JP3320304B2 - Bleach detergent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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 Hitherto, a method has been proposed in which a bleaching agent component is added to a detergent composition to enhance the detergency of the detergent composition against stains and the like.

[0003] For example, Japanese Patent Application Laid-Open No. 59-22999,
JP-A-6-316700 describes a bleaching composition and a bleaching detergent composition containing an organic peracid precursor for producing an organic peracid having an alkyl group having a specific number of carbon atoms and a hydrogen peroxide releasing substance. There is. Organic peracids produced from these organic peracid precursors show very good bleaching power against stain stains, but when added to a normal detergent composition to form a bleaching detergent composition, sufficient No bleaching effect could be demonstrated. The reason is that the surfactant (especially nonionic surfactant) concentration in these detergent composition systems is high, and the organic peracid precursor is taken into micelles of the surfactant and is solubilized, so This is considered to be because the reaction with the hydrogen oxide releasing body was hindered, and the generation of organic peracid, which is a bleaching active species, was inhibited. This tendency was more remarkable as the concentration of the nonionic surfactant in the surfactant component was higher. This point makes it more difficult to mix nonionic surfactants more effectively with sebum stains than with anionic surfactants, and in making both sebum stains and yellowish stains easy to clean. It was a problem.

[0004] On the other hand, the applicant of the present invention uses a crystalline alkali metal silicate having a high alkalinity at a high concentration and enhances the sequestering ability, so that the use concentration of the surfactant can be significantly reduced. It has been found that a high detergency can be exhibited for sebum stains, and a patent application has been filed (Japanese Patent Application No. 6-247279). However, this cleaning method was not sufficient in cleaning performance against lipophilic stains such as yellowed underwear stains.

[0005] Further, as a prior art including a crystalline silicate and a bleaching component as essential components, Japanese Patent Application Laid-Open No. 6-116591 discloses the prior art.
And JP-A-7-53992.
The publication discloses crystalline sodium silicate, a surfactant,
And a bleaching detergent containing a bleaching activator for producing a perfatty acid and a bleaching component comprising sodium percarbonate, but the bleaching detergent having the composition disclosed herein is insufficient with respect to the detergency of sebum stains. In addition, since the mixing ratio of the surfactant is high, the composition is not a composition that can effectively generate the organic peracid generated by the bleaching activator (organic peracid precursor) to be mixed. For example, sufficient effects have not been obtained on lipophilic stains.

[0006]

SUMMARY 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. It is in.

[0007]

Means for Solving the Problems As a result of intensive studies, the present invention has found that the content ratio of a surfactant, a crystalline alkali metal silicate, and other sequestering agents to a nonionic surfactant By making the content ratio of the organic peracid precursor to the specific value, while effectively utilizing the bleaching activity of the organic peracid precursor that generates an organic peracid having an alkyl group having about 7 to 19 carbon atoms, It has also been found that it exhibits excellent cleaning performance not only on lipophilic stains such as underwear yellowing but also on sebum stains.

More specifically, a bleaching activator which produces a perfatty acid having an alkyl group having a carbon number of 7 or more exhibits excellent detergency against yellowing such as underwear and sebum stains. When a large amount of a nonionic surfactant is added to the solution, there is a phenomenon that it is understood that 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 thought that the use of the bleaching activator in a nonionic detergent composition is not suitable.However, the present invention surprisingly is particularly achieved by selecting a specific compounding ratio. Excellent cleaning power,
They found that bleaching power could be achieved, and completed the present invention.

On the other hand, the above-mentioned prior art does not focus on the surfactant in the washing liquid, and therefore does not suggest the compounding ratio of the present invention and does not achieve the detergency of the present invention. . This is clear from the results of the comparative examples corresponding to the prior art cited in the present specification.

