JPH09194883A - Bleach activator particles - Google Patents

Abstract

(57) Abstract: A bleach activator particle having excellent storage stability is provided. SOLUTION: (a) a bleach activator having the following structure, and (b) 20
Bleaching activator particles containing an inorganic salt having no water of crystallization at (° C.), (c) an organic acid containing two or more carboxylic acids in the molecule, and (d) a surfactant in specific proportions. Embedded image [In the formula, R: an alkyl group having 5 to 18 carbon atoms, an alkenyl group having 5 to 18 carbon atoms, an alkanoyloxymethyl group having 2 to 18 carbon atoms in total or a phenyl group L: a leaving group. ]

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to bleach activator particles having excellent storage stability.

[0002]

BACKGROUND OF THE INVENTION Peroxide compounds such as perborates, percarbonates, perphosphates and persilicates, both dyed and undyed textiles. It is effective for chemical bleaching of stains found in. These compounds are most effective at high washing temperatures, for example at or near the boiling temperature of water, but at lower temperatures they are less effective.

Therefore, it is known in the art to use an organic peracid having a higher bleaching effect and an organic peracid precursor (bleach activator) which generates an organic peracid. This organic peracid precursor reacts with an inorganic or organic hydrogen peroxide compound in an aqueous solution to generate a corresponding organic peracid. Most of these organic peracid precursors contain perhydrolyzable N-acyl or O-acyl residues. Many investigators have investigated organic peracid precursors, for example British Patents 836,988 and 854,798 are early patents in the art. They disclose several esters, including those of sodium acetoxybenzene sulfonate and sodium phenol sulfonate. Also, for example, in British Patent No. 855,735, N, N,
Acylorganamides to which N ', N' tetraethylenediamine (TAED) belongs are disclosed.

Such organic peracid precursors are described in detail in the literature, for example Detergent Age June 1967, p.
Al mentioned in ages 18-20, july 1967, pages 30-33 etc.
A series of documents by lanH. Gilbert, as well as British Patent 83698
No. 8, 855735, 907356, 907358, 970950, 10033
No. 10, 1246339, etc., U.S. Pat. No. 3332882, 3277750,
It is described in the specifications of 4128494 and 4412934.

However, since these organic peracid precursors must be used at the same time as the hydrogen peroxide releasing substances such as sodium percarbonate and sodium perborate, they are usually mixed in a bleaching detergent composition. The organic peracid precursor and hydrogen peroxide releasing substance are premixed. Therefore, there is a problem that the organic peracid precursor reacts with hydrogen peroxide or the like during storage and decomposes, and sufficient performance is not exhibited during use.

[0006]

As a result of earnest research, the present inventors have found that the water of crystallization of inorganic salts in the composition affects the stability of the bleach activator during storage, and A bleaching detergent composition containing bleaching activator particles containing an inorganic salt having no water of crystallization, a specific bleaching activator, an organic acid having two or more carboxyl groups in the molecule, and a surfactant. It was found that a bleaching detergent composition having excellent storage stability can be obtained by blending it with the above, and the present invention has been completed.

That is, the present invention provides bleaching activator particles characterized by containing the following components (a) to (d). (a) 10 to 80% by weight of bleach activator having the following structure

[0008]

Embedded image

[Wherein R represents an alkyl group having 5 to 18 carbon atoms, an alkenyl group having 5 to 18 carbon atoms, an alkanoyloxymethyl group having 2 to 18 carbon atoms in total, or a phenyl group L: a leaving group. ] (B) Inorganic salts that do not have water of crystallization at 20 ° C
Wt% (c) Organic acid containing two or more carboxylic acids in the molecule 1
-40 wt% (d) Surfactant 0.1-20 wt%.

The bleach activator, which is the component (a) of the present invention, has the following structure:

[0011]

Embedded image

[Wherein R represents an alkyl group having 5 to 18 carbon atoms, an alkenyl group having 5 to 18 carbon atoms, an alkanoyloxymethyl group having 2 to 18 carbon atoms in total, or a phenyl group L: a leaving group. In particular, those represented by the following general formula are preferable.

[0013]

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[In the formula, R is an alkyl group having 5 to 18 carbon atoms or an alkenyl group having 5 to 18 carbon atoms X is a salt of a sulfonic acid or a carboxylic acid. Among these, the following compounds are more preferable, and among them, those in which an anion group (-COONa, -SO ₃ Na) is bonded at the ortho position or the para position with respect to the RCOO- group which produces an organic peracid is more preferable. It exhibits excellent storage stability.

[0015]

[Chemical 6]

The carbon number of R in the above formula is 5 to 18, preferably 7 to 12, and particularly preferably 8 to 11. In the present invention, the blending amount of the bleach activator is 10 to 80% by weight, preferably 20 to 70% by weight, from the viewpoint of the bleaching effect.

Decomposition of the bleach activator is promoted by moisture in the air during storage. Therefore, in the present invention, the stability of the bleaching activator is improved by using an inorganic salt in which the amount of water of crystallization falls within a specific range. That is, in the present invention, an inorganic salt which does not have 1 mol or more of water of crystallization at 20 ° C. is added as an essential component. Examples of such inorganic salts include sodium nitrate, sodium chloride, potassium sulfate, potassium nitrate, potassium phosphate and the like.
Of these, sodium chloride, potassium sulfate and potassium phosphate are particularly preferable, and sodium chloride is most preferable. The blending amount of these inorganic salts is 0.05 to 20% by weight, more preferably 0.1 to 10% by weight from the viewpoint of the effect of improving the storage stability of the bleaching activator.

The organic salt containing two or more carboxylic acids in one molecule, which is an essential component of the present invention, is necessary for changing the atmosphere of the blended composition from neutral to acidic. Examples of such organic acid include succinic acid, malic acid, maleic acid, citric acid, fumaric acid, tartaric acid, etc., preferably succinic acid and citric acid, and most preferably succinic acid.
The amount of the organic acid compounded is 1 to 40% by weight, preferably 1 to 30% by weight, for the purpose of maintaining an acidic atmosphere and from the viewpoint of the stability of the bleaching activator.

In the present invention, a surfactant is added as the component (d). As the surfactant, at least one surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants is used. The component surfactant is blended in the composition in an amount of 5 to 40% by weight, preferably 10 to 30% by weight, from the viewpoint of solubility and stability of the bleaching activator particles.

Examples of these surfactants are alkylbenzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or Alkenyl ether carboxylates, α-sulfo fatty acid salts, or α-sulfo fatty acid esters, alkyl glyceryl ether sulfonic acid, fatty acid monoglyceride sulfuric acid and sulfonic acid, alkylphenol polyethoxy ether sulfuric acid, 2-acyloxyalkane-1-sulfonic acid, β -Anionic surfactants such as water-soluble salts of alkyloxyalkanesulfonic acids, polyoxyethylene alkyl or alkenyl ethers, polyoxyethylene alkylphenyl ethers , Higher fatty acid alkanolamides or alkylene oxide adducts thereof, nonionic surfactants such as sucrose fatty acid esters and alkyl glycosides, amphoteric surfactants such as amine oxides, sulfobetaines and carbobetaines, or Examples include cationic surfactants such as quaternary ammonium salts. Among these, particularly alkyl (C _{10 to} C ₂₀ ) benzene sulfonates, alkyl or alkenyl sulfates having 10 to 20 carbon atoms, α-olefin sulfonates, 10 to 10 carbon atoms
Particularly preferred are 20 alkyl or alkenyl ether sulfates, polyoxyethylene alkyl or alkenyl ethers having 10 to 20 carbon atoms and 4 to 30 moles of oxyethylene added, and sulfobetaine or carbobetaine having an alkyl group having 8 to 20 carbon atoms. preferable.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION At the time of washing, it is necessary to use hydrogen peroxide or a hydrogen peroxide releasing substance together with the bleach activator particles of the present invention. The bleaching activator as the component (a) reacts with hydrogen peroxide in water to form an organic peracid and exert a bleaching effect.
Examples of hydrogen peroxide emitters include percarbonates, perborates, persulfates and perphosphates. Among these, percarbonate and perborate are preferable, and percarbonate is most preferable. From the viewpoint of the bleaching effect and the stability of the bleaching activator, the amount of the hydrogen peroxide releasing agent is 1 to 80% by weight, preferably 5% by weight based on the total amount of the bleaching activator particles and the hydrogen peroxide releasing agent.
-60% by weight, particularly preferably 10-50% by weight. Although sodium salt is generally used as the percarbonate, a chelating agent such as polyacrylic acid, hydroxypolyacrylic acid, or an organic phosphorus compound may be added, and boric acid or borate (especially sodium metaborate) may be added. The effect of a catalyst that accelerates the decomposition of zeolite or the like can be suppressed by coating with.

Further, the bleach activator particles of the present invention have the above-mentioned components (a) to (d) as essential components, but other optional components may be blended.

For example, the bleaching activator particles of the present invention may optionally contain a sequestering agent. The sequestering agent, 1) phosphoric acid compounds such as phytic acid or their alkali metal salts, alkaline earth metal salts, ammonium salts or alkanolamine salts 2) ethane-1,1-diphosphonic acid, ethane-1, 1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, ethanehydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxy Phosphonic acid such as phosphonic acid or alkali metal salt, alkaline earth metal salt, ammonium salt or alkanolamine salt thereof 3) Acrylic acid, maleic acid, itaconic acid, anicottic acid, methacrylic acid, fumaric acid, 2-hydroxyacrylic acid , Citraconic acid and other polymers or copolymers of two or more of them, having an average molecular weight of 500 to 100,000. Polycarboxylic acids in which one or all of silyl groups may be alkali metal salts, alkaline earth metal salts, ammonium salts, alkanolamine salts 4) 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane- Phosphonocarboxylic acids such as 2,3,4-tricarboxylic acid and α-methylphosphonosuccinic acid or their alkali metal salts, alkaline earth metal salts, ammonium salts or alkanolamine salts 5) Aspartic acid, glutamic acid, glycine, etc. Amino acids or their alkali metal salts, alkaline earth metal salts, ammonium salts or alkanolamine salts 6) Nitrilo 3 acetic acid, iminodiacetic acid, ethylenediamine 4
Aminoacetic acid such as acetic acid, diethylenetriamine pentaacetic acid, glycol ether diamine tetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetramine hexaacetic acid, and dienecoric acid, or their alkali metal salts, alkaline earth metal salts, ammonium salts or alkanolamine salts 7 ) Organic acids such as diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethylsuccinic acid, carboxymethyltartaric acid or alkali metals thereof. Salts, alkaline earth metal salts, ammonium salts or alkanolamine salts 8) Alkaline metal salts of aluminosilicate represented by zeolite A, alkaline earth metal salts and the like.

Of these, at least one selected from 2), 3), 6) and 8) is particularly preferable. The amount of the sequestering agent is 0.05 to 10% by weight in the bleach activator particles.
More preferably, 0.1 to 5% by weight is desirable.

The bleaching activator particles of the present invention may be mixed with washing particles such as sodium carbonate and silicate together with the above-mentioned hydrogen peroxide releasing substance, and conversely, the bleaching activator particles may be used as an auxiliary agent for usual detergent particles. The bleaching detergent composition may be prepared by adding the agent particles and the hydrogen peroxide releasing substance. As the detergent particles used in the bleaching detergent composition, generally known detergent particles are used. As components, in addition to the above-mentioned surfactant and zeolite, for example, an alkaline agent such as sodium carbonate, bleaching fiber Chino Pearl CBS (manufactured by Ciba Geigy) and Chino Pearl SWN as fluorescent whitening agents to increase the bleaching effect.
(Manufactured by Ciba Geigy), fluorescent whitening agents such as color index fluorescent whitening agents 28, 40, 61, 71, etc., lipases, various amylases, proteases, enzymes such as cellulase, and bulking agents such as mirabilite. Etc. can be blended as needed. Further, as an organic builder, an acrylic acid-based polymer such as polyacrylic acid or acrylic acid-maleic acid copolymer, a polyacetal carboxylate typified by Builder U, an organic chelating agent such as a maleate salt or a succinate salt, and the like are blended. be able to. Further, various trace additives such as colorants such as dyes and pigments, fragrances, silicones, bactericides, and ultraviolet absorbers can be blended in appropriate amounts.
These optional components may be added to the bleaching activator particles as long as they do not impair the effects of the bleaching activator particles.

The bleaching activator particles of the present invention are as follows:
Put the bleach activator of the component and the component containing the inorganic salt of the component (b) into a mixer (for example, a high speed mixer),
After mixing and heating, if the component (c) organic acid, component (d) surfactant, or component (d) surfactant does not exhibit binder properties, use polyethylene glycol, etc. as the binder component. The mixture is added and mixed, further compacted by an extrusion granulator, sized and classified to obtain bleach activator particles (granulated product). A bleaching detergent composition can be obtained by dry blending the obtained bleach activator granules with a cleaning component or detergent particles containing a hydrogen peroxide releasing substance such as sodium percarbonate and optional components.

[0027]

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

<Synthesis Method of Organic Peracid Precursor> (1) Synthesis of Bleach Activator a 100 g (0.46 mol) of sodium p-phenol sulfonate, which had been dehydrated in advance, was dispersed in 300 g of dimethylformamide (DMF). While stirring with a mechanical stirrer, lauric acid chloride was added dropwise at 50 ° C over 30 minutes. After completion of dropping, the reaction was carried out for 8 hours. After DMF was distilled off under reduced pressure, recrystallization was carried out with a water / acetone (= 1/1 mol) solvent to obtain a bleaching activator a shown below.

[0029]

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(2) Synthesis of bleach activator b Sodium p-phenolcarboxylate previously dehydrated
100 g (0.46 mol) was dispersed in 300 g of dimethylformamide (DMF), and lauric acid chloride was added dropwise at 50 ° C. over 30 minutes while stirring with a mechanical stirrer. After the dropping was completed, the reaction was carried out for 8 hours. After the DMF was distilled off under reduced pressure, recrystallization was carried out with a water / acetone (= 1/1 mol) solvent to obtain a bleaching activator b shown below.

[0031]

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(3) Synthesis of bleach activator c Sodium p-phenolcarboxylate dehydrated in advance
100 g (0.46 mol) was dispersed in 300 g of dimethylformamide (DMF), and myristic acid chloride was added dropwise at 50 ° C. over 30 minutes while stirring with a mechanical stirrer. After completion of dropping, the reaction was carried out for 8 hours. After DMF was distilled off under reduced pressure, recrystallization was carried out with a water / acetone (= 1/1 mol) solvent to obtain a bleaching activator c shown below.

[0033]

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(4) Synthesis of Bleach Activator d Sodium o-phenolcarboxylate which has been dehydrated in advance
100 g (0.46 mol) was dispersed in 300 g of dimethylformamide (DMF), and lauric chloride was added dropwise at 50 ° C. over 30 minutes while stirring with a mechanical stirrer. After completion of dropping, the reaction was carried out for 8 hours. After DMF was distilled off under reduced pressure, recrystallization was carried out with a water / acetone (= 1/1 mol) solvent to obtain a bleaching activator d shown below.

[0035]

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Example 1 Bleach activator particles having the composition shown in Table 1 were prepared as follows, and the amount of sodium percarbonate shown in Table 1 and a balanced amount of Glauber's salt were dry-blended to form a bleaching detergent composition. The product was prepared and the storage stability was evaluated by the following method. <Manufacturing method of bleach activator particles> After adding the bleach activator and the components shown in the column of bleach activator particles in Table 1 to a mixer (Fukae Kogyo Co., Ltd., High Speed Mixer), jacket temperature 80 ℃, spindle speed 200 rpm,
The rotation speed of the pulverization blade was 1500 rpm, the mixture was heated, the organic acid and polyethylene glycol were added at the ratios shown in Table 2, and the mixture was extracted when the powder temperature reached 70 ° C. The mixture thus obtained was extruded through an extrusion granulator (Fuji Paudal, Pelletable) through a pore size of 800 μm to perform consolidation formation. The extruded granules were cooled by a vibration cooler (Fuji Paudal, vibro, flow dryer) and pulverized by a granulator (Fuji Paudal, knife cutter). The obtained crushed material is classified with a classifier (Tokuju Seisakusho, Kotobuki type vibrating sieve) to obtain a particle size of 200 to 1
It was adjusted to 500 μm. The water content of the granulated product was adjusted to less than 1%. <Evaluation method of storage stability> Each of the ingredients in the table was mixed uniformly with powder, and 10 g of each was placed in a ternary container with a lid and placed in a constant temperature bath at a temperature of 40 ° C and a humidity of 80% for 6 weeks. After storage, the residual rate of the bleach activator was measured by liquid chromatography.

[0037]

[Table 1]

Test Example 2 A bleaching detergent composition having a composition shown in Table 2 was prepared by mixing the bleaching activator particles having the composition shown in Table 2 with sodium percarbonate and the detergent particles shown in Table 2 by the following method. Was prepared and the storage stability was evaluated in the same manner as in Example 1. <Preparation of Bleaching Detergent Composition> The bleaching activator particles prepared according to the method of Example 1 were mixed with the detergent particles in Table 2.
That is, among the components in Table 2, the components except for the bleaching activator particles, a part of sodium carbonate (anhydrous), sodium percarbonate, the enzyme and the nonionic activator were uniformly mixed in a kneader, and the nonion was added thereto. Spray and mix activator. It was molded to some extent with a high-speed mixer (Fukae Kogyo Co., Ltd.) and shaped with a marumerizer. After that, the removed components are added and mixed to obtain the final composition.

[0039]

[Table 2]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location D06L 3/00 D06L 3/00 (72) Inventor Miyuki Hanada 1334 Minato Minato, Wakayama, Wakayama Ken Lab. In-house (72) Inventor Soro Aoyagi 1334 Minato Minato, Wakayama, Wakayama Kao Co., Ltd.

Claims (6)

[Claims] 1. A bleach activator particle comprising the following components (a) to (d). (a) Bleach activator having the following structure: 10 to 80% by weight [Chemical formula 1] [In the formula, R represents an alkyl group having 5 to 18 carbon atoms, an alkenyl group having 5 to 18 carbon atoms, an alkanoyloxymethyl group having 2 to 18 carbon atoms in total, or a phenyl group L: a leaving group. ] (B) Inorganic salts that do not have water of crystallization at 20 ° C
Wt% (c) Organic acid containing two or more carboxylic acids in the molecule 1
〜40wt% (d) Surfactant 0.1〜20wt% 2. The bleach activator particles according to claim 1, wherein the bleach activator as the component (a) is represented by the following general formula. Embedded image [In the formula, R: an alkyl group having 5 to 18 carbon atoms or an alkenyl group having 5 to 18 carbon atoms X: a salt of a sulfonic acid or a carboxylic acid. ] 3. The bleach activator particles according to claim 1, wherein the organic acid having two or more carboxylic acid groups in the molecule of component (c) does not have an unsaturated bond in the molecule. 4. The bleach activator particles according to any one of claims 1 to 3, wherein a pH of the component (b) at 20 ° C. when the inorganic salt having no water of crystallization is dissolved is 7 or less. 5. The bleach activator particles according to claim 1, wherein the inorganic salt having no water of crystallization at 20 ° C. of the component (b) is sodium chloride. 6. The blending amount of the surfactant as the component (d) is 10 to 10.
The bleach activator particles according to any one of claims 1 to 5, which is 30% by weight.