JPH1072597A - Liquid oxygen bleaching composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid oxygen bleaching compsn. which exhibits a high bleaching power and a long-lasting bleaching activity. SOLUTION: This compsn. contains 0.01-30wt.% hydrogen peroxide, 0.01-30wt.% boron compd., 0.01-30wt.% polyol compd., and 0.0005-2wt.% oxidase in a wt. ratio of the boron compd. to the polyol compd. of (1/30)-(10/1) and has a pH in the range of 2-7.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid oxygen bleaching composition, and more particularly to a liquid oxygen bleaching composition exhibiting high bleaching power and exhibiting bleaching activity over a long period of time.

[0002]

2. Description of the Related Art Oxygen bleaching agents have the characteristic that they can be used for colors and patterns, and have become the mainstream bleaching agents for clothing. However, on the other hand, bleaching power is inferior to chlorine bleaching agents, and much research has been conducted on improving the bleaching power of oxygen bleaching agents. One approach is to use an organic peracid precursor. The organic peracid precursor reacts with hydrogen peroxide in the cleaning solution to produce an organic peracid having high bleaching power. As a peroxide that generates hydrogen peroxide in the cleaning solution used here, a powder type bleach,
Alternatively, in a heavy detergent having bleaching performance, sodium percarbonate, sodium perborate, or the like is used, and in a liquid bleach, hydrogen peroxide is used. The organic peracid precursor includes, for example, tetraacetylethylenediamine (T
AED), glucose pentaacetate (PAG), and phenol derivative alkyl esters.

Since these organic peracid precursors have an ester bond, an amide bond, an imide bond, etc. in the structure, they are generally unstable to water and hydrogen peroxide, and have a hydrolysis reaction. Decomposes by hydrogen peroxide decomposition reaction and loses its activity as an organic peracid precursor. Therefore, in order to mix the organic peracid precursor into the liquid bleach composition, it is necessary to suppress hydrolysis and decomposition of hydrogen peroxide.

As a solution to this, use of a micelle reaction field can be considered. It has been reported that in a micelle reaction field, the incorporation of a compound having an ester bond causes a change in the hydrolysis rate (Ogaki Kazuichiro Kagaku and Kogyo, p47 (1988)). By utilizing the control of the rate of the decomposition reaction by the surfactant, the decomposition of the organic peracid precursor in the solution can be suppressed.
No. 07196. However, the system that suppresses the decomposition of the organic peracid precursor in the solution, on the contrary, also suppresses the organic peracid generation reaction rate in the cleaning solution, reduces the organic peracid generation efficiency, and provides satisfactory bleaching power. The problem arises that it is difficult to obtain. In order to exert the effect of the organic peracid precursor, it is necessary to maintain the stability of the organic peracid at the time of formulation without suppressing the reaction between the organic peracid precursor and hydrogen peroxide in the cleaning system. .

As another means for improving the bleaching activity, there is a bleaching method using an enzyme. An example of the bleaching method using these enzymes is described in Japanese Patent Application Laid-Open No. 3-5 / 1993 using peroxidase.
05100, JP-A-4-506229, JP-A-5-03542, and JP-A-58-17200 and JP-A-61-51 as examples using oxidase.
No. 099, JP-A-61-5110 and the like. The optimum pH at which the catalytic effect of these oxidases is most effectively exerted is 6-8. On the other hand, in a liquid oxygen bleach, hydrogen peroxide is used as a main bleaching component, and the pH of the preparation is generally adjusted to acidic (2 to 5) for stabilization. Therefore, the optimum pH of the enzyme does not match the pH of the preparation. In addition, hydrogen peroxide, which is the main bleaching component, cannot exert its effect sufficiently when it is acidic. For this reason, it is common practice to use a liquid oxygen bleach in combination with a detergent.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid oxygen bleaching composition which exhibits high bleaching power and exhibits bleaching activity over a long period of time.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the problems, and as a result, by combining a boron compound with a specific polyol compound and an oxidizing enzyme such as peroxidase, a color pattern is obtained. Have been found to be able to be used with peace of mind, and to exhibit a sufficiently high bleaching effect even when used alone. That is, the liquid oxygen-based bleach of the present invention contains the following components (a), (b), (c) and (d), and the content ratio of the components (b) and (c) is expressed in terms of weight ratio. (B) / (c) = 1/30 to 10/1 (0.03 to 1
0) and the pH is in the range of 2 to 7. Further, the composition of the present invention can further contain the component (e) and / or (f).

(A) 0.01 to 30% by weight of hydrogen peroxide (b) 0.01 to 30% by weight of a boron compound (c) 0.01 to 30% by weight of a polyol compound containing a saccharide (d) Oxidase (E) (e-1) a surfactant having at least one linear or branched chain alkyl or alkenyl group having 8 to 24 carbon atoms; (e-2) a surfactant having 8 to 24 carbon atoms. 0-60% by weight of one or both of the surfactants having at least one aryl group substituted with an alkyl group

(F) (f-1) General formula (1)
(F-2) Chelating agents such as carboxylic acid-based chelating agents such as NTA and EDTA (f-3) Carboxylic acid-based polymers such as acrylic acid polymers having a molecular weight of 1,000 to 100,000 and acrylic acid-maleic acid copolymers Any one or two or more of the agents
0% by weight

[0010]

Embedded image (A: hydrogen or an alkyl group, alkenyl group or hydroxyl group having 1 to 6 carbon atoms B: hydrogen or an alkyl group, alkenyl group or hydroxyl group having 1 to 6 carbon atoms M: hydrogen or an alkali metal atom)

[0011]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, hydrogen peroxide (a) as a bleaching base is contained in an amount of 0.01 to 30% by weight in the composition.
Preferably, 2 to 20% by weight is blended.

Examples of the boron compound used as the component (b) of the present invention include boron in the molecule such as boric acid, sodium borate, potassium borate, ammonium borate, sodium tetraborate, potassium potassium borate, and ammonium borate. Particularly preferred is sodium tetraborate. The boron compound as the component (b) of the present invention is incorporated in the composition in an amount of 0.01 to 30% by weight, preferably 2 to 20% by weight. The compounding amount of the boron compound (b) is 0.1.
When the content is less than 01% by weight, the bleaching effect is reduced.
The bleaching effect is reduced even if it exceeds the weight%.

Examples of the polyol compound containing a saccharide used as the component (c) of the present invention are preferably saccharides, such as glucose, mannose, galactose, fructose, ribose, erythrose, xylulose, gluconic acid, galactonic acid and mannone. Acid, glucuronic acid,
Maltose, cellobiose, lactose, sucrose,
Saccharose and the like, and sugar-based surfactants such as alkyl glucosides as their derivatives can also be used. Examples of polyols other than saccharides include glycerin derivatives such as glycerin and glycerin monoalkyl ether. Diols such as alkyl diol and alkylene diol can be exemplified. The polyol compound of the component (c)
0.01 to 30% by weight, preferably 2 to 20% by weight, in the composition of the present invention is 0.01% by weight.
If it is less than 30% by weight or more than 30% by weight, the bleaching effect is reduced.
As the component (c) of the present invention, a sugar or a derivative thereof may be used alone or in combination of two or more. A polyol other than a saccharide such as glycerin may be used alone or in combination of two or more. And polyols other than saccharides. The component (b) and the component (c) are in a weight ratio of the component (b).
/ (C) = 1/30 to 10/1 (0.03 to 10), preferably 1/20 to 2/1 (0.05 to 2). If this range is smaller than the above ratio, the bleaching effect is reduced, while if it exceeds the above ratio, the bleaching effect is reduced.

Examples of oxidases used as component (d) of the present invention include alkanol oxidase, glucose oxidase, bilirubin oxidase, cholesterol oxidase, laccase, peroxidase,
Catechol oxidase, catalase, alcohol oxidase and the like can be mentioned. The oxidase is present in the composition of the invention at 0.0005 to 2% by weight, preferably at 0.
It is blended in an amount of from 0.01 to 2% by weight. When the blending amount is 0.0005
If the amount is less than the weight percentage, the bleaching effect is not improved.

The surfactant used as the component (e) in the present invention is a surfactant having at least one linear or branched alkyl or alkenyl group having 8 to 24 carbon atoms, or a surfactant having 8 to 24 carbon atoms. A surfactant having at least one aryl group substituted with 24 alkyl groups,
Examples include anionic surfactants such as alkyl benzene sulfonates, soaps, alkyl sulfates, polyoxyethylene alkyl sulfates, fatty acid α-sulfomethyl esters, and the like; and nonionic surfactants include alkyl glycosides, polyoxyethylene Alkyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester,
Oxyethylene oxypropylene block polymers, fatty acid monoglycerides, amine oxides and the like; amphoteric surfactants include carbobetaine, sulfobetaine, hydroxysulfobetaine and the like, and any one of these or a mixture of two or more thereof may be used. ~ 60% by weight
Be blended.

The chelating agent used as the component (f) in the present invention may be any one generally used as a metal sequestering agent in the field of detergents. Examples of the organic phosphonic acid-based chelating agent include those represented by the following general formula (1), and typical examples thereof include hydroxyethanediphosphonic acid, ethane-1,1,2-triphosphonic acid, and ethane- There are 1,1-diphosphonic acids or salts thereof.

[0017]

Embedded image (A: hydrogen or an alkyl group, alkenyl group or hydroxyl group having 1 to 6 carbon atoms B: hydrogen or an alkyl group, alkenyl group or hydroxyl group having 1 to 6 carbon atoms M: hydrogen or an alkali metal atom)

Examples of the polymer chelating agent include polyacrylic acid, polymaleic acid, an acid type of acrylic acid-maleic acid copolymer, and alkali metal salts. The molecular weight of these compounds is conveniently from 1,000 to 100,000, preferably from 10,000 to 80,000. Further examples of carboxylic acid chelating agents include NT
A (nitrilotriacetic acid), EDTA (ethylenediaminetetraacetic acid), citric acid and the like. Any one of these or a mixture of two or more thereof may be used in an amount of 0 to 20% by weight.
Be blended.

The composition of the present invention is balanced by adding water to the above components (a) to (f).
Alcohols such as isopropanol and ethylene glycol, hydrotropes such as polyethylene glycol,
Various surfactants, thickeners, fragrances, pigments, fluorescent dyes, enzymes, and the like can be added as needed, as long as they are components that are generally added to laundry detergents and bleaching agents.

The pH of the stock solution of the composition of the present invention may be selected from acidic substances such as inorganic acids such as hydrochloric acid and sulfuric acid, p-toluenesulfonic acid,
Using an organic acid such as citric acid, a phosphonic acid derivative, or phosphoric acid, and using an alkali component such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, ammonia, or the like, 2 to 7, preferably 3.0. Adjusted to ~ 5.0. When the pH of the composition exceeds 7, the storage stability is significantly reduced.

[0021]

According to the present invention, liquid oxygen bleaching has high bleaching power against all stain stains to be bleached, and has excellent long-term stability even when stored at high and low temperatures. Agent composition is obtained. This composition can be used as a bleaching composition or a bleaching detergent composition.

[0022]

【Example】

Examples 1 to 14 and Comparative Examples 1 to 3 Hereinafter, bleaching compositions having the compositions shown in Examples 1 to 14 of Tables 1, 2 and 3 and Comparative Examples 1 to 3 of Table 4 were prepared, and the present invention was carried out. Although specifically described, the present invention is not limited to these examples. The percentages in each example are weight percentages unless otherwise specified. Evaluation of each item was performed by the following method. (1) Evaluation of Stability of Organic Peracid Precursor After the bleach compositions of Tables 1, 2, 3 and 4 were stored at 40 ° C. for 4 weeks, the residual ratio was measured by HPLC.

(3) Bleaching rate A solution prepared by diluting five bleaching compositions having the compositions shown in Tables 1, 2, 3 and 4 with water to 300 times with five red wine-stained cloths prepared as described below. After being left at 30 ° C. for 1 hour, the cloth was rinsed with tap water, dried, and the reflectance of the cloth surface was measured. The bleaching rate was calculated by the following equation (1).

[0024]

(Equation 1) The reflectivity was measured using a Z- # 80 colorimeter manufactured by Nippon Denshoku Co., Ltd.

Red Wine Contaminated Cloth A plain woven cotton cloth (#) is added to red wine (Suntory Reserve Red).
100), soaked for about 5 minutes, and air-dried. After pressing,
An 8 × 8 cm test piece was used for the experiment.

[0026]

[Table 1]Table 1: Example 1 2 3 4 5 Composition (% by weight)(a) Hydrogen peroxide 5 5 5 5 5 (b) Boric acid 5 − 3 − −Sodium tetraborate − 5 − 10 5 (c) Glucose 12 − − − 10 Sorbitol − 10 − 20 − Mannitol − − 15 − −Glycerin----- (d) Peroxidase *¹0.01 0.01 0.01 − − Laccase *^Two− − − 0.01 −Glucose oxidase * ³ − − − − 0.01 Alcohol ethoxylate *^Four5 5 2 8 10 LAS *^Five1 − − 21 Alkylamine oxide *⁶− − − − 1Hydroxysulfobetaine * ⁷ − − 5 − − NTA − − − − − polyacrylic acid *⁸− − − 2 3Ethane-1-hydroxy-1,1-phosphonate 0.1 0.5 0.3 0.5 1 Perfume flavor 0.1 − 0.1 0.1 0.1Acid dye (PPM) * ⁹ 2 2 − − 2 Ion exchange water balance pH 3.5 4.0 4.0 3.5 3.0 (b) / (c) weight ratio 0.4 0.5 0.2 0.5 0.5 Bleaching rate 69 75 76 70 71  * 1) peroxidase (manufactured by SIGMA) * 2) laccase (manufactured by SIGMA) * 3) glucose oxidase (manufactured by SIGMA) * 4) sophthanol SC90 * 5) alkylbenzenesulfonic acid (alkyl chain length 14) * 6) alkyl chain Length 12 * 7) Lauryl dimethylamine hydroxypropyl sulfobetaine * 8) Average molecular weight: 30,000 (trade name: Julimer AC10L (manufactured by Nippon Pure Chemical)) * 9) C.I. I. Acid Green 27

[0027]

[Table 2]Table 2: Example 6 7 8 9 10 Composition (% by weight)(a) Hydrogen peroxide 5 5 5 5 5 (b) Boric acid − 6 − − −Sodium tetraborate 1-4 4 5 (c) Glucose − − − − − sorbitol − 5 4 3 4 Mannitol − − − − −Glycerin 10 − − − − (d) Peroxidase *¹0.01 − 0.03 0.02 − Laccase *^Two− 0.02 − − − Glucose oxidase * ³ − − − − 0.01 Alcohol ethoxylate *^Four3 3 2 2 3 LAS *^Five− − − − − Alkylamine oxide *⁶− 1 − − − Hydroxysulfobetaine * ⁷ − − 1 − − NTA − − − − − polyacrylic acid *⁸− − 1 − 1 Ethane-1-hydroxy-1,1-phosphonate 0.1 0.1 0.5 0.5 0.5 Perfume--0.1 0.1 0.1 Acid dye (PPM) * ⁹ − − 2 3 2 Ion exchange water balance pH 3.5 4.0 5.0 5.0 4.0 (b) / (c) weight ratio 0.1 0.8 1.0 1.3 1.3 Bleaching rate 68 70 72 74 74 * 1) peroxidase (manufactured by SIGMA) * 2) laccase (manufactured by SIGMA) * 3) glucose oxidase (manufactured by SIGMA) * 4) sophthanol SC90 * 5) alkylbenzenesulfonic acid (alkyl chain length 14) * 6) alkyl chain Length 12 * 7) Lauryl dimethylamine hydroxypropyl sulfobetaine * 8) Average molecular weight: 30,000 (trade name: Julimer AC10L (manufactured by Nippon Pure Chemical)) * 9) C.I. I. Acid Green 27

[0028]

[Table 3]Table 3: Example 11 12 13 14 Composition (% by weight)(a) Hydrogen peroxide 5 5 5 5 (b) Boric acid-5-5Sodium tetraborate 3 − 4 − (c) Glucose----Sorbitol 2-2 1 Mannitol----Glycerin − 3 − − (d) Peroxidase *¹0.01 0.01 0.01 − Laccase *^Two− − − − −Glucose oxidase * ³ − − − 0.01 Alcohol ethoxylate *^Four2 2 2 − LAS *^Five− − 0.5 0.5 Alkylamine oxide *⁶1 − − 3Hydroxysulfobetaine * ⁷ − 1 − − NTA − − 0.3 − Polyacrylic acid *⁸0.5 − − −Ethane-1-hydroxy-1,1-phosphonate 0.5 0.1-0.1 Perfume----Acid dye (PPM) * ⁹ − − − − Ion exchange water balance pH 6.0 4.0 3.5 4.0 (b) / (c) weight ratio 1.5 1.7 2.0 5.0 Bleaching rate 73 75 71 69  * 1) peroxidase (manufactured by SIGMA) * 2) laccase (manufactured by SIGMA) * 3) glucose oxidase (manufactured by SIGMA) * 4) sophthanol SC90 * 5) alkylbenzenesulfonic acid (alkyl chain length 14) * 6) alkyl chain Length 12 * 7) Lauryl dimethylamine hydroxypropyl sulfobetaine * 8) Average molecular weight: 30,000 (trade name: Julimer AC10L (manufactured by Nippon Pure Chemical)) * 9) C.I. I. Acid Green 27

[0029]

Table 4: Comparative Example 12 23 Composition (% by weight) (a) Hydrogen peroxide 5.55 (b) Sodium tetraborate -5- (c) Glucose--5 (d) Peroxidase * ¹ 0.01 - - laccase * ² - - - glucose oxidase * ³ - - - alcohol ethoxylate ^{* 4 4 5 8 LAS * 5} 2 2 - NTA - - - citric acid - - - polyacrylic acid * ⁶ - - - ethane -1 - hydroxy-1,1-diphosphonate 0.1 - - Incense tone perfume 0.1 0.1 - acid dye (PPM) * ⁷ - 2 2 ion exchanged water Balance part pH 3.5 4.0 4.0 (b) / (c) weight ratio - - - Bleaching rate 35 42 38 * 1) peroxidase (manufactured by SIGMA) * 2) laccase (manufactured by SIGMA) * 3) glucose oxidase (manufactured by SIGMA) * 4) SOFTANOL SC90 * 5) Alkylbenzenesulfonic acid (alkyl chain length 14) * 6) Average molecular weight: 30,000 (commodity Jurymer AC10L (manufactured by Japan Pure Chemical Industries)) * 7) C. I. Acid Green 27

The characteristic structure of the present invention is as follows. (1) As a component (e) (e-1) a surfactant having at least one linear or branched alkyl or alkenyl group having 8 to 24 carbon atoms (e-2) an alkyl having 8 to 24 carbon atoms The liquid oxygen-based bleaching composition according to claim 1, comprising 0.1 to 60% by weight of a surfactant having at least one aryl group substituted with a group. (2) As component (f) (f-1) Organic phosphonate of general formula (1) below (f-2) Carboxylic acid chelating agent such as NTA, EDTA, etc. (f-3) Molecular weight of 1,000 The liquid oxygen-based bleaching composition according to claim 1, which contains 0.001 to 20% by weight of one or more of 100,000 acrylic acid polymers and carboxylic acid-based polymers such as acrylic acid-maleic acid copolymer.

[0031]

Embedded image (A: hydrogen or an alkyl group, alkenyl group or hydroxyl group having 1 to 6 carbon atoms B: hydrogen or an alkyl group, alkenyl group or hydroxyl group having 1 to 6 carbon atoms M: hydrogen or an alkali metal atom) (3) (b) component The liquid oxygen bleaching composition according to claim 1, wherein the boron compound is sodium tetraborate. (4) The liquid oxygen-based bleaching composition according to claim 1, wherein the polyol as the component (c) is a sugar compound or a derivative thereof and has a cis structure in the compound and has a continuous hydroxyl group.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location C11D 7:10 7:26 7:42) (72) Inventor Kazuaki Fukano Sumida-ku, Tokyo 1-3-7 in Lion Corporation

Claims (1)

[Claims] 1. It contains the following components (a), (b), (c) and (d), and the content ratio of the components (b) and (c) is (b) / (c) = 1 / A liquid oxygen-based bleaching composition having a pH in the range of 30 to 10/1 and a pH in the range of 2 to 7. (A) 0.01-30% by weight of hydrogen peroxide (b) 0.01-30% by weight of a boron compound (c) 0.01-30% by weight of a polyol compound (d) 0.0005-2% by weight of an oxidase