JPH0892595A - Bleaching cleanser composition - Google Patents

Abstract

PURPOSE: To obtain the subject composition comprising a specific potassium alkylbenzenesulfonate, sodium percarbonate, and an organic peracid precursor at a specified ratio and exhibiting an excellent effect on bleaching staining of blood. CONSTITUTION: This composition comprises (A) 2-30wt.% of an alkylbenzenesulfonate wherein the alkyl has 10-16 carbon atoms, (B) 2-30wt.% of coated sodium percarbonate, and (C) 0.1-10wt.% of an organic peracid precursor of the formula (R is 1-21C alkyl; M is Na, K, Mg; n is 1 when M is Na or K, and n is 2 when M is Mg). The composition preferably contains (D) 2-30wt.% of a 12-22C alkyl or 12-22C alkenyl a-olefin sulfonic acid potassium salt, (E) 1-50wt.% of a crystalline alkali metal silicate salt, and 1-50wt.% of an aluminosilicate salt in addition to the components A, B and C. The component C is preferably added as particles comprising the component C and a thin film-forming high-molecular compound and having an average particle diameter of 300-2000μm.

Description

Detailed Description of the Invention

[0001]

This invention relates to bleaching detergent compositions. More specifically, it relates to a bleaching detergent composition exhibiting an excellent bleaching effect on blood stains.

[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.
These bleach activators are often blended as granules in order to enhance storage stability.

There are various kinds of stains to be bleached. Among them, stains and stains caused by blood are strong and difficult to remove. For bleaching blood stains, it is known that an enzyme (protease) is blended with the above-mentioned oxygen-based bleaching agent, and a certain degree of effect can be obtained by their synergistic effect.

However, when a bleaching agent, particularly an organic peracid, reacts before the action of the protease, the protein in the blood is altered and the effect of the protease is deteriorated. In order to solve this, it is better to delay the production of organic peracid, but if you try to suppress the solubility of the bleach activator granules, undissolved granules will remain. Therefore, there is a problem that the bleaching target is partially decolorized. As described above, hitherto, no bleaching agent capable of exerting a sufficient bleaching effect on blood stains has been obtained.

Therefore, the problem to be solved by the present invention is to provide a bleaching detergent composition which exhibits an excellent bleaching effect against blood stains.

[0008]

As a result of intensive studies to solve the above problems, the present inventors used a specific acyloxybenzene sulfonate as a bleach activator to slow the dissolution of sodium percarbonate. Sodium percarbonate is coated in order to delay the production of organic peracid, and further combined with potassium alkylbenzene sulfonate having 10 to 16 carbon atoms in the alkyl chain, and by blending each in a specific ratio, the bleaching effect on blood stains can be improved. The inventors have found that a sufficient bleaching detergent composition can be obtained, and have completed the present invention.

That is, the present invention comprises: (a) 2 to 30% by weight of potassium alkylbenzene sulfonate having 10 to 16 carbon atoms in the alkyl chain (b) 0.5 to 30% by weight of coated sodium percarbonate (c) Organic peracid precursor of formula (I) 0.1
~ 10% by weight

[0010]

[Chemical 3]

(Wherein R is an alkyl group having 1 to 21 carbon atoms,
M represents a metal atom selected from sodium, potassium and magnesium. n is 1 if M is sodium or potassium, and 2 if M is magnesium. ) Is contained, and a bleaching detergent composition is provided.

Each component of the present invention will be described below.

[Component (a)] The component (a) of the present invention is potassium alkylbenzene sulfonate in which the alkyl chain has 10 to 16 carbon atoms. The alkyl chain preferably has 10 to 14 carbon atoms. If the number of carbon atoms in the alkyl chain is less than 10 or more than 16, the detergency will be poor. The component (a) is 2 to 30 in the composition.
% By weight, preferably 3-28% by weight, more preferably 5-
25% by weight is blended.

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

As the component (b), 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, among others, 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 (b) 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 (c)] The component (c) of the present invention is an organic peracid precursor represented by the above general formula (I).

In the general formula (I), R has 5 to 21 carbon atoms.
Is preferred, and M is preferably sodium or potassium.

The component (c) 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.

