JPH09286996A - Powder bleach composition - Google Patents

Abstract

(57) Abstract: [PROBLEMS] To provide an oxygen-based powder bleaching agent that maintains the transparency of a solution even when left in a high-concentration aqueous solution for a long time and exhibits an excellent bleaching power. A water-insoluble component is substantially contained, containing (a) a peroxide that dissolves in water to generate hydrogen peroxide, (b) a carboxylic acid-based polymer, and (c) a calcium-insensitive surfactant. A powder bleach composition which does not contain the above.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a bleaching composition, an oxygen-based powder bleaching composition suitable for bleaching stains and stains on clothes.

2. Description of the Related Art Oxygen-based bleaching agents are becoming the mainstream of chlorine bleaching agents in clothing bleaching agents because of their less influence on color and patterns, but their bleaching power is inferior to that of chlorine bleaching agents. There is. In recent years, attempts have been made to add a bleach activator to an oxygen-based powder bleaching agent in order to enhance the bleaching power. For example, JP-A-59-022999 discloses a combination of a peroxide and an organic peroxide precursor, and JP-A-6-316700 discloses a combination of sodium percarbonate, an organic peracid precursor and a surfactant. Is disclosed. By dissolving such an oxygen-based bleaching agent in water and usually immersing clothing or the like in this aqueous solution, the bleaching power of the oxygen-based bleaching agent is more effectively exhibited, but in this case, the solution becomes cloudy. Often, they give unfavorable results in use. Particularly, the bleach activator has a drawback that it forms an insoluble salt when used at a high concentration.

[0002]

DISCLOSURE OF THE INVENTION The present invention maintains the transparency of a solution even when it is left in a high-concentration aqueous solution for a long time.
And it aims at providing the oxygen type powder bleaching agent which shows the outstanding bleaching power.

The present invention provides an oxygen-based peroxide, or a system in which an oxygen-based peroxide and a specific organic peracid precursor are combined, in which a specific surfactant and a specific carboxylic acid system are used. This was done based on the finding that the above problems can be solved by the synergistic effect of coexisting polymers.
That is, the present invention contains (a) a peroxide that dissolves in water to generate hydrogen peroxide, (b) a carboxylic acid-based polymer, and (c) a calcium-insensitive surfactant, and a water-insoluble component. A powder bleaching composition is provided which is substantially free of. The present invention also provides the above component (a).
To (c), (d) an organic peracid precursor represented by the general formula I

Embedded image (wherein R represents an alkyl group having 8 to 14 carbon atoms, an alkenyl group, an alkanoyloxymethyl group, or a phenyl group, and L represents a hydrophilic group. The leaving constant has a rate constant of hydrogen peroxide decomposition of the bleaching activator of 5 liter / mol / se
c represents a group that imparts the above property. And a substantially no water-insoluble component.

[0003]

BEST MODE FOR CARRYING OUT THE INVENTION Typical examples of the bleaching base component (a) used in the present invention which is a peroxide which dissolves in water to generate hydrogen peroxide include sodium percarbonate and sodium perborate. Monohydrate, tetrahydrate, potassium monopersulfate and the like can be mentioned. These may be used alone or in combination of two or more. Of these, sodium percarbonate is preferred. As these peroxides, it is preferable to use a powdery material having an average particle size of about 100 to 700 μm, and especially a granulated product, for example, an average particle size of 200 to
It is preferable to use a granulated product of about 500 microns. The content of the component (a) in the present invention in the powder bleaching agent composition is preferably 30 to 80% by weight (hereinafter abbreviated as%), and more preferably 50 to 70%. In the present invention, the carboxylic acid-based polymer used as the component (b) is preferably a water-soluble polymer of a mono- or dicarboxylic acid having 3 to 8 carbon atoms, preferably 3 to 4 carbon atoms, or a water-soluble salt thereof. Specifically, a polymer selected from polyacrylic acid or a salt thereof, polymaleic acid or a salt thereof, and a copolymer of maleic acid and another vinyl monomer (including partially and completely neutralized salts thereof) is used. Is good. Among them, the average molecular weight is 1000 to 10
10,000 is preferable, and more preferably 2000-200.
00.

