JPH11217590A - Breaching and detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of manifesting excellent bleaching detergency even in a system of a chelating reagent containing N atom used together with an organic peracid precursor by including a specific component, the specified peracid precursor, the specific chelating reagent and an alkali agent. SOLUTION: This bleaching and detergent composition comprises (A) 4-80 wt.% component (e.g. percarbonic acid salt) releasing hydrogen peroxide in water and preferably having 200-500 μm mean particle diameter, (B) 0.1-20 wt.% organic peracid precursor which generates organic peracid by reacting with hydrogen peroxide in water, (C) 0.1-40 wt.% water soluble chelating reagent containing N atom in the molecule, having >=4.5 stability constant of Ca chelate (pKCa ) (at 20 deg.C) and having >=80% organic peracid persistence (at 20 deg.C), and (D) an alkali agent. Preferably, the component B is a compound of formula I (R<2> is an 8-15C linear alkyl; Y<1> is a sulfonic acid or the like), and the component C is a compound of formula II [W and X are each H, R, COOM (R is an alkyl or the like; M is H, an alkali metal or the like) or the like; Y and Z are each H, R, SO3 M or the liked.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a bleaching detergent composition having excellent detergency.

[0002]

2. Description of the Related Art Bleaching detergents are classified into chlorine-based and oxygen-based ones. Chlorine-based bleaching detergents are limited in the types of fibers that can be used. As a result, oxygen-based bleaching detergents free of these drawbacks have recently become very popular. As the oxygen-based bleaching detergent, sodium percarbonate and sodium perborate are widely used as bleaching bases in terms of bleaching performance and stability.

[0003] Oxygen-based bleaching detergents have weaker bleaching power than chlorine-based bleaching detergents, and are therefore used in combination with various bleaching activators (organic peracid precursors). As typical bleaching activators, tetraethylenediamine, acetoxybenzenesulfonic acid, tetraacetylglycolyluril, glucose pentacetate and the like are used. Also, JP-A-59-
No. 22999 discloses hydrogen peroxide and the following formula: R'-C
(= O) -L (wherein, R 'is an alkyl group having about 5 to 18 carbon atoms, the longest linear alkylalkyl chain containing a carbonyl carbon has 6 to 10, and L represents a leaving group) A bleaching agent comprising a bleaching activator represented by the formula (1) and having a molar ratio of hydrogen peroxide produced by the peroxygen bleaching compound to the bleaching activator of more than 1.5 is disclosed.

[0004]

However, when the organic peracid generated from the organic peracid precursor reacts with and binds to a hardness component such as Ca ions contained in tap water, sufficient bleaching detergency is obtained. May not be able to demonstrate. In order to prevent the occurrence of such a problem, there is a method of capturing a hardness component such as Ca ions in tap water with a chelating agent. However, in order to separate the hardness component combined with the organic peracid, the C component of the chelating agent itself is used.
a The stability number must be large. As a chelating agent having a large Ca stability number, E containing N atom
DTA and the like. However, a chelating agent such as EDTA having an N atom in the molecule has a high reactivity with an organic peracid, and reacts with an organic peracid in an aqueous solution to be decomposed, which also reduces the bleaching detergency. There is.

Accordingly, an object of the present invention is to provide a bleaching detergent composition capable of exhibiting excellent bleaching detergency even in a combined system of a chelating agent containing an N atom and an organic peracid precursor. .

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found a chelating agent having a low Ca stability and a low reactivity with an organic peracid. The present invention has been completed.

That is, the present invention relates to (a) 4 to 80% by weight of a component which releases hydrogen peroxide in water, and (b) an organic peracid precursor which reacts with hydrogen peroxide in water to generate an organic peracid.
0.1 to 20% by weight, (c) containing N atoms in the molecule,
3. Ca chelate stability constant (pK _Ca ) at 0 ° C.
5 or more and the organic peracid residual ratio at 20 ° C. is 80%
A bleaching detergent composition comprising 0.1 to 40% by weight of the above-mentioned water-soluble chelating agent and (d) an alkali agent.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the component (a) used in the present invention, which releases hydrogen peroxide in water, include inorganic peroxide salts such as percarbonate, perborate and perphosphate. Of these, percarbonates are preferred.

The average particle size of the component (a) is preferably from 200 to 500 μm, particularly preferably from 250 to 4 μm.
00 μm. Further, in order to prevent caking of the bleaching detergent composition, the content of fine powder that passes through a sieve having a pore size of 125 μm is preferably 50% by weight or less, and more preferably 30% by weight or less. Particularly preferred, 2
More preferably, it is 0% by weight or less.

The content of the component (a) in the bleaching detergent composition is from 4 to 80% by weight, preferably from 10 to 80% by weight, in consideration of mixing with other components, while providing sufficient bleaching detergency. 60% by weight, particularly preferably 20 to
60% by weight.

