JPH093497A - Bleaching detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a bleaching detergent composition exhibiting excellent cleanability to a lipophilic stain such as sebum stain and yellowing of underwear, etc. SOLUTION: In this granular or powdery bleaching detergent composition containing an organic acid precursor which is reacted with hydrogen peroxide in water to form a 7-19C alkyl group-containing organic acid and a hydrogen peroxide releasing material, the composition contains (a) a surfactant, (b) a crystalline alkali metal silicate and (c) a sequestering agent except the component (b). The total of the components (a), (b) and (c) amounts to 70-99wt.% in the bleaching detergent composition. The weight ratio of the component (b) to the component (a) of (b)/(c)=90/10 to 45/55, that of the component (b) to the component C of (b)/(c)=7/93 to 75/25. The weight ratio of the organic acid precursor to the nonionic surfactant as the component (a) is 10/90 to 70/30.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a bleaching detergent composition which exhibits excellent detergency against lipophilic stains such as sebum stains and yellowing of underwear.

[0002]

2. Description of the Related Art Conventionally, there has been proposed a method in which a detergent composition is blended with a bleaching agent component to enhance the detergency of the detergent composition against stains and stains.

For example, JP-A-59-22999,
JP-A-6-316700 describes a bleaching agent composition and a bleaching detergent composition containing an organic peracid precursor that produces an organic peracid having an alkyl group having a specific carbon number and a hydrogen peroxide releasing agent. There is. Organic peracids produced from these organic peracid precursors show very good bleaching power against stain stains, but when added to ordinary detergent compositions to form bleaching detergent compositions, they are sufficiently It was not possible to exert such a bleaching effect. The reason is that these detergent composition systems have a high concentration of surfactants (especially nonionic surfactants), so that the organic peracid precursor is incorporated into the micelles of the surfactant and solubilized. It is considered that this is because the reaction with the hydrogen oxide releasing substance is hindered and the generation of the organic peracid, which is a bleaching active species, is hindered. This tendency was more remarkable as the blending concentration of the nonionic surfactant in the surfactant component was higher. This point makes it more difficult to mix non-ionic surfactants more effectively with respect to sebum stains than anionic surfactants, and in order to achieve both cleaning properties for sebum stains and yellowish stains. It was a problem.

On the other hand, the applicant of the present invention, even if the use concentration of the surfactant is remarkably reduced by using the crystalline alkali metal silicate having a high alkali ability at a high concentration and increasing the sequestering ability of the metal ion. It was found that a high detergency can be exhibited against sebum stains, and it has already been filed (Japanese Patent Application No. 6-247279). However, with this cleaning method, the cleaning performance was not sufficient for lipophilic stains such as yellowed underwear stains.

Further, as a prior art in which a crystalline silicate and a bleaching component are essential components, JP-A-6-116591 is known.
JP-A-7-53992 and JP-A-7-53992.
In this publication, crystalline sodium silicate, a surfactant,
And a bleaching detergent containing a bleaching component consisting of sodium percarbonate and a bleaching activator that produces perfatty acid, but the bleaching detergent of the composition disclosed here is insufficient in terms of detergency of sebum stains. In addition, since the blending ratio of the surfactant is high, it is not a composition that can effectively generate the organic peracid generated by the bleaching activator (organic peracid precursor) to be blended. As a result, no sufficient effect was obtained against lipophilic stains.

[0006]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a granular or powdery bleaching detergent composition which exhibits excellent detergency against lipophilic stains such as sebum stains and yellowing of underwear. Especially.

[0007]

As a result of intensive investigations, the inventors of the present invention have found that the content ratio of a surfactant, a crystalline alkali metal silicate, and a sequestering agent other than that, and a nonionic surfactant. While making effective use of the bleaching activity of the organic peracid precursor that produces an organic peracid having an alkyl group having about 7 to 19 carbon atoms by making the content ratio of the organic peracid precursor to a specific value, In addition, it was found that not only lipophilic stains such as yellowing of underwear, but also excellent cleaning performance against sebum stains.

More specifically, a bleaching activator having an alkyl group which produces a perfatty acid having a carbon number of 7 or more exhibits excellent detergency against yellowing such as underwear and sebum stains, however, as described above. There was a phenomenon that it is understood that when a large amount of a nonionic surfactant is added to the above, the reaction with hydrogen peroxide in the aqueous solution is inhibited, and as a result, the generation of organic peracid is suppressed. For this reason, it has been conventionally considered that it is not suitable to use the bleach activator described above in a nonionic detergent composition, but the present invention is surprisingly particularly advantageous by selecting a specific blending ratio. Excellent cleaning power,
The inventors have found that bleaching power can be achieved, and have completed the present invention.

On the other hand, the above-mentioned prior art does not pay attention to the surfactant in the washing liquid, and therefore does not suggest the blending ratio of the present invention and does not achieve the detergency of the present invention. . This is also apparent from the results of the comparative examples corresponding to the prior art mentioned in this specification.

That is, the gist of the present invention is (1) an organic peracid precursor and a hydrogen peroxide releasing substance which react with hydrogen peroxide in water to produce an organic peracid having an alkyl group having 7 to 19 carbon atoms. In a granular or powdery bleaching detergent composition containing, the composition contains the following components: a) a surfactant b) a crystalline alkali metal silicate c) a sequestering agent other than the b component, The total amount of the a, b and c components accounts for 70 to 99% by weight in the bleaching detergent composition, and the ratio of the b component to the a component is b / a = 90/10 to 45/55 in weight ratio, The ratio of b component to c component is b / c = 7 / 93-
75/25 and the ratio of the organic peracid precursor to the nonionic surfactant as the component a is 10 by weight.
/ 90 to 70/30, (2) The content of the nonionic surfactant is 50 to 100% by weight based on the total amount of the surfactant component a (1). (3) The bleaching detergent composition according to (1) or (2) above, wherein the organic peracid produced is a perfatty acid having a linear alkyl group having 7 to 19 carbon atoms. ) The bleaching detergent composition according to the above (3), wherein the organic peracid precursor is represented by the following general formula (I):

[0011]