Examples of the polymaleic acid or its salt used as the component (b) include maleic acid homopolymers and copolymers with other vinyl monomers (including partially and completely neutralized salts thereof). Such a polymer preferably has an average molecular weight of 1,000 to 100,000,
Those of 2000 to 20000 are more preferable. Examples of the copolymer include a copolymer of a vinyl monomer selected from acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, vinyl acetate and the like and maleic acid. In particular, a copolymer with acrylic acid or methacrylic acid is preferable. The monomer ratio of maleic acid and other monomers is maleic acid / monomer = 90 / 10-40 / 60
Is preferably within the range. The maleic acid-based polymer preferably has an average molecular weight of 1,000 to 100,000, more preferably 1,000 to 10,000. Further, a specific phosphinocarboxylic acid such as hydroxyethanediphosphonic acid or a salt thereof is also preferable as the component (b).
The content of the component (b) in the present invention is preferably 1 to 10%, more preferably 3 to 7% in the powder bleaching agent composition. In the present invention, it is essential to contain a calcium insensitive surfactant as the component (c).

Examples of suitable calcium-insensitive surfactants suitable for the present invention are shown below. Α-Olefin sulfonate having an average carbon number of 10 to 20 α-Sulfo fatty acid ester salt having an alkyl group or alkenyl group having an average carbon number of 10 to 20 having a linear or branched alkyl group having an average carbon number of 10 to 20. The polyoxyalkylene alkyl ether sulfate having an average of 0.5 to 8 mol of alkylene oxide added thereto is usually preferably an alkali metal salt such as sodium or potassium. Polyoxyalkylene alkyl ether having a linear or branched alkyl group having an average carbon number of 8 to 20 and having an average of 0.5 to 8 mol of alkylene oxide added thereto. Specific examples of polyoxyalkylene alkyl ether used in the present invention Is an addition of 5 to 15 mol of ethylene oxide per 1 mol of an aliphatic primary alcohol having 11 to 15 carbon atoms, or 1 mol of a secondary alcohol having a branched carbon chain having 10 to 12 carbon atoms. 5-15
The thing which added the ethylene oxide of a mole is mentioned. Further, 5 to 15 mol of ethylene oxide and 1 to 5 mol of propylene oxide per 1 mol of the above alcohol can also be mentioned as a preferable example.

The above surfactants can be used alone or as a mixture of two or more. In the present invention, linear alkylbenzene sulfonate, alkyl sulfate, etc.,
The hardness component in the solution forms a water-insoluble salt and causes white turbidity. Therefore, it is not preferable to contain more than the calcium-insensitive surfactant. The content of the component (c) in the present invention is preferably 0.5 to 20%, more preferably 1 to 10% in the powder bleach composition. The present invention contains the above-mentioned essential components and contains substantially no water-insoluble components. In particular, it is necessary to make the solution cloudy. The present invention provides a powder bleaching composition essentially comprising the above components (a) to (c), and further comprises a peracid precursor represented by the above formula (I) as the component (d). It is preferable to use a certain bleach activator together. Here, in the formula, the leaving group L is a group that generates an organic peracid derived from the R—CO group, and forms an ester bond, an amide bond, or an imide bond with CO of the R—CO group. Is preferable, and the hydrogen peroxide decomposition constant of the bleach activator when subjected to hydrogen peroxide decomposition reaction is 5 liter / mol · sec or more, preferably 50 liter / mol · sec or more, more preferably 50 to Leaving groups at l / mol.sec are preferred. The rate constant of hydrogen peroxide decomposition in the present invention refers to the reaction constant when the bleach activator reacts with hydrogen peroxide at a temperature of 25 ° C. This rate constant is 5 liters / mol
If it is less than sec, the reaction rate between the bleaching activator and hydrogen peroxide in the solution is slow and the desired amount of organic peracid cannot be obtained. Further, the leaving group L in the general formula (I) is preferred to introduce hydrophilic groups to impart water solubility to the bleach activator, preferably -SO ₃ M or -COOM (M Is a group having hydrogen or a salt that imparts water solubility).

The leaving group means that when hydrogen peroxide and a bleaching activator react with each other, the leaving group is eliminated from the RCO-group, and the organic peracid RCOO
It is a group capable of producing O-. Specific examples of the bleach activator of the present invention are preferably those represented by the following general formula (II).

Embedded image R ¹ COO (benzene ring) Y ⁻ M ⁺ ── (II) (In the formula, R ¹ has 8 to 14 carbon atoms, preferably 10 to 12 carbon atoms.
Alkyl group, an alkenyl group, alkanoyloxymethyl group, or a phenyl group, Y is COO-, SO ₃ -, SO
₄ -, PO ₄ - anion groups such as, M is a cation giving a water-soluble hydrogen or an organic peracid precursor. Here, M represents a cation which forms hydrogen or a water-soluble salt such as a substituted or unsubstituted ammonium salt of an alkali metal alkanolamine such as sodium or potassium. In the general formula (II), the bonding position of the benzene ring of the Y group with respect to the R ¹ COO group may be any of the ortho position, the meta position and the para position, but is preferably the para position.