The organic peracid precursor (hereinafter referred to as "organic peracid precursor") used in the present invention, which reacts with hydrogen peroxide in component (b) water to generate an organic peracid (hereinafter referred to as "organic peracid precursor"), is represented by the following general formula: (2):

[0012]

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[Wherein, R ² represents a straight-chain alkyl group having 8 to 15 carbon atoms, and Y ¹ represents a sulfonic acid, a carboxylic acid or an alkali metal, alkaline earth metal or ammonium group thereof. ]. Here, when the carbon number of R ² is 8 or more, the adsorptivity to dirt becomes high, and sufficient bleaching and washing performance can be exhibited. When it is 15 or less, sufficient solubility is imparted even under low-temperature washing conditions. It is preferable because it can be performed.

The organic peracid precursor corresponding to the general formula (2) includes the following general formula (3) or (4):

[0015]

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Wherein R ³ represents a straight-chain alkyl group having 11 to 15 carbon atoms, M ¹ represents a sodium atom, a potassium atom or an ammonium group, and R ⁴ represents a straight-chain alkyl group having 7 to 11 carbon atoms. Is shown. ] Is preferable.

Since the organic peracid precursor of the component (b) alone is unstable, it is preferable to mix it with a water-soluble binder and other components to form a granulated product. The mixing ratio of the organic peracid precursor in the granulated product is preferably 10 to 95% by weight, particularly preferably 10 to 95% by weight, in order to smoothly granulate and not to generate fine powder and to impart sufficient bleaching performance. It is 20 to 80% by weight, more preferably 30 to 70% by weight.

Examples of the water-soluble binder include a water-soluble polymer, a nonionic surfactant and an inorganic binder. Examples of the water-soluble polymer include polycarboxylates such as polyethylene glycol, polypropylene glycol, carboxymethyl cellulose, and sodium polyacrylate. Polyethylene glycol and polypropylene glycol have a molecular weight of 400
A range of from 20,000 to 20,000, preferably from 600 to 10,000 is suitable. As the nonionic surfactant, polyoxyethylene (ethylene oxide addition mole number = 3 to 30)
0) Alkyl C ₈ -C ₂₂ ether, polyoxyethylene alkyl phenyl ether, sucrose fatty acid ester, alkyl glucoside, polyoxyethylene alkylamine, polyoxyethylene-polyoxypropylene glycol, fatty acid monoethanolamide, fatty acid diethanolamide. Can be. Examples of the water-soluble inorganic binder include sodium silicate. Among these water-soluble binders, polyoxyethylene glycol and polypropylene glycol having a melting point of 20 to 80 ° C are preferable. The mixing ratio of the water-soluble binder and water in the granulated product is preferably 0.1 to 40% by weight,
Particularly preferably, it is 0.3 to 30% by weight, more preferably 0.3 to 20% by weight.

In order to enhance the solubility of the granules, an anionic surfactant can be added. Examples of the anionic surfactant include a straight-chain or branched-chain primary or secondary alcohol sulfate having 10 to 18 carbon atoms, and a sulfate having 8 to 8 carbon atoms.
Sulfate, alkylbenzene sulfonate, paraffin sulfonate, α-olefin sulfonate, α-sulfofatty acid salt, α-sulfofatty acid alkyl ester salt or fatty acid salt of an ethoxylated product of 20 alcohols are preferred. In the present invention, particularly, a linear alkylbenzene sulfonate having 12 to 14 carbon atoms in the alkyl chain and an alkyl sulfate having 12 to 18 carbon atoms are preferable. As the counter ion, alkali metals are preferable, and sodium or potassium is particularly preferable. preferable. The compounding ratio of the anionic surfactant in the granulated product is preferably 0 to 40% by weight, particularly preferably 0.3 to 30% by weight, and further preferably 1 to 20% by weight.

In order to further enhance the storage stability of the granulated product, an acidic substance can be blended. As the acidic substance, formic acid, propionic acid, citric acid, succinic acid, organic acids such as fumaric acid, phosphoric acid, inorganic acids such as sodium sulfite,
Zeolite showing solid acidity can be used. Among these, fumaric acid, succinic acid and zeolite exhibiting solid acidity are preferred. The mixing ratio of the acidic substance in the granules is preferably 0 to 40% by weight, particularly preferably 0.1 to 30%.

