JPH08143894A - Bleach detergent composition - Google Patents

Abstract

(57) [Summary] (Modified) [Structure] (a) 0.5 to 30% by weight of sodium percarbonate coated with a polymer or an inorganic salt, and (b) alkyl having 1 to 21 carbon atoms represented by the general formula 1. A bleaching detergent composition containing 0.1 to 10% by weight of an acyloxybenzenecarboxylic acid salt having a group and 0.05 to 5.0% by weight of (c) an alkyl sulfate having an alkyl group having 1 to 5 carbon atoms. [R represents an alkyl group having 1 to 21 or an alkenyl group or an aryl group which may be substituted with an alkyl group, and M represents H or an organic or inorganic cation. [Effect] It has excellent storage stability and solubility, and exhibits a bleaching effect immediately after long-term storage.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a bleaching detergent composition, and more particularly to a bleaching detergent composition having excellent storage stability and solubility.

[0002]

2. Description of the Related Art Oxygen-based bleaching agents which have hitherto been used as bleaching agents for clothes include sodium percarbonate and perboric acid which dissolve in water to release hydrogen peroxide. Sodium is widely used in terms of bleaching performance and safety.

However, since the oxygen-based bleaching agent has a weaker bleaching power than the chlorine-based bleaching agent, various bleaching activators have been used together to enhance the bleaching power.

As such a bleach activator, tetraacetylethylenediamine, acetoxybenzenesulfonate, tetraacetylglycolyl, glucose pentaacetate and the like are typically used.

Generally, these bleach activators are blended as granules in order to suppress decomposition during storage, but storage stability is not sufficient by itself. Further, since the granulated product of the bleaching activator is compacted, the solubility is lowered, and there is a problem that sufficient bleaching performance cannot be exhibited.

Therefore, the problem to be solved by the present invention is to provide a bleaching detergent composition having excellent storage stability and good solubility.

[0007]

As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a specific acyloxybenzenecarboxylic acid salt as a bleach activator and blended sodium percarbonate with a coating. As a result, they have found that the storage stability of the bleaching activator is improved, and that the solubility of the bleaching activator is promoted by blending a lower alkyl sulfate, and the present invention has been completed. That is,
The present invention comprises: (a) 0.5 to 30% by weight of coated sodium percarbonate (b) 0.1 or less of an organic peracid precursor represented by the following general formula (1).
~ 10% by weight

[0008]

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[In the formula, R represents an alkyl group of 1 to 21, an alkenyl group or an aryl group which may be substituted with an alkyl group, and M represents H or an organic or inorganic cation. ] (C) Alkyl sulfate having an alkyl group having 1 to 5 carbon atoms
A bleaching detergent composition characterized by containing 0.05 to 5.0% by weight. Hereinafter, the present invention will be described in detail.

[Component (a)] The component (a) of the present invention is obtained by coating sodium percarbonate (hereinafter referred to as PC) with a water-soluble polymer or an inorganic salt.

As the component (a), sodium percarbonate coated by a known method can be used, and examples thereof include JP-B-47-32200 (PC coated with paraffin) and JP-B-SHO.
53-15717 (PC coated with sodium perborate), U.S. Pat. No. 4,131,562 (PC coated with sodium perborate and ethylene oxide adduct of alcohol), U.S. Pat. No. 4,12081.
No. 2 (PC and sodium perborate coated with polyethylene glycol), German Patent No. 2712139 (PC coated with silicate), German Patent No. 2800916 (PC coated with boric acid), European Patent No. 30759 (PC With wax),
JP-A-58-217599 (PC coated with borate), JP-A-58-217599
59-196399 (PC coated with borate), JP-A-4-31
Those obtained by the method described in No. 498 (PC is sprayed with boric acid and silicate separately) can be used. Among these, especially German Patent No. 2800916,
JP-A-58-217599, JP-A-59-196399, JP-A-4-
Coated PC obtained by the method described in 31498 is preferred.

The component (a) is incorporated in the composition in an amount of 0.5 to 30% by weight, preferably 1 to 25% by weight, more preferably 2 to 20% by weight.

[Component (b)] The component (b) of the present invention is an organic peracid precursor represented by the general formula (1).

[0014]

[Chemical 4]

[In the formula, R represents an alkyl group of 1 to 21, an alkenyl group or an aryl group which may be substituted with an alkyl group, and M represents H or an organic or inorganic cation. In the general formula (1), R is preferably an alkyl group having 5 to 14 carbon atoms, and M is preferably H 2, sodium or potassium. More specific examples include the following compounds.

[0016]

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The component (b) is contained in the composition in an amount of 0.1 to 10% by weight, preferably 0.3 to 8% by weight, more preferably 0.5 to 10% by weight.
6% by weight is blended.

[Component (c)] The component (c) of the present invention is an alkylsulfate having an alkyl chain having 1 to 5 carbon atoms (hereinafter referred to as lower alkylsulfate), and sodium methylsulfate,
Sodium ethylsulfate is particularly preferred. This is compounded in the composition in an amount of 0.05 to 5% by weight, preferably 0.06 to 4.7% by weight, more preferably 0.07 to 4.5% by weight.

The lower alkyl sulfate as the component (c) is
It accelerates the solubilization of the organic peracid precursor of the component (b), and is preferably granulated together with the component (b) and blended in the composition. At that time, it is desirable to mix a thin film-forming polymer compound and mix it into the composition as a granulated product having an average particle diameter of 300 to 2000 μm. As the thin film-forming polymer compound used for forming the granulated product, polyethylene glycol (average molecular weight: 400 to 20000), polyoxyethylene alkyl ether (ethylene oxide addition mole number: 3 to 30)
0, an alkyl chain length of about 8 to 22), and one or more selected from carboxymethyl cellulose are preferable. The blending amount of the thin film-forming polymer compound is not particularly limited, but (b)
About 0 to 50% by weight is desirable with respect to the total of the components and the component (c). The average particle size of the granulated product of the components (b) and (c) is not particularly limited, but is 100 to 2000 μm, preferably about 200 to 1500 μm. Further, it is also preferable to coat the surface of the granulated product in order to maintain stability. Of course, the component (b) and the component (c) may be blended separately,
Further, the composition may be blended without being granulated.

[Optional Components] In addition to the above-mentioned essential components, the bleaching detergent composition of the present invention may contain the following components usually added to bleaching detergent compositions.

(A) Component (d) The composition of the present invention contains a crystalline alkali metal silicic acid represented by the following general formulas (2) and (3) for the purpose of improving the stability of the organic peracid precursor. You may mix | blend a salt as (d) component.

XM ₂ O.ySiO ₂ .z (Me _m O _n ) .wH ₂ O (2) (In the formula, M is an Ia element in the periodic table, and Me is IIa, IIb, IVa.
Alternatively, it represents one or a combination of two or more selected from Group VIII elements, y / x = 0.5 to 4.0, z / x = 0.01 to 1.0
, N / m = 0.5 to 2.0 and w = 0 to 20. _{) M 2 O · x'SiO 2 ·} y'H 2 O (3) ( wherein, M is an alkali metal, x '= 1.5~4.0, y' = 0~
20).

In the crystalline alkali metal silicate of the general formula (2), M is selected from Group Ia elements of the periodic table,
Na and K are preferred. Me is IIa, IIb, IIIa of the periodic table,
It is selected from Group VIII elements, especially Mg, Ca, Zn, Y, Ti, Zr,
Fe and the like are preferable. Of these, Mg and Ca are particularly preferable.
Further, the crystalline alkali metal silicate of the present invention may be a hydrate, and the hydration amount in this case is w = 0.
The range of -20 is preferred.

Further, in the general formula (2), y / x is 0.5 to
It is 4.0, preferably 1.5 to 2.6. y / x
If it is less than 0.5, the water resistance is insufficient, and the caking property, the solubility, and the powder physical properties of the detergent composition are significantly adversely affected. When y / x exceeds 4.0, the ion exchange capacity is low and the ion exchanger is insufficient. z / x is 0.01 ~
It is 1.0, preferably 0.02 to 0.9. z /
If x is less than 0.01, the water resistance is insufficient, and if it exceeds 1.0, the ion exchange capacity tends to be low. x,
There is no particular limitation as long as y and z satisfy the relationships shown in the above y / x and z / x.

The crystalline alkali metal silicate according to the present invention comprises M ₂ O, SiO ₂ , and
It is composed of three to five components of Me _m O _n , and each component is not particularly limited as a raw material, and known compounds are appropriately used.

The method for preparing the crystalline alkali metal silicate according to the present invention is to mix the raw material components in a predetermined quantitative ratio so that the desired x, y, z values of the crystalline alkali metal silicate are obtained. , Usually 300 ~ 1500 ℃, preferably 500 ~ 1000 ℃,
More preferred is a method of crystallization by firing in the range of 600 to 900 ° C. In this case, if the heating temperature is lower than 300 ° C, crystallization is insufficient and the water resistance is poor. Again 1500
If the temperature exceeds ℃, coarse particles are formed and the ion exchange capacity is lowered. The heating time is usually 0.1 to 24 hours. Such firing can be usually performed in a heating furnace such as an electric furnace or a gas furnace.

The crystalline alkali metal silicate according to the present invention has an ion exchange capacity of at least 100 mg CaCO ₃ / g.
As described above, it preferably has 200 to 600 mg CaCO ₃ / g, and is one of the substances having the ion trapping ability in the present invention. The amount of Si eluted into water is usually 110 in terms of SiO _2.
It is below mg / g and practically insoluble in water. In the present invention, “substantially insoluble in water” means that the amount of Si eluted when 2 g of a sample is added to 100 g of ion-exchanged water and stirred at 25 ° C. for 30 minutes is usually less than 110 mg / g in terms of SiO _2. In the present invention, 100 mg / g or less is more preferable in order to satisfy the present effect.

The crystalline alkali metal silicate according to the present invention has an ion-exchange ability as described above, and therefore the washing conditions described above can be suitably adjusted by appropriately adjusting the compounding amount.

In the present invention, the crystalline alkali metal silicate preferably has an average particle size of 0.1 to 20 μm, more preferably 1 to 10 μm. If the average particle size exceeds this range, the rate of ion exchange capacity tends to be slowed down, resulting in deterioration of detergency. On the other hand, if it is less than this range, the hygroscopicity and CO ₂ absorption are increased due to the increase in the specific surface area, and the deterioration of the quality tends to be remarkable. The average particle size here is the median size of the particle size distribution.

Next, the crystalline alkali metal silicate represented by the general formula (3) will be described.

This crystalline alkali metal silicate has the general formula (3) M ₂ O.x'SiO ₂ .y'H ₂ O (3) (wherein M is an alkali metal, x '= 1.5 to 4.0). , Y '= 0
Although represented by 20), x ', y'in the general formula (3)
Is preferably 1.7 ≦ x ′ ≦ 2.2 and y ′ = 0, and a cation exchange capacity of 100 to 400 mgCaCO ₃ / g can be used, and is one of the substances having an ion-trapping capacity in the present invention.
The crystalline alkali metal silicate in the present invention has the alkaline ability and the alkaline buffering effect as described above, and further has the ion exchange ability. Therefore, by appropriately adjusting the blending amount thereof, the above-mentioned washing conditions are suitably adjusted. Can be adjusted.

Such a crystalline alkali metal silicate is described in Japanese Patent Application Laid-Open No. 227895/1985, which is generally prepared by firing amorphous glassy sodium silicate at 200 to 1000 ° C. It is obtained by making it crystalline. Details of the synthesis method are described in, for example, Phys. Chem. Glasses, 7, 127-138 (196
6), Z. Kristallogr., 129, 396-404 (1969) and the like. The crystalline alkali metal silicate is available from Hoechst under the trade name “Na-SKS-6” (δ-Na ₂ Si ₂ O ₅ ) in powder or granular form.

In the present invention, the crystalline alkali metal silicate having the composition of the general formula (3) preferably has an average particle size of 0.1 to 20 μm, like the composition of the general formula (2). More preferably, it is 1 to 10 μm.

The content of the crystalline alkali metal silicate having the composition of the general formulas (2) and (3) as described above is preferably 1 to 50% by weight based on the total composition.

(B) Component (e) The composition of the present invention may contain an aluminosilicate represented by zeolite in an amount of 0 to 50% by weight, preferably 1 to 50% by weight, more preferably 3 to 45% by weight. . By incorporating an aluminosilicate, excellent detergency can be obtained and the physical properties of the powder can be improved.

(C) Surfactant The composition of the present invention may contain a surfactant such as an anionic surfactant or a nonionic surfactant.

The anionic surfactant has an average carbon number of 8
~ 22 alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate ester salt, α-olefin sulfonate, alkane sulfonate, saturated or unsaturated fatty acid salt, N-acyl amino acid type surfactant, Examples thereof include alkyl or alkenyl ether carboxylic acid salts, amino acid type surfactants, alkyl or alkenyl phosphate esters or salts thereof, and the like. Of these, alkylbenzene sulfonates and alkyl sulfate ester salts are preferable, and potassium alkylbenzene sulfonate is particularly preferable as the component (f) in the range of 1 to 60.
It is more preferable to add the composition in a weight percentage.

As the nonionic surfactant, for example, polyoxyalkylene alkyl (or alkenyl) is used.
Examples thereof include ethers, polyoxyethylene alkylphenyl ethers, higher fatty acid alkanolamides or alkylene oxide adducts thereof, sucrose fatty acid esters, alkyl glycosides, fatty acid glycerin monoesters and the like. Of these, the following nonionic surfactants (1) to (3) are particularly preferable.

(1) A polyoxyethylene alkyl ether having an alkyl group having an average carbon number of 10 to 20 and having 1 to 30 mol of ethylene oxide added thereto. (2) A polyoxyethylene alkylphenyl ether having an alkyl group having an average carbon number of 9 to 12 and having 1 to 25 mol of ethylene oxide added thereto. (3) An alkyl glycoside represented by the following general formula (4). R ′ (OC ₂ H ₄ ) _p G _q (4) (wherein R ′ is an alkyl group having 9 to 14 carbon atoms, p is a number from 0 to 2, G is a glucose, fructose, maltose or sucrose residue, q is a number of 1 to 4, preferably 1, 2 or 3.) The amount of the anionic surfactant and nonionic surfactant blended is preferably 1 to 60% by weight in the entire composition.

In addition to the composition of the present invention, a betaine type amphoteric surfactant, a sulfonic acid type amphoteric surfactant, a phosphate ester type surfactant, a cationic surfactant and the like may be added.

(D) Builder The composition of the present invention may contain the following cleaning builders which can be generally added to detergents or bleaches.

[1] Divalent metal ion scavenger One or more builder components of the following various alkali metal salts and alkanolamine salts can be blended in an amount of 0 to 50% by weight. (1) Phosphates such as orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate and phytate. (2) ethane-1,1-diphosphonate, ethane-1,
1,2-triphosphonate, ethane-1-hydroxy-
1,1-diphosphonate and its derivatives, ethanehydroxy-1,1,2-triphosphonic acid, ethane-1,2-
Salts of phosphonic acids such as dicarboxy-1,2-diphosphonic acid and methanehydroxyphosphonic acid. (3) 2-phosphonobutane-1,2-dicarboxylic acid, 1-
Salts of phosphonocarboxylic acids such as phosphonobutane-2,3,4-tricarboxylic acid and α-methylphosphonosuccinic acid. (4) Amino acid salts such as aspartic acid, glutamic acid and glycine. (5) Aminopolyacetates such as nitrilotriacetic acid salts, iminodiacetic acid salts, ethylenediaminetetraacetic acid salts, diethylenetriaminepentaacetic acid salts, glycol etherdiaminetetraacetic acid salts, hydroxyethyliminodiacetic acid salts, triethylenetetramine hexaacetic acid salts and dienecoric acid salts. (6) Polymer electrolytes such as polyacrylic acid, acrylic acid / maleic acid copolymer, polyfumaric acid, polymaleic acid, poly-α-hydroxyacrylic acid, polyacetalcarboxylic acid or salts thereof. (7) diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, gluconic acid, carboxymethyl tartaric acid,
Organic carboxylic acid salts such as carboxymethyl succinic acid.

[2] Alkaline Agent or Inorganic Electrolyte Alkali metal salts are preferable as salts such as silicates, carbonates and sulfates. [3] Anti-redeposition agent Polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, etc. [4] Enzyme Protease, lipase, amylase, cellulase and the like.
Particularly, it is preferable to add 0.1 to 5% by weight of the protease in the composition. [5] Peroxide Stabilizer Magnesium salts such as magnesium sulfate, magnesium silicate, magnesium chloride, magnesium fluorosilicate, magnesium oxide and magnesium hydroxide, and boric acid or salts thereof. [6] Perfume, fluorescent dye, pigment.

[0044]

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

[I] Coated PCs (a-1) and (a-2) were prepared by the following method. Coated PC (a-1) Based on Example 1 of JP-A-59-196399, sodium metaborate / tetrahydrate coated with 5% of sodium percarbonate was used as (a-1). Coated PC (a-2) Based on the manufacturing method of Example 1 of JP-A-4-31498,
What was coated with sodium percarbonate with boric acid and silicate was used as (a-2).

[II] Organic Peracid Precursor Granules Organic peracid precursor granules (b-1) to (b-
3) was prepared. 2.7 kg of organic peracid precursors represented by the following formulas (i) to (iii), 0.6 kg of polyethylene glycol (average molecular weight 6000), and sodium alkylsulfate shown in Table 1
A total of 1.7 kg, 5 kg in total, was charged into a mixer (manufactured by Fukae Kogyo Co., Ltd .; high speed mixer FS-GC-10 type), jacket temperature 80 ° C, spindle speed 200 rpm, crushing blade speed 1500 rp.
Mixing and heating were carried out at m 2, and the mixture was extracted when the temperature of the powder reached 70 ° C.

Then, the obtained mixture was extruded through an extruding granulator (Fuji Paudal Co., Ltd .: Pelleter Double ExD-100 type) through a screen having a pore size of 800 μm to densify it. The obtained extrudate was vibrated and cooled (by Fuji Paudal Co., Ltd .: vibro / flow dryer VDF / 6000).
After cooling with a mold, it was disintegrated with a granulator (manufactured by Fuji Paudal Co., Ltd .: knife cutter FL-200 model). The obtained crushed material is a classifier (Dokuju Seisakusho Co., Ltd .: Kotobuki type vibration sieve)
Particle size is 350-1400μm (weight average particle size)
900 μm) was used as an organic peracid precursor granule.

[0048]

[Chemical 6]

[0049]

[Table 1]

[III] Evaluation of Bleaching Detergent Composition (i) Bleaching Ratio of Black Tea-Contaminated Cloth The bleaching detergent composition shown in Tables 2 and 3 was prepared, and the concentration in the aqueous solution was adjusted to 0.0833%. It was dissolved in water and washed with a tergotometer at 20 ° C. for 10 minutes using a black tea-contaminated cloth (8 cm × 8 cm, 5 pieces) purified by the following method. After washing with water, drying and pressing, the bleaching rate was calculated by the following formula.

[0051]

[Equation 1]

The reflectance is NDR-1 manufactured by Nippon Denshoku Industries Co., Ltd.
Measured with a 460 nm filter at 01DP.

Black tea-contaminated cloth: 80 g of Nitto black tea (yellow package) is boiled in 3 liters of ion-exchanged water for about 15 minutes, and then rubbed with a desalted cotton cloth, and a cotton cloth # 2003 cloth is dipped in this solution. Boil for about 15 minutes. As it is, remove from the heat, leave it for about 2 hours, dry it, wash it with water until the washing liquid does not become colored, dehydrate, press, 8 cm × 8 cm
The test piece was used for the experiment.

(Ii) Measurement of Peracid Generation Rate A bleaching detergent composition having the composition shown in Tables 2 and 3 was added to 0.08
Add to 1 liter of deionized water so that it becomes 33%, and add 10
The mixture was stirred and mixed with a magnetic stirrer at 20 ° C. for 1 minute (using a 1-liter beaker, slurrer piece; length 30 mm, diameter 5 mm, stirring speed; 350 rpm).

Then, 10 ml of a 0.3% aqueous solution of catalase was added and stirred for 10 minutes to destroy excess hydrogen peroxide,
Using a known iodometric titration method, the amount of available oxygen from percarboxylic acid was measured to determine the organic peracid production rate.

(Iii) Storage stability of sodium percarbonate 5 g of 10 g of the bleaching detergent composition having the composition shown in Tables 2-3 was used.
It was put in a 50 ml ternary container with a gap between mm-width filter paper and stored in a storage room at 40 ° C / 80% RD for 2 weeks, and the residual ratio of available oxygen after storage was determined by the iodometric titration method. .

(Iv) Storage Stability of Organic Peroxy Acid Precursor The same preservation as the above sodium percarbonate was carried out, and the residual ratio of the organic peracid precursor was determined by high performance liquid chromatography.

[0058]

[Table 2]

[0059]

[Table 3]

Note) * 1: JIS No. 2 sodium silicate * 2: Layered silicate manufactured by Hoechst, average particle size 5 μm * 3: Average particle size 4 μm * 4: Alkyl group straight-chain alkylbenzene sulfone having 12 to 14 carbon atoms Potassium acid salt * 5: Sodium straight chain alkylbenzene sulfonate having 12 to 14 carbon atoms in the alkyl group * 6: Sodium straight chain alkyl sulfate having 12 to 14 carbon atoms in the alkyl group * 7: 12 carbon atoms in the alkyl group, ethylene oxide Polyoxyethylene alkyl ether with an average addition mole number of 8.5 * 8: Savinase 6.0T (manufactured by NOVO)

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Claims (9)

[Claims] 1. (a) Coated sodium percarbonate 0.5 to
30% by weight (b) Organic peracid precursor represented by the following general formula (1) 0.1
~ 10% by weight [Chemical formula 1] [In the formula, R represents an alkyl group of 1 to 21, an alkenyl group or an aryl group which may be substituted with an alkyl group,
M represents H or an organic or inorganic cation. ] (C) Alkyl sulfate having an alkyl group having 1 to 5 carbon atoms
A bleaching detergent composition containing 0.05 to 5.0% by weight. 2. The bleaching detergent composition according to claim 1, which further contains a crystalline alkali metal silicate as the component (d). 3. The bleaching detergent composition according to claim 1, further comprising an aluminosilicate as the component (e). 4. The bleaching detergent composition according to claim 1, further comprising, as the component (f), an alkylbenzene sulfonate having an alkyl chain having 10 to 16 carbon atoms. 5. The bleaching detergent composition according to claim 4, wherein the component (f) is potassium alkylbenzene sulfonate. 6. The component (b) and the component (c) are blended as a granulated product containing the component (b), the component (c) and a thin film-forming polymer compound and having an average particle diameter of 300 to 2000 μm. The bleaching detergent composition according to claim 1, wherein the bleaching detergent composition is a bleaching detergent composition. 7. The bleaching detergent composition according to claim 6, wherein the thin film-forming polymer compound is one or more selected from polyethylene glycol, polyoxyethylene alkyl ether, and carboxymethyl cellulose. 8. (a) Coated sodium percarbonate 0.5 to
30% by weight (b) Organic peracid precursor represented by the following general formula (1) 0.1
~ 10% by weight [Chemical formula 2] [In the formula, R represents an alkyl group of 1 to 21, an alkenyl group or an aryl group which may be substituted with an alkyl group,
M represents H or an organic or inorganic cation. ] (C) Alkyl sulfate having an alkyl group having 1 to 5 carbon atoms
0.05 to 5.0% by weight (d) Crystalline alkali metal silicate 1 to 50% by weight (e) Aluminosilicate 1 to 50% by weight (f) Alkylbenzenesulfonate having 10 to 16 carbon atoms in the alkyl chain A bleaching detergent composition containing 60% by weight. 9. The component (b) and the component (c) are blended as a granulated product containing the component (b), the component (c) and the thin film-forming polymer compound and having an average particle size of 300 to 2000 μm. 9. The bleaching detergent composition according to claim 8.