The component (d) in the present invention is preferably 1 to 20%, more preferably 3 to 20% in the powder bleaching composition. In addition, as a form of addition of the component (d) in the present invention, a granulated product obtained by mixing and melting the precursor alone or another component, for example, an organic binder, and granulating using an extruder or the like is suitable. The organic binder used here is preferably a water-soluble one that is solid at room temperature and melts when heat is applied, and more preferably has a melting point of 25.
˜100 ° C., more preferably 25 to 80 ° C., most preferably 40 to 80 ° C. Various compounds can be used as long as they satisfy such requirements, and among them, particularly those having an average molecular weight of 400 to 3000.
0 polyethylene glycol is preferably used,
It is more preferably 1000 to 20000, and most preferably 4000 to 20000 polyethylene glycol. It is also preferable to use a polyethylene glycol addition type nonionic surfactant, specifically, a carbon number of 8 to
It is preferable to add 3 to 80 mol, preferably 10 to 50 mol of ethylene glycol per 1 mol of 20 (preferably 10 to 18) aliphatic alcohol. Among the many organic binders, polyethylene glycol and /
Alternatively, when a polyethylene glycol-added nonionic surfactant is used, the solubility of the resulting bleach activator granule can be improved. The content ratio of the bleach activator and the organic binder is 50 to 80%,
It is preferably 65 to 75%, and the balance is an organic binder. In the bleaching detergent composition of the present invention,
In addition to the above essential components, it is preferable to add an alkali builder for improving performance. Suitable examples of alkali builders include carbonates and silicates, which are preferably contained in the title composition in an amount of 20 to 60%.

It is also preferable to add an enzyme in the present invention. The preferred enzyme in the present invention is a bleach-resistant protease, and specific examples thereof include Durazyme manufactured by Novo Industry and Maxapem manufactured by Ibis. These bleach-resistant proteases alone or 2
More than one kind can be used in combination. The content of these bleaching-resistant proteases is usually preferably 0.01 to 5.0%, and more preferably about 0.1 to 2.0%. Furthermore, in the present invention, the following components may be optionally contained within the range that does not impair the effects of the present invention. (1) Chelate builders such as ethylenediamine tetraacetate, hydroxyethylenediamine triacetate, nitrilotriacetate and diethylenetriamine pentaacetate (2) Anti-recontamination agents such as polyethylene glycol (3) Expanders such as sodium sulfate (4) Others, fragrances, pigments, etc.

EFFECTS OF THE INVENTION According to the present invention, there is provided an oxygen-based powder bleaching agent which maintains the transparency of a solution even when left in a high-concentration aqueous solution for a long time and exhibits an excellent bleaching power. Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

[0010]

【Example】

Example 1 Amounts of components shown in Table-1 shown in the table (numerical values in the table are% by weight)
(The rest is sodium carbonate, 100% overall) and they are mixed while spraying with a nonionic surfactant to prepare a powder bleach composition having an average particle size of 250 microns. The performance was evaluated by the following method. Evaluation of transparency of dissolved solution φ30 of 3 liters of tap water adjusted to 30 ° C in advance
Prepare in a 0 mm x H150 mm transparent styrene round water tank, gently add 15 g of the bleaching agent composition therein, stir lightly by hand, leave it for 20 minutes, and visually check the appearance of the solution according to the following criteria. It was judged. ◯: Transparent and no insoluble matter is observed on the bottom. X: The solution is cloudy or insoluble matter is observed at the bottom. The results are shown in Table 1 together with the composition.