Next, a method for producing a granulated product will be described. As a granulation method, it is preferable to apply a consolidation forming method in order to easily disintegrate or dissolve the obtained granules in a solution, but it is not limited thereto. As the consolidation forming method, it is preferable to use an extrusion granulator, and it is preferable that the major axis is
00 μm or more, particularly preferably 500 to 3000
μm, more preferably a method of forming a columnar compaction such as a granule having a major axis of 700 to 2000 μm, compaction into two rotating roll tubes, preferably a thickness of 200 to 100
0 μm, particularly preferably 500 to 5000 μm thick plate-like compacted body, by briquetting, preferably a diameter of 500 to 10000 μm, particularly preferably a diameter of 50 to
A method of forming a tablet-type compacted product of 0 to 5000 μm can be used. Here, in the case where the granular material is formed into a columnar compacted body, the surface area is made as small as possible by keeping the particle shape away from the spherical shape, thereby reducing the contact area with the component (a) and improving the stability. Preferably, the major axis is 1.1 times or more the minor axis,
Particularly preferably, the ratio is 1.2 to 3 times, more preferably 1.3 to 2 times.

The extrusion granulator used in the consolidation forming method includes:
Examples include Fuji Paudal's pellets and Kikusui granulators. Examples of briquetting machines include Shinto Kogyo's briquetters and Kikusui tableting machines.
Among these, an extrusion granulator is preferred from the viewpoint of good solubility and fluidity of the granulated material and excellent productivity. The screen diameter of the extrusion granulator is preferably a weight average diameter of 20.
The thickness is preferably from 0 to 5000 µm, and more preferably from 500 to 5000 µm, and particularly preferably from 500 to 3000 µm, in order to suitably produce a granulated product.
Further, after consolidation molding, if necessary, a method of sizing with a sizing machine to a weight average particle diameter of 200 to 5000 μm,
A method of performing granulation using a marmellaizer or the like can be applied.

The content of the component (b) in the bleaching detergent composition is 0.01 to 30% by weight, preferably 0.1 to 30% by weight, in order to impart sufficient bleaching detergency and prevent caking. To 20% by weight, particularly preferably 1% by weight.
-10% by weight.

The component (c) used in the present invention contains N in the molecule.
And a Ca chelate stability constant (p at 20 ° C.) at a predetermined value determined by the following method.
K _Ca ) and the organic peracid residual ratio at 20 ° C.

The Ca chelate stability constant can be determined by the following method. A 0.1 mol / L NH ₄ Cl—NH ₄ OH (pH 10.0) solution was prepared as a buffer,
This is used to prepare all sample solutions. To measure the Ca ²⁺ concentration, an ion meter 920A manufactured by Orion Co., Ltd. was used.
And a Ca ²⁺ electrode. First, the relationship between the calcium chloride concentration and the potential of the electrode is determined, and a calibration curve is created. Next, calcium 5.36 × 10 ^-2 mol / L chloride solution, a chelating agent sample 5.36 × 10 ^-4 mol / L solution prepared. 1 ml of calcium chloride solution is added to 100 ml of the chelating agent sample solution, and the mixture is stirred for 5 minutes. The remaining Ca ²⁺ concentration is changed to Ca ²⁺
Measure using electrodes. The chelating agent is 1: 1 with Ca ²⁺
And forming a chelate complex with
a Determine the chelate stability constant.

[0026]

(Equation 1)

[Wherein [Ca] is the residual metal ion concentration (mol
/ L), and [L] _Total is the initial chelating agent concentration (mol /
L), and [Ca] _Total is the initial metal ion concentration (mol /
L)]].

The Ca chelate stability constant (pK _Ca ) of the water-soluble chelating agent of the component (c) is 4.5 or more in order to increase the bleaching detergency by capturing hardness components such as Ca ^2+. Is 5 to 12, particularly preferably 6 to 10.

The residual rate of the organic peracid can be determined by the following method. An aqueous solution comprising 100 ppm of sodium percarbonate having an effective oxygen concentration of 12% by weight and ion exchanged water at 35 ° C. is prepared in a 1 L beaker, and 0.1 mmol / L of an organic peracid precursor is added thereto. The concentration of the organic peracid precursor added at this time is represented by the following formula:

[0030]

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Based on the compound represented by Next, 2
After reacting for 0 minutes, the chelating agent is added in an equimolar amount to the organic peracid precursor, and the remaining amount of the organic peracid obtained after the reaction is further performed for 20 minutes is represented by the following formula: Residual rate of organic peracid (% )
= Amount of organic peracid after reaction × 100 / Amount of initial organic peracid. The amount of the organic peracid is measured by a titration method using sodium thiosulfate.

The residual ratio of the organic peracid at 20 ° C. of the water-soluble chelating agent of the component (c) is 80% or more, preferably 90%, in order to suppress the decomposition of the component (b) and enhance the bleaching detergency. And more preferably 95% or more.

As the water-soluble chelating agent of the component (c),
The following general formula (1):

[0034]

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[W and X represent a hydrogen atom, -R, -RO
H, -COOM, -SO ₃ M or -PO ₃ M (wherein, R
Represents an alkyl group or an alkenyl group, M represents a hydrogen atom, an alkali metal, an alkaline earth metal or an ammonium group); Y and Z represent a hydrogen atom, -R, -R
-OH, -COOM, -SO ₃ M or -PO ₃ M or _{^{-R 1 -COOM, -R 1 -SO 3}} M or -R ¹ -PO
₃ M (where M has the same meaning as described above, and R ¹ represents an alkyl group, an alkenyl group or an alkylene group). ] Can be mentioned.

Examples of the water-soluble chelating agent corresponding to the general formula (1) include those represented by the following formula.

[0037]

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[0038] The content of the component (c) in the bleaching detergent composition is from 0.1 to 0.1 in order to impart sufficient bleaching detergency.
It is 40% by weight, preferably 0.5 to 30% by weight, particularly preferably 1 to 20% by weight.

The component (d) used in the present invention is an alkaline agent. Examples of the alkaline agent include sodium carbonate, which is collectively referred to as dense ash and light ash, alkali metal carbonates such as calcium carbonate and magnesium carbonate, and JIS 1
No. 2, No. 3 and the like. These inorganic alkaline agents are effective as a skeleton-forming component of particles during drying of a detergent, and can provide a bleaching detergent composition that is relatively hard and has excellent fluidity. Other than these, sodium sesquicarbonate, sodium hydrogen carbonate, the above-mentioned phosphates, and the like can be given. Further, Japanese Unexamined Patent Application Publication No. 7-8
No. 9712, JP-A-60-227895, Ph
ys. Chem. Glasses. 7, P127-138 (1966), Z. Kristallogr., 1
29, P396-404 (1969) and the like can also be used because they have a property as an alkali agent as a property other than the ion exchange ability.

The content of the component (d) in the bleaching detergent composition is a balance amount when the above components (a) to (c) are blended to make a total of 100% by weight.

The bleaching detergent composition of the present invention may further contain an anionic surfactant, a nonionic surfactant, an amphoteric surfactant and a cationic surfactant. Surfactants and nonionic surfactants are preferred.

As the anionic surfactants, those having 10 carbon atoms
To 18 straight-chain or branched-chain primary or secondary alcohol sulfates, ethoxylates of alcohols having 8 to 20 carbon atoms, sulfates, alkylbenzene sulfonates, paraffin sulfonates, α-olefin sulfones Acid salts, α-sulfofatty acid salts, α-sulfofatty acid alkyl ester salts or fatty acid salts are preferred. In the present invention, particularly, a linear alkylbenzene sulfonate having 12 to 14 carbon atoms in the alkyl chain and an alkyl sulfate having 12 to 18 carbon atoms are preferable. As the counter ion, alkali metals are preferable, and sodium or potassium is particularly preferable. preferable. As nonionic surfactants, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene glycol fatty acid ester,
Polyoxyethylene polyoxypropylene block polymers are preferred. In particular, as a nonionic surfactant,
The HLB value (calculated by the Griffin method) of adding 4 to 20 mol of an alkylene oxide such as ethylene oxide or propylene oxide to a linear or branched primary or secondary alcohol having 10 to 18 carbon atoms is 10.5 to 15. Polyoxyalkylene alkyl ethers which are 0, preferably 11.0 to 14.5 are preferred. The compounding amount of the surfactant is preferably 0.1 to 15% by weight, particularly preferably 0.5 to 10% by weight.

An enzyme can be further added to the bleaching detergent composition of the present invention. Preferred enzymes (enzymes that essentially carry out the enzymatic action during the washing step) are proteases, esterases, lipases, nucleases, cellulases, amylases and pectinases.
Specific examples of proteases include pepsin, trypsin, chymotrypsin, collagenase, keratinase,
Elastase, sptilisin, BPN, papain, promerin, carboxypeptidases A and B, aminopeptidases, aspergillopeptidases A and B,
Commercially available products include Savinase, Alcalase (Novo Industries), API21 (Showa Denko KK), Maxacal (Gyst Procaides), and protease K-14 or K-16 described in JP-A-5-25492. Can be mentioned. Specific examples of esterases include gastric lipase, bankreatic lipase, plant lipases, phospholipases, cholinesterases, and phosphotases. Specific examples of the lipase include commercially available lipases such as lipolase (Novo Industries) and liposam (Showa Denko KK). As cellulase, commercially available cellzyme (Novo Industry Co., Ltd.),
The cellulase described in claim 4 of JP-A-3-264699 can be mentioned, and as the amylase, commercially available termamyl (Novo Industry Co., Ltd.) can be mentioned. Enzymes are separately granulated as stable particles and used in a dry-blended state with detergent fabric (particles). The amount of the enzyme is preferably 0.1 to 5% by weight.

The bleaching detergent composition of the present invention may further contain a crystalline aluminosilicate. Crystalline aluminosilicate generally are those that are said to zeolites, the following general _{^{formula: a (M 1 2 O)}} · Al 2 O 3 · b (Si
O ₂ ) .w (H ₂ O) wherein M ¹ represents an alkali metal;
a, b, and w indicate the number of moles of each component, and is generally 0.7
≦ a ≦ 1.5, 0.8 ≦ b ≦ 6, w indicate any positive number. ] Can be mentioned. Among the crystalline aluminosilicates represented by the above general formula, the following general formula: Na ₂ O.Al ₂ O ₃ .n (SiO ₂ ) .w (H ₂ O) wherein n is 1.8 To 3.0 and w represents the number of 1 to 6].

As the crystalline aluminosilicate, A type, X
Type, average primary particle size 0.1 to typified by P-type zeolite
Preference is given to synthetic zeolites of 10 μm, preferably 0.1-5 μm. The zeolite may be blended as zeolite agglomerated dry particles obtained by drying a powder or a zeolite slurry.

The bleaching detergent composition of the present invention may further contain an amorphous aluminosilicate. As the amorphous aluminosilicate, those containing 30% by weight or more, preferably 40% by weight or more of silicon as SiO ₂ are preferable. When a 5% dispersion having a pH of 9 or more is used, deterioration of the solubility of the composition after storage at high humidity is improved. Amorphous aluminosilicate has not only ion exchange ability but also oil absorption ability, so when a liquid surfactant such as a nonionic surfactant is blended, it is suitable for maintaining powder properties. It is a component and is preferable because a portion contributing to detergency is larger than that of a silica-based oil-absorbing carrier.

The amorphous aluminosilicate has the following general formula: a (M ² ₂ O) .Al ₂ O ₃ .b (SiO ₂ ) .c (H ₂ O) [M ² is an alkali metal A, b, and c indicate the number of moles of each component, and generally 0.7 ≦ a ≦ 2.0, 0.8 ≦ b
≦ 4, c indicates an arbitrary positive number. ] Can be mentioned.

Among the amorphous aluminosilicates represented by the above general formula, the following general formula: Na ₂ O.Al ₂ O ₃ .b (SiO ₂ ) .c (H ₂ O) b represents a number of 1.8 to 3.2 and c represents a number of 1 to 6]
Is preferably represented by

The amorphous aluminosilicate is disclosed in
According to the method described in JP-A-179899, JIS622
It is possible to obtain oils having an oil absorption capacity of 100 ml / 100 g (in terms of anhydrous) or more and a cation exchange capacity of 100 mg CaCO ₃ / g or more.

The bleaching detergent composition of the present invention may further contain an oil-absorbing carrier. The oil-absorbing carrier has an oil-absorbing capacity according to JIS 6220 of 100 ml / 100 g.
(Equivalent to anhydrous) or more are preferred. As such an oil-absorbing carrier, a silica-based compound is preferable, and examples thereof include Toxeal (manufactured by Tokuyama Corporation), Nipseal (manufactured by Nippon Silica), and Thixorex (manufactured by Kofuran Chemical Company). Further, as the oil-absorbing carrier, the above-mentioned amorphous aluminosilicate may be used.

The bleaching detergent composition of the present invention may further contain a crystalline silicate. Crystalline silicates are
Alkali metal salts of silicic acid (SiO ₂ ) are preferred,
% Dispersion has a maximum pH of 11 or more (25 ° C.),
5% or more is required to lower the pH to 10 with 0.1N aqueous hydrochloric acid per 0.1% dispersion 1, which is excellent not only in alkalinity but also in alkali buffering ability. . Of these, SiO ₂ / M ³ ₂ O of an alkali metal silicate (M ³ represents an alkali metal) of 0.5
To 2.6, preferably 1.5 to 2.6 are suitably used. A conventionally known crystalline silicate is SiO ₂ /
Na ₂ O is 1.9 to 4.0, and this ratio is 2.6.
If the ratio exceeds the above, it may not be suitable for the formulation of the high-density detergent which is the object of the present invention.

The crystalline silicate of the present invention has an ion exchange capacity of at least 100 mg CaCO ₃ / g or more.
Preferably, it has a content of 200 to 600 mg CaCO ₃ / g, which is one of the substances having an ion-capturing ability in the present invention. The crystalline silicate has an average particle size of 0.1.
To 100 μm, and preferably 1 to 60 μm. Here, the average particle size is the median size of the particle size distribution. The crystalline silicate having such an average particle size and particle size distribution can be prepared by crushing using a crusher such as a vibration mill, a hammer mill, a ball mill, and a roller mill.

[0053] Suitable as crystalline silicate used in the present invention, the following equation ^{(5): x (M 4} 2 O) · y (SiO 2) · z (Me m O n) · w (H 2 O (5) [In the formula, M ⁴ represents a group Ia element of the periodic table, and Me represents a group selected from a group IIa element, a group IIb element, a group IIIa element, a group IVa element, or a group VIII element of the periodic table. Indicates a species or a combination of two or more species, y / x = 0.5 to 2.6, z / x = 0.
01 to 0.9, w = 0 to 20, and n / m = 0.5 to 2.0. ].