That is, the gist of the present invention is to provide: (1) an organic peracid precursor which reacts with hydrogen peroxide in water to produce an organic peracid having an alkyl group having 7 to 19 carbon atoms, and a hydrogen peroxide emitter A granular or powdery bleaching detergent composition comprising: a) a surfactant; b) a crystalline alkali metal silicate; c) a sequestering agent other than the b component; The total amount of the components a, b, and c accounts for 70 to 99% by weight of the bleaching detergent composition, and the ratio of the component b to the component a is b / a = 90/10 to 45/55 by weight, The ratio of the component b to the component c 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 Der is, of the non-ionic surfactant
Over fatty acids bleaching detergent composition content and wherein 50 to 100 wt% der Rukoto of the total surfactant, an organic peracid to produce (2) having a linear alkyl group of 7 to 19 carbon atoms (1) Symbol placement bleaching detergent composition is, (3) the organic peracid precursor is represented by the following general formula (I) (2) bleaching detergent composition according,

[0011]

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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.) ( 4 ) The nonionic surfactant as the component a has a carbon number of The bleaching detergent composition according to any one of the above (1) to ( 3 ), which is a polyoxyethylene alkyl ether obtained by adding an average of 5 to 15 mol of ethylene oxide to 10 to 18 linear alcohols, ( 5 ) crystalline alkali Metal silicate SiO ₂ / M ₂
O (where M represents an alkali metal) is 0.5 to 2.
6 and above (1) to (4) bleach detergent composition according to any, the above (5) according intended composition (6) crystalline alkali metal silicate is 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. ( 7 ) The bleaching detergent composition according to the above ( 5 ), 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) (wherein M represents an alkali metal and x ′ = 1.5 to 2.
6, y ′ = 0 to 20. ( 8 ) The compounding amount of the crystalline alkali metal silicate is 20 to
The bleaching detergent composition according to any one of the above (1) to ( 7 ), which is 50% by weight, ( 9 ) the bleaching detergent, wherein the hydrogen peroxide-releasing substance is a granular or powdery substance having an effective oxygen concentration of 5 to 15%. 0.5 to 0.5 in the composition
15 wt% content has been that (1) to (8) Bleaching detergent composition according to any, (10) hydrogen peroxide releasing material is sodium percarbonate above (1) to (9) according to any one Bleach detergent composition, average
Each time (11) a surfactant concentration when added in a standard amount of bleaching detergent composition in the washing water 0.07~0.17g / L
The bleaching detergent composition according to any one of the above (1) to ( 10 ).

[0013]

DETAILED DESCRIPTION OF THE INVENTION A bleach detergent composition of the present invention comprises an organic peracid precursor which reacts with hydrogen peroxide in water to produce an organic peracid having an alkyl group having 7 to 19 carbon atoms, and hydrogen peroxide. A granular or powdered bleach detergent composition containing an emitter.

The organic peracid precursors which react with hydrogen peroxide in water to produce organic peracids include alkanoyloxybenzenesulfonates, alkanoyloxybenzoates, N, N, N ', N'-tetra Acetyl ethylenediamine and the like can be mentioned, and alkanoyloxybenzenesulfonate represented by the following general formula (I) is preferably used because of high storage stability and 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 preferably an undecyl group and a dodecyl group. No. Specific examples of M include sodium, potassium and the like, and preferably sodium. The alkanoyloxybenzenesulfonate represented by the general formula (I) may be any of ortho, meta, and para-forms, but is preferably a para-form as a main component.

Regarding the amount of the organic peracid precursor as described above, the ratio of the organic peracid precursor to the nonionic surfactant is from 10/90 to 70/30 by weight, preferably from 15/90 to 70/30. 85 to 50/50. When the proportion of the organic peracid precursor is less than this range, as described above, the surfactant ratio is increased, and the bleaching activator (organic peracid) is not sufficiently generated, and the washing property is sufficient for yellowing stains of underwear. When the amount exceeds this range, the surfactant ratio tends to be relatively low, and the sebum stain cleaning property tends to be low. In addition, as a method for producing the above organic peracid precursor,
A generally known method, for example, a method of reacting a phenolsulfonic acid salt with an acid chloride having a corresponding carbon number or the like is used.

