JPH1095996A - Bleaching detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of exhibiting excellent bleaching performances on spots and stains such as curry, by combining an amylase to hydrolyze a starch with a specific bleaching activator. SOLUTION: This composition comprises (A) a substance (e.g. a percarbonate or a perborate) to release hydrogen peroxide in water, (B) a bleaching activator which is a compound of the formula (R is a 8-15C straight-chain alkyl; Y is a carboxylate or a sulfonate, especially potassium sulfonate or sodium sulfonate) and (C) an amylase such as α-amylase or β-amylase [preferably one mixed with a starch dedranching enzyme such as pullulanase or isoamylase]. Preferably, the composition comprises 1-95wt.% of the component A, the component B in an amount to give the weight ratio of the components A:B 100:1 to 1.5:1 and 0.1-50 units of the component C in 1g of the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bleaching detergent composition which exhibits an excellent effect on stains containing a large amount of starch such as curry.

[0002]

2. Description of the Related Art Oxygen-based bleaching agents which do not have these drawbacks are not available because chlorine-based bleaching agents are limited in the fibers that can be used, cannot be used in colors and patterns, and have a unique odor. Has recently begun to spread significantly. As the oxygen bleaching agent, sodium percarbonate and sodium perborate are particularly used as bleaching bases in terms of bleaching performance and stability.

However, the oxygen bleaching agent has a weak bleaching power as compared with the chlorine bleaching agent, and various bleaching activators are used in combination. As typical bleaching activators, tetraethylenediamine, acetoxybenzenesulfonate, tetraacetylglycoluril, glucose pentaacetate and the like are used.

Japanese Patent Laid-Open Publication No. Sho 59-22999 discloses hydrogen peroxide and a compound represented by the general formula

[0005]

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(Wherein R is an alkyl group having about 5 to 18 carbon atoms, and the longest linear alkyl chain extending from the carbonyl carbon and containing the carbonyl carbon has 6 to 10;
Wherein L is a leaving group), wherein the bleaching agent is characterized in that the molar ratio of hydrogen peroxide to the bleaching activator produced by the peroxygen bleaching compound is greater than 1.5. ing. The publication states that the bleaching composition provides fabrics with very effective and efficient surface bleaching, thereby removing stains and stains from the fabric.

[0007]

However, in general, stains such as curry generally adhere to cloths in a form in which a pigment that causes stains is covered with components such as starch. Therefore, the bleaching action on the dye was not sufficiently achieved only by the combination of the bleaching activator and the peroxygen bleaching agent, so that satisfactory washing and bleaching results could not be obtained.

[0008]

Therefore, as a result of diligent research, the present researcher has found that a combination of an amylase that degrades starch and a bleach activator having a specific structure exhibits excellent bleaching performance. Was.

That is, the present invention provides (a) a substance which releases hydrogen peroxide in water (b) a bleach activator having the following structural formula

[0010]

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(R: a linear alkyl group having 8 to 15 carbon atoms, Y is a salt of a carboxylic acid or a sulfonic acid) (c) A bleaching detergent composition characterized by containing an amylase It is. Hereinafter, the present invention will be described in detail.

The component (a) in the present invention is a substance which releases hydrogen peroxide in water, and is generally a salt of percarbonate, perborate or perphosphate, preferably percarbonate, perborate. Acid salts, particularly preferably sodium percarbonate.
The amount of component (a) is in the range of 1 to 95% by weight, preferably 10 to 80% by weight, particularly preferably 20 to 60% by weight. Within this range, a sufficient concentration of hydrogen peroxide in the solution can be obtained, and the blending of other components becomes easy.

The component (b) in the present invention has the following structure

[0014]

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A bleaching activator having (R: a linear alkyl group having 8 to 15 carbon atoms, Y is a salt of a carboxylic acid or a sulfonic acid), and a particularly preferred structure is a bleaching activator having the following structure: It is.

[0016]

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(R: a straight-chain alkyl group having 11 to 15 carbon atoms, M is sodium or potassium) In the above general formula, when the carbon number of R is less than 8, the adsorptivity to dirt becomes low, and sufficient performance is obtained. Is not exhibited.
On the other hand, if it is 16 or more, sufficient solubility cannot be obtained under low-temperature washing conditions such as in Japan, and thus sufficient bleaching power cannot be obtained.

