JPH06264094A - Detergent composition for clothes - Google Patents

Abstract

PURPOSE:To obtain a detergent compsn. having an excellent detergent effect on stains of clothes caused by spilling or dropping curry, chocolate, fruit juice, etc., thereto at the time of eating on drinking by using a specific pullulanase, a specific soap, and a specific surfactant. CONSTITUTION:This detergent compsn. comprises alkaline (acidic) pullulanase having an alpha-amylase activity which is manifested against soluble starch at the optimum pH of pref. 8 to 11; 0.01-5wt.% soap (e.g. tallow soap) having 8-22C (un)satd. fatty acids neutralized in an amt. of 60 to 100mol%; and 0.5-60wt.% surfactant (e.g. sodium linear-alkyl-benzenesulfonate) other than the soap.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a detergent composition for clothes which is effective against spilled food stains such as curry.

[0002]

2. Description of the Related Art It has been practiced for a long time to incorporate an enzyme into a detergent, and by incorporating an enzyme into the detergent, excellent detergency can be obtained. The enzyme generally used as a cleaning aid is protease, lipase, cellulase, or α-amylase.

[0003] The present inventors have also previously reported that pullulanase,
It has been found that by adding isopululanase and isoamylase to the detergent, the detergent can be effectively acted on the starchy dirt typified by cooked rice firmly adhered to tableware, fibers, etc. to improve the detergency. Kaihei 2-132192 publication,
JP-A-2-132193). However, such a technique is effective against starchy stains typified by cooked rice, and is sufficiently effective against stain stains caused by spilled food such as curry, meat sauce, ketchup, chocolate and fruit juice. Was not.

The so-called stain stain due to spilled food is a stain that has been a concern in the past, and is known as a stain that does not come off even after washing several times. However, the present situation is that no detergent composition has been found that exhibits a sufficient cleaning effect against these stains and stains.

[0005]

[Means for Solving the Problems] The inventors of the present invention have conducted intensive studies on a detergent for clothes which is effective against spilled food stains which are difficult to remove by the conventional techniques, and as a result, an alkali having an α-amylase activity has been obtained. Alternatively, it has been found that a detergent composition having an excellent cleaning effect against spilled food stains can be obtained by blending alkali-resistant pullulanase and soap, and completed the present invention.

That is, the present invention provides the following components (a), (b) and
The present invention provides a detergent composition for clothing, which comprises (c). (a) Alkali- or alkali-resistant pullulanase having α-amylase activity (b) Saturated or unsaturated fatty acid having 8 to 22 carbon atoms
100 mol% neutralized soap 0.01 to 5% by weight (c) Surfactant other than the above (b) 0.5 to 60% by weight.

The (a) alkali or alkali-resistant pullulanase which can be used in the present invention is described in, for example, JP-A-3-290498.
Bacillus sp. KSM-AP
The alkaline pullulanase produced by 1378 (FERM P-10886) can be mentioned, and this enzyme has the following enzymatic properties.

1) Action It acts on pullulan and soluble starch, and mainly forms maltotriose from pullulan and mainly maltotetraose and maltopentaose from soluble starch.
It also acts on glycogen to produce maltotetraose and maltopentaose. 2) Substrate specificity It acts on pullulan, soluble starch and glycogen. 3) Working pH and optimum working pH The working pH for pullulan is in the range of 5 to 12, and the optimum working pH is in the range of 8.5 to 10. The working pH for the soluble starch is in the range of 4 to 12, and the optimum working pH is in the range of 8 to 11. The optimum working pH is measured by the method described in JP-A-3-290498. 4) pH stability It is stable to pullulan in the range of pH 6 to 10.5 and stable to soluble starch in the range of pH 4 to 12 (45
℃, 10 minutes treatment). 5) Working temperature range and optimum working temperature It acts on pullulan and soluble starch in the range of 10 to 65 ° C, and the optimum working temperature is about 50 ° C. 6) Temperature stability It is extremely stable up to 45 ° C (10 mM glycine-pH 9.5-
Treatment with salt-sodium hydroxide buffer for 30 minutes). 7) Molecular weight The molecular weight by sodium dodecyl sulfate (SDS) electrophoresis is 200,000 ± 5,000. 8) Effect of metal ions Pullulanase activity is inhibited by Hg ²⁺ , Mn ²⁺ and Pb ²⁺ . In addition, α-amylase activity is Hg ²⁺ , Mn ²⁺ , Pb ²⁺ , Zn ²⁺ , Cd
^Inhibited by ²⁺ .

In addition to these, there are the following properties. 9) Effects of surfactants Various interfaces such as sodium linear alkylbenzene sulfonate, sodium polyoxyethylene alkyl sulfate ester, sodium α-olefinsulfonate, α-sulfonated fatty acid ester, SDS, soap, and Softanol (registered trademark) Treatment with a 0.05% solution of the activator at 40 ° C for 15 minutes shows almost no activity inhibition. 10) Effect of chelating agent The chelating agents EDTA (10 mM) and EGTA (10 mM) hardly inhibit the pullulanase activity, but significantly inhibit the α-amylase activity. Further, the α-amylase activity inhibited by the chelating agent is restored by adding Ca ²⁺ again. 11) Protease resistance Maxatase (IBIS) and Sabinase (Novo)
Even if an alkaline protease such as coexistent is present at the time of activity measurement, it has strong resistance to any protease.

In the present invention, the alkali or alkali-resistant pullulanase having α-amylase activity is generally supplied in the form of granules and is usually contained in the composition in an amount of 0.1 to 20% by weight, preferably 0.1 to 15% by weight. .

When the detergent composition of the present invention is used for washing, the enzymatic activity of the alkaline or alkaline-resistant pullulanase having α-amylase activity in the washing solution against the soluble starch is DNS (3,5- Dinitrosalicylic acid) activity value of 10 units / g or more (1 per minute)
It is preferable to use the detergent composition of the present invention so that the amount of enzyme that produces μmol of glucose is 1 unit (U), preferably 100 units / g or more.

The method for measuring the enzyme activity of soluble starch by the DNS method is shown below. (1) Substrate: 0.5 wt% Potato-derived soluble starch (reagent, Sigma) solution (2) Preparation of substrate solution 1.0 g of potato-derived soluble starch is dissolved in 100 ml of ion-exchanged water. (3) Preparation of sample Add 0.5 ml of the substrate solution to a test tube and put 100 mM Glycine-
0.4 ml of NaOH buffer solution (pH = 10.0) and 0.1 ml of appropriately diluted enzyme solution are added, and the reaction is carried out in a constant temperature bath at 50 ° C for 15 minutes. After completion of the reaction, 1 ml of a DNS solution is added, color is developed in boiling water for exactly 5 minutes, and immediately after color development, the mixture is put in an ice water bath and cooled. After cooling, add 4 ml of deionized water, mix well, and immediately measure the absorbance at 535 nm. (4) Preparation of blank Put 0.5 ml of the substrate solution into a test tube and put 100 mM Glycine-
0.4 ml of a NaOH buffer solution (pH = 10.0) and 1 ml of a DNS solution are added thereto, and the color is developed in boiling water for exactly 5 minutes. Immediately after the color development, it is put in an ice-water bath and cooled. After cooling, add 4 ml of deionized water, mix well, and immediately measure the absorbance at 535 nm. (5) Preparation of calibration curve Put 0.5 ml of substrate solution into a test tube and put 100 mM Glycine-
Add 0.4 ml of NaOH buffer (pH = 10.0), and add 0.1 ml of glucose solution for calibration curve so that the concentration of glucose will be 250-1500 µmol / l. 1 ml of a DNS solution was added thereto, and the color was developed in boiling water for exactly 5 minutes. After cooling, add 4 ml of deionized water,
Mix well and measure the absorbance at 535 nm immediately. The glucose concentration is plotted on the abscissa and the absorbance is plotted on the ordinate to obtain the slope, and the conversion factor (F) is calculated as follows. F = 1 / (slope) × 1/15 × 1 / 0.1 (6) Calculation of activity The enzyme activity is calculated by the following formula. Activity (U / L) = δ absorbance x F x dilution ratio δ absorbance = (sample absorbance)-(blank absorbance) (7) Preparation of DNS reagent (1 L) Sodium hydroxide 16 g is dissolved in ion-exchanged water 200 ml. To do. To this, 5 g of DNS is gradually added and dissolved.
After the DNS is completely dissolved, 300 g of sodium potassium tartrate is added. After completely dissolving, make up to 100 ml with deionized water.

The soap as the component (b) used in the detergent composition for clothes of the present invention has 8 to 22 carbon atoms, preferably
It is obtained by neutralizing 60 to 100 mol% of 12 to 20 saturated or unsaturated fatty acids, and two or more kinds can be mixed and used. The component (b) is incorporated in the entire detergent composition in an amount of 0.01 to 5% by weight, preferably 0.05 to 3% by weight. If the content of the component (b) is 0.01% by weight or less, a sufficient cleaning effect cannot be obtained, and if it is 5% by weight or more, the enzyme activity decreases, which is not preferable.

Incorporated in the detergent composition for clothes of the present invention
The surfactant as the component (c) is a non-soap surfactant other than the component (b), and examples of the surfactant as the component (c) include the following.

As the anionic surfactant, 1. A linear or branched alkylbenzene sulfonate having an alkyl group having an average carbon number of 10 to 16. 2. It has a linear or branched alkyl or alkenyl group having an average carbon number of 10 to 20, and has an average of 0.5 to 8 mol of ethylene oxide or propylene oxide or butylene oxide or ethylene oxide in one molecule.
Propylene oxide = 0.1 / 9.9 to 9.9 / 0.1 ratio or ethylene oxide / butylene oxide =
Alkyl or alkenyl ether sulfate added in a ratio of 0.1 / 9.9 to 9.9 / 0.1. 3. An alkyl or alkenyl sulfate having an alkyl group or an alkenyl group having an average carbon number of 10 to 20. 4. An olefin sulfonate having an average of 10 to 20 carbon atoms in one molecule. 5. An alkanesulfonate having an average of 10 to 20 carbon atoms in one molecule. 6. It has an alkyl group or an alkenyl group having an average carbon number of 10 to 20, and has an average of 0.5 to 8 mol of ethylene oxide or propylene oxide or butylene oxide or ethylene oxide / propylene oxide = 0.1 / 9.9 to 9.9 / 0.1 per molecule. Or ethylene oxide / butylene oxide = 0.1 / 9.9 to 9.9
Alkyl or alkenyl ether carboxylates added in a ratio of /0.1. 7. An α-sulfo fatty acid or ester represented by the following formula.

[0016]

[Chemical 1]

(In the formula, Y is an alkyl group having 1 to 3 carbon atoms or a counter ion, Z is a counter ion. R is an alkyl group or an alkenyl group having 10 to 20 carbon atoms.) Here, anionic property As the counterion of the surfactant, alkali metal ions such as sodium and potassium, calcium,
Examples thereof include alkaline earth metal ions such as magnesium, ammonium ions, and alkanolamines having 1 to 3 alkanol groups having 2 or 3 carbon atoms (for example, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.). .

As the nonionic surfactant, 8. A polyoxide ethylene alkyl or alkenyl ether having an alkyl group or an alkenynyl group having an average carbon number of 10 to 20, to which 1 to 20 mol of ethylene oxide is added. 9. A polyoxyethylene alkyl phenyl ether having an alkyl group having an average carbon number of 6 to 12, to which 1 to 20 mol of ethylene oxide is added.