Examples of the hydrogen peroxide-releasing substance to be used include granular or powdery percarbonates, perborates, perphosphates, persilicates, etc., preferably percarbonates, particularly preferably percarbonates. Is sodium percarbonate. Such a hydrogen peroxide emitter preferably has an effective oxygen concentration of 5 to 15.
%, More preferably 7 to 13%, in the form of granules or powder, 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, an organic peracid is generated by the above-mentioned organic peracid precursor and hydrogen peroxide-releasing substance. Such organic peracids include perfatty acids and the like, and have 7 carbon atoms. To 19, particularly preferably a perfatty acid having a straight-chain alkyl group having 8 to 14 carbon atoms. When the number of carbon atoms is less than 7, the cleaning power for yellowing such as underwear and sebum dirt tends to be inferior. When the number of carbon atoms exceeds 19, the solubility is poor and the use is difficult.

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, and c) a sequestering agent other than the b component. is there.

The contents and proportions of these components are as follows. That is, the total amount of the 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 the 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 expressed as b
/ A = 90/10 to 45/55, preferably 80
/ 20 to 50/50. If the proportion of the component (b) is less than this range, the production of organic peracids will be suppressed, and sebum dirt cleaning properties will also tend to decrease.

The ratio of the component b to the component c is b / c = 7.
/ 93 to 75/25, preferably 15/85 to 6
5/35. If the ratio of the component b is out of this range, the effect of the present invention tends to be insufficient.

Low surfactant concentrations can be achieved by lowering the detergent concentration in the wash liquor. Detergent concentration is determined from standard usage. The detergent concentration usually depends on the hardness of the washing water used. This is because it is necessary to adjust the amount of the sequestering agent according to the hardness of the washing water.

[0026] The standard usage of detergents varies from country to country in the world. 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 in the past.

That is, the detergent concentration when the initial hardness of the washing liquid is different is as follows. 1) For washing water of 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) For washing water of 6 to 10 ° DH, 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. 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.

Although the standard amount varies depending on the hardness of the water as described above, the surfactant concentration basically does not largely change.
In the present invention, excellent detergents can be obtained even when the detergent concentration is as low as 0.07 to 0.17 g / L, particularly 0.08 to 0.14 g / L, when the detergent concentration is determined by the standard usage amount. You can gain power.

A) Surfactant The surfactant used in the present invention is not particularly limited as long as it is generally used in detergents. Those containing 100% by weight, particularly 70 to 100% by weight are preferred.

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 alkyl phenyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbite fatty acid ester, polyethylene glycol fatty acid ester, and polyoxyethylene polyoxypropylene. Examples include alkyl ether, polyoxyethylene castor oil, polyoxyethylene alkylamine, glycerin fatty acid ester, higher fatty acid alkanolamide, alkyl glucoside, and alkylamine oxide.

Of these, it is desirable to use polyoxyethylene alkyl ether obtained by adding an average of 5 to 15 moles of ethylene oxide to a linear alcohol having 10 to 18 carbon atoms since sebum dirt is easily washed.

Examples of the anionic surfactant include alkyl benzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, α-olefin sulfonate, α-sulfofatty acid salt or ester salt, and alkyl or alkenyl ether carboxylate. Examples thereof include acid salts, amino acid type surfactants, N-acyl amino acid type surfactants, and the like, preferably alkyl benzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate and the like.

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

B) Regarding the crystalline alkali metal silicate As the crystalline alkali metal silicate used in the present invention, alkali metal silicates having various compositions can be used, and SiO ₂ / M ₂ O (however, M represents an alkali metal) is 0.5 to 2.6, preferably 1.
What is 5-2.2 is used suitably. SiO ₂ /
When M ₂ O exceeds 2.6, the sebum dirt cleaning property of the detergent composition tends to decrease, and the generation efficiency of organic peracid tends to decrease. When it is less than 0.5, powder or powder as a granular detergent Decreases physical properties. In the present invention, by using a crystalline silicate, not only high alkali ability but also ion exchange ability can be imparted.

Among 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 of the present invention may be a hydrate, in which case the hydrated amount is w
= 0 to 20.

In the general formula, y / x is 0.5 to
2.6, and 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 property, solubility, and powder properties of the detergent composition are significantly adversely affected. y / x is 2.6
If it exceeds, the alkalinity of the crystalline alkali metal silicate will be low, and it will be insufficient as an alkali agent, and the ion exchange capacity will also be low, making it insufficient as an ion exchanger. z / x is 0.01 to 1.0, preferably 0.1 to 1.0.
02 to 0.9. When z / x is less than 0.01, the water resistance of the crystalline alkali metal silicate is insufficient.
If it exceeds 0, the ion exchange capacity of the crystalline alkali metal silicate becomes low, and it 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,
It is substantially selected from the values of 0.5, 1.0, 1.5 and 2.0.

The crystalline alkali metal silicate of the composition of the present invention, M ₂ O as shown in the above formula (II), which is from the three components of SiO _2, Me _m O _n. Therefore, in order to produce the crystalline alkali metal silicate according to the present invention, each component is required as a raw material. In the present invention, a known compound is appropriately used without any 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 a 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. Silica The SiO ₂ component, kaolin, talc,
Fused silica, sodium silicate and the like are used.

In the method for preparing a crystalline alkali metal silicate according to the present invention, the above-mentioned raw material components are mixed in a predetermined quantitative ratio so that the desired x, y, z values of the crystalline alkali metal silicate are obtained. Mixing, usually 300 to 1500 ° C, preferably 500 to 1000 ° C, more preferably 600 to 900 ° C.
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. If the heating temperature exceeds 1500 ° C., coarse particles are formed and the ion exchange ability is lowered. The heating time is usually 0.1 to 24 hours. Such firing can be usually performed in a heating furnace such as an electric furnace or a gas furnace.

The crystalline alkali metal silicate thus obtained exhibits a pH of 11 or more in a 0.1% by weight dispersion and exhibits excellent alkalinity. 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 according to the present invention has an ion exchange capacity of at least 100 CaCO ₃ mg / g or more, preferably 200 to 200 mg / g.
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 an alkali function and an alkali buffering effect as described above, and furthermore has an ion exchange function. Conditions can be suitably adjusted.

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.
Further, the alkali metal silicate may be an aggregate of primary particles. If the average primary particle size exceeds this range, the rate of onset of ion exchange tends to decrease, leading to 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. Here, the average particle size 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 average particle size and particle size distribution can be prepared by pulverizing using a pulverizer such as a vibration mill, a hammer mill, a ball mill, a roller mill and the like. For example, HB
It can be easily obtained by pulverizing 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. The crystalline alkali metal silicates have the general formula _{(III) M 2 O · x'SiO} 2 · y'H 2 O (III) ( wherein, M represents an alkali metal, x '= 1.5 to 2.
6, preferably 1.5 to 2.2, y ′ = 0 to 20, preferably 0 to 4. ), Wherein x ′ and y ′ in the general formula (III) are 1.7 ≦ x ′ ≦ 2.2 and y ′
= 0 is particularly preferred, and the cation exchange capacity is 100 to
400 CaCO ₃ mg / g can be used, and it is one of the substances having an ion trapping ability in the present invention. As M ₂ O and SiO ₂ in the general formula (III), the same ones as the crystalline alkali metal silicate having the following composition are used. The crystalline alkali metal silicate having the composition according to the present invention thus has an alkali ability and an alkali buffering effect, and further has an ion exchange ability. Conditions can be suitably adjusted.

The production method of such a crystalline alkali metal silicate is described in Japanese Patent Application Laid-Open No. 60-227895.
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. The crystalline alkali metal silicate is available in powder or granule form, for example, from Hoechst-Tokuyama under the trade name “Na-SKS-6” (δ-Na ₂ Si ₂ O ₅ ).

