JPH06172792A - Detergent composition for clothes - Google Patents

Abstract

PURPOSE:To obtain a detergent composition effective for removing a stain of food such as curry by mixing a specified starch side chain-hydrolyzing enzyme with a noionic surfactant and an alkylbenzenesulfonate. CONSTITUTION:This detergent composition is prepared by mixing at least one starch side chain-hydrolyzing enzyme (a) selected from among pullulanase, isopullulanase and isoamylase with a nonionic surfactant (b) and an alkylbenzenesulfonate (c) having linear or branched 10-20C alkyl in amounts to give a total of components (b) and (c) of 5-40wt.% and a (b) to (c) weight ratio of 1/50 to 1/3. This composition is markedly improved in the power of deterging a stain of food such as curry, meat sauce, ketchup, chocolate or fruit juice within a usual washing time.

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 extensive studies on a detergent for clothes which is effective against spilled food stains which were difficult to remove by the conventional techniques, and as a result, starch debranching enzymes such as pullulanase have been found. In addition, it was found that by adding a nonionic surfactant and an alkylbenzene sulfonate at a specific ratio, a cleaning composition having an excellent cleaning effect against spilled food can be obtained, and the present invention was completed. Came to do.

That is, the present invention provides the following components (a), (b) and
(c) (a) One or more starch debranching enzymes selected from the group consisting of pullulanase, isopullulanase and isoamylase.

(B) Nonionic surfactant (c) A straight-chain or branched-chain alkylbenzene sulfonate containing an alkyl group having a carbon chain of 10 to 20, and the above-mentioned components (b) and (c) Is 5 to 40% by weight, and (b)
/ (C) The weight ratio is 1/50 to 1/3, and a detergent composition for clothes is provided.

The component (a) of the present invention, pullulanase, isopullulanase and isoamylase, are involved in the decomposition of starch like α-amylase, but α-amylase is a sugar chain in amylose and amylopectin. Α
-1,4 bond is cleaved, whereas pullulanase and isoamylase cleave α-1,6 bond of sugar chain in amylopectin, and isopululanase cleaves α-1,6 bond near α-1,6 bond of sugar chain.
Known as an enzyme that selectively cleaves 1,4 bonds,
That is, it differs from α-amylase in that it cleaves the branched chain in amylopectin. Starch debranching enzyme is EYCLee
and WJ Whelan, “Glycogen and Starch Debranching
Enzymes in the Enzymes "Vol.5 (PDBoyer ed.) Pp19
2-234, Academic Press, New York. Defined as a feature of plant-derived pullulanase (R enzyme),
When an enzyme that specifically cleaves α-1,6 bond acts on amylopectin, the viscosity decreases, the iodine coloration increases, and the reducing power increases.

The above starch debranching enzyme used in the present invention is obtained from various sources, but is generally derived from fungi. Suitable starch debranching enzymes are pullulanase and isolanase showing amylopectin-6-glucanohydrase activity obtained from bacteria belonging to the genus Klebsiella, bacteria belonging to the genus Bacillus, bacteria belonging to the genus Aspergillus, bacteria belonging to the genus Pseudomonas. They are pullulanase and isoamylase.

The starch debranching enzyme according to the present invention may be a commercially available product. As commercially available pullulanase, "Sprentase" (registered trademark, Amano Pharmaceutical Co., Ltd.), "Promozyme 200L" (registered trademark, Novo Industry), and as isoamylase, "isoamylase" (reagent, raw Chemical Industry Co., Ltd., etc.

These starch debranching enzymes are generally supplied in the form of granules, the enzyme activity of which is about 10 ³ to 10 ⁸ units / g. In the present invention, a starch debranching enzyme which exhibits an optimum action in alkaline, particularly at pH 8 to 11, is preferable, and alkaline pullulanase is particularly preferable. As alkaline pullulanase, Bacillus sp. KSM-AP1876
No.) is available. The optimum working pH is as described in JP-A-3-87.
It is measured by the method described in No. 176.

The starch debranching enzyme according to the present invention is usually added to the composition in a total amount of 0.1 to 10% by weight. When the detergent composition of the present invention is used for washing, the enzyme activity in the washing solution is 10 units / g or more (1 μmol glucose per minute for glucose) as an activity value by the DNS (3,5-dinitrosalicylic acid) method. It is preferable to use the detergent composition of the present invention so that the amount of enzyme produced is 1 unit (U)), preferably 100 units / g or more.

The method for measuring the enzyme activity 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-
Add 0.4 ml of NaOH buffer solution (pH = 10.0) and 0.1 ml of appropriately diluted enzyme solution, and incubate 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,
Promptly 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-
0.4 ml of NaOH buffer solution (pH = 10.0) is added to this, and 0.1 ml of glucose solution for calibration curve is added so that the glucose concentration becomes 250-1500 μmol / l. 1 ml of DNS solution there
After the addition, the color is developed in boiling water for exactly 5 minutes, and immediately after the color development, it is put in an ice-water bath and cooled. After cooling, ion-exchanged water 4
Add ml, mix well, and immediately measure the absorbance at 535 nm. 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 component (b) nonionic surfactant used in the present invention is a linear or branched aliphatic alcohol having 8 to 22 carbon atoms, and ethylene oxide or propylene oxide per mole of the alcohol. Average 5 to 30
It is preferable to add 8 to 20 moles of ethylene oxide on average. Further, a mixture of these can be used, and in that case, the average carbon number of the alkyl chain is preferably 8 to 22, and particularly preferably 12 to 18. Such a nonionic surfactant is usually added to the detergent composition in an amount of 0.5 to 15% by weight, preferably 1 to 10% by weight. In addition to the aliphatic alcohol ethylene oxide and propylene oxide adduct, polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan fatty acid ester as a nonionic surfactant,
Small amount of polyoxyethylene sorbit fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, glycerin fatty acid ester, higher fatty acid alkanolamide, alkyl glycoside, alkylamine oxide, etc. You may.

The alkylbenzene phonate as the component (c) of the present invention has an alkyl chain having 10 to 20 carbon atoms, preferably 12 to 14 carbon atoms, and alkali metals such as sodium and potassium, calcium and magnesium. Alkaline earth metal salts such as, preferably alkali metal salts.

In the present invention, the total of the above components (b) and (c) is 5 to 40% by weight, preferably 20 to 40% by weight, and the (b) / (c) weight ratio is 1 / It should be in the range of 50 to 1/3. 40% by weight of component (b) and component (c) in total
Even if the amount exceeds the above range, the effect does not change effectively, so that the degree of freedom of the combination is impaired, which is not preferable. If it is less than 5% by weight, this effect cannot be obtained regardless of the addition of the component (a).
The same applies to the weight ratio of the component (b) and the component (c), and if the ratio is other than the above, the effect on stain stains is not sufficiently exerted regardless of the addition of the enzyme.

There are no particular restrictions on the other ingredients commonly used in the detergent composition of the present invention, which may be arbitrarily selected according to the intended use and purpose. For example, in addition to the above components, anionic surfactants such as alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, α-olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or Alkenyl ether carboxylate, α-sulfo fatty acid salt or ester, amino acid type surfactant, N-acyl amino acid type surfactant, alkyl or alkenyl acid phosphate ester,
An alkyl or alkenyl phosphate ester or salt thereof, etc., and a carboxy or sulfobetaine type surfactant etc. can be blended as an amphoteric surfactant. Further, potassium and sodium are preferable as these counterions, but calcium, magnesium and the like can be used as the alkyl or alkenyl ether sulfate. The total amount of the surfactants in the composition is 5 to 60% by weight including the component (b), and the surfactant of the component (c) is contained in the total amount of the surfactants.
Must account for 40% or more.

The detergent composition of the present invention also includes a carbonate salt,
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, bleaching agents such as sodium percarbonate and sodium perborate, stabilizers thereof, bleaching activators, carboxymethyl cellulose, polyacrylic acid and carvone of maleic anhydride polymer or copolymer. Water-soluble salts of acid-based polymers, recontamination inhibitors such as polyethylene glycol and polyvinylpyrrolidone, enzymes such as protease, lipase and cellulase, enzyme deactivation inhibitors such as sulfites, fluorescent dyes, pigments, anti-caking agents, solubilizers Agents, fragrances, etc. are added as necessary.

[0021]

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.

[0022]

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 an 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 detergent having the composition shown in Table 1 is dissolved in 4 ° DH hard water to prepare 1 liter of 0.0833% detergent solution. Add 5 pieces of curry artificially contaminated cloth to the detergent 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 tergotometer, and use a tergotometer.
Wash with stirring at 100 rpm and 20 ° C 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.

[0026]

[Equation 1]

Table 1 shows the average values for 5 sheets of soiled cloth. The pH of the aqueous detergent solution before washing was 10.6.

3) Results As shown in Table 1, it is understood that curry stains can be effectively cleaned by incorporating pullulanase.

[0029]

[Table 1]

Note) 1) Alkaline pullulanase: Bacillus sp. KSM-AP1876
(Microtechnology Research Institute No. 10887) Producing enzyme, specific activity 2000 U / g 2) Nonionic surfactant: polyoxyethylene dodecyl ether (average number of moles of ethylene oxide added = 8, alkyl chain length = 20) 3) Non Ionic surfactant: polyoxyethylene dodecyl ether (average number of moles of ethylene oxide added = 20, alkyl chain length = 20) 4) Zeolite: A type synthetic zeolite (average particle size 0.9 µm
) 5) ionic surfactant: linear alkyl (C ₁₂ -C ₁₆₎ sodium benzenesulfonate 6) ionic surfactants: sodium alkyl sulfate, C ₁₂
~ C ₁₆ 7) Average molecular weight 8000 8) Average molecular weight 13000 9) Sumitomo Chemical Co., Ltd.

Claims (3)

[Claims] 1. One or more starch debranching enzymes selected from the group consisting of the following components (a), (b) and (c) (a) pullulanase, isopullulanase and isoamylase. (b) a nonionic surfactant (c) containing a linear or branched alkylbenzene sulfonate having a carbon chain of an alkyl group of 10 to 20, and the total of the components (b) and (c) is 5-40% by weight, and (b)
/ (C) A detergent composition for clothing, characterized in that the weight ratio is 1/50 to 1/3. 2. The nonionic surfactant has 8 to 22 carbon atoms.
The detergent composition for clothes according to claim 1, which is obtained by adding 5 to 30 mol of ethylene oxide or propylene oxide to 1 mol of the linear or branched aliphatic alcohol. 3. The detergent composition for clothes according to claim 1, wherein the optimum action pH of the starch debranching enzyme on the soluble starch is 8 to 11.