10. A polyoxypropylene alkyl or alkenyl ether having an alkyl or alkenyl group having an average carbon number of 10 to 20 and having 1 to 20 mol of propylene oxide added thereto. 11. A polyoxybutylene alkyl or alkenyl ether having an alkyl or alkenyl group having an average carbon number of 10 to 20 and having 1 to 20 mol of butylene oxide added thereto. 12. A nonionic activator having an alkyl group or an alkenyl group having an average carbon number of 10 to 20 and a total of 1 to 30 moles of ethylene oxide and propylene oxide or ethylene oxide and butylene oxide added (ethylene oxide and propylene oxide or butylene. The ratio with oxide is 0.1 / 9.9 to 9.9 / 0.1). 13. A higher fatty acid alkanolamide having an average carbon number of 10 to 20 or an alkylene oxide adduct thereof. 14. Sucrose fatty acid ester consisting of sucrose and fatty acid having an average carbon number of 10 to 20. 15. Fatty acid glycerin monoester consisting of fatty acid having an average carbon number of 10 to 20 and glycerin. 16. Alkyl amine oxide.

Further, as other surfactants, 17. Amphoteric surfactants such as carboxybetaine or sulfobetaine type surfactants. 18. Other cationic surfactants. Can also be mentioned.

Of the above-mentioned surfactants, 1,2,4,5,8,9,10,11,12,13 are particularly preferable in the present invention.
It is desirable to use 1, 2, 3, 8 as the main surfactant. Incidentally, the main surfactant refers to one which accounts for 40% by weight or more in the total surfactant. In the present invention
The blending amount of the component (c) in the composition is the total amount.
The amount is 0.5 to 60% by weight, preferably 10 to 50% by weight.

The cleaning composition of the present invention also includes a carbonate,
It is desirable to incorporate at least one inorganic salt selected from silicates. Examples of these inorganic salts include sodium carbonate, potassium carbonate and sodium silicate. These inorganic salts are incorporated in the composition in an amount of 1 to 30% by weight, preferably 10 to 30% by weight.

In addition to the above-mentioned components, the detergent composition of the present invention contains crystalline or amorphous aluminosilicate such as zeolite, ethylenediaminetetraacetic acid, succinate, malate and citrate. It is desirable to incorporate the divalent metal ion scavenger. By incorporating the divalent metal ion scavenger, the cleaning property in hard water is improved. The divalent metal ion scavenger is preferably incorporated in the detergent composition of the present invention in a total amount of 10 to 60% by weight.

As other components, a bleaching agent such as sodium percarbonate or sodium perborate, a stabilizer thereof, a bleaching activator, carboxymethyl cellulose, polyacrylic acid or a carboxyl group of a maleic anhydride polymer or copolymer. Water-soluble salts of acid-based polymers, recontamination inhibitors such as polyethylene glycol and polyvinylpyrrolidone, porous oil-absorbing carriers such as amorphous silica, enzymes other than the enzyme of the present invention such as protease, lipase, cellulase, sulfite Enzyme deactivators such as, fluorescent dyes, pigments, anti-caking agents, solubilizers, and fragrances are added as necessary.

The form of the detergent composition for clothing of the present invention is not particularly limited, such as powder and liquid, but when it is a high density powder detergent composition, it is disclosed in JP-A-61-69897 and JP-A-61-897. 69891
No. 61-69900, and European Patent No. 513824. Here, the high density means a bulk density of 0.6 to 1.2 g / ml, preferably 0.7 to 0.9 g / ml, and the method of measuring the bulk density is according to JIS K 3362.

[0026]

EFFECTS OF THE INVENTION According to the present invention, there is provided a detergent composition for clothes which has a significantly improved cleaning power for stain stains due to spilled curry, meat sauce, ketchup, chocolate, fruit juice, etc. within a normal cleaning time. can get.

[0027]

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

1) Preparation of artificially contaminated curry cloth Bon Curry Gold Spicy (registered trademark, Otsuka Foods Co., Ltd.)
Is crushed with a mixer, and a cotton cloth is brought into contact with this liquid and brushed to remove excess adhered dirt. A 10 cm × 10 cm test piece was prepared and used for the experiment.

2) Washing conditions, washing method and evaluation method A high-density (0.7-0.9 g / ml) powder detergent or liquid detergent having the composition shown in Table 1 or Table 2 was dissolved in 4 ° DH hard water, Prepare 1 liter of 0.0833% detergent solution. Add 5 sheets of curry artificially contaminated cloth to the detergent aqueous solution, leave it at 30 ° C for 10 minutes, then transfer the detergent solution and artificially contaminated cloth as it is to a stainless beaker for a targotometer, and use a tergotometer at 100 rpm, 20 ° C. Stir for 10 minutes. After rinsing under running water, it was ironed and pressed for reflectance measurement. The cleaning rate was calculated according to the following formula.

460n of original cloth before cleaning and contaminated cloth before and after cleaning
Color meter for reflectance at m (manufactured by Shimadzu Corporation)
And the cleaning rate (%) was calculated by the following formula.

[0031]

[Equation 1]

Tables 1 and 2 show the average values for 5 sheets of soiled cloth. The pH of the detergent solution before washing is 10.6.
Met.

3) Results As shown in Table 1 or Table 2, it is understood that curry stains can be effectively washed by incorporating an alkali or alkali-resistant pullulanase having α-amylase activity.

[0034]

[Table 1]

Note) 1) Alkaline pullulanase: Bacillus sp. KSM-AP1378
(Microtechnology Research Institute, No. 10886) Producing enzyme, specific activity: 2000U /
g 2) Soap: 12 to 14 carbon atoms, 100% neutralization degree 3) Zeolite: A type synthetic zeolite (average particle size 0.9 μm)
) 4) Nonionic surfactant: polyoxyethylene alkyl ether (average number of moles of ethylene oxide added = 8, alkyl chain length = 12) 5) Ionic surfactant: straight chain sodium alkylbenzene sulfonate, C _{12 to} C ₁₆ 6) Ionic surfactant: sodium alkylsulfate, C
_{12 to} C ₁₄ 7) Average molecular weight 8000 8) Average molecular weight 13000 9) Oil absorbing carrier: Tokseal NR (registered trademark, Tokuyama Soda Co., Ltd.) 10) Optical brightener: Chinopearl CBS (registered trademark, Ciba Geigy)

[0036]

[Table 2]

1) Alkaline pullulanase: Bacillus sp. K
SM-AP1378 (Ministry of Microbiology and Biotechnology No. 10886) Producing enzyme, specific activity: 2000 U / g 2) Beef tallow soap: 12 to 14 carbon atoms, 100% neutralization degree 3) Nonionic surfactant: polyoxyethylene alkyl Ether (average number of moles of ethylene oxide added = 7, alkyl chain length = 12 to 14) 4) Ionic surfactant: sodium polyoxyethylene alkylsulfate (average number of moles of ethylene oxide added = 2.
5, alkyl chain length = 12-14) 5) Average molecular weight 8000 6) Optical brightener: Chinopearl CBS (registered trademark, Ciba Geigy)

Claims (2)

[Claims] 1. A detergent composition for clothes, which comprises the following components (a), (b) and (c): (a) Alkali- or alkali-resistant pullulanase having α-amylase activity (b) Saturated or unsaturated fatty acid having 8 to 22 carbon atoms
100 mol% Neutralized soap 0.01-5% by weight (c) Surfactants other than the above (b) 0.5-60% by weight 2. Optimal action of alkali or alkali-resistant pullulanase having α-amylase on soluble starch.
The detergent composition for clothes according to claim 1, which has a pH of 8-11.