In the present invention, the ratio of the substance (a) which releases hydrogen peroxide in water and the bleach activator (b) is
It is preferable that (a) :( b) = 100: 1 to 1.5: 1. Preferably (a) :( b) = 50: 1 to 5: 1, particularly preferably 30: 1 to 7: 1, most preferably 25: 1 to 10: 1.
Range. If the weight ratio exceeds 100: 1, the amount of the bleach activator in the composition is small and sufficient performance cannot be obtained. If the weight ratio is less than 1.5: 1, the concentration of hydrogen peroxide relative to the bleach activator is low. Due to the small amount, the bleaching activating component cannot be converted to an organic peracid, so that bleaching performance cannot be obtained.

In the present invention, an amylase (c) is blended. Amylase is essential for decomposing dirt such as starch. As the amylase, α-amylase, β-amylase
Amylase and the like. As α-amylase, an enzyme obtained from Bacillus licheniformis or Bacillus subtilis is preferable, and as commercial products, termamyl (registered trademark, Novo Industry Co., Ltd.), maxamil (registered trademark, Gist Co., Ltd.) and the like can be mentioned. As β-amylase, enzymes obtained from bacteria such as Bacillus sp., Soybeans, malt, and the like can be used, and as commercial products, Amano (registered trademark Amano Pharmaceutical Co., Ltd.), multitome (registered trademark,
Nagase Seikagaku Corporation).

The amylase desirably contains a starch branching enzyme. Desirable starch debranching enzymes can be obtained from a variety of sources, but are generally derived from fungi. For example, a bacterium belonging to the genus Klebsiella, Baci
Fungi belonging to the genus llus, fungi belonging to the genus Aspergillus, Pseudo
amylopectin obtained from fungi belonging to the genus monas
It is a pullulanase, an isopluranase, or an isoamylase exhibiting 6-glucanohydrase activity. The amount of amylase is 0.1 to 50 units per 1 g of the composition.
Preferably 0.2 to 25 units, particularly preferably 0.5 to 20
Unit. Here, 1 unit / g is the amount of enzyme that produces 1 μmol of glucose per minute,
(3,5-dinitrosalicylic acid). If the amount of the enzyme is less than 0.1 unit, sufficient enzyme activity cannot be obtained and the performance cannot be exhibited. If the amount is more than 50 units, the reducing sugar generated when the amylase degrades the starch kills the organic peracid generated from the bleaching activator, so that the bleaching performance is hardly exhibited.

The method for measuring the enzyme activity by the DNS method is described below. (1) Substrate: 0.5% by weight of 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 Put 0.5 ml of substrate solution into a test tube, and add 100 mM Glycine-
0.4 ml of NaOH buffer (pH = 10.0) and 0.1 ml of an appropriately diluted enzyme solution are added, and the mixture is reacted for 15 minutes in a thermostat at 50 ° C.
After the completion of the reaction, 1 ml of a DNS solution is added, and the color is developed in boiling water for exactly 5 minutes. After cooling, add 4 ml of ion-exchanged water and mix well,
Immediately measure the absorbance at 535 nm. (4) Preparation of blank Add 0.5 ml of the substrate solution to a test tube, and add 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. After the color is developed, it is immediately placed in an ice water bath and cooled. After cooling, add 4 ml of ion-exchanged water, mix well, and immediately measure the absorbance at 535 nm. (5) Preparation of calibration curve Place 0.5 ml of the substrate solution in a test tube, and add 100 mM Glycine-
Add 0.4 ml of NaOH buffer (pH = 10.0) and 0.1 ml of glucose solution for the calibration curve so that the glucose concentration is 250-1500 μmol / l. 1 ml of a DNS solution is added thereto, and the color is developed in boiling water for exactly 5 minutes. After the color is developed, it is immediately placed in an ice water bath and cooled. After cooling, add 4 ml of ion-exchanged water,
Mix well and immediately measure absorbance at 535 nm. The gradient is determined by taking the glucose concentration on the horizontal axis and the absorbance on the vertical axis, and the conversion coefficient (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) = σ absorbance × F × dilution ratio σ absorbance = (absorbance of sample) − (absorbance of blank) (7) Preparation of DNS reagent (for 1 L) Transfer 16 g of sodium hydroxide to 200 ml of ion-exchanged water Dissolve. This is dissolved while gradually adding 5 g of DNS.
After complete dissolution of the DNS, 300 g of sodium potassium tartrate are added. After complete dissolution, make up to 100 ml with ion exchanged water.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The bleaching detergent composition of the present invention is described above.
It contains the components (a) to (c) as essential components, and is in the form of powder or granules.

The bleaching detergent composition of the present invention comprises the above (a)
The following components can be used in combination with the components (c) to (c). In particular, the bleaching detergent composition of the present invention desirably contains (d) a protease. Examples of proteases include Alcalase, Savinase (both from Novo Nordic), API-21 (Showa Denko KK), and Maxacal (Gyst Procaides). Preferably Baci
llus sp. and produced by fungi derived from, for example, alkaline protease K described in JP-A-5-25492.
-14 (Bacillus.sp KSM-14 (Microorganisms No. 12587) and alkaline protease K-16 (Bacillus.sp KSM-16 (
No. 11418). As a compounding amount, the enzyme activity is 0.1 to 1000 APU / L, preferably 1 to 100 APU / L.
L, and a specific compounding amount occupying in the composition is 0.01 to 5% by weight, preferably 0.05 to 2% by weight, particularly preferably 0.1 to 1% by weight. here,
The method for measuring the enzyme activity of the protease is the Anson-hemoglobin method [Anson. M. L. J. Gen. Phys
siol . , Vol. 22, p79 (1938)]. That is, after a reaction was performed for 10 minutes at a temperature of 25 ° C. and a pH of 10.5 in a solution prepared so that the final concentration of urea-denatured hemoglobin used as a substrate was 14.7 mg / ml, trichloroacetic acid was added to the final concentration of the reaction solution. 31.25 mg
/ Ml, and color the soluble portion of trichloroacetic acid with a phenol reagent. The activity per 10 minutes of the reaction is determined from a calibration curve in which the coloration of 1 mmol of tyrosine is 1 APU, and the activity is measured per minute. Therefore, in the present invention, 1 APU
The term “alkaline protease” means the amount of a trichloroacetic acid-soluble component having the same color degree as that of 1 mmol of tyrosine colored by a phenol reagent in one minute.

The components to be added to the bleaching detergent composition of the present invention include, for example, a surfactant, a chelating agent,
Examples include alkaline agents, fluorescent dyes, high molecular polymers, and fragrances. Examples of the surfactant include an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, and a cationic surfactant. Among them, an anionic surfactant and a nonionic surfactant are preferable, and an alkylbenzene is particularly preferable. Sulfonate, alkyl sulfate, alkyl ester sulfate,
And ethylene oxide-added nonionic surfactants. Aluminosilicates (for example, 4A
Zeolite), a crystalline alkali metal silicate [eg, SKS-6 (Hoechst)], or citric acid, succinic acid, maleic acid or a salt thereof. Examples of the alkaline agent include soda ash, tripolyphosphate, and orthophosphate. It is desirable to blend a high molecular weight polymer because it has a high effect of dispersing dirt and preventing re-staining. Examples thereof include polyacrylic acid having a molecular weight of 2,000 to 100,000, an acrylic acid-maleic acid copolymer, polyethylene glycol, carboxymethyl cellulose and the like.

[0025]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the examples.

Example 1 (1) Synthesis of bleach activator The bleach activators (a) to (c) shown in Table 1 were synthesized by the following method. Bleaching activator (a) Sodium p-phenolsulfonate previously dehydrated
100 g (0.46 mol) of dimethylformamide (DMF) 300 g
Then, lauric chloride is added dropwise at 50 ° C. over 30 minutes while stirring with a mechanical stirrer, and after completion of the addition, an aging reaction is performed for 3 hours. DMF under reduced pressure (0.5-1mmH
g), distilled off at 100 ° C., washed with acetone, and recrystallized in a water / acetone (1/1 mol) solvent. The yield was 85%.

Bleaching activator (b) Myristate chloride was used in place of lauric chloride in the same synthesis method as described above. The yield was 75%.

Bleaching activator (c) Dehydrated sodium p-phenolcarboxylate was used in place of sodium p-phenolsulfonate in the same manner as described above. The yield was 65%.

[0029]

[Table 1]

(2) Bleaching and washing test Preparation of curry-contaminated cloth Commercial curry [Bon curry, Otsuka Food Industry Co., Ltd.] 200
g through a coarse sieve to remove the utensil. The filtered curry roux added 50 g of ion-exchanged water to 100 g of the curry roux,
Stir well to make curry liquid. Next, a pre-treated cotton cloth (2003 cloth, cloth rinsed 5 times with a washing machine) was used.
Cut into 10cm x 10cm, put 1g of curry liquid on a piece of cotton cloth, and spread it evenly. The cloth is allowed to dry for one day.

Washing Bleaching Experiment Various cleaning compositions were prepared from the bleaching activator shown in Table 1 and the components shown in Tables 2 to 4 to prepare a bleaching bath having a concentration of 0.5%. Put 5 pieces of each of the curry-stained cloths prepared above in a bleaching bath and stir well every 5 minutes. The bleaching time is one hour. At this time, the evaluation is performed at a constant temperature of 35 ° C. After one hour, the contaminated cloth is taken out, rinsed with running water for one minute, and press-dried. Thereafter, the washing bleaching ratio was calculated by the following equation. The results are shown in Tables 2 to 4. The reflectance was measured at a wavelength of 460 nm using a self-recording colorimeter (manufactured by Shimadzu Corporation).

[0032]

(Equation 1)

[0033]

[Table 2]

[0034]

[Table 3]

[0035]

[Table 4]

(Note) Those with * added to the test No. are comparative products. 1): Activity 7000 U / g, manufactured by Novo Industries 2): Activity 2000 U / g, manufactured by Amano Pharmaceutical 3): Bacillus sp.KSM-AP1876
No.), activity 2000 U / g 4): Bacillus sp.KSM-K16 (No.
1.87 PU / mg activity, purified according to the reference example of JP-A-5-25492. 5): Polyoxyethylene (average number of moles added: 6) alkyl
(C ₁₂ -C ₁₄₎ ether 6): acrylic acid - maleic acid copolymer, average molecular weight 7000
0, BASF 7): crystalline alkali metal silicate, Hoechst

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C11D 3/395 C11D 3/395 7/18 7/18 7/26 7/26 7/34 7/34 7/42 7/42 D06L 3/02 D06L 3/02 (72) Inventor Masakazu Furukawa 1334 Minato 1334 Minato, Wakayama City, Wakayama Pref. (72) Inventor Muneo Aoyagi 1334 Minato 1334 Minato, Wakayama Pref.

Claims (6)

[Claims] (1) a substance which releases hydrogen peroxide in water (b) a bleaching activator having the following structural formula: (R: a linear alkyl group having 8 to 15 carbon atoms, Y is a salt of a carboxylic acid or a sulfonic acid) (c) A bleaching detergent composition containing an amylase. 2. The bleaching detergent composition according to claim 1, wherein the bleach activator (b) has the following structural formula. (R: a linear alkyl group having 11 to 15 carbon atoms, M is sodium or potassium) 3. The bleaching detergent composition according to claim 1, wherein the amylase (c) is α-amylase or β-amylase. 4. The bleaching detergent composition according to claim 1, wherein the amylase (c) contains one or more branching enzymes of pullulanase, isopluranase and isoamylase. 5. The ratio of the substance (a) releasing hydrogen peroxide in water to the bleach activator (b) is (a) :( b) = 100: 1 to 1.
The bleaching detergent composition according to any one of claims 1 to 4, which is in the range of 5: 1. 6. The bleaching detergent composition according to claim 1, further comprising (d) a protease.