In the present invention, the crystalline alkali metal silicate having the following composition preferably has an average primary particle size of 0.1 to 20 μm, more preferably 1 to 10 μm, as in the case of the composition. It is. Moreover, the aggregated primary particles may be used. The average primary particles here can be obtained by a method similar to that of the composition.

In the present invention, the crystalline alkali metal silicates having the above composition and the above composition may be used alone or in combination of two or more kinds.
0% by weight, more preferably 2% by weight.
0 to 35% by weight. When the amount is larger than this range, the powder properties of the obtained detergent tend to decrease, and in addition, sebum dirt-cleaning properties also tend to decrease.If the amount is less than this range, the generation rate of organic peracid decreases, and sebum decreases. 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 is 100 CaCO ₃ mg obtained by the following measurement method.
/ G or more. That is, the method for measuring the ion-capturing ability of the sequestering substance differs depending on whether the sequestering substance to be 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 solution of calcium chloride (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. From that value, the calcium ion exchange capacity (cation exchange capacity) of the sample is determined. 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, the ability to capture Ca ions is measured as follows using a calcium ion electrode. 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 Capability of Capturing Calcium Ions About 0.1 g of a sample is weighed in a 100 ml volumetric flask, and the volume is increased with the above buffer solution. In addition, 2000
A CaCl ₂ aqueous solution (pH 10.0) corresponding to 0 ppm (CaCO ₃ conversion) is dropped from the burette (blanks are also measured). For the dropwise addition, use a CaCl ₂ aqueous solution of 0.1 to
0.2 ml at a time, read the potential at that time,
The calcium ion concentration is determined from the calibration curve of FIG. FIG.
The calcium ion concentration at the dropping amount A of the sample inside becomes the calcium ion trapping ability of the sample. For example, in the present invention, polycarboxylates such as citrate and polycarboxylate polymers such as acrylic acid-maleic acid copolymer are measured as chelating agents.

Among the sequestering agents as described above, C
a It is preferable that the polymer contains 1% by weight or more of a polycarboxylate polymer having an 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), as the alkali metal, Na,
K, Li and the like, and examples of the alkaline earth metal include C
a, Mg and the like.

The polymer or copolymer used in the present invention may be, for example, a polymerization reaction of acrylic acid, (anhydride) maleic acid, methacrylic acid, α-hydroxyacrylic acid, crotonic acid, isocrotonic acid, and salts 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 polymer and copolymer, those having a weight average molecular weight of 800 to 1,000,000 are used, and those having a weight average molecular weight of 5000 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 ratio of the repeating unit of the general formula (IV) and another copolymerizable monomer in the case of copolymerization is not particularly limited, but preferably, the repeating unit of the general formula (IV) / other copolymerized monomer = 1 / 100 to 90/10.

Further, the sequestering agent of the component c further contains an ion exchange capacity represented by the following formula (V) of 200 Ca
Those containing an aluminosilicate of not less than CO ₃ mg / g are 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 aluminosilicates include crystalline ones and amorphous ones. The crystalline ones are particularly preferably those represented by the following general formula. _{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,
Average primary particle size of 0.1 represented by X-type and P-type zeolites.
1-10 μm synthetic zeolites are 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-mentioned 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, an amorphous aluminosilicate represented by the same general formula as that of the above-mentioned 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 to Al ₂ O ₃ is M ₂ O / Al ₂ O ₃ = 1.0 to 2.0;
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.

Next, the resulting white precipitate slurry is heated at 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-
Organic chelating agents such as salts of phosphonocarboxylic acids such as 1,2-dicarboxylic acid, citrates, nitrilotriacetates, and aminopolyacetates such as ethylenediaminetetraacetate.

Other components in the present invention include, as an alkali agent, an alkali metal salt such as an amorphous alkali metal silicate, carbonate and sulfite, and an organic amine such as an alkanolamine.

Further, non-dissociated polymers such as polyethylene glycol, polyvinyl alcohol, and polyvinylpyrrolidone;
Examples of such agents include carboxymethylcellulose, which is generally known to be incorporated into detergents, and is an anti-fading agent and a re-staining agent.

In addition, the detergent composition of the present invention can also contain the following components. That is, enzymes such as protease, lipase, cellulase, and amylase,
Contains about 4 lower alkylbenzene sulfonates, sulfosuccinates, talc, calcium silicate, etc., anti-caking agents, tertiary butylhydroxytoluene, 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. The method for producing the detergent composition is not particularly limited, and a conventionally known method can be used. However, it is preferable that the organic peracid precursor, the hydrogen peroxide-releasing substance and the enzyme are manufactured as separate powders and then dry-blended in order to prevent a decrease in bleaching activity due to a reaction between the two during the manufacturing process. . Specifically, for example,
As a method for obtaining a high bulk density detergent, JP-A-61-6
Methods described in JP-A-9897, JP-A-61-69899, JP-A-61-69900 and JP-A-5-209200 can be used.

[0066]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to 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. In addition, as a method of indicating the ion-capturing ability of the sequestering agent, it is represented by CEC (calcium ion exchange capacity) in the table of the examples, similarly to the alkali metal silicate. The DH hardness was measured by an 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, the ability to capture Ca ions was measured as follows using a calcium ion electrode. All the solutions were prepared using the following buffers. _{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 calcium ion concentration and the potential as shown in FIG. 1 was prepared. (Ii) Measurement of Calcium Ion Capturing Capacity About 0.1 g of a sample is weighed in a 100 ml volumetric flask, and the volume is increased with the above buffer solution. In addition, 2000
A CaCl ₂ aqueous solution (pH 10.0) corresponding to 0 ppm (CaCO ₃ equivalent) was dropped from the burette (blanks were also measured). For the dropwise addition, use a CaCl ₂ aqueous solution of 0.1 to
0.2 ml at a time, read the potential at that time,
The calcium ion concentration was determined from the calibration curve of FIG. FIG.
The calcium ion concentration at the drop amount A of the sample in the middle was defined 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 analyzer. 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 its 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
To 5 parts by weight of sodium hydroxide, 55.9 parts by weight of sodium hydroxide and 8.5 parts by weight of potassium hydroxide were added, 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. for 1 hour in air, quenched, and the obtained fired body was pulverized to obtain a crystalline alkali metal silicate powder A of 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 BF 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 a 6% by weight aqueous solution. 132 g of this aqueous solution and 38.28 g of aqueous sodium aluminate 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 the primary reaction, the reaction system was heated to 50 ° C., and the secondary reaction was performed 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 (No. 5C manufactured by Toyo Roshi Kaisha, Ltd.). The filter cake is washed with water 1000 times and filtered and dried (105 ° C, 300 torr, 10
Time), and the remainder was dried under the same conditions (without washing). Further, crushing was performed to obtain an amorphous aluminosilicate powder of the present invention. The aqueous sodium aluminate solution is 10
243 g of Al (OH) _{3 and} 298.7 g of a 48% aqueous NaOH solution were put in a 00 cc four-necked flask, 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, and Na ₂ O = 18.0.
% (1.0 Na ₂ O · Al ₂ O ₃ · 3.1
0SiO ₂ ). In addition, the ability to capture Ca ions is 185 CaC
O ₃ mg / g, oil absorption capacity 285 ml / 100 g, 0.1
The ratio of the pore volume having a pore diameter of less than μm is 9.4%,
The ratio of the pore volume 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 previously dehydrated, was dispersed in 300 g of dimethylformamide (DMF), and stirred while stirring with a mechanical stirrer. Then, lauric acid chloride was dropped at 30 ° C. over 30 minutes, and reacted for 3 hours after the completion of the dropping. 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 performed in a solvent to obtain sodium lauroyloxybenzenesulfonate (yield 85%).

Further, in the same manner as in the above method except that acetyl chloride is used instead of lauric acid chloride, sodium alkanoyloxybenzenesulfonate (C =
1) was obtained.

Examples 1 to 5 and Comparative Examples 1 to 8 The crystalline alkali metal silicates A obtained in the above preparation examples
To 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, the crystalline alkali metal silicates A to F, the amorphous aluminosilicate, the nonion, the sodium percarbonate, the bleach activator (Na alkanotyloxybenzenesulfonate), the fragrance, and the enzyme were used. Aqueous components (LAS-Na, AS-Na, polyacrylic acid N
a, sodium carbonate, sodium sulfate, etc.) into a 60% solids slurry, spray-dry the resulting particles, place them in a Loedige mixer, and add the remaining powdered raw materials to the liquid nonionic surfactant. Was mixed and granulated while gradually adding. In addition, about sodium percarbonate in each Example and the comparative example, the granular raw material was blended. In this way, the bulk density of the average particle diameter of 300 to 600 μm is 0.6 to
A detergent composition of 1.0 g / ml powder was obtained.

Test Example Using the detergent compositions obtained in the above Examples and Comparative Examples, a cleaning test was performed under the following conditions. <Method for Measuring Sebum Soil Washing Ratio> (1) Preparation of Artificial Soiled Cloth An artificially stained cloth having the following composition was adhered to the cloth to prepare an artificially stained cloth. The adhesion of the artificially contaminated liquid to the cloth is described in JP-A-7-2703.
A gravure type contaminator using a gravure roll coater described in No. 95 was used. The step of preparing the artificially contaminated cloth by adhering the artificially contaminated liquid to the cloth includes a gravure roll cell capacity of 58 cm ³ / cm ² , a coating speed of 1.0 m / min,
The drying was performed at a drying temperature of 100 ° C. for a drying time of 1 minute. The cloth used was a cotton cloth 2003 (manufactured by Tanito Shoten). [Composition of artificial contaminated liquid] Lauric acid 0.44% by weight Myristic acid 3.09% by weight 2.31% by weight pentadecanoic acid 6.18% by weight Heptadecanoic acid 0.44% by weight Stearic acid 1.57% by weight Olein 7.75% by weight of acid 13.06% by weight of triolein 2.18% by weight of n-hexadecyl palmitate 6.53% by weight of squalene 1.94% by weight of egg white lecithin liquid crystal material 8.11% by weight of Kanuma red soil 8.11% by weight of carbon black 0.01 Weight% tap water balance

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

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

<Method for Measuring Washability of Yellowish Stain> (1) Preparation of Model Yellowish Underwear Linoleic acid and squalene (weight ratio 1:10), which are considered as yellowish components, are dispersed and dissolved in chloroform (concentration 10%). 0.6 ml of this solution was dropped onto an 8 cm × 8 cm cotton cloth (cotton gold cloth # 2003) per sheet, 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 yellowing stained cloth.

(2) Washing and bleaching experiment A set of four stained cloths obtained by the above method was used.
Wash with a targotometer (manufactured by Shimadzu Corporation). The conditions are as follows: washing 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 Washing Ratio The reflectance of the original fabric and the stained fabric before and after washing were 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 equation to evaluate the bleaching cleaning performance. The results are shown in Tables 2 to 4.

[0083]

(Equation 1)

[0084]

[Table 2]

[0085]

[Table 3]

[0086]

[Table 4]

The abbreviations and the like in the table are as follows. POE: average ethylene oxide addition mole number LAS-Na: sodium linear alkylbenzene sulfonate AS-Na: sodium alkyl sulfate nonion: polyoxyethylene alkyl ether, addition mole number is 8 mole average Zeolite: 4A type zeolite average particle size 3 μm AA / MA copolymer: a copolymer of acrylic acid and maleic acid as monomers, average molecular weight of 70000, sodium salt of acrylic acid: maleic acid = 70: 30, degree of neutralization of about 80% Amorphous aluminosilicate: Preparation Example 2 Polyacrylic acid sodium: a polymer of sodium acrylate,
Average molecular weight 10,000, degree of neutralization about 80% Other components: oxygen (combined use of protease and cellulase) Fragrance (fragrance described in JP-A-5-202387) Fluorescent dye (combined use of biphenyl and stilbene type) Water

In all of the examples of the present invention, a high sebum dirt cleaning rate and a yellowish dirt cleaning rate were exhibited. On the other hand, Comparative Example 1 in which the number of carbon atoms of the organic peracid is small, Comparative Example 2 in which the crystalline alkali metal silicate SiO ₂ / M ₂ O is too large,
Comparative Examples 3 and 5 where the total amount of components a, b and c is small, Comparative Example 4 which is an anionic detergent composition, Comparative Example where 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 is too large, and Comparative Example 8 in which the amount of the surfactant used is too small, both of the sebum dirt cleaning rate and the yellowish dirt cleaning rate were compared with the examples. Was inferior.

[0089]

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 the 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 illustrating a relationship between a dropping amount of a sample and a calcium ion concentration.

──────────────────────────────────────────────────の Continued on the front page (72) Inventor Noriaki Ushio 1334 Minato, Wakayama City Kao Corporation Research Laboratory (72) Inventor Shigeru Tamura 1334 Minato Wakayama City Research Laboratory Kao Corporation Research Laboratory (72) Inventor Masaki Tsumori Wakayama City 1334 Minato, Research Institute of Kao Corporation (56) References JP-A-7-53992 (JP, A) JP-A-6-316700 (JP, A) International publication 95/2682 (WO, A1) International publication 94/28103 (WO, A1) WO 94/28104 (WO, A1) WO 95/626 (WO, A1) WO 94/28106 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) ) C11D 1/00-19/00

Claims (11)

(57) [Claims] Claims: 1. Reacts with hydrogen peroxide in water and has a carbon number of 7 to
A granular or powdery bleaching detergent composition containing an organic peracid precursor which produces an organic peracid having an alkyl group of 19 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, wherein the total amount of the components a, b, and c accounts for 70 to 99% by weight of the bleaching detergent composition; B / a = 90/10 to 45/55 by weight, and the ratio of b component to c component is b / c = 7/93 to
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 Der is, of the non-ionic surfactant
Bleaching detergent composition content and wherein 50 to 100 wt% der Rukoto of the total surfactant. 2. A bleaching detergent composition according to claim 1 Symbol mounting an over fatty acids are produced organic peracid having a linear alkyl group of 7 to 19 carbon atoms. 3. The bleaching detergent composition according to claim 2, 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.) 4. is a polyoxyethylene alkyl ether nonionic surfactant was an average 5 to 15 mols of ethylene oxide to straight-chain alcohols having 10 to 18 carbon atoms as a component according to claim 1 to 3 The bleaching detergent composition according to any of the above. 5. The crystalline alkali metal silicate SiO ₂
/ M ₂ O (where M represents an alkali metal) is 0.5
The bleaching detergent composition according to any one of claims 1 to 4, wherein 6. The crystalline alkali metal silicate comprises the following (I)
The bleaching detergent composition according to claim 5 , wherein the bleaching detergent composition has the composition represented by 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. ) 7. The crystalline alkali metal silicate comprises the following (II)
The bleaching detergent composition according to claim 5 , which has a composition represented by 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. ) 8. A bleaching detergent composition according to any one of claims 1 to 7 the blending amount of the crystalline alkali metal silicate is 20 to 50 wt%. 9. The hydrogen peroxide-releasing element has an effective oxygen concentration of 5-1.
The bleaching detergent composition according to any one of claims 1 to 8 , wherein the bleaching detergent composition is a 5% granular or powdery substance, and is contained in the bleaching detergent composition in an amount of 0.5 to 15% by weight. 10. A bleaching detergent composition according to claim 1-9, wherein any hydrogen peroxide emitter is sodium percarbonate. 11. A surfactant concentration of 0.07 to 0.17 when a bleaching detergent composition is added to washing water in a standard amount.
The bleaching detergent composition according to any one of claims 1 to 10 , wherein the bleaching detergent composition is g / L.