Me is selected from Group IIa, IIb, IIIa, IVa and VIII elements of the periodic table, for example, Mg, Ca, Zn, Y, Ti, Zr, Fe and the like. Can be. These are not particularly limited, but from the viewpoint of resources and safety, preferably Mg,
Ca. These may be used alone or in admixture of two or more, for example MgO, CaO or the like may constitute the Me _m O _n component are mixed.

In the general formula (5), y / x is 0.5 to
2.6, and preferably 1.5 to 2.6. y / x
If it is less than 0.5, the water resistance will be insufficient and the caking property, solubility and powder properties of the composition will be significantly adversely affected. On the other hand, when y / x exceeds 2.6, the alkali ability becomes low, the alkali agent becomes insufficient, and the ion exchange ability also becomes low, and the ion exchanger becomes insufficient. In the general formula (5), z / x is 0.01 to
0.9, preferably 0.02 to 0.5. z
When / x is less than 0.01, the water resistance is insufficient, and when z / x exceeds 0.9, the ion exchange capacity is lowered and the ion exchanger is insufficient.

X, y, and z are not particularly limited as long as they are in the relationship represented by the y / x ratio and the z / x ratio described above. Note that, as the x (M ⁴ ₂ O), for example, x '(Na ₂ O)
If x "(K ₂ O), x is x '+ x". This relationship is the same in the z in the case where z (Me _m O _n) component consists of two or more. Also, n / m
Represents the number of oxygen ions coordinated to the element, and is substantially selected from values of 0.5, 1.0, 1.5, and 2.0.

[0057] Further, the following equation _{^{(6): M 5 2 O}} · x '(SiO 2) · y' (H 2 O) (6) wherein, M ⁵ represents an alkali metal, x '= 1.5 to 2.6,
y ′ = 0 to 20 is indicated. ] Can also be used.

In the general formula (6), M ⁵ represents I in the periodic table.
It is selected from group a elements, and examples of group Ia elements include Na and K. These can be used alone or, for example, in Na ₂
O and and K ₂ O are mixed may constitute the M ⁵ ₂ O component.
Further, those having x ′ and y ′ of 1.7 ≦ x ′ ≦ 2.2 and y ′ = 0 are preferable, and those having a cation exchange capacity of 100 to 400 mg CaCO ₃ / g can be used, which has the ion trapping ability in the present invention. One of the substances.

The crystalline silicate represented by the general formula (6) is
Generally, amorphous glassy sodium silicate is used for 200 to 10
It is obtained by firing at 00 ° C. to make it crystalline.
For details of the synthesis method, see, for example, Phys. Chem. Glasses. 7, p127-
p138 (1966), Z. Kristallogr., 129, p396-p404 (1969) and the like. The crystalline silicate represented by the general formula (6) can be obtained, for example, from Hoechst under the trade name “Na-SKS-
6 "(δ-Na ₂ Si ₂ O ₅ ) is available in powder or granular form.

In the present invention, general formulas (5) and (6)
Can be used alone or in combination of two or more. The compounding amount of the crystalline silicate is
Preferably it is 0.1 to 10% by weight, particularly preferably 1 to 5% by weight.

The bleaching detergent composition of the present invention may further contain a carboxylic acid polymer such as a copolymer or a homopolymer having a molecular weight of several hundred to 100,000. The carboxylic acid-based polymer has a function of sequestering metal ions, a function of dispersing solid particle dirt from clothes into a washing bath, and a function of preventing the particles from reattaching (recontamination) to clothes. . Examples of the carboxylic acid-based polymer include those having a repeating unit represented by the following general formula. The copolymer is generally a random polymerization.

[0062]

Embedded image

[0063] [wherein, X, P is a hydrogen atom, a hydroxyl group or -CH ₂ OH; Y is a hydrogen atom, -COOM or -CH ₂ COOM; Z is -COOM or -CH ₂
Indicates COOM. M represents an inorganic or organic counter ion].

Among these carboxylic acid polymers,
Acrylic acid - salt of maleic acid copolymers and polyacrylate (Na, K, NH ₄₎ are preferable, the molecular weight 1,000
80,000 are preferred. Carboxylic acid-based polymers can usually be easily obtained by polymerizing unsaturated organic carboxylic acids and organic polycarboxylic acids,
As long as the molecular weight is 2,000 or more and the carboxyl group has 10 or more, the unsaturated carboxylic acid monomer as a raw material is not limited. In addition to the carboxylic acid-based polymers, polymers such as polyglycidylates, cellulose derivatives such as carboxymethylcellulose, and aminocarboxylic acids-based polymers such as polyaspartate also have sequestering ability, dispersing ability, and anti-contamination ability. Therefore, they can be used together in the present invention.

The following components can be further added to the bleaching detergent composition of the present invention, if necessary.

(Phosphorus Compound) As the phosphorus compound, a conventionally known compound that supplements a metal ion is preferable. Particularly, tripolyphosphate, orthophosphate, and metaphosphate are preferable, and sodium tripolyphosphate is particularly preferable.

(Acid Agent) An acid agent can be added so that the pH of the washing liquid (composition solution) does not become too high.
Examples of the acid agent include, in addition to organic sequestering agents, polycarboxylic acids such as lactic acid, succinic acid, malic acid, and gluconic acid.

(Expanding Agent) As an expanding agent (neutral salt), sodium sulfate generally called sodium sulfate can be blended. Sodium sulfate is effective in forming the skeleton of the detergent particles after drying, like the inorganic alkaline agent. Other preferred neutral salts include sodium chloride and potassium chloride.

(Polymers) Polyethylene glycol, polyvinyl alcohol, and the like can be blended as a binder or a powder physical agent when the composition is densified. These polymers also have an effect of preventing re-contamination of the hydrophobic fine particles, and have an average molecular weight of 200 to 200.
200,000 can be used. Further, polyvinylpyrrolidone can be blended for imparting an effect of preventing color transfer.

(Enzyme Stabilizer) As an enzyme stabilizer, a calcium or magnesium salt of a reducing agent (sodium sulfite, sodium hydrogen sulfite), a polyol, a boron compound, or the like can be blended. The reducing agent stabilizes the enzyme by removing chlorine in tap water. Further, sodium sulfite has an effect as an antioxidant in addition to the above effects.

(Bluing agent) As a bluing agent, Japanese Patent Publication No. Sho 4
No. 9-8005, Japanese Patent Publication No. 49-26286,
JP-B-53-45808 can be mentioned.

(Anti-Caking Agent) Examples of the anti-caking agent include paratoluenesulfonate, xylenesulfonate, acetate, sulfosuccinate, talc, finely divided silica, clay, and magnesium oxide.
In addition, clay (smectite-like clay) is also effective as a softening agent.

(Fluorescent dyes) As fluorescent dyes, 4,4'-bis- (2-sulfostyryl) -biphenyl salt, 4,4'-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, 2- (styrylphenyl) naphthothiazole derivative, 4,4′-bis (triazol-2-yl) stilbene derivative, bis (triazinylamino) stilbenzylsulfonic acid derivative, Whitex SA (Sumitomo Chemical Co., Ltd.), Tinopearl CBS (manufactured by Ciba-Geigy) and the like can be mentioned. One or two or more of these fluorescent dyes can be incorporated in the composition in an amount of 0 to 2% by weight.

(Fragrances) As fragrances, fragrances conventionally incorporated in detergents, for example, fragrances described in JP-A-63-101496, dimethylbenzylcarbinyl acetate,
Tricyclo [5.2.1.0 ^2,6 ] -dec-3-en-8-yl acetate, tricyclo [5.2.1.0 ^2,6 ] -dec-3-en-8-isopropionate, 3-amyl-4 -Acetoxytetrahydropyran, 4-tert-butylcyclohexyl acetate, 2-tert-butylcyclohexyl acetate, p-tert-butyl-α-methylhydrocinnamic aldehyde, 4- (4-hydroxy-4-methylpentyl) -3- Cyclohexene-1-carboxaldehyde, α-hexylcinnamic aldehyde, α-amyl cinnamic aldehyde, α, α′-dimethyl-p-ethylhydrocinnamic aldehyde and the like can be mentioned. Of course, in order to prevent deterioration due to other detergent components, the type of each flavor component to be blended and, if necessary, the blending ratio and blending amount are considered.

(Defoaming Agent) Examples of the defoaming agent include conventionally known silicone / silica-based ones. This antifoaming agent is described in Japanese Patent Application Laid-Open No.
The defoamer granules produced by the method described in the lower left column of page 4 of 86307 may be used. First, maltodextrin (enzymatically modified dextrin) manufactured by Nisseki Chemical Co., Ltd. 10
To 0 g, 20 g of a silicone (compound type, PS antifoam) manufactured by Dow Corning as an antifoaming component is added and mixed to obtain a homogeneous mixture. Next, 50% of the obtained homogeneous mixture was mixed with polyethylene glycol (PEG-6000, melting point 5).
8 ° C) 25% and 25% of anhydrous anhydrous nitrate 70-80 ° C
After mixing with an extrusion granulator manufactured by Fuji Paudal Co., Ltd. (Model
Granulate with EXKS-1) to obtain granules.

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EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Examples 1 to 10 and Comparative Examples 1 to 6 Bleaching detergent compositions of Examples and Comparative Examples were produced using Table 1 and the following components.