The organic peracid precursor as the component (c) is preferably blended with a thin film-forming polymer compound and blended in 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 average addition mole number: 3 to 300, alkyl chain length: 8 to 22) ) And one or more selected from carboxymethyl cellulose are preferable. The proportion of the thin film-forming polymer compound is not limited, but is about 0 to 50% by weight with respect to the component (c). The average particle size of the granulated product of component (c) is not limited, but is 100 to 2000 μm, preferably 200 to 1500 μm.
It is a degree. Further, it is also preferable to coat the surface of the granulated product in order to maintain stability. Of course, the component (c) may be blended in the composition without being granulated.

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

(A) Component (e) The composition of the present invention may contain a crystalline alkali metal silicate as the component (e) for the purpose of improving the stability of the organic peracid precursor.

Among the crystalline alkali metal silicates used in the present invention, those having the following composition are preferably exemplified. xM ₂ O ・ ySiO ₂・ z (Me _m O _n ) ・ wH ₂ O
(1) (In the formula, M is the element Ia in the periodic table, and Me is IIa, IIb, II.
One or two selected from Group Ia, IVa or VIII elements
A combination of two or more species is shown, y / x = 0.5 to 4.0, z / x =
0.01-1.0, n / m = 0.5-2.0, w = 0-20. _{) M 2 O · x'SiO 2 ·} y'H 2 O (2) ( wherein, M is an alkali metal, x '= 1.5 ~4.0, y ' = 0~
20).

First, the crystalline alkali metal silicate having the above composition will be described. In the general formula (1), M is selected from the group Ia elements of the periodic table, and examples thereof include Na and K. Me is IIa, IIb, IIIa, IVa or VI of the periodic table
Selected from Group II elements, for example Mg, Ca, Zn, Y, Ti, Zr,
Fe and the like are mentioned, and Mg and Ca are preferable. Further, the crystalline alkali metal silicate in the present invention may be a hydrated acid, and the hydration amount in this case is in the range of w = 0 to 20.

In the general formula, y / x is 0.5 to 4.0.
And preferably 1.5 to 2.6. If y / x is less than 0.5, the water resistance is insufficient and the caking property, solubility, and powder properties of the detergent composition are significantly adversely affected.
When y / x exceeds 4.0, the ion exchange capacity is also low, which is insufficient as an ion exchanger. z / x is 0.01 to 1.0, preferably 0.02 to 0.9. If z / x is less than 0.01, the water resistance is insufficient, and if it exceeds 1.0, the ion-exchange capacity is low, and the ion-exchanger is insufficient. x,
y and z are not particularly limited as long as they have the relationship 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 Me _m O as shown in the above general formula.
It is composed of three to five components of _n , and each component is not particularly limited as a raw material thereof, and a known compound is appropriately used.

The method for preparing a crystalline alkali metal silicate according to the present invention comprises mixing 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 preferable is a method of crystallization by firing in the range of 600 to 900 ° C. In this case, the heating temperature is 300 ℃
If it is less than 1, the crystallization will be insufficient and the water resistance will be poor, and if it exceeds 1500 ° C, coarse particles will be formed and the ion exchange ability will be 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.

Since the crystalline alkali metal silicate in the present invention has an ion exchange capacity as described above, the above washing conditions can be suitably adjusted by appropriately adjusting the compounding amount thereof.

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 diameter exceeds this range, the rate of ion exchange will tend to be slowed, resulting in a decrease in detergency. Further, if it is less than this range, the specific surface area increases, so that the hygroscopicity and CO absorption
₂ of increases, the deterioration of the quality is a significant trend. The average particle size here is the median size of the particle size distribution.

The crystalline alkali metal silicate having such average particle size and particle size distribution can be prepared by pulverizing with a pulverizer such as a vibration mill, a hammer mill, a ball mill, a roller mill. For example, HB-O
It can be easily obtained by crushing with a mold vibration mill (manufactured by Chuo Kakoki Co., Ltd.).

Next, the crystalline alkali metal silicate having the above composition will be described. This crystalline alkali metal silicate has the general formula (2) M ₂ O · x'SiO ₂ · y'H ₂ O (2) (wherein M is an alkali metal, x '= 1.5 to 4.0, y' = 0
20), where x'and y'in the general formula (2) are
It is preferable that 1.7 ≦ x ′ ≦ 2.2 and y ′ = 0, and a cation exchange capacity of 100 to 400 mg CaCO ₃ / g can be used, which 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.

The production method of such crystalline alkali metal silicate is described in JP-A-60-227895. Generally, amorphous glassy sodium silicate is calcined 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 a composition of, like the composition of, preferably has an average particle size of 0.1 to 20 μm, more preferably 1 to 10 μm.

The content of the crystalline alkali metal silicate having the composition as shown above is 1 to 50 in the total composition.
It is preferable to add the composition in a weight percentage.

(B) Component (f) 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. .

(C) Surfactant To the composition of the present invention, in addition to the component (a) potassium alkylbenzene sulfonate, other anionic surfactants, nonionic surfactants and other surfactants should be added. You can

The anionic surfactants include alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfate ester salts, α-olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates. , Amino acid type surfactants, N-acyl amino acid type surfactants, alkyl or alkenyl phosphate esters or salts thereof, and the like. Alkyl sulfate ester salts are particularly preferable. Further, it is desirable that 2 to 30% by weight of potassium α-olefinsulfonate [component (d)] having an alkyl group or an alkenyl group having 12 to 22 carbon atoms is blended in the composition.

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 alkylamine oxides. In the present invention,
The nonionic surfactants (1) to (3) are preferably used.

(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. R ⁴ (OC ₂ H ₄ ) _X G _y (In the formula, R ⁴ is an alkyl group having 9 to 14 carbon atoms, and x is 0 to 2
, G is glucose, fructose, maltose or scroll residue, y is 1 to 4, preferably 1, 2 to 3
Is the number of. ) The amount of the anionic surfactant and nonionic surfactant blended is preferably 1 to 60% by weight in the composition.

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

[D] Builder The composition of the present invention may contain the following washing builder which can be generally added to a detergent or a bleaching agent.

[1] Divalent metal ion scavenger One or more builder components of the following various alkali metal salts and alkanolamine salts may 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) Aminopolyesters such as nitrilotriacetic acid salt, iminodiacetic acid salt, ethylenediaminetetraacetic acid salt, diethylenetriaminepentaacetic acid salt, glycol etherdiaminetetraacetic acid salt, hydroxyethyliminodiacetic acid salt, triethylenetetramine hexaacetic acid salt, and dienecoric acid salt Acetate. (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) Organic persalts such as diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, gluconic acid, carboxymethylsuccinic acid and carboxymethyltartaric acid. Alkali metal salts are suitable as the salt. [2] Alkaline agents or inorganic electrolytes Silicates, carbonates, sulfates. Alkali metal salts are suitable as the salt. [3] Anti-redeposition agent Polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, etc. [4] Enzymes Proteases, lipases, amylases, cellulases, etc.
In particular, it is preferable to add a protease in the composition in an amount of from about 1% by weight. [5] Peroxide Stabilizer Magnesium salts such as magnesium sulfate, magnesium silicate, magnesium chloride, magnesium silicofluoride, magnesium oxide and magnesium hydroxide, and boric acid or salts thereof.

[6] Perfumes, fluorescent dyes, pigments.

[0045]

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

[I] Preparation of Coated Sodium Percarbonate Coated PC-1 Based on Example 1 of JP-A-59-196399, sodium metaborate tetrahydrate was coated at 5% with respect to sodium percarbonate. I used one.

Coated PC-2 Based on the production method of the product (1) of the present invention in Example 1 of JP-A-4-31498, a coating of sodium percarbonate with boric acid and silicate was used.

[II] Organic Peracid Precursor Granules Organic peracid precursor granules (I) to (III) were prepared by the following method and subjected to experiments.

Organic peracid precursors (i) to (iii) shown below
2.7 kg, polyethylene glycol (molecular weight 6000)
6 kg, 1.7 kg of sodium sulfate, 5 kg in total (Fukae Industry Co., Ltd .; High Speed Mixer FS-GC-10 type)
, Jacket temperature 80 ℃, spindle speed 200rpm,
Mixing and heating were carried out at a rotation speed of the crushing blade of 1500 rpm, and the mixture was extracted when the temperature of the powder reached 70 ° C.