[0011]

[Table 1] Table-1 1 2 3 4 * 5 * Sodium percarbonate 50 40 40 50 40 Potassium persulfate ¹⁾ -10 10-10 Maleic acid / acrylic acid copolymer ²⁾ 5 5---Maleic acid / acrylic acid copolymer ³⁾ --5--Nonionic surfactant ⁴⁾ 2 2 2-2 Anionic surfactant ⁵⁾ 2-2--Anionic surfactant ⁶⁾ ---3 2 Zeolite 4A---3-Enzyme ⁷⁾ 0.5 -0.5--Perfume 0.1 0.1 0.1 0.1 0.1 Sodium hydrogen carbonate-2 ---Sodium carbonate Residual Residual Residual Residual Transparency of solution ○ ○ ○ × ×

4 * to 5 * are comparative examples. Note) 1) Brand name: Oxone (manufactured by DuPont) 2) Average molecular weight: 70000 (Brand name "Sokaran CP
5 "(manufactured by BASF) 3) Average molecular weight: 50,000 (trade name" Sokaran CP
7 "(manufactured by BASF)) 4) C ₁₂ ~ ₁₄ secondary alcohol, ethylene oxide 9
Mol adduct: trade name Softanol 90 5) C ₁₄ ~ ₁₈ α -olefin sodium sulfonate 6) sodium linear dodecylbenzenesulfonate 7) Product Name: Tables The components shown in Makisapemu (Gist Co., Ltd.) Example 2 Table 3 Amount shown in the table (Numbers in the table are% by weight
(The rest is sodium carbonate, 100% overall) and they are mixed while spraying with a nonionic surfactant to prepare a powder bleach composition having an average particle size of 250 microns. The performance was evaluated by the following method. As the bleaching activator, bleaching activator A or B polyethylene glycol (average molecular weight 60
No. 00) and a weight ratio of 65/35 were mixed and melted, and the mixture was granulated and used (average particle size: 600 μm).

[0013]

[Table 2] Table-2 R ¹ Y M bleach activator A C ₁₁ H ₂₃ COO H bleach activator B C ₁₁ H ₂₃ SO ₃ Na The above bleach activator is R ¹ COO (benzene ring) Y ^- M
⁺ Is represented by (II), and Y is in the para position with respect to R ¹ COO. Evaluation of transparency of solution Same as in Example 1. Bleaching power evaluation A bleaching agent composition was prepared with tap water at 20 ° C. so as to have a solution concentration of 0.1%, and five contaminated cloths prepared as described below were put therein and left for 30 minutes. . After standing, in a tap water of 20 ° C prepared with a commercially available detergent to a predetermined concentration, using a tergotometer, stirring for 10 minutes, rinsing with tap water,
After drying, the bleaching power was calculated by the following formula.

## EQU1 ## Bleaching power (%) = 100 × (reflectance of bleached cloth-reflectance of contaminated cloth) / (reflectance of pre-treated cloth-reflectance of contaminated cloth) The reflectance is Nippon Denshoku Co., Ltd. Manufactured by Z-Σ80 colorimetric color difference meter. Contamination cloth A plain weave cotton cloth (# 100) was soaked in 1 liter of commercially available red wine, taken out in a wet state, and naturally dried for about half a day to obtain a test piece of 8 × 8 cm, which was subjected to an experiment. The results are shown in Table 3 together with the composition.

[0014]

[Table 3] Table-3 6 7 8 9 10 * 11 * 12 * Sodium percarbonate 50 50--50 50 50 Sodium perborate--50 50---Peracid precursor A 10-10--10-Peracid precursor B-10- 10---Maleic acid / acrylic acid 3 3-----Copolymer ²⁾ Maleic acid / acrylic acid--3 3---Copolymer ³⁾ Nonionic surfactant ⁴⁾ 2 1 2 1-0.5 -Anionic surfactant ⁵⁾ 1 2 1 3---Anionic surfactant ⁶⁾ ----2 3 3 Zeolite 4A------5 Enzyme ⁷⁾ 0.5-0.5----Perfume 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Sodium hydrogen carbonate-2-2---Sodium carbonate Residual Residual Residual Residual Transparency of solution ○ ○ ○ ○ × × × Bleach rate (%) 55 54 55 57 30 45 25 10 * ~ 12 * is a comparative example. Note 2) to 7) in Table-3 are the same as those in Table-2.

Claims (2)

[Claims] 1. A water-insoluble component containing (a) a peroxide which dissolves in water to generate hydrogen peroxide, (b) a carboxylic acid-based polymer, and (c) a calcium-insensitive surfactant. A powder bleaching composition, which is substantially free. 2. (d) An organic peracid precursor represented by the general formula I: R-CO-L-(I) (In the formula, R is an alkyl group having 8 to 14 carbon atoms, alkenyl. Represents a group, an alkanoyloxymethyl group, or a phenyl group, L is a leaving group having a hydrophilic group, and the rate constant of hydrogen peroxide decomposition of the bleach activator is 5 liter / mol / se.
c represents a group that imparts the above property. ) The powder bleaching composition according to claim 1, further comprising: