JPH11279593A - Liquid bleaching agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition having a high storage stability and bleaching power unchanging during a long-term storage by dispersing in a medium percarbonates coated with coating components which comprise a carboxylic acid-based polymer and/or a polyvalent carboxylic acid. SOLUTION: Percarbonates (e.g. sodium percarbonate) having an average particle diameter of preferably 0.1-1,000 μm and coated with at least one coating component selected from carboxylic acid-based polymers obtained from at least one selected from preferably (meth)acrylic acid, maleic acid, α- hydroxyacrylic acid, fumaric acid, (iso)crotonic acid, aconitic acid, itaconic acid and citraconic acid, and polyvalent carboxylic acids are dispersed in a medium, preferably a nonionic surfactant [e.g. C12 H25 O(C2 H4 O)7 -H]. Preferably is further admixed a bleaching activator of the formula, wherein R<1> is a 5-15C alkyl; X is COOM or SO3 M; and M is H, or an alkali or alkaline earth metal atom.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid bleach composition having high storage stability and having no change in bleaching power even during long-term storage.

[0002]

BACKGROUND OF THE INVENTION Liquid oxygen bleaches are preferred by consumers because they are easy to use in that they can be applied directly to soil such as clothing.

[0003] Such a liquid oxygen-based bleach keeps its liquidity acidic in order to increase the stability of components that become bleaching active species. Further, in the case of a liquid oxygen bleach containing a bleach activator for the purpose of enhancing the bleaching power (JP-A-7-82592 and JP-A-6-207196), it is necessary to improve the storage stability. It is necessary to make the acid acidic. For this reason, there is a problem in that it is inconvenient to use because it generates hydrogen peroxide and organic peracid when used, and must be used in combination with a detergent containing an alkaline agent.

[0004] It is an object of the present invention to provide a liquid bleaching composition which has high storage stability even when the liquidity is made alkaline and the bleaching power does not change.

[0005]

DISCLOSURE OF THE INVENTION The present inventors have found that by coating the surface of a percarbonate with a specific carboxylic acid-based coating component, the storage stability can be enhanced even in an alkaline region, and the detergent can be used in combination with a detergent. The present inventors have found that the combination can be eliminated, and completed the present invention.

That is, according to the present invention, a percarbonate is dispersed in a medium, and the percarbonate is coated with at least one coating component selected from a carboxylic acid polymer and a polycarboxylic acid. A liquid bleaching composition is provided.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The liquid bleach composition of the present invention comprises a carboxylic acid-based polymer and a polycarboxylic acid.
Percarbonates coated with at least one kind of coating component (hereinafter, referred to as
"Coated percarbonates") are dispersed in a medium.

The percarbonates used in the present invention include alkali metal salts of percarbonate such as sodium percarbonate. The percarbonates have an average particle size of preferably from 0.1 to 1000 μm, particularly preferably from 0.1 to 1000 μm.
500 μm, more preferably 0.1 to 100 μm
It is.

The carboxylic acid polymer which is a coating component used in the present invention includes acrylic acid, methacrylic acid, maleic acid, α-hydroxyacrylic acid, fumaric acid, crotonic acid, isocrotonic acid, aconitic acid, itaconic acid and citraconic acid. And a homopolymer or copolymer obtained from at least one member selected from the group consisting of: The number average molecular weight of this carboxylic acid polymer is preferably 2,0
00 to 500,000, particularly preferably 5,000.
~ 200,000, more preferably 5,000 ~
100,000.

[0010] The polyvalent carboxylic acid which is a coating component used in the present invention includes citric acid, succinic acid, maleic acid, fumaric acid, iminodiacetic acid, hydroxyethyliminodiacetic acid,
Nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, aspartic acid diacetic acid, glutamic acid diacetic acid, serine diacetic acid, phthalic acid, terephthalic acid,
One or more selected from trimellitic acid and salts thereof can be mentioned.

The method for producing the coated percarbonate includes spraying a solution of the coating component onto the percarbonate, followed by drying.
For example, a method of impregnating the solution of the coating component with percarbonates and then drying the solution can be applied.

[0012] In the production of the coated percarbonate, the use ratio of the percarbonate and the coating component to the percarbonate is preferably 0.01 to 5 times by weight, particularly preferably 0.05 to 5 times the amount of the percarbonate. It is 3 times by weight, more preferably 0.1 to 2 times by weight.

The content of the coated percarbonate in the composition is preferably 0.01 to 50% by weight, particularly preferably 0.05 to 40% by weight, and further preferably 0.1 to 30% by weight. % By weight.

The medium used in the present invention is preferably a non-aqueous medium in order to enhance the dispersibility of the coated percarbonate. Lower alcohols such as methanol, ethanol, isopropanol, ethylene glycol and glycerin; polyethylene glycol phenol ether; Polyoxyethylene methyl ether, polyoxyethylene ethyl ether, polyoxyethylene propyl ether, polyoxyethylene butyl ether, polyoxyethylene hexyl ether, polyoxyethylene octyl ether (the average number of moles of ethylene oxide added is preferably 1 to 10), etc. Polyoxyethylene derivatives; polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyethylene alkyl phenyl ethers, higher fatty acids Luke alkanolamides or alkylene oxide adducts thereof, sucrose fatty acid esters, alkylglucosides, may be mentioned nonionic surfactants such as fatty acid glycerol monoesters.

Among these, nonionic surfactants are preferred because of the good dispersibility of the coated percarbonates, and polyoxyethylene having an alkyl group having an average of 10 to 22 carbon atoms and having 1 to 30 mol of ethylene oxide added thereto. An alkyl ether having an alkyl group having an average carbon number of 9 to 12;
Nonionic surfactants such as polyoxyethylene alkyl phenyl ether with 5 moles of ethylene oxide added are particularly preferred.

The content of the medium in the composition is preferably 10 to 99.9% by weight, particularly preferably 2 to 99.9% by weight.
0 to 99.9% by weight, more preferably 30 to 9% by weight.
9.5% by weight.

In the liquid bleach composition of the present invention, the coated percarbonate is dispersed in the above-mentioned medium. When the percarbonates are dissolved in the medium, the stability is significantly reduced, and the stability of the bleach activator incorporated as an optional component is also reduced. Therefore, in order to disperse the coated percarbonate in the medium without dissolving it, in the combination of the medium and the coated percarbonate, a combination in which the coated percarbonate is insoluble or hardly soluble in the medium is selected. There is a need.

The liquid bleach composition of the present invention further comprises a compound of the general formula (I):

[0019]

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[Wherein, R ¹ represents a linear or branched alkyl group having 5 to 15 carbon atoms, and X represents COOM or SO ₃ M
(Where M represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom). ] Can be added.

As the bleaching activator represented by the general formula (I), in the general formula (I), R ¹ is a linear or branched alkyl group having 7 to 11 carbon atoms, and X is COOH or Those which are SO ₃ Na are preferred. Examples of such a bleach activator include sodium lauroyloxybenzenesulfonate, sodium decanoyloxybenzenesulfonate, sodium octanoyloxybenzenesulfonate, lauroyloxybenzoic acid, decanoyloxybenzoic acid, octanoyloxybenzoic acid and the like. Can be mentioned.

The content of the bleach activator in the composition is preferably 0 to 30% by weight, particularly preferably 0.01 to 20% by weight, and more preferably 0.0 to 20% by weight.
5 to 10% by weight.

The liquid bleach composition of the present invention may further contain one or more selected from anionic surfactants and cationic surfactants. Examples of the anionic surfactant include alkylbenzene sulfonates, alkyl ether sulfates, alkenyl ether sulfates, alkyl sulfates, alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated fatty acid salts,
Unsaturated fatty acid salts, alkyl ether carboxylate salts,
Alkenyl ether carboxylate salts, α-sulfofatty acid salts, α-sulfofatty acid esters and the like can be mentioned; as cationic surfactants, quaternary ammonium salts and the like can be mentioned. Among these, alkyl (C10-20) benzene sulfonates, alkyl (C10-20) ether sulfates, alkenyl (C1
0-20) ether sulfates, alkyl (C10-2
0) Sulfates, alkenyl (C10-20) sulfates, and quaternary ammonium salts having at least one alkyl group having 10 to 20 carbon atoms are preferred.

The amount of the surfactant is preferably 0.1 to 50% by weight, particularly preferably 0.1 to 40% by weight in the composition.

The liquid bleach composition of the present invention may further contain a sequestering agent. As this sequestering agent, those described in JP-A-10-17894, page 7, column 11, line 22 to column 12, line 9 can be mentioned.

In the liquid bleaching composition of the present invention, the pH of a 5% by weight aqueous solution is preferably from 8 to 11, and particularly preferably from 8.5 to 10.5, in order to enhance the bleaching power.

[0027]

EXAMPLES Production Example 1 Sodium percarbonate manufactured by Nippon Peroxide Co., Ltd. was pulverized with a coffee mill to obtain a powder having an average particle size of 40 μm. In 100 ml of ethanol, polyacrylic acid (molecular weight about 8000,
10 g of sodium percarbonate powder was added to a solution in which 5 g of an oligomer D manufactured by Kao Corporation was neutralized with sulfuric acid and then azeotropically dehydrated with ethanol, and the mixture was stirred at room temperature for about 1 hour. Thereafter, the solid content obtained by filtration was dried at 105 ° C. for 2 hours, and then pulverized and sized to obtain a coated sodium percarbonate (PC-A).