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(In the formula, R represents a straight-chain alkyl group or alkylene group having 7 to 19 carbon atoms, and M represents an alkali metal.) (5) The nonionic surfactant as the component a has carbon atoms. The bleaching detergent composition according to any one of (1) to (4), which is a polyoxyethylene alkyl ether obtained by adding 5 to 15 mol of ethylene oxide to 10 to 18 linear alcohols on average, (6) a crystalline alkali Metal silicate SiO ₂ / M ₂
O (however, M represents an alkali metal) is 0.5-2.
The bleaching detergent composition according to any one of (1) to (5), which is 6, (7) The above-mentioned (6), wherein the crystalline alkali metal silicate has a composition represented by the following formula (II): bleaching detergent _{composition, xM 2 O · ySiO 2 ·} zMe m O n · wH 2 O (II) ( wherein, M is group Ia elements of the periodic table, Me represents IIa, II
b, IIIa, IVa or VIII, represents one or a combination of two or more elements, wherein y / x = 0.5 to 2.
6, z / x = 0.01-1.0, n / m = 0.5-2.
0 and w = 0 to 20. (8) The bleaching detergent composition according to (6) above, wherein the crystalline alkali metal silicate has a composition represented by the following formula (III): M ₂ O · x′SiO ₂ · y′H ₂ O (III) (In the formula, M represents an alkali metal, and x ′ = 1.5 to 2.
6, y ′ = 0 to 20. (9) The blending amount of the crystalline alkali metal silicate is 20 to
50% by weight of the bleaching detergent composition according to any one of (1) to (8), (10) the hydrogen peroxide releasing substance is a granular or powdery substance having an effective oxygen concentration of 5 to 15% by weight, and a bleaching detergent. The above (1) to (9), which is contained in the composition in an amount of 0.5 to 15% by weight.
(1) The bleaching detergent composition according to any one of (1) to (10) above, wherein the hydrogen peroxide releasing substance is sodium percarbonate, (12) the bleaching detergent composition in washing water The concentration of surfactant is 0.07-0.17g / L
The bleaching detergent composition according to any one of (1) to (11) above.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The bleaching detergent composition of the present invention comprises an organic peracid precursor and hydrogen peroxide which react with hydrogen peroxide in water to produce an organic peracid having an alkyl group having 7 to 19 carbon atoms. It is a granular or powdery bleaching detergent composition containing an emitter.

As the organic peracid precursor which reacts with hydrogen peroxide in water to produce an organic peracid, alkanoyloxybenzene sulfonates, alkanoyloxybenzoates, N, N, N ', N'-tetra Examples thereof include acetylethylenediamine, and the alkanoyloxybenzenesulfonate represented by the following general formula (I) is preferably used because of its high storage stability and high bleaching performance.

[0015]

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(In the formula, R represents a linear alkyl group or alkylene group having 7 to 19 carbon atoms, and M represents an alkali metal.)

In the general formula (I), specific examples of R include a heptyl group, an octyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group and a nonadecyl group, and an undecyl group and a dodecyl group are preferable. Can be mentioned. Specific examples of M include sodium and potassium, and preferably sodium. The alkanoyloxybenzene sulfonate represented by the above general formula (I) may be any of ortho, meta and para isomers, but those having a para isomer as a main component are preferable.

Regarding the amount of the organic peracid precursor used as described above, the weight ratio of the organic peracid precursor to the nonionic surfactant is 10/90 to 70/30, preferably 15 / 85-50 / 50. If the ratio of the organic peracid precursor is less than this range, as described above, the surfactant ratio becomes high and the bleaching activator (organic peracid) is not sufficiently generated, so that the underwear has sufficient cleaning properties such as yellowing stains. If the amount exceeds this range, the surfactant ratio tends to be relatively low, and the sebum stain cleaning property tends to deteriorate. As a method for producing the above organic peracid precursor,
A generally known method is used, for example, a method of reacting a phenol sulfonate with an acid chloride having a corresponding carbon number.

Examples of the hydrogen peroxide releasing agent used include granular or powdery percarbonates, perborates, perphosphates, persilicates, etc., preferably percarbonates, and particularly preferably Is sodium percarbonate. Such a hydrogen peroxide releasing body preferably has an effective oxygen concentration of 5 to 15
%, More preferably 7 to 13% of a granular or powdery substance, and the amount used in the bleaching detergent composition is preferably 0.5.
-15% by weight, more preferably 1-10% by weight, most preferably 2-7% by weight.

In the present invention, the above-mentioned organic peracid precursor and hydrogen peroxide releasing substance produce an organic peracid, and examples of such an organic peracid include perfatty acids and the like, which have 7 carbon atoms. -19, especially a perfatty acid having a linear alkyl group having 8 to 14 carbon atoms is preferable. When the carbon number is less than 7, the detergency against yellowing such as underwear and sebum stain tends to be poor, and when the carbon number exceeds 19, the solubility is poor and it is difficult to use.

The bleaching detergent composition of the present invention contains, in addition to the above components, the following components: a) a surfactant b) a crystalline alkali metal silicate c) a sequestering agent other than the component b. is there.

The contents and ratios of these components are as follows. That is, the total amount of the above a, b, and c components is
It is 70 to 99% by weight, preferably 80 to 96% by weight in the bleaching detergent composition. If this total amount is less than this range, a sufficient cleaning effect cannot be obtained.

The ratio of the component b to the component a is b by weight.
/ A = 90/10 to 45/55, preferably 80
/ 20 to 50/50. When the proportion of the component b is less than this range, the production of organic peracid is suppressed and, in addition, the detergency of sebum stains tends to deteriorate, and when it exceeds this range, the effect of the present invention tends to be insufficient.

The ratio of the b component to the c component is b / c = 7
/ 93 to 75/25, preferably 15/85 to 6
It is 5/35. If the proportion of the component b deviates from this range, the effect of the present invention tends to be insufficiently obtained.

A low surfactant concentration can be achieved by lowering the detergent concentration in the wash liquor. The detergent concentration is determined from the standard amount used. The detergent concentration usually depends on the hardness of the wash water used. The reason for this is that it is necessary to adjust the amount of sequestering agent according to the hardness of the washing water.

The standard amount of detergent used varies from country to country. This is because tap water hardness varies from country to country.
For example, in Japan, it is usually around 4 ° DH,
In the United States, water with a high hardness of 6 ° DH or more and in Europe exceeding 10 ° DH is used as washing water. This changes the absolute amount of sequestering agent, and consequently the standard usage is adjusted accordingly. Although the amount of the sequestering agent added in the present invention varies depending on the hardness, the concentration of the surfactant in the washing liquid is basically the same, and the standard amount used is smaller than before.

That is, the detergent concentration when the initial hardness of the washing liquid is different is as follows. 1) For washing water at 2 to 6 ° DH, the concentration of the detergent composition in the washing liquid is 0.33 to 0.67 g / L, preferably 0.33 to 0.50 g / L. 2) The concentration of the detergent composition in the washing liquid is 0.50 to 1.20 g / L, preferably 0.50 to 1.00 g / L for 6 to 10 DH of washing water. 3) For washing water of 10 to 20 ° DH, the concentration of the detergent composition in the washing liquid is 0.80 to 2.50 g / L, preferably 1.00 to 2.00 g / L.

The standard amount used varies depending on the hardness of water as described above, but the surfactant concentration basically does not significantly change,
In the present invention, when the detergent concentration is determined by the standard use amount, the detergent concentration is 0.07 to 0.17 g / L, and particularly excellent washing is possible even at a low concentration such as 0.08 to 0.14 g / L. You can get the power.

A) Surfactant As the surfactant used in the present invention, any surfactant generally used in detergents can be used without any particular limitation. Those containing 100% by weight, particularly 70 to 100% by weight, are preferable.

Specifically, it is at least one selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants exemplified below. For example, the same type may be selected only from a plurality of non-ionic surfactants, or various types from anionic surfactants and non-ionic surfactants. May be selected plurally.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene polyoxypropylene. Examples include alkyl ethers, polyoxyethylene castor oil, polyoxyethylene alkylamines, glycerin fatty acid esters, higher fatty acid alkanolamides, alkyl glucosides, and alkyl amine oxides.

Of these, polyoxyethylene alkyl ether obtained by adding 5 to 15 mol of ethylene oxide on average to a straight chain alcohol having 10 to 18 carbon atoms is preferably used because of its high ability to cleanse sebum.

Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, α-olefin sulfonate, α-sulfo fatty acid salt or ester salt, alkyl or alkenyl ether carboxylate. Examples thereof include acid salts, amino acid type surfactants, N-acyl amino acid type surfactants, and the like, with preference given to alkylbenzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, and the like.

Examples of cationic surfactants include quaternary ammonium salts such as alkyl trimethylamine salts. Examples of the amphoteric surfactant include carboxy type and sulfobetaine type amphoteric surfactants.

B) Crystalline alkali metal silicate As the crystalline alkali metal silicate used in the present invention, alkali metal silicates having various compositions can be used, but SiO ₂ / M ₂ O (provided that M represents an alkali metal) is 0.5 to 2.6, preferably 1.
Those having a size of 5 to 2.2 are preferably used. SiO ₂ /
If M ₂ O exceeds 2.6, the detergent composition tends to have poor detergency for sebum stains and the efficiency of generating organic peracid tends to decrease. If it is less than 0.5, it is powder or powder as a granular detergent. Reduce the physical properties. In addition, in the present invention, by using a crystalline silicate, not only high alkaline ability but also ion exchange ability can be imparted.

Of the crystalline alkali metal silicates used in the present invention, those having the following composition are preferably exemplified. _{xM 2 O · ySiO 2 · zMe} m O n · wH 2 O (II) ( wherein, M is Group Ia elements of the periodic table, Me represents IIa, II
b, IIIa, IVa or VIII, represents one or a combination of two or more elements, wherein y / x = 0.5 to 2.
6, z / x = 0.01-1.0, n / m = 0.5-2.
0 and w = 0 to 20. _{) M 2 O · x'SiO 2 ·} y'H 2 O (III) ( wherein, M represents an alkali metal, x '= 1.5~2.
6, y ′ = 0 to 20. )

First, the crystalline alkali metal silicate having the above composition will be described. In the general formula (II), M
Is selected from Group Ia elements of the periodic table, and examples of Group Ia elements include Na and K. These may be used alone or, for example, a mixture of Na ₂ O and K ₂ O to form the M ₂ O component. Me is selected from Group IIa, IIb, IIIa, IVa or VIII elements of the periodic table, for example, Mg, Ca, Zn,
Y, Ti, Zr, Fe and the like can be mentioned. These are not particularly limited, but are preferably Mg and Ca from the viewpoint of resources and safety. These may be used alone or as a mixture of two or more. For example, MgO, CaO
Like are mixed may constitute the Me _m O _n component.
Further, the crystalline alkali metal silicate in the present invention may be a hydrate, and the hydration amount in this case is w.
= 0 to 20.

In the general formula, y / x is 0.5 to
It is 2.6, preferably 1.5 to 2.2. y /
When x is less than 0.5, the water resistance of the crystalline alkali metal silicate is insufficient, and the caking properties, solubility, and powder properties of the detergent composition are significantly adversely affected. y / x is 2.6
If it exceeds, the crystalline alkali metal silicate has a low alkalinity and becomes insufficient as an alkali agent, and also has a low ion exchange ability and is insufficient as an ion exchanger. z / x is 0.01 to 1.0, preferably 0.
02 to 0.9. When z / x is less than 0.01, the water resistance of the crystalline alkali metal silicate is insufficient, and 1.
When it exceeds 0, the ion exchange capacity of the crystalline alkali metal silicate is low, which is insufficient as an ion exchanger. x,
y and z are not particularly limited as long as they have the relationship shown in the above y / x and z / x. As described above, when xM ₂ O is, for example, x′Na ₂ O · x ″ K ₂ O, x is x ′ + x ″. This relationship is the same in the z in the case of ZME _m O _n component composed of two or more. Also, n / m = 0.5
~ 2.0 indicates the number of oxygen ions coordinated to the element,
Substantially selected from the values of 0.5, 1.0, 1.5 and 2.0.

The crystalline alkali metal silicate having the composition of the present invention comprises three components of M ₂ O, SiO ₂ and Me _m O _n as shown in the above general formula (II). Therefore, in order to produce the crystalline alkali metal silicate in the present invention, each component is necessary as a raw material thereof, but in the present invention, a known compound is appropriately used without particular limitation. For example, M ₂ O component, M
The e _m O _n component, alone or oxides of the composite of each of the elements, hydroxides, salts, the element-containing minerals is used. Specifically, for example, as the raw material of the M ₂ O component, NaOH, KOH, Na ₂ CO ₃ , K ₂ CO ₃ , N
a ₂ SO ₄ and the like, as a material of Me _m O _n component, Ca
CO ₃ , MgCO ₃ , Ca (OH) ₂ , Mg (O
H) ₂ , MgO, ZrO ₂ , dolomite and the like. As the SiO ₂ component, silica stone, kaolin, talc,
Fused silica, sodium silicate or the like is used.

The method of preparing the crystalline alkali metal silicate according to the present invention comprises the above raw material components in a predetermined quantitative ratio so that the desired x, y, z values of the crystalline alkali metal silicate can be obtained. Mixing is generally 300 to 1500 ° C, preferably 500 to 1000 ° C, more preferably 600 to 900.
A method of firing and crystallization in the range of ° C. is exemplified. In this case, if the heating temperature is lower than 300 ° C., the crystallization is insufficient and the water resistance is poor. 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 thus obtained has a pH of 11 or more in a 0.1% by weight dispersion and exhibits an excellent alkaline ability. Also, the alkali buffering effect is particularly excellent, and the alkali buffering effect is superior to that of sodium carbonate or potassium carbonate.

The crystalline alkali metal silicate having the composition of the present invention has an ion exchange capacity of at least 100 CaCO ₃ mg / g or more, preferably 200 to.
It has 600 CaCO ₃ mg / g, and is one of the substances having an ion trapping ability in the present invention.

The crystalline alkali metal silicate according to 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 compounding amount thereof, the above-mentioned washing can be performed. The conditions can be adjusted appropriately.

In the present invention, the crystalline alkali metal silicate preferably has an average primary particle size of 0.1 to 20 μm, more preferably 1 to 10 μm.
The alkali metal silicate may be an aggregate of primary particles. If the average primary particle size exceeds this range, the rate of ion exchange development tends to be slow, resulting in a decrease in detergency. Further, when it is less than this range, the hygroscopicity and the CO ₂ absorbing property increase due to the increase in the specific surface area, and the quality tends to be remarkably deteriorated. The average particle size referred to here is the median size of the particle size distribution, and the particle size distribution was measured by a laser diffraction type distribution measuring device described in detail in the following examples.

The crystalline alkali metal silicate having such an 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
It can be easily obtained by crushing with an -O type 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 (III) M ₂ O · x′SiO ₂ · y′H ₂ O (III) (wherein M represents an alkali metal, and x ′ = 1.5 to 2.
6, preferably 1.5 to 2.2, y '= 0 to 20, preferably 0 to 4. ), X ′ and y ′ in the general formula (III) are 1.7 ≦ x ′ ≦ 2.2, y ′.
= 0 is particularly preferable, and the cation exchange capacity is 100 to
400 CaCO ₃ mg / g can be used, which is one of the substances having an ion trapping ability in the present invention. As the M ₂ O and SiO ₂ in the general formula (III), those similar to the crystalline alkali metal silicate having the composition of are used. The crystalline alkali metal silicate having the composition of the present invention has an alkaline ability and an alkaline buffering effect as described above, and further has an ion exchange ability. Therefore, by appropriately adjusting the blending amount thereof, the above-mentioned washing can be performed. The conditions can be adjusted appropriately.

The production method of such a crystalline alkali metal silicate is described in JP-A-60-227895, and generally 200 g of amorphous glassy sodium silicate is used.
It is obtained by firing at ~ 1000 ° C to make it crystalline. For details of the synthesis method, see, for example, Phys. Chem. Glasses.
7, 127-138 (1966), Z. Kristallogr., 129 , 396-404 (19
69) etc. Further, this crystalline alkali metal silicate is available, for example, from Hoechst Tokuyama 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 primary particle size of 0.1 to 20 μm, more preferably 1 to 10 μm. Is. In addition, aggregates of the primary particles may be used. The average primary particle here is obtained by the same method as that of the composition.

In the present invention, the crystalline alkali metal silicates having the above compositions and are used alone or in combination of two or more, and the total amount of 20 to 5 in the total composition is used.
The content is preferably 0% by weight, more preferably 2
It is 0 to 35% by weight. If the amount is more than this range, the powder properties of the resulting detergent tend to be deteriorated, and in addition, the detergency of sebum stains tends to be deteriorated. If the amount is less than this range, the production rate of organic peracid is lowered, The dirt cleaning power also tends to decrease.

C) Sequestering agent other than the component b The sequestering agent other than the component b in the present invention has a numerical value obtained by the following measuring method of 100 CaCO ₃ mg.
/ G or more. That is, the method for measuring the ion-capturing ability of the sequestering substance depends on whether the sequestering substance used is an ion exchanger or a chelating agent. The measuring method for each substance is as follows.

In the case of an ion exchanger, 0.1 g of a sample was precisely weighed and added to 100 ml of an aqueous calcium chloride solution (concentration: 500 ppm as CaCO ₃ ),
After stirring at 25 ° C. for 60 minutes, the mixture is filtered using a membrane filter having a pore size of 0.2 μm (manufactured by Advantech, nitrocellulose), and the amount of Ca contained in 10 ml of the filtrate is measured by EDTA titration. The calcium ion exchange capacity (cation exchange capacity) of the sample is determined from the value. For example, in the present invention, an inorganic substance such as a crystalline alkali metal silicate or an aluminosilicate (such as zeolite) is measured as an ion exchanger. In the case of a chelating agent, a calcium ion electrode is used to measure the Ca ion capturing ability as described below. In addition, all the solutions are prepared using the following buffers. _{Buffer; 0.1M-NH 4 Cl-NH} 4 OH buff
er (pH 10.0) (1) Preparation of calibration curve A standard calcium ion solution is prepared, and a calibration curve showing the relationship between the logarithm of calcium ion concentration and the potential as shown in FIG. 1 is prepared. (2) Measurement of calcium ion-capturing ability About 0.1 g of a sample is weighed in a 100 ml volumetric flask, and the volume of the sample is adjusted with the above buffer solution. To this, 2000
An aqueous CaCl ₂ solution (pH 10.0) corresponding to 0 ppm (calculated as CaCO ₃ ) is dropped from a buret (a blank is also measured). For dripping, 0.1 to 0.1 CaCl ₂ solution is used.
Add 0.2 ml each, read the potential at that time,
The calcium ion concentration is determined from the calibration curve in FIG. FIG.
The calcium ion concentration at the dropped amount A of the sample in the inside becomes the calcium ion trapping ability of the sample. For example, in the present invention, polycarboxylic acid salts such as citrate and polycarboxylate polymers such as acrylic acid-maleic acid copolymer are measured as chelating agents.

Of the above-mentioned sequestering agents, C
It is preferable to contain 1% by weight or more of a polycarboxylate polymer having an a-ion trapping ability of 200 CaCO ₃ mg / g or more. Specific examples of such a polymer include a polymer or a copolymer having a repeating unit represented by the general formula (IV).

[0053]

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(Wherein X ₁ is methyl, H or COOX
₃ , X ₂ represents methyl, H or OH, and X ₃ represents H, an alkali metal, an alkaline earth metal, NH ₄ or ethanolamine. In the general formula (IV), the alkali metal is Na,
Examples of the alkaline earth metal include C and Li.
a, Mg, etc. may be mentioned.

The polymer or copolymer used in the present invention is, for example, a polymerization reaction of acrylic acid, (anhydrous) maleic acid, methacrylic acid, α-hydroxyacrylic acid, crotonic acid, isocrotonic acid, or a salt thereof, or It is synthesized by a copolymerization reaction of each monomer or a copolymerization reaction with another polymerizable monomer. Examples of other copolymer monomers used for copolymerization at this time include, for example, aconitic acid, itaconic acid, citraconic acid, fumaric acid, vinylphosphonic acid, sulfonated maleic acid, diisobutylene, styrene, methyl vinyl ether, ethylene, propylene , Isobutylene, pentene, butadiene, isoprene, vinyl acetate (and vinyl alcohol when hydrolyzed after copolymerization), acrylate, and the like, but are not particularly limited. In addition,
The polymerization reaction is not particularly limited, and a generally known method can be used. Further, a polyacetal carboxylic acid polymer such as polyglyoxylic acid described in JP-A-54-52196 can also be used.

In the present invention, as the above-mentioned polymers and copolymers, those having a weight average molecular weight of 800 to 1,000,000 are used, and those having a weight average molecular weight of 5,000 to 200,000 are preferably used. If the weight average molecular weight is less than 800, the effects of the present invention specific to the polymer cannot be obtained. If the weight average molecular weight exceeds 1,000,000, recontamination occurs due to the influence of the polymer, and the cleaning performance is hindered. Further, the copolymerization rate of the repeating unit of the general formula (IV) and another copolymerization monomer in the case of copolymerization is not particularly limited, but preferably the repeating unit of the general formula (IV) / the other copolymerization monomer = 1 The copolymerization ratio is in the range of / 100 to 90/10.

In the c-component sequestering agent, the ion exchange capacity represented by the following formula (V) was 200 Ca.
The one containing an aluminosilicate of CO ₃ mg / g or more is more preferable. _{x "(M 2 O) ·} Al 2 O 3 · y" (SiO 2) · w "(H 2 O) (V) ( wherein, M represents alkali metals such as sodium and potassium,
x ″, y ″, and w ″ represent the number of moles of each component, and generally 0.7 ≦ x ″ ≦ 1.5, 0.8 ≦ y ″ ≦ 6, and w ″ are arbitrary constants. )

Examples of the above-mentioned aluminosilicates include crystalline ones and amorphous ones. As the crystalline ones, those represented by the following general formula are particularly preferable. _{Na 2 O · Al 2 O 3} · ySiO 2 · wH 2 O ( wherein, y is 1.8 to 3.0, w represents a number of 1-6.) As the crystalline aluminosilicate (zeolite) , Type A,
The average primary particle size represented by X-type and P-type zeolite is 0.
A synthetic zeolite of 1 to 10 μm is preferably used. The zeolite may be used as zeolite agglomerated dry particles obtained by drying the powder and / or the zeolite slurry or the slurry.

The above crystalline aluminosilicate can be produced by a conventional method. For example, JP-A-50-123
81 and JP-A-51-12805 can be used.

On the other hand, the amorphous aluminosilicate represented by the same general formula as the above crystalline aluminosilicate can be produced by a conventional method. For example, SiO ₂ and M ₂ O
(M means an alkali metal) molar ratio of SiO ₂ /
An M ₂ O = 1.0~4.0, the molar ratio of between H ₂ O and M ₂ O is using alkali metal silicate solution is a _{H 2 O / M 2 O =} 12~200, M to The molar ratio of ₂ O and Al ₂ O ₃ is M ₂ O / Al ₂ O ₃ = 1.0 to 2.0, and H
The molar ratio of ₂ O to M ₂ O is H ₂ O / M ₂ O = 6.0 to 50
The aqueous solution of a low alkali alkali metal aluminate, which is 0, is usually added under a strong stirring at a temperature of 15 to 60 ° C, preferably 30 to 50 ° C.

The resulting white precipitate slurry is then heated to a temperature of usually 70 to 100 ° C, preferably 90 to 100 ° C.
It can be advantageously obtained by performing a heat treatment usually for 10 minutes or more and 10 hours or less, preferably 5 hours or less, followed by filtration, washing and drying. At this time, the addition method may be a method of adding an aqueous solution of an alkali metal silicate to an aqueous solution of a low alkali alkali metal aluminate. According to this method, the ion exchange capacity is 100 CaCO ₃ mg / g or more, and the oil absorption capacity is 80 m.
An amorphous aluminosilicate oil-absorbing carrier of 1/100 g or more can be easily obtained (see JP-A-62-191417 and JP-A-62-191419). Other sequestering agents include, for example, aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1.
-Diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), and salts thereof, 2-phosphonobutane-
Examples include organic chelating agents such as salts of phosphonocarboxylic acids such as 1,2-dicarboxylic acid, citrates, nitrilotriacetic acid salts, aminopolyacetic acid salts such as ethylenediaminetetraacetic acid salts.

Other components in the present invention include, as alkali agents, amorphous alkali metal silicates, carbonates, alkali metal salts such as sulfites, and organic amines such as alkanolamines.

Further, non-dissociated polymers such as polyethylene glycol, polyvinyl alcohol and polyvinylpyrrolidone,
Examples of the anti-fading agent, anti-redeposition agent, etc., which are generally known to be blended with detergents, such as carboxymethyl cellulose, are included.

In addition, the detergent composition of the present invention may contain the following components. That is, enzymes such as protease, lipase, cellulase, and amylase, having 1 to 1 carbon atoms
Approximately 4 lower alkylbenzene sulfonates, sulfosuccinates, talc, anti-caking agents such as calcium silicate, tert-butyl hydroxytoluene, antioxidants such as distyrenated cresol, fluorescent dyes, bluing agents, fragrances, etc. However, these are not particularly limited and may be blended according to the purpose.

The detergent composition of the present invention contains the above-mentioned components, but the method for producing the detergent composition is not particularly limited, and conventionally known methods can be used. However, it is preferable that the above-mentioned organic peracid precursor, hydrogen peroxide releasing substance and enzyme are dry-blended after being produced as separate powders in order to prevent a decrease in bleaching activity due to a reaction between them in the production process. . Specifically, for example,
As a method for obtaining a high bulk density detergent, JP-A-61-6
The methods described in JP-A-9897, JP-A-61-69899, JP-A-61-69900, and JP-A-5-209200 can be used.

[0066]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited to these Examples and the like.

(1) Amount of substance having ion-capturing ability The ion-capturing ability was measured by the following method depending on whether the sequestering substance used was an ion exchanger or a chelating agent. As a method of displaying the ion trapping ability of the sequestering agent, CEC (calcium ion exchange capacity) is displayed in the tables of the examples as in the case of alkali metal silicates. The DH hardness was measured by the ion coupling plasma method (ICP method).

In the case of an ion exchanger, 0.1 g of a sample was precisely weighed and added to 100 ml of an aqueous calcium chloride solution (concentration: 500 ppm as CaCO ₃ ),
After stirring at 25 ° C. for 60 minutes, filtration was carried out using a membrane filter having a pore size of 0.2 μm (manufactured by Advantech, nitrocellulose), and the amount of Ca contained in 10 ml of the filtrate was measured by EDTA titration. The calcium ion exchange capacity (cation exchange capacity) of the sample was determined from the value.

In the case of a chelating agent A calcium ion electrode was used to measure the Ca ion capturing ability as follows. All solutions were prepared using the following buffer solutions. _{Buffer; 0.1M-NH 4 Cl-NH} 4 OH buff
er (pH 10.0) (i) Preparation of calibration curve A standard calcium ion solution was prepared and a calibration curve showing the relationship between the logarithm of the calcium ion concentration and the potential as shown in FIG. 1 was prepared. (Ii) Measurement of calcium ion-capturing ability About 0.1 g of a sample is weighed in a 100 ml volumetric flask, and the volume of the sample is raised with the above buffer solution. To this, 2000
An aqueous CaCl ₂ solution (pH 10.0) corresponding to 0 ppm (calculated as CaCO ₃ ) was dropped from a buret (a blank is also measured). For dripping, 0.1 to 0.1 CaCl ₂ solution is used.
Add 0.2 ml each, read the potential at that time,
The calcium ion concentration was determined from the calibration curve in FIG. FIG.
The calcium ion concentration in the dropped amount A of the sample was taken as the calcium ion trapping ability of the sample.

(2) Average particle size and particle size distribution of alkali metal silicate The average particle size and particle size distribution were measured using a laser diffraction type particle size distribution measuring device. That is, about 200 ml of ethanol was injected into a measurement cell of a laser diffraction type particle size distribution analyzer LA-700 type (manufactured by Horiba, Ltd.), and about 0.5 to 5 mg of a sample was suspended. Subsequently, the mixture was stirred for 1 minute while being irradiated with ultrasonic waves, and after sufficiently dispersing the sample, a He-Ne laser (632.8 nm) was incident, and the particle size distribution was measured from the diffraction / scattering pattern.
The analysis uses both the Fraunhofer diffraction theory and the Mie scattering theory to reduce the particle size distribution of suspended particles in the liquid from 0.04 to
It was measured in the range of 262 μm. The average particle size was the median size of the particle size distribution.

Preparation Example 1 (Crystalline alkali metal silicate A
To F) No. 2 sodium silicate (SiO ₂ / Na ₂ O = 2.5) 100
Sodium hydroxide (55.9 parts by weight) and potassium hydroxide (8.5 parts by weight) were added to 0 parts by weight, and the mixture was stirred with a homomixer to dissolve sodium hydroxide and potassium hydroxide. 5.23 parts by weight of finely dispersed anhydrous calcium carbonate and 0.13 parts by weight of magnesium nitrate hexahydrate were added thereto and mixed using a homomixer. An appropriate amount of the mixture was placed in a nickel crucible, fired at 700 ° C. in air for 1 hour, quenched, and the fired body obtained was pulverized to obtain the crystalline alkali metal silicate powder A in the present invention. The ion exchange capacity of this powder was as high as 305 CaCO ₃ mg / g. In the same manner, crystalline alkali metal silicate powders B to F having the compositions shown in Table 1 were obtained.

[0072]

[Table 1]

Preparation Example 2 (amorphous aluminosilicate) Sodium carbonate was dissolved in ion-exchanged water to prepare an aqueous solution having a concentration of 6% by weight. 132 g of this aqueous solution and 38.28 g of sodium aluminate aqueous solution (Conc.
Placed in a 00 ml baffled reaction vessel. No. 3 water glass 20 diluted with 2 times water was added to the obtained mixed solution under strong stirring.
The reaction was carried out at 40 ° C. while dropping 1.4 g over 20 minutes. At this time, the pH of the reaction system was controlled by blowing CO ₂ gas (pH = 10.5) to optimize the reaction rate. After the completion of such a primary reaction, the reaction system was heated to 50 ° C. and the secondary reaction was carried out at the same temperature for 30 minutes. Thereafter, CO ₂ gas was blown into the reaction system to neutralize the excess alkali (pH = 9.0). The obtained neutralized slurry was filtered under reduced pressure using filter paper (Toyo Roshi Kaisha, Ltd. No. 5C). The filter cake was washed with 1000 times of water, filtered and dried (105 ° C, 300 torr, 10
And the rest was dried (without washing) under the same conditions. Furthermore, it crushed and obtained the amorphous aluminosilicate powder of this invention. The aqueous solution of sodium aluminate is 10
In a 00 cc four-necked flask, 243 g of Al (OH) _{3 and} 298.7 g of a 48% NaOH aqueous solution were put and mixed, heated to 110 ° C. with stirring, and dissolved for 30 minutes to prepare.
As a result of atomic absorption analysis and plasma emission analysis, the composition of the obtained amorphous aluminosilicate was Al ₂ O ₃ = 29.6% by weight, SiO ₂ = 52.4% by weight, Na ₂ O = 18.0.
% By weight (1.0 Na ₂ O.Al ₂ O ₃ 3.1
0SiO ₂ ). In addition, the Ca ion trapping capacity is 185 CaC
O ₃ mg / g, oil absorption capacity is 285 ml / 100 g, 0.1
The proportion of the pore volume having a pore diameter of less than μm is 9.4%,
The ratio of the volume of pores having a pore diameter of 0.1 μm or more and 2.0 μm or less was 76.3%, and the water content was 11.2% by weight.

Preparation Example 3 (Na-alkanoyloxybenzenesulfonate) 100 g (0.46 mol) of sodium p-phenolsulfonate, which had been dehydrated in advance, was dispersed in 300 g of dimethylformamide (DMF), and the mixture was stirred with a mechanical stirrer. Lauric acid chloride at 0 ° C was added dropwise over 30 minutes, and the reaction was performed for 3 hours after the completion of the addition. afterwards,
DMF was distilled off at 100 ° C. under reduced pressure (0.5 to 1 mmHg), washed with acetone, and then water / acetone (= 1/1 mol).
Recrystallization was carried out in a solvent to obtain Na lauroyloxybenzenesulfonate (yield 85%).

Alkanoyloxybenzenesulfonic acid Na (C = C) was obtained in the same manner as above except that acetyl chloride was used instead of lauric chloride.
1) was obtained.

Examples 1 to 5, Comparative Examples 1 to 8 Crystalline alkali metal silicate A obtained in the above preparation example
-F, and other components shown in Tables 2 to 4,
A detergent composition having the composition shown in Table 4 was produced by the following method. That is, in Tables 2 to 4, crystalline alkali metal silicates A to F and amorphous aluminosilicates, nonions, Na percarbonate, bleach activator (Na alkanoyloxybenzene sulfonate), fragrances, and enzymes were used. Aqueous component (LAS-Na, AS-Na, polyacrylic acid N
a, sodium carbonate, sodium sulfate, etc.) into a 60% solid content slurry, and the particles obtained by spray-drying this are put into a Loedige mixer, and the remaining powder raw material is further put into a liquid nonionic surfactant. Was gradually added and mixed and granulated. In addition, about sodium percarbonate in each Example and a comparative example, the granular raw material was blended. In this way, the bulk density of the average particle size of 300 to 600 μm is 0.6 to
A 1.0 g / ml powder detergent composition was obtained.

Test Example Using the detergent compositions obtained in the above Examples and Comparative Examples, a cleaning test was conducted under the following conditions. <Method for measuring sebum dirt cleaning rate> (1) Preparation of artificially contaminated cloth An artificially contaminated cloth was prepared by adhering an artificially contaminated liquid having the following composition to the cloth. Adhesion of artificial polluted liquid to cloth is disclosed in JP-A-7-2703.
A gravure-type pollution machine using a gravure roll coater shown in No. 95 was used. The step of producing the artificially contaminated cloth by adhering the artificially contaminated liquid to the cloth is as follows: cell volume of gravure roll: 58 cm ³ / cm ² , coating speed: 1.0 m / min,
The drying temperature was 100 ° C. and the drying time was 1 minute. As the cloth, cotton cloth 2003 cloth (manufactured by Tanigami Shoten) was used. [Composition of artificial contamination liquid] Lauric acid 0.44% by weight Myristic acid 3.09% by weight Pentadecanoic acid 2.31% by weight Palmitic acid 6.18% by weight Heptadecanoic acid 0.44% by weight Stearic acid 1.57% by weight Oleine Acid 7.75 wt% Triolein 13.06 wt% n-Hexadecyl palmitate 2.18 wt% Squalene 6.53 wt% Egg white lecithin liquid crystal 1.94 wt% Kanuma red clay 8.11 wt% Carbon black 0.01 Weight% Tap water balance

(2) Washing conditions Using a tergotometer, the rotation speed is 100 rpm, the washing time is 10 minutes, the temperature is 20 ° C., and the water used is 4 ° DH (Ca / M
g = 3/1), and washing was performed at a detergent concentration of 0.67 g / L. Generally, hardness components of washing water are Ca ²⁺ , Mg ²⁺
And the weight ratio is Ca / Mg = (60 to 85)
/ (40 to 15), but here Ca / Mg = 3/1 was used as model water. 4 ° DH is Mg
It is the hardness when the equimolar amount of ions is replaced by Ca.

(3) Calculation of Washing Rate The reflectance at 550 mμ before and after washing was measured with a self-recording colorimeter (manufactured by Shimadzu Corporation), and the washing rate D (%) was calculated by the following formula. The results are also shown in Tables 2 to 4. D = (L ₂ −L ₁ ) / (L ₀ −L ₁ ) × 100 (%) L ₀ : reflectance of the original cloth L ₁ : of the uncleaned cloth Reflectivity L ₂ : Reflectivity of soiled cloth after washing

<Measurement Method of Yellowing Stain Cleaning Rate> (1) Preparation of Model Yellowing Undergarment Linoleic acid and squalene (weight ratio 1:10), which are considered as yellowing components, are dispersed and dissolved in chloroform (concentration 10%). 0.6 ml of this solution was dropped onto a cotton cloth (cotton metal cloth # 2003) of 8 cm × 8 cm, and chloroform diffused on the cloth was evaporated.
Aging is performed in a constant temperature bath at ℃. A cotton cloth having a b value of 3 or more is used as a model yellowed stain cloth.

(2) Washing and bleaching experiment A set of four contaminated cloths obtained by the above method was used.
Clean with a tergotometer (Shimadzu). The conditions are: cleaning time: 10 minutes, rinsing 3 minutes (tap water) rotation speed: 100 rpm hardness: 4 ° DH temperature: 20 ° C. concentration: 0.67 g / L

(3) Measurement of Bleaching Cleaning Rate The reflectance of the raw cloth and the contaminated cloth before and after cleaning was measured with NDR-101DP manufactured by Nippon Denshoku Industries Co., Ltd. using a filter having a wavelength of 460 nm. The yellowish stain cleaning rate (bleaching cleaning rate) was calculated by the following formula to evaluate the bleaching cleaning performance. The results are also shown in Tables 2 to 4.

[0083]

[Equation 1]

[0084]

[Table 2]

[0085]

[Table 3]

[0086]

[Table 4]

The abbreviations in the table are as follows. POE: Average number of moles of ethylene oxide added LAS-Na: Sodium linear alkylbenzene sulfonate AS-Na: Sodium alkyl sulfate Nonion: Polyoxyethylene alkyl ether, average number of addition moles is 8 moles Zeolite: 4A type zeolite Average particle size 3 μm AA / MA copolymer: acrylic acid, copolymer using maleic acid as a monomer, average molecular weight 70,000, acrylic acid: maleic acid = 70:30, sodium salt having a neutralization degree of about 80% Amorphous aluminosilicate: Preparation example 2 Prepared in Na polyacrylate: Polymer of sodium acrylate,
Average molecular weight 10,000, neutralization degree about 80% Other components: oxygen (protease and cellulase are used together) Perfume (perfume described in JP-A-5-202387) Fluorescent dye (biphenyl, stilbene type are used together) Water

In all the examples of the present invention, a high sebum stain cleaning rate and a yellowing stain cleaning rate were exhibited. In contrast, Comparative Example 1 in which the carbon number of the organic peracid is small, Comparative Example ₂ in which SiO ₂ / M ₂ O of the crystalline alkali metal silicate is too large,
Comparative Examples 3 and 5 in which the total amount of the components a, b, and c is small, Comparative Example 4 which is an anionic detergent composition, and Comparative Examples in which the ratio of the organic peracid precursor to the nonionic surfactant is too high. 6, Comparative Example 7 in which the amount of the crystalline alkali metal silicate used was too large, and Comparative Example 8 in which the amount of the surfactant used was too small, the sebum stain cleaning rate and the yellowing stain cleaning rate were both compared with the examples. Was inferior to

[0089]

EFFECTS OF THE INVENTION The bleaching detergent composition of the present invention can exhibit excellent detergency against lipophilic stains such as sebum stains and yellowing of underwear.

[Brief description of drawings]

FIG. 1 is a diagram showing a calibration curve showing a relationship between a logarithm of calcium ion concentration and a potential.

FIG. 2 is a diagram showing a relationship between a drop amount of a sample and a calcium ion concentration.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Noriaki Ushio 1334 Minato Minato, Wakayama City Kao Corporation Research Institute (72) Inventor Shigeru Tamura 1334 Minato Minato Wakayama City Institute, Kao Corporation (72) Inventor Masaki Tsumadori 1334 Minato Minato, Wakayama City Kao Corporation Research Center

Claims (12)

[Claims] 1. A carbon number of 7 to 10 when reacted with hydrogen peroxide in water.
A granular or powdery bleaching detergent composition containing an organic peracid precursor for producing an organic peracid having 19 alkyl groups and a hydrogen peroxide releasing agent, wherein the composition comprises the following components: a) a surfactant b) a crystalline alkali metal silicate c) a sequestering agent other than the component b, the total amount of the components a, b and c accounting for 70 to 99% by weight in the bleaching detergent composition, and the component a The ratio of the b component to b is 90/45/55, and the ratio of the b component to the c component is b / c = 7/93.
75/25 and the ratio of the organic peracid precursor to the nonionic surfactant as the component a is 10 by weight.
/ 90-70 / 30, The bleaching detergent composition characterized by the above-mentioned. 2. The bleaching detergent composition according to claim 1, wherein the content of the nonionic surfactant is 50 to 100% by weight based on the total amount of the surfactants. 3. The bleaching detergent composition according to claim 1, wherein the produced organic peracid is a perfatty acid having a linear alkyl group having 7 to 19 carbon atoms. 4. The bleaching detergent composition according to claim 3, wherein the organic peracid precursor is represented by the following general formula (I). Embedded image (In the formula, R represents a linear alkyl group or alkylene group having 7 to 19 carbon atoms, and M represents an alkali metal.) 5. The nonionic surfactant as the component a is a polyoxyethylene alkyl ether prepared by adding 5 to 15 mol of ethylene oxide on average to a linear alcohol having 10 to 18 carbon atoms. The bleaching detergent composition according to any one of claims. 6. A crystalline alkali metal silicate, SiO _2.
/ M ₂ O (where M represents an alkali metal) is 0.5
It is -2.6, The bleaching detergent composition in any one of Claims 1-5. 7. The crystalline alkali metal silicate has the following (I
The bleaching detergent composition according to claim 6, which has a composition represented by the formula (I). _{xM 2 O · ySiO 2 · zMe} m O n · wH 2 O (II) ( wherein, M is Group Ia elements of the periodic table, Me represents IIa, II
b, IIIa, IVa or VIII, represents one or a combination of two or more elements, wherein y / x = 0.5 to 2.
6, z / x = 0.01-1.0, n / m = 0.5-2.
0 and w = 0 to 20. ) 8. The crystalline alkali metal silicate has the following (II
The bleaching detergent composition according to claim 6, which has a composition represented by the formula I). _{M 2 O · x'SiO 2 · y'H} 2 O (III) ( wherein, M represents an alkali metal, x '= 1.5~2.
6, y ′ = 0 to 20. ) 9. The bleaching detergent composition according to claim 1, wherein the blending amount of the crystalline alkali metal silicate is 20 to 50% by weight. 10. The hydrogen peroxide releasing body has an effective oxygen concentration of 5 to 5.
The bleaching detergent composition according to any one of claims 1 to 9, which is a granular or powdery substance of 15% and is contained in the bleaching detergent composition in an amount of 0.5 to 15% by weight. 11. The bleaching detergent composition according to claim 1, wherein the hydrogen peroxide releasing agent is sodium percarbonate. 12. A surfactant concentration of 0.07 to 0.17 when a bleaching detergent composition is added to laundry water in a standard amount.
The bleaching detergent composition according to claim 1, which is g / L.