examples 1 to 7 were superior to the cleaning compositions obtained in Comparative Examples 1 to 3 in terms of anti-recontamination property and detergency. It turns out that it is excellent.

[0095]

EFFECTS OF THE INVENTION The detergent composition of the present invention is excellent in recontamination prevention property and detergency, so that it can be used for clothing, curtains,
It can be used for stains on textiles such as carpets, and among others, it has an excellent detergency for stains and stains derived from sebum such as collars and cuffs.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Hiroshi Nishimura 1334 Minato, Wakayama-shi F-term in the Kao Research Laboratories (reference) 4H003 AB03 AB15 AB19 AB27 AC09 AC23 BA10 DA01 DA04 EA09 EA12 EA15 EA16 EA25 EA28 EB08 EB22 EB30 EB36 EC02 EC03 ED02 EE05 FA06 FA32

Claims (6)

[Claims] 1. Surfactant, builder, recontamination at 40 ° C.
Contains cellulase granules with a prevention effect of 110% or more
Cleaning composition. [However, the effect of preventing re-contamination is JIS
K3362: Based on the detergency evaluation method described in 1998
The evaluation is made as follows. Detergent detergent for determining detergency (fluorescent
1.33 g (in terms of anhydride) of water
(CaCl_Two: 55.42 mg / L, MgCl_Two・ 6H
_TwoO: 43.51 mg / L)
Next, carbon black 0.1
Add 25 g and sonicate at 26 ± 1.5 KHz for 5 minutes
Irradiate to uniformly disperse carbon black. Next
Stir it at 40 ° C into a sample cup of a detergency tester.
Transfer, 6cm x 6cm cotton white cloth
Standard product for the preparation of fixed contaminated cloth) 5 sheets, and cellulase granules
With or without addition of 2 mg at a rotation speed of 100 ± 5 rpm
Stir for 10 minutes. Next, take out the white cloth and add
After squeezing by hand so that the rate becomes 200% by weight or less, 4
0 ° C water (CaCl_Two: 55.42 mg / L, Mg
Cl_Two・ 6H _TwoO: 43.51 mg / L) 1000 mL
And a stirring type washing power tester (rotation speed 100 ± 5)
rpm) for 3 minutes, and this rinsing operation is performed twice in total.
Now. Next, after air-drying, ironing is performed, and 550n
The reflectance at m is measured. Prevention of recontamination by the following formula
Seek effect. Recontamination prevention rate (%) = [(Reflection of cotton white cloth after test
Rate) / (reflectance of cotton white cloth before test)] × 100 Anti-soil re-contamination effect (%) = [(re-addition of cellulase granule addition)
Pollution prevention rate / (Prevention of re-contamination without adding cellulase granules)
Rate)] × 100] 2. The cleaning composition according to claim 1, which has an apparent density of 600 g / L or more as measured by a method specified by JIS K 3362: 1998. 3. The cellulase release rate of the cellulase granulated product is 50% or more after 1 minute at 20 ° C.
The cleaning composition according to the above. 4. A cellulase, Bacillus sp (B
acillus sp. 4. The 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. Cleaning composition. 5. A bleach activator-containing particle which releases hydrogen peroxide in an aqueous solution and a bleach activator-containing particle having a solubility in 100 g of water (20 ° C., pH 6) of 5 g or less.
4. The cleaning composition according to any one of 4. 6. The cleaning composition according to claim 1, wherein the builder is a phosphate builder.