Production Example 2 Sodium percarbonate manufactured by Nippon Peroxide Co., Ltd. was pulverized with a coffee mill to obtain a powder having an average particle size of 40 μm. An acrylic acid / maleic acid copolymer (molecular weight: about 50,000, socalane CP- manufactured by BASF) was added to 100 ml of ethanol.
5) Add 5 g of sodium percarbonate powder to the solution
0 g was added and stirred at room temperature for about 1 hour. Thereafter, the solid content obtained by filtration is dried at 105 ° C. for 2 hours,
The mixture was pulverized and sized to obtain a coated sodium percarbonate (PC-B).

Production Example 3 A coated sodium percarbonate (PC-C) was obtained in the same manner as in Production Example 2 except that citric acid was used in place of the acrylic acid / maleic acid copolymer.

Examples 1-5, Comparative Examples 1-2 Sodium percarbonate (average particle size 40 μm), PC-A, P
Using CB, PC-C, the medium of b-1 to b-3 shown below, the bleaching activator of c-1 to c-3, and the sequestering agent of d-1, shown in Table 1. A liquid bleach composition having a composition (in% by weight) was obtained. _{b-1: C 12 H 25} O (C 2 H 4 O) 7 -H

[0031]

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B-3: glycerin

[0033]

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D-1: Citric acid These compositions were tested for storage stability and bleaching performance by the following methods. Table 1 shows the results. (1) Storage stability The change in bleach activator content before and after storage when 80 g of the liquid bleach composition was placed in a 100 ml glass sample bottle and stored at 30 ° C. for 1 month was measured by high performance liquid chromatography. Then, the residual ratio of the bleaching activator was determined from the following formula, and the storage stability was evaluated.

[0035]

(Equation 1)

In the above case, the composition before and after storage was titrated with a 0.1N potassium permanganate solution, and the residual effective oxygen concentration was determined from the following equation to evaluate the storage stability.

[0037]

(Equation 2)

(2) Bleaching performance Preparation of black tea-contaminated cloth 80 g of Nitto black tea (yellow package) was boiled for about 15 minutes in 3 L of ion-exchanged water, and then filtered with desizing bleached cotton. # 2003 was dipped and boiled for 15 minutes. Next, after being removed from the fire and left for 2 hours, the cotton / gold cloth # 2003 was taken out and air-dried. Thereafter, it was washed with water until the washing liquid did not color, dehydrated, pressed and then cut into 10 × 10 cm to obtain a black tea-stained cloth.

Preparation of Curry-Contaminated Cloth After the solid content of house food retort curry (curry Marche) was removed with a net, the resulting liquid component was heated to boiling. Dip cotton cloth # 2003 in this solution,
Boil for a minute. Next, after being removed from the heat and left for 2 hours, the cotton / gold cloth # 2003 was taken out, and the excessively attached curry was removed with a spatula and air-dried. After that, it was pressed and cut into 10 × 10 cm to obtain a curry-contaminated cloth.

Measurement of Bleaching Performance Five pieces of black stained cloth (hydrophilic stain) and five pieces of curry stained cloth (new oily stain) were immersed in 2 liters of tap water and 20 ml of the liquid bleaching composition for 15 minutes. Was. Then, it was taken out, rinsed with tap water, dried, and the bleaching rate was obtained from the following formula, and the bleaching performance was evaluated. The reflectance was measured by NDR-10DP manufactured by Nippon Denshoku Industries Co., Ltd. using a 460 nm filter. The display is an average value of five sheets.

[0041]

(Equation 3)

[0042]

[Table 1]

[0043]

According to the liquid bleach composition of the present invention, the percarbonate serving as a bleaching active species is coated with at least one coating component selected from carboxylic acid polymers and polycarboxylic acids. The carbonates and the bleach activator added as required are stable even in the alkaline region, and the bleaching power does not decrease during storage. Therefore, it is not necessary to use a detergent containing an alkali agent in combination.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI D06L 3/06 D06L 3/06 (72) Inventor Muneo Aoyagi 1334 Minato 1334 Minato, Wakayama-shi, Wakayama, Japan Kao Corporation Research Center

Claims (4)

[Claims] 1. A medium in which percarbonates are dispersed,
A liquid bleaching composition, wherein the percarbonate is coated with at least one coating component selected from a carboxylic acid-based polymer and a polycarboxylic acid. 2. The liquid bleach composition according to claim 1, wherein the medium is a nonionic surfactant. 3. The carboxylic acid-based polymer is acrylic acid,
The liquid bleaching according to claim 1 or 2, which is obtained from one or more selected from methacrylic acid, maleic acid, α-hydroxyacrylic acid, fumaric acid, crotonic acid, isocrotonic acid, aconitic acid, itaconic acid and citraconic acid. Composition. 4. A compound of the general formula (I): [Wherein, R ¹ represents a linear or branched alkyl group having 5 to 15 carbon atoms, X represents COOM or SO ₃ M (where M represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom) Is shown). The bleaching agent composition according to claim 1, 2 or 3, which comprises a bleaching activator represented by the formula: