JP2000328097A - Detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a detergent composition which exhibits a high detergency even at a low water temperature and under weak agitation by incorporating, into the same, (A) detergent particles containing an anionic surfactant and an alkali metal carbonate and having a specified potassium ion content, (B) particles containing alkali cellulase, and (C) particles containing protease having a specified α-keratine decomposition activity. SOLUTION: This composition comprises (A) 70-95 wt.% detergent particles containing 20-50 wt.% anionic surfactant and 10-30 wt.% alkali metal carbonate and having a wt. ratio of potassium ion to total cation of 0.05-0.6, (B) 0.01-5 wt.% (in terms of a zymogen powder) particles containing alkali cellulase, and (C) 0.01-0.5 wt.% (in terms of a zymogen powder) particles containing protease having an α-keratine decomposition activity at 10 deg.C of 0.09×10-3 μg/ mPU.min or higher. If necessary, a polyoxyalkylene alkyl or alkenyl ether having an HLB of 11.5-17 is incorporated into the detergent particles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to detergent compositions.

[0002]

2. Description of the Related Art In recent years, a weak water washing machine has been widely used in order to prevent damage to fibers due to washing. However, at low water temperatures in the winter, under weak water flow conditions, especially in the case of a protein-related stain such as a sock stain or a collar stain, because the action of cleaning enzymes such as proteases and the solubility of detergent builders such as alkali metal carbonates are reduced. Does not provide sufficient detergency. Japanese Patent Application Laid-Open No. 9-224666 discloses a protease which is active at a low temperature, but is not yet satisfactory.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a detergent composition which has high detergency even under low water temperature and weak stirring conditions.

[0004]

The present invention provides: (A) 20 to 50% by weight of an anionic surfactant and 10 to 30% by weight of an alkali metal carbonate, and based on the total cations in the detergent particles. Detergent particles having a potassium ion weight ratio of 0.05 to 0.6 (hereinafter, detergent particles (A)
(B) Particles containing alkaline cellulase (hereinafter referred to as enzyme particles (B)) 0.01 to 5% by weight (as raw enzyme powder) (C) Decomposition of α-keratin at 10 ° C 0.09 activity
Particles containing protease of at least × 10 ⁻³ μg / mPU · min (hereinafter referred to as enzyme particles (C)) 0.01 to
It relates to a detergent composition containing 0.5% by weight (as raw enzyme powder).

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION <Detergent Particles (A)> As the anionic surfactant contained in the detergent particles (A), alkyl benzene sulfonate, alkyl sulfate, alkyl ether sulfate, olefin sulfonate, Alkane sulfonate, fatty acid salt, alkyl or alkenyl ether carboxylate, α-sulfofatty acid salt or ester thereof are mentioned. In particular, alkylbenzene sulfonate having 10 to 20 carbon atoms in the alkyl group, 8 to 18 carbon atoms ( Preferably an alkyl sulfate of 10 to 14), having 8 to 18 carbon atoms.
(Preferably 10 to 14) alkyl ether sulfates,
One or more selected from fatty acid salts derived from palm or tallow having 8 to 18 (preferably 10 to 18) carbon atoms are preferable.
Preferred ethylene oxide average addition mole number of alkyl ether sulfate is 1 to 20, more preferably 1 to 10,
Particularly preferably, it is 1 to 5. As the salt, an alkali metal salt such as sodium and potassium is preferable. The detergent particles (A) preferably contain these anionic surfactants in an amount of from 20 to 50% by weight, particularly from 30 to 45% by weight, in terms of detergency, foaming property and enzyme stability.

The alkali metal carbonate contained in the detergent particles (A) is preferably a sodium salt and / or a potassium salt. The detergent particles (A) are prepared by adding an alkali metal carbonate to 10 to 3 particles.
The content is preferably 0% by weight, particularly preferably 15 to 30% by weight.

The weight ratio of potassium ions to total cations in the detergent particles (A) is from 0.05 to 0.6, preferably from 0.05 to 0.5, more preferably from the viewpoint of solubility and cleaning performance. 0.05 to 0.4. Here, the cations of the present invention are inorganic cations such as sodium ion, potassium ion, magnesium ion and calcium ion (excluding organic cations such as quaternary ammonium salts). Cations can be quantified by an atomic absorption method or the like.

In the present invention, from the viewpoint of the stability of the enzyme in the washing bath, the detergent particles (A) may further contain 11.5 to 17, preferably 12 to 16, polyoxyalkylene alkyl or alkenyl ether in the detergent particles. Is desirable. Here, the alkyl group or alkenyl group has 10 to 18 carbon atoms,
Preferably, 10 to 16 is good. HLB is determined by the method of Griffin, and such a nonionic surfactant is contained in the composition in an amount of 0 to 15% by weight, preferably 0.5 to 10% by weight.

The detergent particles (A) desirably contain a chlorine scavenger in order to prevent inactivation of the enzyme by chlorine present in water. Specific chlorine scavengers include primary amines,
Examples thereof include amines such as secondary amines and alkanolamines, inorganic peroxides such as hydrogen peroxide, sodium percarbonate and sodium perborate, and reducing agents such as sulfites. Sulfite is preferred in view of the stability of the enzyme. The chlorine scavenger may be contained in addition to the detergent particles (A).

In the detergent particles (A), as an optional component, in addition to the above-mentioned anionic surfactants and nonionic surfactants, cationic surfactants such as quaternary ammonium salts, or amine oxides, sulfobetaines, An amphoteric surfactant such as carbobetaine may be contained. The detergent particles (A) can contain crystalline aluminosilicates such as A-type, X-type, and P-type zeolites from the viewpoint of improving the detergency. Particularly, A-type zeolite is preferable. Preferred average primary particle size is 0.1 to 1
0 μm, particularly preferably 0.1 to 5 μm. The preferred content of the crystalline aluminosilicate is 3 to 40% by weight, especially 5 to 30% by weight in the detergent particles (A). The detergent particles (A) are composed of 1 to 50% by weight of an alkali agent such as silicate and sulfate, 1 to 50% by weight of an inorganic electrolyte, and 0.01 to 10% by weight of a re-contamination inhibitor such as polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone and carboxymethyl cellulose. %.

The detergent particles (A) are contained in the composition in an amount of 70-95.
% By weight, preferably 80 to 94% by weight.

<Enzyme Particle (B)> The alkaline cellulase in the enzyme particle (B) is an alkaliphilic microorganism Bacillus sp. KSM-635 (FERM BP-1485).
Alternatively, alkaline cellulase produced from the mutant strain is preferable from the viewpoint of improving washing properties. This alkaline cellulase has an optimum pH of 7 or more when carboxymethylcellulose is used as a substrate, or a relative activity at a pH of 8 or more is 50% or more of the optimum condition. Specific examples of the enzyme granules to be the enzyme particles (B) include KAC500 (registered trademark) manufactured by Kao, Cellzyme 0.7T manufactured by Novo Nordisk, and the like. The enzyme particles (B) are blended in the composition in an amount of 0.01 to 5% by weight, preferably 0.02 to 1% by weight (as a raw enzyme powder). The bulk of the alkaline cellulase in the enzyme particles is preferably 0.1 to 50% by weight.

<Enzyme particles (C)> Protea in enzyme particles
Α-kease at 10 ° C. measured by the method described below.
Latinolytic activity is 0.09 × 10^-3μg / mPU ・ mi
n or more, preferably 0.1 × 10^-3~ 1.0 × 10^-3μ
g / mPU · min, more preferably 0.12 × 10^-3
~ 1.0 × 10^-3μg / mPU · min, more preferred
Is 0.13 × 10 ^-3~ 1.0 × 10^-3μg / mPU ・ m
in, preferably α-keratin degradation activity at 30 ° C.
0.40 × 10^-3μg / mPU min or more
Preferably 0.44 × 10^-3~ 5.0 × 10^-3μg / m
PU · min, more preferably 0.47 × 10^-3~ 5.
0x10^-3μg / mPU · min. This
Examples of Rotases include, for example,
Bacillus sp.Bacillus sp.) KSM-KP
43 (FERM BP-6532), Bacillus SP (Bacillus
 sp.) KSM-KP1790 (FERM BP-6533), Bacill
SP (Bacillus sp.) KSM-KP9860
(FERM BP-6534)
A heterologous strain and a trait having a gene encoding the enzyme
Proteases produced from the transformants can be mentioned.
Especially Bacillus sp. KSM-KP43 and its
Mutants are superior. Enzyme particles (C)
For example, according to Japanese Patent Application Laid-Open No. 62-257990.
Can be obtained by granulation. Enzyme particles (C) are compositions
0.01 to 0.5% by weight, preferably 0.02 to
0.3% by weight (as raw enzyme powder) is blended.

In the present invention, α-keratin at 10 ° C.
Decomposition activity is 0.09 × 10^-3μg / mPU ・ min not yet
Full, especially 0.01 × 10^-3~ 0.07 × 10^-3μg / m
PU-min, preferably α-kerati at 30 ° C
Decomposition activity is 0.40 × 10^-3μg / mPU ・ min not yet
Full, more preferably 0.05 × 10^-3~ 0.35 × 10
^-3μg / mPU · min, more preferably 0.05 × 1
0^-3~ 0.30 × 10^-3μg / mPU · min, especially good
Preferably 0.05 × 10^-3~ 0.20 × 10^-3μg / m
It is preferable to use PU / min protease together
No. In this case, particles containing this protease (hereinafter referred to as “particles”)
It is preferable to mix them as enzyme particles (D).
The enzyme particles (D) include alcalase, sabinase,
Urazyme, everase (both Novo Nordis
Co., Ltd.), Perfect, Maxapem (all
Inc.) and KAP (Kao).
Especially, Kao KAP 4.3G and KAP 11.1G are excellent.
Have been. In the present invention, from the viewpoint of detergency at low temperatures,
The total of the enzyme particles (C) and (D) is 0.02 to 0.5 weight
%, Especially 0.02 to 0.03% by weight
Weight ratio of (D) to (D) and (C) /
(D) is 1/5 to 5/1, particularly 1/2 to 2/1 (enzyme
It is preferable that the content is contained at a ratio of:

Here, the α-keratin degrading activity is as follows:
α) per minute per 1 mPU of casein degrading activity shown in i)
-Expressed as soluble proteolysates (converted to tyrosine) produced from keratin. That is, it is measured by the following methods (i) to (iii).

(I) Preparation of α-keratin Human heel skin (keratin) was scraped off with a scalpel, cut with scissors, and washed with ion-exchanged water. 1 g of this keratin is 8M urea,
The suspension was suspended in 20 to 50 ml of 50 mM Tris-HCl buffer (pH 8.0) containing 25 mM β-mercaptoethanol and stirred overnight. After the swollen keratin is thoroughly ground with a Teflon homogenizer, it is crushed at 30,000 × g for 3 hours.
Centrifuged for 0 minutes. The supernatant obtained by centrifugation was filtered through filter paper (Whatman No. 2), and the filtrate was filtered.
After dialysis against 0 mM Tris-HCl buffer (pH 8.0), the mixture was centrifuged at 100,000 × g for 2 hours. The obtained precipitate was subjected to a 50 mM Tris-HCl buffer (pH 8.0) containing 8 M urea and 25 mM β-mercaptoethanol.
0) and dissolved again in 50 mM Tris-HCl buffer (pH
After dialysis against 8.0), the mixture was centrifuged at 100,000 × g for 2 hours. After removing the supernatant, the precipitate was washed with 8M urea,
After dissolving in 50 mM Tris-HCl buffer (pH 8.0) containing 25 mM β-mercaptoethanol, the solution was dialyzed against ion-exchanged water, freeze-dried to a powder, and used as α-keratin.

(Ii) Measurement of casein-degrading activity A 50 mM borate buffer (pH 10.5) containing 1% (w / v) casein (Hammerstein; Merck) was used.
After keeping the ml at 30 ° C. for 5 minutes, 0.1 ml of the enzyme solution was added and reacted at 30 ° C. for 15 minutes. Next, TCA
2 ml of a solution (0.11 M trichloroacetic acid, 0.22 M sodium acetate, 0.33 M acetic acid) was added and
After standing for 0 minutes, the acid-denatured protein was removed by filtration, and the acid-soluble protein hydrolyzate contained in the filtrate was quantified by the Lowry method. That is, 2.5 m to 0.5 ml of filtrate
l of an alkaline copper solution [1% (w / v) aqueous potassium sodium tartrate solution, 1% (w / v) aqueous copper sulfate solution, 0.1 M sodium hydroxide aqueous solution of sodium carbonate (sodium carbonate concentration 2% (w / V) is 1: 1: 100
(V / v), and the mixture was kept at 30 ° C. for 10 minutes. Then, 0.25 ml of a diluted phenol reagent (a phenol reagent diluted twice with ion-exchanged water) was further added thereto. At 30 ° C for 30 minutes.
The absorbance at 0 nm was measured. The result obtained by adding the TCA solution and allowing the mixture to stand at room temperature for 10 minutes and then adding the enzyme solution was used as a blank. 100 PU of the enzyme was determined to be an amount of an enzyme capable of releasing an acid-soluble protein degradation product corresponding to 1 μmol of tyrosine per minute.

(Iii) Measurement of α-keratinolytic activity 2 mg of α-keratin and 0.9 ml of 50 mM were placed in a test tube.
Add a borate buffer (pH 10.5) and add 10 ° C or 30
C. for 10 minutes. 0.1 ml of a protease solution is added to the mixture so that the casein decomposing activity shown in (ii) above becomes 10 ⁵ mPU, and the mixture is mixed with each other. When calculating the keratin-decomposing activity, the reaction was performed for 10 minutes, and then the reaction solution was filtered. The solubilized protein contained in the filtrate was quantified by the Lowry method, and the α-keratin decomposition activity was measured.

The composition of the present invention may further contain a percarbonate for imparting a bleaching effect. As salt,
Examples thereof include alkali metal salts such as sodium and potassium, ammonium salts, alkanolamine salts and the like, with sodium salts being preferred. From the viewpoint of the stability of the percarbonate, for example, a percarbonate coated with at least one selected from paraffin, (per) borate, an ethylene oxide adduct of alcohol, polyethylene glycol, and a silicate compound is preferable.
The composition of the present invention may contain a bleaching activator represented by the following formula (I) or (II) in order to further enhance the bleaching effect. _{R-COO-Ph-SO 3} M (I) R-COO-Ph-COOM (II) wherein, R represents an alkyl group or alkenyl group having 5 to 13 carbon atoms, Ph is a phenyl group, M represents a hydrogen atom, It is selected from alkali metals, alkaline earth metals and ammonium. In particular, those in which R in the general formula (I) is an alkyl group having 11 to 13 carbon atoms and M is an alkali metal such as sodium are preferable.

The composition of the present invention contains 0.1 to 10% by weight, particularly 0.5 to 5% by weight of percarbonate, and 0.1 to 5% by weight, particularly 0.1 to 5% by weight, of a bleach activator in view of the bleaching effect. 0.5-3% by weight
It is preferable to mix them.

The detergent composition of the present invention may contain an enzyme other than the enzyme particles (B), (C) and (D).
For example, an enzyme such as lipase or amylase may be incorporated in an amount of 0.01 to 0.5% by weight as a raw enzyme powder.

The composition of the present invention has a detergency under a low water temperature and a weak water flow condition.
5% dissolution time is 90 seconds to 400 seconds, especially 100 to 300
Preferably, it is seconds.

Here, the electric conductivity method refers to an inner diameter of 105 mm.
Put 1L of distilled water at 10 ° C into a cylindrical 1L beaker of
Set the conductivity meter. Stirrer piece (length 3
5 mm, diameter 7.5 mm) and stirred with a magnetic stirrer (550 rpm). 1 g of a sample cooled to 10 ° C. is introduced into the center of the water vortex. With this time taken as 0 second, the electrical conductivity is measured at 10 second intervals. If the measured value does not change continuously for 2 minutes or more, 100% dissolution was assumed, and the time to reach a value of 95% of the electric conductivity was defined as a 95% dissolution time.

[0024]

EXAMPLES The detergent compositions shown in Table 1 were prepared using the following components, and the cleaning effect was evaluated. <Detergent Particle A> 2 kg of sodium straight-chain alkyl (C12-14) benzenesulfonate, 0.5 kg of sodium alkyl sulfate (Emal 10 powder manufactured by Kao), polyoxyethylene alkyl ether (average of 9 moles of ethylene oxide added to lauryl alcohol) What was done) 0.
2 kg, acrylic acid-maleic acid copolymer (BASF
Sokaran cp-5) 0.3 kg, sodium tallow fatty acid 0.3 kg, sodium carbonate 0.4 kg, potassium carbonate 0.2 kg, No. 1 silicate 1.5 kg, 4A type zeolite 1.5 kg, sodium sulfite 0.1 kg, A water slurry having a solid content of 50% is prepared from 0.5 kg of sodium sulfate and 0.1 kg of polyethylene glycol, and 0.4 kg of the above polyoxyethylene alkyl ether is further added to the particles obtained by spray-drying the slurry. (FS-GC-10 manufactured by Fukae Kogyo Co., Ltd.) and granulated to obtain detergent particles A. Average particle size 400μm, bulk density 760g
/ L.

<Detergent Particles A ′> The detergent particles A ′ were produced in the same manner as the detergent particles A except that 0.6 kg of sodium carbonate was used without adding potassium carbonate. Average particle size 400μm, bulk density 75
0 g / L.

<Enzyme particles B> KAC500 (Kao alkaline cellulase, enzyme powder content of 10% by weight in particles).

<Enzyme Particle C> Bacillus SP KSM
-Protease produced from KP43 (keratin degradation activity at 10 ° C. 0.14 × 10 ⁻³ μg / mPU · m
α-Keratin degradation activity at 30 ° C. 0.49 ×
10 ⁻³ μg / mPU · min) in JP-A-62-2579.
Granulation was carried out according to Japanese Patent Publication No. 90 to obtain enzyme particles C. The content of the raw enzyme powder in the particles is 20% by weight.

<Enzyme particles D> KAP4.3G (Kao alkaline protease, keratin-decomposing activity at 10 ° C. 0.05 × 10 ⁻³ μg / mPU · min, α-keratin-decomposing activity at 30 ° C. 0.11 × 10 ^{−) 3} μg / mPU
Min, the content of the raw enzyme powder in the particles is 10% by weight).

<Bleaching agent E> Based on Example 1 of JP-A-59-196399, sodium metaborate tetrahydrate coated with 5% of sodium percarbonate was used.
A bleaching agent E was obtained by removing the particles having a small particle size using a 25 μm sieve.

<Bleaching Activator F> Sodium lauroyloxybenzenesulfonate was granulated according to JP-A-8-3593 to obtain a bleaching activator F.

[Evaluation of Detergency] Detergency of Cloth Contaminated with Collar Dirt Five cotton shirts worn by men in their thirties for three days and having a similar collar portion were stained and subjected to an experiment. Using the composition 20g shown in Table 1, the five shirts,
Washing was performed at a water temperature of 10 ° C., 20 ° C. and 30 ° C. in a washing machine hand washing course (National's fully automatic washing machine NA-F50K1). After dehydration and natural drying, the washability of the collar was evaluated by a panel of 10 trained panelists according to the following criteria, and the average score was determined. 1; dirt has been removed to a satisfactory level 2; dirt remains but is not anxious 3; dirt remains to a degree that is worrisome 4; Detergency Wear a white sock (Support & Clean, made of cotton, acrylic, polyester, polyurethane) for 5 days and 6 years old boys for 1 day, select 5 sheets with similar stains and use them for the experiment. did. Washing and evaluation were carried out in the same manner as in the case of washing the above-mentioned collar stains.

[0032]

[Table 1]

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Toshihiro Oki 1334 Minato, Wakayama-shi, Wakayama Prefecture, Kao Corporation (72) Inventor Hitoshi Tanimoto 1334 Minato, Wakayama-shi, Wakayama Prefecture, Kao Corporation (72) Inventor Tsutomu Tokumoto 1334 Minato, Wakayama City, Wakayama Prefecture Kao Co., Ltd. (72) Inventor Nobuyuki Ogura 1334 Minato, Wakayama City, Wakayama Prefecture Kao Co., Ltd.F-term (reference) 4H003 AA03 AB03 AB19 AB27 AB43 AC08 BA09 DA01 DB01 EA12 EA15 EA16 EA18 EA28 EB22 EB30 EB32 EC02 EC03 EE05 FA32 FA43

Claims (3)

[Claims] (1) The composition contains (A) 20 to 50% by weight of an anionic surfactant and 10 to 30% by weight of an alkali metal carbonate, and has a weight ratio of potassium ion to all cations in the particles of 0.05. Detergent particles having a particle size of 0.6 to 70
% By weight (B) Particles containing alkaline cellulase 0.01 to
5% by weight (as raw enzyme powder) (C) α-keratinolytic activity at 10 ° C. is 0.09
A detergent composition containing 0.01 to 0.5% by weight (as a raw enzyme powder) of particles containing a protease of at least × 10 ⁻³ μg / mPU · min. 2. (D) Particles containing a protease having an α-keratin-decomposing activity at 10 ° C. of less than 0.09 × 10 ⁻³ μg / mPU · min, wherein (C) + (D) is 0. 2. The detergent composition according to claim 1, wherein the detergent composition has a weight ratio of (C) / (D) of 1/5 to 5/1 (as a bulk enzyme). 3. The detergent composition according to claim 1, wherein the HLB contains a polyoxyalkylene alkyl or alkenyl ether having an HLB of 11.5 to 17.