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LAS-1: Alkenesulfonate "Alkene L (having 10 to 14 carbon atoms in the alkyl chain)", which is an alkylbenzenesulfonic acid manufactured by Nisseki Detergent Co., Ltd., neutralized with 48% sodium hydroxide AS: Mitsubishi Dopanol 25 sulfate (C
AOS: α-C12 sodium olefin sulfonate Fatty acid salt: sodium palmitate AES: Polyoxyethylene alkyl (C12-15)
Sodium ether sulfate (EO (ethylene oxide) average number of moles added: 2) AE-1: Nonied S-3 (C1 manufactured by Mitsubishi Chemical Corporation)
AE-2: Nippon Shokubai Co., Ltd. Softanol 70 (C12)
EO added to the secondary alcohol of No. 15 to 7 on average) Zeolite: 4A zeolite (average particle size: 3 μm) Crystalline silicate: SKS-6 (δ-Na ₂ Si ₂ O ₅ ), crystalline layer Silicate, average particle diameter 20 μm, manufactured by Hoechst Tokuyama Amorphous silicate: JIS No. 1 sodium silicate Sodium carbonate: dense ash PAA: sodium polyacrylate (average molecular weight 120
00) AA-MA: socarane CP5, acrylic acid-maleic acid copolymer (average molecular weight: 70000) Fluorescent dye: Tinopearl CBS (manufactured by Ciba Geigy)
Whitex SA (manufactured by Sumitomo Chemical Co., Ltd.) blended in the same amount by weight Perfume: Use the perfume composition described in Example of JP-A-8-239700. Enzyme: Sabinase 12.0T type-W (protease) , Lipolase 100T (Lipase), Termamyl 60T (Amylase) (both from Novo Nordisk) and KAC500
(Alkaline cellulase, manufactured by Kao Corporation) in a weight ratio of 2:
1: 1: 1 mixture.

[Detergency Test] The detergency of the compositions of Examples and Comparative Examples was tested by the following method. Table 1 shows the results. (Preparation of artificially contaminated cloth) 1m of knitted cloth (manufactured by Yagami Shoten)
A piece cut into a strip having a size of × 10 cm was immersed gently in a mud solution and then pulled up, and this was repeated three times. Next, after drying, the knitted cloth was cut into 10 × 10 cm to obtain an artificially stained cloth. The mud solution was bilirubin (SIGMA
(Chloroform) (0.6 g / L).

(Washing method) One liter of an aqueous solution of each composition was placed in a beaker, and a 10 × 10 cm artificially stained cloth 5 was placed therein.
The pieces were soaked and washed, and then rinsed. The washing conditions are as follows. Cleaning time 120 minutes Composition concentration 0.5% by weight Water hardness 4 硬度 DH water temperature 20 ° C. Rinse Rinse with tap water for 5 minutes (Evaluation method) The evaluation of detergency is based on the self-recording colorimeter of the reflectance of cloth at 460 nm. (Manufactured by Shimadzu Corporation), the cleaning rate (%) was determined from the following equation, and the average value of the measured values of the five sheets was defined as the cleaning power.

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(Equation 2)

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[Table 1]

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As described above, the bleaching detergent composition of the present invention can be used even when a chelating agent containing an N atom and an organic peracid precursor are used in combination.
It can exhibit stable and excellent bleaching detergency.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C11D 3:39 3:26 3:34 3:36 3: 386) (C11D 7/60 7:18 7:32 7:34 7) : 60 7:38)

Claims (4)

[Claims] (1) a component that releases hydrogen peroxide in water: 4 to 80% by weight, (b) a reaction with hydrogen peroxide in water,
Organic peracid precursor for generating organic peracid 0.1 to 20% by weight, (c) containing N atom in the molecule,
a 0.1 to 40% by weight of a water-soluble chelating agent having a chelate stability constant (pK _Ca ) of 4.5 or more and an organic peracid residual ratio of 80% or more at 20 ° C. and (d) an alkali agent A bleaching detergent composition comprising: 2. The chelating agent of the component (c) has the following general formula (1): [W and X are a hydrogen atom, -R, -R-OH, -COO
M and —SO ₃ M or —PO ₃ M (where R represents an alkyl group or an alkenyl group, and M represents a hydrogen atom, an alkali metal, an alkaline earth metal or an ammonium group); , A hydrogen atom, -R, -R-OH, -CO
OM, -SO ₃ M or -PO ₃ M or -R ¹ -COO
M, -R ¹ -SO ₃ M or -R ¹ -PO ₃ M (where
M has the same meaning as described above, and R ¹ represents an alkyl group, an alkenyl group or an alkylene group). The bleaching detergent composition according to claim 1, which is represented by the formula: 3. The bleaching detergent composition according to claim 1, further comprising 0.1 to 15% by weight of a surfactant. 4. The bleaching detergent composition according to claim 1, further comprising 0.1 to 5% by weight of an enzyme.