Then, the obtained mixture was extruded and granulated by an extruder (manufactured by Fuji Paudal Co., Ltd .: pelleter double ExD-100 type).
Was extruded through a screen with a pore size of 800 μm to consolidate. 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. Organic Peracid Precursor Granules (I): Granules of Organic Peracid Precursor (i) Organic Peracid Precursor Granules (II): Granules of Organic Peracid Precursor (ii) Organic Peroxide Granules of acid precursor (III): Granules of organic peracid precursor (iii)

[0051]

[Chemical 4]

[III] Evaluation of Bleaching Detergent Composition (i) Bleaching Rate of Blood-Contaminated Cloth A bleaching detergent composition having the composition shown in Table 1 was prepared.
It was dissolved in tap water to a concentration of 0833% and washed with a blood-contaminated cloth (8 cm x 8 cm, 5 pieces) prepared by the following method with a tergotometer at 20 ° C for 10 minutes, then washed with water, dried, and then dried. The bleaching rate was calculated by the formula.

[0053]

[Equation 1]

The reflectometer is NDR manufactured by Nippon Denshoku Industries Co., Ltd.
Measured at -101 DP using a 460 nm filter. Blood-contaminated cloth: No.111 contaminated cloth purchased from EMPA was used as an 8 cm × 8 cm test piece for the experiment. Table 1 shows the above measurement results.

[0055]

[Table 1]

Note) * 1: Alkyl group containing 12 to 14 carbon atoms of linear alkylbenzene sulfonate * 2: Alkyl group containing 12 to 14 carbon atoms of linear alkylbenzene sulfonate * 3: Alkyl group containing 12 carbon atoms ~ 14 potassium α-olefin sulfonate * 4: Polyoxyethylene alkyl ether with 12 carbon atoms of the alkyl group and an average addition mole number of ethylene oxide of 8.5 * 5: Layered silicate manufactured by Hoechst * 6: Savinase 6.0T (manufactured by NOVO) )

Claims (8)

[Claims] (A) 2 to 30% by weight of potassium alkylbenzenesulfonate having 10 to 16 carbon atoms in the alkyl chain (b) 0.5 to 30% by weight of coated sodium percarbonate (c) The following general formula (I) Organic peracid precursor represented by 0.1
~ 10% by weight [Chemical formula 1] (In the formula, R represents an alkyl group having 1 to 21 carbon atoms, M represents a metal atom selected from sodium, potassium, and magnesium. N represents 1 when M is sodium or potassium, and 2 when M is magnesium. ). A bleaching detergent composition comprising: 2. The bleaching according to claim 1, which further comprises, as the component (d), 2 to 30% by weight of potassium α-olefinsulfonate having an alkyl group or an alkenyl group having 12 to 22 carbon atoms. Cleaning composition. 3. The bleaching detergent composition according to claim 1, which further contains a crystalline alkali metal silicate as the component (e). 4. The bleaching detergent composition according to claim 1, further comprising an aluminosilicate as the component (f). 5. The component (c) is blended as a granule containing the component (c) and a polymer compound for forming a thin film and having an average particle diameter of 300 to 2000 μm. The bleaching detergent composition according to item 1. 6. The bleaching detergent composition according to claim 5, wherein the thin film-forming polymer compound is one or more selected from polyethylene glycol, polyoxyethylene alkyl ether, and carboxymethyl cellulose. 7. (a) 2 to 30% by weight of potassium alkylbenzenesulfonate having 10 to 16 carbon atoms in the alkyl chain (b) 0.5 to 30% by weight of coated sodium percarbonate (c) The following general formula (I) Organic peracid precursor represented by 0.1
~ 10% by weight [Chemical formula 2] (In the formula, R represents an alkyl group having 1 to 21 carbon atoms, M represents a metal atom selected from sodium, potassium, and magnesium. N represents 1 when M is sodium or potassium, and 2 when M is magnesium. (D) Potassium α-olefin sulfonate having alkyl group or alkenyl group having 12 to 22 carbon atoms 2 to 30% by weight (e) Crystalline alkali metal silicate 1 to 50% by weight (f) Aluminosilicate A bleaching detergent composition containing 1 to 50% by weight. 8. The bleaching washing according to claim 7, wherein the component (c) is blended as a granulated product containing the component (c) and the thin film-forming polymer compound and having an average particle diameter of 300 to 2000 μm. Agent composition.